TW202219118A - Method for producing polyimide precursor and method for producing curable resin composition - Google Patents

Abstract

A method for producing a polyimide precursor having a polymerizable group or a polarity conversion group, the method including a polymerization step in which a dicarboxylic acid compound and a diamine compound are reacted at a temperature of 10 DEG C or lower to obtain a liquid reaction mixture containing an amide compound; and a method for producing a curable resin composition which includes the polyimide precursor obtained by the method for producing a polyimide precursor.

Description

Method for producing polyimide precursor and method for producing curable resin composition

The present invention relates to a method for producing a polyimide precursor and a method for producing a curable resin composition.

Polyimide is suitable for various applications due to its excellent heat resistance and insulating properties. Although it does not specifically limit as said use, if the semiconductor device for encapsulation is exemplified, the use as a material of an insulating film, a sealing material, or a protective film can be mentioned. In addition, it is also used as a base film, a coverlay, and the like of a flexible substrate.

For example, in the above applications, polyimide is used in the form of a curable resin composition containing a polyimide precursor. Such a curable resin composition is applied to a substrate by, for example, coating to form a photosensitive film, and thereafter, if necessary, exposure, development, heating, and the like are performed, whereby a cured product can be formed on the substrate. The above-mentioned polyimide precursor is cyclized by heating, for example, and becomes polyimide in the cured product. Since the curable resin composition can be applied by a known coating method or the like, it can be said that it is excellent in suitability for production, such as the design of the shape, size, and application position of the curable resin composition to be applied at the time of application. High degree of freedom. In addition to the high performance of polyimide, the industrial application of the above-mentioned curable resin composition has been expected more and more from the viewpoint of excellent suitability for such production.

For example, Patent Document 1 describes a resin composition comprising a heterocyclic-containing polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, and an acidic compound having a pKa of 4.0 or less wherein the above-mentioned resin composition is made into a cured film with a thickness of 10 μm, and the conductivity of the cured film after heating at 350° C. for 60 minutes is 1.0×10 ⁵ Ω·cm or less.

[Patent Document 1] International Publication No. 2018/043467

In the curable resin composition, it is required to have a high degree of tolerance for changes in the exposure amount at the time of exposure. In the present invention, the curable resin composition is also referred to as being excellent in exposure latitude as having high tolerance to changes in the exposure amount at the time of exposure.

An object of the present invention is to provide a method for producing a polyimide precursor having excellent exposure latitude when contained in a curable resin composition, and a polyimide comprising the method for producing the above-mentioned polyimide precursor. A method for producing a curable resin composition of an amine precursor.

Examples of typical embodiments of the present invention are shown below. <1> A method for producing a polyimide precursor, comprising: a polymerization step of reacting a dicarboxylic acid compound and a diamine compound at a temperature of 10° C. or lower to obtain a reaction solution containing an imide compound, The obtained polyimide precursor has a polymerizable group or a polarity conversion group. <2> The method for producing a polyimide precursor according to <1>, wherein the polymerization step is carried out in the presence of a basic condensing agent. <3> The method for producing a polyimide precursor according to <2>, wherein the basic condensing agent is a carbodiimide condensing agent. <4> The method for producing a polyimide precursor according to any one of <1> to <3>, comprising adding water or water to the reaction solution at a temperature of 10°C or lower after the polymerization step Alcohol quenching step. <5> The method for producing a polyimide precursor according to any one of <1> to <4>, which further includes a reprecipitation step after the polymerization step. <6> The method for producing a polyimide precursor according to <4>, further comprising a reprecipitation step after the quenching step, After the above-mentioned quenching step and before starting the reprecipitation step, the reaction solution is stored at 10° C. or lower. <7> The method for producing a polyimide precursor according to <4>, further comprising a reprecipitation step after the quenching step, After storing the reaction solution after the quenching step at 10°C or lower, the temperature of the reaction solution was raised to 10°C or higher, and the reprecipitation step was started within 5 hours after the temperature of the reaction solution became 10°C or higher. <8> The method for producing a polyimide precursor according to any one of <5> to <7>, wherein the reprecipitation step is a process of adding a reaction solution containing the imide compound to water or alcohol. step. <9> The method for producing a polyimide precursor according to any one of <1> to <8>, comprising adding an acidity of an acidic compound to a reaction solution containing the above-mentioned imide compound after the polymerization step Compound addition steps. <10> The method for producing a polyimide precursor according to any one of <1> to <9>, further comprising a purification step of purifying a reaction solution containing the imide compound after the polymerization step . <11> The method for producing a polyimide precursor according to any one of <1> to <10>, further comprising a drying step of drying the above-mentioned imide compound after the polymerization step. <12> A method for producing a curable resin composition, comprising: A step of mixing the polyimide precursor obtained by the method for producing a polyimide precursor described in any one of <1> to <11> and other components. <13> The method for producing a curable resin composition according to <12>, wherein at least one compound selected from the group consisting of an organometallic complex having a radical polymerization initiating ability and a photosensitizer is further mixed. [Inventive effect]

According to the present invention, it is possible to provide a method for producing a polyimide precursor having excellent exposure latitude when contained in a curable resin composition, and a polyimide comprising the method for producing the above-mentioned polyimide precursor. A method for producing a curable resin composition of an amine precursor.

Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the illustrated embodiments. In this specification, the numerical range shown using the symbol "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit, respectively. In this specification, the word "step" includes not only independent steps, but also steps that cannot be clearly distinguished from other steps as long as the intended function of the step can be achieved. In the notation of groups (atomic groups) in this specification, the notation of substituted and unsubstituted groups includes groups without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups), but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Moreover, as light used for exposure, the bright-line spectrum of a mercury lamp, extreme ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams and other actinic rays and radiation can be mentioned. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic" means "acrylic acid" and "methacrylate" "Acrylic" or "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl". In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content means the total mass of the components after removing the solvent from all the components of the composition. In addition, in this specification, the solid content concentration refers to the mass percentage of other components other than the solvent with respect to the total mass of the composition. In this specification, unless otherwise stated, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC), and are defined as polystyrene conversion values. In this specification, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) can be obtained by using, for example, HLC-8220GPC (manufactured by TOSOH CORPORATION) as a column to protect the column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (the above are manufactured by TOSOH CORPORATION) were connected in series to obtain the result. Unless otherwise stated, these molecular weights were measured using THF (tetrahydrofuran) as an eluent. However, NMP (N-methyl-2-pyrrolidone) can also be used when THF is not suitable as an eluent, for example, when its solubility is low. In addition, unless otherwise stated, it is assumed that a detector with a wavelength of 254 nm of UV rays (ultraviolet rays) is used for detection in the GPC measurement. In this specification, when describing the positional relationship of each layer constituting the layered product as "upper" or "lower", it is sufficient that there are other layers on the upper side or lower side of the layer serving as a reference among the plurality of layers concerned. . That is, a third layer or element may be further interposed between the layer serving as the reference and the other layers described above, and the layer serving as the reference and the other layers described above do not need to be in contact. Also, unless otherwise specified, the direction in which the layers are gradually stacked with respect to the base material is referred to as "up", or, when there is a resin composition layer, the direction from the base material toward the resin composition layer is referred to as "up", The opposite direction is called "down". In addition, the setting of the up-down direction is for the convenience of this specification, and in an actual aspect, the "up" direction in this specification may be different from the vertical direction. In the present specification, unless otherwise specified, the composition may contain two or more kinds of compounds corresponding to the components as each component contained in the composition. In addition, unless otherwise stated, the content of each component in the composition means the total content of all the compounds corresponding to the component. In this specification, unless otherwise stated, the temperature is 23° C., the air pressure is 101,325 Pa (one air pressure), and the relative humidity is 50% RH.

(Method for producing polyimide precursor) The method for producing a polyimide precursor of the present invention includes a polymerization step of reacting a dicarboxylic acid compound and a diamine compound at a temperature below 10° C. to obtain a reaction solution containing an imide compound, and the obtained polyamide The imine precursor has a polymerizable group or a polarity conversion group.

According to the method for producing a polyimide precursor of the present invention, a polyimide precursor excellent in exposure latitude when contained in a curable resin composition (hereinafter, also simply referred to as "resin composition") can be obtained. Although the mechanism by which the above-mentioned effect is obtained is not clear, it is presumed as follows.

In general, when a dicarboxylic acid compound and a diamine compound are reacted to obtain an amide compound, the polymerization reaction is performed, for example, at room temperature (25° C.). Specifically, for example, after adding the solution of the basic catalyst and the diamine compound to the solution of the dicarboxylic acid compound under ice-cooling, it returns to room temperature and performs a polymerization reaction. However, by carrying out the polymerization at room temperature as in the past, the imidization of the resin proceeds in the reaction system, and the imidization ratio (the cyclic imide structure and the cyclic isoimide in the resin) is obtained. The total content of imine structures) is a high polyimide precursor. Therefore, the amount of polymerizable groups, polarity conversion groups, etc. introduced into the amide acid moiety of the polyimide precursor through the ester bond is reduced, so that the composition of the curable resin composition containing the polyimide precursor is reduced. In the photosensitive film, the exposure latitude will decrease. In the present invention, it is considered that progress of the above imidization can be suppressed by performing the polymerization step at a temperature of 10°C or lower. Therefore, it is presumed that the imidization rate in the polymer is lowered, and the exposure latitude at the time of forming a photosensitive film is improved. Furthermore, since the polyimide precursor obtained by the production method of the present invention has a low imidization rate, the transparency of the polymer is improved, and the transmittance of the exposure light of the photosensitive film is expected to be improved. Sex is also improved.

Here, in Patent Document 1, there is no description at all about performing the polymerization step at a temperature of 10°C or lower. Below, each step included in the manufacturing method of the polyimide precursor of this invention is demonstrated.

<Polymerization step> The method for producing a polyimide precursor of the present invention includes a polymerization step of reacting a dicarboxylic acid compound and a diamine compound at a temperature below 10° C. to obtain a reaction solution containing an imide compound, and the obtained polyamide The imine precursor has a polymerizable group or a polarity conversion group.

The polymerizable group contained in the polyimide precursor is a group capable of performing a crosslinking reaction by the action of heat, radicals, and the like, and a radically polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an oxymethyl group, an epoxy group, an oxetanyl group, and a benzoxazole. group, blocked isocyanate group, methylol group, amine group. As the radically polymerizable group of the polyimide precursor, a group having an ethylenically unsaturated bond is preferable. A vinyl group, a (meth)allyl group, a (meth)acryloyl group, etc. are mentioned as a group which has an ethylenically unsaturated bond, (meth)acryloyl group is preferable.

An acid-decomposable group is mentioned as a polarity conversion group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group and a carboxyl group. An acetal group, a ketal group, a silyl group, and a silyl ether group are included. , a tertiary alkyl ester group, etc. are preferable, and an acetal group is more preferable from the viewpoint of exposure sensitivity. Specific examples of acid-decomposable groups include tertiary butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, and ethoxymethyl. group, trimethylsilyl group, tertiary butoxycarbonyl methyl group, trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.

The temperature in the polymerization step is 10°C or lower, preferably 5°C or lower, and more preferably 0°C or lower. Although it does not specifically limit as a lower limit of the said temperature, -20 degreeC or more is preferable. Furthermore, it is sufficient that at least a part of the polymerization step is carried out within the above-mentioned temperature range, but 50% or more of the time in the polymerization step is preferably carried out within the above-mentioned temperature range, and 80% or more is preferably carried out within the above-mentioned temperature range, More preferably, it is carried out within the above temperature range for more than 90%. The upper limit of the above ratio is not particularly limited, and may be 100%.

The reaction time in the above-mentioned polymerization step is not particularly limited, as long as the type of the dicarboxylic acid compound or diamine compound, the presence or absence of the halogenating agent described later, the type and amount of the basic condensing agent described later, the molecular weight of the resin, and the reaction solution are considered. The concentration of the raw materials, stirring efficiency, and the amount of water contained in the reaction system can be appropriately set, for example, 0.5 to 24 hours is preferred, 0.5 to 18 hours is more preferred, and 1 to 12 hours is further preferred.

式（O）中，R ¹¹⁵表示4價的有機基。 作為R ¹¹⁵中之4價的有機基，包含芳香環之4價的有機基為較佳，下述式（5）或式（6）所表示之基為更佳。 式（5）或式（6）中，*分別獨立地表示與其他結構的鍵結部位。 [化學式2]

式（5）中，R ¹¹²為單鍵或2價的連接基，單鍵或選自可以經氟原子取代之碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO ₂-及-NHCO-以及該等的組合中之基為較佳，單鍵、選自可以經氟原子取代之碳數1～3的伸烷基、-O-、-CO-、-S-及-SO ₂-中之基為更佳，選自包括-CH ₂-、-C（CF ₃） ₂-、-C（CH ₃） ₂-、-O-、-CO-、-S-及-SO ₂-之群組中之2價的基為進一步較佳。 [Dicarboxylic acid compound] The dicarboxylic acid compound in the polymerization step may be used alone or in combination of two or more. As the dicarboxylic acid compound in the polymerization step, a dicarboxylic acid compound derived from tetracarboxylic dianhydride is preferable, and a dicarboxylic acid compound derived from tetracarboxylic dianhydride represented by the following formula (O) is more preferable , the diester of tetracarboxylic dianhydride represented by the following formula (O) is more preferable. [Chemical formula 1]

In formula (O), R ¹¹⁵ represents a tetravalent organic group. As the tetravalent organic group in R ¹¹⁵ , a tetravalent organic group including an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. In formula (5) or formula (6), * each independently represents a bonding site with another structure. [Chemical formula 2]

In formula (5), R ¹¹² is a single bond or a divalent linking group, and the single bond or is selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms, -O-, -CO-, -S-, which can be substituted by fluorine atoms , -SO ₂ - and -NHCO- and the groups in their combination are preferred, single bond, selected from alkylene with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -CO-, The groups in -S- and -SO ₂ - are more preferably selected from the group consisting of -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, - A bivalent base in the group of S- and -SO ₂ - is further preferred.

Specific examples of tetracarboxylic dianhydride include the following: pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4, 4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid Dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6 ,7-Naphthalenetetracarboxylic dianhydride, 1,4,5,7-Naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis( 2,3-Dicarboxyphenyl) propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4 ,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10 -Perylene tetracarboxylic dianhydride, 1,2,4,5-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,8,9,10-phenanthrene tetracarboxylic acid Dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, 1,2,3,4 -Mellitic dianhydride, and these alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

Moreover, as a preferable example, the tetracarboxylic dianhydride (DAA-1) - (DAA-5) described in the 0038 paragraph of International Publication No. 2017/038598 can also be mentioned.

As the dicarboxylic acid compound derived from tetracarboxylic dianhydride, a compound represented by the following formula (O-1) is preferable.

式（O-1）中，R ¹¹⁵表示4價的有機基，A ¹及A ²分別獨立地表示氧原子或-NH-，R ¹¹³及R ¹¹⁴分別獨立地表示1價的有機基。 [Chemical formula 3]

In formula (O-1), R ¹¹⁵ represents a tetravalent organic group, A ¹ and A ² each independently represent an oxygen atom or -NH-, and R ¹¹³ and R ¹¹⁴ each independently represent a monovalent organic group.

In formula (O-1), A ¹ and A ² each independently represent an oxygen atom or -NH-, and an oxygen atom is preferable. In formula (O-1), R ¹¹⁵ has the same meaning as R ¹¹⁵ in formula (O), and the preferred aspects are also the same. In formula (O-1), it is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and it is more preferable that both of them contain a polymerizable group. Examples and preferred aspects of the polymerizable group are the same as the examples and preferred aspects of the polymerizable group contained in the above-mentioned polyimide precursor. Moreover, it is preferable that R ¹¹³ or R ¹¹⁴ is a group represented by the following formula (III).

[Chemical formula 4]

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and a hydrogen atom or a methyl group is preferred. In formula (III), * represents a bonding site with other structures. In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -, a cycloalkylene group or a polyalkeneoxy group. Preferred examples of R ²⁰¹ include ethylidene, propylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecane and other alkylenes. alkylene, 1,2-butanediyl, 1,3-butanediyl, -CH ₂ CH(OH)CH ₂ -, polyalkyleneoxy, more preferably alkylene such as ethylidene, propylidene, -CH ₂ CH(OH)CH ₂ -, cyclohexyl, polyalkylene, and more preferably alkylene such as ethylidene and propylidene, or polyalkeneoxy. In the present invention, the polyalkeneoxy group refers to a group in which two or more alkaneoxy groups are directly bonded. The alkylene groups in the plural alkyleneoxy groups contained in the polyalkeneoxy group may be the same or different, respectively. When the polyalkeneoxy group contains a plurality of alkeneoxy groups with different alkylene groups, the arrangement of the alkeneoxy groups in the polyalkeneoxy group may be random, may be an arrangement with blocks, or It is an arrangement with alternating patterns. The carbon number of the above-mentioned alkylene (when the alkylene has a substituent, including the carbon number of the substituent) is preferably 2 or more, more preferably 2-10, more preferably 2-6, and further 2-5 Preferably, 2 to 4 are further preferred, 2 or 3 are particularly preferred, and 2 is the most preferred. Moreover, the said alkylene group may have a substituent. As a preferable substituent, an alkyl group, an aryl group, a halogen atom, etc. are mentioned. In addition, the number of alkeneoxy groups contained in the polyalkeneoxy group (the number of repetitions of the polyalkeneoxy group) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkeneoxy group includes polyetheneoxy, polypropoxy, polytrimethyleneoxy, polytetramethyleneoxy, or a polytetramethyleneoxy group, or a polytetramethyleneoxy group. A group formed by bonding an oxy group and a plurality of propeneoxy groups is preferable, a polyethoxy group or a polypropeneoxy group is more preferable, and a polyethoxy group is further preferable. In the group formed by the bonding of the above-mentioned plural ethoxy groups and plural propoxy groups, the ethoxy groups and the propoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged alternately Equal pattern. Preferable aspects of the number of repetitions of ethoxy and the like in these groups are as described above.

In formula (O-1), when R ¹¹³ is a hydrogen atom or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor can form a conjugate base with a tertiary amine compound having an ethylenically unsaturated bond. As an example of the tertiary amine compound which has such an ethylenically unsaturated bond, N,N- dimethylamino propyl methacrylate is mentioned.

In formula (O-1), at least one of R ¹¹³ and R ¹¹⁴ may be a polarity converting group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group and a carboxyl group. An acetal group, a ketal group, a silyl group, and a silyl ether group are included. , a tertiary alkyl ester group, etc. are preferable, and an acetal group or a ketal group is more preferable from the viewpoint of exposure sensitivity. Specific examples of acid-decomposable groups include tertiary butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, and ethoxymethyl. group, trimethylsilyl group, tertiary butoxycarbonyl methyl group, trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.

式（III-1）中，R ²⁰⁰及R ²⁰¹的含義分別與式（III）中的R ²⁰⁰及R ²⁰¹相同，較佳態樣亦相同。 [Dicarboxylic acid compound synthesis step] The production method of the polyimide precursor of the present invention may include a dicarboxylic acid compound synthesis step of synthesizing a dicarboxylic acid compound derived from tetracarboxylic dianhydride before the polymerization step. The dicarboxylic acid compound obtained by the dicarboxylic acid compound synthesis step can be used as the dicarboxylic acid compound in the above-mentioned polymerization step. The above-mentioned dicarboxylic acid compound synthesis step is, for example, a step of reacting tetracarboxylic dianhydride with a compound having at least one of a hydroxyl group and an amine group, and preferably, the tetracarboxylic dianhydride and the compound having a hydroxyl group are reacted. steps are better. As a compound which has at least one of the said hydroxyl group and an amino group, the compound which can obtain the structure of the said R ¹¹³ and R ¹¹⁴ in formula (O-1) may be suitably selected, for example. For example, if a compound having a hydroxyl group is used, a compound in which A ¹ or A ² in the formula (O-1) is an oxygen atom can be synthesized, and if a compound having an amine group is used, A in the formula (O-1) can be synthesized A compound in which ¹ or A ² is -NH-. For example, in order to obtain a dicarboxylic acid compound in which A ¹ and A ² are oxygen atoms in the above formula (O-1) and R ¹¹³ and R ¹¹⁴ are the structure represented by the above formula (III), the following formula (III) can be used. The compound represented by -1) is the compound having the above-mentioned hydroxyl group. [Chemical formula 5]

In formula (III-1), R ²⁰⁰ and R ²⁰¹ have the same meanings as R ²⁰⁰ and R ²⁰¹ in formula (III), respectively, and the preferred aspects are also the same.

Regarding the reaction conditions, reaction methods and the like in the above-mentioned dicarboxylic acid synthesis step, it is sufficient to refer to the reaction conditions and reaction methods in the known esterification reaction or known amidation reaction.

[Diamine compound] The diamine compound in the polymerization step may be used alone or in combination of two or more. As a diamine compound, a linear or branched aliphatic, cyclic aliphatic or aromatic diamine etc. are mentioned. Although it does not specifically limit as a diamine compound, The compound represented by following formula (Da-1) is preferable.

式（Da-1）中，R ¹¹¹表示2價的有機基。 作為2價的有機基，可以例示出包含直鏈或支鏈的脂肪族基、環狀的脂肪族基及芳香族基之基，碳數2～20的直鏈或支鏈的脂肪族基、碳數3～20的環狀的脂肪族基、碳數3～20的芳香族基或由該等的組合構成之基為較佳，包含碳數6～20的芳香族基之基為更佳。上述直鏈或支鏈的脂肪族基的鏈中的烴基可以經包含雜原子之基取代，上述環狀的脂肪族基及芳香族基的環員的烴基可以經包含雜原子之基取代。作為本發明的較佳實施形態，可以例示出-Ar-及-Ar-L-Ar-所表示之基，特佳為-Ar-L-Ar-所表示之基。其中，Ar分別獨立地為芳香族基，L為單鍵、可以經氟原子取代之碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO ₂-或-NHCO-或由上述中的2個以上的組合構成之基。該等的較佳範圍如上所述。 [Chemical formula 6]

In formula (Da-1), R ¹¹¹ represents a divalent organic group. As the divalent organic group, there can be exemplified groups including linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, linear or branched aliphatic groups having 2 to 20 carbon atoms, A cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and a group comprising an aromatic group having 6 to 20 carbon atoms is more preferable. . The hydrocarbon group in the chain of the straight or branched aliphatic group may be substituted with a group containing a heteroatom, and the hydrocarbon group of the ring members of the cyclic aliphatic group and the aromatic group may be substituted with a group containing a heteroatom. As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- can be exemplified, and groups represented by -Ar-L-Ar- are particularly preferred. Wherein, Ar is each independently an aromatic group, L is a single bond, an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or - NHCO- or a group consisting of a combination of two or more of the above. The preferred ranges of these are as described above.

Specifically, it includes a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof. The diamine of the base is preferable, and the diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. The hydrocarbon group in the chain of the straight or branched aliphatic group may be substituted with a group containing a hetero atom, and the hydrocarbon group of the ring members of the cyclic aliphatic group and the aromatic group may be substituted with a group containing a hetero atom. As an example of the group containing an aromatic group, the following are mentioned. Specifically, it includes a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof. The diamine of the base is preferable, and the diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. The hydrocarbon group in the chain of the straight or branched aliphatic group may be substituted with a group containing a hetero atom, and the hydrocarbon group of the ring members of the cyclic aliphatic group and the aromatic group may be substituted with a group containing a hetero atom. As an example of the group containing an aromatic group, the following are mentioned.

式中，A為單鍵或2價的連接基，單鍵或選自可以經氟原子取代之碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-SO ₂-、-NHCO-或該等的組合中之基為較佳，單鍵、選自可以經氟原子取代之碳數1～3的伸烷基、-O-、-C（=O）-、-S-或-SO ₂-中之基為更佳，-CH ₂-、-O-、-S-、-SO ₂-、-C（CF ₃） ₂-或-C（CH ₃） ₂-為進一步較佳。 式中，*表示與其他結構的鍵結部位。 [Chemical formula 7]

In the formula, A is a single bond or a divalent linking group, and the single bond or is selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be substituted by fluorine atoms, -O-, -C(=O)-, -S- , -SO ₂ -, -NHCO- or the combination of these groups are preferred, single bond, selected from alkylene with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -C (= The base in O)-, -S- or -SO ₂ - is more preferred, -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ - or -C(CH 2 - ₃ ) _2- is further preferred. In the formula, * represents a bonding site with other structures.

Specifically, as the diamine, at least one diamine selected from the group consisting of 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminopropane, ,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclopentane Aminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-amino) cyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophorone diamine; m- or p-phenylenediamine, diaminotoluene, 4, 4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- and 3,3'-diphenyl ether Aminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diamine Biphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl) phenyl) hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2 -Bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) bismuth, bis(4-amino-3-hydroxyphenyl) bismuth, 4,4'-diamino-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4 -(4-Aminophenoxy)phenyl]sine, bis[4-(3-aminophenoxy)phenyl]ssene, bis[4-(2-aminophenoxy)phenyl]ssenes , 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminobis Phenyl benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene , 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane Amino octafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexa Fluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetramine diphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis( 4-Aminophenyl) benzene, 4,4'-dimethyl-3,3'-diaminodiphenylene, 3,3',5,5'-tetramethyl-4,4'- Diaminodiphenylmethane, 2,4- and 2,5-Diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetguanidine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6 -Trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diamino Pyrene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzylaniline, ester of diaminobenzoic acid, 1,5-diamino Naphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis( 4-Aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl ] Hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5 -Dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis( 4-Amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4 -Amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl, 4,4'-bis (3-Amino-5-trifluoromethylphenoxy)diphenyl, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoro Propane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl , 2,2',5,5',6,6'-hexafluorotris-tetraphenyl and 4,4'-diamino-p-tetraphenyl.

Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. WO 2017/038598 are also preferred.

In addition, diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 can also be preferably used.

From the viewpoint of the flexibility of the obtained organic film, R ¹¹¹ is preferably represented by -Ar-L-Ar-. Wherein, Ar is each independently an aromatic group, L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO- or A base consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms, -O-, -CO-, -S- or -SO ₂ - which may be substituted by a fluorine atom. The aliphatic hydrocarbon group here is preferably an alkylene group.

式（51）中，R ⁵⁰～R ⁵⁷分別獨立地為氫原子、氟原子或1價的有機基，R ⁵⁰～R ⁵⁷中的至少1個為氟原子、甲基或三氟甲基，*分別獨立地表示與式（Da-1）中的氮原子的鍵結部位。 作為R ⁵⁰～R ⁵⁷的1價的有機基，可以舉出碳數1～10（較佳為碳數1～6）的未經取代之烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 [化學式9]

式（61）中，R ⁵⁸及R ⁵⁹分別獨立地為氟原子、甲基或三氟甲基，*分別獨立地表示與式（Da-1）中的氮原子的鍵結部位。 作為提供式（51）或（61）的結構之二胺，可以舉出2,2’-二胺基聯苯胺、2,2’-雙（三氟甲基）-4,4’-二胺基聯苯、2,2’-雙（氟）-4,4’-二胺基聯苯、4,4’-二胺基八氟聯苯等。該等可以使用一種或者組合使用兩種以上。 In addition, from the viewpoint of i-ray transmittance, it is preferable that R ¹¹¹ is a divalent organic group represented by the following formula (51) or formula (61). In particular, the divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability. Formula (51) [Chemical Formula 8]

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group or a trifluoromethyl group, * Each independently represents the bonding site to the nitrogen atom in the formula (Da-1). Examples of the monovalent organic group of R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably carbon number 1 to 6), and an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably carbon number 1 to 10). 1-6) fluorinated alkyl groups, etc. [Chemical formula 9]

In the formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding site to the nitrogen atom in the formula (Da-1). 2,2'-diaminobenzidine and 2,2'-bis(trifluoromethyl)-4,4'-diamine are mentioned as the diamine which provides the structure of formula (51) or (61). Biphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These can be used alone or in combination of two or more.

[Halogenating agent] In the polymerization step, in order to carry out amidation, the carboxyl group in the dicarboxylic acid compound may be halogenated using a halogenating agent. The halogenating agent is not particularly limited, and compounds known in the amination reaction can be used, and examples thereof include thionyl chloride, phosphonium chloride, and the like.

[Basic Condensing Agent] In order to carry out the amidation in the polymerization step, it is preferable to carry out the polymerization step in the presence of a basic condensing agent. When a basic condensing agent is used, the imidization rate of the above-mentioned polyimide precursor is easily increased by the action of the base during or after the synthesis, so that the effect of the present invention can be more easily obtained. It does not specifically limit as a basic condensing agent, A well-known basic condensing agent in an amidation reaction can be used, For example, the following compounds are mentioned. In addition, as the basic condensing agent, carbodiimide compounds are preferable, N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, 1-(3-diimide Methylaminopropyl)-3-ethylcarbodiimide or 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide methyl iodide (methiodide) is more preferred , N,N'-dicyclohexylcarbodiimide is further preferred. [Chemical formula 10]

The amount of the basic condensing agent is not particularly limited, but is preferably 0.1 to 4.0 mol, more preferably 0.2 to 3.0 mol, relative to 1.0 mol of the dicarboxylic acid compound.

[Solvent] In addition, it is preferable to carry out the reaction step in the presence of an organic solvent. The organic solvent can be appropriately determined according to the raw material, and examples thereof include pyridine, γ-butyrolactone, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrole. pyridone. These may be used individually by 1 type, and may be used in combination.

〔operate〕 In the reaction step, for example, the dicarboxylic acid compound can be dissolved in the organic solvent at a reaction temperature of 10°C or lower (preferably 5°C or lower, more preferably 0°C or lower, and preferably -20°C or higher). The obtained solution is carried out by adding a solution obtained by dissolving the above-mentioned diamine compound in the above-mentioned organic solvent. The addition method is not particularly limited, and a method such as adding dropwise the organic solvent solution of the above-mentioned diamine compound to the organic solvent solution of the above-mentioned dicarboxylic acid compound over 10 to 300 minutes can be used. When the above-mentioned reaction step is carried out in the presence of the above-mentioned basic condensing agent, the above-mentioned reaction step can be carried out by dissolving the above-mentioned dicarboxylic acid compound in the above-mentioned solution before adding the solution obtained by dissolving the above-mentioned diamine compound in the above-mentioned organic solvent. The solution obtained by adding the organic solvent to the solution obtained by dissolving the above-mentioned basic condensing agent in the above-mentioned organic solvent is added. The addition method is not particularly limited, and a method such as adding dropwise the organic solvent solution of the above-mentioned diamine compound to the organic solvent solution of the above-mentioned dicarboxylic acid compound over 10 to 300 minutes can be used. The temperature at the time of adding the above-mentioned basic condensing agent is not particularly limited, but is preferably 10°C or lower, more preferably 5°C or lower, and more preferably 0°C or lower. Although it does not specifically limit as a lower limit of the said temperature, -20 degreeC or more is preferable. In this case, the solution which melt|dissolved the said diamine compound in the said organic solvent is added to the solution containing the said dicarboxylic acid compound, the said basic condensing agent, and the said organic solvent.

Moreover, in a polymerization process, after adding the said diamine compound, you may make it react further by specific reaction temperature and reaction time. In the above reaction, it is preferable to stir the mixed solution to which the diamine compound is added. The stirring mechanism is not particularly limited, and a well-known method such as a stirrer may be used. The reaction temperature is preferably 10°C or lower, more preferably 5°C or lower, and more preferably 0°C or lower. In addition, the lower limit is not particularly limited, but -20°C or higher is preferable. Although it does not specifically limit as said reaction time, For example, it can be 0.5-24 hours.

<Quenching step> Preferably, the method for producing a polyimide precursor of the present invention includes a quenching step of adding water or alcohol to the reaction solution obtained by the above-mentioned polymerization step. In addition, the quenching step is preferably a step of adding water or alcohol to the reaction solution at a temperature of 10° C. or lower after the polymerization step. In the present invention, the reaction solution to which water or alcohol is added after the quenching step is also referred to as a "reaction mixture". The temperature of the quenching step is not particularly limited, but is preferably 10°C or lower, preferably 5°C or lower, and more preferably 0°C or lower. Although it does not specifically limit as a lower limit of the said temperature, -20 degreeC or more is preferable. In addition, at least a part of the quenching step may be performed within the above-mentioned temperature range, but the temperature at which the quenching step is started is preferably within the above-mentioned range. It is considered that the imidization rate in the polyimide precursor decreases by the temperature at the time of starting the quenching step being within the above-mentioned range.

In the above-mentioned quenching step, water or alcohol is added to the reaction solution, but it is more preferable to add alcohol. As said alcohol, methanol, ethanol, propanol, isopropanol, butanol etc. are mentioned, ethanol is preferable. For example, the addition amount of water or alcohol can be 0.01 to 1.00 g, preferably 0.05 to 0.50 g, relative to 1 g of the resin in the reaction liquid.

〔operate〕 The above-mentioned quenching step is performed, for example, by adding water or alcohol to the above-mentioned reaction solution. The temperature at the time of the above addition is preferably 10°C or lower, more preferably 5°C or lower, and more preferably 0°C or lower. Although it does not specifically limit as a lower limit of the said temperature, -20 degreeC or more is preferable.

In addition, in the quenching, after adding the above-mentioned water or alcohol, the reaction may be further carried out at a specific reaction temperature and reaction time. In the above reaction, it is preferable to stir the mixed solution to which water or alcohol is added. The stirring mechanism is not particularly limited, and a well-known method such as a stirrer may be used. The reaction temperature is preferably 30°C or lower, more preferably 20°C or lower, more preferably 10°C or lower, further preferably 5°C or lower, and particularly preferably 0°C or lower. In addition, the lower limit is not particularly limited, but -20°C or higher is preferable. Although it does not specifically limit as said reaction time, For example, it can be 0.5-24 hours.

<Filtering step> The method for producing a polyimide precursor of the present invention may include a filtration step of removing precipitates deposited in the reaction solution by filtration after the quenching step. The method of filtering is not particularly limited, and may be performed by a known method.

<Reprecipitation step> Preferably, the manufacturing method of the polyimide precursor of the present invention further includes a reprecipitation step. The reprecipitation step is to make the obtained amide compound (polyamide) in the above-mentioned reaction solution (the reaction solution after the quenching step when the quenching step is included) obtained by the polymerization step and containing the polyimide precursor. The step of precipitation of imine precursors to obtain amide compounds (polyimine precursors). Thereby, at least a part of the impurities contained in the reaction liquid can be removed, and a polyimide precursor with high purity can be obtained. As a method for obtaining the precipitated polyimide precursor, filtration and the like can be mentioned, and a known method can be used without particular limitation. The temperature in the reprecipitation step is not particularly limited, and for example, it can be performed at a temperature of 0°C to 40°C.

The reprecipitation step is preferably the step of adding the above-mentioned reaction solution (if the quenching step is included, the reaction solution after the quenching step) into the poor solvent of the obtained polyimide precursor, and the above-mentioned reaction solution is added The step into water or alcohol is more preferred. The poor solvent refers to a solvent having a low solubility of the polyimide precursor, and a solvent having a solubility of the polyimide precursor of 10 g/L or less is preferable. The amount of the poor solvent, water, or alcohol to be added is not particularly limited, as long as it is an amount to precipitate the polyimide precursor, and relative to the total mass of the reaction solution, 50 to 4,000 mass % is preferably, 100 -2,000 mass % is more preferable.

Preferably, the method for producing the polyimide precursor of the present invention further includes a reprecipitation step after the quenching step. When the reprecipitation step is included after the quenching step, the reprecipitation step may be performed after storing the reaction solution after the quenching step for a certain period of time, or the reprecipitation step may be performed immediately after the quenching step is completed. In addition, when performing the above-mentioned filtration step, it is preferable to perform the filtration step between the quenching step and the reprecipitation step.

A first preferred aspect of the method for producing a polyimide precursor of the present invention is an aspect in which the above-mentioned filtration step is performed immediately after the quenching step, and the reprecipitation step is performed immediately after the filtration step.

In a second preferred aspect of the method for producing a polyimide precursor of the present invention, the above-mentioned filtration step is performed after storing the reaction solution after the quenching step, and the reprecipitation step is performed immediately after the filtration step. The storage conditions of the reaction solution after the quenching step are not particularly limited. For example, storage at 40° C. or lower is preferable, storage at 30° C. or lower is more preferable, storage at 20° C. or lower is more preferable, and storage at 10° C. or lower is more preferable. More preferably, storage at 5°C or lower is particularly preferable. The lower limit of the said storage temperature is not specifically limited, For example, what is necessary is just to make it -20 degreeC or more. The storage period is not particularly limited, and can be set to 0.5 hours to 1 month or the like. Moreover, it is preferable to carry out the said storage under airtight conditions and light-shielding conditions.

A third preferred aspect of the method for producing a polyimide precursor of the present invention is an aspect in which the above-mentioned filtration step is performed on the reaction solution after the quenching step, and the reprecipitation step is performed after storing the filtrate after the filtration step. As storage conditions of the said filtrate, the same conditions as the storage conditions of the reaction liquid after the quenching step described in the said 2nd preferable aspect are mentioned. Moreover, for example, when the filtrate is stored at a low temperature such as lower than 10°C, it is preferable to perform the reprecipitation step after raising the filtrate to 10°C or higher. In this case, it is preferable to start the reprecipitation step within 5 hours after the completion of the temperature increase of the filtrate, and it is more preferable to start the reprecipitation step within 3 hours. Moreover, in the said 3rd preferable aspect, the filtration process may be performed with respect to the reaction liquid immediately after the quenching process, and the filtration process may be performed after storing the reaction liquid after the quenching process. When storing the reaction solution after the quenching step, the storage conditions are the same as the storage conditions after the quenching step described in the above-mentioned second preferred aspect.

Among them, as a preferable aspect of the method for producing a polyimide precursor of the present invention, a reprecipitation step is further included after the quenching step, and a reprecipitation step is further included after the quenching step and starts after the quenching step. The state of the reaction solution was stored at 10° C. or lower before the reprecipitation step. The temperature at the time of said storage should just be 10 degrees C or less, Preferably it is 5 degrees C or less. The above-mentioned storage period is not particularly limited, and can be set to 0.5 hour to 1 month or the like. When a filtration step is included in the above aspect, it is preferable to perform the filtration step immediately before the reprecipitation step.

In addition, as a preferable aspect of the method for producing a polyimide precursor of the present invention, there can be mentioned an aspect in which a reprecipitation step is further included after the quenching step, and the quenching step is stored at 10° C. or lower. After the reaction solution after the quenching step, the temperature of the reaction solution was raised to 10°C or higher, and the reprecipitation step was started within 5 hours after the temperature of the reaction solution became 10°C or higher. When the filtration step is included in the above aspect, it is preferable to perform the filtration step immediately after the quenching step, and to store the filtrate as the reaction solution. The temperature at the time of said storage should just be 10 degrees C or less, Preferably it is 5 degrees C or less. The above-mentioned storage period is not particularly limited, and can be set to 0.5 hour to 1 month or the like. The starting point of the reprecipitation step may be within 5 hours after the temperature reaches 10°C or higher, preferably within 3 hours, more preferably within 2 hours.

<Redissolution step> Furthermore, the method for producing a polyimide precursor of the present invention may further include a redissolving step of dissolving the polyimide precursor obtained by the reprecipitation step in a solvent to prepare a solution. As said solvent, the organic solvent etc. which were described in the said polymerization process are mentioned. In the present invention, the aspect of repeating the reprecipitation step and the redissolving step is also one of the preferred aspects of the present invention.

<Acid compound addition step> The method for producing a polyimide precursor of the present invention preferably includes an acidic compound addition step of adding an acidic compound to the reaction solution containing the above-mentioned imide compound after the above-mentioned polymerization step. When a reprecipitation step is included, the method for producing the polyimide precursor of the present invention preferably includes an acidic compound addition step after the reprecipitation step. Examples of the acidic compound in the above-mentioned acidic compound addition step include p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, 10-camphorsulfonic acid, or hydrates thereof. The amount of the acidic compound added is preferably 0.05-0.5 mol %, more preferably 0.10-0.30 mol %, relative to the molar amount of the amide compound.

<Purification step> Preferably, the method for producing a polyimide precursor of the present invention further includes a purification step of purifying the reaction solution containing the above-mentioned imide compound after the above-mentioned polymerization step. The above-mentioned residues such as halogenating agents and basic condensing agents or their derivatives can be removed by the purification step, and when the production method of the polyimide precursor includes the acid compound addition step, the acid compound residues and the like can be removed. It does not specifically limit as a purification method, A well-known method can be used, for example, the method of making an ion exchange resin contact with the solution containing a polyimide precursor, etc. is mentioned.

<Drying step> It is also preferable that the manufacturing method of the polyimide precursor of the present invention further comprises a drying step of drying the above-mentioned amide compound. The drying step is preferably a step of obtaining the amide compound precipitated in the above reprecipitation step by, for example, filtration or the like, and drying the obtained product. It does not specifically limit as a drying method, What is necessary is just to carry out by a well-known method. For example, drying by a well-known vacuum dryer, etc. are mentioned. The drying conditions are not particularly limited, and, for example, conditions such as drying under reduced pressure at 20°C to 60°C are exemplified.

式（2）中，A ¹及A ²分別獨立地表示氧原子或NH，R ¹¹¹表示2價的有機基，R ¹¹⁵表示4價的有機基，R ¹¹³及R ¹¹⁴分別獨立地表示氫原子或1價的有機基。 式（2）中之R ¹¹⁵的含義與上述式（O）中之R ¹¹⁵相同，較佳態樣亦相同。 式（2）中之A ¹、A ²、R ¹¹³及R ¹¹⁴的含義與上述式（O-1）中之A ¹、A ²、R ¹¹³及R ¹¹⁴相同，較佳態樣亦相同。 式（2）中之R ¹¹¹的含義與上述式（Da-1）中之R ¹¹¹相同，較佳態樣亦相同。 [Polyimide Precursor] The polyimide precursor obtained by the method for producing a polyimide precursor of the present invention is a polyimide precursor containing a repeating unit represented by the following formula (2) is better. [Chemical formula 11]

In formula (2), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or Monovalent organic group. The meaning of R ¹¹⁵ in the formula (2) is the same as that of R ¹¹⁵ in the above-mentioned formula (O), and the preferred aspects are also the same. The meanings of A ¹ , A ² , R ¹¹³ and R ¹¹⁴ in the formula (2) are the same as those of A ¹ , A ² , R ¹¹³ and R ¹¹⁴ in the above formula (O-1), and the preferred aspects are also the same. The meaning of R ¹¹¹ in the formula (2) is the same as that of R ¹¹¹ in the above-mentioned formula (Da-1), and the preferred aspects are also the same.

[Total content of cyclic imide structure and cyclic isoimide structure] The total content of the cyclic imide structure and the cyclic isoimide structure in the polyimide precursor is preferably 0 to 0.30 mmol/g. When the polyimide precursor has at least one of a cyclic imide structure and a cyclic isoimide structure, it may have a cyclic imide structure and a cyclic isoimide structure on the side chain At least one of them, but it is preferable to have at least one of a cyclic imide structure and a cyclic isoimide structure on the main chain. In this specification, the main chain of the resin refers to the relatively longest molecular chain in the molecule. The lower limit of the total content is preferably 0.01 mmol/g or more, and more preferably 0.03 mmol/g or more. The upper limit of the total content is preferably 0.30 mmol/g or less, and more preferably 0.25 mmol/g or less. The said total content is calculated by the method described in an Example, for example.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and further preferably 15,000 to 40,000. Moreover, as for the number average molecular weight (Mn), 2,000-40,000 are preferable, 3,000-30,000 are more preferable, 4,000-20,000 are still more preferable. The dispersity of the molecular weight of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the dispersion degree of the molecular weight of the polyimide precursor is not particularly specified, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In this specification, the dispersion degree of molecular weight is a value calculated from weight average molecular weight/number average molecular weight. When the curable resin composition described later contains a plurality of polyimide precursors, the weight average molecular weight, number average molecular weight and dispersity of at least one polyimide precursor are preferably within the above ranges. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated using the above-mentioned plural types of polyimide precursors as one resin are respectively within the above-mentioned ranges.

(Manufacturing method of curable resin composition) The method for producing a curable resin composition of the present invention preferably includes a step of mixing the polyimide precursor obtained by the method for producing a polyimide precursor of the present invention and other components. The mixing method is not particularly limited, and can be performed by a conventionally known method. In addition, in the method for producing a curable resin composition of the present invention, in the above-mentioned mixing step, at least one compound selected from the group consisting of an organometallic complex having a radical polymerization initiating ability and a sensitizer described later is further mixed as better. Moreover, in the manufacturing method of the curable resin composition of this invention, you may mix|blend another other component in the said mixing process. The content of the polyimide precursor in the curable resin composition of the present invention is preferably 20 mass % or more, more preferably 30 mass % or more, and 40 mass % relative to the total solid content of the curable resin composition The above is more preferable, and 50 mass % or more is further preferable. In addition, the content of the resin in the composition of the present invention is preferably 99.5 mass % or less, more preferably 99 mass % or less, more preferably 98 mass % or less, and 97 mass % with respect to the total solid content of the composition. The following is more preferable, and 95 mass % or less is still more preferable. The curable resin composition of the present invention may contain only one type of polyimide precursor, or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above-mentioned range.

Moreover, it is preferable that the manufacturing method of the curable resin composition includes the step of performing filtration using a filter for the purpose of removing foreign matter such as dust and particles in the curable resin composition. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter can be pre-cleaned with an organic solvent. In the filter filtering step, a plurality of filters can be connected in series or in parallel for use. When using multiple filters, filters with different pore sizes or materials can be used in combination. Also, various materials can be filtered multiple times. When filtering multiple times, you can filter for loops. Moreover, filtration can be performed by pressurization. When filtration is performed by pressurization, the pressurization pressure is preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using a filter, removal of impurities using an adsorbent material can also be performed. It is also possible to combine filter filtration and impurity removal treatment using adsorbent material. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be mentioned.

The curable resin composition of the present invention is preferably used for forming a photosensitive film for exposure and development, and is preferably used for forming a film for exposure and development using a developer containing an organic solvent. Moreover, it is preferable that the curable resin composition of this invention is used for forming the photosensitive film for negative image development. In the present invention, negative-tone development refers to development to remove non-exposed parts by development during exposure and development, and positive-tone development refers to development to remove exposed parts by development. As the above-mentioned exposure method, the above-mentioned developer, and the above-mentioned development method, for example, the exposure method described in the exposure step in the description of the manufacturing method of the cured product described later, the developer solution and the development described in the development step can be used. method. Hereinafter, the organometallic complex, the sensitizer, and other components contained in the curable resin composition obtained by the method for producing the curable resin composition of the present invention are referred to as components contained in the curable resin composition to explain. In the manufacturing method of the curable resin composition of this invention, a curable resin composition is obtained by mixing these components as needed.

<Organometallic complex> It is preferable that the curable resin composition contains an organometallic complex. The organometallic complex is only required to be an organic complex compound containing a metal atom, but a complex compound containing a metal atom and an organic group is preferable, and a compound in which the organic group is coordinated on the metal atom is more preferable. Compounds are further preferred. In the present invention, the metallocene compound refers to an organometallic complex having two cyclopentadienyl anion derivatives which may have substituents as η5-ligands. The above-mentioned organic group is not particularly limited, but a hydrocarbon group or a group composed of a combination of a hydrocarbon group and a hetero atom is preferable. As a hetero atom, an oxygen atom, a sulfur atom, and a nitrogen atom are preferable. In the present invention, at least one organic group is preferably a cyclic group, and at least two are preferably a cyclic group. The above-mentioned cyclic group is preferably selected from a 5-membered ring cyclic group and a 6-membered ring cyclic group, and more preferably a 5-membered ring cyclic group. The above-mentioned cyclic group may be a hydrocarbon ring or a heterocyclic ring, but a hydrocarbon ring is preferable. As the 5-membered cyclic group, a cyclopentadienyl group is preferable. In addition, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

The metal contained in the organometallic complex is not particularly limited, but is preferably a metal corresponding to a Group 4 element, more preferably at least one metal selected from the group consisting of titanium, zirconium and hafnium, At least one metal selected from the group consisting of titanium and zirconium is further preferred, and titanium is particularly preferred.

The organometallic complex may contain two or more metal atoms, or may contain only one metal atom, but it is preferable to contain only one metal atom. When the organometallic complex contains two or more metal atoms, only one metal atom may be contained, or two or more metal atoms may be contained.

Organometallic complexes are preferably ferrocene compounds, titanocene compounds, zirconocene compounds or hafnium compounds, preferably titanocene compounds, zirconocene compounds or hafnium compounds, and titanocene compounds are more preferred. Compounds or zirconocene compounds are further preferred, and titanocene compounds are particularly preferred.

The aspect that the organometallic complex has the ability to initiate photo-radical polymerization is also one of the preferred aspects of the present invention. In the present invention, having the ability to initiate photoradical polymerization refers to being able to generate a radical capable of initiating radical polymerization by irradiation of light. For example, when a composition comprising a radical crosslinking agent and an organometallic complex is irradiated with light in a wavelength region in which the organometallic complex absorbs light and the radical crosslinking agent does not absorb light, by confirming that the radical crosslinking agent The presence or absence of disappearance of the linking agent can confirm the presence or absence of the photoradical polymerization initiation ability. In order to confirm the disappearance, an appropriate method can be selected according to the type of the radical crosslinking agent, for example, IR measurement (infrared spectroscopy) or HPLC measurement (high performance liquid chromatography) may be used to confirm. When the organometallic complex has the ability to initiate photo-radical polymerization, the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnium compound, and a titanocene compound Compounds or zirconocene compounds are further preferred, and titanocene compounds are particularly preferred. When the organometallic complex does not have the ability to initiate photo-radical polymerization, the organometallic complex is selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium halide compounds, titanium chelate compounds, dicocene compounds At least one compound selected from the group of zirconium compounds and hafnocene compounds is preferably, at least one compound selected from the group comprising titanocene compounds, zirconocene compounds and hafnocene compounds is more preferably, selected from At least one compound from the group comprising titanocene compounds and zirconocene compounds is further preferred, and titanocene compounds are particularly preferred.

The molecular weight of the organometallic complex is preferably 50 to 2,000, more preferably 100 to 1,000.

式（P）中，M為金屬原子，R分別獨立地為取代基。 上述R分別獨立地選自芳香族基、烷基、鹵素原子及烷基磺醯氧基為較佳。 As an organometallic complex, the compound represented by following formula (P) is mentioned preferably. [Chemical formula 12]

In formula (P), M is a metal atom, and R is each independently a substituent. Preferably, the above-mentioned Rs are each independently selected from an aromatic group, an alkyl group, a halogen atom and an alkylsulfonyloxy group.

In the formula (P), as the metal atom represented by M, an iron atom, a titanium atom, a zirconium atom or a hafnium atom is preferable, a titanium atom, a zirconium atom or a hafnium atom is more preferable, and a titanium atom or a zirconium atom is further preferable , titanium atoms are particularly good. Examples of the aromatic group in R in the formula (P) include aromatic groups having 6 to 20 carbon atoms, and preferably, aromatic hydrocarbon groups having 6 to 20 carbon atoms include phenyl and 1-naphthyl. Or 2-naphthyl, etc. As the alkyl group in R in the formula (P), an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable, and examples thereof include methyl group, ethyl group, propyl group, and octyl group. base, isopropyl, tertiary butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl and the like. As a halogen atom in said R, F, Cl, Br, and I are mentioned. As the alkyl group constituting the alkylsulfonyloxy group in the above R, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and methyl, ethyl, and propyl groups are mentioned. base, octyl, isopropyl, tertiary butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl and the like. The above-mentioned R may further have a substituent. Examples of the substituent include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, Aryloxycarbonyl, aryloxy, monoalkylamine, dialkylamine, monoarylamine and diarylamine, etc.

Specific examples of the organometallic complex are not particularly limited, and tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, and diisopropoxybis(ethylacetate) can be exemplified. Titanium, diisopropoxybis(acetoacetone)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl) (yl)phenyl)titanium, pentamethylcyclopentadienyltrimethoxytitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium and The following compounds. [Chemical formula 13]

In addition, the compounds described in paragraphs 0078 to 0088 of International Publication No. 2018/025738 can also be used, but are not limited thereto.

The content of the organometallic complex is preferably 0.1 to 30 mass % with respect to the total solid content of the curable resin composition. The lower limit is more preferably 1.0 mass % or more, more preferably 1.5 mass % or more, and particularly preferably 3.0 mass % or more. The upper limit is more preferably 25% by mass or less. One type or two or more types of organometallic complexes can be used. When two or more kinds are used, the total amount is preferably within the above range.

<Other resins> The resin composition of the present invention may contain the above-mentioned specific resins and other resins different from the specific resins (hereinafter, also simply referred to as “other resins”). Examples of other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, and urethane resins , butyral resin, styrene resin, polyether resin, polyester resin, etc. For example, by further adding a (meth)acrylic resin, a resin composition excellent in coatability can be obtained, and a pattern (hardened product) excellent in solvent resistance can be obtained. For example, by replacing or in addition to the polymerizable compound described later, a polymerizable base value having a weight average molecular weight of 20,000 or less is high (for example, the molar content of the polymerizable group in 1 g of resin is 1 ×10 ⁻³ mol/g or more) (meth)acrylic resin is added to the resin composition to improve the coatability of the resin composition, the solvent resistance of the pattern (hardened product), and the like.

When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and more preferably 1% by mass or more, relative to the total solid content of the resin composition. Preferably, 2 mass % or more is further more preferable, 5 mass % or more is still more preferable, and 10 mass % or more is still more preferable. Further, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less, relative to the total solid content of the resin composition. 60 mass % or less is more preferable, and 50 mass % or less is further more preferable. Moreover, as a preferable aspect of the resin composition of this invention, the aspect in which content of another resin is a low content can also be used. In the above aspect, the content of other resins is preferably 20 mass % or less, more preferably 15 mass % or less, more preferably 10 mass % or less, and 5 mass % or less with respect to the total solid content of the resin composition. More preferably, 1 mass % or less is further more preferable. The lower limit of the content is not particularly limited as long as it is 0 mass % or more. The resin composition of this invention may contain only 1 type of other resin, and may contain 2 or more types. When two or more types are included, it is preferable that the total amount falls within the above-mentioned range.

＜Solvent＞ The resin composition of the present invention preferably contains a solvent. As the solvent, any known solvent can be used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfites, amides, ureas, and alcohols.

As esters, preferable examples include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, gamma-butyrolactone, epsilon-caprolactone, delta-valerolactone, alkyl alkoxyacetates (for example, alkoxyacetic acid Methyl ester, ethyl alkoxyacetate, butyl alkoxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetate ethyl acetate, etc.), 3-alkoxypropionic acid alkyl esters (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, 3-methoxypropionate) acid methyl ester, 3-methoxy ethyl propionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, etc.)), 2-alkoxy propionate alkyl esters (such as , methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, 2-methoxypropionate acid ethyl ester, 2-methoxy propionate propyl ester, 2-ethoxy propionate methyl ester, 2-ethoxy propionate ethyl ester)), 2-alkoxy-2-methyl propionate methyl ester And 2-alkoxy-2-methyl propionate ethyl ester (for example, 2-methoxy-2-methyl propionate methyl ester, 2-ethoxy-2-methyl propionate ethyl ester, etc.), Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, Ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

As ethers, preferable examples include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, Triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl seleuronate, ethyl seleuronate, diethylene glycol Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol Monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether, etc.

As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosone, dihydro Levoglucosone, etc.

As cyclic hydrocarbons, preferable examples include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

As the sulfites, preferred ones include, for example, dimethyl sulfene.

Preferable examples of the amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dipyrrolidone Methylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy base-N,N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine, etc.

Preferable examples of the urea include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.

Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxyl Ethyl-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol Monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methyl benzyl alcohol, n-amyl alcohol, methyl amyl alcohol and Diacetone alcohol, etc.

From the viewpoint of improvement of the properties of the coating surface, etc., it is also preferable that two or more kinds of solvents are mixed.

In the present invention, it is selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl xelousel acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate Ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, gamma-butyrolactone, dimethylsulfoxide, ethyl carbitol acetate, butyl carbitol Alcohol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, one solvent or a mixed solvent consisting of two or more kinds of L-glucosone and dihydro-lev-glucosone better. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone in combination or N-methyl-2-pyrrolidone and ethyl lactate in combination.

From the viewpoint of coatability, the content of the solvent is preferably set to an amount in which the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, and the total solid content concentration of the resin composition of the present invention is It is more preferable to set the total solid content concentration of the resin composition of the present invention in an amount of 5 to 75 mass %, and the total solid content concentration of the resin composition of the present invention is further preferably set to an amount of 10 to 70 mass %. More preferably, it is 20 to 70 mass %. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method.

The resin composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more kinds of solvents are contained, it is preferable that the total is within the above-mentioned range.

[Polymerization initiator] The resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat. In particular, it is preferable to contain a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited, and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light from the ultraviolet region to the visible region is preferable. Moreover, it can also be an activator which produces|generates active radicals by some action with the sensitizer excited by light.

The photo-radical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L·mol ⁻¹ ·cm ⁻¹ in the wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, it is preferable to measure at a concentration of 0.01 g/L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As the photoradical polymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, a compound having a triazole skeleton, a compound having an oxadiazole skeleton, a compound having a trihalomethyl group, etc.), an acyl phosphine compound such as an acyl phosphine oxide, and a hexaaryl group can be mentioned. Oxime compounds such as biimidazole and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-amino ketone compounds such as aminoacetophenone, α-amino ketone compounds such as hydroxyacetophenone Hydroxyketone compounds, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron aromatic complexes, etc. For details of these, reference can be made to the descriptions of paragraphs 0165 to 0182 of JP 2016-027357 A and paragraphs 0138 to 0151 of International Publication No. 2015/199219, the contents of which are incorporated into the present specification. In addition, the compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A, the compounds described in JP 6301489 A, and the compounds described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019 can be mentioned. Peroxide-based photopolymerization initiator, photopolymerization initiator described in International Publication No. 2018/221177, photopolymerization initiator described in International Publication No. 2018/110179, Japanese Patent Laid-Open No. 2019-043864 The photopolymerization initiator described in Gazette No. 2019-044030, the photopolymerization initiator described in Japanese Patent Application Laid-Open No. 2019-044030, and the peroxide-based initiator described in Japanese Patent Application Laid-Open No. 2019-167313, These contents are also incorporated into this specification.

Examples of the ketone compound include compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated in the present specification. Among the commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

In one embodiment of the present invention, as the photo-radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used. incorporated into this manual.

As the α-hydroxyketone-based starter, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (the above are manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE- 2959, IRGACURE 127 (trade name: all manufactured by BASF).

As the α-amino ketone-based starter, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (the above are manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all from BASF Corporation) can be used manufacture).

As the aminoacetophenone-based initiator, the compounds described in Japanese Patent Laid-Open No. 2009-191179, the content of which are incorporated in the present specification, can also be used which have a maximum absorption wavelength matched to a light source having a wavelength of 365 nm or 405 nm.

As an acylphosphine oxide-based initiator, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, etc. are mentioned. In addition, Omnirad 819, Omnirad TPO (the above are manufactured by IGM Resins B.V.), IRGACURE-819 or IRGACURE-TPO (trade name: all manufactured by BASF Corporation) can be used.

Examples of the metallocene compound include IRGACURE-784, IRGACURE-784EG (all manufactured by BASF Corporation), Keycure VIS 813 (manufactured by King Brother Chem Corporation), and the like.

As a photoradical polymerization initiator, an oxime compound can be mentioned more preferably. By using the oxime compound, the exposure latitude can be improved more effectively. The oxime compound is particularly preferred because it has a wide exposure latitude (exposure margin) and also functions as a photohardening accelerator.

Specific examples of the oxime compound include compounds described in JP 2001-233842 A, compounds described in JP 2000-080068 A, and JP 2006-342166 A. Compounds, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 156-162) The compounds described in pages 202-232), the compounds described in JP 2000-066385 A, the compounds described in JP 2004-534797 A, the compounds described in JP 2017-019766 A Compounds described, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015/152153, compounds described in International Publication No. 2017/051680, Japanese Patent Laid-Open No. 2017-198865 The compounds described in WO 2017/164127, the compounds described in paragraphs 0025 to 0038 of WO 2017/164127, the compounds described in WO 2013/167515, and the like, are incorporated herein by reference.

Examples of preferable oxime compounds include compounds having the following structures, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-Propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1- Ketone, 2-Benzyloxyimino-1-phenylpropan-1-one, 3-(4-Tosyloxy)iminobutan-2-one and 2-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one, etc. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator. The oxime-based photo-radical polymerization initiator has a linking group >C=N-O-C(=O)- in the molecule.

[Chemical formula 14]

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, Japanese Patent Laid-Open 2012- Photo-radical polymerization initiator 2) described in Gazette 014052. In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Trolly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used . In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Moreover, the oxime compound of the following structure can also be used. [Chemical formula 15]

As a photoradical polymerization initiator, an oxime compound having a perylene ring can also be used. Specific examples of the oxime compound having a perylene ring include the compound described in JP 2014-137466 A and the compound described in JP 06636081 , the contents of which are incorporated in the present specification.

As the photoradical polymerization initiator, an oxime compound having at least one benzene ring of a carbazole ring serving as a skeleton of a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. WO 2013/083505, the contents of which are incorporated in the present specification.

Moreover, the oxime compound which has a fluorine atom can also be used. Specific examples of such oxime compounds include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 24-500852 A. The content of the compound (C-3) and the like described in paragraph 0101 of Laid-Open Publication No. 2013-164471 is incorporated into the present specification.

As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is a dimer. Specific examples of the oxime compound having a nitro group include those described in paragraphs 0031 to 0047 of JP 2013-114249 A and 0008 to 0012 and 0070 to 0079 in JP 2014-137466 A and the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, the contents of which are incorporated in the present specification. Moreover, ADEKA ARKLS NCI-831 (made by ADEKA CORPORATION) can also be mentioned as an oxime compound which has a nitro group.

As a photoradical polymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.

As the photoradical polymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton can also be used. As such a photopolymerization initiator, the compound described in International Publication No. 2019/088055, etc. are mentioned, and the content is incorporated in this specification.

As the photopolymerization initiator, an oxime compound (hereinafter, also referred to as an oxime compound OX) having an aromatic ring group Ar ^OX1 having an electron withdrawing group introduced into an aromatic ring can also be used. Examples of the electron withdrawing group possessed by the above-mentioned aromatic ring group Ar ^OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, The arylsulfonyl group and the cyano group are preferably an acyl group and a nitro group, and since it is easy to form a film with excellent light resistance, an acyl group is more preferable, and a benzyl group is still more preferable. The benzyl group may have a substituent. As a substituent, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkenyl group, a sulfanyl goup , an aryl hydrogen thio group, an amide group or an amine group is preferred, and an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxygen group, an alkyl hydrogen thio group, an aryl hydrogen thio group or an amine group are More preferably, an alkoxy group, an alkyl hydrogen thio group or an amine group is further preferred.

式中，R ^X1表示烷基、烯基、烷氧基、芳基、芳氧基、雜環基、雜環氧基、烷基氫硫基、芳基氫硫基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、醯基、醯氧基、胺基、亞膦醯基（phosphinoyl gruop）、胺甲醯基或胺磺醯基， R ^X2表示烷基、烯基、烷氧基、芳基、芳氧基、雜環基、雜環氧基、烷基氫硫基、芳基氫硫基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、醯氧基或胺基， R ^X3～R ^X14分別獨立地表示氫原子或取代基。 其中，R ^X10～R ^X14中的至少一個為拉電子基團。 The oxime compound OX is preferably at least one selected from the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and the compound represented by the formula (OX2) is more preferably. [Chemical formula 16]

In the formula, R ^X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkyl hydrogen thiol group, an aryl hydrogen thiol group, an alkyl sulfinyl group R ^X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkyl hydrogen thio group, an aryl hydrogen thio group, an alkyl sulfinyl group, an arylidene group In the sulfonyl group, the alkylsulfonyl group, the arylsulfonyl group, the yloxy group or the amine group, R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent. Wherein, at least one of R ^X10 to R ^X14 is an electron withdrawing group.

In the above formula, R ^X12 is an electron withdrawing group, and R ^X10 , R ^X11 , R ^X13 and R ^X14 are preferably hydrogen atoms.

Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated in the present specification.

As the optimum oxime compound, the oxime compound having a specific substituent shown in JP-A No. 2007-269779 or the oxime compound having a thioaryl group described in JP-A No. 2009-191061 can be mentioned, , the contents of which are incorporated into this manual.

From the viewpoint of exposure sensitivity, the photo-radical polymerization initiator is selected from the group consisting of trihalomethyltrisium compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene - Compounds in the group of present-iron complexes and salts thereof, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.

Further preferred photo-radical polymerization initiators are trihalomethyltrizine compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium Salt compounds, benzophenone compounds, acetophenone compounds, selected from the group consisting of trihalomethyltriazole compounds, α-amino ketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, benzophenone It is further preferable to use at least one compound in the group of compounds, and it is even more preferable to use a metallocene compound or an oxime compound.

In addition, N,N'- benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's Tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl Aromatic ketones such as base-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1, quinones such as alkyl anthraquinones and condensed aromatic rings, benzoin alkyl ethers Benzoin ether compounds such as benzoin, benzoin compounds such as benzoin and alkylbenzoin, benzyl derivatives such as benzyl dimethyl ketal, and the like. Moreover, the compound represented by following formula (I) can also be used.

[Chemical formula 17]

In formula (I), R ^I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a carbon atom. Alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 12 carbon atoms, halogen atom, cyclopentyl group, cyclohexyl group, alkenyl group having 2 to 12 carbon atoms, 2 to carbon carbon group interrupted by one or more oxygen atoms The alkyl group of 18 and the phenyl group or biphenyl group substituted by at least one of the alkyl groups of 1 to 4 carbon atoms, R ^I01 is the group represented by the formula (II) or the same group as R ^I00 , R ^I02 ~R ^I04 is each independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or a halogen atom.

[Chemical formula 18]

In the formula, R ^I05 to R ^I07 are the same as R ^I02 to R ^I04 of the above formula (I).

In addition, the compounds described in paragraphs 0048 to 0055 of International Publication No. WO 2015/125469 can also be used as the photo-radical polymerization initiator, the contents of which are incorporated in this specification.

As the photoradical polymerization initiator, a bifunctional or trifunctional or more photoradical polymerization initiator can be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, the crystallinity is lowered and the solubility in a solvent or the like is improved, so that precipitation over time is difficult, and the stability over time of the resin composition can be improved. Specific examples of the bifunctional or trifunctional or more than trifunctional photo-radical polymerization initiators include JP 2010-527339 A, JP 2011-524436 A, WO 2015/004565, JP 2011-524436 Dimers of oxime compounds described in paragraphs 0407 to 0412 of Table 2016-532675, paragraphs 0039 to 0055 of International Publication No. 2017/033680, and compounds described in JP 2013-522445 (E) and compound (G), Cmpd 1 to 7 described in International Publication No. 2016/034963, oxime ester-based photoinitiators described in paragraph No. 0007 of Japanese Patent Application Publication No. 2017-523465, Japanese Patent Application Photoinitiator (A) described in paragraphs 0020 to 0033 of Unexamined Patent Application Publication No. 2017-167399, photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Unexamined Patent Application Publication No. 2017-151342, Japanese Patent Application The content of the oxime ester photoinitiator and the like described in Gazette No. 6469669 is incorporated in the present specification.

When a photopolymerization initiator is included, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and further preferably 0.5 to 15 mass % relative to the total solid content of the resin composition of the present invention. The mass % is more preferably 1.0 to 10 mass %. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more photopolymerization initiators are contained, the total amount thereof is preferably within the above-mentioned range. In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, crosslinking by the photopolymerization initiator may be further performed by heating in an oven, a hot plate, or the like.

[Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state contacts with a thermal radical polymerization initiator, a photoradical polymerization initiator, etc. to produce electron transfer, energy transfer, and heat generation. Thereby, the thermal radical polymerization initiator and the photoradical polymerization initiator undergo chemical change and decompose, thereby generating radicals, acids, or bases. As sensitizers that can be used, benzophenone-based, micheler's ketone-based, coumarin-based, pyrazoleazo-based, anilinoazo-based, triphenylmethane-based, anthraquinone-based, and anthracene-based sensitizers can be used series, anthrapyridone series, benzylidene (benzylidene) series, oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenothiazine series, Compounds of pyrrolopyrazole methine azo series, Kouyamaguchi galaxy, phthalocyanine series, benzopyran series, indigo series, etc. Examples of sensitizers include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane Alkane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4 ,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminobenzylidene (cinnamylidene)indanone , p-dimethylaminobenzylidene dihydroindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylidene) ) benzothiazole, 2-(p-dimethylaminophenylvinylidene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis (4'-Diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin , 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylamino Coumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl ester), N-phenyl-N'-ethyl Ethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, diethylaminobenzene Isoamyl formate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2- (p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl) Acetyl) styrene, diphenylacetanilide, benzalanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. Moreover, other sensitizing dyes can also be used. For details of the sensitizing dye, the descriptions in paragraphs 0161 to 0163 of JP 2016-027357 A can be referred to, the contents of which are incorporated in the present specification.

When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and 0.5 to 10 mass % relative to the total solid content of the resin composition. Further preferred. A sensitizer may be used individually by 1 type, and may use 2 or more types together.

[Chain Transfer Agent] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, on pages 683-684 of the Polymer Dictionary, 3rd Edition (Edited by the Society for Polymer Science, 2005). As the chain transfer agent, for example, a group of compounds having -SS-, -SO ₂ -S-, -NO-, SH, PH, SiH and GeH in the molecule, RAFT (Reversible Addition Fragmentation chain Transfer: Reversible Addition Fragmentation chain Transfer) can be used. Fragmentation chain transfer polymerization) Dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compound having a thiocarbonylthio group used in polymerization. These can generate free radicals by supplying hydrogen to less reactive free radicals, or by deprotonation after oxidation. In particular, a thiol compound can be preferably used.

In addition, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used, the contents of which are incorporated in the present specification.

When the resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total solid content of the resin composition of the present invention, and 0.1 to 10 parts by mass is More preferably, 0.5-5 mass parts is more preferable. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more kinds of chain transfer agents, it is preferable that the total of them is within the above-mentioned range.

[Photoacid generator] It is preferable that the resin composition of this invention contains a photoacid generator. The photoacid generator represents a compound that generates at least one of a Brynster acid and a Lewis acid by irradiation with light of 200 nm to 900 nm. The light to be irradiated is preferably light having a wavelength of 300 nm to 450 nm, more preferably light having a wavelength of 330 nm to 420 nm. When a photoacid generator is used alone or in combination with a sensitizer, it is preferable to use a photoacid generator that can generate an acid by being sensitive to light. Preferable examples of the acid to be generated include hydrogen halide, carboxylic acid, sulfonic acid, sulfinic acid, thiosulfinic acid, phosphoric acid, phosphoric acid monoester, phosphoric acid diester, boron derivatives, and phosphorus derivatives. , Antimony derivatives, halogen peroxide (halogen peroxide), sulfonamides, etc.

Examples of the photoacid generator used in the resin composition of the present invention include quinonediazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, dioxane compounds, onium salt compounds, and the like. From the viewpoints of sensitivity and storage stability, organohalogen compounds, oxime sulfonate compounds, and onium salt compounds are preferable, and from the viewpoints of mechanical properties of the formed film, and the like, oxime esters are preferable.

As the quinonediazide compound, sulfonic acid of quinonediazide is ester-bonded to a monovalent or polyvalent hydroxy compound, and sulfonic acid of quinonediazide is bonded to monovalent or polyvalent hydroxy compound with sulfonamide. A valent amine compound, a sulfonic acid of quinonediazide is ester-bonded and/or a sulfonamide is bonded to a polyhydroxy polyamine-based compound, and the like. All functional groups of these polyhydroxy compounds, polyamine compounds, and polyhydroxy polyamine compounds may not be substituted by quinonediazide, but on average, more than 40 mol% of the whole functional groups are substituted by quinonediazide as better. By containing such a quinonediazide compound, a resin composition sensitive to i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm), which are general ultraviolet mercury lamps, can be obtained.

Specific examples of the hydroxy compound include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, tertiary butanol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS- 2P, BisRS-3P, BisP-OCHP, Methylenetri-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X , DML-EP, DML-POP, Dihydroxymethyl-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp- BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (the above are trade names, manufactured by ASAHI YUKIZAI CORPORATION), 2,6-two Methoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diethyloxymethyl-p-cresol, naphthol, tetrahydroxy Benzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), novolak resin, etc., but It is not limited to these.

Specific examples of the amine compound include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'- Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, etc., but not limited to these.

In addition, as the polyhydroxy polyamine compound, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-dihydroxybenzidine, etc. can be mentioned specifically, but It is not limited to these.

Among these, as the quinonediazide compound, a phenol compound and an ester with a 4-naphthoquinonediazidesulfonyl group are preferable. Thereby, higher sensitivity and higher resolution for i-ray exposure can be obtained.

The content of the quinonediazide compound in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the resin. By making content of a quinonediazide compound into this range, the contrast of an exposed part and an unexposed part can be obtained, and it becomes possible to achieve higher sensitivity. Moreover, a sensitizer etc. can be added as needed.

The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as "oxime sulfonate compound"). The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), formula (OS-103), formula (OS-104), or formula (OS-105) described later The represented oxime sulfonate compounds are preferred.

[Chemical formula 19]

In formula (OS-1), X ³ represents an alkyl group, an alkoxy group or a halogen atom. When there are plural X ³ 's, they may be the same or different. The alkyl group and the alkoxy group in the above-mentioned X ³ may have a substituent. As the alkyl group in the aforementioned X ³ , a straight-chain or branched-chain alkyl group having 1 to 4 carbon atoms is preferable. As the alkoxy group in the above-mentioned X ³ , a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom in the above-mentioned X ³ , a chlorine atom or a fluorine atom is preferable. In formula (OS-1), m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3, a plurality of ^X3 may be the same or different. In formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 10 carbon atoms. The halogenated alkoxy group of 5, the phenyl group which may be substituted with W, the naphthyl group which may be substituted with W, or the anthracenyl group which may be substituted with W are preferred. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms. , an aryl group with a carbon number of 6-20, a halogenated aryl group with a carbon number of 6-20.

In formula (OS-1), m3 is ³ , ^X3 is a methyl group, the substitution position of X3 is an ortho position, ^R34 is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl- Compounds of 2-oxonorbornylmethyl or p-tolyl are particularly preferred.

Specific examples of the oxime sulfonate compound represented by the formula (OS-1) include paragraphs 0064 to 0068 of JP 2011-209692 A, and paragraphs 0158 to JP 2015-194674 The following compounds described in 0167 are incorporated into this specification.

[Chemical formula 20]

In formulas (OS-103) to (OS-105), R ^s1 represents an alkyl group, an aryl group or a heteroaryl group, and when there are plural R ^s2 in some cases, each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group. Halogen atom, when there are plural R ^s6 each independently represents a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, Xs represents O or S, ns Represents 1 or 2, and ms represents an integer from 0 to 6. In formula (OS-103) to formula (OS-105), the alkyl group represented by R ^s1 (preferably with 1 to 30 carbon atoms), aryl group (preferably with 6 to 30 carbon atoms) or heteroaryl ( (preferably, carbon number is 4 to 30) within a range in which the effects of the present invention can be obtained, and may have a known substituent.

In formulas (OS-103) to (OS-105), R ^s2 is preferably a hydrogen atom, an alkyl group (preferably carbon number 1-12) or an aryl group (carbon number 6-30 is preferable), A hydrogen atom or an alkyl group is more preferable. Among the R ^s2 when there may be two or more in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is preferably an alkyl group, an aryl group or a halogen atom, and one is preferably an alkyl group, an aryl group or a halogen atom. It is particularly preferred that one is an alkyl group and the rest are hydrogen atoms. The alkyl group or aryl group represented by R ^s2 may have a known substituent within a range in which the effects of the present invention can be obtained. In formula (OS-103), formula (OS-104) or formula (OS-105), Xs represents O or S, and O is preferred. In the above formulae (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.

In formulas (OS-103) to (OS-105), ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is preferably 2. In formula (OS-103) to formula (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and alkoxy group (preferably having 1 to 30 carbon atoms) represented by R ^s6 may have a substituent . In formulas (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

In addition, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), the above formula (OS-104) ) represented by the compound represented by the following formula (OS-107) is particularly preferred, and the compound represented by the above formula (OS-105) is represented by the following formula (OS-108) or formula (OS-109) The compounds indicated are particularly preferred. [Chemical formula 21]

In formulas (OS-106) to (OS-111), R ^t1 represents an alkyl group, an aryl group or a heteroaryl group, R ^t7 represents a hydrogen atom or a bromine atom, and R ^t8 represents a hydrogen atom or an alkane having 1 to 8 carbon atoms group, halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl or chlorophenyl, R ^t9 represents hydrogen atom, halogen atom, methyl or methoxy group, R ^t2 represents hydrogen atom or methyl group. In the formulae (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.

In formulas (OS-106) to (OS-111), R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, and a methoxymethyl group , phenyl or chlorophenyl, preferably an alkyl group with 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group with 1 to 8 carbon atoms, still more preferably an alkyl group with 1 to 6 carbon atoms , particularly preferably methyl.

In the formulas (OS-106) to (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and a hydrogen atom is preferable. R ^t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In addition, among the above-mentioned oxime sulfonate compounds, the three-dimensional structure (E, Z) of the oxime may be any of them, or a mixture may be used. Specific examples of the oxime sulfonate compounds represented by the above formulae (OS-103) to (OS-105) include paragraph numbers 0088 to 0095 of JP 2011-209692 A, JP 2015-A The compounds described in paragraphs 0168 to 0194 of Gazette 194674 are incorporated in the present specification.

As another preferable aspect of the oxime sulfonate compound containing at least one oxime sulfonate group, the compound represented by following formula (OS-101) and formula (OS-102) is mentioned.

[Chemical formula 22]

In formula (OS-101) or formula (OS-102), R ^u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group group, cyano group, aryl group or heteroaryl group. The aspect where R ^u9 is a cyano group or an aryl group is more preferable, and the aspect where R ^u9 is a cyano group, a phenyl group, or a naphthyl group is more preferable. In formula (OS-101) or formula (OS-102), R ^u2a represents an alkyl group or an aryl group. In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, -NR ^u5 -, -CH ₂ -, ^{-CR u6} H- or CR ^u6 R ^u7 - , R ^u5 to R ^u7 each independently represent an alkyl group or an aryl group.

In formula (OS-101) or formula (OS-102), R ^u1 to R ^u4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkyl group carbonyl, arylcarbonyl, amido, sulfo, cyano or aryl. Two of R ^u1 to R ^u4 may each be bonded to each other to form a ring. At this time, the ring may be condensed to form a condensed ring together with the benzene ring. As R ^u1 to R ^u4 , a hydrogen atom, a halogen atom, or an alkyl group is preferable, and an aspect in which at least two of R ^u1 to R ^u4 are bonded to each other to form an aryl group is also preferable. Among them, the aspect in which all of R ^u1 to R ^u4 are hydrogen atoms is preferable. All of the above-mentioned substituents may further have a substituent.

作為市售品，能夠舉出WPAG-336（FUJIFILM Wako Pure Chemical Corporation製造）、WPAG-443（FUJIFILM Wako Pure Chemical Corporation製造）、MBZ-101（Midori Kagaku Co.,Ltd.製造）等。 More preferably, the compound represented by the above formula (OS-101) is the compound represented by the formula (OS-102). Moreover, among the above-mentioned oxime sulfonate compounds, the three-dimensional structure (E, Z, etc.) of the oxime or benzothiazole ring may be any of them, respectively, or a mixture may be used. Specific examples of the compound represented by the formula (OS-101) include those described in paragraphs 0102 to 0106 of JP 2011-209692 A, and paragraphs 0195 to 0207 of JP 2015-194674 A compounds, which are incorporated into this specification. Among the above-mentioned compounds, the following b-9, b-16, b-31, and b-33 are preferable. [Chemical formula 23]

As a commercial item, WPAG-336 (made by FUJIFILM Wako Pure Chemical Corporation), WPAG-443 (made by FUJIFILM Wako Pure Chemical Corporation), MBZ-101 (made by Midori Kagaku Co., Ltd.), etc. are mentioned.

Moreover, as a preferable example, the compound represented by the following structural formula can also be mentioned. [Chemical formula 24]

Specific examples of the organic halogenated compound include Wakabayashi et al. "Bull Chem. Soc Japan" 42, 2924 (1969), US Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, and Japanese Patent Laid-Open No. 48-36281 No. 55-32070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241 No., JP 62-212401, JP 63-70243, JP 63-298339, M.P.Hutt "Jurnal of Heterocyclic Chemistry" 1 (No3), (1970), etc. The compounds described in this specification are incorporated into this specification. In particular, as a preferable example, a trihalomethyl-substituted oxazole compound: S-triazole compound can be mentioned. More preferably, at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-tris-tris-s-tris-s-tris-derivatives, and specifically, for example, 2,4,6-tris (Monochloromethyl)-s-tris-tris, 2,4,6-tris (dichloromethyl)-s-tris, 2,4,6-tris (trichloromethyl)-s-tris, 2-Methyl-4,6-bis(trichloromethyl)-s-tris𠯤, 2-n-propyl-4,6-bis(trichloromethyl)-s-𠯤, 2-(α,α , β-trichloroethyl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-phenyl-4,6-bis(trichloromethyl)-s-tris, 2- (p-Methoxyphenyl)-4,6-bis(trichloromethyl)-s-tris, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl) -s-tris-tris, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-[1-(p-methoxyphenyl)-2,4- Butadienyl]-4,6-bis(trichloromethyl)-s-tris, 2-styryl-4,6-bis(trichloromethyl)-s-tris, 2-(p- Methoxystyryl)-4,6-bis(trichloromethyl)-s-tristyryl, 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl)- s-tris-tris, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-(4-naphthoxynaphthyl)-4,6-bis(trichloro) methyl)-s-tris', 2-phenylsulfanyl-4,6-bis(trichloromethyl)-s-tris', 2-benzylsulfanyl-4,6-bis(trichloromethyl)- s-Tris(Tris), 2,4,6-Tris(dibromomethyl)-s-Tris, 2,4,6-Tris(Tribromomethyl)-s-Tris, 2-Methyl-4, 6-bis(tribromomethyl)-s-tris-tris, 2-methoxy-4,6-bis(tribromomethyl)-s-s-tris, etc.

Specific examples of the organic borate compound include JP 62-143044 A, JP 62-150242 A, JP 9-188685 A, and JP 9-188686 A. , Japanese Patent Laid-Open No. 9-188710, Japanese Patent Laid-Open No. 2000-131837, Japanese Patent Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Laid-Open No. 2002-116539, etc. and Kunz, Martin "Rad Tech'98. Proceeding April 19-22, 1998, Chicago", etc., in the organic borates described in Japanese Patent Laid-Open No. 6-157623, Japanese Patent Laid-Open No. 6-175564, and Japanese Patent Laid-Open No. Hei 6-175561 Organoboronium complexes or organoboroxoxonium complexes described, Japanese Patent Laid-Open No. 6-175554, Organoboronium complexes described in Japanese Patent Laid-Open No. 6-175553, Japanese Patent Laid-Open No. 6-175553 Organoboron phosphonium complexes described in Gazette No. 9-188710, Japanese Patent Laid-Open No. 6-348011, No. 7-128785, No. 7-140589, No. 7-306527 The organoboron transition metal complex complexes of the official gazette, Japanese Unexamined Patent Application Publication No. 7-292014 and the like are incorporated in the present specification.

The diazonium compound and the diazodione compound described in Japanese Patent Application Laid-Open No. 61-166544, Japanese Patent Application No. 2001-132318 and the like can be mentioned as the dioxane compound.

Examples of the above-mentioned onium salt compounds include the diazonium salts described in S.I.Schlesinger, Photogr.Sci.Eng., 18, 387 (1974), T.S. Bal et al., Polymer, 21,423 (1980), US Pat. No. 4,069,055 No. specification, ammonium salts described in Japanese Patent Laid-Open No. 4-365049, etc., phosphonium salts described in each specification of US Pat. No. 4,069,055, US Pat. No. 4,069,056, European Patent No. 104,143, US Pat. No., each specification of U.S. Patent No. 410,201, the iodonium salt described in Japanese Patent Laid-Open No. 2-150848, Japanese Patent Laid-Open No. 2-296514, European Patent No. 370,693, European Patent No. 390,214, European Patent No. 233,567 No., European Patent No. 297,443, European Patent No. 297,442, US Patent No. 4,933,377, US Patent No. 161,811, US Patent No. 410,201, US Patent No. 339,049, US Patent No. 4,760,013, US Patent No. 4,734,444, Permamate salts described in each specification of US Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, German Patent No. 3,604,581, J.V.Crivello et al., Macromolecules, 10(6), 1307(1977), Selenium salts as described in J.V.Crivello et al., J.Polymer Sci., Polymer Chem.Ed., 17, 1047 (1979), C.S.Wen et al., Teh, Proc. Arsenic salts, onium salts such as pyridinium salts, and the like described in (1988) are incorporated into the present specification.

式（RI-I）中，Ar ₁₁表示可以具有1～6個取代基之碳數20以下的芳基，作為較佳的取代基，可以舉出碳數1～12的烷基、碳數2～12的烯基、碳數2～12的炔基、碳數6～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的烷基胺基、碳數2～12的二烷基胺基、烷基的碳數為1～12的烷基醯胺基或芳基的碳數為6～20的芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫代烷基、碳數1～12的硫代芳基。Z ₁₁ ^-表示1價的陰離子，為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子，從穩定性的方面而言，過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子為較佳。式（RI-II）中，Ar ₂₁、Ar ₂₂各自獨立地表示可以具有1～6個取代基之碳數1～20的芳基，作為較佳的取代基，可以舉出碳數1～12的烷基、碳數2～12的烯基、碳數2～12的炔基、碳數1～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的單烷基胺基、烷基的碳數分別獨立地為1～12的二烷基胺基、烷基的碳數為碳數1～12的烷基醯胺基或芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫代烷基、碳數1～12的硫代芳基。Z21 ^-表示1價的陰離子，為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子，從穩定性、反應性的方面而言，過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、羧酸離子為較佳。式（RI-III）中，R ₃₁、R ₃₂、R ₃₃各自獨立地表示可以具有1～6個取代基之碳數6～20以下的芳基或烷基、烯基、炔基，較佳地，從反應性、穩定性的方面而言，芳基為較佳。作為較佳的取代基，可以舉出碳數1～12的烷基、碳數2～12的烯基、碳數2～12的炔基、碳數1～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的單烷基胺基、烷基的碳數分別獨立地為碳數1～12的二烷基胺基、烷基的碳數為碳數1～12的烷基醯胺基或芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫代烷基、碳數1～12的硫代芳基。Z ₃₁ ^-表示1價的陰離子，為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子，從穩定性、反應性的方面而言，過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、羧酸離子為較佳。 Examples of the onium salt include those represented by the following general formulae (RI-I) to (RI-III). [Chemical formula 25]

In formula (RI-I), Ar ₁₁ represents an aryl group with 20 or less carbon atoms which may have 1 to 6 substituents, and preferable substituents include an alkyl group with 1 to 12 carbons, an alkyl group with 2 carbons Alkenyl group of to 12, alkynyl of carbon number of 2 to 12, aryl group of carbon number of 6 to 12, alkoxy of carbon number of 1 to 12, aryloxy group of carbon number of 1 to 12, halogen atom, carbon number of 1 Alkylamine group of ~12, dialkylamine group of carbon number of 2 to 12, alkylamide of alkyl group of carbon number of 1 to 12, or arylamide of aryl group of carbon number of 6 to 20 group, carbonyl group, carboxyl group, cyano group, sulfonyl group, thioalkyl group having 1 to 12 carbon atoms, and thioaryl group having 1 to 12 carbon atoms. Z ₁₁ ^- represents a monovalent anion, which is halogen ion, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfate ion, stable from stable In terms of properties, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, and sulfinic acid ion are preferable. In formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 1 to 20 carbon atoms, which may have 1 to 6 substituents, and preferable substituents include 1 to 12 carbon atoms. alkyl, alkenyl with 2-12 carbons, alkynyl with 2-12 carbons, aryl with 1-12 carbons, alkoxy with 1-12 carbons, aryloxy with 1-12 carbons , halogen atom, monoalkylamine group with 1 to 12 carbon atoms, dialkylamine group with 1 to 12 carbon atoms in the alkyl group, and alkyl amide group with 1 to 12 carbon atoms in the alkyl group An amino group or an aryl amido group, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z21 ^- represents a monovalent anion, which is halogen ion, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, and sulfate ion. In terms of reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, and carboxylate ion are preferable. In formula (RI-III), R ₃₁ , R ₃₂ , and R ₃₃ each independently represent an aryl group, an alkyl group, an alkenyl group, and an alkynyl group having 1 to 6 substituents and a carbon number of 6 to 20 or less, preferably In general, aryl groups are preferred from the viewpoint of reactivity and stability. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an aryl group having 1 to 12 carbon atoms. Alkoxy group of 12, aryloxy group of carbon number of 1 to 12, halogen atom, monoalkylamine group of carbon number of 1 to 12, dialkylamine of carbon number of alkyl group each independently being carbon number of 1 to 12 The carbon number of the group and the alkyl group is an alkyl amido group or an aryl amido group with a carbon number of 1 to 12, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group with a carbon number of 1 to 12, a carbon number 1-12 thioaryl groups. Z ₃₁ ^- represents a monovalent anion, which is a halide ion, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, and sulfate ion, from stable In terms of properties and reactivity, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, and carboxylate ion are preferable.

[化學式27]

[化學式28]

[化學式29]

Specific examples of preferable photoacid generators include the following. [Chemical formula 26]

[Chemical formula 27]

[Chemical formula 28]

[Chemical formula 29]

The photoacid generator is preferably used in 0.1 to 20 mass %, more preferably 0.5 to 18 mass %, more preferably 0.5 to 10 mass %, and 0.5 to 3 mass % relative to the total solid content of the resin composition. % is more preferable, and it is even more preferable to use 0.5 to 1.2 mass %. A photoacid generator may be used individually by 1 type, and may be used in combination of a plurality of types. In the case of a combination of plural kinds, the total amount of these is preferably within the above-mentioned range. Moreover, in order to provide the photosensitivity with respect to a desired light source, it is also preferable to use together with a sensitizer.

<Thermal acid generator> The curable resin composition may contain a thermal acid generator. The thermal acid generator has the effect of generating an acid by heating, thereby promoting a compound selected from the group consisting of a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group, an epoxy compound, an oxetane compound, and a benzene compound. and the cross-linking reaction of at least one of the compounds.

The thermal decomposition initiation temperature of the thermal acid generator is preferably 50°C to 270°C, more preferably 50°C to 250°C. In addition, if the composition is applied to the substrate and then dried (pre-baking: about 70 to 140° C.), acid is not generated, and the final heating (curing: about 70° C.) after patterning is performed in subsequent exposure and development. 100 to 400° C.) which generates an acid as a thermal acid generator can suppress the decrease in sensitivity at the time of development, so it is preferable. The thermal decomposition initiation temperature was determined as the peak temperature of the exothermic peak with the lowest temperature when the thermal acid generator was heated to 500° C. in a pressure-resistant capsule at 5° C./min. Q2000 (manufactured by TA Instruments) etc. are mentioned as an apparatus used when measuring the thermal decomposition start temperature.

Acid-based strong acids generated by thermal acid generators are preferred, such as arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid, or trifluoromethanesulfonic acid. Halogenated alkyl sulfonic acids such as sulfonic acid are preferred. Examples of such thermal acid generators include those described in paragraph 0055 of JP 2013-072935 A.

Among them, from the viewpoint of less residue in the organic film and less likely to degrade the physical properties of the organic film, those that generate alkyl sulfonic acids having 1 to 4 carbon atoms or halogenated alkyl sulfonic acids having 1 to 4 carbon atoms are more preferable, and methanesulfonic acid is preferred. Acid (4-hydroxyphenyl) dimethyl perionate, methanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)dimethyl perionium, benzyl (4-hydroxyphenyl) methyl methanesulfonate bismuth, benzyl (4-((methoxycarbonyl)oxy)phenyl)methyl methanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methylmethanesulfonate) (4-hydroxyphenyl) dimethylsulfanium trifluoromethanesulfonate, (4-((methoxycarbonyl)oxy)phenyl) dimethylsulfanium trifluoromethanesulfonate, trifluoromethane Benzyl sulfonate (4-hydroxyphenyl) methyl sulfamate, benzyl trifluoromethanesulfonate (4-((methoxycarbonyl)oxy)phenyl)methyl sulfamate, trifluoromethanesulfonic acid (4- Hydroxyphenyl)methyl((2-methylphenyl)methyl)strontium, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-ylidene )-2-(o-tolyl)propionitrile and 2,2-bis(3-(methanesulfonamido)-4-hydroxyphenyl)hexafluoropropane are preferable as the thermal acid generator.

Moreover, the compound described in the 0059 paragraph of Japanese Unexamined Patent Application Publication No. 2013-167742 is also preferable as a thermal acid generator.

The content of the thermal acid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, relative to 100 parts by mass of the polyimide precursor. Since a crosslinking reaction can be accelerated|stimulated by containing 0.01 mass part or more, the mechanical property and solvent resistance of an organic film can be improved further. In addition, from the viewpoint of the electrical insulating properties of the organic film, 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is still more preferable.

<Alkali Generator> The resin composition of the present invention may contain an alkali generator. Here, the base generator is a compound capable of generating a base by physical or chemical action. As a preferable alkali generator for the resin composition of this invention, a thermal alkali generator and a photobase generator are mentioned. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains an alkali generator. When the resin composition contains a thermal alkali generator, for example, the cyclization reaction of the precursor can be accelerated by heating, so that the cured product has good mechanical properties or chemical resistance, for example, as a rewiring layer included in a semiconductor package The performance with the interlayer insulating film becomes good. As an alkali generator, an ionic alkali generator may be sufficient, and a nonionic alkali generator may be sufficient. Examples of the base generated by the base generator include secondary amines and tertiary amines. The alkali generator of the present invention is not particularly limited, and known alkali generators can be used. As known base generators, for example, carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, carbamoyl amine compounds, acetamide compounds, urethane compounds, and benzyl carbamic acid esters can be used. Compounds, Nitrobenzyl Carbamate Compounds, Sulfonamide Compounds, Imidazole Derivative Compounds, Aminoimide Compounds, Pyridine Derivative Compounds, α-Aminoacetophenone Derivative Compounds, Quaternary Ammonium Salt Derivatives Compounds, pyridinium salts, α-lactone ring derivative compounds, amide imide compounds, phthalimide derivative compounds, acyloxyimine-based compounds, and the like. As a specific compound of a nonionic base generator, the compound represented by a formula (B1), a formula (B2), or a formula (B3) is mentioned. [Chemical formula 30]

In formula (B1) and formula (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group without a tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb ¹ and Rb ² do not become hydrogen atoms at the same time. In addition, none of Rb ¹ , Rb ² and Rb ³ has a carboxyl group. In addition, in this specification, a tertiary amine structure means the structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, when the bonded carbon atom is a carbon atom constituting a carbonyl group, that is, when an amide group is formed together with a nitrogen atom, it is not limited thereto.

In formulae (B1) and (B2), about Rb ¹ , Rb ² and Rb ³ , it is preferable that at least one of them contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring formed by condensing two monocyclic rings is preferable. The single ring system is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. Monocyclic cyclohexane ring and benzene ring are preferable, and cyclohexane ring is more preferable.

More specifically, Rb ¹ and Rb ² are hydrogen atoms, alkyl (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), alkenyl (having 2 to 24 carbon atoms) is better, 2-18 is better, 3-12 is further better), aryl (carbon number 6-22 is better, 6-18 is better, 6-10 is further better) or aryl Alkyl groups (preferably having 7 to 25 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12) are preferred. These groups may have a substituent within a range in which the effects of the present invention are exhibited. Rb ¹ and Rb ² may be bonded to each other to form a ring. As the ring to be formed, a nitrogen-containing heterocyclic ring having 4 to 7 members is preferable. Rb ¹ and Rb ² are especially linear, branched or cyclic alkyl groups that may have substituents (the number of carbon atoms is preferably 1-24, more preferably 2-18, and more preferably 3-12) Preferably, a cycloalkyl group which may have a substituent (3-24 carbon atoms are preferable, 3-18 is more preferable, and 3-12 is a further preferable) is more preferable, and a cyclohexyl group which may have a substituent group is further preferable .

Examples of Rb ³ include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), and an aryl group (preferably having 6 to 22 carbon atoms, and having 6 to 18 carbon atoms). is more preferable, 6-10 is further preferable), alkenyl (carbon number 2-24 is preferable, 2-12 is more preferable, 2-6 is further preferable), arylalkyl (carbon number 7- 23 is better, 7-19 is better, 7-12 is further better), arylalkenyl (carbon number 8-24 is better, 8-20 is better, 8-16 is further better) , alkoxy (carbon number 1-24 is preferred, 2-18 is more preferred, 3-12 is further preferred), aryloxy (carbon number 6-22 is preferred, 6-18 is more preferred, 6 to 12 are more preferred) or arylalkoxy (the number of carbon atoms is preferably 7 to 23, more preferably 7 to 19, and more preferably 7 to 12). Among them, cycloalkyl groups (preferably carbon numbers of 3 to 24, more preferably 3 to 18, and even more preferably 3 to 12), arylalkenyl and arylalkoxy are preferred. Rb ³ may further have a substituent within a range in which the effects of the present invention are exhibited.

The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2). [Chemical formula 31]

In the formula, Rb ¹¹ and Rb ¹² and Rb ³¹ and Rb ³² are the same as Rb ¹ and Rb ² in the formula (B1), respectively. Rb ¹³ is alkyl (preferably carbon number 1-24, more preferably 2-18, further preferably 3-12), alkenyl (preferably carbon number 2-24, more preferably 2-18, 3-12 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), arylalkyl (carbon number 7-23 is preferred) , 7 to 19 are more preferable, and 7 to 12 are further preferable), and may have a substituent within the scope of exerting the effect of the present invention. Among them, Rb ¹³ -series arylalkyl groups are preferred.

Rb ³³ and Rb ³⁴ are independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 3), an alkenyl group (preferably having a carbon number of 2 to 12). preferably, 2-8 is more preferred, 2-3 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is further preferred), arylalkyl (The number of carbon atoms is preferably 7 to 23, more preferably 7 to 19, and even more preferably 7 to 11), and a hydrogen atom is more preferable.

Rb ³⁵ is alkyl (preferably carbon number 1-24, more preferably 1-12, further preferably 3-8), alkenyl (preferably carbon number 2-12, more preferably 2-10, 3-8 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), arylalkyl (carbon number 7-23 is preferred) , 7-19 are better, 7-12 are further better), aryl is better.

It is also preferable that the compound represented by the formula (B1-1) is the compound represented by the formula (B1-1a). [Chemical formula 32]

Rb ¹¹ and Rb ¹² have the same meanings as Rb ¹¹ and Rb ¹² in formula (B1-1). Rb ¹⁵ and Rb ¹⁶ are hydrogen atoms, alkyl groups (preferably carbon number 1-12, more preferably 1-6, further preferably 1-3), alkenyl (preferably carbon number 2-12, 2 ～6 is better, 2-3 is further better), aryl (carbon number is 6-22 is better, 6-18 is better, 6-10 is further better), arylalkyl (carbon number is better) 7-23 are preferable, 7-19 are more preferable, 7-11 are further preferable), hydrogen atom or methyl group is preferable. Rb ¹⁷ is alkyl (preferably carbon number 1-24, more preferably 1-12, and further preferably 3-8), alkenyl (preferably carbon number 2-12, more preferably 2-10, 3-8 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), arylalkyl (carbon number 7-23 is preferred) , 7-19 are more preferable, 7-12 are further preferable), among which aryl group is preferable.

[Chemical formula 33]

In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the route of the linking chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the linking chain being 3 or more. In addition, R ^N1 and R ^N2 each independently represent a monovalent organic group.

In the present specification, the "linking chain" refers to the atomic chain on the path between two atoms or atomic groups connecting the connecting objects by the shortest (minimum number of atoms) path connecting the connecting objects. For example, in a compound represented by the following formula, L consists of a phenylene ethylidene group, and has an ethylidene group as a saturated hydrocarbon group, the connecting chain consists of 4 carbon atoms, and the number of atoms on the path of the connecting chain (that is, the composition The number of atoms connecting the chain, hereinafter also referred to as "connecting chain length" or "connecting chain length".) is 4. [Chemical formula 34]

The number of carbon atoms in L in the formula (B3) (including carbon atoms other than carbon atoms in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, more preferably 10 or less, and particularly preferably 8 or less. More preferably, the lower limit is 4 or more. From the viewpoint of rapidly advancing the above-mentioned intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and 4 is the best. Specific preferred compounds of the base generator include, for example, compounds described in paragraphs 0102 to 0168 of International Publication No. 2020/066416, and compounds described in paragraphs 0143 to 0177 of International Publication No. 2018/038002. Compounds described.

Moreover, it is also preferable that the base generator contains a compound represented by the following formula (N1). [Chemical formula 35]

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group, R ^C1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

L is a divalent linking group, and a divalent organic group is preferable. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. As an upper limit, 12 or less is preferable, 8 or less is more preferable, and 5 or less is more preferable. The linking chain length is the number of atoms present on the atomic arrangement that makes the shortest path between the two carbonyl groups in the formula.

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group (preferably carbon number 1-24, more preferably 2-18, further preferably 3-12), hydrocarbon group (carbon number 1 to 24 are preferred, 1 to 12 are more preferred, and 1 to 10 are further preferred), and specifically, aliphatic hydrocarbon groups (1 to 24 carbon atoms are preferred, and 1 to 12 are preferred) More preferably, 1-10 is further preferred) or aromatic hydrocarbon group (preferably carbon number 6-22, 6-18 is more preferred, 6-10 is further preferred), aliphatic hydrocarbon group is preferred. When an aliphatic hydrocarbon group is used as R ^N1 and R ^N2 , since the basicity of the generated base is high, it is preferable. In addition, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain or in the aromatic ring or in the substituent. In particular, the aspect in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain can be exemplified.

Examples of the aliphatic hydrocarbon groups constituting R ^N1 and R ^N2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to combinations of chain alkyl groups and cyclic alkyl groups, and groups in the chain. An alkyl group with an oxygen atom. The straight or branched chain alkyl group having 1 to 24 carbon atoms is preferable, 2 to 18 is more preferable, and 3 to 12 is further preferable. Examples of linear or branched chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl. , isopropyl, isobutyl, secondary butyl, tertiary butyl, isopentyl, neopentyl, tertiary pentyl, isohexyl, etc. Preferably, the cyclic alkyl group has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. As a cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group etc. are mentioned, for example. The carbon number involved in the combination of the chain alkyl group and the cyclic alkyl group is preferably 4-24, more preferably 4-18, and even more preferably 4-12. As a group concerning the combination of a chain alkyl group and a cyclic alkyl group, a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, an ethylcyclohexylethyl group etc. are mentioned, for example. Preferably, the alkyl group having an oxygen atom in the chain has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. Among them, R ^N1 and R ^N2 are preferably alkyl groups having 5 to 12 carbon atoms, from the viewpoint of increasing the boiling point of the decomposed base to be described later. However, in formulations that place importance on adhesion at the time of lamination with a metal (for example, copper), a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.

R ^N1 and R ^N2 may be connected to each other to form a ring structure. When a cyclic structure is formed, an oxygen atom or the like may be present in the chain. In addition, the cyclic structure formed by R ^N1 and R ^N2 may be a single ring or a condensed ring, but a single ring is preferable. The cyclic structure to be formed is preferably a 5-membered ring or a 6-membered ring containing a nitrogen atom in the formula (N1), and examples thereof include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, and a pyrrolidine ring. , an imidazoline ring, a pyrazole ring, a piperidine ring, a piperidine ring, a morpholine ring, and the like, preferably a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperidine ring, and a morpholine ring.

R ^C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

As the protective group, a protective group decomposed by the action of an acid or a base is preferable, and a protective group decomposed by an acid is preferably used.

Specific examples of the protecting group include a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain. As a chain or cyclic alkyl group, a methyl group, an ethyl group, an isopropyl group, a tertiary butyl group, a cyclohexyl group, etc. are mentioned. Specific examples of the chain-like alkyl group having an oxygen atom in the chain include alkoxyalkyl groups, and more specifically, methoxymethyl (MOM) groups, ethoxyethyl base (EE) group, etc. As a cyclic alkyl group which has an oxygen atom in a chain, an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyran (THP) group, etc. are mentioned.

The divalent linking group constituting L is not particularly limited, but a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is more preferable. The hydrocarbon group may have a substituent, and may have atoms other than carbon atoms in the hydrocarbon chain. More specifically, a divalent hydrocarbon linking group that may have an oxygen atom in the chain Preferably, a bivalent aliphatic hydrocarbon group that may have an oxygen atom in the chain, a bivalent aromatic hydrocarbon group, or a combination of a bivalent aliphatic hydrocarbon group that may have an oxygen atom in the chain and a bivalent aromatic hydrocarbon group. The group involved is more preferable, and the divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is further preferable. These groups preferably do not have oxygen atoms. Preferably, the divalent hydrocarbon linking group has 1 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6. The divalent aliphatic hydrocarbon group has preferably 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The divalent aromatic hydrocarbon group has preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The group involved in the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group (for example, an aryl-extended alkyl group) is preferably one with a carbon number of 7 to 22, more preferably 7 to 18, and 7 to 10 Further preferred.

As the linking group L, specifically, a straight-chain or branched chain alkylene group, a cyclic alkylene group, a group involved in a combination of a chain-shaped alkylene group and a cyclic alkylene group, a group having an oxygen in the chain Atomic alkylene, linear or branched chain alkenylene, cyclic alkenylene, aryl, and arylalkylene are preferred. The linear or branched chain alkylidene system having 1 to 12 carbon atoms is preferred, 2 to 6 are more preferred, and 2 to 4 are further preferred. Preferably, the cyclic alkylene group has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The carbon number of the group involved in the combination of the chain alkylene and the cyclic alkylene is preferably 4-24, more preferably 4-12, and even more preferably 4-6. The alkylene group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. The alkylidene system having an oxygen atom in the chain has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.

The linear or branched chain alkenylene group has preferably 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The number of C=C bonds of the linear or branched chain alkenylene group is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 3. The cyclic alkenylene group having 3 to 12 carbon atoms is preferable, and 3 to 6 are more preferable. The number of C=C bonds of the cyclic alkenylene group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2. The carbon number of the aryl extended group is preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 10. The arylidene alkylene group has 7-23 carbon atoms, more preferably 7-19, and even more preferably 7-11. Among them, a chain-like alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain-like alkenylene group, an aryl group, and an arylene group are preferred, and 1,2-extended Ethyl, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylidene (especially cis-vinylidene), phenylene (1,2-phenylene), phenylmethylene (especially 1,2-phenylene), ethoxyethylidene (especially 1,2-ethoxy- 1,2-ethylidene) is more preferred.

As the base generator, the following examples can be given, but the present invention should not be construed as being limited thereto.

[Chemical formula 36]

The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

Specific preferred compounds of the ionic base generator include, for example, the compounds described in Paragraph Nos. 0148 to 0163 of International Publication No. 2018/038002.

Specific examples of the ammonium salt include the following compounds, but the present invention is not limited to these. [Chemical formula 37]

Specific examples of the iminium salt include the following compounds, but the present invention is not limited to these. [Chemical formula 38]

When the resin composition of the present invention contains an alkali generator, the content of the alkali generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less. One type or two or more types of alkali generators can be used. When two or more kinds are used, the total amount is preferably within the above range.

<Polymerizable compound> It is preferable that the resin composition of this invention contains a polymerizable compound. As a polymerizable compound, a radical crosslinking agent or another crosslinking agent is mentioned.

[Radical crosslinking agent] The resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radically polymerizable group. The radically polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing the above-mentioned ethylenically unsaturated bond include vinyl group, allyl group, vinylphenyl group, (meth)acryloyl group, maleimide group, and (meth)acrylamide group. A group having an ethylenically unsaturated bond, such as a group. Among these, as the above-mentioned group containing an ethylenically unsaturated bond, a (meth)acrylamide group, a (meth)acrylamide group, and a vinylphenyl group are preferable, and from the viewpoint of reactivity, (Meth)acryloyl groups are more preferred.

The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds. As the above-mentioned compound having two or more ethylenically unsaturated bonds, a compound having 2-15 ethylenically unsaturated bonds is preferable, a compound having 2-10 ethylenically unsaturated bonds is more preferable, and a compound having 2-6 ethylenically unsaturated bonds is more preferable. These compounds are further preferred. In addition, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention may also include a compound having two ethylenically unsaturated bonds and the above-mentioned compound having three or more ethylenically unsaturated bonds is better.

The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

Specific examples of the radical crosslinking agent include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, amides The amines are preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. In addition, the addition reaction products of unsaturated carboxylates or amides with nucleophilic substituents such as hydroxyl groups, amine groups, and hydrogen thiol groups and monofunctional or polyfunctional isocyanates or epoxides can also be preferably used. , or a dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid, etc. In addition, the addition reaction of unsaturated carboxylates or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols can also be preferably used. Compounds, unsaturated carboxylic acid esters or amides with leaching substituents such as halogeno group or tosyloxy group, and monofunctional or polyfunctional alcohols, amines, thiols class of substitution reactants. In addition, as another example, a compound group substituted with vinylbenzene derivatives such as unsaturated phosphonic acid and styrene, vinyl ether, and allyl ether, etc., can also be used instead of the above-mentioned unsaturated carboxylic acid. As a specific example, reference can be made to the descriptions of paragraphs 0113 to 0122 of JP 2016-027357 A, which are incorporated in the present specification.

In addition, it is also preferable that the radical crosslinking agent is a compound having a boiling point of 100° C. or higher under normal pressure. Examples of this include adding ethylene oxide or propylene oxide to polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, and neopentyl glycol di(meth)acrylate. (Meth)acrylate, Neopentaerythritol tri(meth)acrylate, Neotaerythritol tetra(meth)acrylate, Dipivalerythritol penta(meth)acrylate, Dipivalerythritol hexa (meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tris(acrylooxypropyl)ether, tris(acrylooxyethyl)isocyanurate, glycerin or trimethylolpropane Compounds that have been (meth)acrylated on polyfunctional alcohols such as methylolethane, such as Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Publication No. 51-037193 Urethane (meth)acrylates described in each publication, polymers described in Japanese Patent Publication No. Sho 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490 Polyfunctional acrylates such as ester acrylates, epoxy acrylates which are reaction products of epoxy resins and (meth)acrylic acid, methacrylates, and mixtures thereof. In addition, compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also preferred. Moreover, polyfunctional (meth)acrylate etc. obtained by making a compound which has a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate, react with a polyfunctional carboxylic acid are also mentioned.

In addition, as a preferable radical crosslinking agent other than the above-mentioned ones, those having a pyrene ring described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, Japanese Patent No. 4364216 and the like can also be used A compound or cardo resin having two or more groups containing an ethylenically unsaturated bond.

In addition, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, and Japanese Patent Publication No. 01-040336, or Japanese Patent Publication No. Hei 02 can also be cited. - Vinylphosphonic acid-based compounds and the like described in Gazette No. 025493. Moreover, the compound containing a perfluoroalkyl group described in Unexamined-Japanese-Patent No. 61-022048 can also be used. In addition, those introduced as photopolymerizable monomers and oligomers in the Journal of Adhesion Association of Japan, vol. 20, No. 7, pp. 300 to 308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP 2015-034964 A and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used. incorporated into this manual.

In addition, as described in Japanese Patent Laid-Open No. 10-062986 as formula (1) and formula (2) together with specific examples, ethylene oxide or propylene oxide is added to a polyfunctional alcohol, and then ( Meth)acrylated compounds can also be used as free crosslinkers.

In addition, the compounds described in paragraphs 0104 to 0131 of JP 2015-187211 A can also be used as a radical crosslinking agent, and these contents are incorporated in the present specification.

As the radical crosslinking agent, dipeotaerythritol triacrylate (available as a commercial item: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipeotaerythritol tetraacrylate (available as a commercial item as KAYARAD D-320; Nippon Kayaku Co., Ltd., A-TMMT: Shin-Nakamura Chemical Co., Ltd. -310; manufactured by Nippon Kayaku Co., Ltd.), dipivaloerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues is preferable. These oligomeric forms can also be used.

Commercially available products of the radical crosslinking agent include, for example, SR-494, which is a tetrafunctional acrylate having four vinyloxy chains, manufactured by Sartomer Company, Inc., and SR-494, which is a tetrafunctional acrylate having four vinyloxy chains. Functional methacrylates SR-209, 231, 239 manufactured by Sartomer Company, Inc., DPCA-60 as a hexafunctional acrylate having 6 pentenoxy chains, manufactured by Nippon Kayaku Co., Ltd., as TPA-330 of trifunctional acrylate having 3 isobutenyloxy chains, urethane oligomer UAS-10, UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

As the radical crosslinking agent, for example, the amino groups described in Japanese Patent Publication No. Sho 48-041708, Japanese Patent Publication No. Sho 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765 Formate acrylates, or the epoxy resins described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 Urethane compounds with an ethane-based skeleton are also preferred. In addition, as the radical crosslinking agent, those described in Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. Hei 01-105238 having an amino group in the molecule can also be used. Compounds of structure or sulfide structure.

The free-radical cross-linking agent may also be a free-radical cross-linking agent having an acid group such as a carboxyl group and a phosphoric acid group. The free-radical crosslinking agent with an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride reacts with the unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acid group. Free radical crosslinking agents are more preferred. Particularly preferably, in the free-radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, the aliphatic polyhydroxy compound is neopentylerythritol or dipivale Compounds of tetraols. As a commercial item, M-510, M-520 etc. are mentioned as a polybasic acid-modified acrylic oligomer by TOAGOSEI CO., LTD., for example.

The preferred acid value of the radical crosslinking agent having an acid group is 0.1-300 mgKOH/g, and particularly preferably 1-100 mgKOH/g. When the acid value of the radical crosslinking agent is within the above-mentioned range, workability in production is excellent, and furthermore, developability is excellent. In addition, the polymerizability was good. The said acid value is measured based on the description of JISK0070:1992.

It is preferable to use bifunctional methacrylate or acrylate as a resin composition from a viewpoint of the analytical property of a pattern and the stretchability of a film. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethylacrylate can be used Base Acrylate, PEG600 Diacrylate, PEG600 Dimethacrylate, Polytetraethylene Glycol Diacrylate, Polytetraethylene Glycol Dimethacrylate, Neopentyl Glycol Diacrylate, Neopentyl Glycol Dimethacrylate Ethyl acrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclic Decane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethyl bisphenol A Acrylates, PO (propylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-propenyloxypropyl methacrylate , isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, and 2-functional acrylate with urethane bond, 2-functional methacrylic acid with urethane bond ester. Two or more of these can be mixed and used as needed. In addition, for example, PEG200 diacrylate refers to a polyethylene glycol diacrylate, and the formula weight of the polyethylene glycol chain is about 200. In the resin composition of the present invention, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent from the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the pattern (hardened product). As the monofunctional radical crosslinking agent, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylate can be preferably used Butoxyethyl acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (Meth)acrylic acid derivatives such as (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, N-ethylene pyrrolidone, N-vinyl compounds such as N-vinyl caprolactam, allyl glycidyl ether, etc. As the monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, a compound having a boiling point of 100° C. or higher under normal pressure is also preferred. Moreover, as a bifunctional or more radical crosslinking agent, allyl compounds, such as diallyl phthalate and triallyl trimellitate, are mentioned.

When a radical crosslinking agent is contained, it is preferable that the content exceeds 0 mass % and 60 mass % or less with respect to the total solid content of the resin composition of this invention. The lower limit is more preferably 5 mass % or more. The upper limit is more preferably 50 mass % or less, and even more preferably 30 mass % or less.

A radical crosslinking agent may be used individually by 1 type, and may be used in mixture of 2 or more types. When two or more types are used in combination, it is preferable that the total amount thereof falls within the above-mentioned range.

[Other cross-linking agents] It is also preferable that the resin composition of the present invention contains other cross-linking agents different from the above-mentioned radical cross-linking agents. In the present invention, the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, and has a plurality of cross-linking agents in the molecule that are promoted in the composition by the photosensitive acid generator or the photo-base acid generator. The other compounds in the composition or the reaction products of the other compounds or their reaction products are preferably the bases of the reaction that form covalent bonds, and have a plurality of compounds in the molecule that are promoted by the action of acids or bases to interact with the other compounds in the composition or their compounds. The compounds of the reaction bases in which covalent bonds are formed between the reaction products are preferred. The above acid or base is preferably an acid or base generated by a photoacid generator or a photobase generator in the exposure step. As other cross-linking agents, compounds having at least one group selected from the group consisting of oxymethyl, hydroxymethyl and alkoxymethyl are preferred, and compounds having at least one group selected from the group consisting of oxymethyl, hydroxymethyl and alkoxymethyl are preferred. A compound in which at least one group in the group of a methyl group and an alkoxymethyl group is directly bonded to a nitrogen atom is more preferable. As other crosslinking agents, for example, compounds having an amine group such as formaldehyde or formaldehyde and alcohols reacted with melamine, glycoluril, urea, alkylene urea, benzoguanamine, etc., and oxymethyl, A compound in which a hydroxymethyl group or an alkoxymethyl group is substituted for the hydrogen atom of the above-mentioned amine group. The production method of these compounds is not particularly limited as long as it is a compound having the same structure as the compound produced by the above-mentioned method. Moreover, the oligomer which the hydroxymethyl group of these compounds self-condenses may be sufficient. The cross-linking agent using melamine as the above-mentioned amine group-containing compound is called a melamine-based cross-linking agent, and the cross-linking agent using glycoluril, urea, or alkylene urea is called a urea-based cross-linking agent. The crosslinking agent using alkylene urea is called alkylene urea crosslinking agent, and the crosslinking agent using benzoguanamine is called benzoguanamine crosslinking agent. Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based crosslinking agent and a melamine-based crosslinking agent, and contains a compound selected from the group consisting of glycoluril-based crosslinking agents described later. At least one compound in the group of a melamine-based crosslinking agent and a melamine-based crosslinking agent is more preferred.

As a compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention, an alkoxymethyl group or an acyloxymethyl group in an aromatic group or the following urea can be mentioned as a structural example The compound directly substituted on the nitrogen atom of the structure or on the three 𠯤. Preferably, the alkoxymethyl group or alkoxymethyl group of the above compound has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. The total number of the alkoxymethyl group and the acyloxymethyl group contained in the above-mentioned compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6. The molecular weight of the above-mentioned compound is preferably 1500 or less, more preferably 180-1200.

[Chemical formula 39]

R ₁₀₀ represents an alkyl group or an acyl group. R ₁₀₁ and R ₁₀₂ each independently represent a monovalent organic group, and may be bonded to each other to form a ring.

As a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted with an aromatic group, for example, a compound having the following general formula can be mentioned.

[Chemical formula 40]

In the formula, X represents a single bond or a 2-valent organic group, each R ₁₀₄ independently represents an alkyl group or an acyl group, and R ₁₀₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or an acid group. _The group that decomposes and generates an ^{alkali - soluble} group by the action of the ~4 alkyl group, R ⁵ represents a group that is released by the action of an acid.)). R ₁₀₅ each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1-3, d is 0-4, e is 0-3, f is 0-3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less. The group decomposed by the action of an acid to generate an alkali-soluble group, the group that is released by the action of an acid, and R ⁵ in the group represented by -C(R ⁴ ) ₂ COOR ⁵ are, for example, -C. (R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), -C(R ₀₁ )(R ₀₂ )(OR ₃₉ ), and the like. In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable. The above-mentioned alkyl group may be linear or branched. As the cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable. The above-mentioned cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring. The above-mentioned aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group. As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable. The above-mentioned aralkyl group refers to an aryl group substituted with an alkyl group, and the preferred aspects of the alkyl group and the aryl group are the same as the preferred aspects of the above-mentioned alkyl group and the aryl group. The above-mentioned alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. In addition, these groups may further have known substituents within the range in which the effects of the present invention can be obtained.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

As a group that is decomposed by the action of an acid to generate an alkali-soluble group, or a group that is released by the action of an acid, a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. are preferred. . Further preferred are tertiary alkyl ester groups and acetal groups.

As a compound which has an alkoxymethyl group, the following structures are mentioned specifically,. As a compound which has an alkoxymethyl group, the compound which changed the alkoxymethyl group of the following compounds to an alkoxymethyl group can be mentioned. As a compound which has an alkoxymethyl group or an alkoxymethyl group in a molecule|numerator, the following compounds can be mentioned, but it is not limited to these.

[Chemical formula 41]

[Chemical formula 42]

As a compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available one may be used, or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an alkoxymethyl group is directly substituted on an aromatic ring or a trisic ring is preferable.

Specific examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine, and the like.

Specific examples of the urea-based crosslinking agent include, for example, monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, and monomethoxy methylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxy Methylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxy Methylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxy Glycoluril based cross-linking agents such as methylated glycoluril; Urea-based crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea and bisbutoxymethyl urea; Monohydroxymethylated ethyl urea or dihydroxymethylated ethyl urea, monomethoxymethylated ethyl urea, dimethoxymethylated ethyl urea, monoethoxymethylated ethyl urea , diethoxymethylated ethyl urea, monopropoxymethylated ethyl urea, dipropoxymethylated ethyl urea, monobutoxymethylated ethyl urea or dibutoxymethyl ethyl urea Ethyl urea and other ethyl urea crosslinking agents; Monohydroxymethylated propylene glycol, dihydroxymethylated propylene glycol, monomethoxymethylated propylene glycol, dimethoxymethylated propylene glycol , diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethyl propylene urea Propylene urea based crosslinking agent such as propylene propylene urea; 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazole pyridone etc.

Specific examples of the benzoguanamine-based crosslinking agent include, for example, monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, and tetrahydroxymethylated benzoguanamine. Methylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzene guanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine Amine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, Monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, etc.

In addition, as a compound having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl, it can also be preferably used directly bonded to an aromatic ring (preferably a benzene ring) with a group selected from the group consisting of hydroxymethyl and alkoxymethyl. Compounds that include at least one group in the group of hydroxymethyl and alkoxymethyl. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl) base) benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)biphenyl (Methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methyl Methoxymethylphenyl oxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylene yltris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxyl -1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

As other crosslinking agents, commercially available products can also be used, and preferable ones include 46DMOC, 46DMOEP (the above are manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML- OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML- BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are Honshu Chemical Industry Co., Ltd.), NIKARAC (registered trademark, the same below) MX-290, NIKARAC MX-280, NIKARAC MX-270, NIKARAC MX-279, NIKARAC MW-100LM, NIKARAC MX-750LM (the above are manufactured by Sanwa Chemical Co., Ltd.), etc.

In addition, it is also preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds and benzoquinone compounds as another crosslinking agent.

-Epoxy compounds (compounds with epoxy groups)- As an epoxy compound, the compound which has two or more epoxy groups in 1 molecule is preferable. The epoxy group undergoes a cross-linking reaction at 200° C. or lower, and does not generate a dehydration reaction derived from the cross-linking, so film shrinkage is unlikely to occur. Therefore, containing an epoxy compound is effective for the suppression of low-temperature hardening and warpage of the resin composition of this invention.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the elastic modulus is further reduced, and the warpage can be suppressed. The polyethylene oxide group refers to those having 2 or more repeating units of ethylene oxide, and preferably 2 to 15 repeating units.

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol Glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether and other alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins; polypropylene glycol diglycidyl Polyalkylene glycol type epoxy resins such as glycerol ethers; epoxy-containing silicones such as polymethyl(glycidoxypropyl)siloxane, etc., but not limited to these. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP- 4700, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (the above are trade names, manufactured by DIC Corporation), Rika Resin (registered trademark) BEO-20E, Rika Resin (registered trademark) BEO-60E, Rika Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (trade name, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are trade names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD ( registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (the above are trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN- 104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are trade names, manufactured by Nippon Kayaku Co., Ltd.), etc. In addition, the following compounds can also be preferably used.

[Chemical formula 43]

In the formula, n is an integer of 1-5, and m is an integer of 1-20.

Among the above-mentioned structures, it is preferable that n is 1 to 2, and m is 3 to 7, from the viewpoint of both improving heat resistance and elongation.

-oxetane compounds (compounds with oxetanyl groups)- Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4 -Benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As a specific example, ARON OXETANE series (for example, OXT-121, OXT-221) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone or in combination of two or more.

-Benzo㗁𠯤 compounds (compounds with a benzo㗁𠯤 group)- The benzodiazepine compound is preferable because the crosslinking reaction originating from the ring-opening addition reaction does not cause outgassing during curing, and further reduces thermal shrinkage and suppresses warpage.

Preferable examples of benzodiazepine compounds include P-d-type benzodiazepines, F-a-type benzodiazepines (the above are trade names, manufactured by SHIKOKU CHEMICALS CORPORATION), and benzodiazepines of polyhydroxy styrene resins. The finished product, phenol novolac type dihydrobenzo 㗁𠯤 compound. These may be used alone or in combination of two or more.

With respect to the total solid content of the resin composition of the present invention, the content of other cross-linking agents is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, further preferably 0.5 to 15 mass %, and 1.0 to 1.0 mass %. 10% by mass is particularly preferred. The other crosslinking agents may be contained only by one, or two or more of them may be contained. When two or more other crosslinking agents are contained, it is preferable that the total of them is within the above range.

<Metal Adhesion Improver> It is preferable that the resin composition of this invention contains the metal adhesion improver for improving the adhesion with the metal material used for electrodes, wiring, etc.. Examples of the metal adhesion improver include silane coupling agents having an alkoxysilyl group, aluminum-based adhesive agents, titanium-based adhesive agents, compounds having a sulfonamide structure, and compounds having a thiourea structure, Phosphoric acid derivative compounds, β-keto ester compounds, amine compounds, etc.

[Silane coupling agent] Examples of the silane coupling agent include compounds described in paragraph 0167 of International Publication No. 2015/199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, and compounds described in International Publication No. 2011/080992 The compounds described in paragraphs 0063 to 0071 of JP 2014-191252 A, the compounds described in paragraphs 0060 to 0061 of JP 2014-191252 A, the compounds described in paragraphs 0045 to 0052 of JP 2014-041264 A, The compounds described in paragraph 0055 of International Publication No. 2014/097594 and the compounds described in paragraphs 0067 to 0078 of JP 2018-173573 are incorporated in the present specification. Furthermore, as described in paragraphs 0050 to 0058 of JP-A No. 2011-128358, it is also preferable to use two or more different silane coupling agents. Moreover, it is also preferable to use the following compounds as a silane coupling agent. In the following formula, Me represents a methyl group, and Et represents an ethyl group.

[Chemical formula 44]

Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-glycidoxysilane. 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl triethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3 - Methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, N-2- (Aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane Oxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-amine propyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane , 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropyl succinic anhydride. These can be used alone or in combination of two or more.

[Aluminum-based Adhesives] As an aluminum-based adhesive agent, for example, tris(ethylacetate)aluminum, tris(acetoacetate)aluminum, ethylacetatealuminum diisopropyl ester, etc. are mentioned.

In addition, as other metal adhesion improving agents, the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A and the vulcanization described in paragraphs 0032 to 0043 of JP 2013-072935 A can also be used compounds, the contents of which are incorporated into this specification.

The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the specific resin . By setting it as the said lower limit or more, the adhesiveness of a pattern and a metal layer becomes favorable, and by setting it as the said upper limit or less, the heat resistance and mechanical properties of a pattern become favorable. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more kinds are used, it is preferable that the sum of them is within the above-mentioned range.

<Migration inhibitor> It is preferable that the resin composition of the present invention further contains a migration inhibitor. By including the migration inhibitor, the movement of metal ions originating from the metal layer (metal wiring) into the film can be effectively suppressed.

The migration inhibitor is not particularly limited, and examples include heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring) ring, pyridine ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, tri-pyran ring) compounds, thioureas And compounds with a hydrogen thiol group, hindered phenol-based compounds, salicylic acid derivative-based compounds, and hydrazine derivative-based compounds. In particular, 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole can be preferably used Triazole-based compounds such as azoles, and tetrazole-based compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole.

Alternatively, an ion scavenger that captures anions such as halogen ions can also be used.

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, and JP 2011 A can be used. - Compounds described in paragraph 0052 of Japanese Patent Publication No. 059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Laid-Open Publication No. 2012-194520, compounds described in paragraph 0166 of International Publication No. 2015/199219, etc. , which are incorporated into this manual.

Specific examples of the migration inhibitor include the following compounds.

[Chemical formula 45]

When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, relative to the total solid content of the resin composition of the present invention. 0.1-1.0 mass % is more preferable.

The migration inhibitor may be only one type or two or more types. When there are two or more kinds of migration inhibitors, it is preferable that the total is within the above-mentioned range.

<Polymerization inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenol-based compounds, quinone-based compounds, amine-based compounds, N-oxyl radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic ring-based compounds, and metal compounds Wait.

As a specific compound of the polymerization inhibitor, p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tertiary butyl-p-cresol, gallic phenol, p-tertiary phenol can be preferably used Butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'- Methylene bis(4-methyl-6-tertiary butylphenol), N-nitrosophenylhydroxylamine first cerium salt, N-nitroso-N-phenylhydroxylamine aluminum salt, N- Nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tertiary butyl -4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-( N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tertiarybutyl)benzene Ethylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris𠯤-2,4,6-(1H ,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 2,2,6,6-tetramethylpiperidine 1-oxyl Free radicals, phenothiazine, phenothiam, 1,1-diphenyl-2-picrylhydrazine, copper(II) dibutyldithiocarbamate, nitrobenzene, N-nitroso-N -Phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. In addition, the polymerization inhibitors described in paragraph 0060 of JP 2015-127817 A and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used, the contents of which are incorporated in the present specification.

When the resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, relative to the total solid content of the resin composition of the present invention. 0.05-10 mass % is more preferable.

Only one type of polymerization inhibitor may be used, or two or more types may be used. When there are two or more kinds of polymerization inhibitors, it is preferable that the total is within the above-mentioned range.

＜Acid scavenger＞ It is preferable that the resin composition of this invention contains an acid scavenger in order to reduce the performance change by time from exposure to heating. Here, the acid scavenger refers to a compound capable of capturing an acid by being present in the system, and a compound having a low acidity and a high pKa is preferable. As the acid scavenger, compounds with amine groups are preferred, primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred, primary amines, secondary amines, tertiary amines, ammonium salts It is more preferable, and secondary amine, tertiary amine and ammonium salt are further preferable. As the acid scavenger, compounds having an imidazole structure, a diazabicyclic structure, an onium structure, a trialkylamine structure, an aniline structure, or a pyridine structure, and an alkylamine derivative having a hydroxyl group and/or an ether bond can be preferably used. compounds, aniline derivatives with hydroxyl and/or ether bonds, etc. When it has an onium structure, the acid scavenger is a salt having a cation selected from ammonium, diazo, iodonium, perium, phosphonium, pyridinium, etc. and an anion of an acid whose acidity is lower than that of the acid generated by the acid generator. good.

As an acid scavenger having an imidazole structure, imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzimidazole, etc. are mentioned. As an acid scavenger having a diazabicyclic structure, 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]nonane- 5-ene, 1,8-diazabicyclo[5,4,0]undec-7-ene, etc. Examples of the acid scavenger having an onium structure include tetrabutylammonium hydroxide, triaryl perionium hydroxide, benzylmethyl perionium hydroxide, and perium hydroxide having a 2-oxoalkyl group. Specifically, Triphenyl perium hydroxide, tris(tertiary butylphenyl) perionium hydroxide, bis(tertiary butylphenyl) iridium hydroxide, benzylmethylthiophenium hydroxide, 2- Oxopropylthiophenium, etc. Tri(n-butyl)amine, tri(n-octyl)amine, etc. are mentioned as an acid scavenger which has a trialkylamine structure. As an acid scavenger having an aniline structure, 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, N,N-dihexylaniline, etc. are mentioned. As an acid scavenger having a pyridine structure, pyridine, 4-picoline, etc. can be mentioned. Examples of alkylamine derivatives having a hydroxyl group and/or ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris(methoxyethoxyethyl)amine, and the like. N,N-bis(hydroxyethyl)aniline etc. are mentioned as an aniline derivative which has a hydroxyl group and/or an ether bond.

Specific examples of preferable acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, Cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine , 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, sperm triamine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methyl piperidine, piperidine, tropane, N-phenylbenzylamine, 1,2-diphenylaminoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, Phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylmorpholine, etc.

These acid scavengers may be used alone or in combination of two or more. The composition of the present invention may or may not contain an acid scavenger. When it does, the content of the acid scavenger is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the total solid content of the composition.

The usage ratio of the acid generator and the acid scavenger is preferably acid generator/acid scavenger (molar ratio)=2.5 to 300. That is, from the viewpoints of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing the decrease in resolution caused by the time-dependent thickening of the relief pattern until the post-exposure heat treatment, 300 The following are preferred. The acid generator/acid scavenger (molar ratio) is more preferably 5.0 to 200, further preferably 7.0 to 150.

＜Other additives＞ The resin composition of the present invention can contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, as necessary within the range where the effects of the present invention can be obtained. , antioxidants, anti-agglomeration agents, phenolic compounds, other polymer compounds, plasticizers and other additives (eg, defoaming agents, flame retardants, etc.), etc. By appropriately containing these components, properties such as film properties can be adjusted. These components can be referred to, for example, the descriptions in paragraph No. 0183 of JP 2012-003225 A (corresponding to paragraph No. 0237 in the specification of US Patent Application Laid-Open No. 2013/0034812 ) and the paragraphs in JP 2008-250074 A The descriptions of Nos. 0101 to 0104, 0107 to 0109, etc., are incorporated into this specification. When these additives are blended, the total blending amount is preferably 3 mass % or less of the solid content of the resin composition of the present invention.

[Surfactant] As the surfactant, various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, and a hydrocarbon-based surfactant can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

By containing a surfactant in the photosensitive resin composition of the present invention, the solution properties (especially fluidity) when prepared as a coating solution are further improved, so that the uniformity of coating thickness and the liquid saving property can be further improved. . That is, when a coating liquid containing a composition containing a surfactant is used to form a film, the interfacial tension between the coated surface and the coating liquid is reduced, and the wettability of the coated surface is improved, thereby improving the surface to be coated. The coatability of the coated surface is improved. Therefore, it is possible to more appropriately form a film with a uniform thickness with little thickness unevenness.

Examples of fluorine-based surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (the above are manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novec FC4430, Novec FC4432 (the above are manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (ASAHI GLASS CO above ., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP 2015-117327 A and the compounds described in paragraphs 0117 to 0132 of JP 2011-132503 A can also be used. incorporated into this manual. As the fluorine-based surfactant, a block polymer can also be used, and specific examples thereof include compounds described in JP-A No. 2011-89090, the contents of which are incorporated in the present specification. The fluorine-based surfactant can also preferably use a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a 2 or more (preferably 5 or more) alkaneoxy group (preferably The following compounds can also be exemplified as the fluorine-based surfactant used in the present invention as a fluorine-containing polymer compound which is a repeating unit of a (meth)acrylate compound of ethoxy-extendoxy and propoxy-extendoxy. [Chemical formula 46]

The weight average molecular weight of the above-mentioned compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000. Regarding the fluorine-based surfactant, a fluoropolymer having an ethylenically unsaturated group in a side chain can also be used as the fluorine-based surfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP 2010-164965 A, the contents of which are incorporated in the present specification. Moreover, as a commercial item, MEGAFACE RS-101 by DIC Corporation, RS-102, RS-718K etc. are mentioned, for example.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective from the viewpoint of the uniformity of the thickness of the coating film or the liquid saving property, and the solubility in the composition is also good.

Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (the above are Dow Corning Toray Co. ., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (the above are manufactured by Momentive Performance Materials Inc.), KP-341, KF6001, KF6002 (the above are Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, BYK330 (the above are manufactured by BYK Chemie GmbH), and the like.

Examples of hydrocarbon-based surfactants include PIONIN A-76, New Kalgen FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, PIONIN P-4050-T, etc. (the above are manufactured by Takemoto Oil & Fat Co., Ltd.), etc.

Examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate) base, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol Dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, etc. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112-W, D-6315 (Takemoto Oil & Fat Co., Ltd. manufacture), OLFIN E1010, Surfynol 104, 400, 440 (Nissan Chemical Industries, Ltd. manufacture) and the like.

Specific examples of the cationic surfactant include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer Polyflow No. 75, No.77, No.90, No.95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.

As an anionic surfactant, W004, W005, W017 (made by Yusho Co., Ltd.), SANDET BL (made by SANYO KASEI CO., LTD.) etc. are mentioned specifically,.

Only one type of surfactant may be used, or two or more types may be used in combination. The content of the surfactant is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, relative to the total solid content of the composition.

[Higher fatty acid derivatives] In order to prevent polymerization inhibition caused by oxygen, the resin composition of the present invention may be added with a higher fatty acid derivative such as behenic acid or behenamide to be non-uniformly distributed in the present invention during the drying process after coating. The surface of the inventive resin composition.

In addition, the compound described in the paragraph 0155 of International Publication No. 2015/199219 can also be used as a higher fatty acid derivative, the content of which is incorporated in the present specification.

When the resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. Only one type of higher fatty acid derivatives may be used, or two or more types may be used. When there are two or more kinds of higher fatty acid derivatives, it is preferable that the total is within the above-mentioned range.

[Thermal polymerization initiator] The resin composition of the present invention may contain a thermal polymerization initiator, especially a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy to initiate or promote the polymerization reaction of the polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also proceed, so that the solvent resistance can be further improved. In addition, the above-mentioned photopolymerization initiator may have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A, the contents of which are incorporated in the present specification.

When a thermal polymerization initiator is included, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and further preferably 0.5 to 15 mass % with respect to the total solid content of the resin composition of the present invention. quality%. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal polymerization initiators are contained, it is preferable that the total of them is within the above-mentioned range.

[Inorganic particles] The resin composition of the present invention may contain inorganic particles. Specifically, as inorganic particles, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc. can be included.

The average particle diameter of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The said average particle diameter of an inorganic particle is a primary particle diameter, and it is a volume average particle diameter. The volume average particle diameter can be measured by a dynamic light scattering method based on Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). When it is difficult to perform the above-mentioned measurement, it can also be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction/scattering method.

[Ultraviolet absorber] The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, ultraviolet absorbers such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and trisulfuric acid-based absorbers can be used. Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, p-octylphenyl salicylate, p-tertiary butylphenyl salicylate, and the like, and examples of the benzophenone-based ultraviolet absorber include Examples of the agent include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ',4,4'-Tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxydiphenyl ketone etc. Moreover, as an example of a benzotriazole type ultraviolet absorber, 2-(2'-hydroxy-3',5'-di-tertiary butylphenyl)-5-chlorobenzotriazole, 2 -(2'-Hydroxy-3'-tertiarybutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tertiary pentyl-5' -isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2- (2'-Hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tertiary butyl Phenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetrakis Methyl)phenyl]benzotriazole, etc.

Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like . Moreover, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6 is mentioned as an example of a tris-type ultraviolet absorber -Bis(2,4-dimethylphenyl)-1,3,5-tris𠯤, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2- Hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tris𠯤, 2-(2,4-dihydroxyphenyl)-4,6-bis( 2,4-Dimethylphenyl)-1,3,5-tris(hydroxyphenyl)tris-compounds such as 2,4-bis(2-hydroxy-4-propoxyphenyl)-6 -(2,4-Dimethylphenyl)-1,3,5-tris𠯤, 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4 -Methylphenyl)-1,3,5-tris𠯤, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethyl Phenyl)-1,3,5-tris(bis(hydroxyphenyl)tris) compounds such as bis(hydroxyphenyl)tris; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-bis) Butoxyphenyl)-1,3,5-tris𠯤, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tris𠯤, 2,4, 6-Tris[2-Hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-Tris(hydroxyphenyl)tris 𠯤 compounds, etc.

In the present invention, the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more. The composition of the present invention may or may not contain the ultraviolet absorber, but when the ultraviolet absorber is contained, the content of the ultraviolet absorber is 0.001 mass % or more and 1 mass % or less with respect to the total solid content mass of the composition of the present invention More preferably, 0.01 mass % or more and 0.1 mass % or less are more preferable.

[Organo-titanium compound] The resin composition of the present embodiment may contain an organic titanium compound. When the resin composition contains an organic titanium compound, even when it is cured at a low temperature, a resin layer excellent in chemical resistance can be formed.

As an organotitanium compound that can be used, a titanium atom has an organic group bonded to it via a covalent bond or an ionic bond. Specific examples of organotitanium compounds are shown in the following I) to VII): I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable from the viewpoint that the storage stability of the resin composition is good and a good hardened pattern can be obtained. Specific examples are bis(triethanolamine)diisopropoxytitanium, bis(2,4-glutarate)di(n-butoxy)titanium, bis(2,4-glutarate)diisopropoxide base titanium, bis(tetramethylpimelate) diisopropoxytitanium, bis(ethyl acetate) diisopropoxytitanium, etc. II) Tetraalkoxytitanium compounds: for example, tetrakis(n-butoxy)titanium, tetraethoxytitanium, tetrakis(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium Titanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonyloxy)titanium, tetrakis(n-propoxytitanium), tetrastearyloxytitanium , Four [bis{2,2-(allyloxymethyl)butoxy}] titanium, etc. III) Titanocene compounds: for example, titanium pentamethylcyclopentadienyltrimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium , bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) titanium, etc. IV) Monoalkoxytitanium compounds: for example, tris(dioctylphosphate)isopropoxytitanium, tris(dodecylbenzenesulfonate)isopropoxytitanium, and the like. V) Titanium oxide compounds: for example, bis(glutarate) titanium oxide, bis(tetramethylpimelate) titanium oxide, phthalocyanine titanium oxide, and the like. VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate, etc. VII) Titanate coupling agent: for example, isopropyl tris(dodecyl)benzenesulfonyl titanate and the like.

Among them, the organotitanium compound is selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound and III) titanocene compound from the viewpoint of exhibiting better chemical resistance At least one compound is preferred. In particular, bis(ethylacetate)diisopropoxytitanium, tetrakis(n-butoxy)titanium, and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-di) Fluoro-3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

When the organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the specific resin. When the compounding amount is 0.05 parts by mass or more, the obtained cured pattern effectively exhibits good heat resistance and chemical resistance, and on the other hand, when it is 10 parts by mass or less, the storage stability of the composition is more excellent.

〔Antioxidants〕 The composition of the present invention may contain antioxidants. By containing an antioxidant as an additive, the elongation characteristic of the film after hardening and the adhesiveness with a metal material can be improved. As an antioxidant, a phenol compound, a phosphite compound, a thioether compound, etc. are mentioned. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. A hindered phenol compound is mentioned as a preferable phenol compound. A compound having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position) is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. In addition, it is also preferable that the antioxidant is a compound having a phenol group and a phosphite group in the same molecule. In addition, phosphorus-based antioxidants can also be preferably used as antioxidants. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2] Dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tertiarybutyldibenzo[d,f] [1,3,2]Diethylphosphine-2-yl)oxy]ethyl]amine, bis(2,4-di-tert-butyl-6-methylphenol)ethyl phosphite, etc. . Examples of commercially available antioxidants include ADKSTAB AO-20, ADKSTAB AO-30, ADKSTAB AO-40, ADKSTAB AO-50, ADKSTAB AO-50F, ADKSTAB AO-60, ADKSTAB AO-60G, ADKSTAB AO- 80. ADKSTAB AO-330 (the above are manufactured by ADEKA CORPORATION), etc. In addition, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used as antioxidants, the contents of which are incorporated in the present specification. Moreover, the composition of this invention may contain a latent antioxidant as needed. As a potential antioxidant, a compound whose site acting as an antioxidant is protected by a protective group can be mentioned by heating at 100 to 250°C or heating at 80 to 200°C in the presence of an acid/base catalyst. A compound in which the protecting group is removed to function as an antioxidant. Examples of potential antioxidants include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219, the contents of which are incorporated in the present specification. As a commercial item of a latent antioxidant, ADEKA ARKLS GPA-5001 (made by ADEKA CORPORATION) etc. are mentioned. Examples of preferable antioxidants include 2,2-thiobis(4-methyl-6-tertiary butylphenol), 2,6-di-tertiary butylphenol, and formula (3) the indicated compound.

[Chemical formula 47]

In the general formula (3), R ⁵ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably carbon number 2 to 10), and R ⁶ represents an extension having carbon number 2 or more (preferably carbon number 2 to 10). alkyl. R ⁷ represents an alkylene group having 2 or more carbon atoms (preferably, a carbon number of 2 to 10), and a 1- to 4-valent organic group containing at least one of an oxygen atom and a nitrogen atom. k represents an integer of 1-4.

The compound represented by the formula (3) suppresses the oxidative deterioration of the aliphatic group or the phenolic hydroxyl group contained in the resin. Moreover, metal oxidation can be suppressed by the rust preventive effect on metal materials.

Since it can act on a resin and a metal material at the same time, k is an integer of 2 to 4 more preferably. Examples of R ⁷ include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, and an allyl group. group, vinyl group, heterocyclic group, -O-, -NH-, -NHNH-, a combination of these, etc., and may further have a substituent. Among them, those having an alkyl ether group and -NH- are preferred from the viewpoints of solubility in a developing solution and metal adhesion, and from the viewpoints of interaction with resins and metal adhesion by metal complexation For example, -NH- is better.

Examples of the compound represented by the general formula (3) include the following, but are not limited to the following structures.

[Chemical formula 48]

[Chemical formula 49]

[Chemical formula 50]

[Chemical formula 51]

The addition amount of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to the resin. By setting the addition amount to 0.1 parts by mass or more, the elongation properties or the effect of improving the adhesion to metal materials can be easily obtained even in a high temperature and high humidity environment, and by setting it to 10 parts by mass or less, for example, in the The sensitivity of the resin composition is improved by the interaction of the sensitizer. As for the antioxidant, only one type may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount of these is in the above-mentioned range.

[Anti-agglomeration agent] The resin composition of this embodiment may contain an anti-agglomeration agent as needed. As an anti-agglomeration agent, sodium polyacrylate etc. are mentioned.

In the present invention, an anti-agglomeration agent may be used alone or in combination of two or more. The composition of the present invention may or may not contain an anti-agglomeration agent. When included, the content of the anti-agglomeration agent is preferably 0.01% by mass or more and 10% by mass or less relative to the total solid content of the composition of the present invention. More preferably, it is 0.02 mass % or more and 5 mass % or less.

[Phenolic compounds] The resin composition of this embodiment may contain a phenolic compound as needed. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP- CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC , BIR-PTBP, BIR-BIPC-F (the above are trade names, manufactured by ASAHI YUKIZAI CORPORATION).

In the present invention, the phenolic compound may be used alone or in combination of two or more. The composition of the present invention may or may not contain a phenolic compound, and when included, the content of the phenolic compound is preferably 0.01% by mass or more and 30% by mass or less relative to the total solid content mass of the composition of the present invention. More preferably, it is 0.02 mass % or more and 20 mass % or less.

[Other polymer compounds] Examples of other polymer compounds include siloxane resins, (meth)acrylic polymers obtained by copolymerizing (meth)acrylic acid, novolak resins, resol resins, polyhydroxystyrene resins, and the like. Copolymers, etc. Other polymer compounds may also be modified bodies into which cross-linking groups such as methylol, alkoxymethyl, and epoxy groups are introduced.

In the present invention, other polymer compounds may be used alone or in combination of two or more. The composition of the present invention may or may not contain other polymer compounds. When included, the content of the other polymer compounds is 0.01% by mass or more and 30% by mass or less relative to the total solid mass of the composition of the present invention. Preferably, it is 0.02 mass % or more and 20 mass % or less is more preferable.

<Characteristics of the resin composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, 1,000 mm ² /s to 12,000 mm ² /s is preferable, 2,000 mm ² /s to 10,000 mm ² /s is more preferable, and 3,000 mm ² /s to 8,000 mm ² / s is further preferred. In the said range, it becomes easy to obtain the coating film with high uniformity. When it is 1,000 mm ² /s or less, it is difficult to coat with a film thickness required as an insulating film for rewiring, for example, and when it is 12,000 mm ² /s or more, the coating surface shape may be deteriorated.

<Restrictions on substances contained in resin compositions> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. When it is 2.0% or more, the storage stability of the resin composition may be impaired. As a method of maintaining the moisture content, adjustment of the humidity under storage conditions, reduction of the porosity of the storage container at the time of storage, and the like are exemplified.

From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million: parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm good. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, and the like, excluding metals contained in the form of complexes of organic compounds and metals. When a plurality of metals are contained, it is preferable that the sum of these metals is within the above-mentioned range.

Further, as a method for reducing metal impurities unintentionally contained in the resin composition of the present invention, methods such as selecting a raw material with a small metal content as a raw material constituting the resin composition of the present invention; The raw material of the composition is filtered through a filter; the apparatus is lined with polytetrafluoroethylene, etc., and the distillation is carried out under conditions that suppress contamination as much as possible.

In the resin composition of the present invention, considering the use as a semiconductor material, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm from the viewpoint of wiring corrosion. ppm is further preferred. Among them, it is preferable that it is less than 5 mass ppm in the state of a halogen ion, and it is more preferable that it is less than 1 mass ppm, and it is more preferable that it is less than 0.5 mass ppm. As a halogen atom, a chlorine atom and a bromine atom are mentioned. It is preferable that the total of chlorine atom and bromine atom, or chlorine ion and bromide ion is each in the said range. As a method for adjusting the content of halogen atoms, ion exchange treatment and the like can be preferably used.

As a container of the resin composition of the present invention, a conventionally known container can be used. In addition, as the container, for the purpose of suppressing contamination of impurities into the raw material or the composition of the present invention, a multi-layer bottle in which the inner wall of the container is made of 6 kinds of resins with 6 layers or a bottle with a 7-layer structure made of 6 kinds of resins can also be used. is better. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<The cured product of the resin composition> By curing the resin composition of the present invention, a cured product of the resin composition can be obtained. The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. The curing system of the resin composition is preferably based on heating, and the heating temperature is more preferably in the range of 120°C to 400°C, more preferably in the range of 140°C to 380°C, and in the range of 170°C to 350°C Excellent inside. The form of the cured product of the resin composition is not particularly limited, and a film form, a rod form, a spherical form, a granular form, and the like can be selected according to the application. In the present invention, the cured product is preferably in the form of a film. In addition, the resin composition can be patterned to form a protective film on a wall surface, form a via hole for conduction, adjust impedance, electrostatic capacitance, internal stress, and impart a heat release function. shape of hardened material. The film thickness of the cured product (film composed of the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage rate at the time of curing the resin composition of the present invention is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage of the volume change before and after curing of the resin composition, and can be calculated from the following formula. Shrinkage rate [%]=100-(volume after hardening÷volume before hardening)×100

<Characteristics of cured product of resin composition> The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. When it is less than 70%, the mechanical properties of the cured product may be deteriorated. The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

<Preparation of resin composition> The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be performed by a conventionally known method. The mixing can employ mixing based on a stirring blade, mixing based on a ball mill, mixing by rotating the tank itself, and the like. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and particles in the resin composition of the present invention. The filter pore diameter is, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. When the filter material is polyethylene, HDPE (high density polyethylene) is better. The filter can be pre-cleaned with an organic solvent. In the filter filtering step, a plurality of filters can be connected in series or in parallel for use. When using multiple filters, filters with different pore sizes or materials can be used in combination. As a connection aspect, for example, a first stage HDPE filter having a pore diameter of 1 μm and a second stage HDPE filter having a pore diameter of 0.2 μm are connected in series. Also, various materials can be filtered multiple times. When filtering multiple times, you can filter for loops. Moreover, filtration can be performed by pressurization. When filtration is performed by pressurization, the pressurized pressure can be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less, More preferably, it is 0.05 MPa or more and 0.5 MPa or less. In addition to filtration using a filter, removal of impurities using an adsorbent material can also be performed. It is also possible to combine filter filtration and impurity removal treatment using adsorbent material. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be mentioned. Furthermore, after the filtration using a filter, the resin composition filled in the bottle may be subjected to a degassing step under reduced pressure.

(Manufacturing method of hardened product) It is preferable that the manufacturing method of the hardened|cured material of this invention includes the film formation process of forming a film by applying a resin composition to a base material. Moreover, the manufacturing method of the hardened|cured material of this invention includes the said film formation process, the exposure process of selectively exposing the film formed by the film formation process, and developing the film exposed by the exposure process using a developing solution. The developing step to form the pattern is more preferred. The manufacturing method of the hardened|cured material of this invention includes the said film formation process, the said exposure process, the said development process, the heating process of heating the pattern obtained by the development process, and the exposure process of the pattern obtained by the development process. At least one of the post-development exposure steps is particularly preferred. Moreover, it is also preferable that the manufacturing method of this invention includes the said film formation step and the step of heating the said film. Hereinafter, the details of each step will be described.

<Film formation step> The resin composition of the present invention can be used in a film-forming step in which it is applied to a substrate to form a film. It is preferable that the manufacturing method of the hardened|cured material of this invention includes the film formation process of forming a film by applying a resin composition to a base material.

(substrate) The type of the substrate can be appropriately determined according to the application, and examples thereof include semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, etc. Reflective film, metal substrates such as Ni, Cu, Cr, and Fe (for example, any one of a substrate formed of metal and a substrate formed with a metal layer by electroplating or vapor deposition, for example), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrate, mold substrate, electrode plate of plasma display panel (PDP), etc., are not particularly restricted. In the present invention, especially semiconductor manufacturing substrates are preferred, and silicon substrates, Cu substrates and molding substrates are more preferred. Moreover, these base materials may be provided with layers, such as an adhesive layer and an oxide layer, which consist of hexamethyldisilazane (HMDS) etc. on the surface. In addition, the shape of the base material is not particularly limited, and may be circular or rectangular. As a size of a base material, if it is a circle, a diameter is 100-450 mm, for example, Preferably it is 200-450 mm. In the case of a rectangle, the length of the short side is, for example, 100 to 1000 mm, preferably 200 to 700 mm. Moreover, as a base material, the base material (substrate) of a plate shape, preferably a panel shape, is used, for example.

Furthermore, when a resin composition is applied to the surface of a resin layer (eg, a layer composed of a cured product) or a surface of a metal layer to form a film, the resin layer or the metal layer becomes a base material.

As a method of applying the resin composition of the present invention to a substrate, coating is preferable.

Specific examples of the applicable method include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, and spin coating. , slit coating method, inkjet method, etc. From the viewpoint of uniformity of film thickness, a spin coating method, a slit coating method, a spray coating method, or an ink jet method is more preferable, and from the viewpoint of uniformity of film thickness and productivity, a spin coating method is used. And the slit coating method is preferable. A resin layer having a desired thickness can be obtained by appropriately adjusting the solid content concentration and coating conditions according to the method. In addition, the coating method can also be appropriately selected according to the shape of the substrate. In the case of a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and a rectangular substrate is narrowly applied. Slit coating method, spray method, ink jet method, etc. are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Moreover, the method of transcribe|transferring the coating film previously provided by the said application method and formed on the temporary support body to a base material can also be applied. Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can also be preferably used in the present invention. . In addition, the step of removing the excess film may be performed at the end of the base material. Examples of such steps are edge bead residue rinse (EBR), back rinse, etc. In addition, before applying the resin composition to the substrate, various solvents may be applied to the substrate to improve the wettability of the substrate, and then the resin composition may be applied.

<Drying step> The above-mentioned film may be subjected to a step (drying step) of drying the formed film (layer) in order to remove the solvent after the film forming step (layer forming step). That is, the manufacturing method of the hardened|cured material of this invention may include the drying process which dries the film formed by the film formation process. Moreover, it is preferable to perform the said drying process after a film formation process and before an exposure process. The drying temperature of the film in the drying step is preferably 50°C to 150°C, more preferably 70°C to 130°C, and further preferably 90°C to 110°C. Moreover, drying can be performed by reducing pressure. As the drying time, 30 seconds to 20 minutes can be exemplified, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

<Exposure step> The said film can be used for the exposure step of selectively exposing the film. That is, the manufacturing method of the hardened|cured material of this invention may include the exposure process which selectively exposes the film formed by the film formation process. Selectively exposing means exposing a portion of the film. Moreover, by selectively exposing, an exposed area (exposed part) and an unexposed area (non-exposed part) are formed on the film. The exposure amount is not particularly limited as long as the resin composition of the present invention can be cured. For example, in terms of exposure energy at a wavelength of 365 nm, it is preferably 50 to 10,000 mJ/cm ² , and more preferably 200 to 8,000 mJ/cm ² . good.

The exposure wavelength can be appropriately defined in the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

If the exposure wavelength is described in relation to the light source, (1) semiconductor lasers (wavelengths of 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamps, and (3) high-pressure mercury lamps can be mentioned. , g-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), broadband (three wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, (7) YAG laser The second harmonic of 532nm, the third harmonic of 355nm, etc. For the resin composition of the present invention, exposure based on a high-pressure mercury lamp is particularly preferable, and exposure based on i-rays is preferable. Thereby, a particularly high exposure sensitivity can be obtained. In addition, the method of exposure is not particularly limited, as long as at least a part of the film composed of the resin composition of the present invention is exposed, and examples include exposure using a mask, and laser direct imaging. ) The exposure of the law, etc.

<Heating step after exposure> The above-mentioned film may be used in a post-exposure heating step (post-exposure heating step). That is, the manufacturing method of the hardened|cured material of this invention may include the post-exposure heating process which heats the film exposed by the exposure process. The post-exposure heating step can be performed after the exposure step and before the developing step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. From the temperature at the start of heating to the maximum heating temperature, the heating rate in the post-exposure heating step is preferably 1 to 12°C/min, more preferably 2 to 10°C/min, and still more preferably 3 to 10°C/min good. In addition, the temperature increase rate can be appropriately changed in the middle of heating. The heating means in the post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters, and the like can be used. In addition, it is also preferable to perform heating in an atmosphere with a low oxygen concentration by flowing inert gas such as nitrogen, helium, and argon.

<Development step> The above-mentioned film after exposure can be used for a developing step of forming a pattern by developing with a developing solution. That is, the manufacturing method of the hardened|cured material of this invention can include the developing process which develops the film exposed by the exposure process using a developing solution, and forms a pattern. By performing development, one of an exposed part and a non-exposed part of a film is removed, and a pattern is formed. Here, the development of removing the non-exposed portion of the film by the development step is called negative development, and the development of removing the exposed portion of the film by the development step is called positive development.

[Developer] As the developing solution used in the developing step, an alkaline aqueous solution or a developing solution containing an organic solvent can be exemplified.

When the developing solution is an alkaline aqueous solution, the alkaline compounds that can be contained in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, preferably TMAH (hydrogen Tetramethylammonium oxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyl diethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraamylammonium hydroxide, tetrahexylammonium hydroxide, tetrahydroxide Octylammonium, Ethyltrimethylammonium hydroxide, Butyltrimethylammonium hydroxide, Methyltripentylammonium hydroxide, Dibutyldipentylammonium hydroxide, Dimethylbis(2- Hydroxyethyl)ammonium, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, piperidine, more preferably TMAH. For example, when TMAH is used, the content of the alkaline compound in the developer is preferably 0.01-10% by mass, more preferably 0.1-5% by mass, and even more preferably 0.3-3% by mass in the total mass of the developer solution .

When the developer contains an organic solvent, as the organic solvent, the esters include, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, and propionic acid. Butyl, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkoxyacetate esters (e.g.: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethyl methoxyacetate) Methyl oxyacetate, ethyl ethoxyacetate, etc.), 3-alkoxy propionate alkyl esters (for example: 3-alkoxy propionate methyl ester, 3-alkoxy ethyl propionate, etc.) (For example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxy Alkyl propionates (for example: methyl 2-alkoxy propionate, ethyl 2-alkoxy propionate, propyl 2-alkoxy propionate, etc. (for example, 2-methoxy propionate) methyl ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy -Methyl 2-methylpropanoate and ethyl 2-alkoxy-2-methylpropanoate (eg, methyl 2-methoxy-2-methylpropanoate, 2-ethoxy-2- ethyl methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, 2-oxobutane acid ethyl ester, etc., and, as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cyluthyl acetate, Ethyl Cyrus acetate, Diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, Propylene glycol monomethyl ether (PGME), Propylene glycol monomethyl ether acetate (PGMEA) , propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and, as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3 -Heptanone, N-methyl-2-pyrrolidone, etc., and, as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, etc., and cyclic terpenes such as limonene are preferably used Alkenes, dimethyl sulfites are preferably used as the sulfites, and methanol, ethanol, propanol, isopropanol, butanol, amyl alcohol, octyl alcohol are preferably used as the alcohols. Alcohol, diethylene glycol, propylene glycol, methyl isobutyl carbitol, triethylene glycol, etc., and, as amides, N-methylpyrrolidone, N-ethylpyrrole, etc. can be preferably mentioned pyridone, dimethylformamide, etc.

When the developer contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, a developer especially comprising at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone and cyclohexanone More preferably, the developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone and dimethylsulfoxide is more preferable, and the developer containing cyclopentanone is the most preferable.

When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and more preferably 90% by mass or more Excellent. Moreover, the said content may be 100 mass %.

The developer may further contain other components. As another component, a well-known surfactant, a well-known antifoamer, etc. are mentioned, for example.

[How to supply developer] The method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and there are a method of immersing the substrate on which the film is formed in the developer, and a method of supplying the developer to the film formed on the substrate using a nozzle using a spinner The method of immersion development or continuous supply of developer. The type of the nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoints of the permeability of the developer, the removal of the non-image area, and the efficiency in manufacturing, the method of supplying the developer with a straight nozzle or the method of continuously supplying it with a spray nozzle is preferable. From the viewpoint of the permeability of the image area, the method of supplying with a spray nozzle is more preferable. In addition, after continuously supplying the developer with the straight nozzle, the substrate can be rotated to remove the developer from the substrate, and after spin drying, the developer can be continuously supplied again with the straight nozzle, and then the substrate can be rotated and removed from the substrate. The step of developing solution, and this step can be repeated several times. Further, as a method of supplying the developer in the developing step, a step of continuously continuously supplying the developer to the substrate, a step of holding the developer in a substantially stationary state on the substrate, or applying an ultrasonic wave or the like to the developer can be employed. The step of vibrating on the substrate and the step of combining these, etc.

The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly limited, but it is preferably 10 to 45°C, more preferably 18 to 30°C.

In the developing step, after the treatment with the developing solution, cleaning (rinsing) of the pattern based on the rinsing solution may be further performed. In addition, a method such as supplying a rinsing liquid may be employed while the developer contacting the pattern is not completely dried.

[Rinse fluid] When the developing solution is an alkaline aqueous solution, for example, water can be used as the rinsing solution. When the developing solution is a developing solution containing an organic solvent, as the rinsing solution, for example, a solvent different from the solvent contained in the developing solution (for example, water, an organic solvent different from the organic solvent contained in the developing solution) can be used.

In the case of the organic solvent when the rinse liquid contains an organic solvent, as esters, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, and butyl propionate can be preferably mentioned. Esters, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetate Esters (eg: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetate) methyl ethyl acetate, ethyl ethoxy acetate, etc.), 3-alkoxy propionate alkyl esters (for example: 3-alkoxy propionate methyl ester, 3-alkoxy ethyl propionate, etc. ( For example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxy Alkyl propionates (e.g. methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g. methyl 2-methoxypropionate) ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy- Methyl 2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate ethyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, 2-oxobutyric acid Ethyl esters, etc., and, as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cyrus acetate, ethyl acetate, etc. Gysellus Acetate, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monobutyl Ether, Propylene Glycol Monomethyl Ether (PGME), Propylene Glycol Monomethyl Ether Acetate (PGMEA), Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and, as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3- Heptanone, N-methyl-2-pyrrolidone, etc., and, as the cyclic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. can be preferably mentioned, and the sulfites can be preferably Preferably, dimethyl sulfoxide is used, and as alcohols, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl alcohol can be preferably used. Isobutylcarbitol, triethylene glycol, etc., and as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. are preferably mentioned.

When the rinsing liquid contains an organic solvent, one type of organic solvent can be used or two or more types of organic solvents can be used in combination. In the present invention, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME are particularly preferred, and cyclopentanone, γ-butyrolactone are preferred. Esters, dimethylsulfoxide, PGMEA, and PGME are more preferable, and cyclohexanone and PGMEA are further preferable.

When the rinsing liquid contains an organic solvent, more than 50 mass % in the washing liquid is preferably an organic solvent, more preferably 70 mass % or more is an organic solvent, and more preferably 90 mass % or more is an organic solvent. Moreover, in a rinse liquid, 100 mass % may be an organic solvent.

The rinse fluid may further contain other ingredients. As another component, a well-known surfactant, a well-known antifoamer, etc. are mentioned, for example.

[How to supply the rinse solution] The method of supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed, and there are a method of immersing the substrate in the rinsing liquid, a method of supplying the rinsing liquid to the substrate by holding the liquid, and a method of spraying the substrate to the substrate. The method of supplying the rinsing liquid, and the method of continuously supplying the rinsing liquid to the substrate using a mechanism such as a straight nozzle. From the viewpoint of the permeability of the rinse liquid, the removal of the non-image area, and the efficiency in manufacturing, the method of supplying the rinse liquid by a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying it by a spray nozzle are: Preferably, from the viewpoint of the permeability of the rinse liquid to the image portion, the method of supplying it with a spray nozzle is more preferable. The type of the nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. That is, the rinsing step is preferably a step of supplying or continuously supplying a rinse liquid to the film after exposure using a straight nozzle, and more preferably a step of supplying the rinse liquid using a spray nozzle. Further, as a method of supplying the developer in the rinsing step, a step of continuously supplying the rinsing liquid to the substrate, a step of holding the rinsing liquid on the substrate in a substantially static state, and using an ultrasonic wave or the like to supply the rinse liquid to the substrate can be employed. The step of vibrating on the substrate and the step of combining these, etc.

The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid at the time of rinsing is not particularly limited, but it is preferably 10 to 45°C, more preferably 18 to 30°C.

<Heating step> The pattern obtained by the development step (the rinsed pattern when the rinse step is performed) can be used in the heating step of heating the pattern obtained by the above development. That is, the manufacturing method of the hardened|cured material of this invention may include the heating process which heats the pattern obtained by the developing process. Moreover, the manufacturing method of the hardened|cured material of this invention may include the heating process which heats the pattern obtained by another method without performing a developing process, or the film obtained by the film forming process. In the heating step, resins such as polyimide precursors are cyclized to become resins such as polyimide. Moreover, the crosslinking etc. of the unreacted crosslinkable group in a specific resin or a crosslinking agent other than a specific resin are also performed. As the heating temperature (maximum heating temperature) in the heating step, 50-450°C is preferable, 150-350°C is more preferable, 150-250°C is further preferable, 160-250°C is further preferable, 160-230°C ℃ is particularly good.

The heating step is preferably a step of promoting the cyclization reaction of the above-mentioned polyimide precursor within the above-mentioned pattern by the action of the base or the like generated by the above-mentioned base generator by heating.

The heating in the heating step is preferably performed at a temperature increase rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature. The temperature increase rate is more preferably 2 to 10° C./min, and even more preferably 3 to 10° C./min. By setting the temperature increase rate to 1°C/min or more, the productivity can be ensured and excessive volatilization of the acid or solvent can be prevented, and the residual stress of the cured product can be reduced by setting the temperature increase rate to 12°C/min or less. Furthermore, in the case of an oven capable of rapid heating, the heating rate is preferably 1 to 8°C/sec, more preferably 2 to 7°C/sec, from the temperature at the start of heating to the maximum heating temperature, and 3 to 3°C/sec. 6°C/sec is more preferable.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at which the step of heating up to the maximum heating temperature is started. For example, when the resin composition of the present invention is applied to a substrate and then dried, it means that the temperature of the dried film (layer) is, for example, lower than the boiling point of the solvent contained in the resin composition of the present invention. It is preferable to raise the temperature at a temperature of 30 to 200°C.

The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

In particular, when forming a multilayered laminate, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and particularly 120°C or higher, from the viewpoint of the adhesion between layers. good. The upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.

Heating can be performed in stages. As an example, the following steps can be performed: increase the temperature from 25°C to 120°C at 3°C/min, hold at 120°C for 60 minutes, increase the temperature from 120°C to 180°C at 2°C/min, and hold at 180°C for 120 minute. Moreover, as described in the specification of US Pat. No. 9,159,547, it is also preferable to perform treatment while irradiating ultraviolet rays. By such a pretreatment step, the properties of the film can be improved. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, the pretreatment step of the first stage may be performed in the range of 100 to 150°C, and then the pretreatment of the second stage may be performed in the range of 150 to 200°C. step. Cooling after heating may be further performed, and the cooling rate at this time is preferably 1 to 5°C/min.

From the viewpoint of preventing decomposition of the specific resin, it is preferable to perform the heating step in an atmosphere with a low oxygen concentration by discharging an inert gas such as nitrogen, helium, and argon under reduced pressure. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less. It does not specifically limit as a heating means in a heating process, For example, a hotplate, an infrared furnace, an electric heating oven, a hot air oven, an infrared oven etc. are mentioned.

<Exposure step after development> The pattern obtained by the development step (when the rinse step is performed, the rinsed pattern) can be used in place of the above heating step or in addition to the above heating step, for exposing the pattern after the development step. Exposure after development step. That is, the manufacturing method of the hardened|cured material of this invention may include the post-development exposure process which exposes the pattern obtained by the development process. The manufacturing method of the cured product of the present invention may include a heating step and an exposure step after development, or may include only one of a heating step and an exposure step after development. In the post-development exposure step, for example, a reaction of cyclization of a polyimide precursor or the like by exposure to a photobase generator, or a reaction of detachment of an acid-decomposable group by exposure to a photoacid generator can be accelerated. Wait. In the post-development exposure step, at least a part of the pattern obtained in the development step may be exposed, but it is preferable that all of the above-mentioned patterns are exposed. The exposure amount in the exposure step after development is converted to the exposure energy at the wavelength at which the photosensitive compound has sensitivity, and is preferably 50-20,000 mJ/cm ² , more preferably 100-15,000 mJ/cm ² . The post-development exposure step can be performed using, for example, the light source in the above-mentioned exposure step, preferably broadband light.

<Metal layer formation step> The pattern obtained by the developing step (preferably for at least one of the heating step and the post-exposure developing step) can be used in the metal layer forming step of forming the metal layer on the pattern. That is, the manufacturing method of the cured product of the present invention includes a metal layer forming step of forming a metal layer on the pattern obtained by the developing step (preferably for at least one of the heating step and the post-development exposure step) is better.

The metal layer is not particularly limited, and existing metals can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, alloys containing these metals, copper and aluminum. More preferred, copper is further preferred.

The method of forming the metal layer is not particularly limited, and conventional methods can be applied. For example, Japanese Patent Application Laid-Open No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Laid-Open No. 2004-214501, Japanese Patent Application Laid-Open No. 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. the method described. For example, photolithography, PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), lithography, electrolytic plating, electroless plating, etching, printing, methods of combining these, and the like can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electrolytic plating can be mentioned. As a preferable aspect of electroplating, electrolytic electroplating using copper sulfate or copper cyanide electroplating solution can be mentioned.

As the thickness of the metal layer, the thickest portion is preferably 0.01 to 50 μm, and more preferably 1 to 10 μm.

＜Use＞ As the field to which the cured product of the present invention can be produced, or the cured product of the present invention, an insulating film of an electronic device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like can be mentioned. In addition, patterning of sealing films, substrate materials (base films or cover films of flexible printed boards, interlayer insulating films), or insulating films for encapsulation as described above, by etching, etc., can be exemplified. For such applications, see, for example, SCIENCE AND TECHNOLOGY CO., LTD. "High Functionalization and Application Technology of Polyimide" April 2008, Masaki Kakimoto/Supervisor, CMC Technical library "Polyimide Materials "Basics and Development", published in November 2011, edited by Japan Polyimide and Aromatic Polymer Research Association "Latest Polyimide Fundamentals and Applications" NTS Inc., August 2010, etc.

In addition, the method for producing the cured product of the present invention or the cured product of the present invention can also be used for the production of printing plates such as offset printing plates and screen printing plates, use in etching of molded components, electronics, especially micro- Manufacturing of protective varnish and dielectric layer in electronics.

(Laminated body and method for manufacturing the laminated body) The laminate system of the present invention refers to a structure having a plurality of layers composed of the cured product of the present invention. The layered body of the present invention is a layered body including two or more layers composed of a cured product, and may be a layered body in which three or more layers are layered. At least one of the two or more layers composed of the cured product contained in the above-mentioned laminate is a layer composed of the cured product of the present invention, from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product accompanying the shrinkage, etc. In other words, it is also preferable that all the layers composed of the cured product contained in the above-mentioned laminate are layers composed of the cured product of the present invention.

That is, it is preferable that the manufacturing method of the laminated body of this invention includes the manufacturing method of the hardened|cured material of this invention, and it is more preferable to repeat the manufacturing method of the hardened|cured material of this invention a plurality of times.

The layered product of the present invention is preferably an aspect including two or more layers composed of a cured product and including a metal layer between any of the layers composed of the cured products. The above-mentioned metal layer is preferably formed by the above-mentioned metal layer forming step. That is, it is preferable that the manufacturing method of the laminated body of this invention further includes the metal layer formation step of forming a metal layer on the layer which consists of hardened|cured materials before performing the manufacturing method of the hardened|cured material several times. The preferred aspect of the metal layer forming step is as described above. As the above-mentioned layered product, for example, a layered product having at least a layer structure consisting of three layers, a layer composed of a first cured product, a metal layer, and a layer composed of a second cured product, can be mentioned as a preferable one. Layered sequentially. It is preferable that both the layer which consists of the said 1st hardened|cured material and the said layer which consists of the said 2nd hardened|cured material are the layers which consist of the hardened|cured material of this invention. The resin composition of the present invention for forming the layer composed of the first cured product and the resin composition of the present invention for forming the layer composed of the second cured product may have the same composition or may be make up different compositions. The metal layer in the laminate of the present invention can be preferably used as a metal wiring such as a rewiring layer.

<Lamination step> It is preferable that the manufacturing method of the laminated body of this invention includes a lamination|stacking step. The lamination step includes sequentially performing (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, (d) a heating step, and a One of a series of steps in at least one of the post-development exposure steps. However, at least one of the film forming step (a) and the (d) heating step and the post-development exposure step may be repeatedly performed. Moreover, (e) metal layer formation process may be included after at least one of (d) heating process and post-development exposure process. Of course, the above-mentioned drying step, heating step, etc. may be further appropriately included in the lamination step.

When the layering step is further performed after the layering step, the surface activation treatment step may be further performed after the above-mentioned exposure step, after the above-mentioned heating step, or after the above-mentioned metal layer forming step. As the surface activation treatment, plasma treatment can be exemplified. Details of the surface activation treatment will be described later.

Preferably, the above-mentioned layering step is performed 2 to 20 times, more preferably 2 to 9 times. For example, as in resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, the resin layer is preferably two or more and 20 or less layers, and two or more and nine or less layers are preferable. The constitution is further preferable. The composition, shape, film thickness, etc. of the above-mentioned layers may be the same or different.

In the present invention, it is particularly preferable to form a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer after the metal layer is provided. Specifically, at least one of the (a) film formation step, (b) exposure step, (c) development step, (d) heating step, and post-development exposure step (e) metal layer formation step can be mentioned. An aspect of performing it repeatedly in order, or an aspect of performing it repeatedly in the order of (a) a film forming step, (d) a heating step, and at least one of the post-development exposure step, and (e) a metal layer forming step. The resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated by alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer forming step.

(Surface activation treatment step) It is preferable that the manufacturing method of the layered product of the present invention includes a surface activation treatment step of subjecting at least a part of the metal layer and the resin composition layer to a surface activation treatment. The surface activation treatment step is usually performed after the metal layer formation step, but the metal layer formation step may be performed after the surface activation treatment step for the resin composition layer after the above-described development step. The surface activation treatment may be performed only on at least a part of the metal layer, may be performed only on at least a part of the exposed resin composition layer, or may be performed on at least a part of both the metal layer and the exposed resin composition layer, respectively. conduct. The surface activation treatment is preferably performed on at least a part of the metal layer, and the surface activation treatment is preferably performed on a part or the whole of the region of the metal layer where the resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesiveness with the resin composition layer (film) provided on the surface can be improved. Moreover, it is preferable to also perform surface activation treatment on a part or all of the resin composition layer (resin layer) after exposure. In this way, by subjecting the surface of the resin composition layer to the surface activation treatment, the adhesion to the metal layer or the resin layer provided on the surface activation treatment can be improved. In particular, when the resin composition layer is hardened, such as during negative development, it is less likely to be damaged by surface treatment, and the adhesiveness is likely to be improved. Specifically, the surface activation treatment is selected from plasma treatment of various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, CF4 _- based treatment Etching treatment of /O ₂ , NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ /O ₂ , surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film, and then immersion in water containing The treatment in the organic surface treatment agent of the compound of at least one of the amine group and the thiol group, the mechanical roughening treatment using a brush, preferably the plasma treatment, especially the oxygen plasma treatment using oxygen in the raw material gas is: better. In the case of corona discharge treatment, the energy is preferably 500 to 200,000 J/m ² , more preferably 1000 to 100,000 J/m ² , and most preferably 10,000 to 50,000 J/m ² .

(Manufacturing method of electronic device) Furthermore, the present invention discloses a semiconductor device including the cured product of the present invention or the laminate of the present invention. Moreover, this invention also discloses the manufacturing method of the semiconductor device containing the manufacturing method of the hardened|cured material of this invention or the manufacturing method of the laminated body of this invention. As a specific example of a semiconductor device using the resin composition of the present invention for the formation of an interlayer insulating film for rewiring layers, reference can be made to the descriptions in paragraphs 0213 to 0218 of JP-A No. 2016-027357 and the descriptions in FIG. 1 . etc. are incorporated into this manual. [Example]

Hereinafter, the present invention will be described in more detail with reference to Examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise stated, "part" and "%" are based on quality.

<The manufacturing method of resin A-1> In each Example or a comparative example, 23.48 g of 4,4'- oxydiphthalic dianhydride (ODPA) and 4,4'- diphthalic dianhydride (BPDA) 22.27g was put into a separate flask, and 39.69g of 2-hydroxyethyl methacrylate (HEMA) and 136.83g of γ-butyrolactone were put in, stirred at room temperature, and added while stirring Pyridine 24.66g was obtained as a reaction liquid. After the heat generated by the reaction was completed, it was naturally cooled to room temperature and left at room temperature for 16 hours. Next, at the reaction temperature X1 described in the column of "X1 (°C)" in the following table, the reaction was carried out while dissolving 62.46 g of dicyclohexylcarbodiimide (DCC) in 61.57 g of γ-butyrolactone. It was added to the reaction liquid while stirring for 40 minutes, and then 27.42 g of 4,4'-diaminodiphenyl ether (DADPE) was suspended in 119.73 g of γ-butyrolactone for 60 minutes while stirring. to join. Furthermore, at the reaction temperature X2 described in the column "X2 (°C)" of the following table, the reaction time Y1 described in the column "Y1 (°C)" of the following table was stirred to obtain a precursor containing polyimide. the reaction solution. (Polymerization step) After that, 7.17 g of ethanol was added to the reaction solution at the temperature X3 described in the column "X3 (°C)" in the following table, and further described in the column "X4 (°C)" in the following table. The mixture was stirred at the reaction temperature X4 for the time Y2 described in the column of "Y2 (°C)" in the following table, and then 136.83 g of γ-butyrolactone was added (quenching step). The reaction liquid obtained by treating the reaction liquid after the quenching step under the condition Z1 described in the column of "Condition Z1" in the following table was added to 716.21 g of ethanol, and a precipitate consisting of a crude polymer was produced. The produced crude polymer was filtered off, and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, and the obtained precipitate was filtered out, followed by vacuum drying to obtain a powdery resin (polyimide precursor) A- 1. The molecular weight of resin A-1 was measured by gel permeation chromatography (standard polystyrene conversion). The measured weight average molecular weight (Mw) is described in the column of "Mw" in the table. The structure of resin A-1 is presumed to be a structure represented by the following formula (A-1). [Chemical formula 52]

<Method for producing resins A-2 and A-3> Except that 4,4'-oxydiphthalic dianhydride (ODPA), 4,4'-oxydiphthalic dianhydride (ODPA), 4,4'-oxydiphthalic dianhydride (ODPA) and 4,4'-oxydiphthalic dianhydride (ODPA), 4, 4, Resin A-2 or A-3 was synthesized by the same method as that of resin A-1 except for 4'-bisphthalic dianhydride (BPDA) and 2-hydroxyethyl methacrylate (HEMA). The structures of the resins A-2 and A-3 are presumed to be the structures represented by the following formulae (A-2) and (A-3), respectively. [Chemical formula 53]

<The manufacturing method of resin A-4, A-5> In the production method of resin A-1, except that 62.46 g of dicyclohexylcarbodiimide (DCC) was changed to DIC (diisopropylcarbodiimide) in an equimolar amount, by mixing with resin A- Resin A-4 was synthesized in the same manner as in the production method of 1. In the production method of resin A-1, except that 62.46 g of dicyclohexylcarbodiimide (DCC) was changed to an equimolar amount of EDC (N-ethyl-N'-(3-dimethylaminopropane) Resin A-4 was synthesized by the same method as the production method of Resin A-1 except for carbodiimide).

<Manufacturing method of resin A-6> In the production method of resin A-1, after the polymerization step, 2.9 g of p-toluenesulfonic acid monohydrate was added to the reaction solution, and the mixture was further stirred at room temperature for 1 hour. The operations after the quenching step were carried out in the same manner as in the production method, thereby obtaining resin A-6.

<Manufacturing method of resin A-7> In the production method of resin A-1, after the quenching step, the reaction solution was added to 716.21 g of ethanol and filtered off to obtain a crude polymer. The crude polymer was dissolved in 287.20 g of tetrahydrofuran. To this, 25.0 g of water and 50.3 g of ion exchange resin UP6040 (manufactured by AmberTec) were added, and the mixture was stirred for 4 hours. Then, the ion exchange resin was removed by filtration, and 6000 g of water was added to the obtained polymer solution to obtain a precipitate. The precipitate was collected by filtration and dried under reduced pressure at 45° C. for 24 hours to obtain resin A-7.

<Manufacturing method of resin A-8> In the production method of resin A-1, 7.17 g of ethanol in the quenching step was replaced with water of the same mass, and thereafter, the same steps as in the production method of resin A-1 were performed to synthesize resin A-8.

<Manufacturing method of resin A-9> In the production method of resin A-1, except that 7.17 g of ethanol in the quenching step was replaced with water of the same mass, 716.21 g of ethanol for obtaining a precipitate consisting of a crude polymer after the quenching step was changed. Resin A-9 was synthesized by carrying out the same procedure as in the production method of resin A-1 except for 716.21 g of water.

<Manufacturing method of resin A-10> In the production method of resin A-1, the same procedure as in the production method of resin A-1 was carried out except that 716.21 g of ethanol used to obtain the precipitate consisting of the crude polymer after the quenching step was changed to 716.21 g of water. step, resin A-10 was synthesized.

[Measurement of imidization rate] In each Example or Comparative Example, the total molar content of the cyclic imide structure and the cyclic isoimide structure in 1 g of the resin was measured by the following method ( mmol/g), and described in the column of "imidization rate (mmol/g)" in the table. 0.10 g of resin was dissolved in 0.90 g of heavy DMSO (dimethylsene-d6), and the total molar content of the polymer powder was measured using ¹ H NMR. Specifically, from the ratio of the proton peaks of the cyclic imide structure and the cyclic isoimide structure to the proton peaks of the total aromatic rings, the ratios of the cyclic imide structure and the cyclic isoimide structure were calculated. ratio.

[Table 1] Resin structure X1 (℃) X2 (℃) Y1 (h) X3 (℃) X4 (℃) Y2 (h) Condition Z1 Imidization rate (mmol/g) Mw Example 1 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 2 A-1 0 0 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.08 20000 3 A-1 -5 -5 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.03 19500 4 A-1 10 10 2 0 0 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.11 21000 5 A-1 10 10 2 0 25 1 After quenching and standing at room temperature for 3 hours, the resulting precipitate in the reaction mixture was filtered off over a period of 1 hour. Reprecipitation started immediately after filtration. 0.23 21000 6 A-1 10 10 6 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.12 21500 7 A-1 0 0 2 0 25 3 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.10 20000 8 A-1 -5 -5 2 0 25 1 The quenched reaction mixture was stored at a refrigeration temperature of 3°C for 15 hours. Thereafter, the resulting precipitate in the reaction mixture was filtered off over a period of 1 hour. Reprecipitation started in the resulting filtrate. 0.14 19500 9 A-1 -5 -5 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour. Then, the filtrate was stored at a refrigeration temperature of 3°C for 15 hours. After being refrigerated and taken out, the temperature was raised to 10° C. for 3 hours, and reprecipitation started. 0.14 19500 10 A-2 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.15 21000 11 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 12 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 13 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 14 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000

[Table 2] Resin structure X1 (℃) X2 (℃) Y1 (h) X3 (℃) X4 (℃) Y2 (h) Condition Z1 Imidization rate (mmol/g) Mw Example 15 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 16 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 17 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 18 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 19 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 20 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 twenty one A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 twenty two A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 twenty three A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 twenty four A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 25 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 26 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 27 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 28 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 29 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000

[table 3] Resin structure X1 (℃) X2 (℃) Y1 (h) X3 (℃) X4 (℃) Y2 (h) Condition Z1 Imidization rate (mmol/g) Mw Example 30 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 31 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 32 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 33 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 34 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 35 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 36 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 37 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 38 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 39 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 40 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 41 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 42 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 43 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 44 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000

[Table 4] Resin structure X1 (℃) X2 (℃) Y1 (h) X3 (℃) X4 (℃) Y2 (h) Condition Z1 Imidization rate (mmol/g) Mw Example 45 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 46 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 47 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 48 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 49 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 50 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 51 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 52 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 53 A-3 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 54 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 55 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 56 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 57 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 58 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 59 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000

[table 5] Resin structure X1 (℃) X2 (℃) Y1 (h) X3 (℃) X4 (℃) Y2 (h) Condition Z1 Imidization rate (mmol/g) Mw Example 60 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 61 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 62 A-1 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 63 A-3 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 64 A-3 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 65 A-4 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 66 A-5 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 22000 67 A-6 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.10 21000 68 A-7 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 69 A-8 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 70 A-9 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 71 A-10 10 10 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.14 21000 Comparative example 1 A-1 15 25 2 0 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.35 21500 2 A-1 15 25 2 25 25 1 Immediately after quenching, the resulting precipitate in the reaction mixture was filtered off over 1 hour, and reprecipitation started immediately after filtration. 0.35 21500 3 A-1 15 25 2 0 25 1 The quenched reaction mixture was stored at 25°C for 15 hours. Thereafter, the resulting precipitate in the reaction mixture was filtered off over a period of 1 hour. Reprecipitation started in the resulting filtrate. 0.66 21500

<Preparation of curable composition> In each Example, each curable resin composition was obtained by mixing the components described in the following table, respectively. In addition, in each comparative example, each composition for comparison was obtained by mixing the components described in the following table, respectively. Specifically, the content of each component described in the table is the amount (parts by mass) described in parentheses in each column of the table. In addition, about resin, the resin manufactured in each Example or each comparative example was used in the quantity described in the column of "resin (mass part)" of a table|surface. The obtained curable resin composition and the composition for comparison were subjected to pressure filtration using a filter made of polytetrafluoroethylene having a pore width of 0.8 μm. In addition, in the table|surface, the description of "-" shows that a composition does not contain the corresponding component.

[Table 6] Resin (parts by mass) sensitizer Organometallic complexes cross-linking agent polymerization inhibitor additive Metal Adhesion Improver solvent Exposure conditions Exposure wavelength nm Development conditions Exposure latitude Example 1 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 2 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden A 3 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden A 4 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 5 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden C 6 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 7 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden A 8 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 9 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 10 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 11 35 B-1 (3.0) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden A 12 35 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden A 13 35 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden A 14 35 B-1 (0.7) B-2 (0.7) X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden A

[Table 7] Resin (parts by mass) sensitizer Organometallic complexes cross-linking agent polymerization inhibitor additive Metal Adhesion Improver solvent Exposure conditions Exposure wavelength nm Development conditions Exposure latitude Example 15 35 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden A 16 35 B-1 (1.4) - X-2 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 17 35 B-1 (1.4) - X-3 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden A 18 35 B-1 (1.4) - X-4 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 19 35 B-1 (1.4) - X-5 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 20 35 B-1 (1.4) - X-6 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B twenty one 35 B-1 (1.4) - X-7 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B twenty two 35 B-1 (1.4) - X-8 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B twenty three 35 B-1 (1.4) - X-1 (2.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden A twenty four 35 - - X-1 (2.4) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden A 25 35 B-1 (1.4) - X-1/X-2 (1.0/1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden A 26 35 B-1 (1.4) - - C-2 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 27 35 B-1 (1.4) - - C-1 (6.8) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden A 28 35 B-1 (1.4) - - C-1 (3.4) D-2 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 29 35 B-1 (1.4) - - C-1 (3.4) D-3 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B

[Table 8] Resin (parts by mass) sensitizer Organometallic complexes cross-linking agent polymerization inhibitor additive Metal Adhesion Improver solvent Exposure conditions Exposure wavelength nm Development conditions Exposure latitude Example 30 35 B-1 (1.4) - - C-1 (3.4) D-4 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 31 35 B-1 (1.4) - - C-1 (3.4) D-5 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 32 35 B-1 (1.4) - - C-1 (3.4) D-6 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 33 35 B-1 (1.4) - - C-1 (3.4) D-7 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 34 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.4) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 35 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) - - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 36 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) - E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 37 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (4.8) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 38 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (1.8) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 39 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-2 (0.7) NMP (45.1) EL (11.3) M 405 burden B 40 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-3 (0.7) NMP (45.1) EL (11.3) M 405 burden B 41 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-4 (0.7) NMP (45.1) EL (11.3) M 405 burden B 42 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-5 (0.7) NMP (45.1) EL (11.3) M 405 burden B 43 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-6 (0.7) NMP (45.1) EL (11.3) M 405 burden B 44 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (2.0) NMP (45.1) EL (11.3) M 405 burden B

[Table 9] Resin (parts by mass) sensitizer Organometallic complexes cross-linking agent polymerization inhibitor additive Metal Adhesion Improver solvent Exposure conditions Exposure wavelength nm Development conditions Exposure latitude Example 45 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) DMSO (11.3) γBL (45.1) M 405 burden B 46 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (11.3) EL (45.1) M 405 burden B 47 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) D 405 burden B 48 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) D 405 burden B 49 35 B-2 (1.4) - - C-1 (3.4) D-5 (0.2) E-3 (2.4) - - F-3 (0.7) DMSO (11.3) γBL (45.1) M 405 burden B 50 35 B-2 (1.4) - - C-1 (3.4) D-5 (0.2) E-3 (2.4) - - F-3 (0.7) DMSO (11.3) γBL (45.1) M 405 burden B 51 35 B-2 (1.4) - X-1 (1.0) C-1 (3.4) D-5 (0.2) E-3 (2.4) - - F-3 (0.7) DMSO (11.3) γBL (45.1) M 405 burden A 52 35 B-2 (1.4) - X-1 (1.0) C-1 (3.4) D-5 (0.2) E-3 (2.4) - - F-3 (0.7) DMSO (11.3) γBL (45.1) M 405 burden A 53 35 - - - - - E-4 (2.4) E-5 (0.5) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 just A 54 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 55 35 B-1 (1.4) - - C-1 (3.4) D-2 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 56 35 B-1 (1.4) - - C-1 (3.4) D-3 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 57 35 B-1 (1.4) - - C-1 (3.4) D-4 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 58 35 B-1 (1.4) - - C-1 (3.4) D-5 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 59 35 B-1 (1.4) - - C-1 (3.4) D-6 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B

[Table 10] Resin (parts by mass) sensitizer Organometallic complexes cross-linking agent polymerization inhibitor additive Metal Adhesion Improver solvent Exposure conditions Exposure wavelength nm Development conditions Exposure latitude Example 60 35 B-1 (1.4) - - C-1 (3.4) D-7 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 61 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 365 burden B 62 35 B-1 (1.4) - - C-1 (3.4) D-2 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) NMP (45.1) EL (11.3) M 365 burden B 63 35 - - - - - E-4 (2.4) E-5 (0.5) - F-1 (0.7) NMP (45.1) EL (11.3) M 365 just A 64 35 - - - - - E-4 (2.4) E-5 (0.5) - F-1 (0.7) NMP (45.1) EL (11.3) D 405 just A 65 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 66 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden B 67 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden A 68 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden A 69 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden C 70 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden C 71 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden C Comparative example 1 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden D 2 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden D 3 35 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 burden E

The details of each component described in Tables 6 to 10 are as follows.

[Photosensitive agent (photoradical polymerization initiator)] ·B-1 to B-3: compounds of the following structures [Chemical formula 54]

上述X-1及X-3為具有光自由基聚合起始能力之化合物。 [Organometallic complex] X-1: bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)benzene base) titanium X-2: pentamethylcyclopentadienyltrimethoxytitanium X-3: bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro) Phenyl) titanium X-4: tetraisopropoxytitanium (manufactured by Matsumoto Fine Chemical Co., Ltd.) X-5: diisopropoxybis(acetylacetone) titanium (Matsumoto Fine Chemical Co., Ltd.) X-6 to X-8: compounds of the following structures [Chemical formula 55]

The above-mentioned X-1 and X-3 are compounds having the ability to initiate photoradical polymerization.

[Crosslinking agent (radical crosslinking agent)] C-1 to C-2: compounds of the following structures [Chemical formula 56]

[Polymerization inhibitor, migration inhibitor] D-1 to D-7: compounds of the following structures [Chemical formula 57]

[Additives] E-1 to E-6: Compounds of the following structures [Chemical Formula 58]

上述結構式中，Me表示甲基，Et表示乙基。 [Metal Adhesion Improver] F-1 to F-6: Compounds of the following structures [Chemical formula 59]

In the above structural formula, Me represents a methyl group, and Et represents an ethyl group.

[Solvent (solvent)] · NMP: N-methyl-2-pyrrolidone EL: ethyl lactate DMSO: dimethyl sulfoxide γBL: γ-Butyrolactone

<Evaluation> [Evaluation of Exposure Latitude] In each Example or Comparative Example, the prepared curable resin composition or the composition for comparison was applied on a silicon wafer by a spin coating method. The above-mentioned silicon wafer was dried on a hot plate at 100° C. for 5 minutes, thereby forming a curable resin composition layer with a uniform thickness of 20 μm on the silicon wafer. In the example described as "M" in the exposure conditions, the curable resin composition layer on the silicon wafer was exposed using a stepper. In exposure, the light of the wavelength described in "Exposure wavelength nm" in the table|surface was used, and exposure was performed using the mask of the fuse box of 1 micrometer scale from 5 micrometers to 25 micrometers. In the example described as "D" in the exposure conditions, exposure was performed using a direct exposure device (ADTEC DE-6UH III). In the exposure, at a wavelength of 405 nm, laser direct imaging exposure was performed so that the exposure portion became a line portion in a line and space pattern of 1 μm scale from 5 μm to 25 μm. The exposed curable resin composition layer was developed in cyclopentanone for 60 seconds, and then rinsed with PGMEA (propylene glycol monomethyl ether acetate). In this evaluation, the exposure amount was changed to nine exposure amounts of 100, 200, 300, 400, 500, 600, 700, 800, and 900 mJ/cm ² , respectively. In addition, in the pattern obtained after developing, the line width of the line pattern with the smallest line width among the line patterns exposed by the silicon wafer between the line patterns is regarded as the "minimum line width". Based on the range of the exposure amount in which the minimum pore diameter that can be analyzed is 6 to 8 μm, the evaluation was performed according to the following evaluation criteria. The evaluation results are described in the "exposure latitude" column in the table. -Evaluation Criteria- A: The minimum line width of 6 to 8 μm can be analyzed in the range of 8 or more exposures. B: The minimum line width of 6 to 8 μm can be analyzed in the range of 6 to 7 exposure doses. C: The minimum line width of 6 to 8 μm can be analyzed in the range of 4 to 5 exposure doses. D: The minimum line width of 6 to 8 μm can be analyzed in the range of 2 to 3 exposure amounts. E: In one exposure amount range, the minimum line width of 6 to 8 μm can be analyzed, or the minimum line width of 6 to 8 μm cannot be analyzed.

From the above results, it can be seen that the curable resin composition using the polyimide precursor obtained by the method for producing the polyimide precursor of the present invention is excellent in exposure latitude. The resins used in Comparative Examples 1 to 3 were subjected to the polymerization step at 15°C. It can be seen that when this resin is used, the exposure latitude is poor.

<Example 101> The curable resin composition used in Example 1 was applied to the surface of the copper thin layer of the resin substrate with the copper thin layer formed on the surface in a layer form by spin coating, and dried at 100°C for 4 days. After forming a photosensitive film with a film thickness of 20 μm in minutes, exposure was performed using a stepper (Nikon Co., Ltd., NSR1505 i6). Exposures were performed at a wavelength of 365 nm through a mask (binary mask with 1:1 line and space pattern, 10 μm line width). After exposure, it was heated at 100°C for 4 minutes. After the above heating, it was developed in cyclohexanone for 2 minutes, and rinsed with PGMEA for 30 seconds to obtain a layer pattern. Next, the temperature was increased at a temperature increase rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained at 230° C. for 120 minutes to form an interlayer insulating film for rewiring layers. This interlayer insulating film for rewiring layers is excellent in insulating properties. Furthermore, a semiconductor device was manufactured using these interlayer insulating films for rewiring layers, and as a result, it was confirmed that it operates without any problem.

Claims (13)

A method for producing a polyimide precursor, comprising: a polymerization step of reacting a dicarboxylic acid compound and a diamine compound at a temperature below 10° C. to obtain a reaction solution containing an imide compound, The obtained polyimide precursor has a polymerizable group or a polarity conversion group. The method for producing a polyimide precursor as claimed in claim 1, wherein The aforementioned polymerization step is carried out in the presence of a basic condensing agent. The method for producing a polyimide precursor as claimed in claim 2, wherein The aforementioned basic condensing agent is a carbodiimide condensing agent. The method for producing a polyimide precursor according to any one of claim 1 to claim 3, wherein After the aforementioned polymerization step, a quenching step of adding water or alcohol to the aforementioned reaction solution at a temperature of 10° C. or lower is included. The method for producing a polyimide precursor according to any one of claim 1 to claim 3, wherein A reprecipitation step is further included after the aforementioned polymerization step. The method for producing a polyimide precursor as claimed in claim 4, wherein Further comprising a reprecipitation step after the aforementioned quenching step, After the aforementioned quenching step and before starting the reprecipitation step, the reaction solution is stored at 10° C. or lower. The method for producing a polyimide precursor as claimed in claim 4, wherein Further comprising a reprecipitation step after the aforementioned quenching step, After storing the reaction solution after the quenching step at 10°C or lower, the temperature of the reaction solution was raised to 10°C or higher, and the reprecipitation step was started within 5 hours after the temperature of the reaction solution became 10°C or higher. The method for producing a polyimide precursor as claimed in claim 5, wherein The aforementioned reprecipitation step is a step of adding the reaction solution containing the aforementioned amide compound to water or alcohol. The method for producing a polyimide precursor according to any one of claim 1 to claim 3, wherein An acidic compound addition step of adding an acidic compound to the reaction liquid containing the aforementioned amide compound is included after the aforementioned polymerization step. The method for producing a polyimide precursor according to any one of claim 1 to claim 3, wherein A purification step of purifying the reaction solution containing the aforementioned amide compound is further included after the aforementioned polymerization step. The method for producing a polyimide precursor according to any one of claim 1 to claim 3, wherein A drying step of drying the aforementioned amide compound is further included after the aforementioned polymerization step. A method for manufacturing a curable resin composition, comprising: A step of mixing the polyimide precursor obtained by the method for producing a polyimide precursor according to any one of claim 1 to claim 11 and other components. The method for producing a curable resin composition according to claim 12, wherein At least one compound selected from the group consisting of an organometallic complex having a radical polymerization initiating ability and a photosensitizer is further mixed.