TW202136375A - Resin composition, cured film, laminate, production method for cured film, and semiconductor device - Google Patents

Abstract

A resin composition that includes at least one type of resin selected from the group that consists of polyimides and polyimide precursors, the solid portion of the resin composition including a structure that is represented by formula (1-1). A cured film that is formed by curing the resin composition, a laminate that includes the cured film, a production method for the cured film, and a semiconductor device that includes the cured film or the laminate.

Description

Resin composition, cured film, laminate, cured film manufacturing method, and semiconductor element

The present invention relates to a method for manufacturing a resin composition, a cured film, a laminate, a cured film, and a semiconductor element.

Since polyimide has excellent heat resistance and insulation properties, it is suitable for various applications. The use is not particularly limited, and if a semiconductor element for actual mounting is exemplified, the use as a material of an insulating film or a sealing material or a protective film can be cited. In addition, it is also used as a base film or coverlay film of a flexible substrate.

For example, in the above applications, polyimine is in the form of a resin composition containing polyimine itself or a resin composition containing polyimine precursors (also called "polyimine precursors"). use. Such a resin composition is applied to a substrate by, for example, coating, and then exposure, development, heating, etc. are performed as necessary, so that the cured resin can be formed on the substrate. Since the resin composition can be applied by a known coating method or the like, it can be said that it is excellent in manufacturing adaptability. For example, the applied resin composition has a high degree of freedom in design such as the shape, size, and application position of the applied resin composition. In addition to the high performance of polyimide, from the viewpoint of such excellent manufacturing adaptability, the industrial application and development of resin compositions containing polyimine or polyimine precursors is increasing. Expected.

For example, Patent Document 1 describes a negative photosensitive resin composition containing a polyimide precursor having a specific structural unit: 100 parts by mass, (B) photopolymerization initiator: 1-20 Parts by mass and at least one compound or polymer selected from the group consisting of (C) a compound or polymer having a specific structure and (D) a compound or polymer having a specific structure: 0.1-30 mass share.

[Patent Document 1] JP 2011-059656 A

The following step is performed, that is, a resin composition containing at least one resin selected from the group consisting of polyimine and polyimide precursors is used to form a cured film on the metal layer. In such applications, it is desired to provide a resin composition having excellent adhesion between the cured film and metal.

The object of the present invention is to provide a resin composition, a cured film formed by curing the resin composition, a laminate including the cured film, a method for manufacturing the cured film, and a semiconductor element including the cured film or the laminate, With this resin composition, a cured film excellent in adhesion to metal can be obtained.

式（1-1）中，R¹ 及R² 分別獨立地表示脂肪族基或芳香族基，上述脂肪族基或芳香族基的碳原子或烴基可以經雜原子取代，X¹ 表示氧原子或硫原子，L¹ 表示-C（=O）-或-S（=O）₂ -，*¹ 及*² 分別獨立地表示與其他結構的鍵結部位，R¹ 、R² 、與*¹ 鍵結之結構及與*² 鍵結之結構中的至少2個可以鍵結而形成環結構。 ＜2＞如＜1＞所述之樹脂組成物，其中，上述樹脂包含上述式（1-1）所表示之結構。 ＜3＞如＜1＞或＜2＞所述之樹脂組成物，其係還包含為包含上述式（1-1）所表示之結構之化合物且與上述樹脂不同之化合物。 ＜4＞如＜1＞至＜3＞之任一項所述之樹脂組成物，其係包含下述式（1-2）所表示之結構作為上述式（1-1）所表示之結構。 [化學式2]

式（1-2）中，R²¹ 及R²² 分別獨立地表示脂肪族基或芳香族基，上述脂肪族基或芳香族基的碳原子或烴基可以經雜原子取代，R²³ 表示氫原子或1價的有機基，*表示與其他結構的鍵結部位，R²¹ 、R²² 、R²³ 及與*鍵結之結構中的至少2個可以鍵結而形成環結構。 ＜5＞如＜1＞至＜4＞之任一項所述之樹脂組成物，其中，上述式（1-1）所表示之結構的含有莫耳量相對於樹脂組成物的總固體成分為0.01～1.0mmol/g。 ＜6＞如＜1＞至＜5＞之任一項所述之樹脂組成物，其係還包含光聚合起始劑。 ＜7＞如＜1＞至＜6＞之任一項所述之樹脂組成物，其係還包含交聯劑。 ＜8＞如＜1＞至＜7＞之任一項所述之樹脂組成物，其係用於再配線層用層間絕緣膜的形成。 ＜9＞一種硬化膜，其係將＜1＞至＜8＞之任一項所述之樹脂組成物硬化而成。 ＜10＞一種積層體，其係具有2層以上的＜9＞所述之硬化膜，並且在任意上述硬化膜彼此之間具有金屬層。 ＜11＞一種硬化膜的製造方法，其係包括膜形成步驟，在該膜形成步驟將＜1＞至＜8＞之任一項所述之樹脂組成物適用於基板而形成膜。 ＜12＞如＜11＞所述之硬化膜的製造方法，其係包括在50～450℃下對上述膜進行加熱之步驟。 ＜13＞一種半導體元件，其係具有＜9＞所述之硬化膜或＜10＞所述之積層體。 [發明效果]Examples of representative embodiments of the present invention are shown below. <1> A resin composition containing at least one resin selected from the group consisting of polyimine and polyimide precursors, and containing the structure represented by formula (1-1) in the solid content. [Chemical formula 1]

In formula (1-1), R ¹ and R ² each independently represent an aliphatic group or an aromatic group. The carbon atom or hydrocarbon group of the aliphatic group or aromatic group may be substituted by a heteroatom, and X ¹ represents an oxygen atom or Sulfur atom, L ¹ represents -C(=O)- or -S(=O) ₂ -, * ¹ and * ² each independently represent the bonding site with other structures, R ¹ , R ² , and * ¹ bond At least two of the structure of the knot and the structure of * ^{2 can be bonded to form a ring structure.} <2> The resin composition according to <1>, wherein the resin includes the structure represented by the formula (1-1). <3> The resin composition as described in <1> or <2>, which further includes a compound that includes the structure represented by the above formula (1-1) and is different from the above resin. <4> The resin composition according to any one of <1> to <3>, which contains the structure represented by the following formula (1-2) as the structure represented by the above formula (1-1). [Chemical formula 2]

In formula (1-2), R ²¹ and R ²² each independently represent an aliphatic group or an aromatic group. The carbon atom or hydrocarbon group of the aliphatic group or aromatic group may be substituted with a hetero atom, and R ²³ represents a hydrogen atom or For a monovalent organic group, * indicates a bonding site with another structure ^{, and at least two of R 21} , R ²² , R ²³ and the structure bonded to * may be bonded to form a ring structure. <5> The resin composition according to any one of <1> to <4>, wherein the molar content of the structure represented by the above formula (1-1) is relative to the total solid content of the resin composition 0.01～1.0mmol/g. <6> The resin composition according to any one of <1> to <5>, which further contains a photopolymerization initiator. <7> The resin composition according to any one of <1> to <6>, which further contains a crosslinking agent. <8> The resin composition according to any one of <1> to <7>, which is used for the formation of an interlayer insulating film for a rewiring layer. <9> A cured film obtained by curing the resin composition described in any one of <1> to <8>. <10> A laminate having two or more layers of the cured film described in <9>, and having a metal layer between any of the cured films. <11> A method for producing a cured film, which includes a film forming step in which the resin composition described in any one of <1> to <8> is applied to a substrate to form a film. <12> The method for producing a cured film as described in <11>, which includes the step of heating the film at 50 to 450°C. <13> A semiconductor element having the cured film described in <9> or the laminated body described in <10>. [Effects of the invention]

According to the present invention, there can be provided a resin composition, a cured film formed by curing the resin composition, a laminate including the cured film, a method for manufacturing the cured film, and a semiconductor element including the cured film or the laminate, With this resin composition, a cured film excellent in adhesion to metal can be obtained.

Hereinafter, the main embodiment of the present invention will be described. However, the present invention is not limited to the explicitly shown embodiment. In this specification, the numerical range indicated by the symbol "-" refers to a range that includes the numerical values described before and after the "-" as the lower limit and the upper limit, respectively. In this specification, the term "step" not only refers to an independent step, but as long as it can achieve the intended effect of the step, it also refers to a step that cannot be clearly distinguished from other steps. Regarding the label of the group (atomic group) in this specification, the label that does not indicate substituted and unsubstituted includes both a group (atomic group) without a substituent and a group (atomic group) with a substituent. For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl) but also substituted alkyl (substituted alkyl). 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. In addition, as the light used for exposure, actinic rays or radiation such as the bright line spectrum of a mercury lamp, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams can be cited. In this specification, "(meth)acrylate" means either or both of "acrylate" and "methacrylate", and "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid" "Two or either of these, "(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 refers to the total mass of all the components of the composition excluding the solvent. In addition, in this specification, the solid content concentration is the mass percentage of other components other than the solvent with respect to the total mass of the composition. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene conversion values according to gel permeation chromatography (GPC measurement). In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) can be used, for example, by using HLC-8220GPC (manufactured by TOSOH CORPORATION), and using guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000 , TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) are calculated as the column. Unless otherwise specified, these molecular weights are those measured using THF (tetrahydrofuran) as a washing solution. In addition, unless otherwise specified, the detection in the GPC measurement is to use a UV ray (ultraviolet) wavelength 254nm detector. In this specification, when describing the positional relationship of the layers constituting the layered body as "upper" or "lower", it is only necessary to have another layer on the upper side or the lower side of the layer that becomes the reference among the plurality of layers of interest. . That is, a third layer or a third element may be further interposed between the layer serving as the reference and the other layer described above, and the layer serving as the reference need not be in contact with the other layer described above. In addition, unless otherwise specified, the direction in which the layers are gradually stacked with respect to the substrate is referred to as "up", or, in the case of a photosensitive layer, the direction from the substrate to the photosensitive layer is referred to as "up." The opposite direction is called "down". In addition, the setting of such up and down directions is for the convenience of description of this specification. In actual conditions, the "up" direction in this specification may also be different from the vertical direction. In this specification, unless otherwise stated, in the composition, as each component contained in the composition, two or more compounds corresponding to the component may be included. 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 manual, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, a combination of preferred aspects is a better aspect.

(Resin composition) The resin composition of the present invention (hereinafter, also simply referred to as "the composition of the present invention".) contains at least one resin selected from the group consisting of polyimine and polyimine precursors, and is in solid content Contains the structure represented by formula (1-1). Hereinafter, at least one resin selected from the group including polyimine and polyimine precursors is also referred to as "specific resin".

式（1-1）中，R¹ 及R² 分別獨立地表示脂肪族基或芳香族基，上述脂肪族基或芳香族基的碳原子或烴基可以經雜原子取代，X¹ 表示氧原子或硫原子，L¹ 表示-C（=O）-或-S（=O）₂ -，*¹ 及*² 分別獨立地表示與其他結構的鍵結部位，R¹ 、R² 、與*¹ 鍵結之結構及與*² 鍵結之結構中的至少2個可以鍵結而形成環結構。[Chemical formula 3]

In formula (1-1), R ¹ and R ² each independently represent an aliphatic group or an aromatic group. The carbon atom or hydrocarbon group of the aliphatic group or aromatic group may be substituted by a heteroatom, and X ¹ represents an oxygen atom or Sulfur atom, L ¹ represents -C(=O)- or -S(=O) ₂ -, * ¹ and * ² each independently represent the bonding site with other structures, R ¹ , R ² , and * ¹ bond At least two of the structure of the knot and the structure of * ^{2 can be bonded to form a ring structure.}

The following step is performed, that is, a resin composition containing at least one resin selected from the group consisting of polyimine and polyimide precursors is used to form a cured film on the metal layer. The above-mentioned cured film is used, for example, in various elements such as insulating films, sealing materials, protective films, base films of flexible substrates, cover films, and the like. In such a cured film formed on the metal layer, it is required that the cured film is not easily peeled from the metal layer, that is, the metal layer and the cured film have excellent adhesion. As a result of intensive studies, the inventors of the present invention found that in the above-mentioned resin composition, by including the structure represented by the formula (1-1) in the solid content, the adhesion between the metal layer and the cured film can be improved. Although the mechanism by which the above-mentioned effect can be obtained is not clear, it is presumed that this is because the structure contained in the cured film formed of the above-mentioned resin composition interacts with the metal contained in the metal layer. In addition, it is believed that by the above interaction, the resin composition according to the present invention, even when the cured film and the metal layer are heated (for example, heated at 175°C for 1,000 hours), the cured film and the metal layer The adhesion is excellent.

Among them, Patent Document 1 does not describe or suggest a resin composition containing a structure represented by formula (1-1) in a solid content. Hereinafter, the resin composition of the present invention will be described in detail.

<The structure represented by formula (1-1)> The structure represented by formula (1-1) may be included in the solid content of the resin composition. For example, the structure represented by formula (1-1) may be included in the structure of a specific resin, and the resin composition may include the above The compound of the structure represented by the formula (1-1) includes a compound different from the above-mentioned resin (hereinafter, also referred to as "specific compound"). In addition, the resin composition includes a resin having a structure represented by formula (1-1), and may include a specific compound.

[R ¹ and R ² ] In the formula (1-1), R ¹ and R ² each independently represent an aliphatic group or an aromatic group, an aliphatic hydrocarbon group or an aromatic hydrocarbon group is preferable, and an aliphatic hydrocarbon group is more preferable. As the above-mentioned aliphatic hydrocarbon group, saturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms are preferred, saturated aliphatic hydrocarbon groups having 3 to 10 carbon atoms are more preferred, and saturated aliphatic hydrocarbon groups having 3 to 6 carbon atoms are more preferred. Propyl or cyclohexyl is more preferred. The aforementioned aliphatic hydrocarbon group may have a well-known substituent, but not having a substituent is also one of the preferred aspects of the present invention. As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, a phenyl group or a naphthyl group is more preferable, and a phenyl group is still more preferable. The said aromatic hydrocarbon group may have a well-known substituent, and an alkyl group can be mentioned as a substituent. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 5 to 10 carbon atoms is more preferable, and a branched chain having 3 to 6 carbon atoms is more preferable. The alkyl group is more preferred, and the isopropyl group is particularly preferred. The number of the above-mentioned substituents is not particularly limited, but 1 to 5 are preferred, 1 to 3 are more preferred, and 2 is even more preferred. In addition, the carbon atom or hydrocarbon group of the aliphatic group or aromatic group in ^{R 1} and R ^{2 may be substituted with a hetero atom.} As a hetero atom, an oxygen atom, a nitrogen atom, a sulfur atom, etc. can be mentioned. Specifically, the aliphatic group or the aromatic group may contain structures such as -O-, -NR ^N -, -N=, -S-, etc. The above-mentioned R ^N represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is more preferable, and a hydrogen atom is particularly preferable.

[X ¹ ] In the formula (1-1), X ¹ represents an oxygen atom or a sulfur atom, and an oxygen atom is preferred.

[L ¹ ] In the formula (1-1), L ¹ represents -C(=O)- or -S(=O) ₂ -, preferably -C(=O)-.

[Ring structure] In the formula (1-1), ^{at least two of R 1} , R ² , a structure bonded ^{to *1} , and a ^{structure bonded to *2} may be bonded to form a ring structure. Examples of the ring structure formed include a hydantoin ring, an N-amidazolidone ring, and the like, but are not limited to these. Moreover, in the present invention, the aspect in which any one of R ¹ , R ² , the structure bonded to * ¹ and the structure bonded to * ² does not form a ring structure is also one of the preferred aspects.

式（1-2）中，R²¹ 及R²² 分別獨立地表示脂肪族基或芳香族基，上述脂肪族基或芳香族基的碳原子或烴基可以經雜原子取代，R²³ 表示氫原子或1價的有機基，*表示與其他結構的鍵結部位，R²¹ 、R²² 、R²³ 及與*鍵結之結構中的至少2個可以鍵結而形成環結構。<The structure represented by the formula (1-2)> The resin composition of the present invention preferably contains the structure represented by the following formula (1-2) as the structure represented by the formula (1-1). [Chemical formula 4]

In formula (1-2), R ²¹ and R ²² each independently represent an aliphatic group or an aromatic group. The carbon atom or hydrocarbon group of the aliphatic group or aromatic group may be substituted with a hetero atom, and R ²³ represents a hydrogen atom or For a monovalent organic group, * indicates a bonding site with another structure ^{, and at least two of R 21} , R ²² , R ²³ and the structure bonded to * may be bonded to form a ring structure.

[R ²¹ and R ²² ] In formula (1-2), R ²¹ and R ^{22 have the same meanings as R 1} and R ² in formula (1-1), and preferred aspects are also the same.

[R ²³ ] In the formula (1-2), R ²³ represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and more preferably a hydrogen atom. Examples of the aliphatic hydrocarbon group or aromatic hydrocarbon group include the aliphatic hydrocarbon group or aromatic hydrocarbon group in R ¹ described above, and the preferred aspects are also the same.

[Ring structure] In the formula (1-2), ^{at least two of R 21} , R ²² , R ²³ and the structure bonded to * may be bonded to form a ring structure. Examples of the ring structure formed include a hydantoin ring, an N-amidazolidone ring, and the like, but are not limited to these. Furthermore, in the present invention, the ^{aspect in which any one of R 21} , R ²² , R ²³ and the structure bonded with * does not form a ring structure is also one of the preferred aspects.

〔content〕 From the viewpoint of improving adhesion, the molar content of the structure represented by formula (1-1) is preferably 0.01 to 1.0 mmol/g relative to the total solid content of the resin composition, and 0.01 to 0.85 mmol/g is More preferably, 0.015 to 0.75 mmol/g is even more preferable. It is considered that as long as the molar content is equal to or less than the lower limit, it is easy to obtain a cured film having excellent adhesion to metal. In addition, it is considered that as long as the molar content is below the upper limit, it is easy to obtain a cured film with excellent storage stability of the composition such as suppression of the cyclization of the polyimide precursor and suppression of the cleavage of the main chain of the specific resin. . The measuring method of the above content is not particularly limited, but for example, the measuring method in the below-mentioned examples can be cited. The method for measuring the above total solid content is not particularly limited, but for example, the measuring method in the following examples can be cited, and the resin composition can be dried while confirming that the resin composition has no volatile components except for the solvent.的方法。 The method. However, the method of measuring the total solid content is not limited to this as long as it can determine the content of the components other than the solvent in the resin composition as the total solid content. The above content is the molar amount of the structure represented by formula (1-1) relative to the total solid content of the resin composition. For example, the resin composition contains a resin having a structure represented by formula (1-1) and contains In the case of a specific compound, the total amount of the structure represented by formula (1-1) contained in the resin and the structure represented by formula (1-1) contained in the specific compound is preferably within the above-mentioned range.

＜Resin＞ The resin composition of the present invention includes at least one resin (specific resin) selected from the group consisting of polyimine and polyimide precursors. The resin composition of the present invention preferably contains a polyimide precursor as the specific resin. Furthermore, it is preferable that the specific resin has a radical polymerizable group. In the case where the specific resin has a radical polymerizable group, the resin composition preferably contains a radical polymerization initiator described below as the polymerization initiator, and contains the radical polymerization initiator described below as a photosensitizer and contains the radical polymerization initiator described below. The linking agent is more preferable, and it is more preferable to include the radical polymerization initiator described below as the polymerization initiator, the radical crosslinking agent described below, and the sensitizer described below. From such a resin composition, for example, a negative photosensitive layer is formed. In addition, the specific resin may have a polarity conversion group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the resin composition preferably contains a photoacid generator described later. From such a resin composition, for example, a chemically amplified positive photosensitive layer or a negative photosensitive layer is formed.

Moreover, it is preferable that the specific resin contains the structure represented by formula (1-1). Preferred aspects of the structure represented by formula (1-1) are as described above. When the specific resin includes the structure represented by the formula (1-1), the specific resin may have the structure represented by the formula (1-1) in the main chain, but it is preferable to have the structure in the side chain. In this specification, the "main chain" refers to the relatively longest bonding chain in the molecules of the polymer compound constituting the resin, and the "side chain" refers to other bonding chains. When the specific resin contains the structure represented by the formula (1-1), the specific resin contains the repeating unit represented by the formula (2-1) mentioned later or contains the structure represented by the formula (2-2) mentioned later at the end. good. In addition, the resin composition may include a specific resin containing the structure represented by the formula (1-1) and a specific resin not containing the structure represented by the formula (1-1).

式（2）中，A¹ 及A² 分別獨立地表示氧原子或NH，R¹¹¹ 表示2價的有機基，R¹¹⁵ 表示4價的有機基，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價的有機基。[Polyimine Precursor] The type and the like of the polyimine precursor used in the present invention are not specifically defined, but it is preferable to include a repeating unit represented by the following formula (2). [Chemical formula 5]

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.

^{A 1} and A ² in formula (2) each independently represent an oxygen atom or NH, and an oxygen atom is preferred. ^{R 111} in formula (2) represents a divalent organic group. Examples of divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, including linear or branched aliphatic groups having 2 to 20 carbon atoms, A cycloaliphatic group having 6 to 20 carbons, an aromatic group having 6 to 20 carbons, or a combination of these groups are preferred, and a group containing an aromatic group having 6 to 20 carbons is more preferred. As a particularly preferred embodiment of the present invention, a group represented by -Ar-L-Ar- can be exemplified. Wherein, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group including 1 to 10 carbons which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ -or -NHCO- Or a combination of two or more of the above groups. The preferable ranges of these are as described above.

Preferably, R ^{111 is} derived from diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, it includes a straight or branched chain aliphatic group with 2 to 20 carbons, a cyclic aliphatic group with 6 to 20 carbons, an aromatic group with 6 to 20 carbons, or a combination of these groups The diamine is preferred, and the diamine containing a group including an aromatic group having 6 to 20 carbon atoms is more preferred. As an example of an aromatic group, the following can be mentioned.

式中，A為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-、-SO₂ -、-NHCO-或該等的組合中之基團為較佳，單鍵或選自可以經氟原子取代之碳數1～3的伸烷基、-O-、-C（=O）-、-S-或-SO₂ -中之基團為更佳，-CH₂ -、-O-、-S-、-SO₂ -、-C（CF₃ ）₂ -或-C（CH₃ ）₂ -為進一步較佳。 式中，*表示與其他結構的鍵結部位。[Chemical formula 6]

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

As the diamine, specifically, at least one diamine selected from the group consisting of 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1 ,4-Diaminobutane and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-di 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; meta- or p-phenylenediamine, diaminotoluene, 4,4'- Or 3,3'-diaminodiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- and 3,3'-diaminodiphenyl ether Phenylmethane, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'- or 3, 3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl , 3,3'-Dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl) 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) sulfide, double (4-amino-3-hydroxyphenyl) sulfide, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4 -Aminophenoxy) phenyl] ash, bis[4-(3-aminophenoxy)phenyl] ash, bis[4-(2-aminophenoxy)phenyl] ash, 1, 4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfide , 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3, 3'-Diethyl-4,4'-Diaminodiphenylmethane, 3,3'-Dimethyl-4,4'-Diaminodiphenylmethane, 4,4'-Diamino octa Fluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl Ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-amine Phenyl) pyrene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfonium, 3,3',5,5'-tetramethyl-4,4'-diamino Diphenylmethane, 2,4- and 2,5 -Diaminocumene, 2,5-Dimethyl-p-phenylenediamine, Betaguanidine, 2,3,5,6-Tetramethyl-p-phenylenediamine, 2,4,6-trimethyl Group-m-phenylenediamine, bis(3-aminopropyl) tetramethyldisiloxane, 2,7-diaminopyridine, 2,5-diaminopyridine, 1,2-bis(4- Aminophenyl) ethane, diaminobenzaniline, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-amino) Phenyl) hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4 -Aminophenyl) tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminobenzene) Oxy)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 sulfide, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl Suspension, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4 '-Diaminobiphenyl, 4,4'-Diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotriphenyl 𠯤 and 4,4'-diamino p-bitetraphenyl.

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

In addition, diamines having two or more alkylene glycol units in the main chain described in paragraphs 032 to 0034 of International Publication No. 2017/038598 can also be preferably used.

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

式（51）中，R⁵⁰ ～R⁵⁷ 分別獨立地為氫原子、氟原子或1價的有機基，R⁵⁰ ～R⁵⁷ 中的至少1個為氟原子、甲基或三氟甲基。 作為R⁵⁰ ～R⁵⁷ 的1價的有機基，可以舉出碳數1～10（較佳為碳數1～6）的未取代烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 [化學式8]

式（61）中，R⁵⁸ 及R⁵⁹ 分別獨立地為氟原子或三氟甲基。 作為提供式（51）或式（61）的結構之二胺化合物，可以舉出2,2’-二甲基聯苯胺、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。Moreover, from the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, the divalent organic group represented by the formula (61) is more preferable. Formula (51) [Chemical Formula 7]

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, ^{and at least one of R 50} to R ⁵⁷ is a fluorine atom, a methyl group, or a trifluoromethyl group. ^Examples of the monovalent organic groups of R ⁵⁰ to R 57 include unsubstituted alkyl groups having 1 to 10 carbons (preferably 1 to 6 carbons), and 1 to 10 carbons (preferably 1 to 6 carbons). 6) The fluorinated alkyl group and so on. [Chemical formula 8]

In the formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom or a trifluoromethyl group. As the diamine compound providing the structure of formula (51) or formula (61), 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'- Diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These can be used singly or in combination of two or more.

In addition, the following diamines can also be preferably used. [Chemical formula 9]

式（5）中，R¹¹² 為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-、-SO₂ -及-NHCO-以及該等的組合中之基團為較佳，單鍵或選自可以經氟原子取代之碳數1～3的伸烷基、-O-、-CO-、-S-及-SO₂ -中之基團為更佳，選自包括-CH₂ -、-C（CF₃ ）₂ -、-C（CH₃ ）₂ -、-O-、-CO-、-S-及-SO₂ -的群組中之2價的基團為進一步較佳。 ^{R 115} in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing 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), * represents the bonding site with other structures. Formula (5) [Chemical Formula 10]

In formula (5), R ¹¹² is a single bond or is selected from aliphatic hydrocarbon groups having 1 to 10 carbons which may be substituted with fluorine atoms, -O-, -CO-, -S-, -SO ₂ -and -NHCO- And the groups in these combinations are preferred, single bonds or selected from alkylene groups with 1 to 3 carbons, -O-, -CO-, -S- and -SO ₂ -which may be substituted by fluorine atoms The group in is more preferred, and is selected from -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- and -SO _2- The divalent group in the group of is further preferred.

Formula (6) [Chemical formula 11]

式（O）中，R¹¹⁵ 表示4價的有機基。R¹¹⁵ 的較佳範圍與式（2）中之R¹¹⁵ 的含義相同，較佳範圍亦相同。Specifically, R ¹¹⁵ includes the tetracarboxylic acid residue remaining after removing the acid anhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. Tetracarboxylic dianhydride is preferably represented by the following formula (O). Formula (O) [Chemical formula 12]

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The same meaning and preferred range of the formula R ¹¹⁵ (2) is in the R ^115, the preferred ranges are also the same.

Specific examples of tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4' -Diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride , 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4' -Biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic 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- Perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride Anhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4- Phenyltetracarboxylic dianhydride and these C1-C6 alkyl groups and C1-C6 alkoxy derivatives.

In addition, as a preferred example, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 can also be cited.

It is also preferable that at least one of ^{R 111} and R ^{115 has an OH group.} More specifically, as R ¹¹¹ , a residue of a diaminophenol derivative can be mentioned.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. It ^{is preferred that at least one of R 113} and R ¹¹⁴ contains a polymerizable group, and it is more preferred that both of them contain a polymerizable group. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, etc., and a radical polymerizable group is preferred. Specific examples of polymerizable groups include groups having ethylenically unsaturated bonds, alkoxymethyl, hydroxymethyl, oxymethyl, epoxy, oxobutyl, and benzoxazole Groups, blocked isocyanate groups, methylol groups, amine groups. As the radical polymerizable group possessed by the polyimide precursor, etc., a group having an ethylenically unsaturated bond is preferred. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (methyl)allyl group, a group represented by the following formula (III), etc. The group represented by the following formula (III) is Better.

[Chemical formula 13]

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a hydrogen atom is preferred. In the formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -or a polyalkyleneoxy group. Examples of preferred R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene Methyl, octamethylene, dodecamethylene, -CH ₂ CH(OH)CH ₂ -, polyoxyethylene, ethylene, propylene, trimethylene, -CH ₂ CH(OH) CH ₂ -and polyoxyalkylene are more preferable, and from the viewpoint of easily satisfying formula (1) or (2) in the cured film, polyoxyalkylene is more preferable. In the present invention, the polyalkoxyl group refers to a group to which two or more alkoxyl groups are directly bonded. The alkylene groups in the plurality of alkylene groups contained in the polyalkoxy group may be the same or different. In the case where the polyalkoxyl group contains a plurality of alkoxyl groups with different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl group may be a random arrangement or a block arrangement. It may also be an arrangement with alternating patterns. The carbon number of the above-mentioned alkylene group (when the alkylene group has a substituent, including the carbon number of the substituent) is preferably 2 or more, more preferably 2-10, more preferably 2-6, more preferably 2-5 To be further preferred, 2 to 4 are further preferred, 2 or 3 is particularly preferred, and 2 is the most preferred. In addition, the above-mentioned alkylene group may have a substituent. As a preferable substituent, an alkyl group, an aryl group, a halogen atom, etc. can be mentioned. In addition, the number of alkoxyl groups contained in the polyalkoxyl group (the number of repetitions of the polyalkoxyl group) is preferably 2-20, more preferably 2-10, and still more preferably 2-6. As polyoxyethylene group, from the viewpoint of solvent solubility and solvent resistance, polyoxyethylene group, polyoxypropylene group, polytrimethyleneoxy group, polytetramethyleneoxy group or a plurality of oxyethylene groups A group formed by bonding a group and a plurality of propoxy groups is preferred, polyoxyethylene or polyoxypropylene is more preferred, and polyoxyethylene is further preferred. In the group formed by bonding the above-mentioned plural ethoxy groups and plural propoxy groups, the ethoxy groups and propoxy groups can be arranged randomly, or they can be arranged in blocks, or they can be arranged into Alternate and other patterns. Preferred aspects of the number of repetitions such as ethoxylate in these groups are as described above.

R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom or a monovalent organic group. As the monovalent organic group, one, two, or three of the carbons constituting the aryl group can be exemplified, and an aromatic group and an aralkyl group having an acidic group bonded to one are preferable. Specifically, a C6-C20 aromatic group which has an acidic group, and a C7-25 aralkyl group which has an acidic group are mentioned specifically,. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned. The acidic group is preferably an OH group. R ¹¹³ or R ¹¹⁴ is a hydrogen atom, and it is also more preferable that a 2-hydroxybenzyl group, a 3-hydroxybenzyl group and a 4-hydroxybenzyl group are used.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. As the monovalent organic group, it is preferable to include a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group, and an alkyl group substituted with an aromatic group is more preferable. The carbon number of the alkyl group is preferably 1-30. The alkyl group may be any of linear, branched, and cyclic. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and tetradecyl. Base, octadecyl, isopropyl, isobutyl, second butyl, tertiary butyl, 1-ethylpentyl, 2-ethylhexyl 2-(2-(2-methoxyethoxy Group) ethoxy) ethoxy, 2-(2-(2-ethoxyethoxy) ethoxy) ethoxy) ethoxy, 2-(2-(2-(2-methoxy) Ethoxy) ethoxy) ethoxy) ethoxy and 2-(2-(2-(2-ethoxyethoxy) ethoxy) ethoxy) ethoxy. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, camphenyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, camphenyl and bicyclo Hexyl and pinenyl. Among them, the cyclohexyl group is the most preferable from the viewpoint of compatibility with high sensitivity. In addition, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferred. As the aromatic group, specifically, substituted or unsubstituted benzene ring, naphthalene ring, pentacyclopentadiene ring, indene ring, azulene ring, heptene ring, indenene ring, perylene ring, fused pentacene Rings, acenaphthylene rings, phenanthrene rings, anthracene rings, fused benzene rings, fen rings, terphenylene rings, pyrene rings, biphenyl rings, pyrrole rings, furan rings, thiophene rings, imidazole rings, azole rings, thiazole rings Ring, pyridine ring, pyridine ring, pyrimidine ring, pyridine ring, indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinoline ring, Nylidine ring, quinalidine ring, quinoline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thiamine ring, chromene ring, mouth Yamaguchi star ring, brown ring, brown ring or brown ring. The benzene ring is the best.

In formula (2), 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. Examples of such tertiary amine compounds having ethylenically unsaturated bonds include N,N-dimethylaminopropyl methacrylate.

At least one of R ¹¹³ and R ¹¹⁴ may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed under the action of an acid to generate alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups, but acetal groups, ketal groups, silyl groups, and silyl ethers A group, 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 butoxycarbonylmethyl group, trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

Furthermore, it is also preferable that the polyimide precursor has a fluorine atom in the structural unit. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

In addition, for the purpose of improving the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

式（2-A）中，A¹ 及A² 表示氧原子，R¹¹¹ 及R¹¹² 分別獨立地表示2價的有機基，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價的有機基，R¹¹³ 及R¹¹⁴ 中的至少一者為包含聚合性基之基團，兩者為聚合性基為較佳。The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors and the like used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). With such a structure, the width of the exposure latitude can be further expanded. Formula (2-A) [Chemical Formula 14]

In the formula (2-A), A ¹ and A ² represent an oxygen atom, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, At least one of R ¹¹³ and R ¹¹⁴ is a group containing a polymerizable group, and both of them are preferably a polymerizable group.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ^{114 respectively independently have the same meanings as A 1} , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2), and the preferred ranges are also the same. The same meaning as R ¹¹² in the formula R (5) in the ^112, the preferred ranges are also the same.

The polyimide precursor may include one type of repeating structural unit represented by formula (2), or two or more types. In addition, the structural isomer of the repeating unit represented by formula (2) may also be included. Furthermore, it goes without saying that the polyimide precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (2).

As an embodiment of the polyimide precursor in the present invention, it can be exemplified that 50 mol% or more of all repeating units, further 70 mol% or more, especially 90 mol% or more, are represented by formula (2) Represents the polyimide precursor of the repeating unit.

式（2-1）中，R¹¹¹ 表示2價的有機基，R¹¹⁵ 表示4價的有機基，R^X1 及R^X2 分別獨立地表示包含式（1-1）所表示之結構之基團或下述式（R-1）所表示之基團，R^X1 及R^X2 中的至少一者表示包含式（1-1）所表示之結構之基團。 [化學式16]

式（R-1）中，A³ 表示氧原子或NH，R^X3 分別獨立地表示氫原子或1價的有機基，*表示與R¹¹⁵ 的鍵結部位。Moreover, when the polyimide precursor has a structure represented by formula (1-1), it is preferable that the polyimine precursor contains a repeating unit represented by the following formula (2-1). [Chemical formula 15]

In formula (2-1), R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ^X1 and R ^X2 each independently represent a group including the structure represented by formula (1-1) or In the group represented by the following formula (R-1), ^{at least one of R X1} and R ^X2 represents a group including the structure represented by the formula (1-1). [Chemical formula 16]

In the formula (R-1), A ³ represents an oxygen atom or NH, R ^X3 each independently represents a hydrogen atom or a monovalent organic group, and * represents a bonding site ^{with R 115.}

In formula (2-1), R ¹¹¹ and R ^{115 have the same meanings as R 111} and R ¹¹⁵ in formula (2), and preferred aspects are also the same.

式（X-1）中，R¹ 及R² 分別獨立地表示脂肪族基或芳香族基，上述脂肪族基或芳香族基的碳原子或烴基可以經雜原子取代，X¹ 表示氧原子或硫原子，L¹ 表示-C（=O）-或-S（=O）₂ -，*表示與R¹¹⁵ 的鍵結部位。 式（X-1）中，R¹ 、R² 、X¹ 及L¹ 與式（1-1）中的R¹ 、R² 、X¹ 及L¹ 的含義相同，較佳態樣亦相同。 式（X-1）中，R³ 與式（1-2）中的R²³ 的含義相同，較佳態樣亦相同。In formula (2-1), ^{at least one of R X1} and R ^X2 represents a group including the structure represented by formula (1-1). The group containing the structure represented by the above formula (1-1) is preferably a group represented by the following formula (X-1). [Chemical formula 17]

In formula (X-1), R ¹ and R ² each independently represent an aliphatic group or an aromatic group. The carbon atom or hydrocarbon group of the aliphatic group or aromatic group may be substituted by a heteroatom, and X ¹ represents an oxygen atom or Sulfur atom, L ¹ represents -C(=O)- or -S(=O) ₂ -, * represents the bonding site ^{with R 115.} Of formula (X-1) in a, R ^1, the R ^2, X ¹ and L ¹ in the formula ^{(1-1) R 1, R 2} , X and ^a have the same meaning of L ^1, preferred aspects are also the same. In formula (X-1), R ^{3 has the same meaning as R 23} in formula (1-2), and preferred aspects are also the same.

As specific examples of the group represented by the formula (X-1), the following groups can be given, but they are not limited to these. In the following formula, * represents the bonding site ^{with R 115.} [Chemical formula 18]

In formula (2-1), one of R ^X1 and R ^X2 may be a group represented by formula (R-1). In formula (R-1), A ³ and R ^{X3 have the same meanings as A 2} and R ¹¹³ in formula (2), and preferred aspects are also the same.

The content of the repeating unit represented by formula (2-1) in the polyimide precursor is not particularly limited, as long as it contains the structure represented by formula (1-1) relative to the total solid content of the resin composition The molar amount may be appropriately adjusted to an amount within the above range. The content of the group represented by the formula (X-1) in the polyimide precursor is, for example, preferably 0.01 to 1.0 mmol/g, and more preferably 0.01 to 0.85 mmol/g.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and still more preferably 22,000 to 25,000. In addition, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200. The dispersion of the molecular weight of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and even more preferably 2.8 or more. The upper limit of the dispersion of the molecular weight of the polyimide precursor is not particularly specified. For example, 4.5 or less is preferred, 4.0 or less is more preferred, 3.8 or less is more preferred, 3.2 or less is more preferred, and 3.1 or less is It is even more preferable, 3.0 or less is still more preferable, and 2.95 or less is particularly preferable. In this specification, the degree of molecular weight dispersion is a value calculated using weight average molecular weight/number average molecular weight.

〔Polyimide〕 The polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide soluble in a developer containing an organic solvent as a main component. In this specification, alkali-soluble polyimide means that 0.1g or more of polyimide is dissolved at 23°C with respect to 100g of 2.38% by mass tetramethylammonium aqueous solution, and 0.5g is dissolved from the viewpoint of pattern formation. The above polyimine is preferable, and it is more preferable to dissolve 1.0 g or more of polyimine. The upper limit of the above-mentioned dissolution amount is not particularly limited, but 100 g or less is preferable. Moreover, from the viewpoint of the film strength and insulation properties of the cured film obtained, the polyimide is preferably a polyimide having a plurality of imine structures in the main chain. In this specification, the "main chain" refers to the relatively longest bonding chain in the molecules of the polymer compound constituting the resin, and the "side chain" refers to other bonding chains.

-Fluorine atom- From the viewpoint of the film strength of the cured film obtained, it is preferable that the polyimide has a fluorine atom. The fluorine atom is preferably contained in R ^{132 in the repeating unit represented by the following formula (4) or R 131} in the repeating unit represented by the following formula (4), and is included as a fluorinated alkyl group in the following formula ( 4) R ^{132 in the repeating unit represented or R 131} in the repeating unit represented by formula (4) described later is more preferred. The amount of fluorine atoms is preferably 1-50 mol/g, and more preferably 5-30 mol/g relative to the total mass of the polyimide.

-Silicon atom- From the viewpoint of the film strength of the cured film obtained, it is preferable that the polyimide has a silicon atom. ^{For example, the silicon atom is preferably contained in R 131} in the repeating unit represented by the following formula (4), and is included in the repeating unit represented by the following formula (4) as an organic modified (poly)siloxane structure described later The R ¹³¹ is better. In addition, the above-mentioned silicon atom or the above-mentioned organically modified (poly)siloxane structure may also be included in the side chain of the polyimide, but it is preferably included in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 0.01-5 mol/g, more preferably 0.05-1 mol/g.

-Ethylene unsaturated bond- From the viewpoint of the film strength of the cured film to be obtained, it is preferable that the polyimide has an ethylenic unsaturated bond. The polyimide may have an ethylenically unsaturated bond at the end of the main chain or may have an ethylenically unsaturated bond in the side chain, but it is preferred to have an ethylenically unsaturated bond in the side chain. It is preferable that the said ethylenic unsaturated bond has radical polymerizability. The ethylenically unsaturated bond is preferably contained in R ^{132 in the repeating unit represented by the following formula (4) or R 131} in the repeating unit represented by the following formula (4), as the group having an ethylenically unsaturated bond The group is more preferably contained in R ^{132 in the repeating unit represented by formula (4) described below or R 131} in the repeating unit represented by formula (4) described below. ^{Among them, the ethylenically unsaturated bond is preferably contained in R 131} in the repeating unit represented by the following formula (4), and it is contained in the following formula (4) as a group having an ethylenically unsaturated bond. ^{R 131} in the repeating unit shown is more preferable. Examples of groups having ethylenically unsaturated bonds include vinyl groups, allyl groups, vinyl phenyl groups, etc., which are directly bonded to aromatic rings and may be substituted with vinyl groups, and (meth)acrylic acid Group, (meth)acryloxy group, a group represented by the following formula (IV), etc.

[Chemical formula 19]

In the formula (IV), R ²⁰ represents a hydrogen atom or a methyl group, and a methyl group is preferred.

In the formula (IV), R ²¹ represents an alkylene having 2 to 12 carbon atoms, -O-CH ₂ CH(OH)CH ₂ -, -C(=O)O-, -O(C=O)NH- , (Poly) alkoxylate with 2-30 carbons (the carbon number of the alkylene is preferably 2-12, more preferably 2-6, especially 2 or 3; repeating number 1-12 is Preferably, 1 to 6 are more preferable, and 1 to 3 are particularly preferable) or a group formed by combining two or more of these.

式（R1）～式（R3）中，L表示單鍵或碳數2～12的伸烷基、碳數2～30的（聚）伸烷氧基或將該等中的2個以上鍵結而成之基團，X表示氧原子或硫原子，*表示與其他結構的鍵結部位，●表示與式（III）中的R²⁰¹ 所鍵結之氧原子的鍵結部位。 式（R1）～式（R3）中，L中之碳數2～12的伸烷基或碳數2～30的（聚）伸烷氧基的較佳態樣與上述的R²¹ 中之碳數2～12的伸烷基或碳數2～30的（聚）伸烷氧基的較佳態樣相同。 式（R1）中，X為氧原子為較佳。 式（R1）～式（R3）中，*與式（IV）中的*的含義相同，較佳態樣亦相同。 式（R1）所表示之結構例如藉由使具有酚性羥基等羥基之聚醯亞胺與具有異氰酸酯基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸2-異氰酸酯基乙酯等）進行反應而獲得。 式（R2）所表示之結構例如藉由使具有羧基之聚醯亞胺與具有羥基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸2-羥乙酯等）進行反應而獲得。 式（R3）所表示之結構例如藉由使具有酚性羥基等羥基之聚醯亞胺與具有縮水甘油基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸縮水甘油酯等）進行反應而獲得。 作為聚伸烷氧基，從溶劑溶解性及耐溶劑性的觀點考慮，聚伸乙氧基、聚伸丙氧基、聚三亞甲氧基、聚四亞甲氧基或由複數個伸乙氧基和複數個伸丙氧基鍵結而成之基團為較佳，聚伸乙氧基或聚伸丙氧基為更佳，聚伸乙氧基為進一步較佳。在由上述複數個伸乙氧基和複數個伸丙氧基鍵結而成之基團中，伸乙氧基和伸丙氧基可以無規排列，亦可以形成嵌段而排列，亦可以排列成交替等圖案狀。該等基團中之伸乙氧基等的重複數的較佳態樣如上所述。Among them, R ²¹ is preferably a group represented by any one of the following formulas (R1) to (R3), and more preferably a group represented by formula (R1). [Chemical formula 20]

In formulas (R1) to (R3), L represents a single bond or an alkylene group having 2 to 12 carbons, a (poly)alkylene group having 2 to 30 carbons, or two or more of these are bonded X represents an oxygen atom or a sulfur atom, * represents a bonding site with other structures, and ● represents a bonding site with an oxygen atom bonded to ^{R 201 in formula (III).} In the formulas (R1) to (R3), the preferred aspect of the alkylene group having 2 to 12 carbons or the (poly)alkylene group having 2 to 30 carbons in L is the same as the carbon in the above-mentioned R ²¹ The preferred aspects of the alkylene group having 2 to 12 or the (poly)alkylene group having 2 to 30 are the same. In the formula (R1), X is preferably an oxygen atom. In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and preferred aspects are also the same. The structure represented by the formula (R1) is formed, for example, by combining a polyimide having a hydroxyl group such as a phenolic hydroxyl group and a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate, etc.) Obtained by reaction. The structure represented by the formula (R2) is obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.). The structure represented by the formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate, etc.) get. As polyoxyethylene group, from the viewpoint of solvent solubility and solvent resistance, polyoxyethylene group, polyoxypropylene group, polytrimethyleneoxy group, polytetramethyleneoxy group or a plurality of oxyethylene groups A group formed by bonding a group and a plurality of propoxy groups is preferred, polyoxyethylene or polyoxypropylene is more preferred, and polyoxyethylene is further preferred. In the group formed by bonding the above-mentioned plural ethoxy groups and plural propoxy groups, the ethoxy groups and propoxy groups can be arranged randomly, or they can be arranged in blocks, or they can be arranged into Alternate and other patterns. Preferred aspects of the number of repetitions such as ethoxylate in these groups are as described above.

In the formula (IV), * represents the bonding site with other structures, and the bonding site with the main chain of the polyimide is preferred.

The amount of ethylenically unsaturated bonds is preferably 0.05-10 mol/g, and more preferably 0.1-5 mol/g relative to the total mass of the polyimide. In addition, from the viewpoint of manufacturing suitability, the amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.0005 to 0.05 mol/g.

-Crosslinkable group other than ethylenic unsaturated bond- Polyimide may have a crosslinkable group other than ethylenic unsaturated bond. Examples of crosslinkable groups other than ethylenically unsaturated bonds include cyclic ether groups such as epoxy groups and oxycyclobutyl groups, alkoxymethyl groups such as methoxymethyl groups, and hydroxymethyl groups. The crosslinkable group other than the ethylenically unsaturated bond is preferably contained in R ¹³¹ in the repeating unit represented by the formula (4) described below, for example. The amount of crosslinkable groups other than the ethylenically unsaturated bond is preferably 0.05 to 10 mol/g, and more preferably 0.1 to 5 mol/g relative to the total mass of the polyimide. In addition, from the viewpoint of manufacturing suitability, the amount of crosslinkable groups other than ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol/g, and 0.001 to 0.05 mol/g is Better.

-Polar conversion group- Polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group described in R ¹¹³ and R ¹¹⁴ in the above formula (2), and preferred aspects are also the same.

-Acid value- When polyimine is used for alkali development, from the viewpoint of improving developability, the acid value of polyimine is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and 70 mgKOH/g or more To be further preferred. In addition, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less. In addition, when polyimine is used for development (for example, "solvent development" described below) using a developer with an organic solvent as the main component, the acid value of polyimine is 2 to 35 mgKOH/g Preferably, 3-30 mgKOH/g is more preferable, and 5-20 mgKOH/g is still more preferable. The above-mentioned acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. In addition, as the acid group contained in the polyimide, from the viewpoint of achieving both storage stability and developability, an acid group having a pKa of 0-10 is preferable, and an acid group having a pKa of 3-8 is more preferable. pKa is the one that takes into account the dissociation reaction of releasing hydrogen ions from the acid and expresses its equilibrium constant Ka with its negative common logarithm pKa. As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

-Phenolic hydroxyl group- From the viewpoint of making the development speed based on the alkali developer appropriate, it is preferable that the polyimide has a phenolic hydroxyl group. The polyimide may have a phenolic hydroxyl group at the end of the main chain, or may have a phenolic hydroxyl group at the side chain. The phenolic hydroxyl group is preferably contained in R ^{132 in the repeating unit represented by formula (4) described below or R 131} in the repeating unit represented by formula (4) described below, for example. The amount of the phenolic hydroxyl group is preferably 0.1 to 30 mol/g, and more preferably 1 to 20 mol/g relative to the total mass of the polyimide.

式（4）中，R¹³¹ 表示2價的有機基，R¹³² 表示4價的有機基。 在具有聚合性基之情況下，聚合性基可以位於R¹³¹ 及R¹³² 中的至少一者上，如下述式（4-1）或式（4-2）所示，亦可以位於聚醯亞胺的末端。 [化學式22]

式（4-1）中，R¹³³ 為聚合性基，其他基團與式（4）的含義相同。 [化學式23]

R¹³⁴ 及R¹³⁵ 中的至少一者為聚合性基，在不是聚合性基之情況下為有機基，其他基團與式（4）的含義相同。The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imine ring, but it preferably contains a repeating unit represented by the following formula (4), including the formula ( 4) A compound having a polymerizable group with the repeating unit represented is more preferable. Formula (4) [Chemical Formula 21]

In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group. In the case of having a polymerizable group, the polymerizable group may be located ^{on at least one of R 131} and R ¹³² , as shown in the following formula (4-1) or formula (4-2), or may be located on polyamide The end of the amine. [Chemical formula 22]

In the formula (4-1), R ¹³³ is a polymerizable group, and other groups have the same meaning as in the formula (4). [Chemical formula 23]

At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other groups have the same meaning as in formula (4).

The polymerizable group has the same meaning as the polymerizable group described in the polymerizable group possessed by the polyimide precursor and the like. R ¹³¹ represents a divalent organic group. ^{As a divalent organic group, the same thing as R 111} in Formula (2) can be illustrated, and a preferable range is also the same. Moreover, as R ¹³¹ , the diamine residue remaining after removing the amine group of the diamine can be mentioned. Examples of diamines include aliphatic, cycloaliphatic, or aromatic diamines. As a specific example, an example ^{of R 111} in the formula (2) of the polyimide precursor can be given.

From the viewpoint of more effectively suppressing warpage during calcination, R ¹³¹ is preferably a diamine residue having at least two alkylene glycol units in the main chain. It is more preferable that a total of two or more diamine residues of either or both of ethylene glycol chains and propylene glycol chains are contained in one molecule, and it is still more preferable that the diamine residue does not contain an aromatic ring.

Examples of diamines containing two or more of ethylene glycol chains and propylene glycol chains or both in a molecule include JEFFAMINE (registered trademark) KH-511, ED-600, and ED-900 , ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (the above are trade names, manufactured by HUNTSMAN), 1-(2-(2-(2- Aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2- Amine etc. are not limited to these.

R ¹³² represents a tetravalent organic group. ^{As a tetravalent organic group, the same thing as R 115} in Formula (2) can be illustrated, and a preferable range is also the same. For example, ^{the four bonders of the tetravalent organic group exemplified as R 115} are bonded to the four -C(=O)- moieties in the above formula (4) to form a condensed ring.

In addition, R ¹³² includes the tetracarboxylic acid residue remaining after removing the acid anhydride group from the tetracarboxylic dianhydride. As a specific example, an example ^{of R 115} in the formula (2) of the polyimide precursor can be given. From the viewpoint of the strength of the cured film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferable that at least one of ^{R 131} and R ^{132 has an OH group.} More specifically, as R ¹³¹ , preferred examples include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl) Base) hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, the above (DA- 1) to (DA-18), as R ¹³² , the above-mentioned (DAA-1) to (DAA-5) can be cited as more preferable examples.

式（2-2）中，R¹³¹ 表示2價的有機基，R¹³² 表示4價的有機基，R^X1 及R^X2 分別獨立地表示包含式（1-1）所表示之結構之基團或有機基，R^X1 及R^X2 中的至少一者為包含式（1-1）所表示之結構之基團。 式（2-2）中，R¹³¹ 及R¹³² 分別與式（4）中的R¹³¹ 及R¹³² 的含義相同，較佳態樣亦相同。 式（2-1）中，R^X1 及R^X2 中的至少一者表示包含式（1-1）所表示之結構之基團。 包含上述式（1-1）所表示之結構之基團為上述式（X-1）所表示之基團為較佳。In the case where the polyimide includes the structure represented by the formula (1-1), the structure represented by the formula (1-1) may be located at the end of the polyimide represented by the following formula (2-2). [Chemical formula 24]

In formula (2-2), R ¹³¹ represents a divalent organic group, R ¹³² represents a tetravalent organic group, and R ^X1 and R ^X2 each independently represent a group including the structure represented by formula (1-1) or The organic group, ^{at least one of R X1} and R ^X2 is a group including the structure represented by formula (1-1). In formula (2-2), R ¹³¹ and R ^{132 have the same meanings as R 131} and R ¹³² in formula (4), and preferred aspects are also the same. In formula (2-1), ^{at least one of R X1} and R ^X2 represents a group including the structure represented by formula (1-1). The group containing the structure represented by the above formula (1-1) is preferably the group represented by the above formula (X-1).

In the formula (2-1), one of R ^X1 and R ^X2 may be a group represented by the above formula (R-1).

In addition, when the polyimide includes the structure represented by the formula (1-1), the polyimine may include the structure represented by the above formula (2-1). When the polyimide includes the structure represented by the formula (2-1), ^{at least one of R X1} and R ^X2 in the formula (2-1) may be closed to form an imide ring.

Moreover, it is also preferable that the polyimide has a fluorine atom in the structural unit. The content of the fluorine atom in the polyimide is preferably 10% by mass or more, and preferably 20% by mass or less.

In addition, for the purpose of improving adhesion to the substrate, polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

Furthermore, in order to improve the storage stability of the composition, it is preferable to seal the main chain end of the polyimide with a blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monochloride compound, and a monoactive ester compound. Among these, it is more preferable to use monoamines. Preferred compounds for monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8 -Hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7 -Aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5 -Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4 -Aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-amino Benzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol , 4-Aminothiophenol, etc. Two or more of these can be used, and by reacting a plurality of kinds of end-capping agents, a plurality of different end groups can be introduced.

-Imidation rate (closed loop rate)-From the viewpoint of film strength and insulation of the cured film obtained, the imidization rate of polyimide (also referred to as "closed loop rate") is 70% or more More preferably, more than 80% is more preferable, and more than 90% is more preferable. The upper limit of the above-mentioned imidization rate is not particularly limited, as long as it is 100% or less. The said imidization rate is measured by the following method, for example. The infrared absorption spectrum of the polyimide was measured, and the peak intensity P1 in the vicinity ^{of 1377 cm-1} , which is the absorption peak derived from the imine structure, was determined. Next, after the polyimide was heat-treated at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity P2 in the vicinity of ^{1377 cm -1 was obtained.} Using the obtained peak intensities P1 and P2, the imidization rate of polyimide can be obtained according to the following formula. The imidization rate (%)=(peak intensity P1/peak intensity P2)×100

The polyimide may all contain a ^{repeating structural unit of the above formula (4) containing one kind of R 131} or R ¹³² , or may contain a repeat of the above formula (4) containing two or more different types of R ¹³¹ or R ¹³² unit. In addition, the polyimide may include other types of repeating structural units in addition to the repeating unit of the above formula (4).

Polyimine can be synthesized by, for example, the following method: a method of reacting a tetracarboxylic dianhydride with a diamine compound (a blocking agent that partially replaces a monoamine) at a low temperature; and a method of making a tetracarboxylic acid at a low temperature A method of reacting a dianhydride (a blocking agent that replaces a part of an acid anhydride or a monochloride compound or a monoactive ester compound) with a diamine compound; the diester is obtained by tetracarboxylic dianhydride and alcohol, and then combined with Diamine (a capping agent that replaces a part of monoamine) is reacted in the presence of a condensing agent; the diester is obtained from tetracarboxylic dianhydride and alcohol, and then the remaining dicarboxylic acid is chlorinated , And make it react with diamine (a blocking agent that replaces part of monoamine) to obtain polyimide precursor, and use the known imidization reaction method to make it completely imine Or, stop the imidization reaction in the middle, and introduce a part of the imine structure; and by mixing the fully imidized polymer and the polyimide precursor to introduce a part of the imine Structure method. As commercial products of polyimide, Durimide (registered trademark) 284 (manufactured by FUJIFILM Co., Ltd.) and Matrimide 5218 (manufactured by HUNTSMAN) can be exemplified.

The weight average molecular weight (Mw) of the polyimide can be 4,000 to 100,000, preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain a cured film with excellent mechanical properties, it is particularly preferred that the weight average molecular weight is 20,000 or more. In addition, when two or more types of polyimines are contained, the weight average molecular weight of at least one type of polyimines is preferably within the above-mentioned range.

[Manufacturing methods of polyimide precursors, etc.] The polyimide precursor or the like is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent such as a thiochloride, and then reacting with a diamine.

Moreover, it is also preferable to synthesize using a non-halogen-based catalyst instead of the above-mentioned halogenating agent. As the above-mentioned non-halogen-based catalysts, well-known amination catalysts that do not contain halogen atoms can be used without particular limitation. Examples include boroxine compounds, N-hydroxy compounds, and tertiary amines. , Phosphate esters, amine salts, urea compounds, etc., carbodiimide compounds. Examples of the carbodiimide compound include N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, (2,6-diisopropylphenyl) Carbodiimide and so on.

In the production method of polyimide precursors and the like, it is preferable to use an organic solvent when the reaction is carried out. The organic solvent may be one type or two or more types. The organic solvent can be appropriately specified depending on the raw material, and pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone can be exemplified. Polyimine can be cyclized by thermal imidization, chemical imidization (for example, by using a catalyst to promote the cyclization reaction) after synthesizing the polyimine precursor. For manufacturing, polyimide can also be synthesized directly.

-Capping agent- In the production method of polyimide precursors, etc., in order to further improve storage stability, the ends of polyimide precursors, etc. are sealed with end-capping agents such as acid anhydrides, monocarboxylic acids, monochloride compounds, and monoactive ester compounds. For better. As a blocking agent, it is more preferable to use a monoamine. As a preferable compound of a monoamine, aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8- Hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7- Aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5- Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4- Aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzene Sulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and so on. Two or more of these can be used, and by reacting a plurality of kinds of end-capping agents, a plurality of different end groups can be introduced.

-Solid precipitation- When producing polyimide precursors, etc., a step of precipitating solids may be included. Specifically, by precipitating the polyimide precursor in the reaction liquid in water, and dissolving it in a soluble solvent such as the polyimide precursor such as tetrahydrofuran, the solid can be precipitated. Then, by drying the polyimide precursor and the like, a powdery polyimide precursor and the like can be obtained.

-Introduction of the structure represented by formula (1-1)- When the specific resin contains the structure represented by formula (1-1), the above-mentioned specific resin is synthesized, for example, by the method described in (1) or (2) below. (1) The carbodiimide compound is used as a non-halogen-based catalyst in the above-mentioned method for producing a polyimide precursor, and the reaction time, reaction temperature, and timing of adding the carbodiimide compound are appropriately adjusted. (2) The polyimide precursor or the polyimine and the carbodiimide compound obtained by the above-mentioned production method of the polyimide precursor are reacted in a solvent. As a specific example of these methods, the method described in the synthesis example mentioned later can be mentioned, but it is not limited to these.

〔content〕 The content of the specific resin in the composition of the present invention relative to the total solid content of the composition is preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, and 50% by mass or more Further better. Furthermore, the content of the resin in the composition of the present invention relative to the total solid content of the composition is preferably 99.5% by mass or less, more preferably 99% by mass or less, more preferably 98% by mass or less, and 97% by mass or less To be more preferable, 95% by mass or less is still more preferable. The resin composition of the present invention may include only one type of specific resin, or may include two or more types. When two or more are contained, it is preferable that the total amount falls within the above-mentioned range.

＜Specific compounds＞ The resin composition of the present invention is preferably a compound containing the structure represented by the above formula (1-1) and containing a compound (specific compound) different from the above resin.

The specific compound includes the structure represented by the formula (1-1), and other than this, it is not particularly limited, but a low-molecular compound is preferred. Specifically, the molecular weight of the specific compound is preferably from 75 to 1,000, more preferably from 100 to 800, and even more preferably from 150 to 500.

式（3-1）中，R¹ 及R² 分別獨立地表示脂肪族基或芳香族基，上述脂肪族基或芳香族基的碳原子或烴基可以經雜原子取代，X¹ 表示氧原子或硫原子，L¹ 表示-C（=O）-或-S（=O）₂ -，R³ 表示氫原子或1價的有機基，R⁴ 表示1價的有機基，R¹ 、R² 、R³ 及R⁴ 中的至少2個可以鍵結而形成環結構。The specific compound is preferably a compound represented by the following formula (3-1). [Chemical formula 25]

In formula (3-1), R ¹ and R ² each independently represent an aliphatic group or an aromatic group. The carbon atom or hydrocarbon group of the aliphatic group or aromatic group may be substituted by a heteroatom, and X ¹ represents an oxygen atom or Sulfur atom, L ¹ represents -C(=O)- or -S(=O) ₂ -, R ³ represents a hydrogen atom or a monovalent organic group, R ⁴ represents a monovalent organic group, R ¹ , R ² , At least two of R ³ and R ⁴ may be bonded to form a ring structure.

In formula (3-1), R ¹ , R ² , X ¹ and L ^{1 have the same meanings as R 1} , R ² , X ¹ and L ¹ in formula (1-1), and preferred aspects are also the same . In formula (3-2), R ^{3 has the same meaning as R 23} in formula (1-2), and preferred aspects are also the same.

In the formula (3-1), R ⁴ is a monovalent organic group, and a hydrocarbon group is preferred. As the above-mentioned hydrocarbon group, an aliphatic hydrocarbon group or an aromatic hydrocarbon group is preferable, and an aromatic hydrocarbon group is more preferable. As the aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable, and a saturated aliphatic hydrocarbon group having 3 to 10 carbon atoms is more preferable. As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, a phenyl group or a naphthyl group is more preferable, and a phenyl group is still more preferable. The ^{monovalent organic group in R 4} may have a substituent, and examples of the substituent include an alkyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. Among these, as R ⁴ , a phenyl group, an alkylphenyl group, or an alkoxycarbonylphenyl group is preferable, and the phenyl group, a tertiary butylphenyl group, or an alkyl group having 1 to 4 carbon atoms Phenyl is further preferred.

In formula (3-1), ^{at least two of R 1} , R ² , R ³ and R ⁴ may be bonded to form a ring structure. Examples of the ring structure formed include a hydantoin ring, an N-amidazolidone ring, and the like, but are not limited to these. Furthermore, in the present invention, the ^{aspect in which any one of R 1} , R ² , R ³ and R ⁴ does not form a ring structure is also one of the preferred aspects.

[化學式27]

Specific examples of preferred aspects of specific compounds are given below, but the present invention is not limited to these. [Chemical formula 26]

[Chemical formula 27]

When the resin composition contains a specific compound, its content is not particularly limited, as long as the molar content of the structure represented by formula (1-1) relative to the total solid content of the resin composition is appropriately adjusted to the above The amount within the range is sufficient. In addition, when the resin composition contains a specific compound, the content thereof is preferably 0.01 to 1.0% by mass relative to the total solid content of the resin composition of the present invention, more preferably 0.01 to 0.85% by mass, and 0.015 to 0.75. The mass% is more preferable. The specific compound may be used singly, but two or more types may also be used. In the case of using two or more types at the same time, it is preferable that the total amount thereof falls within the above-mentioned range.

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

As esters, preferred ones include, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (for example, alkoxyacetic acid Methyl methoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxy Ethyl acetate, etc.)), 3-alkoxypropionic acid alkyl esters (for example, 3-alkoxypropionic acid methyl ester, 3-alkoxypropionic acid ethyl ester, etc. (for example, 3-methoxypropionate Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionic acid alkyl esters (for example , 2-alkoxy methyl propionate, 2-alkoxy ethyl propionate, 2-alkoxy propyl propionate, etc. (for example, 2-methoxy propionic acid methyl ester, 2-methoxy propionate Ethyl ester, 2-methoxypropionate, 2-ethoxypropionate, 2-ethoxypropionate)), 2-alkoxy-2-methylpropionate And ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl caproate, Ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

As the ethers, preferred ones include, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl siloxol acetate, ethyl siloxol ethyl Ester, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol mono Butyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, etc.

As the ketones, preferred examples include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-methylcyclohexanone, levoglucan, and dihydrolevoglucan. 3-heptanone and so on.

Preferred examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

As the sulfenite, a preferable one is, for example, dimethyl sulfenite.

As the amides, preferred ones include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-di Methylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide Amine, N-formylmorpholine, N-acetylmorpholine, etc.

As the ureas, preferable ones 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-methoxy 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 phenyl methanol, n-pentanol, methyl pentanol and Diacetone alcohol and so on.

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

In the present invention, it is selected from the group consisting of 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethyl cyrus acetoacetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate Ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfene, ethyl carbitol acetate, butyl carbitol One solvent of alcohol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or a mixed solvent composed of two or more types is preferred. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone at the same time. In addition, N-methyl-2-pyrrolidone and ethyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, cyclopentanone and γ-butyrolactone The combination is also preferable.

From the viewpoint of coatability, the content of the solvent is preferably such that 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 The amount is more preferably from 5 to 75% by mass, and the total solid content concentration of the resin composition of the present invention is more preferably from 10 to 70% by mass, and it is set as the total solid content concentration of the resin composition of the present invention It is more preferable to be 40 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating film and the coating method.

The solvent may contain only one type or two or more types. When two or more kinds of solvents are contained, the total of them is preferably within the above-mentioned range.

＜Other resins＞ In addition to the above-mentioned specific resin, the composition of the present invention may also contain another resin different from the specific resin (hereinafter, also referred to simply as "other resin"). Examples of other resins include polyamide imide, polyamide imide precursors, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing silicone structures, acrylic resins, etc. . For example, by further adding an acrylic resin, a composition having excellent coatability can be obtained, and a cured film having excellent solvent resistance can be obtained. For example, instead of or in addition to the polymerizable compound described below, an acrylic resin with a high polymerizable base value having a weight average molecular weight of 20,000 or less is added to the composition to improve the coating properties of the composition. Solvent resistance of the cured film, etc.

When the composition of the present invention contains other resins, the content of the other resin relative to the total solid content of the composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and more preferably 1% by mass or more , 2% by mass or more is more preferable, 5% by mass or more is still more preferable, and 10% by mass or more is still more preferable. In addition, the content of other resins in the composition of the present invention is preferably 80% by mass or less relative to the total solid content of the composition, more preferably 75% by mass or less, more preferably 70% by mass or less, and 60% by mass The following is more preferable, and 50% by mass or less is even more preferable. In addition, as a preferable aspect of the composition of the present invention, the content of other resins can also be a low content aspect. In the above aspect, the content of other resins relative to the total solid content of the composition is preferably 20% by mass or less, more preferably 15% by mass or less, more preferably 10% by mass or less, and furthermore, 5% by mass or less. Preferably, 1% by mass or less is more preferable. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more. The composition of the present invention may contain only one kind of other resin, or may contain two or more kinds. When two or more are contained, it is preferable that the total amount falls within the above-mentioned range.

＜Polymerization initiator＞ The resin composition of the present invention preferably contains a polymerization initiator. As the polymerization initiator, a photopolymerization initiator is preferred.

〔Photopolymerization initiator〕 The resin composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. The radical photopolymerization initiator is not particularly limited, and it can be appropriately selected from known radical photopolymerization initiators. For example, a radical photopolymerization initiator having sensitivity to light from the ultraviolet region to the visible region is preferred. In addition, it can also be an active agent that generates active free radicals by having a certain effect with a sensitizer excited by light.

The photoradical 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 range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured using a known method. For example, by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian), it is preferable to use an ethyl acetate solvent to measure at a concentration of 0.01 g/L.

As the photoradical polymerization initiator, any known compound can be used arbitrarily. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazole skeleton, compounds having a diazole skeleton, compounds having a trihalomethyl group, etc.), phosphonium phosphine compounds such as oxyphosphine oxide, hexaaryl Oxime compounds such as biimidazole and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, and azide compounds , Metallocene compounds, organoboron compounds, iron arene complexes, etc. For the details, refer to the descriptions in paragraphs 0165 to 0182 of JP 2016-027357 A, and paragraphs 0138 to 0151 of International Publication No. 2015/199219, which are incorporated into this specification.

As the ketone compound, for example, the compound described in paragraph 0087 of JP 2015-087611 A can be exemplified, and this content is incorporated in this specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

In one aspect of the present invention, as the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and phosphine compounds can be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969 and the phosphonium oxide-based initiator described in Japanese Patent No. 4225898 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (brand names: all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, IRGACURE 907, IRGACURE 369, and IRGACURE 379 (brand names: all manufactured by BASF Corporation), which are commercially available products, can be used.

As the aminoacetophenone-based initiator, the compound described in Japanese Patent Application Laid-Open No. 2009-191179 whose absorption maximum wavelength matches with a wavelength light source such as 365 nm or 405 nm can also be used.

Examples of the phosphine-based initiator include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. In addition, IRGACURE-819 or IRGACURE-TPO (brand name: both manufactured by BASF Corporation), which are commercially available products, can be used.

As the metallocene compound, IRGACURE-784 (manufactured by BASF Corporation) and the like can be exemplified.

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

As specific examples of the oxime compound, the compounds described in Japanese Patent Application Publication No. 2001-233842, the compounds described in Japanese Patent Application Publication No. 2000-080068, and the compounds described in Japanese Patent Application Publication No. 2006-342166 can be used. .

As a preferable oxime compound, for example, a compound having the following structure or 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-Propyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1- Ketone, 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one and the like. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group >C=N-O-C(=O)- in the molecule.

[Chemical formula 28]

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are made by BASF Corporation), Adeka Optomer N-1919 (made by ADEKA CORPORATION, Japan Special Publication 2012- The photo-radical polymerization initiator described in 014052 No. 2). In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. In addition, DFI-091 (manufactured by Daito Chemix Corporation) can be used. Moreover, the oxime compound of the following structure can also be used. [Chemical formula 29]

As the photopolymerization initiator, an oxime compound having a sulphur ring can also be used. Specific examples of the oxime compound having a sulphur ring include the compound described in JP 2014-137466 A and the compound described in Japanese Patent No. 06636081.

As the photopolymerization initiator, an oxime compound in which at least one benzene ring having a carbazole ring becomes the skeleton of a naphthalene ring can also be used. As a specific example of such an oxime compound, the compound described in International Publication No. 2013/083505 can be cited.

Furthermore, an oxime compound having a fluorine atom can also be used. Specific examples of such oxime compounds include the compounds described in Japanese Patent Application Publication No. 2010-262028, the compounds described in paragraph 0345 of Japanese Patent Application Publication No. 2014-500852, and Japanese Patent Application Publication No. 2014-500852. The compound (C-3) and the like described in paragraph 0101 of the Publication No. 2013-164471.

As the optimal oxime compound, the oxime compound having a specific substituent shown in JP 2007-269779 A, or the oxime compound having a thioaryl group shown in JP 2009-191061, etc. can be mentioned.

From the viewpoint of exposure sensitivity, the photo-radical polymerization initiator is selected from the group consisting of trihalomethyl triketal compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene- The present-iron complexes and their salts, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds are preferably compounds in the group.

Further preferred photo-radical polymerization initiators are trihalomethyl tri-ketone compounds, α-amino ketone compounds, phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, Onium salt compounds, benzophenone compounds, and acetophenone compounds, selected from the group consisting of trihalomethyltriketone compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds At least one compound in the group is more preferable, a metallocene compound or an oxime compound is more preferable, and an oxime compound is still more preferable.

In addition, the photoradical polymerization initiator can also use N,N'- such as benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michelone), etc. Tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methanone 1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1 and other aromatic ketones, alkylanthraquinones and other quinones condensed with aromatic rings, benzoin alkyl ethers Benzoin ether compounds, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyl dimethyl ketal. Moreover, the compound represented by following formula (I) can also be used.

[Chemical formula 30]

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

[Chemical formula 31]

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

In addition, the photoradical polymerization initiator can also use the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469.

When the photopolymerization initiator is contained, its content is preferably 0.1-30% by mass relative to the total solid content of the resin composition of the present invention, more preferably 0.1-20% by mass, and still more preferably 0.5- 15% by mass, more preferably 1.0 to 10% by mass. The photopolymerization initiator may contain only one type, or two or more types. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above-mentioned range.

〔Thermal polymerization initiator〕 The resin composition of the present invention may include a thermal polymerization initiator as a polymerization initiator, and may particularly include a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates free radicals by heat energy to initiate or promote the polymerization reaction of the polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the specific resin and the polymerizable compound can also proceed in the heating step described later, and therefore the chemical resistance can be further improved.

Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A.

When the thermal polymerization initiator is contained, its content is preferably 0.1-30% by mass relative to the total solid content of the resin composition of the present invention, more preferably 0.1-20% by mass, and still more preferably 5-5%. 15% by mass. The thermal polymerization initiator may contain only one kind or two or more kinds. When two or more types of thermal polymerization initiators are contained, the total amount is preferably within the above-mentioned range.

〔Photoacid generator〕 In addition, the composition of the present invention may contain a photoacid generator. By containing the photoacid generator, for example, acid is generated in the exposed part of the composition layer, and the solubility of the exposed part to the developer (for example, an aqueous alkali solution) is increased, and a positive pattern in which the exposed part is removed by the developer can be obtained. In addition, it can also be set as a form in which the composition contains a photoacid generator and a polymerizable compound other than the radical polymerizable compound described later, for example, the acid generated in the exposed portion is used to promote the crosslinking of the polymerizable compound. The reaction makes the exposed part less likely to be removed by the developer than the non-exposed part. According to this aspect, a negative pattern can be obtained.

The photoacid generator is not particularly limited as long as it generates acid by exposure, and examples include onium salt compounds such as quinonediazide compounds, diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts, and imines. Sulfonate compounds such as sulfonate, oxime sulfonate, diazo disulfide, disulfide, o-nitrobenzyl sulfonate, etc.

As the quinonediazide compound, a sulfonic acid in which quinonediazide is bonded to a polyhydroxy compound via an ester, and a sulfonic acid in which a quinonediazide is bonded to a polyamine compound via a sulfonamide can be mentioned. An acid, a sulfonic acid in which a quinonediazide is bonded to a polyhydroxy polyamine compound via at least one of an ester bond and a sulfonamide bond, and the like. In the present invention, for example, it is preferable that 50 mol% or more of the entire functional group of the polyhydroxy compound or polyamine compound is substituted with a quinonediazide group.

In the present invention, the quinone diazide can preferably use any of 5-naphthoquinone diazide sulfonyl and 4-naphthoquinone diazide sulfonyl. The 4-naphthoquinone diazide sulfonate compound has absorption in the i-ray region of the mercury lamp and is suitable for i-ray exposure. The absorption of the 5-naphthoquinone diazide sulfonate compound extends to the g-ray region of the mercury lamp, which is suitable for g-ray exposure. In the present invention, it is preferable to select the 4-naphthoquinone diazide sulfonate compound and the 5-naphthoquinone diazide sulfonate compound according to the exposure wavelength. In addition, it may contain a naphthoquinone diazide sulfonyl ester compound having 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group in the same molecule, or 4-naphthoquinone diazide sulfonyl ester compound Azosulfonate compound and 5-naphthoquinone diazide sulfonate compound.

The above-mentioned naphthoquinonediazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinonediazide sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide compounds, the resolution, sensitivity, and residual film rate are further improved. As the above-mentioned naphthoquinone diazide compound, for example, 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid, the And other compounds such as salts or ester compounds.

As the onium salt compound or the sulfonate compound, the compounds described in paragraphs 0064 to 0122 of JP 2008-013646 A, etc. can be cited.

It is also preferable that the photoacid generator is 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), the following formula (OS-103), formula (OS-104) or formula (OS-105) The oxime sulfonate compound represented is preferred.

[Chemical formula 32]

In the formula (OS-1), X ³ represents an alkyl group, an alkoxy group, or a halogen atom. When there are a plurality of X ³ , they may be the same or different. The alkyl group and alkoxy group in the above X ^{3 may have a substituent.} As the X in the alkyl group, C 1-4 straight chain or branched chain alkyl group having ³¹ to 4 is preferred. As ^{the alkoxy group in X 3} , a linear or branched alkoxy group having 1 to 4 carbon atoms is preferred. As the halogen atom in the above X ³ , a chlorine atom or a fluorine atom is preferable. In the formula (OS-1), m3 represents an integer of 0 to 3, and 0 or 1 is preferred. When m3 is 2 or 3, a plurality of X ³ may be the same or different. In the formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbons, an alkoxy group having 1 to 10 carbons, a halogenated alkyl group having 1 to 5 carbons, and a carbon number of 1 to The halogenated alkoxy group of 5, the phenyl group which may be substituted by W, the naphthyl group which may be substituted by W, or the anthryl group which may be substituted by W is preferable. W represents halogen atom, cyano group, nitro group, C1-C10 alkyl group, C1-C10 alkoxy group, C1-C5 halogenated alkyl group or C1-C5 halogenated alkoxy group , C6-C20 aryl group, C6-C20 halogenated aryl group.

In the formula (OS-1), m3 is 3, X ³ is a methyl group, ^{the substitution position of X 3} is an ortho position, R ³⁴ is a linear alkyl group having 1 to 10 carbons, and 7,7-dimethyl- Compounds of 2-oxonorkanylmethyl or p-tolyl are particularly preferred.

As specific examples of the oxime sulfonate compound represented by the formula (OS-1), Paragraph Nos. 0064 to 0068 of JP 2011-209692 A and Paragraph Nos. 0158 to 0158 of JP 2015-194674 A can be exemplified. The following compounds described in 0167 are incorporated in this specification.

[Chemical formula 33]

In formulas (OS-103) to (OS-105), R ^s1 represents an alkyl group, an aryl group or a heteroaryl group, and sometimes there are plural R ^s2 each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen Atom, sometimes a plurality of R ^s6 each independently represents a halogen atom, alkyl group, alkoxy group, sulfonic acid group, aminosulfonyl group or alkoxysulfonyl group, Xs represents O or S, ns represents 1 Or 2, ms represents an integer of 0-6. In formulas (OS-103) to (OS-105), ^{the alkyl group represented by R s1} (the carbon number is preferably 1 to 30), the aryl group (the carbon number is preferably 6 to 30), or the heteroaryl group ( (4 to 30 carbon atoms are preferred) may have a substituent T.

In formulas (OS-103) to (OS-105), R ^s2 is preferably a hydrogen atom, an alkyl group (preferably with a carbon number of 1 to 12) or an aryl group (preferably with a carbon number of 6 to 30), A hydrogen atom or an alkyl group is more preferable. In the compound sometimes there are more than two R ^s2 , one or two is preferably an alkyl group, an aryl group or a halogen atom, one is an alkyl group, an aryl group or a halogen atom is more preferred, and one is The alkyl group and the rest are hydrogen atoms are particularly preferred. The alkyl group or aryl group represented by R ^{s2 may have a substituent T.} In formula (OS-103), formula (OS-104) or formula (OS-105), Xs represents O or S, and O is preferred. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.

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

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), and the above formula (OS-104) The compound represented by) is particularly preferably represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is represented by the following formula (OS-108) or formula (OS-109) The compound shown is particularly good. [Chemical formula 34]

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 and an alkane with 1 to 8 carbon atoms. Group, halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl or chlorophenyl, R ^t9 represents a hydrogen atom, halogen atom, methyl or methoxy group, R ^t2 represents hydrogen Atom or methyl. In formulas (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, and a hydrogen atom is preferred.

In formulas (OS-106) to (OS-111), R ^t8 represents a hydrogen atom, a C 1-8 alkyl group, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group , Phenyl or chlorophenyl, preferably C1-C8 alkyl group, halogen atom or phenyl group, C1-C8 alkyl group is more preferable, C1-C6 alkyl group is more preferable , Methyl is particularly preferred.

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 preferred. R ^t2 represents a hydrogen atom or a methyl group, and a hydrogen atom is preferred. In addition, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z) of the oxime may be any one of them, or a mixture. As specific examples of the oxime sulfonate compound represented by the above formula (OS-103) to formula (OS-105), paragraph numbers 0088 to 0095 of Japanese Patent Application Publication No. 2011-209692 and Japanese Patent Application Publication No. 2015- The compounds described in paragraph numbers 0168 to 0194 of 194674 are incorporated in this specification.

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

[Chemical formula 35]

In the 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 carbamethan group, a sulfamoyl group, a sulfo group , Cyano, aryl or heteroaryl. The aspect in which R ^u9 is a cyano group or an aryl group is more preferable, and the aspect in which R ^u9 is a cyano group, a phenyl group, or a naphthyl group is even more preferable. In formula (OS-101) or formula (OS-102), ^Ru2a 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- , ^Ru5 to ^Ru7 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 alkylcarbonyl group , Arylcarbonyl, amide, sulfo, cyano or aryl. Two of R ^u1 to R ^u4 may be bonded to each other to form a ring, respectively. In this case, 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 preferred, and ^{it is also preferred that at least two of R u1} to R ^u4 are bonded to each other to form an aryl group. Wherein, R ^u1 ~ R ^u4 are hydrogen atoms are preferred aspect. Each of the above-mentioned substituents may further have a substituent.

除此以外，作為光酸產生劑，亦可以使用市售品。作為市售品，可以舉出WPAG-145、WPAG-149、WPAG-170、WPAG-199、WPAG-336、WPAG-367、WPAG-370、WPAG-443、WPAG-469、WPAG-638、WPAG-699（均為FUJIFILM Wako Pure Chemical Corporation製造）、Omnicat 250、Omnicat 270（均為IGM Resins B.V.公司製造）、Irgacure 250、Irgacure 270、Irgacure 290（均為BASF公司製造）、MBZ-101（Midori Kagaku Co.,Ltd.製造）等。It is more preferable that the compound represented by the above formula (OS-101) is the compound represented by the formula (OS-102). In addition, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z, etc.) of the oxime or benzothiazole ring may be any one of them, or may be a mixture. As specific examples of the compound represented by the formula (OS-101), the paragraphs 0102 to 0106 of JP 2011-209692 and the paragraphs 0195 to 0207 of JP 2015-194674 can be exemplified. The contents of these compounds are included in this specification. Among the above compounds, b-9, b-16, b-31, and b-33 are preferred. [Chemical formula 36]

In addition, as a photoacid generator, a commercially available product can also be used. As commercially available products, WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-443, WPAG-469, WPAG-638, WPAG- 699 (all made by FUJIFILM Wako Pure Chemical Corporation), Omnicat 250, Omnicat 270 (all made by IGM Resins BV), Irgacure 250, Irgacure 270, Irgacure 290 (all made by BASF), MBZ-101 (Midori Kagaku Co.) .,Ltd.) etc.

Moreover, as a preferable example, the compound represented by the following structural formula can also be mentioned. [Chemical formula 37]

As a photoacid generator, organic halogenated compounds can also be applied. Specific examples of the organic halogenated compound include "Bull Chem. Soc Japan" 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-004605, Japanese Patent Application Publication No. 48-036281, etc. No. 55-032070, Japanese Special Publication No. 55-032070, Japanese Special Publication No. 60-239736, Japanese Special Publication No. 61-169835, Japanese Special Publication No. 61-169837, Japanese Special Publication No. 62-058241, Japanese Special Publication The compounds described in Sho 62-212401, JP Sho 63-070243, JP Sho 63-298339, MP Hutt "Jurnal of Heterocyclic Chemistry" 1 (No 3), (1970), etc., in particular, include The azole compound substituted with trihalomethyl: S-tri 𠯤 compound. More preferably, at least one mono-, di-, or tri-halogen substituted methyl group is bonded to an s-tricyclic ring to form an s-tris derivative. Specifically, for example, 2, 4, 6 -Tris(monochloromethyl)-s-tris, 2,4,6-tris(dichloromethyl)-s-tris, 2,4,6-tris(trichloromethyl)-s-tris 𠯤, 2-methyl-4,6-bis(trichloromethyl)-s-tris, 2-n-propyl-4,6-bis(trichloromethyl)-s-tris, 2-( α,α,β-Trichloroethyl)-4,6-bis(trichloromethyl)-s-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(trichloro Methyl)-s-tris, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-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-tris, 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl) Group)-s-tris, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-tris, 2-(4-naphthyloxynaphthyl)-4,6-bis (Trichloromethyl)-s-tris, 2-phenylthio-4,6-bis(trichloromethyl)-s-tris, 2-benzylthio-4,6-bis(trichloromethyl) Group)-s-tris, 2,4,6-tris(dibromomethyl)-s-tris, 2,4,6-tris(tribromomethyl)-s-tris, 2-methyl -4,6-bis(tribromomethyl)-s-tris, 2-methoxy-4,6-bis(tribromomethyl)-s-tris, etc.

As a photoacid generator, an organic borate compound can also be applied. As the organoborate compound, specific examples include, for example, JP-A 62-143044, JP-A 62-150242, JP-A 9-188685, JP-A 9-188686, and JP-A. 9-188710, Japanese Patent Publication 2000-131837, Japanese Patent Publication 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc. and Kunz, Martin "Rad Tech'98. Proceeding April 19-22 , 1998, "Chicago", etc., the organoborate compound described in Japanese Patent Laid-Open No. 6-157623, Japanese Patent Laid-Open No. 6-175564, and Japanese Patent Laid-Open No. 6-175561 Or organoboron oxo-aluminium complexes, the organoboron complexes described in Japanese Patent Laid-Open No. 6-175554, Japanese Patent Laid-Open No. 6-175553, and those described in Japanese Patent Laid-Open No. 9-188710 Organoboron phosphonium complexes, Japanese Patent Application Publication No. 6-348011, Japanese Patent Application Publication No. 7-128785, Japanese Patent Application Publication No. 7-140589, Japanese Patent Application Publication No. 7-306527, Japanese Patent Application Publication No. 7-292014 Bulletin and other organoboron transition metal coordination complexes, etc.

As the photoacid generator, disulfite compounds can also be applied. Examples of the dioxin compounds include the compounds described in Japanese Patent Application Publication No. 61-166544, Japanese Patent Application 2001-132318, and the like, and diazo disulfide compounds.

Examples of the onium salt compound include the diazonium salt described in SI Schlesinger, Photogr. Sci. Eng., 18,387 (1974), TSBal et al, Polymer, 21,423 (1980), and US Patent No. 4,069,055 The ammonium salt described in the specification, Japanese Patent Laid-Open No. 4-365049, etc., the phosphonium salt described in each specification of U.S. Patent No. 4,069,055 and U.S. Patent No. 4,069,056, European Patent No. 104,143, and U.S. Patent No. 339,049 , The specifications of U.S. Patent No. 410,201, 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, European Patent No. 297,443, European Patent No. 297,442, U.S. Patent No. 4,933,377, U.S. Patent No. 161,811, U.S. Patent No. 410,201, U.S. Patent No. 339,049, U.S. Patent No. 4,760,013, U.S. Patent No. 4,734,444, U.S. Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, German Patent No. 3,604,581 described in each specification, JVCrivello et al, Macromolecules, 10(6), 1307 (1977), JVCrivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979) selenium salt, CSWen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988 ) Onium salts such as arsenic salts and pyridinium salts described in.

式（RI-I）中，Ar₁₁ 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1～12的烯基、碳數1～12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的烷基胺基、碳數1～12的二烷基胺基、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。Z₁₁ ^- 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，從穩定性的方面考慮，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，Ar₂₁ 、Ar₂₂ 各自獨立地表示可以具有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1～12的烯基、碳數1～12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的烷基胺基、碳數1～12的二烷基胺基、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、反應性的方面考慮，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，R₃₁ 、R₃₂ 、R₃₃ 各自獨立地表示可以具有1～6個取代基之碳數20以下的芳基或烷基、烯基、炔基，較佳地，從反應性、穩定性的方面考慮，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1～12的烯基、碳數1～12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的烷基胺基、碳數1～12的二烷基胺基、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。Z₃₁ ^- 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、反應性的方面考慮，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 onium salts include onium salts represented by the following general formulas (RI-I) to (RI-III). [Chemical formula 38]

In the formula (RI-I), Ar ₁₁ represents an aryl group with a carbon number of 20 or less that may have 1 to 6 substituents. Preferred substituents include alkyl groups with 1 to 12 carbons and 1 carbon atoms. ~12 alkenyl, carbon 1-12 alkynyl, carbon 1-12 aryl, carbon 1-12 alkoxy, carbon 1-12 aryloxy, halogen atom, carbon 1 -12 alkylamino groups, dialkylamino groups with 1-12 carbons, alkylamino or arylamino groups with 1-12 carbons, carbonyl, carboxyl, cyano, sulfonyl, carbon A thioalkyl group having 1 to 12, and a thioaryl group having 1 to 12 carbons. Z ₁₁ ^- represents a monovalent anion, which is halide ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfuric acid ion, from stable In terms of performance, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, and sulfinic acid ion are preferred. In the formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group with a carbon number of 20 or less that may have 1 to 6 substituents. As a preferred substituent, one with 1 to 12 carbons may be mentioned. Alkyl groups, alkenyl groups having 1 to 12 carbons, alkynyl groups having 1 to 12 carbons, aryl groups having 1 to 12 carbons, alkoxy groups having 1 to 12 carbons, aryloxy groups having 1 to 12 carbons, Halogen atom, C1-C12 alkylamino group, C1-C12 dialkylamino group, C1-C12 alkylamino or arylamino group, carbonyl group, carboxyl group, cyano group , Sulfonyl, thioalkyl having 1 to 12 carbons, and thioaryl having 1 to 12 carbons. Z ₂₁ ^- represents a monovalent anion, which is halide ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfate ion, which is stable In terms of performance and reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, and carboxylic acid ion are preferred. In the 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, which may have 1 to 6 substituents and a carbon number of 20 or less, preferably, From the viewpoint of reactivity and stability, an aryl group is preferred. Preferred substituents include alkyl groups having 1 to 12 carbons, alkenyl groups having 1 to 12 carbons, alkynyl groups having 1 to 12 carbons, aryl groups having 1 to 12 carbons, and aryl groups having 1 to 12 carbons. 12 alkoxy, C 1-12 aryloxy, halogen atom, C 1-12 alkylamino group, C 1-12 dialkylamino group, C 1-12 alkyl group Amido or arylamido, carbonyl, carboxy, cyano, sulfonyl, thioalkyl having 1 to 12 carbons, and thioaryl having 1 to 12 carbons. Z ₃₁ ^- represents a monovalent anion, which is halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfuric acid ion, from stable In terms of performance and reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, and carboxylic acid ion are preferred.

[化學式40]

[化學式41]

[化學式42]

As a specific example, the following can be mentioned. [Chemical formula 39]

[Chemical formula 40]

[Chemical formula 41]

[Chemical formula 42]

In the case of containing the photoacid generator, its content is preferably 0.1-30% by mass relative to the total solid content of the composition of the present invention, more preferably 0.1-20% by mass, and more preferably 2-15% by mass. good. The photoacid generator may contain only one type or two or more types. When two or more kinds of photoacid generators are contained, the total amount is preferably within the above-mentioned range.

＜Hot acid generator＞ The composition of the present invention may contain a thermal acid generator. The thermal acid generator has the following effect: generating acid by heating promotes a compound selected from the group consisting of hydroxymethyl, alkoxymethyl, or oxymethyl, epoxy compounds, oxetane compounds, and benzos Crosslinking reaction of at least one of the compounds.

The thermal decomposition start 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 70-140°C), acid will not be generated, and the subsequent exposure and development will be patterned and then the final heating (curing: about 100 (~400°C), as a thermal acid generator, the one that generates acid at the time of development is preferable because it can suppress the decrease in sensitivity during development. Regarding the thermal decomposition start temperature, when the thermal acid generator is heated to 500°C at 5°C/min in a pressure-resistant capsule, it is determined as the peak temperature of the heat generation peak with the lowest temperature. As a device used when measuring the start temperature of thermal decomposition, Q2000 (manufactured by TA Instruments) and the like can be cited.

The acid generated from the thermal acid generator is preferably a strong acid, such as aryl sulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid, alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid, or trifluoromethane Halogenated alkyl sulfonic acids such as sulfonic acid and the like are preferred. As an example of such a thermal acid generator, the one described in paragraph 0055 of JP 2013-072935 A can be cited.

Among them, from the viewpoint that there is little residue in the cured film and it is difficult to reduce the physical properties of the cured film, it is more preferable to produce alkyl sulfonic acid with 1 to 4 carbons or haloalkyl sulfonic acid with 1 to 4 carbons, and methanesulfonic acid (4-Hydroxyphenyl) dimethyl sulfonium, methanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl) dimethyl sulfonium, benzyl methanesulfonate (4-hydroxyphenyl) methyl Alumium, benzyl methanesulfonate (4-((methoxycarbonyl)oxy)phenyl) methyl alumite, methanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl ) Alumite, trifluoromethanesulfonic acid (4-hydroxyphenyl) dimethyl alumite, trifluoromethanesulfonic acid (4-((methoxycarbonyl)oxy) phenyl) dimethyl alumite, trifluoromethanesulfonate Acid benzyl (4-hydroxyphenyl) methyl alumite, trifluoromethanesulfonic acid benzyl (4-((methoxycarbonyl)oxy) phenyl) methyl alumite, trifluoromethanesulfonic acid (4-hydroxyl Phenyl)methyl((2-methylphenyl)methyl)aluminium, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-ylidene) -2-(o-tolyl)propionitrile and 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane are preferred as the thermal acid generator.

In addition, the compound described in paragraph 0059 of JP 2013-167742 A is also preferable as a thermal acid generator.

The content of the thermal acid generator is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the specific resin, and more preferably 0.1 parts by mass or more. By containing 0.01 parts by mass or more to promote the crosslinking reaction, the mechanical properties and solvent resistance of the cured film can be further improved. Moreover, from the viewpoint of the electrical insulation of the cured 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 more preferable.

＜Onium salt＞ The resin composition of the present invention may further include an onium salt. In particular, when the resin composition of the present invention contains a polyimide precursor as the specific resin, it is preferable to contain an onium salt. There are no particular restrictions on the type of onium salt, and preferably ammonium salt, imino (Iminium) salt, sulfonium salt, phosphonium salt, or phosphonium salt. Among these, from the viewpoint of high thermal stability, an ammonium salt or an iminium salt is preferable, and from the viewpoint of compatibility with the polymer, a sulfonium salt, an phosphonium salt, or a phosphonium salt is preferable.

In addition, the onium salt is a salt of a cation and an anion having an onium structure, and the above-mentioned cation and anion may or may not be bonded via a covalent bond. That is, the onium salt may be an intramolecular salt having a cation part and an anion part in the same molecular structure, or may be an intermolecular salt formed by ionic bonding of cationic molecules and anionic molecules of different molecules, but intermolecular Salt is preferred. In addition, in the resin composition of the present invention, the cation part or cation molecule and the anion part or anion molecule may be bonded by an ionic bond or may be dissociated. As the cation in the onium salt, an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferred, and at least one cation selected from the group consisting of tetraalkylammonium cations, sulfonium cations and phosphonium cations is more preferred. good.

The onium salt used in the present invention may be a thermal base generator described later. The thermal base generator refers to a compound that generates a base by heating, and for example, a compound that generates a base when heated to 40° C. or higher can be mentioned. Examples of the onium salt include the onium salt described in paragraphs 0122 to 0138 of International Publication No. 2018/043262. Moreover, in addition to this, onium salts used in the field of polyimide precursors can be used without particular limitations.

When the resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, more preferably 0.85% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and may be 5% by mass or less, or may be 4% by mass or less. One kind or two or more kinds of onium salts can be used. When two or more are used, the total amount is preferably within the above-mentioned range.

<Thermal base generator> The resin composition of the present invention may further contain a thermal base generator. In particular, when the resin composition of the present invention contains a polyimide precursor as the specific resin, it is preferable to contain a thermal base generator. The other thermal base generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermal base generator other than the above-mentioned onium salt. Examples of thermal base generators other than the above-mentioned onium salts include nonionic thermal base generators. As the nonionic thermal base generator, a compound represented by formula (B1) or formula (B2) can be mentioned. [Chemical formula 43]

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 simultaneously become hydrogen atoms. In addition, Rb ¹ , Rb ² and Rb ³ do not all have a carboxyl group. In addition, in this specification, the tertiary amine structure refers to a structure in which all three bonding bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, when the carbon atom to be bonded is a carbon atom constituting a carbonyl group, that is, when it forms an amide group together with a nitrogen atom, it is not limited to this.

In the formula (B1) and the formula (B2), as for 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. A single ring is preferably a 5-membered ring or a 6-membered ring, and a 6-membered ring is more preferred. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, and a cyclohexane ring is more preferable.

More specifically, Rb ¹ and Rb ² are hydrogen atoms, alkyl groups (the carbon number is preferably 1-24, 2-18 is more preferably, and 3-12 is more preferably), alkenyl (carbon number 2-24 Is preferred, 2-18 is more preferred, 3-12 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is further preferred) or aryl group Alkyl groups (7 to 25 carbon atoms are preferred, 7 to 19 are more preferred, and 7 to 12 are even more preferred) are preferred. These groups may have substituents within the 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 formed, a 4- to 7-membered nitrogen-containing heterocyclic ring is preferred. Rb ¹ and Rb ^{2 are} especially linear, branched or cyclic alkyl groups which may have substituents (the carbon number is preferably 1-24, 2-18 is more preferably, 3-12 is more preferably). , A cycloalkyl group that may have a substituent (the carbon number is preferably 3-24, more preferably 3-18, and even more preferably 3-12) is more preferable, and a cyclohexyl group that may have a substituent is even more preferable.

Examples of Rb ³ include alkyl groups (the carbon number is preferably 1-24, 2-18 is more preferable, and 3-12 is more preferable), and aryl groups (the carbon number is preferably 6-22, 6-18 More preferably, 6-10 is further preferred), alkenyl (carbon number 2-24 is preferred, 2-12 is more preferred, 2-6 is further preferred), arylalkyl (carbon number 7~ 23 is preferred, 7-19 is more preferred, 7-12 is further preferred), arylalkenyl (carbon number 8-24 is preferred, 8-20 is more preferred, 8-16 is further preferred) , Alkoxy (the carbon number is 1-24 is preferable, 2-18 is more preferable, and 3-12 is more preferable), aryloxy (the carbon number is 6-22 is preferable, 6-18 is more preferable, 6-12 is more preferable) or arylalkoxy (carbon number 7-23 is preferable, 7-19 is more preferable, 7-12 is more preferable). Among them, cycloalkyl (3 to 24 carbon atoms is preferred, 3 to 18 is more preferred, and 3 to 12 is even more preferred), arylalkenyl, and arylalkoxy are preferred. Rb ³ may have a substituent within the 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 44]

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 an alkyl group (the carbon number is preferably 1-24, 2-18 is more preferable, and 3-12 is more preferable), alkenyl group (the carbon number is 2-24 is preferable, and 2-18 is more preferable, 3-12 is more 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 more preferable), and may have a substituent within the range of exerting the effects of the present invention. Among them, Rb ¹³ is preferably an arylalkyl group.

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

Rb ³⁵ is an alkyl group (the carbon number is preferably 1-24, 1-12 is more preferable, and 3-8 is even more preferable), alkenyl (the carbon number is preferably 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 is more preferred, 7-12 is further preferred), aryl is preferred.

It is also preferable that the compound represented by formula (B1-1) is a compound represented by formula (B1-1a). [Chemical formula 45]

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

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

As specific examples of compounds that are thermal base generators among the above-mentioned onium salts or specific examples of thermal base generators other than the above-mentioned onium salts, the following compounds can be given.

[Chemical formula 46]

[Chemical formula 47]

[Chemical formula 48]

The content of the other thermal alkali generator is preferably 0.1 to 50% by mass relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. One kind or two or more kinds of thermal base generators can be used. When two or more are used, the total amount is preferably within the above-mentioned range.

＜Crosslinking agent＞ The resin composition of the present invention preferably contains a crosslinking agent. As a crosslinking agent, a radical crosslinking agent or other crosslinking agents can be mentioned.

＜Free radical crosslinking agent＞ The resin composition of the present invention preferably further contains a free radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. As the radical polymerizable group, a group containing an ethylenically unsaturated bond is preferred. Examples of the group containing an ethylenically unsaturated bond include groups having an ethylenically unsaturated bond, such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth)acryloyl group. Among these, as the group containing the ethylenically unsaturated bond, a (meth)acryloyl group is preferable, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferable.

The radical crosslinking agent may be a compound having one or more ethylenic unsaturated bonds, and a compound having two or more is more preferable. The compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing ethylenically unsaturated bonds described above. In addition, from the viewpoint of the film strength of the obtained pattern (cured film), the resin composition of the present invention preferably contains a compound having three or more ethylenic unsaturated bonds as a radical crosslinking agent. As the above-mentioned compound having 3 or more ethylenic unsaturated bonds, a compound having 3 to 15 ethylenic unsaturated bonds is preferred, and a compound having 3 to 10 ethylenic unsaturated bonds is more preferred, with 3 to 15 ethylenic unsaturated bonds. Six compounds are further preferred. In addition, the compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 or more of the groups containing ethylenic Compounds with -10 are more preferred, and compounds with 3-6 are particularly preferred. In addition, from the viewpoint of the film strength of the obtained pattern (cured film), the resin composition of the present invention includes a compound having two ethylenically unsaturated bonds and the compound having three or more ethylenically unsaturated bonds. Better.

The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and 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 free radical crosslinking agents include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters, The amines are preferably esters of unsaturated carboxylic acids and polyol compounds and amines of unsaturated carboxylic acids and polyamine compounds. In addition, unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl, amino, sulfanyl group, and monofunctional or polyfunctional isocyanates or epoxy groups can also be preferably used. Addition reaction product or dehydration condensation reaction product with monofunctional or polyfunctional carboxylic acid, etc. In addition, the addition of unsaturated carboxylic acid esters or amines having electron withdrawing substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols can also be preferably used. Reactants, as well as unsaturated carboxylic acid esters or amides with detachable substituents such as halogeno group or tosyloxy group, and monofunctional or polyfunctional alcohols, amines, Substitution reactant of mercaptans. Also, as another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, vinyl benzene derivatives such as styrene, vinyl ether, and allyl ether in place of the above-mentioned unsaturated carboxylic acid. As a specific example, reference can be made to the descriptions in paragraphs 0113 to 0122 of JP 2016-027357 A, and these contents are incorporated in this specification.

In addition, the radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples thereof include the addition of ethylene oxide or propylene oxide to polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, and neopentyl glycol di(meth)acrylate. (Meth) acrylate, neopentyl erythritol tri(meth) acrylate, neopentyl erythritol tetra (meth) acrylate, dineopentaerythritol penta(meth) acrylate, dineopentaerythritol hexa (Meth)acrylate, hexanediol (meth)acrylate, trimethylolpropane tris(acryloxypropyl) ether, tris(acryloxyethyl) isocyanurate, glycerin or trihydroxymethyl Compounds that have been (meth)acrylated with polyfunctional alcohols such as methyl ethane, such as Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Application Publication No. 51-037193. Urethane (meth)acrylates described in the gazette, and polyesters described in each gazette of JP Sho 48-064183, JP Sho 49-043191, and JP Sho 52-030490 Polyfunctional acrylates or methacrylates such as acrylates, epoxy acrylates which are reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof. In addition, the compounds described in paragraphs 0254 to 0257 of JP 2008-292970 A are also preferable. In addition, polyfunctional (meth)acrylates obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth)acrylate with a polyfunctional carboxylic acid and the like are also mentioned.

In addition, as a preferable free radical crosslinking agent other than the above, it is also possible to use those described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, Japanese Patent No. 4364216, etc. Cyclic compound or cardo resin with two or more ethylenically unsaturated bond-containing groups.

In addition, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, or Japanese Patent Application Publication No. 02 Vinylphosphonic acid-based compounds and the like described in Bulletin -025493. In addition, the perfluoroalkyl group-containing compound described in JP 61-022048 A can also be used. In addition, it is also possible to use those introduced as photopolymerizable monomers and oligomers in the Journal of the Adhesive Association of Japan vol.20, No.7, pages 300 to 308 (1984).

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Unexamined Patent Publication No. 2015-034964, and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used. It is included in this manual.

In addition, the addition of ethylene oxide or propylene oxide to a polyfunctional alcohol was carried out after the addition of ethylene oxide or propylene oxide to a polyfunctional alcohol as described in Formula (1) and Formula (2) in Japanese Patent Application Laid-Open No. 10-062986. (Base) acrylated compounds can also be used as free radical 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 this specification.

As a free-radical crosslinking agent, dineopentaerythritol triacrylate (as a commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dineopentaerythritol tetraacrylate (as a commercially available product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dineopentaerythritol penta(meth)acrylate (as a commercially available product is KAYARAD D -310; manufactured by Nippon Kayaku Co., Ltd.), dineopentaerythritol hexa(meth)acrylate (as a commercial product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth)acrylic groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. These oligomer types can also be used.

As a commercially available product of a radical crosslinking agent, for example, SR-494 manufactured by Sartomer Company, Inc. as a 4-functional acrylate having 4 ethoxy chains, and SR-494 as having 4 ethoxy chains are mentioned. SR-209, 231, 239 manufactured by Sartomer Company, Inc. and DPCA-60 as a hexafunctional acrylate with 6 pentenoxy chains manufactured by Nippon Kayaku Co., Ltd. , TPA-330 as a trifunctional acrylate with 3 methacryloxy 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 a radical crosslinking agent, for example, the amino groups described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Application Publication No. 02-016765 Formate acrylates or ethylene oxide as 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 Carbamate compounds with alkane structure are also preferred. In addition, as the free radical crosslinking agent, those described in JP-A 63-277653, JP-A 63-260909, and JP-A 01-105238 that have an amino group in the molecule can also be used. Structure or sulfide structure compound.

The free radical crosslinking agent may also be a free radical crosslinking agent having acid groups such as carboxyl groups and phosphoric acid groups. The free radical crosslinking agent with an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. The non-aromatic carboxylic acid anhydride is reacted with the unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acid group. The free radical crosslinking agent is more preferable. Particularly preferably, in the free radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, the aliphatic polyhydroxy compound is neopentyl erythritol or di-neopentyl Tetraol compound. As a commercially available product, for example, as a polyacid-modified acrylic oligomer manufactured by TOAGOSEI CO., LTD., M-510, M-520, and the like can be cited.

The preferred acid value of the free radical crosslinking agent with an acid group is 0.1-40 mgKOH/g, particularly preferably 5-30 mgKOH/g. As long as the acid value of the radical crosslinking agent is within the above range, the workability in production is excellent, and the developability is also excellent. In addition, the polymerizability is good. The above-mentioned acid value is measured in accordance with the description of JIS K 0070:1992.

From the viewpoints of pattern resolution and film stretchability, the resin composition of the present invention preferably uses bifunctional methacrylate or acrylate. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 diacrylate can be used. Methacrylate, PEG600 Diacrylate, PEG600 Dimethacrylate, Polytetraethylene Glycol Diacrylate, Polytetraethylene Glycol Dimethacrylate, Neopentyl Glycol Diacrylate, Neopentyl Glycol Diacrylate Methacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tri Cyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO adduct of bisphenol A diacrylate, EO adduct of bisphenol A dimethacrylate, bisphenol A PO adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid EO modified diacrylic acid Ester, isocyanuric acid modified dimethacrylate, and bifunctional acrylate with urethane bond, and bifunctional methacrylate with urethane bond. Two or more of these can be mixed and used according to requirements. In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate and the formula weight of the polyethylene glycol chain is about 200. In addition, from the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the pattern (cured film), as the radical crosslinking agent, a monofunctional radical crosslinking agent can be preferably used. As a monofunctional free radical crosslinking agent, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth) Butoxyethyl acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (Meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate and other (meth)acrylic acid derivatives, N-ethylene N-vinyl compounds such as pyrrolidone, N-vinylcaprolactam, allyl compounds such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. Class etc. As a 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 preferable.

When it contains a radical crosslinking agent, it is preferable that its 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% by mass or more. The upper limit is more preferably 50% by mass or less, and more preferably 30% by mass or less.

One kind of radical crosslinking agent may be used alone, but two or more kinds may be mixed and used. In the case of using two or more types at the same time, it is preferable that the total amount thereof falls within the above-mentioned range.

＜Other crosslinking agents＞ The resin composition of the present invention preferably contains another crosslinking agent different from the above-mentioned free radical crosslinking agent. In the present invention, other cross-linking agents refer to cross-linking agents other than the above-mentioned free radical cross-linking agents, which have multiple molecules in the molecule to promote other compounds in the composition or their reaction by the photosensitization of the above-mentioned photosensitizers. Compounds with reaction groups that form covalent bonds between products are preferred. They have a plurality of groups in the molecule that promote the formation of covalent relationships with other compounds in the composition or their reaction products by the action of acids or bases. The compound of the group of the bond reaction is preferable. The above-mentioned acid or base is preferably an acid or base generated from the photosensitizer in the exposure step. As other crosslinking agents, compounds having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl are preferred, and compounds having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl are preferred. Compounds in which at least one group is directly bonded to the nitrogen atom are more preferred. As other crosslinking agents, for example, there can be mentioned a compound containing amine groups such as formaldehyde or formaldehyde and alcohol and melamine, glycoluril, urea, alkylene urea, benzoguanamine, etc. A compound with the structure of the hydrogen atom of the above amino group substituted by a methyl group. The production method of these compounds is not particularly limited, as long as they are compounds having the same structure as the compounds produced by the above-mentioned methods. Moreover, it may be an oligomer formed by self-condensation of the methylol groups of these compounds. The crosslinking agent that uses melamine as the above-mentioned amine group-containing compound is called melamine-based crosslinking agent, and the crosslinking agent that uses glycoluril, urea or alkylene urea is called urea-based crosslinking agent. The crosslinking agent of alkylene urea is called alkylene urea-based crosslinking agent, and the crosslinking agent using benzoguanamine is called benzoguanamine-based crosslinking agent. Among them, 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 preferably contains at least one compound selected from the group consisting of the glycoluril-based crosslinking agent described below. And at least one compound in the group of melamine-based crosslinking agents is more preferable.

Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutylmelamine, and the like.

As specific examples of the urea-based crosslinking agent, for example, monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxy Methylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril Alkylated glycoluril, trimethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril Glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril or tetrabutoxymethylated glycoluril Diglycoluril and other glycoluril crosslinking agents; Urea crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea; Monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxy methylated ethylene urea , Diethoxy methylated ethylene urea, monopropoxy methylated ethylene urea, dipropoxy methylated ethylene urea, monobutoxy methylated ethylene urea or dibutoxy methyl Ethidium urea cross-linking agents such as oxyethylene urea; Monohydroxymethylated propylene urea, dihydroxy methylated propylene urea, monomethoxy methylated propylene urea, dimethoxy methylated propylene urea, monoethoxy methylated propylene urea , Diethoxy methylated propylene urea, monopropoxy methylated propylene urea, dipropoxy methylated propylene urea, monobutoxy methylated propylene urea or dibutoxy methyl Propionyl urea crosslinking agents such as oxypropionyl urea; 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazole Pyridone and so on.

As specific examples of the benzoguanamine-based crosslinking agent, for example, monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethyl Alkylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzene Guanidine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine , Monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, single Butoxymethylated 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 for direct bonding to an aromatic ring (preferably a benzene ring) There is a compound having at least one group selected from the group consisting 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, hydroxymethyl phenyl hydroxymethyl benzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, double (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 Tris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy -1,3-Benzenediethanol], 3,3',5,5'-tetra(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

As other crosslinking agents, commercially available products can also be used. Preferred commercially available products 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 Sanwa Chemical Co., Ltd.), etc.

In addition, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzophenone compounds as the other crosslinking agent.

[Epoxy compounds (compounds with epoxy groups)] As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes cross-linking reaction below 200°C and does not produce dehydration reaction from cross-linking, so film shrinkage is unlikely to occur. Therefore, containing the epoxy compound is effective for the low-temperature hardening of the resin composition and the suppression of warpage.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the modulus of elasticity is further reduced, and warpage can be suppressed. The polyethylene oxide group means the number of repeating units of ethylene oxide of 2 or more, and the number of repeating units is preferably 2-15.

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, butane Alkylene glycol type epoxy resin or polyol hydrocarbon type epoxy resin such as glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether; polypropylene glycol diglycidyl ether Polyalkylene glycol type epoxy resins such as glycerol ether; epoxy epoxy-based silicones such as polymethyl (glycidoxypropyl) silicone, etc., but are 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) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered Trademarks) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) ) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740, Rika Resin (registered trademark) ) BEO-20E (the above are trade names, manufactured by DIC Corporation), Rika Resin (registered trademark) BEO-60E (trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, Rika Resin ( Registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200, EP-4088S, EP-3950S (the above are the trade names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, 2081, 2000, 3000, EHPE3150, EPOLEAD (registered trademark) GT400, CELVENUS (registered trademark) B0134, B0177 (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, B REN-S, BREN-10S (the above are trade names, manufactured by Nippon Kayaku Co., Ltd.), etc.

[Oxycyclobutane compounds (compounds with oxycyclobutyl)] Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyl oxetane, and 1,4-bis{[ (3-Ethyl-3-oxocyclobutyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylate Acid-bis[(3-ethyl-3-oxocyclobutyl)methyl] ester and the like. As a specific example, ARON OXETANE series manufactured by TOAGOSEI CO., LTD. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, which can be used alone or in combination of two or more .

〔Benzo 㗁𠯤 compounds (compounds with benzo 㗁𠯤 group)〕 The benzoxa compound does not cause outgassing during curing due to the cross-linking reaction derived from the ring-opening addition reaction, and further reduces thermal shrinkage and suppresses warpage, which is therefore preferred.

As a preferable example of the benzoglyph compound, Ba-type benzoglyph, Bm-type benzoglyph, Pd-type benzoglyph, Fa-type benzoglyph (the above are the trade names, SHIKOKU CHEMICALS CORPORATION Manufacturing), polyhydroxy styrene resin benzo 㗁 adduct, phenol novolak type dihydro benzo 㗁 𠯤 compound. These can be used alone or in a mixture of two or more.

The content of other crosslinking agents is preferably 0.1-30% by mass relative to the total solid content of the resin composition of the present invention, more preferably 0.1-20% by mass, more preferably 0.5-15% by mass, and 1.0-10 The quality% is particularly good. The other crosslinking agent may contain only one type or two or more types. When two or more other crosslinking agents are contained, it is preferable that the total thereof is within the above-mentioned range.

＜Migration inhibitor＞ The resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the migration of metal ions from the metal layer (metal wiring) into the resin composition layer.

The migration inhibitor is not particularly limited, and examples include heterocycles (pyrrole ring, furan ring, thiophene ring, triazole ring, imidazole ring, azole ring, thiazole ring, pyrazole ring, isoazole ring, iso Thiazole ring, tetrazole ring, pyridine ring, pyran ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, three ring) Compounds, compounds having thioureas and sulfhydryl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazine derivative compounds. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

Alternatively, an ion scavenger that traps 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, and JP 2011 can be used. -059656, the compound described in paragraph 0052 of JP 2012-194520, the compound described in paragraphs 0114, 0116, and 0118 of JP 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015/199219, etc. .

As specific examples of migration inhibitors, the following compounds can be given.

[Chemical formula 49]

When the resin composition has a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the resin composition is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and 0.1 to 1.0% by mass To be further preferred.

There may be only one type of migration inhibitor, or two or more types. When there are two or more migration inhibitors, the total of them is preferably within the above-mentioned range.

＜Polymerization inhibitor＞ The resin composition of the present invention preferably contains a polymerization inhibitor.

As the polymerization inhibitor, for example, hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallic phenol, p-tert-butylcatechol, 1,4-Benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4- Methyl-6-tertiary butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothidium, N-nitroso diphenylamine, N-phenylnaphthylamine, 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-nitrosophenylhydroxylamine first cerium salt, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium Salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-Trimethyl-2,4,6-(1H,3H,5H)-triketone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical , Phenothionine, 1,1-diphenyl-2-picrylhydrazine, copper(II) dibutyldithiocarbamate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt , N-nitroso-N-phenylhydroxylamine ammonium salt, N,N'-diphenyl-p-phenylenediamine, 2,4-di-tertiary butylphenol, di-tertiary butylhydroxyl Toluene, 1,4-naphthoquinone, etc. In addition, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817 A and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

In addition, the following compounds (Me is a methyl group) can be used.

[Chemical formula 50]

When the resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solid content of the resin composition of the present invention is 0.01 to 20.0% by mass, preferably 0.01 to 5% by mass 0.02 to 3% by mass is more preferable, and 0.05 to 2.5% by mass is still more preferable.

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

＜Metal adhesion improver＞ The resin composition of the present invention preferably contains a metal adhesive modifier for improving the adhesiveness with metal materials used in electrodes, wiring, and the like. Examples of metal adhesion improvers include silane coupling agents, aluminum-based adhesives, titanium-based adhesives, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, and β-keto acids Esters (β keto ester) compounds, amine-based compounds, etc.

Examples of silane coupling agents include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP 2014-191002, and International Publication No. 2011/ The compound described in paragraphs 0063 to 0071 of 080992, the compound described in paragraphs 0060 to 0061 of JP 2014-191252, and the compound described in paragraphs 0045 to 0052 of JP 2014-041264 , The compound described in paragraph 0055 of International Publication No. 2014/097594. In addition, as described in paragraphs 0050 to 0058 of JP 2011-128358 A, it is also preferable to use two or more different silane coupling agents. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulae, Et represents an ethyl group.

作為其他矽烷偶合劑，例如可以舉出乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、2-（3,4-環氧環己基）乙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、N-2-（胺基乙基）-3-胺基丙基甲基二甲氧基矽烷、N-2-（胺基乙基）-3-胺基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基甲矽烷基-N-（1,3-二甲基-亞丁基）丙胺、N-苯基-3-胺基丙基三甲氧基矽烷、三-（三甲氧基甲矽烷基丙基）異氰脲酸酯、3-脲基丙基三烷氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷、3-三甲氧基甲矽烷基丙基丁二酸酐。該等能夠單獨使用一種或者組合使用兩種以上。[Chemical formula 51]

Examples of other silane coupling agents include vinyl trimethoxy silane, vinyl triethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, and 3-glycidoxy silane. Propylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxy Silane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methylpropene Acrylic oxypropyl methyl diethoxy silane, 3-methacrylic oxy propyl triethoxy silane, 3- propylene oxy propyl trimethoxy silane, N-2-(amino ethyl Group)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethyl Oxysilane, tris-(trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercapto Propyl trimethoxy silane, 3-isocyanate propyl triethoxy silane, 3-trimethoxy silyl propyl succinic anhydride. These can be used individually by 1 type or in combination of 2 or more types.

〔Aluminum series adhesive additives〕 As an aluminum-based adhesive agent, for example, tris(ethylacetate) aluminum, tris(acetacetone)aluminum, ethyl aluminum diisopropylacetate, etc. may be mentioned.

In addition, as the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A, and the sulfides described in paragraphs 0032 to 0043 of JP 2013-072935 can also be used. Department of compounds.

The content of the metal adhesion modifier is preferably 0.1-30 parts by mass relative to 100 parts by mass of the specific resin, more preferably in the range of 0.5-15 parts by mass, and still more preferably in the range of 0.5-5 parts by mass Surrounding. By setting it to be more than the above lower limit, the adhesion between the cured film and the metal layer after the curing step becomes better, and by setting it to be less than the above upper limit, the heat resistance and mechanical properties of the cured film after the curing step become good. There may be only one type of metal adhesion improver, or two or more types. When two or more are used, the total amount is preferably within the above-mentioned range.

＜Other additives＞ The resin composition of the present invention can be blended with various additives, such as sensitizers, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, hardeners, hardening touches, as required, within the range that the effects of the present invention can be obtained. Medium, filler, antioxidant, ultraviolet absorber, anti-agglomeration agent, etc. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the resin composition.

〔Sensitizer〕 The resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in an electronically excited state comes into contact with a thermal hardening accelerator, a thermal radical polymerization initiator, a photo radical polymerization initiator, etc., to generate electron transfer, energy transfer, heat generation, and the like. Thereby, the thermal hardening accelerator, the thermal radical polymerization initiator, and the photo radical polymerization initiator cause chemical changes and decompose, thereby generating free radicals, acids, or bases. As the sensitizer, for example, Michelone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylamino)benzylidene) cyclopentan 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-dimethylaminobenzene allylindanone, p-di Methylaminobenzylidene indanone, 2-(p-dimethylaminophenyl biphenylene)-benzothiazole, 2-(p-dimethylaminophenyl vinylene) benzo Thiazole, 2-(p-dimethylaminophenyl vinylene) isonaphthiazole, 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-diethylaminocoumarin , 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine , 4-morpholinyl benzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-Mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylamine) Styryl) naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetamide, benzalaniline, N-methyl ethyl Aniline, 3',4'-dimethylacetaniline, etc. As a sensitizer, a sensitizing dye can also be used. For the details of the sensitizing dye, refer to the description in paragraphs 0161 to 0163 of JP 2016-027357 A, which is incorporated into this specification.

When the resin composition of the present invention contains a sensitizer, the content of the sensitizer relative to the total solid content of the resin composition of the present invention is preferably 0.01-20% by mass, more preferably 0.1-15% by mass , 0.5-10% by mass is more preferable. The sensitizer may be used singly, or two or more of them may be used at the same time.

〔Chain transfer agent〕 The resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, on pages 683-684 of the third edition of the Polymer Dictionary (Edited by the Society of Polymer Science, 2005). As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule can be used. These can supply hydrogen to low-activity free radicals to generate free radicals, or generate free radicals by deprotonation after oxidation. In particular, thiol compounds 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.

When the resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01-20 parts by mass, and 1-10 parts by mass relative to 100 parts by mass of the total solid content of the resin composition of the present invention. It is more preferable, and 1 to 5 parts by mass is still more preferable. The chain transfer agent may be only one type or two or more types. When there are two or more chain transfer agents, the total of them is preferably within the above-mentioned range.

又，界面活性劑亦能夠使用國際公開第2015/199219號的0159～0165段中所記載的化合物。 關於氟系界面活性劑，亦能夠將在側鏈中具有乙烯性不飽和基之含氟聚合物用作氟系界面活性劑。作為具體例，可以舉出日本特開2010-164965號公報的0050～0090段及0289～0295段中所記載之化合物，例如DIC Corporation製造的MEGAFACE RS-101、RS-102、RS-718K等。[Surfactant] From the viewpoint of further improving coating properties, various types of surfactants can be added to the resin composition of the present invention. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. In addition, the following surfactants are also preferable. In the following formula, the parentheses representing the repeating unit of the main chain represent the content (mol %) of each repeating unit, and the parentheses representing the repeating unit of the side chain represent the repeating number of each repeating unit. [Chemical formula 52]

In addition, as the surfactant, the compounds described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used. Regarding the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP 2010-164965 A, such as MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

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. From the viewpoint of uniformity of the thickness of the coating film and liquid-saving properties, a fluorine-based surfactant having a fluorine content within this range is effective, and its 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.), KP341, KF6001, KF6002 (the above are Shin-Etsu Chemical Co. ., Ltd.), BYK307, BYK323, BYK330 (the above are manufactured by BYK Chemie GmbH), etc.

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 these ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate). Base compounds, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol two Laurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901 , 904, 150R1 (manufactured by BASF Corporation), Solsperse 20000 (manufactured by Lubrizol Japan Limited.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W , D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), etc.

Specific examples of the cationic surfactant include organosiloxane polymer KP341 (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.

Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), SANDET BL (manufactured by SANYO KASEI CO., LTD.), and the like.

When the resin composition of the present invention has a surfactant, the content of the surfactant relative to the total solid content of the resin composition of the present invention is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass . The surfactant may be only one type or two or more types. When there are two or more surfactants, it is preferable that the sum total is within the above-mentioned range.

〔Higher fatty acid derivatives〕 In order to prevent the polymerization inhibition caused by oxygen, the resin composition of the present invention can be added with higher fatty acid derivatives such as behenic acid or behenic acid amide to make it unevenly distributed during the drying process after coating. On the surface of the resin composition.

In addition, the higher fatty acid derivatives can also use the compounds described in paragraph 0155 of International Publication No. 2015/199219.

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. There may be only one type of higher fatty acid derivative, or two or more types. When there are two or more higher fatty acid derivatives, it is preferable that the sum total is within the above-mentioned range.

〔Inorganic particles〕 The resin composition of the present invention may contain inorganic particles. As the inorganic particles, specifically, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc. can be contained.

The average particle diameter of the above-mentioned inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. If the average particle diameter of the inorganic particles is less than 0.01 μm, the mechanical properties of the cured film may be deteriorated. In addition, if the average particle diameter of the above-mentioned inorganic particles exceeds 2.0 μm, the resolution may decrease due to the scattering of exposure light.

〔Ultraviolet absorber〕 The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, it is possible to use ultraviolet absorbers such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and tris-based ultraviolet absorbers. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, etc., as benzophenone-based ultraviolet absorbers Examples of agents 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-octoxybenzophenone Methyl ketone and so on. Also, as an example of a benzotriazole-based ultraviolet absorber, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2 -(2'-hydroxy-3'-tertiary butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tertiary amyl-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-tert-butyl Phenyl) benzotriazole, 2-(2'-hydroxy-5'-methylphenyl) benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetra Methyl)phenyl]benzotriazole and the like.

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

In the present invention, the above-mentioned various ultraviolet absorbers may be used singly or in combination of two or more. The composition of the present invention may or may not contain an ultraviolet absorber, but in the case of including an ultraviolet absorber, the content of the ultraviolet absorber relative to the total solid content of the composition of the present invention is 0.001% by mass or more and 1% by mass or less is preferable, and 0.01% by mass or more and 0.1% by mass or less are more preferable.

〔Organic Titanium Compounds〕 The resin composition of this embodiment may contain an organic titanium compound. Since the resin composition contains an organic titanium compound, even when curing is performed at a low temperature, a resin layer with excellent chemical resistance can be formed.

Examples of the organotitanium compound that can be used include those having an organic group bonded to a titanium atom 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, since the storage stability of the negative photosensitive resin composition is good and a good hardened pattern can be obtained, a titanium chelate compound having two or more alkoxy groups is more preferable. Specific examples are bis(triethanolamine)diisopropoxide titanium, bis(2,4-glutarate)di(n-butoxy)titanium, bis(2,4-glutarate)diisopropoxide Base titanium, bis(tetramethylpimelate) titanium diisopropoxide, bis(ethylacetate) titanium diisopropoxide, etc. II) Tetraalkoxide titanium compound: for example, tetra(n-butoxy) titanium, tetraethoxytitanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxy Titanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonoxy)titanium, tetra(n-propoxy)titanium, tetrastearyloxytitanium , Four [bis{2,2-(allyloxymethyl)butoxy}] titanium and so on. III) Titanocene compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, 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) Monoalkoxide titanium compound: for example, tris(dioctyl phosphate) titanium isopropoxide, tris(dodecylbenzene sulfonate) titanium isopropoxide, and the like. V) Titanium oxide compound: for example, bis(glutarate) titanium oxide, bis(tetramethylpimelate) titanium oxide, phthalocyanine titanium oxide, and the like. VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate. VII) Titanate coupling agent: for example, isopropyl tri(dodecyl)benzenesulfonyl titanate and the like.

Among them, the organic titanium compound is selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxy titanium compound, and III) titanocene compound from the viewpoint of exerting better chemical resistance. At least one compound is preferred. In particular, bis(ethylacetate)diisopropoxide titanium, tetra(n-butoxy)titanium and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6 -Difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

In the case of compounding the organic titanium compound, the compounding amount is preferably 0.05-10 parts by mass relative to 100 parts by mass of the precursor of the cyclized resin, and more preferably 0.1-2 parts by mass. When the compounding amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are shown in the obtained hardened pattern. On the other hand, when the compounding amount is less than 10 parts by mass, the composition is stable in storage. The sex is excellent.

〔Antioxidants〕 The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, it is possible to improve the elongation characteristic of the cured film and the adhesion to the metal material. Examples of antioxidants include phenol compounds, phosphite compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. As a preferable phenol compound, hindered phenol compound can be mentioned. A compound having a substituent at the 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 preferred. Furthermore, it is also preferable that the antioxidant is a compound having a phenol group and a phosphite group in the same molecule. In addition, as the antioxidant, phosphorus-based antioxidants can also be preferably used. Examples of phosphorus antioxidants include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2] Dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f] [1,3,2]Diphosphoheptin-2-yl)oxy]ethyl]amine, bis(2,4-di-tert-butyl-6-methylphenol) ethyl phosphite, etc. . Commercial products of antioxidants include, for example, 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, as the antioxidant, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used. In addition, the composition of the present invention may contain a latent antioxidant as needed. As a potential antioxidant, a compound in which the part that functions as an antioxidant is protected by a protective group can be cited by heating at 100 to 250°C or by heating at 80 to 200°C in the presence of an acid/base catalyst. A compound whose protective group is detached to act as an antioxidant. Examples of potential antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Patent Application Publication No. 2017-008219. As a commercially available product of a potential antioxidant, ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION) and the like can be cited. As examples of preferable antioxidants, 2,2-thiobis(4-methyl-6-tertiary butylphenol), 2,6-di-tertiary butylphenol, and general formula (3) can be cited The compound represented.

[Chemical formula 53]

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

The compound represented by the general formula (3) suppresses the oxidative deterioration of the aliphatic group or phenolic hydroxyl group of the resin. In addition, the rust-preventing effect on metal materials can inhibit metal oxidation.

Since it can act on the resin and the metal material at the same time, it is more preferable that k is an integer of 2 to 4. Examples of R ⁷ include alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkylsilyl groups, alkoxysilyl groups, aryl groups, aryl ether groups, carboxyl groups, carbonyl groups, and allyl groups. A group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, a combination of these, etc., and may further have a substituent. Among them, from the viewpoint of solubility in the developer or metal adhesion, it is preferable to have an alkyl ether and -NH-, and from the viewpoint of the interaction with the resin and the metal adhesion based on the formation of metal complexes. In other words, -NH- is better.

As an example of the compound represented by the following general formula (3), the following can be mentioned, but it is not limited to the following structure.

[Chemical formula 54]

[Chemical formula 55]

[Chemical formula 56]

[Chemical formula 57]

The amount of the antioxidant added is preferably 0.1-10 parts by mass relative to the resin, and more preferably 0.5-5 parts by mass. When the addition amount is less than 0.1 parts by mass, it is difficult to obtain the effect of improving the elongation characteristics after the reliability test or the adhesion to metal materials, and when the amount is more than 10 parts by mass, it may be combined with photosensitive The interaction of the agent causes the sensitivity of the resin composition to decrease. Only one type of antioxidant may be used, or two or more types may be used. In the case of using two or more types, the total amount of these is preferably within the above-mentioned range.

＜Regarding restrictions on other contained substances＞ From the viewpoint of coating surface properties, the moisture content of the resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and more preferably less than 0.6% by mass. As a method of maintaining the moisture content, the adjustment of the humidity under the storage conditions, the reduction of the porosity of the storage container, and the like can be cited.

From the viewpoint of insulation, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and more preferably less than 0.5 mass ppm. . Examples of metals include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When a plurality of metals are included, the total of these metals is preferably within the above-mentioned range.

In addition, as a method of reducing the metal impurities accidentally contained in the resin composition of the present invention, the following methods can be cited: selecting a raw material with a low metal content as the raw material constituting the resin composition of the present invention; The raw material of the composition is filtered by a filter; the device is lined with polytetrafluoroethylene, etc., and the distillation is carried out under the condition of suppressing pollution as much as possible.

In the resin composition of the present invention, considering the use as a semiconductor material, from the viewpoint of wiring corrosion, 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 To be further preferred. Among them, it is preferably less than 5 mass ppm in the state of halogen ions, more preferably less than 1 mass ppm, and more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of the chlorine atom and the bromine atom or the chlorine ion and the bromine ion each fall within the above-mentioned range. As a method of adjusting the content of halogen atoms, ion exchange treatment and the like can be preferably cited.

As the storage container of the resin composition of the present invention, a conventionally known storage container can be used. In addition, as a storage container, for the purpose of preventing impurities from mixing into the raw material or resin composition, it is also preferable to use a multilayer bottle with 6 types of 6-layer resins on the inner wall of the container or a 7-layer structure with 6 types of resins. . As such a container, for example, the container described in JP 2015-123351 A can be cited.

＜Use of resin composition＞ The resin composition of the present invention is preferably used for the formation of an interlayer insulating film for a rewiring layer. Moreover, in addition to this, it can also be used for formation of an insulating film of a semiconductor element, formation of a stress buffer film, and the like.

＜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 it can be performed by a conventionally known method.

In addition, for the purpose of removing foreign substances such as dust and particles in the resin composition, it is preferable to perform filtration using a filter. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. On the other hand, from the viewpoint of productivity, 5 μm or less is preferable, 3 μm or less is more preferable, and 1 μm or less is more preferable. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter can be cleaned in advance with an organic solvent. In the filter filtering step, multiple filters can be connected in series or in parallel. When multiple filters are used, filters with different pore sizes or materials can be used in combination. In addition, various materials can be filtered multiple times. In the case of filtering multiple times, it can be cyclic filtering. In addition, filtration can be performed by applying pressure. In the case of filtering by pressurization, the pressurization pressure is preferably 0.05 MPa or more and 0.3 MPa or less. On the other hand, from the viewpoint of productivity, 0.01 MPa or more and 1.0 MPa or less are preferable, 0.03 MPa or more and 0.9 MPa or less are more preferable, and 0.05 MPa or more and 0.7 MPa or less are more preferable. In addition to filtration using filters, it can also be used to remove impurities using adsorbent materials. It is also possible to combine filter filtration and impurity removal treatment using adsorbent materials. 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 cited.

(Cured film, laminated body, semiconductor element and manufacturing methods of these) Next, the cured film, the laminated body, the semiconductor element, and the manufacturing method thereof will be described.

The cured film of the present invention is a cured film obtained by curing the resin composition of the present invention. The film thickness of the cured film of this invention can be made into 0.5 micrometer or more, for example, and can also be made into 1 micrometer or more. Moreover, as an upper limit, it can be 100 micrometers or less, and can also be 30 micrometers or less.

Two or more layers of the cured film of the present invention can be laminated, and 3 to 7 layers can be laminated to form a laminated body. The laminate of the present invention preferably includes two or more cured films, and preferably includes a metal layer between any of the cured films. For example, a preferable one may include a laminate having at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order. The first cured film and the second cured film are both cured films of the present invention. As a preferred one, for example, any one of the first cured film and the second cured film may be the resin of the present invention. The state of the film formed by curing the composition. The resin composition of the present invention used for the formation of the above-mentioned first cured film and the resin composition of the present invention used for the formation of the above-mentioned second cured film may have the same composition or 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.

Examples of the field to which the cured film of the present invention can be applied include an insulating film of a semiconductor element, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. In addition to this, the patterning of a sealing film, a substrate material (a base film or a cover film of a flexible printed board, an interlayer insulating film), or an insulating film for actual mounting purposes as described above by etching, etc., can be mentioned. Regarding these uses, for example, you can refer to SCIENCE AND TECHNOLOGY CO., LTD. "High-functionalization and application technology of polyimide" April 2008, Kakimoto Yamin/Supervisor, CMC Technical library "Polyimide material "Basic and Development" issued in November 2011, edited by Japan Polyimide/Aromatic Polymer Research Association "Newest Polyimide Fundamentals and Applications" NTS Inc., August 2010, etc.

In addition, the cured film of the present invention can also be used in the manufacture of printing plates such as offset printing plates or screen printing plates, use in the etching of molded components, and protective paints and media in electronics, especially microelectronics. Manufacturing of electrical layers, etc.

The production method of the cured film of the present invention (hereinafter, also simply referred to as "the production method of the present invention") preferably includes a film forming step of applying the resin composition of the present invention to a substrate to form a film. The method for producing a cured film of the present invention preferably includes the above-mentioned film forming step, an exposure step of exposing the above-mentioned film, and a development step of developing the above-mentioned film. Furthermore, it is more preferable that the method for producing a cured film of the present invention includes the above-mentioned film forming step and, if necessary, the above-mentioned development step, and includes a heating step of heating the above-mentioned film at 50 to 450°C. Specifically, it is also preferable to include the steps (a) to (d) below. (A) Film formation step of applying the resin composition to the substrate to form a film (resin composition layer) (B) Exposure step of exposing the film after the film formation step (C) The developing step of developing the exposed film (D) Heating step of heating the developed film at 50～450℃ By heating in the above heating step, the resin layer hardened by exposure can be further hardened. In this heating step, for example, the above-mentioned hot alkali generator is decomposed to obtain sufficient hardenability.

The manufacturing method of the laminated body of the preferable embodiment of this invention includes the manufacturing method of the cured film of this invention. The manufacturing method of the laminated body of this embodiment forms a cured film according to the manufacturing method of the said cured film, and further performs the process of (a) or the process of (a)-(c), or the process of (a)-(d) again. In particular, it is preferable to perform the above-mentioned steps multiple times in sequence, for example, 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured film in this way, a laminate can be formed. In the present invention, it is particularly preferable to provide a metal layer on the part provided with the cured film or between the cured film or between the part provided with the cured film and the cured film. In addition, it is not necessary to repeat all the steps (a) to (d) when manufacturing the laminate. As described above, by performing (a) at least a plurality of times, preferably (a) to (c) or (a) In the step (d), a laminated body of a cured film can be obtained.

<Film formation step (layer formation step)> The manufacturing method of the preferred embodiment of the present invention includes a film forming step (layer forming step) of applying a resin composition to a substrate to form a film (layered).

The type of substrate can be appropriately specified according to the application. It can be used for semiconductors such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, vapor-deposited film, magnetic film, reflection Film, Ni, Cu, Cr, Fe and other metal substrates, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, electrode plates of plasma display panels (PDP), etc., It is not subject to special restrictions. In addition, a layer such as an adhesion layer or an oxide layer may be provided on the surface of these substrates. In the present invention, it is particularly preferable to manufacture a semiconductor substrate, and a silicon substrate, a Cu substrate, and a mold substrate are more preferable. In addition, a layer such as an adhesion layer or an oxide layer formed of hexamethyldisilazane (HMDS) or the like may be provided on the surface of the substrates. In addition, as the base material, for example, a plate-shaped base material (substrate) can be used. The shape of the substrate is not particularly limited, and may be circular or rectangular, but rectangular is preferable. As long as the size of the substrate is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. As long as it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.

In addition, when the resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer becomes the base material.

As a method of applying the resin composition to the substrate, coating is preferred.

Specifically, as the applicable method, the dip coating method, the air knife coating method, the curtain coating method, the wire bar coating method, the gravure coating method, the extrusion coating method, the spray coating method, and the spin coating method can be exemplified. Coating method, slit coating method, inkjet method, etc. From the viewpoint of the uniformity of the thickness of the resin composition layer, the spin coating method, the slit coating method, the spray coating method, and the inkjet method are more preferable. By appropriately adjusting the solid content concentration or coating conditions according to the method, a resin layer with a desired thickness can be obtained. In addition, the coating method can also be appropriately selected according to the shape of the substrate. For round substrates such as wafers, spin coating, spray coating, inkjet, etc. are preferred, and for rectangular substrates, narrow A slit coating method, a spray coating method, an inkjet 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 2,000 rpm for about 10 seconds to 1 minute. In addition, depending on the viscosity of the photosensitive resin composition or the film thickness to be set, it is also preferable to apply it at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds. In addition, in order to obtain uniformity of the film thickness, it is also possible to combine a plurality of rotation speeds for coating. In addition, it is also possible to apply a method of transferring a coating film previously applied by the above-mentioned applying method and formed on a temporary support onto a substrate. Regarding the transfer method, the production described in paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 can also be preferably used in the present invention. method. In addition, a step of removing excess film may be performed at the end of the base material. Examples of such steps include edge bead residue rinse (EBR), air knife (air knife), back rinse (back rinse), and the like. In addition, the following pre-wetting step may also be adopted: before applying the resin composition to the substrate, various solvents are applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

＜Drying step＞ The manufacturing method of the present invention may include a step of drying in order to remove the solvent after the film formation step (layer formation step) after forming the above-mentioned film (resin composition layer). The preferred drying temperature is 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. As the drying time, 30 seconds to 20 minutes can be exemplified, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

<Exposure Step> The manufacturing method of the present invention may include an exposure step of exposing the above-mentioned film (resin composition layer). Regarding the amount of exposure, as long as the resin composition can be cured, there are no special regulations. For example, it is ^{better to irradiate 100 to 10,000 mJ/cm 2} in terms of exposure energy at a wavelength of 365 nm, and more preferably to irradiate 200 to 8,000 mJ/cm ² good.

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

If the exposure wavelength is described in relation to the light source, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-ray ( Wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (3 wavelengths of g, h, and i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F ₂ excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, (7) the second harmonic of YAG laser Wave 532nm and third harmonic 355nm and so on. For the resin composition of the present invention, exposure based on high-pressure mercury lamps is particularly preferred, and exposure based on i-rays is preferred. By this, in particular, high exposure sensitivity can be obtained. In addition, from the viewpoint of operation and productivity, a wide (3 wavelengths of g, h, and i rays) light source for a high-pressure mercury lamp or a semiconductor laser of 405 nm is also preferable.

<Development step> The manufacturing method of the present invention may include a development step of developing the exposed film (resin composition layer) (developing the above-mentioned film). The unexposed part (non-exposed part) is removed by developing. The developing method is not particularly limited as long as the desired pattern can be formed. For example, spraying of the developer from the nozzle, spray spray, immersion of the substrate in the developer, etc. can be mentioned, and spraying from the nozzle can be preferably used. In the developing step, the step of continuously supplying the developer to the substrate, the step of holding the developer on the substrate in a substantially stationary state, the step of vibrating the developer with ultrasonic waves, etc., and a combination of these can be used. Steps and so on.

Regarding development, a developer is used. The developer can be used without particular limitation as long as it can remove the unexposed part (non-exposed part). As the developer, a developer containing an organic solvent or an aqueous alkali solution can be used.

In the present invention, the developer preferably contains an organic solvent with a ClogP value of -1 to 5, and more preferably contains an organic solvent with a ClogP value of 0 to 3. The ClogP value can be obtained by entering the structural formula in ChemBioDraw as a calculated value.

When the developer is a developer containing an organic solvent, as for the organic solvent, as esters, for example, ethyl acetate, n-butyl acetate, pentyl formate, isoamyl acetate, and isobutyl acetate are preferably mentioned. Ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkane Alkyl oxyacetate (e.g. methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, ethyl methoxyacetate) Butyl ester, methyl ethoxy acetate, ethyl ethoxy acetate, etc.), 3-alkoxy propionic acid alkyl esters (for example: 3-alkoxy propionic acid methyl ester, 3-alkoxy propionate Ethyl acid, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), Alkyl 2-alkoxypropionate (for example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, 2-methyl propionate) Methyl oxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2 -Methyl alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy Ethyl-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, 2 -Ethyl oxobutyrate, etc., and, as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cyrus Acetate, ethyl celoxol acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 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, etc. Ketones, N-methyl-2-pyrrolidone, etc., and, as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. can be preferably cited, and as the sulfenes, for example, Particularly, dimethyl sulfoxide is mentioned, and a mixture of these organic solvents can also be preferably mentioned.

When the developer is a developer containing an organic solvent, in the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. In addition, when the developer contains an organic solvent, one type of organic solvent may be used, or two or more types may be mixed and used.

In the case that the developer is a developer containing an organic solvent, it is preferable that 50% by mass or more of the developer is an organic solvent, more than 70% by mass is an organic solvent, and more than 90% by mass is an organic solvent. good. In addition, in the developer, 100% by mass may be an organic solvent.

〔Method of supplying developer〕 The supply method of the developer is not particularly limited as long as the desired pattern can be formed. There are methods of immersing the substrate in the developer, spin immersion development in which the developer is supplied onto the substrate using a nozzle, or continuous supply. The developer method. The type of nozzle is not particularly limited, and examples include straight nozzles, shower nozzles, spray nozzles, and the like. From the viewpoints of the permeability of the developer, the removal of the non-image area, and the efficiency of manufacturing, the method of supplying the developer with a straight nozzle or the method of continuous supply with a spray nozzle is preferable. From the viewpoint of permeability, the method of supplying with a spray nozzle is better. In addition, after continuously supplying the developer with a straight nozzle, the substrate is rotated to remove the developer from the substrate, and after spin drying, after continuous supply with a straight nozzle again, the substrate is rotated and removed from the substrate. The step of developing solution can be repeated several times. In addition, as a method of supplying the developer in the development step, the step of continuously supplying the developer to the substrate, the step of holding the developer on the substrate in a substantially stationary state, and the use of ultrasonic waves to make the developer The step of vibrating on the substrate, the step of combining the same, and the like.

When the developer is an alkaline aqueous solution, examples of the alkaline compound that can be contained in the alkaline aqueous solution include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), sodium carbonate, etc., and TMAH is preferred. For example, in the case of using TMAH, the content of the alkaline compound in the developer is preferably 0.01-10% by mass in the total mass of the developer, more preferably 0.1-5% by mass, and more preferably 0.3-3% by mass. Better.

〔Method of supplying developer〕 The supply method of the developer is not particularly limited as long as the desired pattern can be formed. There are methods of immersing the substrate in the developer, spin immersion development in which the developer is supplied onto the substrate using a nozzle, or continuous supply. The developer method. The type of nozzle is not particularly limited, and examples include straight nozzles, shower nozzles, spray nozzles, and the like. From the viewpoints of the permeability of the developer, the removal of the non-image area, and the efficiency of manufacturing, the method of supplying the developer with a straight nozzle or the method of continuous supply with a spray nozzle is preferable. From the viewpoint of permeability, the method of supplying with a spray nozzle is better. In addition, after continuously supplying the developer with a straight nozzle, the substrate is rotated to remove the developer from the substrate, and after spin drying, after continuous supply with a straight nozzle again, the substrate is rotated and removed from the substrate. The step of developing solution can be repeated several times. In addition, as a method of supplying the developer in the development step, the step of continuously supplying the developer to the substrate, the step of holding the developer on the substrate in a substantially stationary state, and the use of ultrasonic waves to make the developer The step of vibrating on the substrate, the step of combining the same, and the like.

As the development time, 5 seconds to 10 minutes are preferable, and 10 seconds to 5 minutes are more preferable. The temperature of the developing solution during development is not particularly defined, but it can usually be performed at 10 to 45°C, preferably 20 to 40°C.

After the treatment using the developer is performed, further rinsing can be performed. In addition, a method such as supplying a rinse liquid before the developer in contact with the pattern is not completely dried can be adopted. Rinsing is preferably carried out in a solvent different from the developer. For example, the solvent contained in the resin composition can be used for rinsing. When the developer is a developer containing an organic solvent, examples of the rinse liquid include PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropanol), etc., and PGMEA is preferred. In addition, as a rinsing liquid for development based on a developer containing an alkaline aqueous solution, water is preferable. The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, and even more preferably 5 seconds to 1 minute. The temperature of the rinsing liquid during rinsing is not particularly defined, but it can be preferably performed at 10 to 45°C, more preferably 18 to 30°C.

Regarding the organic solvent when the rinse solution contains an organic solvent, as esters, for example, ethyl acetate, n-butyl acetate, pentyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, Isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate ( For example: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetic acid Methyl ester, ethyl ethoxy acetate, etc.), 3-alkoxypropionic acid alkyl esters (for example: 3-alkoxypropionic acid methyl ester, 3-alkoxypropionic acid ethyl ester, etc. (for example, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionic acid Alkyl esters (for example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy-2- Methyl methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate Ethyl ester, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate Etc., and, as the ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl siloxol acetate, ethyl sulfonate Luthose 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 mono Ethyl 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 aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. can be preferably cited, and as the sulfenes, for example, Examples include dimethyl sulfide, and, as alcohols, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl iso Butyl carbitol, triethylene glycol, etc., and as the amines, preferably N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. can be cited.

In the case where the rinsing liquid contains an organic solvent, one organic solvent can be used or two or more of them can be mixed and used. In the present invention, cyclopentanone, γ-butyrolactone, dimethylsulfene, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME are particularly preferred, and cyclopentanone, γ-butyrolactone Esters, dimethyl sulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are even more preferred.

When the rinsing liquid contains an organic solvent, it is preferable that 50% by mass or more of the rinsing liquid is an organic solvent, more preferably 70% by mass or more is an organic solvent, and more preferably 90% by mass or more is an organic solvent. In addition, in the rinse liquid, 100% by mass may be an organic solvent.

The rinsing fluid may also contain other ingredients. As other components, a well-known surfactant, a well-known defoamer, etc. are mentioned, for example.

〔Method of supplying rinsing fluid〕 Regarding the supply method of the rinsing liquid, as long as the desired pattern can be formed, there are no particular restrictions. There are methods of immersing the substrate in the rinsing liquid, spin immersion development on the substrate, and spraying the substrate to the substrate. The method of supplying the rinse liquid, the method of continuously supplying the developer liquid to the substrate by means of a straight nozzle or the like. From the viewpoint of the permeability of the rinse liquid, the removal of the non-image area, and the efficiency of manufacturing, the method of supplying the rinse liquid with spray nozzles, straight nozzles, spray nozzles, etc., is better than the continuous supply of spray nozzles. 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 nozzle is not particularly limited, and examples include straight nozzles, shower nozzles, spray nozzles, and the like. That is, it is preferable that the rinsing step is a step of supplying the above-mentioned exposed film with a straight nozzle or a step of continuously supplying a rinsing liquid, and a step of supplying a rinsing liquid with a spray nozzle is more preferable. In addition, as a method of supplying the developer in the rinsing step, the step of continuously supplying the rinsing liquid to the substrate, the step of holding the rinsing liquid on the substrate in a substantially stationary state, and the use of ultrasonic waves to make the rinsing liquid The step of vibrating on the substrate, the step of combining the same, and the like.

＜Heating step＞ The manufacturing method of the present invention preferably includes a step of heating the developed film at 50 to 450°C (heating step). It is preferable to include a heating step after the film formation step (layer formation step), the drying step, and the development step. In the heating step, for example, the above-mentioned hot alkali generator is decomposed to generate an alkali, and the cyclization reaction as a precursor of the specific resin proceeds. In addition, the resin composition of the present invention may contain a radical polymerizable compound other than the specific resin precursor, but it can also be carried out in this step other than the unreacted specific resin precursor. The hardening and so on. As the heating temperature (maximum heating temperature) of the layer in the heating step, 50°C or higher is preferred, 80°C or higher is more preferred, 140°C or higher is more preferred, 150°C or higher is more preferred, and 160°C or higher is even more preferred. More preferably, 170°C or higher is even more preferable. As the upper limit, 500°C or less is preferred, 450°C or less is more preferred, 350°C or less is more preferred, 250°C or less is more preferred, and 220°C or less is even more preferred.

Regarding heating, it is preferable to perform the heating rate from the temperature at the start of heating to the maximum heating temperature at a temperature increase rate of 1 to 12°C/min, more preferably 2 to 10°C/min, and still more preferably 3 to 10°C/min. By setting the heating rate to 1°C/min or more, productivity can be ensured while preventing excessive volatilization of amines, and by setting the heating rate to 12°C/min or less, the residual stress of the cured film can be reduced. Furthermore, in the case of an oven capable of rapid heating, it is preferable to proceed from the temperature at the start of heating to the maximum heating temperature at a rate of temperature increase of 1 to 8°C/sec, and more preferably 2 to 7°C/sec. 3 to 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 more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at which the step of heating to the highest heating temperature is started. For example, when the resin composition is applied to the substrate and then dried, the temperature of the dried film (layer), for example, is 30 to 200°C lower than the boiling point of the solvent contained in the resin composition It is better to start to warm up gradually.

The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and more preferably 30 to 240 minutes.

In particular, in the case of forming a multilayer laminate, the heating temperature is preferably 180°C to 320°C, more preferably 180°C to 260°C, from the viewpoint of the adhesion between the layers of the cured film. Although the reason is not clear, it is thought that the reason is that the ethynyl groups of the specific resins between the layers undergo a crosslinking reaction by setting the temperature to this temperature.

Heating can be carried out in stages. As an example, the following pretreatment steps can be performed: heating from 25°C to 180°C at 3°C/min, holding at 180°C for 60 minutes, and heating from 180°C to 200°C at 2°C/min, at 200°C Keep it for 120 minutes. The heating temperature as the pretreatment step is preferably 100 to 200°C, more preferably 110 to 190°C, and even more preferably 120 to 185°C. In this pretreatment step, as described in the specification of US Patent No. 9159547, it is also preferable to perform treatment while irradiating ultraviolet rays. Through such a pretreatment step, the characteristics of the film can be further improved. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and 15 seconds to 30 minutes is more preferable. The pretreatment may also be a two-stage or more step. For example, the pretreatment step 1 may be performed in the range of 100 to 150°C, and then the pretreatment step 2 may be performed in the range of 150 to 200°C.

Furthermore, cooling may be performed after heating, 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 flowing inert gas such as nitrogen, helium, and argon. 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 mechanism, For example, a hotplate, an infrared furnace, an electric heating type oven, a hot air type oven, etc. are mentioned.

＜Metal layer formation steps＞ The manufacturing method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the film (resin composition layer) after development.

The metal layer is not particularly limited. Existing metal types can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper, aluminum, and alloys containing these metals are more preferable , Copper is further preferred.

The method of forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, and Japanese Patent Application Publication No. 2004-101850 can be applied. For example, methods such as photolithography, lift off, electrolytic plating, electroless plating, etching, printing, and combinations thereof can be considered. More specifically, a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electroplating can be cited.

As for the thickness of the metal layer, at the thickest part, 0.01 to 100 μm is preferable, 0.1 to 50 μm is more preferable, and 1 to 10 μm is more preferable.

＜Layering Steps＞ Preferably, the manufacturing method of the present invention further includes a layering step.

The layering step includes performing (a) the film formation step (layer formation step), (b) the exposure step, (c) the development step, and (d) the heating step in sequence again on the surface of the cured film (resin layer) or the metal layer. A series of steps. However, it may be the aspect in which only the (a) film forming step is repeatedly performed. In addition, it can be set as the aspect in which the heating step (d) is collectively performed at the end or in the middle of the build-up layer. That is, it can be set as follows: the steps (a) to (c) are repeated a specified number of times, and then (d) heating is performed to collectively harden the laminated resin composition layer. In addition, after the (c) development step, the (e) metal layer forming step may be included. In this case, the heating of (d) may be performed every time, or the heating of (d) may be performed collectively after a specified number of laminations. It is self-evident that the above-mentioned drying step, heating step, etc. can also be included in the layering step as appropriate.

In the case where a layering step is further performed after the layering step, a surface activation treatment step may be further performed after the heating step, after the exposure step, or after the metal layer forming step. As the surface activation treatment, plasma treatment can be exemplified.

The above-mentioned layering step is preferably performed 2 to 20 times, more preferably 2 to 5 times, and even more preferably 3 to 5 times. In addition, each layer in the layering step may have the same composition, shape, film thickness, etc., or may be different layers.

For example, a structure such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferable to have a resin layer of 2 or more and 20 layers or less, and a resin layer of 3 or more and 7 layers or less. The structure is more preferable, and 3 layers or more and 5 layers or less are more preferable.

In the present invention, it is particularly preferable to form a cured film (resin layer) of the resin composition to cover the metal layer after the metal layer is provided. Specifically, there can be mentioned a state in which (a) a film formation step, (b) an exposure step, (c) a development step, (e) a metal layer formation step, and (d) a heating step are repeated in the order of (a) The sequence of a) film formation step, (b) exposure step, (c) development step, and (e) metal layer formation step is repeated and the (d) heating step is set at the end or in the middle. By alternately performing the laminating step of the laminated resin composition layer (resin layer) and the metal layer forming step, the resin composition layer (resin layer) and the metal layer can be alternately laminated.

The present invention also discloses a semiconductor element including the cured film or laminate of the present invention. As a specific example of a semiconductor element using the resin composition of the present invention for the formation of an interlayer insulating film for a rewiring layer, refer to the description in paragraphs 0213 to 0218 of JP 2016-027357 A and the description in FIG. 1. And other contents are incorporated into this manual.

(Surface activation treatment step) The manufacturing method of the laminate of the present invention may include a surface activation treatment step of subjecting at least a part of the metal layer and the photosensitive resin composition layer to a surface activation treatment. The surface activation treatment step is usually performed after the metal layer formation step, but after the above-mentioned exposure and development step, the photosensitive resin composition layer may be subjected to the surface activation treatment step and then the metal layer formation step may be performed. The surface activation treatment may be performed only on at least a part of the metal layer, or only on at least a part of the photosensitive resin composition layer after exposure, or on both the metal layer and the photosensitive resin composition layer after exposure. At least part of it is carried out separately. It is preferable to perform a surface activation treatment on at least a part of the metal layer, and it is preferable to perform a surface activation treatment on a part or all of the area where the photosensitive resin composition layer is formed on the surface of the metal layer. In this way, by performing surface activation treatment on the surface of the metal layer, the adhesion with the resin layer provided on the surface can be improved. In addition, it is preferable to also perform surface activation treatment on part or all of the photosensitive resin composition layer (resin layer) after exposure. In this way, by subjecting the surface of the photosensitive resin composition layer to surface activation treatment, it is possible to improve the adhesion with the metal layer or the resin layer provided on the surface subjected to the surface activation treatment. The surface activation treatment is specifically selected from various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.) plasma treatment, corona discharge treatment, based on CF ₄ /O ₂ , NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ /O ₂ etching treatment, surface treatment based on ultraviolet (UV) ozone method, immersed in hydrochloric acid aqueous solution to remove oxide film, and immersed in amine containing amine The treatment in the organic surface treatment agent of the compound of at least one of the thiol group and the thiol group, the mechanical roughening treatment using a brush, the plasma treatment is better, especially the oxygen plasma treatment using oxygen in the raw gas is better good. 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 . [Example]

Examples are given below to further specifically illustrate the present invention. The materials, usage amount, ratio, processing content, processing procedure, etc. shown in the following examples can be appropriately changed as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are quality standards.

<Synthesis Example 1> [Synthesis of polyimide precursor (A-1) from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate] 14.06g mixed (64.5 millimoles) of pyromellitic dianhydride (obtained by drying at 140°C for 12 hours), 16.8 g (129 millimoles) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4g of pyridine (258 millimoles) and 100g of diglyme (diethylene glycol dimethyl ether) were stirred at 60°C for 18 hours to produce pyromellitic acid and methyl Diester of 2-hydroxyethyl acrylate. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 millimoles) of SOCl _{2 was} added over 10 minutes while maintaining the temperature at -10±4°C. During the addition of SOCl ₂ , the viscosity increased. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution prepared by dissolving 11.08 g (58.7 millimoles) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was dropped at -5 to 0°C for 20 minutes Add to the reaction mixture. Next, after the reaction mixture was allowed to react at 0°C for 1 hour, 70 g of ethanol was added and stirred at room temperature overnight. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimine precursor mixture was stirred at a speed of 5,000 rpm (revolutions per minute) for 15 minutes. The polyimide precursor was obtained by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Next, under a reduced pressure state, the obtained polyimine precursor was dried at 45° C. for 3 days, thereby obtaining a polyimine precursor A-1. The weight average molecular weight of the polyimide precursor A-1 was 19,000. It is estimated that the obtained polyimide precursor A-1 contains a repeating unit represented by the following formula (A-1). [Chemical formula 58]

<Synthesis Example 2> [Synthesis of polyimide precursor from 3,3',4,4'-biphenyltetracarboxylic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-2)] Mix 20.0g (64.5 millimoles) of 3,3',4,4'-biphenyltetracarboxylic anhydride (obtained by drying at 140°C for 12 hours), 16.8g (129 millimoles) Ears) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 20.4g (258 millimoles) of pyridine and 100g of diglyme (water content of 88ppm) at a temperature of 60°C After stirring for 18 hours, a diester of 3,3',4,4'-biphenyltetracarboxylic acid and 2-hydroxyethyl methacrylate was produced. Next, the obtained diester was _{chlorinated with SOCl 2 and} then converted into a polyimide precursor using 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and the same as in Synthesis Example 1. The polyimide precursor A-2 was obtained in the same way. The weight average molecular weight of the polyimide precursor A-2 was 20,000. It is estimated that the obtained polyimide precursor A-2 contains a repeating unit represented by the following formula (A-2). In the repeating unit represented by formula (A-2), there are single bonds contained in the biphenyl structure derived from 3,3',4,4'-biphenyltetracarboxylic anhydride and 3,3',4 ,4'-Biphenyltetracarboxylic acid anhydride and 2-hydroxyethyl methacrylate ester structure exists in the meta position on the benzene ring and in the para position (for example, the following formula (A-2- 2) Repeating units etc.), it is considered that these structures are mixed in the polyimide precursor A-2. In the same way, in the following synthesis examples, it represents the polyamide produced when 3,3',4,4'-biphenyltetracarboxylic anhydride or 4,4'-oxydiphthalic anhydride is used as the acid dianhydride. The chemical formula of the repeating unit contained in the precursor of the imine is derived from the single bond contained in the biphenyl structure of 3,3',4,4'-biphenyltetracarboxylic anhydride or 4,4'-oxydi The positional relationship of the ether bond contained in the phthalic anhydride, the ester bond bonded to the benzene ring contained in each repeating unit, and the amide bond on the benzene ring is not limited to the structure described in the chemical formula, and can be set Because the above-mentioned positional relationship is different, there are also mixed. [Chemical formula 59]

<Synthesis Example 3> [Synthesis of polyimide precursor (A- 3)] Mix 20.0 g (64.5 millimoles) of 4,4'-oxydiphthalic anhydride (obtained by drying at 140°C for 12 hours) and 16.8 g (129 millimoles) of methacrylic acid 2-hydroxyethyl, 0.05g of hydroquinone, 20.4g of pyridine (258 millimoles) and 100g of diglyme were stirred at 60°C for 18 hours to produce 4,4' -Diester of oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was _{chlorinated with SOCl 2 and} then converted into a polyimide precursor using 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and the same as in Synthesis Example 1. The polyimide precursor A-3 was obtained in the same way. The weight average molecular weight of the polyimide precursor A-3 was 18,000. It is estimated that the obtained polyimide precursor A-3 contains a repeating unit represented by the following formula (A-3). [Chemical formula 60]

<Synthesis Example 4> [From 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (tolidine) and methacrylic acid 2 -Hydroxyethyl synthetic polyimide precursor (A-4)] Mix 20.0g (64.5 millimoles) of 4,4'-oxydiphthalic anhydride (obtained by drying at 140°C for 12 hours) ), 16.8g (129 millimoles) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 20.4g of pyridine (258 millimoles) and 100g of diglyme (moisture content of 67ppm) , And stirred at a temperature of 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was _{chlorinated with SOCl 2 and} then converted into polyimide using 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example 1. The precursor, and the polyimide precursor A-4 was obtained by the same method as in Synthesis Example 1. The weight average molecular weight of this polyimide precursor A-4 was 19,000. It is estimated that the obtained polyimide precursor A-4 contains a repeating unit represented by the following formula (A-4). [Chemical formula 61]

＜Synthesis example 5＞ [Synthesis of polyimide precursor (A”-5) from 4,4’-oxydiphthalic anhydride, 4,4’-diaminodiphenyl ether and 2-hydroxyethyl methacrylate] Mix 20.0 g (64.5 millimoles) of 4,4'-oxydiphthalic anhydride (obtained by drying at 140°C for 12 hours) and 16.8 g (129 millimoles) of 2-hydroxy methacrylic acid Ethyl ester, 0.05 g of hydroquinone, 20.4 g of pyridine (258 millimoles) and 200 g of γ-butyrolactone were stirred at room temperature for 36 hours to produce 4,4'-oxydiphthalic acid And the diester of 2-hydroxyethyl methacrylate. Next, under ice cooling, a solution in which 26.6 g of dicyclohexylcarbodiimide (DCC) was dissolved in 25 g of γ-butyrolactone was added dropwise while stirring. Then, while stirring, over 60 minutes, 12.0 g of 4,4'-diaminodiphenyl ether was suspended in 45 ml of γ-butyrolactone and 3.8 g of DCC was dissolved in 10 g of γ-butyrolactone. Solution. Furthermore, after stirring for 2 hours at room temperature, 30 ml of ethanol was added and stirred for 1 hour, and then 100 ml of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction liquid. Next, the polyimide precursor was precipitated in 3 liters of water, and the water-polyimine precursor mixture was stirred at a speed of 5,000 rpm (revolutions per minute) for 15 minutes. The polyimide precursor was obtained by filtration and dissolved in 300 mL of tetrahydrofuran, and then again as a precipitate in 2 liters of water to obtain the polyimide precursor. Under reduced pressure, the obtained polyimine precursor was dried at 45°C for 3 days to obtain polyimine precursor A"-5. The polyimine precursor A"-5 was The weight average molecular weight is 22,000.

＜Synthesis example 6＞ [Synthesis of polyimide precursor (A”-6) from pyromellitic dianhydride, 4,4’-diaminodiphenyl ether and 2-hydroxyethyl methacrylate] Mix 14.1g (64.5 millimoles) of pyromellitic dianhydride, 16.8g (129 millimoles) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, and 20.4g (258 millimoles) of Pyridine and 200 g of γ-butyrolactone were stirred at room temperature for 36 hours to produce a diester of 3,3',4,4'-biphenyltetracarboxylic acid and 2-hydroxyethyl methacrylate. Next, using DCC, the obtained diester was converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same method as in Synthesis Example 5, and obtained by the same method as Synthesis Example 5. The polyimide precursor A"-6 was prepared. The weight average molecular weight of the polyimide precursor A"-6 was 20,000.

<Synthesis Example 7> [Synthesis of polyimide precursor (A"-7 from 3,3',4,4'-biphenyltetracarboxylic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate )] Mix 19.0g (64.5 millimoles) of 3,3',4,4'-biphenyltetracarboxylic anhydride, 16.8g (129 millimoles) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 20.4g (258 millimoles) of pyridine and 200g of γ-butyrolactone were stirred at room temperature for 36 hours to produce 3,3',4,4'-biphenyltetracarboxylic acid and methacrylic acid 2 -The diester of hydroxyethyl. Next, using DCC, the obtained diester was converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same method as in Synthesis Example 5, and obtained by the same method as Synthesis Example 5. The polyimide precursor A"-7. The weight average molecular weight of the polyimide precursor A"-7 is 21,000.

＜Synthesis example 8＞ 〔Synthesized from 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (tolidine) and 2-hydroxyethyl methacrylate Polyimide precursor (A”-8)] Mix 19.0g (64.5 millimoles) of 4,4'-oxydiphthalic anhydride, 16.8g (129 millimoles) of 2-hydroxyethyl methacrylate, 0.05g hydroquinone, 20.4g ( 258 millimoles) of pyridine and 200 g of γ-butyrolactone were stirred at room temperature for 36 hours to produce 3,3',4,4'-biphenyltetracarboxylic acid and 2-hydroxyethyl methacrylate The diester of an ester. Next, using DCC, the obtained diester was converted into polyimide with 4,4'-diamino-2,2'-dimethylbiphenyl (tolidine) in the same manner as in Synthesis Example 5. The polyimide precursor A"-8 was obtained by the same method as in Synthesis Example 5. The weight average molecular weight of the polyimide precursor A"-8 was 19,000.

<Synthesis Example 1-1> [Pyromellitic dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate modified polyimide precursor A-1 (polyamide Synthesis of imine precursor A'-1)] 20 g of polyimine precursor A-1 obtained in Synthesis Example 1 was dissolved in 200 g of tetrahydrofuran. Next, under ice cooling, a solution of 13.0 g of DCC dissolved in 50 g of tetrahydrofuran was added dropwise while stirring. Stirring was continued for 2 hours under ice cooling. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction liquid. Next, the polyimide precursor was precipitated in 3 liters of water, and the water-polyimine precursor mixture was stirred at a speed of 5,000 rpm (revolutions per minute) for 15 minutes. The polyimide precursor was obtained by filtration, and under reduced pressure, the obtained polyimine precursor was dried at 45°C for 3 days, thereby obtaining the polyimide precursor A'-1 . The weight average molecular weight of the polyimide precursor A'-1 was 20,500. It is estimated that the polyimide precursor A'-1 contains a repeating unit of the structure represented by the following formula (A'-1). [Chemical formula 62]

<Synthesis Example 2-1> [Modified Polypropylene by 3,3',4,4'-biphenyltetracarboxylic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate Amine precursor A-2 (synthesis of polyimide precursor A'-2)] In Synthesis Example 1-1, 20 g of polyimine precursor A-2 obtained in Synthesis Example 2 was used instead Except for the polyimide precursor A-1, a polyimide precursor A'-2 as a modified polyimine precursor was obtained in the same manner as in Synthesis Example 1-1. The weight average molecular weight of the polyimide precursor A'-2 was 21,200. It is estimated that the polyimide precursor A'-2 contains a repeating unit of the structure represented by the following formula (A'-2). [Chemical formula 63]

<Synthesis Example 3-1> [Modified polyimide precursor from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate A-3 (Synthesis of polyimide precursor A'-3)] In Synthesis Example 1-1, 20 g of polyimide precursor A-3 obtained in Synthesis Example 3 was used instead of polyimide Except for the amine precursor A-1, a polyimide precursor A'-3 as a modified polyimine precursor was obtained in the same manner as in Synthesis Example 1-1. The weight average molecular weight of the polyimide precursor A'-3 was 18,500. It is estimated that the polyimide precursor A'-3 contains a repeating unit of the structure represented by the following formula (A'-3). [Chemical formula 64]

<Synthesis Example 4-1> [From 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (tolidine) and methyl 2-hydroxyethyl acrylate modified polyimide precursor A-4 (synthesis of polyimide precursor A'-4)] In Synthesis Example 1-1, the polyimide precursor obtained in Synthesis Example 4 was used Except that 20 g of the polyimide precursor A-4 was substituted for the polyimide precursor A-1, a modified polyimide precursor A'-4 was obtained in the same manner as in Synthesis Example 1-1. The weight average molecular weight of the polyimide precursor A'-4 was 20,500. It is estimated that the polyimide precursor A'-4 contains a repeating unit of the structure represented by the following formula (A'-4). [Chemical formula 65]

<Synthesis Example 5-1> [Modification of polyamide by 3,3',4,4'-biphenyltetracarboxylic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate Amine precursor A-2 (synthesis of polyimide precursor A'-5)] In Synthesis Example 1-1, 20 g of polyimine precursor A-2 obtained in Synthesis Example 2 was used instead Polyimide precursor A-1, and using diisopropylcarbodiimide (DIC) instead of DCC, except that the modified polyimide precursor was obtained in the same way as Synthesis Example 1-1物A'-5. The weight average molecular weight of the polyimide precursor A'-5 was 21,000. It is estimated that the polyimide precursor A'-5 contains a repeating unit of the structure represented by the following formula (A'-5). [Chemical formula 66]

<Synthesis Example 6-1> [Modified Polypropylene by 3,3',4,4'-biphenyltetracarboxylic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate Amine precursor A-2 (synthesis of polyimide precursor A'-6)] In Synthesis Example 1-1, 20 g of polyimine precursor A-2 obtained in Synthesis Example 2 was used instead Polyimide precursor A-1, and using (2,6-diisopropylphenyl)carbodiimide (DIPC) instead of DCC, except that it was obtained by the same method as Synthesis Example 1-1 The modified polyimide precursor A'-6. The weight average molecular weight of this polyimide precursor A'-6 was 21,500. It is estimated that the polyimide precursor A'-6 contains a repeating unit of the structure represented by the following formula (A'-6). [Chemical formula 67]

<Synthesis Example 7-1> [Modified polyimide precursor from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate A-3 (Synthesis of polyimide precursor A'-7)] In Synthesis Example 1-1, 20 g of polyimide precursor A-3 obtained in Synthesis Example 3 was used instead of polyimide The modified polyimide precursor A'-7 was obtained in the same manner as in Synthesis Example 1-1 except that DIC was used instead of DCC as the amine precursor A-1. The weight average molecular weight of this polyimide precursor A'-7 was 19,000. It is estimated that the polyimide precursor A'-7 contains a repeating unit of the structure represented by the following formula (A'-7). [Chemical formula 68]

<Synthesis example 8-1> [Synthesis of polyimide P-1]] In a flask equipped with a condenser and a stirrer, the anhydride represented by the following formula (a-1) (a- 1) 11.4g (25 millimoles) is dissolved in 33.1g of N-methylpyrrolidone (NMP). Next, 2.70 g (25 millimoles) of 1,3-phenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, stirred at 25°C for 3 hours, and further stirred at 45°C for 3 hours. Next, 7.50 g (94.8 millimoles) of pyridine, 6.38 g (62 millimoles) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) were added, followed by stirring at 80°C for 3 hours, and adding N-methyl 50 g of pyrrolidone (NMP) was diluted. The reaction liquid was precipitated in 1.2 liters of methanol, and stirred at a speed of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes, and filtered again. In a reduced pressure state, the obtained resin was dried at 40° C. for 1 day, thereby obtaining a closed-loop polyimide P-1. The molecular weight of P-1 is weight average molecular weight (Mw) = 74,300, and number average molecular weight (Mn) = 30,100. It is estimated that the structure of P-1 is a structure represented by the following formula (P-1). [Chemical formula 69]

＜Synthesis example H-1＞ In a three-necked flask, 41.3 g (0.20 mol) of dicyclohexylcarbodiimide and 200 mL of tetrahydrofuran were mixed. Next, a solution in which 24.4 g (0.02 mol) of benzoic acid was dissolved in 200 mL of tetrahydrofuran was added dropwise to the flask at room temperature for 30 minutes using a dropping funnel. After the dripping was completed, the reaction was continued for 30 minutes at room temperature and then allowed to stand for 24 hours. The precipitate was filtered and the filtrate was recovered. After concentrating the recovered filtrate (THF solution), compound H-1 was obtained as a white powder by recrystallization operation. The structure of compound H-1 is presumed to be a structure represented by formula (H-1) described later.

＜Synthesis example H-2＞ In Synthesis Example H-1, except that 36.0 g (0.2 mol) of monomethyl phthalate was used instead of benzoic acid, compound H-2 was obtained in the same manner as Synthesis Example H-1. The structure of the compound H-2 is estimated to be the structure represented by the formula (H-2) described later.

＜Synthesis example H-3＞ In Synthesis Example H-1, 44.5 g (0.2 mol) of 1,3-bis-p-tricarbodiimide was changed from dicyclohexylcarbodiimide, and benzoic acid was changed to 4-tert-butylbenzoic acid Except for 35.2 g (0.2 mol), the compound H-3 was obtained in the same manner as in Synthesis Example H-1. The structure of compound H-3 is presumed to be a structure represented by formula (H-3) described later.

＜Synthesis example H-4＞ In Synthesis Example H-1, the dicyclohexylcarbodiimide was changed to 1,3-bis-p-tricarbodiimide 44.5g (0.2mol), and the benzoic acid was changed to monomethyl phthalate 36.0 g (0.2 mol), except for this, compound H-4 was obtained in the same manner as in Synthesis Example H-1. The structure of the compound H-4 is estimated to be the structure represented by the formula (H-4) described later.

＜Synthesis example H-5＞ In Synthesis Example H-1, the dicyclohexylcarbodiimide was changed to 72.5g (0.2mol) of bis(2,6-diisopropylphenyl)carbodiimide. Otherwise, the same as in Synthesis Example Compound H-5 was obtained in the same way as H-1. The structure of compound H-5 is presumed to be the structure represented by formula (H-5) described later.

＜Synthesis example H-6＞ The dicyclohexylcarbodiimide used in Synthesis Example H-1 was changed to 44.5g (0.2mol) of 1,3-bis-p-tricarbodiimide, and benzoic acid was changed to phthalic acid monobutyl Except for 44.4 g (0.2 mol) of the ester, compound H-6 was obtained in the same manner as in Synthesis Example H-1. The structure of compound H-6 is presumed to be the structure represented by formula (H-6) described later.

＜Synthesis example H-7＞ 10.0 g (78 mmol) of 5,5-dimethylhydantoin and 40 mL of pyridine were mixed in a three-necked flask. 11.0 g (78 mmol) of chlorinated benzyl groups were added dropwise to the flask over 30 minutes at room temperature. After the dropwise addition was completed, the reaction was carried out at 170°C for 15 hours. After the reaction was completed, it was concentrated under reduced pressure and then diluted with ethyl acetate. After filtering with silica gel, it was recrystallized with ethyl acetate/hexane (a solvent made by mixing ethyl acetate and hexane with ethyl acetate:hexane=1:9 (volume ratio)) to obtain compound H -7 as a white powder. The structure of compound H-7 is presumed to be the structure represented by formula (H-7) described later.

<Synthesis Example H-8> In a three-necked flask, 1.26 g (10 mmol) of diisopropylcarbodiimide, 100 mL of tetrahydrofuran, and 1.41 g (10 mmol) of benzoyl chloride were mixed. Stirring was continued for 48 hours at room temperature. Then, 1.04 g (10 mmol) of 1,3-dimethylthiourea was added, and further stirring was continued for 12 hours. The reaction solution was concentrated under reduced pressure, by silica gel column chromatography using ethyl acetate/hexane (mixing ethyl acetate and hexane with ethyl acetate:hexane=1:9 (volume ratio)) Solvent) was purified to obtain compound H-8 as a white solid. The structure of the compound H-8 is presumed to be the structure represented by the formula (H-8) described later. [Chemical formula 70]

<Examples and Comparative Examples> In each of the Examples and Comparative Examples, the components described in Table 1 below were mixed to obtain a resin composition or a comparative composition. The values in the column of each component except for the solvents described in Table 1 indicate the content (parts by mass) of each component. The obtained resin composition and the comparative composition were filtered under pressure through a filter made of polytetrafluoroethylene having a pore width of 0.8 μm. In addition, in Table 1, the description of "-" indicates that the corresponding component is not contained.

[Table 1] Resin Thermal alkali generator Free radical polymerization initiator Radical polymerizable compound Polymerization inhibitor Migration inhibitor Silane coupling agent Specific compound Solvent Other additives Specific structure content type Mass parts type Mass parts type Mass parts type Mass parts type Mass parts type Mass parts type Mass parts type Mass parts type Mass parts type Mass parts type Mass parts type Mass parts mmol/g Example 1 A-1 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.10 2 A"-5 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.11 3 A'-1 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 - - I-1 43.3 I-2 14.4 - - J-2 1 0.09 4 A"-5 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 - - I-1 43.3 I-2 14.4 - - J-2 1 0.04 5 A-1 34.8 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-1 0.2 I-1 42.2 I-2 14.1 - - J-2 1 0.014 6 A-1 33.0 B-1 0.75 C-1 1.26 D-1 4.85 E-1 0.084 F-1 0.126 G-1 0.63 H-1 10.3 I-1 36.7 I-2 12.3 - - J-2 1 0.62 7 A-3 25.2 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 - - I-1 43.3 I-2 14.4 - - J-2 1 0.01 A"-5 8.4 8 A-2 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-2 0.084 F-1 0.126 G-3 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.10 9 A-3 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-2 0.126 G-1 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.10 10 A-4 33.6 B-2 0.75 C-1 1.26 D-1 5.88 E-3 0.084 F-1 0.126 G-1 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.10 11 A"-6 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-2 0.126 G-1 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.11 12 A"-7 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.11 13 A"-8 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.11 14 A'-2 33.6 B-1 0.75 C-1 1.26 D-2 5.88 E-1 0.084 F-1 0.126 G-1 0.63 - - I-1 43.3 I-2 14.4 - - J-2 1 0.07 15 A'-3 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 - - I-1 43.3 I-2 14.4 - - J-2 1 0.05 16 A'-4 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-3 0.126 G-1 0.63 - - I-1 43.3 I-2 14.4 - - J-2 1 0.04 17 A-2 16.8 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 - - I-1 I-1 43.3 I-2 14.4 - - J-2 1 0.05 A"-7 16.8 18 A-1 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-3 0.084 F-1 0.126 G-2 0.63 H-2 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.09 19 A-1 33.6 B-1 0.75 C-2 1.26 D-1 5.88 E-2 0.084 F-1 0.126 G-1 0.63 H-3 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.09 20 A-2 33.6 B-3 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-4 1.5 I-3 56.3 - - - - J-2 1 0.09 twenty one A-3 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-4 0.126 G-1 0.63 H-5 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.08 twenty two A-3 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-6 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.08 twenty three A-3 33.6 B-1 0.75 C-3 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-7 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.15 twenty four A-2 33.6 B-4 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-8 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.12 25 A'-5 33.6 B-5 0.75 C-1 1.26 D-3 5.88 E-1 0.084 F-1 0.126 G-1 0.63 - - I-1 43.3 I-2 14.4 - - J-2 1 0.05 26 A'-6 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 - - I-1 43.3 I-2 14.4 - - J-2 1 0.05 27 A'-7 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 - - I-1 43.3 I-2 14.4 - - J-2 1 0.04 28 A-1 33.6 - - C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-1 2.3 I-1 42.2 I-2 14.1 - - J-2 1 0.16 29 P-1 33.6 - - C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-1 1.5 I-3 57.0 - - - - J-2 1 0.10 30 A-4 33.6 B-2 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-4 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - J-2 1 0.10 31 A-4 28 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-1 twenty two I-1 33.2 I-2 8.1 - - J-2 1 1.14 32 A-1 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - - - 0.10 33 A"-5 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 H-1 1.5 I-1 42.2 I-2 14.1 - - - - 0.10 Comparative example 1 A-4 35.0 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-2 0.126 G-1 0.63 - - I-3 56.3 - - - - J-2 1 0.00 2 A-4 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-2 0.126 G-1 0.63 - - I-3 56.3 - - J-1 1.5 J-2 1 0.00

The details of each component described in Table 1 are as follows.

〔Resin〕 ・A-1～A-4, A”-5～A”-8, A'-1～A'-7, P-1: Polyimide precursor A-1 synthesized in the above synthesis example ～A-4, polyimide precursor A"-5～A"-8, polyimide precursor A'-1～A'-7, polyimine P-1

[Thermal base generator] ・B-1～B-5: Compounds represented by the following formulas (B-1)～(B-5) [Chemical formula 71]

〔Initiator for radical polymerization〕 ・C-1: IRGACURE OXE 01 (manufactured by BASF) ・C-2: IRGACURE OXE 02 (manufactured by BASF) ・C-3: IRGACURE 369 (manufactured by BASF Corporation)

[Radical polymerizable compound] ・D-1: A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.) ・D-2: SR-209 (manufactured by Sartomer Company, Inc, compound with the following structure) ・D -3: A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.) [Chemical formula 72]

〔Polymerization inhibitor〕 ・E-1: 2-nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・E-2: p-benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・E-3: p-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Migration inhibitor] ・F-1～F-4: Compounds of the following structure [Chemical formula 73]

[Silane Coupling Agent (Metal Adhesion Improver)] ・G-1 to G-4: Compounds with the following structures. In the following structural formulae, Et represents an ethyl group. [Chemical formula 74]

〔Specific compounds〕 ・H-1～H-8: The above compounds H-1～H-8

[Other additives] ・J-1: Compound represented by the following formula (J-1) ・J-2: N-phenyldiethanolamine [Chemical formula 75]

〔Solvent〕 ・I-1: N-Methyl-2-pyrrolidone ・I-2: Ethyl lactate ・I-3: γ-butyrolactone: dimethyl sulfide = 80% by mass: 20% by mass mixed solvent

＜Evaluation＞ [Quantification of specific structures] The method for quantifying the content of the specific structure when the additives (compounds H-1 to H-8) are added and when they are bonded to the polymer is as follows.

-When added as an additive- _{NMR analysis was performed on the prepared composition with d 6} -DMSO (dimethyl sulfide-d ₆ ) to calculate the molar ratio of the polymer and the additive. Next, after diluting the composition with tetrahydrofuran, a mixed solvent of water:acetone=50% by mass:50% by mass was added, the precipitate was filtered, and the obtained filtrate was dried. The mass of the polymer is obtained by calculating the dry mass. The content of additives is quantified based on the molar ratio of polymer/additive and the quality of the polymer. -When bonding with polymer- After diluting the composition with tetrahydrofuran, a mixed solvent of water:acetone=50% by mass:50% by mass is added, the precipitate is filtered, and the obtained filtrate is dried. The mass of the polymer is obtained by calculating the dry mass. NMR analysis was performed on the obtained polymer with d ₆ -DMSO to calculate the molar ratio of the polymer and the additive. Quantify the content of a specific structure based on the mass of the polymer and the molar ratio. In addition, regarding the total solid content of the resin composition, the solvent was dried under the conditions of 70° C./0.1 Torr/3 hours, and the mass of the dried residue was defined as the total solid content. 1 Torr is a value representing one-760th of 1 atmospheric pressure, and is set to 133.322 Pa. In the above drying, it was ^{confirmed by 1} H-NMR of the volatile components (using DMSO (dimethyl sulfide)-d ₆ as the solvent) that there were no volatile components other than the solvent. The content (mol/g) of the structure represented by formula (1-1) relative to the total solid content of the resin composition was quantified by the above method, and the quantitative result was described in Table 1 "Content of specific structure" Bar.

[Evaluation of storage stability] Regarding the resin composition and the comparative composition prepared in each of the Examples and Comparative Examples, the viscosity was measured with an E-type viscometer immediately after preparation. At this time, the value of the measured viscosity is set to "viscosity (0 days)". After that, the resin composition and the comparative composition in each of the Examples and Comparative Examples were allowed to stand for 14 days under light-shielding and 25°C conditions in an airtight container, and then the viscosity was measured again using an E-type viscometer. At this time, set the value of the measured viscosity as "viscosity (14 days)". Calculate the viscosity change rate according to the following formula. Based on the above-mentioned viscosity change rate, the evaluation was performed in accordance with the following evaluation criteria. The evaluation results are described in the "Storage Stability" column of Table 2. It can be said that the lower the rate of change in viscosity, the higher the storage stability. Viscosity change rate=|100×{1-(viscosity (14 days)/viscosity (0 days))}| The measurement of viscosity is performed at 25°C, and other measurement conditions are based on JIS Z 8803:2011. -Evaluation criteria- A: The viscosity variation rate is 5% or less. B: The viscosity change rate exceeds 5%.

[Evaluation of Adhesion] The resin composition or comparative composition prepared in each of the Examples and Comparative Examples was applied to a copper substrate in a layer form by a spin coating method, thereby forming a resin composition layer or comparison Use the composition layer. The copper substrate on which the obtained resin composition layer or the comparative composition layer was formed was dried on a hot plate at 100°C for 5 minutes, thereby forming a resin composition layer or comparison with a uniform thickness of 20 μm on the copper substrate. Use the composition layer. Use a stepper (Nikon NSR 2005 i9C), use a mask that forms a 100μm square non-masked part, and use i-rays to expose the resin composition layer on the copper substrate with an exposure energy of ^{500mJ/cm 2 or compare} The composition layer was exposed to light, and then developed with cyclopentanone for 60 seconds to obtain a square-shaped resin layer of 100 μm square. Furthermore, it heated at 230 degreeC for 3 hours in a nitrogen atmosphere, and formed the resin layer (pattern). In an environment of 25°C and 65% relative humidity (RH), use a bonding strength tester (manufactured by XYZTEC Corporation, CondorSigma) to measure the shear force of a 100μm square resin layer on a copper substrate, and evaluate as follows Benchmarks were evaluated. The evaluation results are described in the "adhesion" column of Table 2. It can be said that the greater the shear force, the better the metal adhesion (copper adhesion) of the cured film. -Evaluation criteria- A: The shear force exceeds 40gf. B: Shear force exceeds 35 gf and is 40 gf or less. C: The shear force exceeds 25 gf and is 35 gf or less. D: Shear force is 25 gf or less. In addition, 1gf is 0.00980665N.

[Evaluation of reliability (metal adhesion after heating)] In each example or comparative example, in the evaluation of the above-mentioned adhesion, after heating at 230°C for 3 hours to form a resin layer, the resin layer was subjected to 1,000 hours in a constant temperature bath at 175°C, and then the shear force was measured. Except for this, the evaluation of the metal adhesion after heating was performed in accordance with the same evaluation method and evaluation criteria as the evaluation method in the evaluation of the adhesion described above. The evaluation results are described in the "reliability" column of Table 2. It can be said that the greater the shear force, the better the metal adhesion (copper adhesion) of the cured film.

[Table 2] Storage stability Adhesion reliability Example 1 A A A Example 2 B A A Example 3 A A A Example 4 B A A Example 5 A B B Example 6 A B B Example 7 A B B Example 8 A A A Example 9 A A A Example 10 A A A Example 11 B A A Example 12 B A A Example 13 B A A Example 14 A A A Example 15 A A A Example 16 A A A Example 17 A A A Example 18 A A A Example 19 A A A Example 20 A A A Example 21 A A A Example 22 A A A Example 23 A A A Example 24 A A A Example 25 A A A Example 26 A A A Example 27 A A A Example 28 A A A Example 29 A A A Example 30 A A A Example 31 B C C Example 32 A B B Example 33 B B B Comparative example 1 B D D Comparative example 2 B D D

Based on the above results, it can be seen that the solid content contains at least one resin selected from the group consisting of polyimine and polyimide precursors and the structure represented by formula (1-1) is used in the present invention. In the case of the resin composition, a cured film with excellent adhesion to the metal layer can be obtained. The composition for comparison described in Comparative Example 1 to Comparative Example 3 does not include the structure represented by the formula (1-1) in the solid content. It can be seen that the adhesiveness between the cured film and the metal layer obtained from such a comparative composition is poor.

<Example 101> The 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 by the spin coating method, and dried at 100°C for 5 minutes After forming a resin composition layer with a film thickness of 20 μm, exposure was performed using a stepper (manufactured by Nikon Co., Ltd., NSR1505 i6). The exposure was performed by irradiating light with a wavelength of 365 nm through a mask (a binary mask with a pattern of 1:1 lines and spaces and a line width of 10 μm). After exposure, it was developed with cyclopentanone for 30 seconds, and washed with PGMEA for 20 seconds, thereby obtaining a pattern of the layer. Then, it heated at 230 degreeC for 3 hours, and the interlayer insulating film for rewiring layers was formed. The interlayer insulating film for the rewiring layer has excellent insulating properties. In addition, semiconductor elements were manufactured using these interlayer insulating films for rewiring layers. As a result, normal operation was confirmed.

without.

Claims (13)

A resin composition comprising at least one resin selected from the group consisting of polyimine and polyimide precursors, and containing the structure represented by formula (1-1) in the solid content,

In the formula (1-1), R ¹ and R ² each independently represent an aliphatic group or an aromatic group. The carbon atom or hydrocarbon group of the aliphatic group or aromatic group may be substituted by a heteroatom, and X ¹ represents an oxygen atom or Sulfur atom, L ¹ represents -C(=O)- or -S(=O) ₂ -, * ¹ and * ² each independently represent the bonding site with other structures, R ¹ , R ² , and * ¹ bond At least two of the structure of the knot and the structure of * ^{2 can be bonded to form a ring structure.} The resin composition according to claim 1, wherein The aforementioned resin includes the structure represented by the aforementioned formula (1-1). The resin composition according to claim 1 or claim 2, which further includes a compound that includes the structure represented by the aforementioned formula (1-1) and is different from the aforementioned resin. The resin composition according to claim 1 or claim 2, which contains the structure represented by the following formula (1-2) as the structure represented by the aforementioned formula (1-1),

In the formula (1-2), R ²¹ and R ²² each independently represent an aliphatic group or an aromatic group. The carbon atom or hydrocarbon group of the aforementioned aliphatic group or aromatic group may be substituted with a hetero atom, and R ²³ represents a hydrogen atom or For a monovalent organic group, * indicates a bonding site with another structure ^{, and at least two of R 21} , R ²² , R ²³ and the structure bonded to * may be bonded to form a ring structure. The resin composition according to claim 1 or claim 2, wherein The molar content of the structure represented by the aforementioned formula (1-1) is 0.01 mmol/g to 1.0 mmol/g with respect to the total solid content of the resin composition. The resin composition according to claim 1 or claim 2, which further contains a photopolymerization initiator. The resin composition according to claim 1 or claim 2, which further contains a crosslinking agent. The resin composition according to claim 1 or claim 2, which is used for the formation of an interlayer insulating film for a rewiring layer. A cured film obtained by curing the resin composition according to any one of claims 1 to 8. A laminate having two or more layers of the cured film as described in claim 9 and a metal layer between any of the foregoing cured films. A method for producing a cured film includes a film forming step in which the resin composition according to any one of claims 1 to 8 is applied to a substrate to form a film. The method for producing a cured film according to claim 11, which includes the step of heating the film at 50°C to 450°C. A semiconductor element having the cured film described in claim 9.