CN105051608B

CN105051608B - Photosensitive resin composition, interlayer insulating film and method for producing same, liquid crystal display device, and organic electroluminescent display device

Info

Publication number: CN105051608B
Application number: CN201480017166.2A
Authority: CN
Inventors: 山田悟; 松田知树; 霜山达也; 山﨑健太
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2013-03-27
Filing date: 2014-03-25
Publication date: 2020-03-13
Anticipated expiration: 2034-03-25
Also published as: CN105051608A; WO2014157171A1; JPWO2014157171A1; KR20150107847A; TW201500846A; JP6116668B2; TWI598686B

Abstract

The invention provides a photosensitive resin composition, a method for manufacturing a cured film, a liquid crystal display device and an organic electroluminescent display device. The photosensitive resin composition can maintain high sensitivity, improve chemical resistance and further reduce relative dielectric constant. The photosensitive resin composition comprises: (A) a polymer component containing a polymer satisfying at least one of (1) and (2), (1) a polymer having (a1) a constituent unit containing a group in which an acid group is protected by an acid-decomposable group and (a2) a constituent unit containing a crosslinkable group, (2) a polymer having a constituent unit (a1) and a polymer having a constituent unit (a 2); (B) a photoacid generator; and (C) a solvent; the polymer component (A) contains at least one (a4) lactone structure-containing constituent unit or at least one polymer which contains the constituent unit (a4) and does not contain the constituent unit (a1) or the constituent unit (a 2).

Description

Photosensitive resin composition, interlayer insulating film and method for producing same, liquid crystal display device, and organic electroluminescent display device

Technical Field

The present invention relates to a photosensitive resin composition (hereinafter, may be simply referred to as "the composition of the present invention"). The present invention also relates to a method for producing a cured film using the photosensitive resin composition, a cured film obtained by curing the photosensitive composition, and various image display devices using the cured film.

More specifically, the present invention relates to a photosensitive resin composition suitable for forming a planarization film, a protective film, or an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic electroluminescence (organic EL) display device, an integrated circuit element, or a solid-state imaging element, and a method for producing a cured film using the photosensitive resin composition.

Background

In electronic components such as a thin Film transistor (hereinafter, referred to as "tft (thin Film transistor)") type liquid crystal display element, a magnetic head element, an integrated circuit element, and a solid-state imaging element, an interlayer insulating Film is generally provided to insulate between wirings arranged in a layered manner. As a material for forming the interlayer insulating film, a material having a sufficient flatness and a small number of steps for obtaining a desired pattern shape is preferable, and therefore, a photosensitive resin composition is widely used (for example, see patent documents 1 to 4).

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent laid-open publication No. 2011-221494

[ patent document 2] Japanese patent laid-open No. 2005-220360

[ patent document 3] Japanese patent laid-open No. 2004-46206

[ patent document 4] Japanese patent laid-open No. 2004-46098

Disclosure of Invention

Problems to be solved by the invention

In recent years, a photosensitive resin composition having a further reduced relative dielectric constant while maintaining high sensitivity and improving chemical resistance has been demanded.

As a result of studies, the inventors of the present invention have considered that in a photosensitive resin composition containing a group in which an acid group is protected with an acid-decomposable group and a crosslinkable group in the composition, the proportion of the acid-decomposable group or the acid group to be blended in the photosensitive resin composition is increased in order to increase the sensitivity to a higher level than before, but it is found that the chemical resistance is decreased in this case. In addition, it is known that if the ratio of the crosslinking group is increased to compensate for chemical resistance, the relative dielectric constant becomes too high.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a photosensitive resin composition which can maintain high sensitivity, can improve chemical resistance, and can further reduce the relative dielectric constant.

Means for solving the problems

The present inventors have conducted studies based on the above-described situation and have found that chemical resistance can be improved and relative dielectric constant can be reduced by blending a constituent unit containing a group in which an acid group is protected by an acid-decomposable group, a constituent unit containing a crosslinkable group, and a constituent unit containing a lactone structure into a photosensitive resin composition. Further, they found that high sensitivity can be maintained, and thus completed the present invention.

The reason for this is presumed to be that, by blending a constituent unit containing a group in which an acid group is protected by an acid-decomposable group and a constituent unit containing a crosslinkable group in a photosensitive resin composition and blending a constituent unit containing a lactone structure, it is possible to suppress a decrease in chemical resistance due to a group having developability while maintaining high sensitivity, and as a result, chemical resistance can be improved and the relative dielectric constant can be further decreased.

Specifically, the problems described above are preferably solved by the following solving means <1> and <2> to <15 >.

<1> a photosensitive resin composition comprising: (A) a polymer component containing a polymer satisfying at least one of the following (1) and (2),

(1) having a polymer having (a1) a constituent unit containing a group in which an acid group is protected by an acid-decomposable group and (a2) a constituent unit containing a crosslinkable group, or

(2) A polymer having the above constituent unit (a1) and a polymer having the above constituent unit (a 2);

(B) a photoacid generator; and

(C) a solvent;

the polymer component (A) contains at least one component (a4) having a lactone structure, or

Comprises at least one polymer which contains the above-mentioned constituent unit (a4) and does not contain the above-mentioned constituent unit (a1) and the above-mentioned constituent unit (a 2).

<2> the photosensitive resin composition according to <1>, wherein the lactone structure-containing constituent unit (a4) contains a group represented by the following general formula (1).

General formula (1)

[ solution 1]

(in the general formula (1), R^A1Represents a substituent, n₁R is^A1Are independent, can be the same or different. Z¹Represents a monocyclic structure or a polycyclic structure containing-O-C (═ O) -. n is₁Represents an integer of 0 or more)

<3> the photosensitive resin composition according to <1> or <2>, wherein the lactone structure-containing constituent unit (a4) is represented by the following general formula (2).

General formula (2)

[ solution 2]

(in the general formula (2), RX¹Represents a hydrogen atom or an alkyl group. R^A2Represents a substituent, n₂R is^A2Are independent, can be the same or different. A. the¹Represents a single bond or a divalent linking group. Z²Represents a monocyclic structure or a polycyclic structure containing a group represented by-O-C (═ O) -. n is₂Represents an integer of 0 or more)

<4> the photosensitive resin composition according to any one of <1> to <3>, wherein the lactone structure-containing constituent unit (a4) is represented by the following general formula (3).

General formula (3)

[ solution 3]

(in the general formula (3), RX₂Represents a hydrogen atom or an alkyl group. R^A3Represents a substituent, n₃R is^A3Are independent, can be the same or different. A. the²Represents a single bond or a divalent linking group. Z³Represents a monocyclic structure or a polycyclic structure containing a group represented by-O-C (═ O) -. n is₃Represents an integer of 0 or more. X¹Represents an oxygen atom or-NR' -. R' represents a hydrogen atom or an alkyl group)

<5> the photosensitive resin composition according to any one of <1> to <4>, wherein the above lactone structure is a lactone structure forming a 5-or 6-membered ring.

<6> the photosensitive resin composition according to any one of <1> to <5>, wherein the above-mentioned constituent unit (a1) is a constituent unit containing a group having a carboxyl group protected in the form of acetal.

<7> the photosensitive resin composition according to any one of <1> to <6>, wherein the above-mentioned constituent unit (a1) is a constituent unit represented by the following general formula (1-11).

General formula (1-11)

[ solution 4]

(in the general formula (1-11), R¹And R²Each represents a hydrogen atom, an alkyl group or an aryl group, at least R¹And R²Is alkyl or aryl, R³Represents alkyl or aryl, R¹Or R²And R³May be linked to form a cyclic ether, R⁴Represents a hydrogen atom or a methyl group, X represents a single bond or an arylene group)

<8>According to<1>To<7>The photosensitive resin composition according to any one of the above, wherein the crosslinkable group is selected from the group consisting of an epoxy group, an oxetanyl group and-NH-CH₂-OR (R is a hydrogen atom OR an alkyl group having 1 to 20 carbon atoms).

<9> the photosensitive resin composition according to any one of <1> to <8>, wherein the above-mentioned (B) photoacid generator is an oxime sulfonate compound or an onium salt compound.

<10> the photosensitive resin composition according to any one of <1> to <9>, wherein the lactone structure-containing constituent unit (a4) is represented by the following general formulae (4) to (7).

General formula (4) general formula (5) general formula (6) general formula (7)

[ solution 5]

<11> the photosensitive resin composition according to any one of <1> to <10>, wherein the lactone structure-containing constituent unit (a4) is represented by the following general formula (4).

General formula (4)

[ solution 6]

<12> a method for producing a cured film, comprising:

(1) a step of coating the photosensitive resin composition according to any one of <1> to <11> on a substrate;

(2) a step of removing the solvent from the applied photosensitive resin composition;

(3) a step of exposing the photosensitive resin composition from which the solvent has been removed, to actinic rays;

(4) a step of developing the exposed photosensitive resin composition with an aqueous developer; and

(5) and a post-baking step of thermally curing the developed photosensitive resin composition.

<13> a cured film formed by curing the photosensitive resin composition according to any one of <1> to <11>, or formed by the method for producing a cured film according to <12 >.

<14> the cured film according to <13>, which is an interlayer insulating film.

<15> a liquid crystal display device or an organic electroluminescent display device comprising the cured film according to <13> or <14 >.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a photosensitive resin composition having a further reduced relative dielectric constant while maintaining high sensitivity and improving chemical resistance can be provided.

Drawings

Fig. 1 is a conceptual diagram showing an example of a liquid crystal display device. A liquid crystal display device is shown in a schematic cross-sectional view of an active matrix substrate, and has a cured film 17 as an interlayer insulating film.

Fig. 2 is a conceptual diagram illustrating a configuration of an example of the organic EL display device. A schematic cross-sectional view of a substrate in an organic EL display device of bottom emission type is shown, and has a planarization film 4.

Description of the symbols

1：TFT

2: wiring harness

3: insulating film

4: planarizing film

5: a first electrode

6: glass substrate

7: contact hole

8: insulating film

10: liquid crystal display device having a plurality of pixel electrodes

12: backlight unit

14. 15: glass substrate

16：TFT

17: hardened film

18: contact hole

19: ITO transparent electrode

20: liquid crystal display device

22: color filter

Detailed Description

The present invention will be described in detail below. The following description of the constituent elements may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In the present specification, "to" is used in a meaning including numerical values described before and after the "to" as a lower limit value and an upper limit value.

In the expression of a group (atomic group) in the present specification, the expression that is not substituted or unsubstituted includes a group (atomic group) having no substituent and also includes a group (atomic group) having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The composition of the present invention comprises: (A) a polymer component containing a polymer satisfying at least one of the following (1) and (2),

(B) a photoacid generator; and

(C) a solvent;

Comprises at least one polymer (3) containing the above-mentioned constituent unit (a4) and not containing the above-mentioned constituent unit (a1) and the above-mentioned constituent unit (a 2).

Examples of the form in which the polymer component (a) contains at least one lactone structure-containing constituent unit (a4) include the following (1) to (5).

(1): (A) the polymer component contains at least one polymer (hereinafter, also referred to as polymer (a2)) having at least one of (a1) a constituent unit containing a group in which an acid group is protected by an acid-decomposable group, (a2) a constituent unit containing a crosslinkable group, and (a4) a constituent unit containing a lactone structure.

(2): (A) the polymer component includes a polymer (hereinafter, also referred to as a polymer (A2a)) and a polymer (hereinafter, also referred to as a polymer (A2b)), the polymer (A2a) includes a constituent unit (a1) including a group whose acid group is protected by an acid-decomposable group and a constituent unit (A2) including a crosslinkable group, and the polymer (A2b) includes a constituent unit (a4) including a lactone structure and does not include a constituent unit (a1) including a group whose acid group is protected by an acid-decomposable group and a constituent unit (A2) including a crosslinkable group.

(3): (A) the polymer component includes a polymer (hereinafter, also referred to as a polymer (A2c)) and a polymer (hereinafter, also referred to as a polymer (A2d)), the polymer (A2c) includes a constituent unit (a1) having a group in which an acid group is protected by an acid-decomposable group and a constituent unit (a4) having a lactone structure, and the polymer (A2d) includes a constituent unit (A2) having a crosslinkable group.

(4): (A) the polymer component includes a polymer (hereinafter, also referred to as a polymer (A2e)) and a polymer (hereinafter, also referred to as a polymer (A2f)), the polymer (A2e) includes a constituent unit (a1) having a group in which an acid group is protected by an acid-decomposable group, and the polymer (A2f) includes a constituent unit (A2) having a crosslinkable group and a constituent unit (a4) having a lactone structure.

(5): (A) the polymer component includes a polymer (hereinafter, also referred to as a polymer (A2g)), a polymer (hereinafter, also referred to as a polymer (A2h)), and a polymer (hereinafter, also referred to as a polymer (A2i)), the polymer (A2g) includes a constituent unit (a1) having a group in which an acid group is protected by an acid-decomposable group, the polymer (A2h) includes a constituent unit (A2) having a crosslinkable group, and the polymer (A2i) includes a constituent unit (a4) having a lactone structure.

The lactone structure in the present invention means a cyclic ester having a-COO-group in the ring. The lactone structure-containing constituent unit in the present invention means the above-mentioned lactone structure-containing constituent unit, and means, for example, a single ring structure or a multi-ring structure formed by a ring contraction of another ring structure in the lactone structure. In the lactone structure-containing constituent unit used in the present invention, the lactone structure may be directly bonded to the main chain.

In the present invention, by blending a constituent unit containing a group in which an acid group is protected by an acid-decomposable group, a constituent unit containing a crosslinkable group, and a constituent unit containing a lactone structure into a photosensitive resin composition, when a high-concentration alkaline developer (for example, a tetramethylammonium Hydroxide (TMAH) aqueous solution of 2.0 mass% or more) is used, the developability can be further improved. The reason for this is presumed to be that when the composition of the present invention is developed with a high-concentration alkaline developer, the lactone structure is opened to generate carboxylic acid, and as a result, the solubility of the composition of the present invention in the alkaline developer is further improved.

< Polymer ingredient (A) >

(A) The polymer component is preferably an addition polymerization type resin, and more preferably a polymer containing a constituent unit derived from (meth) acrylic acid and/or an ester thereof. Further, the resin composition may have a constituent unit other than the constituent unit derived from (meth) acrylic acid and/or an ester thereof, for example, a constituent unit derived from styrene, a constituent unit derived from a vinyl compound, or the like. The "constituent unit derived from (meth) acrylic acid and/or an ester thereof" is also referred to as a "(meth) acrylic acid-based constituent unit". (A) The polymer component is preferably 60 mass% or more of the total solid content, which becomes the main component of the component other than the solvent in the composition of the present invention.

(a1) constituent Unit containing a group wherein acid group is protected by acid-decomposable group

(A) The polymer component has at least a constituent unit (a1) containing a group in which an acid group is protected by an acid-decomposable group. The photosensitive resin composition having extremely high sensitivity can be obtained by providing the polymer component (A) with the constituent unit (a 1).

The "group in which the acid group is protected with an acid-decomposable group" in the present invention may be any known group including an acid group and an acid-decomposable group, and is not particularly limited.

Specific examples of the acid group include a carboxyl group and a phenolic hydroxyl group.

Further, as a specific acid-decomposable group, a group which is relatively easily decomposed by an acid (for example, an ester structure, an acetal functional group such as a tetrahydropyranyl ester group or a tetrahydrofuranyl ester group, which will be described later) or a group which is relatively hardly decomposed by an acid (for example, a tertiary alkyl group such as a tributyl ester group or a tertiary alkyl carbonate group such as a tributyl carbonate group) can be used.

The constituent unit (a1) is preferably a constituent unit containing a protected carboxyl group protected by an acid-decomposable group or a constituent unit containing a protected phenolic hydroxyl group protected by an acid-decomposable group.

The constituent unit (a1-1) containing a protected carboxyl group protected by an acid-decomposable group and the constituent unit (a1-2) containing a protected phenolic hydroxyl group protected by an acid-decomposable group will be described in order below.

(a1-1) constituent Unit containing protected carboxyl group protected with acid-decomposable group >

The constituent unit (a1-1) is a carboxyl group-protected constituent unit in which the carboxyl group of the constituent unit having a carboxyl group is protected with an acid-decomposable group described in detail below.

The carboxyl group-containing constituent unit that can be used for the constituent unit (a1-1) is not particularly limited and a known constituent unit can be used. Examples thereof include: and a constituent unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in a molecule thereof, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid.

Hereinafter, the constituent unit (a1-1-1) that can be used as the above-mentioned carboxyl group-containing constituent unit will be described.

(a1-1-1) constituent Unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, etc. ]

As the unsaturated carboxylic acid used in the present invention, those listed below can be used.

That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α -chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, and 2- (meth) acryloyloxyethyl-phthalic acid.

Examples of the unsaturated dicarboxylic acid include: maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and the like.

The unsaturated polycarboxylic acid used for obtaining the constituent unit having a carboxyl group may be an acid anhydride thereof. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. The unsaturated polycarboxylic acid may be a mono (2-methacryloxyalkyl) ester of a polycarboxylic acid, and examples thereof include: mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) succinate, mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like. Further, the unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxylic polymer at both ends thereof, and examples thereof include ω -carboxy polycaprolactone monoacrylate, ω -carboxy polycaprolactone monomethacrylate and the like. Further, as the unsaturated carboxylic acid, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, monoalkyl maleate, monoalkyl fumarate, 4-carboxystyrene, and the like can be used.

Among them, in terms of developability, in order to form the above-mentioned constituent unit (a1-1-1), acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, or an anhydride of an unsaturated polycarboxylic acid is preferably used, and acrylic acid, methacrylic acid, and 2- (meth) acryloyloxyethyl hexahydrophthalic acid are more preferably used.

The constituent unit (a1-1-1) may be one kind alone or two or more kinds.

"acid-decomposable base usable for constituent Unit (a 1-1)"

As the above-mentioned acid-decomposable group which can be used in the constituent unit (a1-1), the above-mentioned acid-decomposable group can be used.

Among these acid-decomposable groups, a group having a structure in which the acid-decomposable group is protected in the form of an acetal is preferable. For example, from the viewpoint of basic physical properties of the photosensitive resin composition, particularly sensitivity, pattern shape, contact hole formability, and storage stability of the photosensitive resin composition, it is preferable that the carboxyl group is a protected carboxyl group protected by an acetal form. Further, from the viewpoint of sensitivity, it is more preferable that the carboxyl group is a protected carboxyl group protected in the form of acetal represented by the following general formula (a 1-10). When the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10), the whole protected carboxyl group is ═ O) -O-CR¹⁰¹R¹⁰²(OR¹⁰³) The structure of (1).

General formula (a1-10)

[ solution 7]

(in the formula (a1-10), R¹⁰¹And R¹⁰²Each independently represents a hydrogen atom or an alkyl group, wherein R is excluded¹⁰¹And R¹⁰²Both in the case of hydrogen atoms. R¹⁰³Represents an alkyl group. R¹⁰¹Or R¹⁰²And R¹⁰³May be linked to form a cyclic ether

In the above general formula (a1-10), R¹⁰¹～R¹⁰³Each independently represents a hydrogen atom or an alkyl group. The alkyl group may be linear, branched or cyclic. Here, R is absent¹⁰¹And R¹⁰²All represent hydrogen atoms, R¹⁰¹And R¹⁰²At least one of (a) and (b) represents an alkyl group.

The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specifically, there may be mentioned: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, n-pentyl, neopentyl, n-hexyl, 2, 3-dimethyl-2-butyl (thexyl), n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl and the like.

The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl and the like.

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When having a halogen atom as a substituent, R¹⁰¹、R¹⁰²、R¹⁰³To a haloalkyl group, R when having an aryl group as a substituent¹⁰¹、R¹⁰²、R¹⁰³To form an aralkyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these halogen atoms, a fluorine atom or a chlorine atom is preferable.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and specifically, phenyl, α -methylphenyl, naphthyl and the like are exemplified, and the aralkyl group which is an alkyl group substituted with an aryl group as a whole is exemplified by benzyl, α -methylbenzyl, phenethyl, naphthylmethyl and the like.

The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and still more preferably a methoxy group or an ethoxy group.

When the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and when the alkyl group is a linear or branched alkyl group, the cycloalkyl group may have 3 to 12 carbon atoms as a substituent.

These substituents may be further substituted with the above-mentioned substituents.

In the above general formula (a1-10), when R is¹⁰¹、R¹⁰²And R¹⁰³When the aryl group is represented, the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The aryl group may have a substituent, and the substituent is preferably an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a silyl group, a cumenyl group, and a 1-naphthyl group.

In addition, R¹⁰¹、R¹⁰²And R¹⁰³May be bonded to each other and form a ring together with these bonded carbon atoms. As R¹⁰¹And R¹⁰²、R¹⁰¹And R¹⁰³Or R¹⁰²And R¹⁰³Examples of the ring structure in the bonding include: cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, tetrahydrofuryl, adamantyl, tetrahydropyranyl and the like.

In the general formula (a1-10), R is preferably R¹⁰¹And R¹⁰²Is a hydrogen atom or a methyl group.

The radical polymerizable monomer used for forming the constituent unit having a protected carboxyl group represented by the above general formula (a1-10) may be a commercially available radical polymerizable monomer, or a radical polymerizable monomer synthesized by a known method may be used. For example, the synthesis can be carried out by the synthesis methods described in paragraphs 0037 to 0040 of Japanese patent laid-open publication No. 2011-221494, and the contents thereof are incorporated into the present specification.

A first preferred embodiment of the above-mentioned constituent unit (a1-1) is a constituent unit represented by the following general formula (1-11).

[ solution 8]

(in the formula (1-11), R¹And R²Each represents a hydrogen atom, an alkyl group or an aryl group, at least R¹And R²Any one of (A) represents an alkyl group or an aryl group, R³Represents alkyl or aryl, R¹Or R²And R³May be linked to form a cyclic ether, R⁴Represents a hydrogen atom or a methyl group, X represents a single bond or an arylene group)

When R is¹And R²When the alkyl group is used, the alkyl group preferably has 1 to 10 carbon atoms. When R is¹And R²When aryl, phenyl is preferred. R¹And R²Each of which is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R³Represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

X represents a single bond or an arylene group, preferably a single bond.

A second preferred embodiment of the above-mentioned constituent unit (a1-1) is a constituent unit represented by the following general formula (1-12).

General formula (1-12)

[ solution 9]

(in the formula (1-12), R¹²¹L represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms¹Represents a carbonyl group or a phenylene group, R¹²²～R¹²⁸Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

R¹²¹Preferably a hydrogen atom or a methyl group.

L¹Preferably a carbonyl group.

R¹²²～R¹²⁸Preferably a hydrogen atom.

As a preferred specific example of the above-mentioned constituent unit (a1-1), the following constituent units can be exemplified. In the following constituent units, R represents a hydrogen atom or a methyl group.

[ solution 10]

< (a1-2) containing a phenolic hydroxyl group-protecting constituent Unit protected with an acid-decomposable group >

The constituent unit (a1-2) is a phenolic hydroxyl group-containing constituent unit having a phenolic hydroxyl group-protected constituent unit (a1-2-1) protected with an acid-decomposable group, which will be described in detail below.

(a1-2-1) structural Unit having phenolic hydroxyl group

The phenolic hydroxyl group-containing constituent unit includes a hydroxystyrene-based constituent unit or a constituent unit in a novolac-based resin, and among these constituent units, from the viewpoint of sensitivity, a constituent unit derived from hydroxystyrene or α -methylhydroxystyrene is preferable, and from the viewpoint of sensitivity, a constituent unit represented by the following general formula (a1-20) is also preferable.

General formula (a1-20)

[ solution 11]

(in the general formula (a1-20), R²²⁰Represents a hydrogen atom or a methyl group, R²²¹Represents a single bond or a divalent linking group, R²²²Represents a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, a represents an integer of 1 to 5, b represents an integer of 0 to 4, and a + b is 5 or less. Further, when there are more than 2R²²²When R is equal to²²²Different from each other or the same)

In the above general formula (a1-20), R²²⁰Represents a hydrogen atom or a methyl group, preferably a methyl group.

In addition, R²²¹Represents a single bond or a divalent linking group. When R is²²¹The single bond is preferable because the sensitivity and the transparency of the cured film can be improved. As R²²¹The divalent linking group of (2) may be exemplified by an alkylene groupR²²¹Specific examples of the alkylene group include: methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, tert-butylene, pentylene, isopentylene, neopentylene, hexylene, and the like. Wherein R is²²¹Preferably a single bond, methylene group or ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group, and the like. In addition, a represents an integer of 1 to 5, but from the viewpoint of the effect of the present invention or the ease of production, a is preferably 1 or 2, and more preferably a is 1.

In addition, when R is to be reacted with²²¹When the carbon atom to be bonded is the base (1-position), the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position.

R²²²Is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, there may be mentioned: fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tertiary butyl group, pentyl group, isopentyl group, neopentyl group, etc. Among them, a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of ease of production.

In addition, b represents 0 or an integer of 1 to 4.

"acid-decomposable base usable for constituent Unit (a 1-2)"

The acid-decomposable group that can be used for the structural unit (a1-2) is not particularly limited, and a known acid-decomposable group can be used, as is the acid-decomposable group that can be used for the structural unit (a 1-1). Among the acid-decomposable groups, a constituent unit containing a protective phenolic hydroxyl group protected with acetal is preferable from the viewpoint of basic physical properties of the photosensitive resin composition, particularly sensitivity and pattern shape, storage stability of the photosensitive resin composition, and formation of contact holes. Further, among the acid-decomposable groups, from the viewpoint of sensitivity, it is more preferable that the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of acetal represented by the above general formula (a 1-10). Further, when the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of acetal represented by the above general formula (a1-10)Protecting the phenolic hydroxyl group as a whole to form-Ar-O-CR¹⁰¹R¹⁰²(OR¹⁰³) The structure of (1). Ar represents an arylene group.

Preferred examples of the structure of the acetal ester of a phenolic hydroxyl group include R¹⁰¹＝R¹⁰²＝R¹⁰³Methyl or R¹⁰¹＝R¹⁰²Is methyl and R¹⁰³A combination of ═ benzyl groups.

Examples of the radical polymerizable monomer for forming a structural unit containing a protective phenolic hydroxyl group in which the phenolic hydroxyl group is protected by an acetal form include the radical polymerizable monomers described in paragraph 0042 of Japanese patent application laid-open No. 2011-215590.

Among these, from the viewpoint of transparency, preferred are a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate.

Specific examples of the acetal-protecting group for a phenolic hydroxyl group include a 1-alkoxyalkyl group, and examples thereof include a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, a 1-isobutoxyethyl group, a1- (2-chloroethoxy) ethyl group, a1- (2-ethylhexyloxy) ethyl group, a 1-n-propoxyethyl group, a 1-cyclohexyloxyethyl group, a1- (2-cyclohexylethoxy) ethyl group, and a 1-benzyloxyethyl group, and these groups may be used alone or in combination of two or more kinds thereof.

As the radical polymerizable monomer for forming the constituent unit (a1-2), commercially available radical polymerizable monomers can be used, and radical polymerizable monomers synthesized by a known method can also be used. For example, the compound can be synthesized by reacting a compound having a phenolic hydroxyl group with a vinyl ether in the presence of an acid catalyst. The above synthesis may be carried out by copolymerizing a phenolic hydroxyl group-containing monomer with another monomer in advance and then reacting with a vinyl ether in the presence of an acid catalyst.

Preferred specific examples of the above-mentioned constituent unit (a1-2) include the following constituent units, but the present invention is not limited to these constituent units.

[ solution 12]

[ solution 13]

[ solution 14]

The constituent unit (a1-1) is characterized by faster development than the constituent unit (a 1-2). Therefore, when rapid development is desired, the constituent unit (a1-1) is preferable. Conversely, when the development is to be slowed, the constituent element (a1-2) is preferably used.

(a2) constituent Unit having crosslinkable group

(A) The polymer component has a constituent unit (a2) containing a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment.

Preferred examples of the crosslinkable group-containing constituent unit include those containing a group selected from the group consisting of an epoxy group, an oxetanyl group and an-NH-CH group₂A constituent unit of at least one group selected from the group consisting of a group represented by-O-R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) and an ethylenically unsaturated group, preferably selected from the group consisting of an epoxy group, an oxetanyl group and a group consisting of-NH-CH₂At least one of groups represented by-O-R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). Among these, the photosensitive resin composition of the present invention preferably contains a constituent unit containing at least one of an epoxy group and an oxetanyl group in the polymer component (a), and more preferably contains a constituent unit containing an epoxy group. More specifically, the following may be mentioned.

< structural Unit having epoxy group and/or oxetanyl group (a2-1) >

The polymer component (A) preferably contains a constituent unit having an epoxy group and/or an oxetanyl group (hereinafter, also referred to as a constituent unit (a 2-1)).

The constituent unit (a2-1) may have at least one epoxy group or oxetane group in 1 constituent unit, and may have 1 or more epoxy groups and 1 or more oxetane groups, 2 or more epoxy groups, or 2 or more oxetane groups, and is not particularly limited, but preferably has 1 to 3 epoxy groups and/or oxetane groups in total, more preferably has 1 or 2 epoxy groups and/or oxetane groups in total, and still more preferably has 1 epoxy group or oxetane group.

Specific examples of the radical polymerizable monomer for forming a constituent unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α -glycidyl ethacrylate, α -n-propyl glycidyl acrylate, α -n-butyl glycidyl acrylate, 3, 4-epoxybutyl methacrylate, 3, 4-epoxycyclohexyl methyl acrylate, 3, 4-epoxycyclohexyl methyl methacrylate, α -3, 4-epoxycyclohexyl methyl ethacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and compounds containing an alicyclic epoxy skeleton described in japanese patent No. 4168443, paragraph No. 0031 to paragraph No. 0035, and the contents of these can be incorporated in the present specification.

Specific examples of the radical polymerizable monomer for forming a constituent unit having an oxetanyl group include (meth) acrylates having an oxetanyl group described in paragraphs 0011 to 0016 of Japanese patent laid-open No. 2001-330953, and compounds described in paragraph 0027 of Japanese patent laid-open No. 2012-088459, and the contents of these are incorporated in the present specification.

Specific examples of the radical polymerizable monomer for forming the structural unit (a2-1) having an epoxy group and/or an oxetanyl group are preferably a monomer having a methacrylate structure and a monomer having an acrylate structure.

Among these, glycidyl methacrylate, 3, 4-epoxycyclohexylmethyl acrylate, 3, 4-epoxycyclohexylmethyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, (3-ethyloxetan-3-yl) methyl acrylate and (3-ethyloxetan-3-yl) methyl methacrylate are preferable from the viewpoint of improving the copolymerization reactivity and various characteristics of the cured film. These constituent units may be used singly or in combination of two or more.

As a preferred specific example of the above-mentioned constituent unit (a2-1), the following constituent units can be exemplified. In the following constituent units, R represents a hydrogen atom or a methyl group.

[ solution 15]

< constituent Unit having ethylenically unsaturated group (a2-2) >

One of the crosslinkable group-containing constituent units (a2) is a constituent unit (a2-2) having an ethylenically unsaturated group. The constituent unit (a2-2) is preferably a constituent unit having an ethylenically unsaturated group in a side chain, and more preferably a constituent unit having an ethylenically unsaturated group at an end thereof and a side chain having 3 to 16 carbon atoms.

Further, as the constituent unit (a2-2), compounds described in paragraphs 0072 to 0090 of japanese patent laid-open publication No. 2011-215580 and paragraphs 0013 to 0031 of japanese patent laid-open publication No. 2008-256974 are cited as preferable examples, and the contents of these are incorporated in the present specification.

<< alpha > 2-3 > has a chemical formula of-NH-CH₂Constituent unit of group represented by-O-R (R is hydrogen atom or alkyl group having 1 to 20 carbon atoms)>

The polymer component (A) used in the present invention preferably contains a polymer having a structure represented by the formula-NH-CH₂A group represented by-O-R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms)Constituting unit (a 2-3). By containing the constituent unit (a2-3), a curing reaction can be caused by mild heat treatment, and a cured film having excellent properties can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be any of linear, branched, and cyclic alkyl groups, but is preferably a linear or branched alkyl group. The constituent unit (a2-3) is more preferably a constituent unit having a group represented by the following general formula (a 2-30).

General formula (a2-30)

[ solution 16]

(in the general formula (a2-30), R¹Represents a hydrogen atom or a methyl group, R²Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms)

R²Preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be any of linear, branched, and cyclic alkyl groups, but is preferably a linear or branched alkyl group.

As R²Specific examples of (3) include: methyl, ethyl, n-butyl, isobutyl, cyclohexyl, and n-hexyl. Among them, isobutyl, n-butyl, and methyl are preferable.

(a4) lactone Structure-containing building Block

The composition of the present invention contains, in the polymer component (a), at least one (a4) lactone structure-containing constituent unit, or at least one polymer which contains the above-mentioned constituent unit (a4) and does not contain the above-mentioned constituent unit (a1) and the above-mentioned constituent unit (a 2).

By blending (a4) a lactone structure-containing constituent unit with the composition of the present invention, a photosensitive resin composition can be provided which can maintain high sensitivity, can have good chemical resistance, and can further reduce the relative dielectric constant.

The lactone structure in the lactone structure-containing constituent unit is not particularly limited, and lactone structures of any structure can be used. In particular, the lactone structure used in the present invention is preferably a lactone structure forming a 5-to 7-membered ring, and more preferably a lactone structure forming a 5-or 6-membered ring.

In addition, as the lactone structure-containing constituent unit used in the present invention, in the lactone structure forming the 5-to 7-membered ring, other ring structures may be condensed in the lactone structure to form a polycyclic structure, but it is preferable that other ring structures are not condensed in the lactone structure. When the other ring structure is condensed in the lactone structure forming the 5-to 7-membered ring, it is preferable that the other ring structure is condensed in the form of forming a bicyclic structure or a spiro structure. Examples of the other ring structure include a cyclic hydrocarbon group having 3 to 20 carbon atoms, a heterocyclic group having 3 to 20 carbon atoms, and the like. The heterocyclic group is not particularly limited, and examples thereof include heterocyclic groups having 1 or more heteroatoms among the atoms constituting the ring, or aromatic heterocyclic groups. The heterocyclic group is preferably a 5-or 6-membered ring, and particularly preferably a 5-membered ring. Specifically, the heterocyclic group preferably contains at least one oxygen atom, and examples thereof include: an oxolane ring, an oxan ring, a dioxane ring, etc.

When the other ring structure in the lactone structure-containing constituent unit is condensed in the lactone structure to form a polycyclic structure, the number of the other ring structures condensed in the lactone structure is preferably 1 to 5, more preferably 1 to 3.

The lactone structure used in the present invention may or may not have a substituent, but preferably has no substituent. The substituent is not particularly limited, and examples thereof include: an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, an acid-decomposable group, and the like. More preferably an alkyl group having 1 to 4 carbon atoms or a cyano group.

The alkyl group is preferably a straight-chain alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, and more preferably a straight-chain alkyl group having 1 to 3 carbon atoms.

When the lactone structure has a substituent, the number of the substituent is not particularly limited, but is preferably 1 to 4, more preferably 1 or 2. When the lactone structure used in the present invention has a plurality of substituents, the plurality of substituents may be the same as or different from each other. In addition, when other ring structures are condensed in the lactone structure, the other ring structures may have a substituent.

The lactone structure-containing constituent unit used in the present invention preferably contains a group represented by the following general formula (1).

General formula (1)

[ solution 17]

In the general formula (1), R^A1Represents a substituent, n₁R is^A1Are independent, can be the same or different. R^A1The meanings of (A) are the same as those of the substituents which the lactone structure may have, and the preferable ranges are also the same.

In the general formula (1), Z¹Represents a monocyclic structure or a polycyclic structure containing-O-C (═ O) -, preferably a monocyclic structure. When Z is¹When the structure represents a monocyclic structure, the monocyclic structure is preferably a lactone structure forming a 5-to 7-membered ring, and more preferably a lactone structure forming a 5-or 6-membered ring. When Z is¹When a polycyclic structure is represented, as the polycyclic structure, it is preferable that other ring structures are condensed in the lactone structure in such a manner as to form a bicyclic structure or a spiro structure. The other ring structure has the same meaning as the other ring structure described above, and the preferable range is also the same.

In the general formula (1), n₁Represents an integer of 0 or more, preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and still more preferably 0. When n is₁When an integer of 2 or more is used, a plurality of substituents may be the same or different from each other. In addition, there areThe plural substituents may bond to each other to form a ring, but preferably do not bond to each other to form a ring.

The constituent unit (a4) is preferably represented by the following general formula (2).

General formula (2)

[ solution 18]

In the general formula (2), RX¹Represents a hydrogen atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. The alkyl group may have a substituent. The substituent is preferably a hydroxyl group or a halogen atom (particularly, a fluorine atom).

In the general formula (2), R^A2Represents a substituent, n₂R is^A2Are independent, can be the same or different. R^A2The meanings of (A) are the same as those of the substituents which the lactone structure may have, and the preferable ranges are also the same.

In the general formula (2), A¹Represents a single bond or a divalent linking group. Examples of divalent linking groups include: straight, branched or cyclic alkylene, arylene, -O-, -COO-, -S-, -NR "-, -CO-, -NR" CO-, -SO₂Divalent radicals or combinations comprising these radicals. Here, R' represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and preferably a hydrogen atom. The divalent linking group is preferably at least one of-O-, -COO-, -S-, -NH-and-CO-, or a group containing these groups and- (CH)₂)_mA group of a combination of (m is an integer of 1 to 10, preferably an integer of 1 to 6, more preferably an integer of 1 to 4).

In the general formula (2), Z²Represents a monocyclic structure or a polycyclic structure containing a group represented by-O-C (═ O) -, and has the same meaning as Z in the general formula (1)¹Similarly, the preferred ranges are also the same.

In the general formula (2), n₂Represents an integer of 0 or more, and the meaning of n in the general formula (1)₁Similarly, the preferred ranges are also the same.

The constituent unit (a4) is preferably represented by the following general formula (3).

General formula (3)

[ solution 19]

In the general formula (3), R^A3Represents a substituent, n₃R is^A3Are independent, can be the same or different. R^A3The meanings of (A) are the same as those of the substituents which the lactone structure may have, and the preferable ranges are also the same.

In the general formula (3), A²Represents a single bond or a divalent linking group. As divalent linking group, the same as A in the general formula (2) is used¹The same applies to the divalent linking group. As the preferable divalent linking group, at least one of-COO-, -CO-or a group containing these groups and- (CH) is preferable₂)_mA group of a combination of (m is an integer of 1 to 10, preferably an integer of 1 to 6, more preferably an integer of 1 to 4). In particular, as A in the general formula (3)²Preferably a single bond.

In the general formula (3), Z³Represents a monocyclic structure or a polycyclic structure containing a group represented by-O-C (═ O) -, and has the same meaning as Z in the general formula (1)¹Are identical to each otherThe preferred ranges are also the same.

In the general formula (3), n₃Represents an integer of 0 or more, and the meaning of n in the general formula (1)₁Similarly, the preferred ranges are also the same.

In the general formula (3), X¹Represents an oxygen atom or-NR "-, preferably an oxygen atom. R' represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom.

The structural unit (a4) preferably has a structure represented by any one of the following general formulae (LC1-1) to (LC1-21) as the structure represented by the general formula (1).

More preferred structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14) and (LC1-17), and particularly preferred structures are (LC1-1), (LC1-4) and (LC 1-17). By having such a structure in the constituent unit (a4), the chemical resistance of the composition of the present invention can be improved, and the relative dielectric constant can be further reduced.

[ solution 20]

In the structures represented by the general formulae (LC1-1) to (LC1-21), (Rb)₂) Represents a substituent, may have (Rb)₂) And may or may not have (Rb)₂) But preferably does not have (Rb)₂) (that is, in the general formulae (LC1-1) to (LC1-21), n4 is 0). As preferred substituent (Rb)₂) The meaning is the same as that of the substituent which the lactone structure may have, and the preferable range is also the same.

In the structures represented by the general formulae (LC1-1) to (LC1-21), n4 has the same meaning as n in the general formula (1)₁Similarly, the preferred ranges are also the same.

The lactone structure-containing constituent unit usually has optical isomers, and any of the optical isomers can be used. In addition, one optical isomer may be used alone, or a plurality of optical isomers may be used in combination. When one optical isomer is mainly used, the optical purity (enantiomeric excess (ee)) is preferably 90% or more, more preferably 95% or more.

Specific examples of the lactone structure-containing constituent unit usable in the present invention will be described below, but the present invention is not limited thereto.

[ solution 21]

(wherein Rx represents H, CH₃、CH₂OH or CF₃。)

[ solution 22]

(wherein Rx represents H, CH₃、CH₂OH or CF₃。)

[ solution 23]

(wherein Rx represents H, CH₃、CH₂OH or CF₃。)

In particular, the lactone structure-containing constituent unit (a4) usable in the present invention is preferably represented by the following general formulae (4) to (7), and more preferably represented by the following general formula (4).

General formula (4) general formula (5) general formula (6) general formula (7)

[ solution 24]

The composition of the present invention may also use two or more lactone structure-containing constituent units in combination. When two or more kinds of lactone structure-containing constituent units are used in combination, the total amount thereof is preferably within the numerical range of the constituent unit (a4) described later.

Other constituent units (a3)

In the present invention, the polymer component (a) may have a constitutional unit (a3) other than the above-mentioned constitutional unit (a1), constitutional unit (a2) and constitutional unit (a 4). The above-mentioned polymer (1) and/or polymer (2) may contain a constituent unit (a 3). In addition to the polymer (1) or the polymer (2), a polymer containing substantially no constituent unit (a1) and no constituent unit (a2) and containing another constituent unit (a3) may be used.

The monomer to be the constituent unit (a3) is not particularly limited, and examples thereof include: styrenes, alkyl (meth) acrylates, cyclic alkyl (meth) acrylates, aryl (meth) acrylates, unsaturated dicarboxylic diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic anhydrides, and other unsaturated compounds. Further, as described later, the resin composition may have a constituent unit containing an acid group. The monomers to be the other constituent unit (a3) may be used alone or in combination of two or more.

Specifically, the constituent units (a3) include those composed of styrene, methylstyrene, hydroxystyrene, α -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, 3-methacryloxypropyl 4-hydroxybenzoate, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, N-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acryloylmorpholine, N-cyclohexylmaleimide, acrylonitrile, and ethylene glycol monoacetoacetate mono (meth) acrylate, and other compounds described in Japanese patent application laid-open No. 2004-264623, paragraph No. 0021 to paragraph No. 0024.

In addition, as the other constituent unit (a3), styrene and a group having an alicyclic skeleton are preferable from the viewpoint of electrical characteristics, and specific examples thereof include styrene, methylstyrene, hydroxystyrene, α -methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate.

Further, as the other constituent unit (a3), an alkyl (meth) acrylate is preferable from the viewpoint of adhesiveness. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable.

It is preferable that the acid group-containing repeating unit is contained as the other constituent unit (a 3). The acid group is contained, and therefore, the compound is easily dissolved in an alkaline developer, and the effect of the present invention is more effectively exhibited. In general, an acid group is introduced into a polymer by using a monomer capable of forming an acid group as a constituent unit containing an acid group. When the polymer contains such a constituent unit containing an acid group, the polymer tends to be easily dissolved in an alkaline developer.

Examples of the acid group used in the present invention include an acid group derived from a carboxylic acid group, an acid group derived from a sulfonamide group, an acid group derived from a phosphonic acid group, an acid group derived from a sulfonic acid group, an acid group derived from a phenolic hydroxyl group, a sulfonamide group, and a sulfonylimide group, and the acid group is preferably an acid group derived from a carboxylic acid group and/or an acid group derived from a phenolic hydroxyl group.

The constituent unit containing an acid group used in the present invention is more preferably a constituent unit derived from styrene, a constituent unit derived from a vinyl compound, or a constituent unit derived from (meth) acrylic acid and/or an ester thereof. For example, compounds described in paragraphs 0021 to 0023 and paragraphs 0029 to 0044 of Japanese patent laid-open publication No. 2012 and 88459 can be used, and the contents thereof can be incorporated into the present specification. Among them, preferred are constituent units derived from p-hydroxystyrene, (meth) acrylic acid, maleic acid, and maleic anhydride.

As such a polymer, a resin having a carboxyl group in a side chain is preferable. Examples thereof include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like as disclosed in Japanese patent laid-open publication No. 59-44615, Japanese patent laid-open publication No. 54-34327, Japanese patent laid-open publication No. 58-12577, Japanese patent laid-open publication No. 54-25957, Japanese patent laid-open publication No. 59-53836 and Japanese patent laid-open publication No. 59-71048, acid cellulose derivatives having a carboxyl group in a side chain, acid anhydrides added to polymers having a hydroxyl group, and the like, and further, polymer polymers having a (meth) acryloyl group in a side chain are exemplified as preferable polymers.

Examples thereof include: benzyl (meth) acrylate/(meth) acrylic acid copolymer, 2-hydroxyethyl (meth) acrylate/(benzyl (meth) acrylate/(meth) acrylic acid copolymer, 2-hydroxypropyl (meth) acrylate/polystyrene macromonomer (macromonomer)/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, and benzyl methacrylate/methacrylic acid copolymer, as described in Japanese patent application laid-open No. 7-140654 And the like.

In addition, known polymer compounds described in Japanese patent laid-open No. Hei 7-207211, Japanese patent laid-open No. Hei 8-259876, Japanese patent laid-open No. Hei 10-300922, Japanese patent laid-open No. Hei 11-140144, Japanese patent laid-open No. Hei 11-174224, Japanese patent laid-open No. 2000-5 56118, Japanese patent laid-open No. 2003-233179, Japanese patent laid-open No. 2009-52020 and the like can be used, and the contents of these can be incorporated into the present specification.

These polymers may contain only one kind or two or more kinds.

As these polymers, commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, manufactured by Sartomer corporation), Armoring (ARUFON) UC-3000, Armoring (ARUFON) UC-3510, Armoring (ARUFON) UC-3900, Armoring (ARUFON) UC-3910, armoring (aron) UC-3920, Armoring (ARUFON) UC-3080 (above, manufactured by east asian synthesis (stock)), tsukamur's force (Joncryl)690, tsukaki's force (Joncryl)678, tsukaki's force (Joncryl)67, tsukuki's force (Joncryl) 586 (above, manufactured by BASF), and the like can be used.

In the present invention, from the viewpoint of sensitivity, a constituent unit having a carboxyl group or a constituent unit having a phenolic hydroxyl group is particularly preferably contained. For example, compounds described in paragraphs 0021 to 0023 and paragraphs 0029 to 0044 of Japanese patent laid-open publication No. 2012-88459 can be used, and the contents thereof can be incorporated into the present specification.

The constituent unit containing an acid group is preferably 1 to 80 mol%, more preferably 1 to 50 mol%, even more preferably 5 to 40 mol%, particularly preferably 5 to 30 mol%, and particularly preferably 5 to 25 mol% of all constituent units of the polymer component.

Preferred embodiments of the polymer component (A) of the present invention will be described below, but the present invention is not limited to these embodiments.

(embodiment 1)

(A) The polymer component comprises one or more polymers (A2).

(A) The content of the constituent unit (a1) in all the constituent units of the polymer component (polymer (a2)) is preferably 3 to 70 mol%. The content of the constituent unit (a2) in all the constituent units of the polymer (a2) is preferably 3 to 70 mol%. The content of the constituent unit (a4) in all the constituent units of the polymer (a2) is preferably 1 to 80 mol%, more preferably 1 to 50 mol%, and still more preferably 3 to 20 mol%.

The polymer (a2) may contain the above-mentioned constituent unit (a 3). When the polymer (a2) contains the above-mentioned constituent unit (A3), the content of the constituent unit (A3) in all the constituent units of the polymer (a2) is preferably 1 to 50 mol%.

In the polymer component (a), the content of the polymer other than the polymer (a2) is preferably 10% by mass or less in the polymer component (a).

(embodiment 2)

(A) The polymer component comprises a polymer (A2a) and a polymer (A2 b). In addition, the polymer (A2a) does not usually contain (a4) a lactone structure-containing constituent unit. In addition, the polymer (A2b) does not generally contain the constituent unit (a1) and the constituent unit (A2).

(A) The content of the constituent unit (a1) in all the constituent units of the polymer component (polymer (A2a) and polymer (A2b)) is preferably 3 to 70 mol%. The content of the constituent unit (A2) in all the constituent units of the polymer (A2a) and the polymer (A2b) is preferably 3 to 70 mol%.

The content of the constituent unit (a4) in all the constituent units of the polymer (A2a) and the polymer (A2b) is preferably 1 to 80 mol%, more preferably 1 to 50 mol%, and still more preferably 3 to 20 mol%.

The polymer (A2a) and/or the polymer (A2b) may further contain the above-mentioned constituent unit (a 3). (A) The content of the constituent unit (a3) in all the constituent units of the polymer component (polymer (A2a) and polymer (A2b)) is preferably 1 to 50 mol%.

When the polymer (A2a) contains the above-mentioned constituent unit (a3), the total of the constituent unit (a1), the constituent unit (A2) and the constituent unit (a3) in the polymer (A2a) is 100 mol%.

When the polymer (A2b) contains the above-mentioned constituent unit (a3), the total of the constituent unit (a3) and the constituent unit (a4) in the polymer (A2b) is 100 mol%.

(A) In the polymer component, the composition ratio of the polymer (A2a) to the polymer (A2b) is preferably (polymer (A2 a)/polymer (A2b)) ═ 1 to 20, and more preferably 2 to 10, in terms of mass ratio.

In the polymer component (a), the content of the polymer other than the polymer (A2a) and the polymer (A2b) is preferably 10% by mass or less in the polymer component (a).

Of all the constituent units in the polymer (A2a), the content of the constituent unit (a1) in the polymer (A2a) is preferably 3 to 90 mol%, more preferably 10 to 80 mol%. Of all the constituent units in the polymer (A2a), the content of the constituent unit (A2) in the polymer (A2a) is preferably 3 to 70 mol%, more preferably 10 to 60 mol%. When the polymer (A2a) further contains the constituent unit (a3), the content of the constituent unit (a3) in the polymer (A2a) is preferably 3 to 70 mol%, more preferably 10 to 50 mol%, of all the constituent units in the polymer (A2 a).

The content of the constituent unit (a4) in the polymer (A2b) among all the constituent units in the polymer (A2b) is preferably 2 to 95 mol%, more preferably 3 to 90 mol%, and still more preferably 5 to 85 mol%. When the polymer (A2b) further contains the constituent unit (a3), the content of the constituent unit (a3) in the polymer (A2b) is preferably 3 to 70 mol%, more preferably 10 to 50 mol%, of all the constituent units in the polymer (A2 b).

(embodiment 3)

(A) The polymer component comprises a polymer (A2c) and a polymer (A2 d). In addition, the polymer (A2c) generally does not contain the constituent unit (A2). The polymer (A2d) does not generally contain the constituent unit (a1) and the constituent unit (a4) having a lactone structure.

(A) The content of the constituent unit (a1) in all the constituent units of the polymer component (polymer (A2c) and polymer (A2d)) is preferably 3 to 70 mol%. (A) The content of the constituent unit (a2) in all the constituent units of the polymer component is preferably 3 to 70 mol%. (A) The content of the constituent unit (a4) in all the constituent units of the polymer component is preferably 1 to 80 mol%, more preferably 1 to 50 mol%, and still more preferably 3 to 20 mol%.

In the polymer component (a), the content of the polymer other than the polymer (A2c) and the polymer (A2d) is preferably 10% by mass or less in the polymer component (a).

The polymer (A2c) and/or the polymer (A2d) may further contain the above-mentioned constituent unit (a 3). (A) The content of the constituent unit (a3) in all the constituent units of the polymer component (polymer (A2c) and polymer (A2d)) is preferably 1 to 50 mol%.

When the polymer (A2c) contains the above-mentioned constituent unit (a3), the total of the constituent unit (a1), the constituent unit (a3) and the constituent unit (a4) in the polymer (A2c) is 100 mol%.

When the polymer (A2d) contains the above-mentioned constituent unit (a3), the total of the constituent unit (A2) and the constituent unit (a3) in the polymer (A2d) is 100 mol%.

(A) In the polymer component, the composition ratio of the polymer (A2c) to the polymer (A2d) is preferably (polymer (A2 c)/polymer (A2d)) -0.5 to 5, more preferably 0.8 to 2.5, in terms of mass ratio.

The content of the constituent unit (a1) in the polymer (A2c) in all the constituent units in the polymer (A2c) is preferably 3 to 90 mol%, more preferably 10 to 80 mol%. The content of the constituent unit (a4) in the polymer (A2c) in all the constituent units in the polymer (A2c) is preferably 2 to 95 mol%, more preferably 3 to 90 mol%, and still more preferably 5 to 85 mol%. When the polymer (A2c) further contains the constituent unit (a3), the content of the constituent unit (a3) in the polymer (A2c) is preferably 3 to 70 mol%, more preferably 10 to 50 mol%, of all the constituent units in the polymer (A2 c).

The content of the constituent unit (A2) in the polymer (A2d) in all the constituent units in the polymer (A2d) is preferably 1 to 90 mol%, more preferably 40 to 80 mol%. When the polymer (A2d) further contains the constituent unit (a3), the content of the constituent unit (a3) in the polymer (A2d) is preferably 3 to 70 mol%, more preferably 10 to 50 mol%, of all the constituent units in the polymer (A2 d).

(embodiment 4)

(A) The polymer component comprises a polymer (A2e) and a polymer (A2 f). The polymer (A2e) does not generally contain the constituent unit (A2) and the constituent unit (a4) having a lactone structure. In addition, the polymer (A2f) generally does not contain the constituent unit (a 1).

(A) The content of the constituent unit (a1) in all the constituent units of the polymer component (polymer (A2e) and polymer (A2f)) is preferably 3 to 70 mol%. The content of the constituent unit (A2) in all the constituent units of the polymer (A2e) and the polymer (A2f) is preferably 3 to 70 mol%. The content of the constituent unit (a4) in all the constituent units of the polymer (A2e) and the polymer (A2f) is preferably 1 to 80 mol%, more preferably 1 to 50 mol%, and still more preferably 3 to 20 mol%.

In the polymer component (a), the content of the polymer other than the polymer (A2e) and the polymer (A2f) is preferably 10% by mass or less in the polymer component (a).

The polymer (A2e) and/or the polymer (A2f) may further contain the above-mentioned constituent unit (a 3). (A) The content of the constituent unit (a3) in all the constituent units of the polymer component (polymer (A2e) and polymer (A2f)) is preferably 1 to 50 mol%.

When the polymer (A2e) contains the above-mentioned constituent unit (a3), the total of the constituent unit (a1) and the constituent unit (a3) in the polymer (A2e) is 100 mol%.

When the polymer (A2f) contains the above-mentioned constituent unit (a3), the total of the constituent unit (A2), the constituent unit (a3) and the constituent unit (a4) in the polymer (A2f) is 100 mol%.

(A) In the polymer component, the composition ratio of the polymer (A2e) to the polymer (A2f) is preferably (polymer (A2 e)/polymer (A2f)) -0.5 to 5, more preferably 0.8 to 2.5, in terms of mass ratio.

The content of the constituent unit (a1) in the polymer (A2e) in all the constituent units in the polymer (A2e) is preferably 3 to 90 mol%, more preferably 10 to 80 mol%. When the polymer (A2e) further contains the constituent unit (a3), the content of the constituent unit (a3) in the polymer (A2e) is preferably 3 to 70 mol%, more preferably 10 to 50 mol%, of all the constituent units in the polymer (A2 e).

The content of the constituent unit (A2) in the polymer (A2f) in all the constituent units in the polymer (A2f) is preferably 1 to 90 mol%, more preferably 40 to 80 mol%. The content of the constituent unit (a4) in the polymer (A2f) in all the constituent units in the polymer (A2f) is preferably 2 to 95 mol%, more preferably 3 to 90 mol%, and still more preferably 5 to 85 mol%. When the polymer (A2f) further contains the constituent unit (a3), the content of the constituent unit (a3) in the polymer (A2f) is preferably 1 to 70 mol%, more preferably 3 to 50 mol%, of all the constituent units in the polymer (A2 f).

(embodiment 5)

(A) The polymer component comprises polymer (A2g), polymer (A2h) and polymer (A2 i). The polymer (A2g) does not generally contain the constituent unit (A2) and the constituent unit (a4) having a lactone structure. The polymer (A2h) does not generally contain the constituent unit (a1) and the constituent unit (a4) having a lactone structure. In addition, the polymer (A2i) does not generally contain the constituent unit (a1) and the constituent unit (A2).

(A) The content of the constituent unit (a1) in all the constituent units of the polymer component (polymer (A2g), polymer (A2h), and polymer (A2i)) is preferably 3 to 70 mol%. The content of the constituent unit (A2) in all the constituent units of the polymer (A2g), the polymer (A2h), and the polymer (A2i) is preferably 3 to 70 mol%. The content of the constituent unit (a4) in all the constituent units of the polymer (A2g), the polymer (A2h), and the polymer (A2i) is preferably 1 to 80 mol%, more preferably 1 to 50 mol%, and still more preferably 3 to 20 mol%.

In the polymer component (a), the content of the polymer other than the polymer (A2g), the polymer (A2h) and the polymer (A2i) in the polymer component (a) is preferably 10% by mass or less in the polymer component (a).

At least one of the polymer (A2g), the polymer (A2h), and the polymer (A2i) may further contain the above-mentioned constituent unit (a 3). (A) The content of the constituent unit (a3) in all the constituent units of the polymer component (polymer (A2g), polymer (A2h), and polymer (A2i)) is preferably 1 to 50 mol%.

When the polymer (A2g) contains the above-mentioned constituent unit (a3), the total of the constituent unit (a1) and the constituent unit (a3) in the polymer (A2g) is 100 mol%.

When the polymer (A2h) contains the above-mentioned constituent unit (a3), the total of the constituent unit (A2) and the constituent unit (a3) in the polymer (A2h) is 100 mol%.

When the polymer (A2i) contains the above-mentioned constituent unit (a3), the total of the constituent unit (a3) and the constituent unit (a4) in the polymer (A2i) is 100 mol%.

The composition ratio of the total amount of the polymer (A2g) and the polymer (A2h) to the polymer (A2i) is preferably ((polymer (A2g) + polymer (A2 h))/polymer (A2i)) -1 to 20, more preferably 2 to 10, in terms of mass ratio. Further, the composition ratio of the polymer (A2g) to the polymer (A2h) is preferably (polymer (A2 g)/polymer (A2h)) -0.5 to 5, more preferably 0.8 to 2.5, in terms of mass ratio.

The content of the constituent unit (a1) in the polymer (A2g) in all the constituent units in the polymer (A2g) is preferably 3 to 90 mol%, more preferably 10 to 80 mol%. When the polymer (A2g) further contains the constituent unit (a3), the content of the constituent unit (a3) in the polymer (A2g) is preferably 3 to 70 mol%, more preferably 10 to 50 mol%, of all the constituent units in the polymer (A2 g).

The content of the constituent unit (A2) in the polymer (A2h) in all the constituent units in the polymer (A2h) is preferably 1 to 90 mol%, more preferably 40 to 80 mol%. When the polymer (A2h) further contains the constituent unit (a3), the content of the constituent unit (a3) in the polymer (A2h) is preferably 3 to 70 mol%, more preferably 10 to 50 mol%, of all the constituent units in the polymer (A2 h).

The content of the constituent unit (a4) in the polymer (A2i) in all the constituent units in the polymer (A2i) is preferably 2 to 95 mol%, more preferably 3 to 90 mol%, and still more preferably 5 to 85 mol%. When the polymer (A2i) further contains the constituent unit (a3), the content of the constituent unit (a3) in the polymer (A2i) is preferably 3 to 70 mol%, more preferably 10 to 50 mol%, of all the constituent units in the polymer (A2 i).

Molecular weight of Polymer (A)

(A) The molecular weight of the polymer is preferably 1,000 to 200,000, more preferably 2,000 to 50,000, in terms of polystyrene-equivalent weight average molecular weight. When the value is within the above range, various properties are good. The ratio (degree of dispersion) of the number average molecular weight to the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.

Process for producing Polymer component (A)

Various methods are also known for synthesizing the polymer component (a), and for example, a radical polymerization initiator is used to polymerize a radical polymerizable monomer mixture containing at least a radical polymerizable monomer for forming the constituent unit represented by the above (a1) and (a2) in an organic solvent. Alternatively, it can be synthesized by a so-called polymer reaction.

The (a) polymer component preferably contains 50 mol% or more, more preferably 80 mol% or more, of the constituent unit derived from (meth) acrylic acid and/or an ester thereof, based on all the constituent units.

[ photoacid Generator (B) >

The photosensitive resin composition of the present invention contains (B) a photoacid generator. The photoacid generator used in the present invention is preferably a compound that generates an acid by the induction of actinic rays having a wavelength of 300nm or more, preferably 300nm to 450nm, but is not limited by its chemical structure. In addition, as for the photoacid generator which does not directly sense actinic rays having a wavelength of 300nm or more, if it is a compound which generates an acid by sensing actinic rays having a wavelength of 300nm or more in combination with a sensitizer, it may be preferably used in combination with a sensitizer. The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and most preferably a photoacid generator that generates an acid having a pKa of 2 or less.

Examples of the photoacid generator include: trichloromethyl-s-triazines, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, oxime sulfonate compounds, and the like. Among these photoacid generators, oxime sulfonate compounds are preferably used from the viewpoint of insulation properties. These photoacid generators may be used singly or in combination of two or more. Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include the compounds described in paragraphs 0083 to 0088 of Japanese patent laid-open publication No. 2011-221494, and the contents of these are incorporated in the present specification.

As the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure represented by the following general formula (B1-1) can be preferably exemplified.

General formula (B1-1)

[ solution 25]

(in the general formula (B1-1), R²¹Represents an alkyl group or an aryl group. Wavy lines indicate bonds to other bases)

In the general formula (B1-1), any group may be substituted, R²¹The alkyl group in (2) may be linear, branched or cyclic. The permissible substituents are described below.

As R²¹The alkyl group of (2) is preferably a linear alkyl group or a branched alkyl group having 1 to 10 carbon atoms. R²¹The alkyl group (C) may be substituted with a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (including bridged alicyclic groups such as 7, 7-dimethyl-2-oxonorbornyl group, preferably bicycloalkyl group).

As R²¹The aryl group of (2) is preferably an aryl group having 6 to 11 carbon atoms, and more preferably a phenyl group or a naphthyl group. R²¹The aryl group of (a) may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.

The above-mentioned compound having an oxime sulfonate structure represented by the above-mentioned general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-2).

General formula (B1-2)

[ solution 26]

(in the formula (B1-2), R⁴²Represents an alkyl group or an aryl group which may be substituted, X represents an alkyl group, an alkoxy group or a halogen atom, m4 represents an integer of 0 to 3, and when m4 is 2 or 3, X's may be the same or different)

As R⁴²With the above-mentioned R²¹The preferred ranges of (a) are the same.

The alkyl group as X is preferably a linear alkyl group or a branched alkyl group having 1 to 4 carbon atoms. The alkoxy group as X is preferably a linear alkoxy group or a branched alkoxy group having 1 to 4 carbon atoms. The halogen atom as X is preferably a chlorine atom or a fluorine atom.

m4 is preferably 0 or 1. In the above general formula (B1-2), m4 is particularly preferably 1, X is methyl, the substitution position of X is ortho, R is⁴²A linear alkyl group having 1 to 10 carbon atoms, a 7, 7-dimethyl-2-oxonorbornylmethyl group, or a p-toluyl group.

The compound having an oxime sulfonate structure represented by the above general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-3).

General formula (B1-3)

[ solution 27]

(in the formula (B1-3), R⁴³With R in the formula (B1-2)⁴²Same as X¹Represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and n4 represents an integer of 0 to 5)

As R in the above general formula (B1-3)⁴³Preferably methyl, ethyl, n-propyl, n-butylThe group is n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro-n-butyl, p-tolyl, 4-chlorophenyl or pentafluorophenyl, with n-octyl being particularly preferred.

X¹Preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.

n4 is preferably 0 to 2, particularly preferably 0 to 1.

As specific examples of the compound represented by the above general formula (B1-3) and preferred specific examples of oxime sulfonate compounds, reference is made to the descriptions of paragraphs 0080 to 0082 of Japanese patent laid-open No. 2012-163937, which are incorporated herein by reference.

The compound having an oxime sulfonate structure represented by the above general formula (B1-1) is also preferably a compound represented by the following general formula (OS-1).

[ solution 28]

In the above general formula (OS-1), R¹⁰¹Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfonic acid group, a cyano group, an aryl group, or a heteroaryl group. R¹⁰²Represents an alkyl group or an aryl group.

X¹⁰¹represents-O-, -S-, -NH-, -NR¹⁰⁵-、-CH₂-、-CR¹⁰⁶H-, or-CR¹⁰⁵R¹⁰⁷-，R¹⁰⁵～R¹⁰⁷Represents an alkyl group or an aryl group.

R¹²¹～R¹²⁴Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfonic acid group, a cyano group, or an aryl group. R¹²¹～R ¹²⁴2 of them may be bonded to each other to form a ring.

As R¹²¹～R¹²⁴Preferred are a hydrogen atom, a halogen atom and an alkyl group, and R is also preferably mentioned¹²¹～R¹²⁴At least two mutual bonds ofThe structure forms an aryl form. Among them, R is preferable from the viewpoint of sensitivity¹²¹～R¹²⁴All in the form of hydrogen atoms.

The functional groups described above may each further have a substituent.

The compound represented by the above general formula (OS-1) is preferably a compound represented by the general formula (OS-2) described in, for example, paragraphs No. 0087 to No. 0089 of Japanese patent laid-open No. 2012-163937, which can be incorporated herein.

Specific examples of the compounds represented by the general formula (OS-1) which can be suitably used in the present invention include compounds described in paragraphs 0128 to 0132 of Japanese patent laid-open publication No. 2011-221494 (exemplary compounds b-1 to exemplary compounds b-34), but the present invention is not limited thereto.

In the present invention, the compound having an oxime sulfonate structure represented by the above general formula (B1-1) is preferably an oxime sulfonate compound represented by the following general formula (OS-3), the following general formula (OS-4) or the following general formula (OS-5).

[ solution 29]

In the general formulae (OS-3) to (OS-5), R²²、R²⁵And R²⁸Each independently represents alkyl, aryl or heteroaryl, R²³、R²⁶And R²⁹Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R²⁴、R²⁷And R³⁰Each independently represents a halogen atom, an alkyl group, an alkoxy group, a sulfonic group, an aminosulfonyl group or an alkoxysulfonyl group, X¹～X³Each independently represents an oxygen atom or a sulfur atom, n1 to n3 each independently represents 1 or 2, m1 to m3 each independently represents an integer of 0 to 6)

For the general formulae (OS-3) to (OS-5), for example, the descriptions of paragraphs 0098 to 0115 in Japanese patent laid-open No. 2012 and 163937 can be referred to and incorporated in the present specification.

The compound having an oxime sulfonate structure represented by the above general formula (B1-1) is particularly preferably a compound represented by any one of the general formulae (OS-6) to (OS-11) described in, for example, paragraph 0117 of Japanese patent laid-open No. 2012-163937, and the contents can be incorporated in the present specification.

The preferable ranges of the general formulae (OS-6) to (OS-11) are the same as the preferable ranges of (OS-6) to (OS-11) described in paragraphs 0110 to 0112 of Japanese patent laid-open publication No. 2011-221494, and such contents are incorporated in the present specification.

Specific examples of the oxime sulfonate compounds represented by the general formulae (OS-3) to (OS-5) include those described in paragraphs 0114 to 0120 of Japanese patent laid-open publication No. 2011-221494, which are incorporated herein by reference. The present invention is not limited to these compounds.

The compound having an oxime sulfonate structure represented by the above general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-4).

General formula (B1-4)

[ solution 30]

(in the general formula (B1-4), R¹Represents alkyl or aryl, R²Represents an alkyl group, an aryl group, or a heteroaryl group. R³～R⁶Each represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. Wherein R is³And R⁴、R⁴And R⁵Or R⁵And R⁶May be bonded to form an alicyclic or aromatic ring. X represents-O-or-S-)

R¹Represents an alkyl group or an aryl group. The alkyl group is preferably an alkyl group having a branched structure or an alkyl group having a cyclic structure.

The number of carbon atoms of the alkyl group is preferably 3 to 10. Particularly, when the alkyl group has a branched structure, the alkyl group preferably has 3 to 6 carbon atoms, and when the alkyl group has a cyclic structure, the alkyl group preferably has 5 to 7 carbon atoms.

Examples of the alkyl group include a propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, a third butyl group, a pentyl group, an isopentyl group, a neopentyl group, a1, 1-dimethylpropyl group, a hexyl group, a 2-ethylhexyl group, a cyclohexyl group, and an octyl group, and preferably an isopropyl group, a third butyl group, a neopentyl group, and a cyclohexyl group.

The aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, and still more preferably 6 to 7 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.

R¹The alkyl group and the aryl group may have a substituent. Examples of the substituent include: halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), straight-chain, branched or cyclic alkyl group (e.g., methyl group, ethyl group, propyl group, etc.), alkenyl group, alkynyl group, aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclyloxy group, acyloxy group, amino group, nitro group, hydrazino group, heterocyclic group, etc. Further, these groups may be further substituted. Preferably a halogen atom or a methyl group.

In the photosensitive resin composition of the present invention, R is R in terms of transparency¹Preferably an alkyl group, R is a group having both storage stability and sensitivity¹Preferably an alkyl group having a branched structure and 3 to 6 carbon atoms, an alkyl group having a cyclic structure and 5 to 7 carbon atoms, or a phenyl group, more preferably an alkyl group having a branched structure and 3 to 6 carbon atoms, or an alkyl group having a cyclic structure and 5 to 7 carbon atoms. By using such bulky radicals (in particular bulky alkyl radicals) as R¹Thereby further improving the transparency.

Among the bulky substituents, isopropyl, tertiary butyl, neopentyl and cyclohexyl are preferable, and tertiary butyl and cyclohexyl are more preferable.

R²Represents an alkyl group, an aryl group, or a heteroaryl group. As R²The alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl groupEthyl group, propyl group, isopropyl group, n-butyl group, tertiary butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, etc., preferably methyl group.

The aryl group is preferably an aryl group having 6 to 10 carbon atoms. Examples of the aryl group include a phenyl group, a naphthyl group, and a p-toluyl group (p-methylphenyl), and a phenyl group and a p-toluyl group are preferable.

Examples of heteroaryl groups include: pyrrolyl, indolyl, carbazolyl, furyl, thienyl and the like.

R²The alkyl group, the aryl group, and the heteroaryl group may have a substituent. As substituents, the meanings of which are given in connection with R¹The alkyl group and the aryl group may have the same substituent.

R²Preferably an alkyl group or an aryl group, more preferably an aryl group, and even more preferably a phenyl group. The substituent for the phenyl group is preferably a methyl group.

R³～R⁶Each represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom). As R³～R⁶Alkyl radicals having the meaning of R²The alkyl groups represented are the same, and the preferred ranges are also the same. In addition, as R³～R⁶Aryl of the formula¹The aryl groups represented are the same, and the preferred ranges are also the same.

R³～R⁶In the middle, R³And R⁴、R⁴And R⁵Or R⁵And R⁶May be bonded to form a ring, and the ring is preferably an alicyclic ring or an aromatic ring, and more preferably a benzene ring.

R³～R⁶Preferably a hydrogen atom, an alkyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom), or R³And R⁴、 R⁴And R⁵Or R⁵And R⁶Bonded to form a benzene ring, more preferably a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom or R³And R⁴、R⁴And R⁵Or R⁵And R⁶Bonded to form a benzene ring.

R³～R⁶Preferred embodiments of the present invention are as follows.

(form 1) at least two are hydrogen atoms.

(form 2) the number of alkyl, aryl or halogen atoms is 1 or less.

(form 3) R³And R⁴、R⁴And R⁵Or R⁵And R⁶Bonded to form a benzene ring.

(embodiment 4) an embodiment satisfying the above-described

embodiments

1 and 2, and/or an embodiment satisfying the above-described

embodiments

1 and 3.

X represents-O-or-S-.

Specific examples of the above general formula (B1-4) include the following compounds, but the present invention is not particularly limited thereto. In the exemplified compounds, Ts represents a tosyl group (p-tosyl group), Me represents a methyl group, Bu represents a n-butyl group, and Ph represents a phenyl group.

[ solution 31]

As the imide sulfonic acid ester compound, a compound represented by the following general formula (B1-5) can be preferably used.

[ solution 32]

(in the formula (B1-5), R⁷Independently represent a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. n represents an integer of 0 to 4. X represents an integer of 1 to 20, Y represents an integer of 0 to 20, Z represents 0 to 20, W represents an integer of 0 to 5)

Specific examples of the imide sulfonate compound include compounds described in paragraph 0084 of Japanese patent laid-open No. 2012-155115, which is incorporated herein by reference.

In the photosensitive resin composition of the present invention, the amount of the photoacid generator added is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, based on the total solid content in the photosensitive resin composition of the present invention. Two or more photoacid generators may be used in combination. When two or more photoacid generators are used in combination, the total amount thereof is preferably within the above numerical range.

< solvent (C) >

The photosensitive resin composition of the present invention contains a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and optional components described later are dissolved in a solvent. As the solvent used for the preparation of the composition of the present invention, one which uniformly dissolves essential components and optional components and does not react with each component can be used.

As the solvent used in the photosensitive resin composition of the present invention, known solvents can be used, and examples thereof include: ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones, and the like. Specific examples of the solvent used in the photosensitive resin composition of the present invention include solvents described in japanese patent laid-open nos. 0174 to 0178 of 2011-221494 and 0167 to 0168 of 2012-194290, and these are incorporated herein.

Further, if necessary, a solvent such as benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate, or the like may be further added to these solvents. These solvents may be used alone or in combination of two or more. The solvent usable in the present invention is preferably one kind used alone or two kinds used in combination, more preferably two kinds used in combination, and still more preferably propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates and diethylene glycol dialkyl ethers, or esters and butanediol alkyl ether acetates used in combination.

The solvent is preferably a solvent having a boiling point of 130 ℃ or higher but less than 160 ℃, a solvent having a boiling point of 160 ℃ or higher, or a mixture thereof.

Examples of the solvent having a boiling point of 130 ℃ or higher and less than 160 ℃ include: propylene glycol monomethyl ether acetate (boiling point: 146 ℃ C.), propylene glycol monoethyl ether acetate (boiling point: 158 ℃ C.), propylene glycol methyl-n-butyl ether (boiling point: 155 ℃ C.), and propylene glycol methyl-n-propyl ether (boiling point: 131 ℃ C.).

Examples of the solvent having a boiling point of 160 ℃ or higher include: ethyl 3-ethoxypropionate (boiling point 170 ℃), diethylene glycol methyl ethyl ether (boiling point 176 ℃), propylene glycol monomethyl ether propionate (boiling point 160 ℃), dipropylene glycol methyl ether acetate (boiling point 213 ℃), 3-methoxy butyl ether acetate (boiling point 171 ℃), diethylene glycol diethyl ether (boiling point 189 ℃), diethylene glycol dimethyl ether (boiling point 162 ℃), propylene glycol diacetate (boiling point 190 ℃), diethylene glycol monoethyl ether acetate (boiling point 220 ℃), dipropylene glycol dimethyl ether (boiling point 175 ℃), 1, 3-butanediol diacetate (boiling point 232 ℃).

The content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass, more preferably 60 to 90 parts by mass, relative to 100 parts by mass of all the components in the photosensitive resin composition.

< other ingredients >

In the photosensitive resin composition of the present invention, in addition to the above components, a sensitizer, a crosslinking agent, an alkoxysilane compound, a basic compound, a surfactant, and an antioxidant are preferably added as needed. Further, known additives such as an acid-proliferating agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic anti-settling agent may be added to the photosensitive resin composition of the present invention. Further, as these compounds, for example, the compounds described in paragraphs 0201 to 0224 of japanese patent laid-open publication No. 2012-88459 can be used, and the contents thereof can be incorporated into the present specification.

Sensitizer

The photosensitive resin composition of the present invention preferably contains a sensitizer in combination with the photoacid generator to promote decomposition of the photoacid generator. The sensitizer absorbs actinic rays or radiation to become an electron excited state. The sensitizer in an electron excited state comes into contact with the photoacid generator to produce an action such as electron transfer, energy transfer, or heat generation. This causes the photoacid generator to chemically change and decompose, thereby generating an acid. Examples of preferred sensitizers include compounds belonging to the following classes of compounds and having an absorption wavelength in any one of wavelength regions of 350 nm to 450 nm.

Polynuclear aromatics (e.g., pyrene, perylene, triphenylene, anthracene, 9, 10-dibutoxyanthracene, 9, 10-diethoxyanthracene, 3, 7-dimethoxyanthracene, 9, 10-dipropoxyanthracene), xanthenes (xanthene) (e.g., fluorescein (fluoroescein), eosin, erythrosine (erythrosine), Rose Bengal B (Rhodamine B), Rose Bengal (Rose Bengal)), xanthenes (e.g., xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (e.g., thiacarbocyanine, xanthocyanine), merocyanines (e.g., merocyanine, carbocyanine), rhodanines, oxones, thiazines (e.g., thiacyanine, methylene blue, toluidine blue), acridines (e.g., acridine, chlorotoxin, acriflavine), acridines (e.g., acridone, 10-butyl-2-chloroacridone), Anthraquinones (e.g., anthraquinones), squarylium salts (e.g., squarylium salts), styryls, basic styryls (e.g., 2- [2- [4- (dimethylamino) phenyl ] vinyl ] benzoxazole), coumarins (e.g., 7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 2, 3, 6, 7-tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6, 7, 8-ij ] quinolizin-11-one).

Among these sensitizers, polynuclear aromatic compounds, acridone compounds, styrene compounds, basic styrene compounds, and coumarin compounds are preferable, and polynuclear aromatic compounds are more preferable. Among the polynuclear aromatic compounds, anthracene derivatives are most preferred.

The amount of the sensitizer added to the photosensitive resin composition of the present invention is preferably 0 to 100% by mass, more preferably 0.1 to 50% by mass, and still more preferably 0.5 to 20% by mass, based on the total solid content in the photosensitive resin composition of the present invention. Two or more sensitizers may be used in combination.

Crosslinking agent

The photosensitive resin composition of the present invention preferably contains a crosslinking agent as needed. By adding a crosslinking agent, a cured film obtained from the photosensitive resin composition of the present invention can be made stronger.

The crosslinking agent is not limited as long as it causes a crosslinking reaction by heat (except for the component a). For example, a compound having 2 or more epoxy groups or oxetane groups in the molecule, a crosslinking agent containing an alkoxymethyl group, a compound having at least one ethylenically unsaturated double bond, a blocked isocyanate (blocked isocyanate) compound, or the like, which will be described below, may be added.

The amount of the crosslinking agent added to the photosensitive resin composition of the present invention is preferably 0.01 to 50% by mass, more preferably 0.1 to 30% by mass, and still more preferably 0.5 to 20% by mass, based on the total solid content in the photosensitive resin composition of the present invention. When the amount of the organic solvent is in this range, a cured film having excellent mechanical strength and solvent resistance can be obtained. The crosslinking agent may be used in combination of plural kinds, and in this case, the total content of all the crosslinking agents is calculated.

< Compound having 2 or more epoxy groups or oxetanyl groups in the molecule >

Specific examples of the compound having 2 or more epoxy groups in the molecule include: bisphenol a type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin, and the like.

These compounds are available as commercially available products. Examples thereof include JER152, JER157S70, JER157S65, JER806, JER828 and JER1007 (manufactured by Mitsubishi Chemical Holdings), commercially available products described in paragraph 0189 of Japanese patent laid-open publication No. 2011-221494, and in addition to Denacol EX-611, EX-612, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-931, EX-841, EX-911, EX-941, EX-920, EX-212L, EX-214L, EX-216L 214, EX-220, EX-III-Z, EX-Z-D-, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (made by Kasei-Shih), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (made by Nissian iron chemical Co., Ltd.), and the like. These may be used alone or in combination of two or more.

Among these, bisphenol a type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, and aliphatic epoxy resins are more preferable, and bisphenol a type epoxy resins are particularly preferable.

Specific examples of the compound having 2 or more oxetanyl groups in the molecule include linoleoxycyclobutane (ARONE OXETANE) OXT-121, OXT-221, OX-SQ, and PNOX (manufactured by Toyo Synthesis (Ltd.)).

The oxetanyl group-containing compound is preferably used alone or in combination with an epoxy group-containing compound.

Further, as other crosslinking agents, alkoxymethyl group-containing crosslinking agents described in Japanese patent laid-open Nos. 2012-8223, paragraphs No. 0107 to No. 0108, compounds having at least one ethylenically unsaturated double bond, and the like can be preferably used, and the contents of these crosslinking agents are incorporated in the present specification. The alkoxymethyl group-containing crosslinking agent is preferably alkoxymethylated glycoluril.

< blocked isocyanate Compound >

In the photosensitive resin composition of the present invention, a blocked isocyanate compound can also be preferably used as a crosslinking agent. The blocked isocyanate compound is not particularly limited as long as it has a blocked isocyanate group, but from the viewpoint of hardening properties, a compound having 2 or more blocked isocyanate groups in 1 molecule is preferable.

The blocked isocyanate group in the present invention is a group that can generate an isocyanate group by heat, and for example, a group in which an isocyanate group is protected by reacting a blocking agent with an isocyanate group is preferable. The blocked isocyanate group is preferably a group that can generate an isocyanate group by heating at 90 to 250 ℃.

The blocked isocyanate compound is not particularly limited in its skeleton, and any compound may be used as long as it has 2 isocyanate groups in 1 molecule, and it may be an aliphatic, alicyclic or aromatic polyisocyanate, and for example: 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 3-trimethylene diisocyanate, 1, 4-tetramethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, 2, 4, 4-trimethylhexamethylene diisocyanate, 1, 9-nonamethylene diisocyanate, 1, 10-decamethylene diisocyanate, 1, 4-cyclohexane diisocyanate, 2 '-diethyl ether diisocyanate, diphenylmethane-4, 4' -diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylenebis (cyclohexyl isocyanate), cyclohexane-1, isocyanate compounds such as 3-dimethylene diisocyanate, cyclohexane-1, 4-dimethylene diisocyanate, 1, 5-naphthalene diisocyanate, p-phenylene diisocyanate, 3 ' -methylenexylene-4, 4 ' -diisocyanate, 4 ' -diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, hydrogenated 1, 3-xylylene diisocyanate, and hydrogenated 1, 4-xylylene diisocyanate, and prepolymer type skeleton compounds derived from these compounds. Among these, Toluene Diisocyanate (TDI) or diphenylmethane Diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), Isophorone Diisocyanate (IPDI) are particularly preferable.

The parent structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention includes: biuret type, isocyanurate type, adduct type, difunctional prepolymer type, and the like.

Examples of the blocking agent for forming the blocking structure of the blocked isocyanate compound include: oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, thiol compounds, imidazole compounds, imide compounds, and the like. Among these, blocking agents selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds are particularly preferable.

Examples of the oxime compound include oximes and ketoximes, and specifically, examples thereof include: acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketoxime, cyclohexanone oxime, benzophenone oxime, and the like.

Examples of the lactam compound include: epsilon-caprolactam, gamma-butyrolactam, and the like.

Examples of the phenol compound include: phenol, naphthol, cresol, xylenol, halogen-substituted phenol, and the like.

Examples of the alcohol compound include: methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, alkyl lactate, and the like.

Examples of the amine compound include primary amines and secondary amines, and examples thereof include any of aromatic amines, aliphatic amines, and alicyclic amines: aniline, diphenylamine, ethyleneimine, polyethyleneimine, etc.

Examples of the active methylene compound include: diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate, and the like.

Examples of the pyrazole compound include: pyrazole, methylpyrazole, dimethylpyrazole, and the like.

Examples of the thiol compound include: alkyl thiols, aryl thiols, and the like.

The blocked isocyanate compound usable in the photosensitive resin composition of the present invention is commercially available, and for example, the following are preferably used: coconote (Coronate) AP Sttib (Stable) M, Coronate (Coronate)2503, 2515, 2507, 2513, 2555, Millikeite (Millionote) MS-50 (above, made by Nippon Polyurethane Industry (Inc.)), Takenite (Takenate) B-830, B-815N, B-820NSU, B-842 6-846N, B-N, B-874N, B-882N (above, made by Mitsui Chemicals), Polynaide (Duranate) 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80, SBN-70-D, SBB-4670 (above, made by MF-60 German), Asahi (Kadsite) 737 (above), Mikui (made by Sanshui Chemicals), Derma Kadside (German) B-830, made by Nakadsura) B-60PX (above, MF-60-737), and Mitsukuri (made by Sanshu) BL (German) L), wherein, BL1265 MPA/X, BL3575/1, BL3272MPA, BL3370MPA, BL3475BA/SN, BL5375MPA, VPLS2078/2, BL4265SN, PL340, PL350, Sumidur BL3175 (manufactured by Sumika Bayer Urethane (Sumika Bayer Urethane) (Co., Ltd.)), and the like.

Alkoxysilane compound

The photosensitive resin composition of the present invention may contain an alkoxysilane compound. When the alkoxysilane compound is used, the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed from the photosensitive resin composition of the present invention can be adjusted. The alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is preferably a compound that improves the adhesion of an inorganic substance to be a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum, to an insulating film. Specifically, known silane coupling agents and the like are also effective.

Examples of the silane coupling agent include γ -aminopropyltrimethoxysilane, γ -aminopropyltriethoxysilane, γ -glycidoxypropyltrialkoxysilane, γ -glycidoxypropyldialkoxysilane, γ -methacryloxypropyltrialkoxysilane, γ -methacryloxypropyldialkoxysilane, γ -chloropropyltrialkoxysilane, γ -mercaptopropyltrialkoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrialkoxysilane, and vinyltrialkoxysilane, among these, γ -glycidoxypropyltrialkoxysilane or γ -methacryloxypropyltrialkoxysilane is more preferable, γ -glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is even more preferable, and these may be used alone or in combination of two or more.

In addition, compounds represented by the following general formula can also be preferably used.

(R¹)_4-n-Si-(OR²)_n

In the general formula, R¹A C1-20 hydrocarbon group having no reactive group, R²Is alkyl or phenyl with 1-3 carbon atoms, and n is an integer of 1-3.

Specific examples thereof include the following compounds.

[ solution 33]

[ chemical 34]

In the above, Ph is a phenyl group.

The alkoxysilane compound in the photosensitive resin composition of the present invention is not particularly limited to these compounds, and known compounds can be used.

The content of the alkoxysilane compound in the photosensitive resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, based on the total solid content in the photosensitive resin composition of the present invention.

Basic compound

The photosensitive resin composition of the present invention may contain a basic compound. The basic compound may be arbitrarily selected from basic compounds used for a chemically amplified resist. Examples thereof include: aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples of these compounds include those described in japanese patent laid-open publication No. 2011-221494, paragraph No. 0204 to paragraph No. 0207, and the contents of these compounds are incorporated in the present specification.

Specifically, examples of the aliphatic amine include: trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine, dicyclohexylmethylamine and the like.

Examples of the aromatic amine include: aniline, benzylamine, N-dimethylaniline, diphenylamine, and the like.

Examples of heterocyclic amines include: pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2, 4, 5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-hydroxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N' - [2- (4-morpholinyl) ethyl ] thiourea, 1, 5-diazabicyclo [4.3.0] -5-nonene, 1, 8-diazabicyclo [5.3.0] -7-undecene, and the like.

Examples of the quaternary ammonium hydroxide include: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.

Examples of quaternary ammonium salts of carboxylic acids include: tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate, and the like.

The basic compound usable in the present invention may be used singly or in combination of two or more.

The content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 3% by mass, and more preferably 0.005 to 1% by mass, based on the total solid content in the photosensitive resin composition of the present invention.

Surface active agent

The photosensitive resin composition of the present invention may contain a surfactant. As the surfactant, any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant can be used, but a preferable surfactant is a nonionic surfactant. Examples of the surfactant used in the composition of the present invention include surfactants described in paragraphs 0201 to 0205 of Japanese patent laid-open publication No. 2012-88459 and surfactants described in paragraphs 0185 to 0188 of Japanese patent laid-open publication No. 2011-215580, and the descriptions of these surfactants are incorporated in the present specification.

Examples of the nonionic surfactant include: polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants. In addition, the following trade names may be listed: KP-341, X-22-822 (manufactured by shin-Etsu chemical industry (Inc.)), Pelizalo (Polyflow) No.99C (manufactured by Council chemical company (Inc.)), Efotopop (Eftop) (manufactured by Mitsubishi Material Kasei corporation), Megafac (Megafac) (manufactured by Diegon (DIC) (Inc.), Froude (Fluorad), Nobeck (Novec) FC-4430 (manufactured by Mitsubishi 3M (Inc.)), Sharflon (Surflon) S-242 (manufactured by AGC Mermac (AGC SEIMICHEMICAL)), Polifys (PolyFox) 6320 (manufactured by OMNOVA), SH-8400 (manufactured by Tokyo Lankangning silicone (Toray Dow Corg silicone)), Jettel (Ftergent) X-218 series (Netrosgen).

Further, as the surfactant, a copolymer containing a constituent unit a and a constituent unit B represented by the following general formula (I-1-1) and having a weight average molecular weight (Mw) in terms of polystyrene as measured by gel permeation chromatography using Tetrahydrofuran (THF) as a solvent of 1,000 to 10,000 is preferable.

General formula (I-1-1)

[ solution 35]

Constituent Unit A constituent Unit B

(in the formula (I-1-1), R⁴⁰¹And R⁴⁰³Each independently represents a hydrogen atom or a methyl group, R⁴⁰²Represents a linear alkylene group having 1 to 4 carbon atoms, R⁴⁰⁴Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q represent mass percentages representing polymerization ratios, p represents a numerical value of 10 to 80 mass%, q represents a numerical value of 20 to 90 mass%, r represents an integer of 1 to 18, s represents an integer of 1 to 10)

L is preferably a branched alkylene group represented by the following general formula (I-1-2). R in the general formula (I-1-2)⁴⁰⁵Represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 2 or 3 carbon atoms, from the viewpoint of compatibility and wettability with respect to the surface to be coated. The sum of p and q (p + q) is preferably 100, that is, 100 mass%.

General formula (I-1-2)

[ solution 36]

The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 to 5,000.

These surfactants may be used singly or in combination of two or more.

The amount of the surfactant added to the photosensitive resin composition of the present invention is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and still more preferably 0.01% by mass to 3% by mass, based on the total solid content in the photosensitive resin composition of the present invention.

Antioxidant agent

The photosensitive resin composition of the present invention may contain an antioxidant. Known antioxidants may be contained as the antioxidant. By adding the antioxidant, the following advantages are achieved: can prevent the coloring of the cured film, can reduce the decrease in film thickness caused by decomposition, and has excellent heat-resistant transparency.

Examples of such antioxidants include: phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, saccharides, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like. Among these antioxidants, a phenol antioxidant, an amide antioxidant, a hydrazide antioxidant and a sulfur antioxidant are particularly preferable from the viewpoint of coloring of a cured film and reduction in film thickness, and a phenol antioxidant is most preferable. These antioxidants may be used singly or in combination of two or more.

Specific examples thereof include the compounds described in paragraphs 0026 to 0031 of Japanese patent laid-open No. 2005-29515, the contents of which are incorporated in the present specification.

Preferred commercially available products include: addicusta wave (Adekastab) AO-60, Addicusta wave (Adekastab) AO-80, Irganox 1726, Irganox 1035, Irganox 1098.

The content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and particularly preferably 0.5 to 4% by mass, based on the total solid content in the photosensitive resin composition of the present invention. When the amount is within this range, the formed film can have sufficient transparency, and the sensitivity in pattern formation is also good.

[ acid proliferating agent ]

In order to improve the sensitivity, an acid amplifier may be used in the photosensitive resin composition of the present invention.

The acid-proliferating agent that can be used in the present invention is a compound that can further generate an acid by the reaction of an acid catalyst and increase the acid concentration in the reaction system, and is a compound that is stably present in the absence of an acid.

Specific examples of such acid-proliferating agents include those described in Japanese patent laid-open publication No. 2011-221494, paragraphs 0226 to 0228, and the contents thereof are incorporated into the present specification.

[ developing accelerator ]

The photosensitive resin composition of the present invention may contain a development accelerator.

As the development accelerator, reference is made to the descriptions of paragraphs 0171 to 0172 of japanese patent laid-open publication No. 2012 and 042837, which are incorporated in the present specification.

The developing accelerator may be used singly or in combination of two or more.

From the viewpoint of sensitivity and residual film ratio, the amount of the development accelerator added to the photosensitive resin composition of the present invention is preferably 0 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and most preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the total solid content of the photosensitive composition.

Further, as other additives, the thermal radical generators described in Japanese patent laid-open Nos. 2012-8223, paragraphs 0120 to 0121, and the nitrogen-containing compounds and thermal acid generators described in WO 2011/136074A 1 may be used, and the contents thereof are incorporated in the present specification.

< method for producing photosensitive resin composition >

The photosensitive resin composition is prepared by mixing the respective components at a predetermined ratio by an arbitrary method and then stirring and dissolving the mixture. For example, the resin composition may be prepared by dissolving the components in a solvent in advance to prepare solutions, and then mixing the solutions at a predetermined ratio. The composition solution prepared in the above manner can also be used after filtration using, for example, a filter or the like having a pore size of 0.2 μm.

[ method for producing cured film ]

Next, a method for producing a cured film of the present invention will be described.

The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).

(1) Applying the photosensitive resin composition of the present invention to a substrate;

The respective steps will be explained in turn.

In the application step (1), the photosensitive resin composition of the present invention is preferably applied (preferably, coated) to a substrate to form a wet film containing a solvent. The substrate is preferably cleaned by alkali cleaning, plasma cleaning, or the like before the photosensitive resin composition is applied to the substrate, and more preferably, the substrate surface is treated with hexamethyldisilazane after the substrate is cleaned. By performing this treatment, the adhesiveness of the photosensitive resin composition to the substrate tends to be improved. The method of treating the surface of the substrate with hexamethyldisilazane is not particularly limited, and examples thereof include a method of exposing the substrate to hexamethyldisilazane vapor in advance.

Examples of the substrate include: inorganic substrates, resins, resin composites, and the like.

Examples of the inorganic substrate include: glass, quartz, silicone, silicon nitride, and composite substrates obtained by vapor deposition of molybdenum, titanium, aluminum, copper, and the like on these substrates.

Examples of the resin include the following: examples of the resin include synthetic resins such as polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, polybenzoxazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, and the like, liquid crystal polymers, acrylic resins, epoxy resins, silicone resins, ionomer resins, cyanate resins, crosslinked fumaric acid diester, cyclic polyolefins, aromatic ethers, maleimide-olefins, cellulose, episulfide compounds, and the like.

These substrates are rarely used in the above-described form as they are, and usually, a multilayer laminated structure such as a TFT element is formed depending on the form of a final product.

The method of application to the substrate is not particularly limited, and for example, the following can be used: slit coating, spraying, roll coating, spin coating, casting, slit and spin (slit and spin) methods, and the like.

The wet film thickness in the application is not particularly limited, and the coating can be applied to a film thickness according to the application, but is usually used in the range of 0.5 to 10 μm.

Furthermore, the so-called prewet (prewet) method as described in Japanese patent laid-open No. 2009-145395 may be applied before the composition used in the present invention is applied to a substrate.

In the solvent removal step of (2), the solvent is removed from the above-mentioned film applied by pressure reduction (vacuum) and/or heating, etc., to form a dried coating film on the substrate. The heating condition in the solvent removal step is preferably about 30 seconds to 300 seconds at 70 ℃ to 130 ℃. When the temperature and time are within the above ranges, the pattern adhesion tends to be more favorable and the residue tends to be further reduced.

In the exposure step (3), the substrate provided with the coating film is irradiated with actinic rays in a predetermined pattern. In this step, the photoacid generator decomposes and generates an acid. The acid generated from the acid-decomposable gene contained in the coating composition is hydrolyzed by the action of a catalyst to form a carboxyl group or a phenolic hydroxyl group.

As the exposure Light source using actinic rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, a Light Emitting Diode (LED) Light source, an excimer laser generator, and the like can be used, and actinic rays having a wavelength of 300nm to 450nm such as i-ray (365nm), h-ray (405nm), g-ray (436nm), and the like can be preferably used. The irradiation light may be adjusted by a spectral filter such as a long-wavelength cut filter, a short-wavelength cut filter, or a band-pass filter, if necessary. The exposure amount is preferably 1mJ/cm²～500mJ/cm²。

As the exposure apparatus, various types of exposure machines such as a mirror projection aligner (mirror projection aligner), a stepper, a scanner, a proximity type, a contact type, a microlens array type, a lens scanner type, and a laser exposure type can be used.

In the region where the acid catalyst is generated, in order to accelerate the above hydrolysis reaction, post-exposure heat treatment may be performed: post Exposure Bake (hereinafter, also referred to as "PEB"). The PEB promotes the formation of a carboxyl group or a phenolic hydroxyl group derived from an acid-decomposable group. The temperature for carrying out PEB is preferably 30 ℃ or higher and 130 ℃ or lower, more preferably 40 ℃ or higher and 110 ℃ or lower, and particularly preferably 50 ℃ or higher and 100 ℃ or lower.

However, since the acid-decomposable group in the present invention has a low activation energy for acid decomposition, it is easily decomposed by an acid derived from an acid generator generated by exposure to light to generate a carboxyl group or a phenolic hydroxyl group, and thus a positive image (positive image) can be formed by development without necessarily carrying out PEB.

In the developing step of (4), the copolymer having a free carboxyl group or phenolic hydroxyl group is developed using an alkaline developer. The exposed region of the resin composition containing a carboxyl group or a phenolic hydroxyl group which is easily dissolved in an alkaline developer is removed, thereby forming a positive image.

It is preferable that the developer used in the developing step contains an alkali compound. As the basic compound, for example, there can be used: alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline hydroxide; aqueous solutions of sodium silicate, sodium metasilicate, and the like. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkali aqueous solution may be used as the developer.

Preferred examples of the developer include: a 0.4 to 2.5 mass% aqueous solution of tetramethylammonium hydroxide.

The pH of the developer is preferably 10.0 to 14.0.

The developing time is preferably 30 seconds to 500 seconds, and the developing method may be any of a liquid coating method (dip method), a shower method, a dipping method, and the like.

After development, a rinsing step may also be performed. In the rinsing step, the developed substrate is cleaned with pure water or the like, whereby the developer adhering thereto is removed and the development residue is removed. The rinsing method may be a known method. Examples thereof include a spray rinsing and a dip rinsing.

In the post-baking step of (5), the obtained positive image is heated, whereby the acid-decomposable group is thermally decomposed to generate a carboxyl group or a phenolic hydroxyl group, and the carboxyl group or the phenolic hydroxyl group is crosslinked with a crosslinkable group, a crosslinking agent, or the like, thereby forming a cured film. The heating is preferably performed at a predetermined temperature, for example, 180 to 250 ℃ for a predetermined time, for example, on a hot plate using a heating device such as a hot plate or an oven, for 5 to 90 minutes, or for 30 to 120 minutes in the case of an oven. By performing the crosslinking reaction as described above, a protective film or an interlayer insulating film having more excellent heat resistance, hardness, and the like can be formed. In addition, when the heat treatment is performed, the heat treatment may be performed in a nitrogen atmosphere, thereby further improving the transparency.

Before the post-baking, the intermediate baking may be performed after the baking at a relatively low temperature (addition of the intermediate baking step). When the intermediate baking is performed, it is preferable to perform post baking at a high temperature of 200 ℃ or higher after heating at 90 to 150 ℃ for 1 to 60 minutes. The intermediate baking and the post baking may be divided into 3 or more stages to heat the material. By the design of the intermediate baking and the post baking, the cone angle of the pattern can be adjusted. For the heating, a known heating method such as a hot plate, an oven, or an infrared heater can be used.

Further, the substrate having a pattern formed thereon may be subjected to a blanket re-exposure (post-exposure) with actinic rays before the post-baking, and then subjected to the post-baking, whereby an acid is generated from the photoacid generator present in the unexposed portion and is caused to function as a catalyst for promoting the crosslinking step, whereby the hardening reaction of the film can be promoted. As the preferred exposure amount when the post-exposure step is included, 100mJ/cm is preferred²～3,000mJ/cm²Particularly preferably 100mJ/cm²～500mJ/cm²。

Furthermore, the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist (drying resist). When a hardened film obtained by thermal hardening through a post-baking step is used as a dry etching resist, dry etching treatment such as ashing, plasma etching, ozone etching, or the like may be performed as etching treatment.

[ hardened film ]

The cured film of the present invention is obtained by curing the photosensitive resin composition of the present invention.

The cured film of the present invention can be suitably used as an interlayer insulating film. The cured film of the present invention is preferably a cured film obtained by the method for forming a cured film of the present invention.

The photosensitive resin composition of the present invention can provide an interlayer insulating film having excellent insulating properties and high transparency even when baked at high temperatures. The interlayer insulating film formed using the photosensitive resin composition of the present invention has high transparency and excellent physical properties of a cured film, and is therefore useful for applications to liquid crystal display devices and organic EL display devices.

[ liquid Crystal display device ]

The liquid crystal display device of the present invention includes the cured film of the present invention.

The liquid crystal display device of the present invention is not particularly limited except for having a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal display devices having various structures can be exemplified.

For example, specific examples of the TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include: amorphous silicon-TFT, low temperature polysilicon-TFT, oxide semiconductor TFT, etc. The cured film of the present invention is excellent in electrical characteristics, and therefore can be preferably used in combination with these TFTs.

In addition, as a liquid crystal driving method that can be adopted by the liquid crystal display device of the present invention, there can be mentioned: a Twisted Nematic (TN) mode, a Vertical Alignment (VA) mode, an In-Plane-Switching (IPS) mode, a Fringe Field Switching (FFS) mode, an Optically Compensated Bend (OCB) mode, and the like.

In the panel structure, the cured film of the present invention can be used even in a Color Filter on Allay (COA) type liquid crystal display device, and can be used as an organic insulating film (115) of Japanese patent laid-open No. 2005-284291 or an organic insulating film (212) of Japanese patent laid-open No. 2005-346054, for example. As a specific alignment mode of the liquid crystal alignment film that can be used in the liquid crystal display device of the present invention, a rubbing alignment method, a photo-alignment method, and the like can be mentioned. Further, the Polymer orientation support can also be obtained by the Polymer stabilized orientation (PSA) technique described in Japanese patent laid-open Nos. 2003-149647 and 2011-257734.

The photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above applications, and can be used for various applications. For example, the present invention can be suitably used for a protective film of a color filter, a spacer for keeping a thickness of a liquid crystal layer in a liquid crystal display device constant, a microlens provided on a color filter in a solid-state imaging device, and the like, in addition to a planarizing film or an interlayer insulating film.

Fig. 1 is a conceptual sectional view showing an example of an active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface thereof, and the liquid crystal panel is provided with elements of TFTs 16 corresponding to all pixels arranged between 2

glass substrates

14 and 15 to which polarizing films are attached. In each element formed on the glass substrate, an ITO transparent electrode 19 forming a pixel electrode is wired through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, a layer of liquid crystal 20 and an RGB color filter 22 in which a black matrix is arranged are provided.

The light source of the backlight is not particularly limited, and a known light source can be used. Examples thereof include: white LEDs, multicolor LEDs such as blue, red, and green, fluorescent lamps (cold cathode tubes), and organic ELs.

The liquid crystal display device may be a 3D (stereoscopic) type device or a touch panel type device. Further, the interlayer insulating film may be flexible and may be used as the 2 nd interlayer insulating film (48) described in Japanese patent laid-open publication No. 2011-145686 or the interlayer insulating film (520) described in Japanese patent laid-open publication No. 2009-258758.

[ organic EL display device ]

The organic EL display device of the present invention includes the cured film of the present invention.

The organic EL display device of the present invention is not particularly limited except for a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known organic EL display devices or liquid crystal display devices having various structures can be used.

For example, specific examples of the TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include: amorphous silicon-TFT, low temperature polysilicon-TFT, oxide semiconductor TFT, etc. The cured film of the present invention is excellent in electrical characteristics, and therefore can be preferably used in combination with these TFTs.

Fig. 2 is a conceptual diagram of the structure of an example of the organic EL display device. A schematic cross-sectional view of a substrate in an organic EL display device of bottom emission type is shown, and has a planarization film 4.

A bottom gate type TFT1 is formed on a glass substrate 6, and Si is contained in a state of covering the TFT1₃N₄And an insulating film 3. After forming a contact hole (not shown) in the insulating film 3, a wiring 2 (having a height of 1.0 μm) connected to the TFT1 is formed on the insulating film 3 through the contact hole. The wiring 2 is a line for connecting the organic EL element formed between the TFTs 1 or in a subsequent step to the TFT 1.

Further, in order to planarize the irregularities caused by the formation of the wiring 2, the planarization film 4 is formed on the insulating film 3 in a state where the irregularities caused by the wiring 2 are buried.

An organic EL element of bottom emission type is formed on the planarization film 4. That is, the first electrode 5 including ITO is connected to the wiring 2 through the contact hole 7, and is formed on the planarization film 4. The first electrode 5 corresponds to an anode of the organic EL element.

The insulating film 8 is formed in a shape covering the periphery of the first electrode 5, and by providing the insulating film 8, short-circuiting between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

Further, although not shown in fig. 2, an active matrix organic EL display device is obtained in which a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited by vapor deposition through a desired pattern mask, a second electrode containing Al is formed over the entire surface above the substrate, and then the second electrode is bonded to a sealing glass plate using an ultraviolet curable epoxy resin to seal the second electrode, whereby a TFT1 for driving each organic EL element is connected to each organic EL element.

Since the photosensitive resin composition of the present invention has excellent curability and cured film properties, a resist pattern formed using the photosensitive resin composition of the present invention is used as a partition wall in a structural member of an element for a Micro Electro Mechanical Systems (MEMS) or a part of a mechanical drive component. Examples of such MEMS devices include: surface Acoustic Wave (SAW) filters, Bulk Acoustic Wave (BAW) filters, gyro sensors, microshutters for displays, image sensors, electronic paper, inkjet heads, biochips, sealants, and the like. More specific examples are exemplified in japanese patent laid-open publication 2007 & 522531, japanese patent laid-open publication 2008 & 250200, japanese patent laid-open publication 2009 & 263544, and the like.

The photosensitive resin composition of the present invention is excellent in flatness and transparency, and therefore can be used for forming, for example, a bank layer (16) and a planarizing film (57) described in fig. 2 of japanese patent application laid-open No. 2011-107476, a barrier wall (12) and a planarizing film (102) described in fig. 4(a) of japanese patent application laid-open No. 2010-9793, a bank layer (221) and a3 rd interlayer insulating film (216b) described in fig. 10 of japanese patent application laid-open No. 2010-27591, a2 nd interlayer insulating film (125) and a3 rd interlayer insulating film (126) described in fig. 4(a) of japanese patent application laid-open No. 2009-128577, a planarizing film (12) and a pixel separation insulating film (14) described in fig. 3 of japanese patent application laid-open No. 2010-182638, and the like. In addition, the present invention can be suitably used for spacers for keeping the thickness of a liquid crystal layer in a liquid crystal display device constant, or microlenses of an imaging optical system or an optical fiber connector of a color filter mounted on a crystal such as a facsimile, an electronic copier, or a solid-state imaging device.

[ examples ]

The present invention will be described more specifically with reference to examples. The materials, the amounts used, the proportions, the contents of the treatments, the procedures of the treatments and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

[ Table 1]

[ Table 2]

V-601: dimethyl 2, 2' -azobis (2-methyl propionate) (manufactured by Wako pure chemical industries, Ltd.)

V-65: 2, 2' -azobis (2, 4-dimethylvaleronitrile) (Wako pure chemical industries, Ltd.)

MEDG (diethylene glycol ethyl methyl ether): fizeavir (Hisolve) EDM (manufactured by Toho chemical industries, Ltd.)

PGMEA (propylene glycol monomethyl ether acetate): (manufactured by SHOWA AND ELECTRIC WORKS CO., LTD.)

ANON (cyclohexanone): (manufactured by Tokyo chemical industry Co., Ltd.)

[ component A ]

(raw Material for constituting Unit (a 1))

< Synthesis of MAEVE >

0.5 part of phenothiazine was added to 144.2 parts (2 molar equivalents) of ethyl vinyl ether, and 86.1 parts (1 molar equivalent) of methacrylic acid was added dropwise while cooling to 10 ℃ or lower in the reaction system, followed by stirring at room temperature (25 ℃) for 4 hours. After 5.0 parts of pyridinium p-toluenesulfonate was added, the mixture was stirred at room temperature for 2 hours and then allowed to stand at room temperature overnight. To the reaction mixture were added 5 parts of sodium bicarbonate and 5 parts of sodium sulfate, and the mixture was stirred at room temperature for 1 hour, and after filtration of insoluble matter, the mixture was concentrated under reduced pressure at 40 ℃ or lower, and the yellow oily substance of the residue was distilled under reduced pressure to obtain 134.0 parts of 1-ethoxyethyl methacrylate as a colorless oily substance having a boiling point (bp.) of 43 ℃/7mmHg to 45 ℃/7mmHg fraction.

< Synthesis of MATHF >

Methacrylic acid (86g, 1mol) was first cooled to 15 ℃ and then camphorsulfonic acid (4.6g, 0.02mol) was added. To this solution was added dropwise 2-dihydrofuran (71g, 1mol, 1.0 equiv). After stirring for 1 hour, saturated sodium bicarbonate (500mL) was added, extraction was performed with ethyl acetate (500mL), the mixture was dried over magnesium sulfate, insoluble materials were filtered, the filtrate was concentrated under reduced pressure at 40 ℃ or lower, and the yellow oily substance of the residue was distilled under reduced pressure to obtain 125g (yield 80%) of tetrahydro-2H-furan-2-yl Methacrylate (MATHF) as a colorless oily substance having a boiling point (bp.) of 54 ℃/3.5mmHg to 56 ℃/3.5mmHg fraction.

(raw Material for constituting Unit (a 4))

Lactone (1): 2-oxooxooxolane-3-yl ═ methacrylate

[ solution 37]

Lactone (2): 5-oxooxooxolane-3-yl ═ methacrylate

[ solution 38]

Lactone (3): 6-cyano-5-oxo-4-oxatricyclo [4.2.1.0^3.7]Nonan-2-yl ═ methacrylate

[ solution 39]

Lactone (4): condensed cyclic lactone monomer A

[ solution 40]

< Synthesis of Cyclic lactone monomer A (lactone (4) >

Synthesized according to the method described in paragraphs 0256 to 0259 of Japanese patent laid-open No. 2006-146143 (synthetic example 1).

Lactone (5): 5, 5-dimethyl-2-oxooxooxooxolane-3-yl ═ methacrylate

[ solution 41]

Synthesis of 5, 5-dimethyl-2-oxooxooxooxolane-3-yl ═ methacrylate (lactone (5))

Acetonitrile (500mL), pantolactone (130 g, manufactured by tokyo chemical synthesis), and triethylamine (101 g, manufactured by tokyo chemical synthesis) were dissolved in a three-necked flask, cooled to 0 ℃ in an ice bath, and then methacryloyl chloride (104 g, manufactured by tokyo chemical synthesis) was added dropwise. The temperature was raised to room temperature and stirred for 2 hours. Water and ethyl acetate were added to the reaction solution, and the organic layer was extracted, dried over magnesium sulfate, and concentrated. The concentrate was subjected to silica gel column chromatography, whereby the objective compound (160g, 81%) was obtained.

(raw Material for constituting Unit (a 3))

N-cyclohexyl maleimide

[ solution 42]

4-hydroxyphenyl methacrylate

[ solution 43]

[ component B ]

B-1: a compound of the structure

[ solution 44]

B-2: a compound of the structure

[ solution 45]

B-3: a compound of the structure

[ solution 46]

B-4: yanjiaguo (IRGACURE) PAG-103

[ solution 47]

B-7: a compound of the structure

[ solution 48]

< example of polymerization of Polymer A-1 >

(example of introduction of Gamma-Butyrolactone Methacrylate (GBLMA))

Into a three-necked flask, MEDG (41g) was introduced under a nitrogen atmosphere (N)₂Flow 50ml/min), stirring at 200rpm at 70 ℃. MATHF (40 mol%, 24.99g), MAA (10 mol%, 3.44g), MMA (10 mol%, 4.00g), GMA (30 mol%, 17.06g), GBLMA (10 mol%, 6.81g) and V-65 (4 mol%, 3.97g relative to the monomer) were slowly added to the solution over 2 hours at room temperature to dissolve in the MEDG (41 g). After-reaction was carried out at 70 ℃ and stirred for 4 hours, thereby obtaining a polymer A-1.

Further, a polymer solution having a solid content concentration of 40 mass% was prepared. The solid content concentration was defined as monomer mass/(monomer mass + solvent mass) × 100 (unit: mass%).

< Synthesis examples of Polymer A-2 to Polymer A-50 >

Other polymers A-2 to A-50 were synthesized by changing the kind of monomers as shown in the following table. The solid content concentration of the polymer was set to 40 mass%.

< example of polymerization of Polymer A' -1 >

Into a three-necked flask, MEDG (40g) was introduced under nitrogen (N)₂Flow 50ml/min), stirring at 200rpm at 70 ℃. To this solution was slowly added MATHF (40 mol%, 24.99g), MAA (10 mol%, 3.44g), MMA (10 mol%, 4) at room temperature over a period of 2 hours00g), GMA (30 mol%, 17.06g), HEMA (10 mol%, 5.21g) and V-65 (4 mol%, 3.97g relative to the monomer) were dissolved in MEDG (40 g). After-reaction was carried out at 70 ℃ and stirred for 4 hours, thereby obtaining A' -1.

< examples of polymerization of Polymer A '-2 to Polymer A' -18 >

Other polymers A '-2 to A' -18 were synthesized by changing the kind of monomers as shown in the following table. The solid content concentration of each of the polymers A '-2 to A' -18 was 40% by mass.

In tables 3 to 7, the numerical values in the tables without particularly added units have mol% as a unit. The numerical values of the polymerization initiator and the additive are mol% of the monomer component of 100 mol%. The solid content concentration is expressed as mass of monomer/(mass of monomer + mass of solvent) × 100 (unit: mass%). When V-601 was used as a polymerization initiator, the reaction temperature was set to 90 ℃ and when V-65 was used as a polymerization initiator, the reaction temperature was set to 70 ℃.

< preparation of photosensitive resin composition >

The polymer, photoacid generator, sensitizer, basic compound, crosslinking agent, antioxidant, alkoxysilane compound, surfactant and other components were dissolved and mixed in a solvent (MEDG) so that the solid content ratio was as shown in tables 8 to 12 below until the solid content concentration became 25 mass%, and then filtered using a filter made of polytetrafluoroethylene having a bore diameter of 0.2 μm, to obtain photosensitive resin compositions of various examples and comparative examples.

< evaluation of sensitivity >

A glass substrate (EAGLEXG, 0.7mm thick (manufactured by corning corporation)) was exposed to Hexamethyldisilazane (HMDS) vapor for 30 seconds, and each photosensitive resin composition was spin-coated, and then prebaked on a hot plate at 90 ℃ for 120 seconds to volatilize the solvent, thereby forming a photosensitive resin composition layer having a film thickness of 3.0. mu.m.

Subsequently, the obtained photosensitive resin composition layer was exposed to light through a predetermined mask using MPA 5500CF (high pressure mercury lamp) manufactured by canon (stock). Then, the exposed photosensitive resin composition layer was developed with an alkaline developer (2.38% aqueous tetramethylammonium hydroxide solution) at 23 ℃ for 60 seconds, and then rinsed with ultrapure water for 20 seconds. The most preferable i-ray exposure amount (Eopt) when a 10 μm hole is analyzed by these operations is taken as the sensitivity.

A: less than 100mJ/cm²

B：100mJ/cm²Above and below 200mJ/cm²

C：200mJ/cm²Above and below 300mJ/cm²

D：300mJ/cm²Above and below 400mJ/cm²

E：400mJ/cm²The above

< evaluation of chemical resistance >

A glass substrate was exposed to Hexamethyldisilazane (HMDS) vapor for 30 seconds, each photosensitive resin composition was spin-coated on the substrate, and then prebaked on a hot plate at 90 ℃ for 120 seconds to volatilize the solvent, thereby forming a photosensitive resin composition layer having a film thickness of 3.0. mu.m. Then, an ultra-high pressure mercury lamp was used so that the cumulative dose became 300mJ/cm²(energy intensity: 20mW/cm²I-ray) exposure usingThe oven heats the substrate at 230 ℃ for 30 minutes.

The thickness of the obtained cured film was measured (T1). Then, the substrate on which the cured film was formed was subjected to a treatment of controlling the temperature to 60 ℃ in dimethylsulfoxide: monoethanolamine ═ 3: 7 for 3 minutes, the film thickness of the cured film after the immersion was measured (T1), and the film thickness change rate { | tl-T1|/T1 }. times.100 [% ] due to the immersion was calculated. The results are shown in the following table.

The smaller the size, the better the value, the level of C or more is practically at no problem.

A: less than 2 percent

B: more than 2 percent and less than 3 percent

C: more than 3 percent and less than 4 percent

D: more than 4 percent and less than 6 percent

E: more than 6 percent

< evaluation of relative dielectric constant >

Each photosensitive resin composition was spin-coated on a bare wafer substrate (N-type low resistance) (manufactured by Mitsubishi (SUMCO)) and then prebaked on a hot plate at 90 ℃ for 120 seconds to volatilize the solvent, thereby forming a photosensitive resin composition layer having a film thickness of 3.0. mu.m. Then, an ultra-high pressure mercury lamp was used so that the cumulative dose became 300mJ/cm²(energy intensity: 20mW/cm²I-ray) and the substrate was heated in an oven at 230 ℃ for 30 minutes.

The relative dielectric constant of the cured film was measured at a measurement frequency of 1MHz using CVmap92A (manufactured by Four Dimensions Inc.).

A: less than 3.6

B: more than 3.6 and less than 3.8

C: more than 3.8 and less than 4.0

D: 4.0 or more and less than 4.2

E: 4.2 or more

The numerical values in tables 8 to 12 below are based on "mass%".

As is clear from the above results, it is found that the composition of the present invention can maintain high sensitivity, improve chemical resistance, and further lower the relative dielectric constant by including at least one of (a4) a lactone structure-containing constituent unit or at least one of (a4) a constituent unit containing the constituent unit (a4) and not containing (a1) a group in which an acid group is protected by an acid-decomposable group and (a2) a crosslinkable group-containing constituent unit in the polymer component (a).

< example 127>

Example 127 was carried out in the same manner as in example 16 except that the exposure machine was changed from MPA 5500CF manufactured by Canon (stock) to FX-803M (gh-Line stepper) manufactured by Nikon (stock). The sensitivity was evaluated at the same level as in example 1.

< example 128>

Example 128 was carried out in the same manner as in example 1 except that 355nm laser exposure was carried out by changing the MPA 5500CF manufactured by canon (stock) exposure machine to a 355nm laser exposure machine. Here, "AEGIS" (wavelength: 355nm, pulse width: 6nsec) manufactured by V-Technology, Inc. was used as the 355nm laser exposure machine, and "PE 10B-V2" manufactured by Oxfield (OPHIR) was used to measure the exposure amount.

The sensitivity was evaluated at the same level as in example 1.

< example 129>

In the active matrix type liquid crystal display device described in fig. 1 of japanese patent No. 3321003, a cured film 17 was formed as an interlayer insulating film in the following manner, and the liquid crystal display device of example 55 was obtained. That is, the cured film 17 was formed as an interlayer insulating film using the photosensitive resin composition of example 1.

That is, as a pretreatment for improving the wettability between the substrate and the interlayer insulating film 17 in the 58 th stage of japanese patent No. 3321003, the substrate was exposed to Hexamethyldisilazane (HMDS) vapor for 30 seconds, and thereafter, the photosensitive resin composition of example 1 was spin-coated, and then, a prebaking was performed on a hot plate at 90 ℃ for 2 minutes to volatilize the solvent, thereby forming a photosensitive resin composition layer having a film thickness of 3 μm. Then, MPA 5500CF (high pressure mercury vapor lamp) manufactured by Canon (parts by weight) was used with a gap therebetween

To become 80mJ/cm²The obtained photosensitive resin composition layer was exposed to light. Then, the exposed photosensitive resin composition layer was subjected to liquid-coating development with an alkaline developer (2.38% aqueous tetramethylammonium hydroxide solution) at 23 ℃ for 60 seconds, and then rinsed with ultrapure water for 20 seconds. Then, an ultra-high pressure mercury lamp was used so that the cumulative dose became 300mJ/cm²(energy intensity: 20mW/cm²I-ray), and thereafter, the substrate was heated at 230 ℃ for 30 minutes using an oven to obtain a hard filmAnd (5) film formation.

The photosensitive resin composition has good coating property when coated, and no wrinkles or cracks are observed in a cured film obtained after exposure, development and calcination.

As a result of applying a driving voltage to the obtained liquid crystal display device, it was found that the liquid crystal display device exhibited good display characteristics and had high reliability.

< example 130>

A liquid crystal display device similar to that of example 129 was obtained by changing only the following process. That is, even when the photosensitive resin composition of example 1 was applied without Hexamethyldisilazane (HMDS) treatment as a pretreatment of the substrate, the cured film obtained was in a good state without pattern deletion or peeling. The performance of the liquid crystal display device was also good as in example 129. The reason for this is considered to be: the composition of the present invention has excellent adhesion to a substrate. From the viewpoint of improving productivity, it is also preferable to omit the step of pretreating the substrate.

< example 131>

A liquid crystal display device similar to that of example 129 was obtained by changing only the following process. That is, even when a reduced pressure drying step (Vacuum Dry, VCD) is introduced after the prebaking, the obtained cured film is in a good state without pattern deletion or peeling. The performance of the liquid crystal display device was also good as in example 129. It is also preferable to introduce the reduced-pressure drying step in order to suppress coating unevenness depending on the solid content concentration or film thickness of the composition.

< example 132>

A liquid crystal display device similar to that of example 129 was obtained by changing only the following process. That is, even if the PEB step is introduced from the time of mask exposure to the time of the development step, the obtained cured film is in a good state without pattern deletion or peeling. The performance of the liquid crystal display device was also good as in example 129. From the viewpoint of improving dimensional stability, it is also preferable to introduce a PEB step.

< example 133>

A liquid crystal display device similar to that of example 129 was obtained by changing only the following process. That is, even when the alkali developer was changed from a 2.38% tetramethylammonium hydroxide aqueous solution to a 0.4% tetramethylammonium hydroxide aqueous solution, the cured film obtained was in a good state without pattern defects or peeling. The performance of the liquid crystal display device was also good as in example 129. The reason for this is considered to be: the composition of the present invention has excellent adhesion to a substrate.

< example 134>

A liquid crystal display device similar to that of example 129 was obtained by changing only the following process. That is, even when the alkali development method is changed from the coating solution development to the shower development, the cured film obtained is in a good state without pattern defects or peeling. The performance of the liquid crystal display device was also good as in example 129. The reason for this is considered to be: the composition of the present invention has excellent adhesion to a substrate.

< example 135>

A liquid crystal display device similar to that of example 129 was obtained by changing only the following process. That is, even when the alkali developer was changed from a 2.38% tetramethylammonium hydroxide aqueous solution to a 0.04% KOH aqueous solution, the cured film obtained was in a good state without pattern defects or peeling. The performance of the liquid crystal display device was also good as in example 129. The reason for this is considered to be: the composition of the present invention has excellent adhesion to a substrate.

< example 136>

A liquid crystal display device similar to that of example 129 was obtained by changing only the following process. That is, the step of blanket exposure after development and rinsing was omitted, and the cured film was obtained by heating at 230 ℃ for 30 minutes in an oven. The performance of the obtained liquid crystal display device was also good in the same manner as in example 129. The reason for this is considered to be: the compositions of the invention have excellent chemical resistance. From the viewpoint of improving productivity, it is also preferable to omit the blanket exposure step.

< example 137>

A liquid crystal display device similar to that of example 129 was obtained by changing only the following process. That is, a step of heating on a hot plate at 100 ℃ for 3 minutes was added between the step of blanket exposure and the step of heating at 230 ℃ for 30 minutes in an oven. The performance of the obtained liquid crystal display device was also good in the same manner as in example 129. From the viewpoint of aligning the shapes of the hole patterns, it is also preferable to add this step.

< example 138>

A liquid crystal display device similar to that of example 129 was obtained by changing only the following process. That is, a step of heating on a hot plate at 100 ℃ for 3 minutes was added between the step of developing and rinsing and the step of blanket exposure. The performance of the obtained liquid crystal display device was also good in the same manner as in example 129. From the viewpoint of aligning the shapes of the hole patterns, it is also preferable to add this step.

An organic EL display device using TFTs was produced by the following method (see fig. 2).

A bottom gate type TFT1 is formed on a glass substrate 6, and Si is contained in a state of covering the TFT1₃N₄And an insulating film 3. Then, after a contact hole (not shown) is formed in the insulating film 3, a wiring 2 (having a height of 1.0 μm) connected to the TFT1 is formed in the insulating film 3 through the contact hole. The wiring 2 is a line for connecting the organic EL element formed between the TFTs 1 or in a subsequent step to the TFT 1.

Further, in order to planarize the irregularities caused by the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state where the irregularities caused by the wiring 2 are buried. The planarization film 4 on the insulating film 3 was formed by spin-coating the photosensitive resin composition of example 1 on a substrate, prebaking it on a hot plate (90 ℃ C./120 seconds), and then irradiating it from the mask with 80mJ/cm using a high-pressure mercury lamp²(energy intensity 20mW/cm²) Then developed with an alkaline aqueous solution (2.38% aqueous solution of TMAH) to form a pattern, and irradiated with cumulative light using an ultrahigh pressure mercury lampThe amount became 300mJ/cm²(energy intensity: 20mW/cm²I-ray), followed by a heat treatment at 230 ℃ for 30 minutes.

The coating property when the photosensitive resin composition is coated is good, and wrinkles or cracks are not found in a cured film obtained after exposure, development and calcination. The average level difference of the wiring 2 was 500nm, and the thickness of the planarization film 4 was 2,000 nm.

Then, an organic EL element of bottom emission type is formed on the obtained planarization film 4. First, the first electrode 5 including ITO is connected to the wiring 2 via the contact hole 7, and is formed on the planarization film 4. Thereafter, a resist is applied, prebaked, exposed to light through a mask having a desired pattern, and developed. Patterning is performed by wet etching using an ITO etchant with the resist pattern as a mask. Thereafter, the resist pattern was peeled off at 50 ℃ using a resist stripper (Remover100, manufactured by AZ Electronic Materials). The first electrode 5 obtained in the above manner corresponds to an anode of the organic EL element.

Then, the insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. The photosensitive resin composition of example 1 was used for the insulating film 8, and the insulating film 8 was formed in the same manner as described above. By providing this insulating film 8, short-circuiting between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

Further, in the vacuum vapor deposition apparatus, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited by vapor deposition through a desired pattern mask. Then, a second electrode containing Al is formed over the entire surface above the substrate. The obtained substrate was taken out from the vapor deposition machine and sealed by bonding it to a glass plate for sealing using an ultraviolet-curable epoxy resin.

As described above, an active matrix organic EL display device was obtained in which the TFT1 for driving each organic EL element was connected. As a result of voltage application via the driver circuit, it was found that the organic EL display device exhibited good display characteristics and had high reliability.

Claims

1. A positive photosensitive resin composition for alkali development, which is for forming an interlayer insulating film, comprising: a polymer component A containing a polymer satisfying at least one of the following 1 and 2,

1: a polymer having a constituent unit a1 containing a group in which an acid group is protected by an acid-decomposable group and a constituent unit a2 containing a crosslinkable group, 2: a polymer having the constituent unit a1 and a polymer having the constituent unit a 2;

a photoacid generator B; and

a solvent C;

in the polymer component A, at least one constituent unit a4 containing a lactone structure is contained, or

Comprising at least one polymer which comprises the structural unit a4 and does not comprise the structural unit a1 and the structural unit a2,

the constituent unit a1 is a constituent unit represented by the following general formula 1 to 11 containing a group having a carboxyl group protected in the form of acetal,

general formulas 1 to 11

In the general formulae 1 to 11, R¹And R²Each represents a hydrogen atom, an alkyl group or an aryl group, at least R¹And R²Is alkyl or aryl, R³Represents alkyl or aryl, R¹Or R²And R³Can be linked to form a cyclic ether, R⁴Represents a hydrogen atom or a methyl group, X represents a single bond or an arylene group,

the lactone structure-containing structural unit a4 is represented by the following general formulae 4 and 5,

2. the positive photosensitive resin composition for alkali development according to claim 1, wherein the crosslinkable group is selected from the group consisting of an epoxy group, an oxetanyl group and-NH-CH₂At least one of-OR, R is hydrogen atom OR alkyl with 1-20 carbon atoms.

3. The positive photosensitive resin composition for alkali development according to claim 1 or 2, wherein the photoacid generator B is an oxime sulfonate compound or an onium salt compound.

4. The positive photosensitive resin composition for alkali development according to claim 1 or 2, wherein the lactone structure-containing constituent unit a4 is represented by the following general formula 4,

general formula 4

5. A method of manufacturing an interlayer insulating film, comprising:

a step of applying the positive photosensitive resin composition for alkali development according to claim 1 or 2 onto a substrate;

a step of removing the solvent from the applied photosensitive resin composition;

a step of exposing the photosensitive resin composition from which the solvent has been removed, to actinic rays;

a step of developing the exposed photosensitive resin composition with an aqueous developer; and

and a post-baking step of thermally curing the developed photosensitive resin composition.

6. An interlayer insulating film formed by curing the positive photosensitive resin composition for alkali development according to claim 1 or 2.

7. A liquid crystal display device comprising the interlayer insulating film according to claim 6.

8. An organic electroluminescent display device comprising the interlayer insulating film according to claim 6.