WO2014002861A1

WO2014002861A1 - Photosensitive resin composition, method for producing cured film, cured film, organic el display device, and liquid crystal display device

Info

Publication number: WO2014002861A1
Application number: PCT/JP2013/066914
Authority: WO
Inventors: 大助柏木; 山田　悟
Original assignee: 富士フイルム株式会社
Priority date: 2012-06-27
Filing date: 2013-06-20
Publication date: 2014-01-03
Also published as: TWI579644B; JPWO2014002861A1; JP5941543B2; TW201407274A; CN104395826B; CN104395826A; KR20150013791A; KR101791024B1

Abstract

Provided is a photosensitive resin composition. This photosensitive resin composition contains (A) a polymer component which contains a polymer that satisfies (1) and/or (2) described below, (B) a photoacid generator, (C) an alicyclic epoxy compound having a molecular weight of less than 1,000, and (D) a solvent. (1) a polymer which has (a1) a constituent unit having a residue wherein an acid group is protected with an acid-decomposable group and (a2) a constituent unit having an epoxy group (2) (a1) a polymer which has a constituent unit having a residue wherein an acid group is protected with an acid-decomposable group, and (a2) a polymer which has a constituent unit having an epoxy group

Description

Photosensitive resin composition, method for producing cured film, cured film, organic EL display device and liquid crystal display device

The present invention relates to a photosensitive resin composition (hereinafter sometimes 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 apparatuses using the cured film.
More specifically, a photosensitive resin composition suitable for forming a planarizing film, a protective film, and an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL display device, an integrated circuit element, and a solid-state image sensor, and the use thereof The present invention relates to a method for producing a cured film.

Organic EL display devices, liquid crystal display devices, and the like are provided with a patterned interlayer insulating film. In forming the interlayer insulating film, photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.

In addition to the properties of the cured film, such as insulating properties, solvent resistance, heat resistance, hardness, and indium tin oxide (ITO) sputtering suitability, the interlayer insulating film in the above display device is desired to have high transparency. Yes. For this reason, it has been attempted to use an acrylic resin having excellent transparency as a film-forming component. For example, those described in Patent Document 1 are known.

JP 2011-209681 A

However, when the present inventor examined, it was found that the contact hole uniformity was insufficient in the photosensitive resin composition described in Patent Document 1. The present invention aims to solve such problems, and an object thereof is to provide a photosensitive resin composition capable of forming a uniform contact hole while maintaining high sensitivity and transparency after heat resistance. And

As a result of investigation by the inventors of the present invention under such circumstances, an alicyclic ring having a molecular weight of less than 1000 is used as a crosslinking agent using a structural unit having an epoxy group as a structural unit of a crosslinkable group contained in a polymer component. It has been found that a uniform contact hole can be formed by blending the formula epoxy compound while maintaining high sensitivity and transparency after heating. Although this mechanism is not clear, it is considered that the alicyclic epoxy compound quickly traps the acid generated by the acid generator, so that a uniform contact hole can be formed.

Specifically, the above problem has been solved by the following means <1>, preferably <2> to <17>.
<1> (A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2):
(1) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a structural unit having an epoxy group,
(2) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit having an epoxy group,
(B) Photoacid generator (C) A photosensitive resin composition containing an alicyclic epoxy compound having a molecular weight of less than 1000, and (D) a solvent.
<2> The photosensitive resin composition according to claim 1, wherein the (C) alicyclic epoxy compound is represented by the following formula (1).
Formula (1)

(In the formula (1), n represents an integer of 1 to 4. R ¹ represents an organic group having 1 to 30 carbon atoms.)
<3> The photosensitive resin composition according to <2>, wherein R ¹ represents an organic group having 1 to 15 carbon atoms.
<4> The photosensitive resin composition according to <1> or <2>, wherein the (C) alicyclic epoxy compound is represented by the following formula (2).
Formula (2)

(In the formula (2), R ² represents an organic group having 1 to 15 carbon atoms.)
<5> The photosensitive resin composition according to <1> or <2>, wherein the (C) alicyclic epoxy compound is represented by the following formula (3).
Formula (3)

(In the formula (3), R ³ represents an organic group having 1 to 15 carbon atoms.)
<6> The photosensitive resin composition according to any one of <1> to <5>, further comprising a crosslinking agent other than the (C) alicyclic epoxy compound.
<7> The photosensitive resin composition according to <1> or <2>, wherein the (C) alicyclic epoxy compound is represented by the following formula (X-1).
Formula (X-1)

(In the formula (X-1), R ⁴ represents an organic group having 1 to 27 carbon atoms. R ⁵ represents a substituent having 1 to 27 carbon atoms, respectively, except for one alicyclic epoxy group. (The number of carbon atoms is 3 to 30.)
<8> The photosensitive resin composition according to any one of <1>, <2>, and <7>, wherein the (C) alicyclic epoxy compound is represented by the following formula (X-2): .
Formula (X-1)

(In the formula (X-2), R ⁴ represents an organic group having 1 to 27 carbon atoms, and R ⁵ represents a substituent having 1 to 27 carbon atoms, except for one alicyclic epoxy group. (The number of carbon atoms is 3 to 30.)
<9> The photosensitive material according to any one of <1>, <2>, <7>, and <8>, wherein the (C) alicyclic epoxy compound is represented by the following formula (X-3): Resin composition.
Formula (X-1)

(In formula (X-3), each R ⁴ represents an organic group having 1 to 27 carbon atoms. However, the number of carbon atoms excluding one alicyclic epoxy group is 3 to 30.)
<10> The photosensitive resin composition according to any one of <1> to <9>, wherein the acid-decomposable group is a group having a structure protected in the form of an acetal.
<11> The photosensitive resin composition according to any one of <1> to <10>, wherein any of the polymer components (A) is a polymer further containing an acid group.
<12> The photosensitive resin composition according to any one of <1> to <11>, wherein the (B) photoacid generator is an oxime sulfonate compound.
<13> (1) A step of applying the photosensitive resin composition according to any one of <1> to <12> 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 with actinic radiation,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) A method for producing a cured film, comprising a post-baking step of thermosetting the developed photosensitive resin composition.
<14> The method for forming a cured film according to <13>, including a step of exposing the entire surface of the developed photosensitive resin composition after the developing step and before the post-baking step.
<15> A cured film formed by the method according to <13> or <14>.
<16> The cured film according to <15>, which is an interlayer insulating film.
<17> An organic EL display device or a liquid crystal display device having the cured film according to <15> or <16>.

Further, the above-mentioned problem has been solved by the following means.
<18> The photosensitive resin composition according to any one of the above, wherein (A) the polymer component is 50 to 99.9 parts by mass and (B) the photoacid generator is 100 parts by mass of the total solid content. A composition comprising 0.1 to 10 parts by mass of (C) 0.1 to 10 parts by mass of an alicyclic epoxy compound having a molecular weight of less than 1000.

The present invention makes it possible to provide a photosensitive resin composition capable of forming a uniform contact hole while maintaining high sensitivity and transparency after heat resistance.

1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. The schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film. 1 shows a conceptual diagram of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has 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 photosensitive resin composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) is (A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2):
(1) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a structural unit having an epoxy group,
(2) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit having an epoxy group,
(B) A photoacid generator (C) includes an alicyclic epoxy compound having a molecular weight of less than 1,000, and (D) a solvent. In addition, the photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition.
Hereinafter, the composition of the present invention will be described in detail.

<(A) Polymer component>
The composition of the present invention comprises (1) (a1) a structural unit having a group in which an acid group is protected with an acid-decomposable group and (a2) a polymer having a structural unit having an epoxy group, as a polymer component, and (2) At least one of (a1) a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group and (a2) a polymer having a structural unit having an epoxy group are included. Furthermore, polymers other than these may be included. The polymer component (A) in the present invention (hereinafter referred to as “component (A)”) is added in addition to the above (1) and / or (2) unless otherwise stated. Including those polymers.

<< Structural Unit (a1) >>
Component A has (a1) at least a structural unit having a group in which an acid group is protected with an acid-decomposable group. When the component (A) has the structural unit (a1), a highly sensitive photosensitive resin composition can be obtained.
As the “group in which the acid group is protected with an acid-decomposable group” in the present invention, those known as an acid group and an acid-decomposable group can be used, and are not particularly limited. Specific examples of the acid group preferably include a carboxyl group and a phenolic hydroxyl group. The acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an acetal group such as an ester structure of a group represented by the formula (A1), a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group) A functional group) or a group that is relatively difficult to decompose with an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group).

(A1) The structural unit having a group in which the acid group is protected with an acid-decomposable group is a structural unit having a protected carboxyl group protected with an acid-decomposable group, or a protected phenolic group protected with an acid-decomposable group. A structural unit having a hydroxyl group is preferred.
Hereinafter, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in order. To do.

<<< (a1-1) Structural Unit Having a Protected Carboxyl Group Protected with an Acid-Decomposable Group >>>
The structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a protected carboxyl in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described in detail below. A structural unit having a group.
The structural unit having a carboxyl group that can be used for the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group is not particularly limited, and a known structural unit can be used. For example, a structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid, And a structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride.
Hereinafter, (a1-1-1) used as a structural unit having a carboxyl group, a structural unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, and (a1-1-2) ethylene The structural units having both the unsaturated group and the structure derived from the acid anhydride will be described in order.

<<<<< (a1-1-1) Structural Unit Derived from Unsaturated Carboxylic Acid etc. Having at least One Carboxyl Group in the Molecule >>>>
Examples of the unsaturated carboxylic acid used in the present invention as the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule include those listed below. . 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, and 2- (meth) acrylic acid. Examples include leuoxyethyl hexahydrophthalic acid and 2- (meth) acryloyloxyethyl-phthalic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. Moreover, the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to obtain the structural unit which has a carboxyl group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid, such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
Among them, from the viewpoint of developability, in order to form the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, or unsaturated polyhydric carboxylic acid anhydride It is preferable to use acrylic acid, methacrylic acid, and 2- (meth) acryloyloxyethyl hexahydrophthalic acid.
The structural unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule may be composed of one kind alone or two or more kinds. May be.

<<<< (a1-1-2) Structural unit having both an ethylenically unsaturated group and a structure derived from an acid anhydride >>>>
The structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride is obtained by reacting a hydroxyl group present in the structural unit having an ethylenically unsaturated group with an acid anhydride. A unit derived from the obtained monomer is preferred.
As the acid anhydride, known ones can be used, and specifically, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, etc. Dibasic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, and the like. Among these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.
The reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol% from the viewpoint of developability.

<<<< acid-decomposable group that can be used for the structural unit (a1-1) >>>>
As the acid-decomposable group that can be used for the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group, the above-mentioned acid-decomposable groups can be used.
Among these acid-decomposable groups, it is a protected carboxyl group in which the carboxyl group is protected in the form of an acetal. It is preferable from the viewpoint of the storage stability of the composition. Further, among the acid-decomposable groups, the carboxyl group is more preferably a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10) from the viewpoint of sensitivity. 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 entire protected carboxyl group is — (C═O) —O—CR ¹⁰¹ The structure is R ¹⁰² (OR ¹⁰³ ).

Formula (a1-10)

(In formula (a1-10), R ¹⁰¹ and R ¹⁰² each independently represents a hydrogen atom or an alkyl group, except that R ¹⁰¹ and R ¹⁰² are both hydrogen atoms, and R ¹⁰³ represents an alkyl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be linked to form a cyclic ether.)

In the general formula (a1-10), R ¹⁰¹ to R ¹⁰³ each independently represents a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched or cyclic. Here, both R ¹⁰¹ and R ¹⁰² do not represent a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

In the general formula (a1-10), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an alkyl group, the alkyl group may be linear, branched or cyclic.
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, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group 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 a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When it has a halogen atom as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become a haloalkyl group, and when it has an aryl group as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become 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, 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 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an α-methylphenyl group, and a naphthyl group. Examples of the entire alkyl group substituted with an aryl group, ie, an aralkyl group, include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.
The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.
When the alkyl group is a cyclic alkyl group, the cyclic alkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group In the case of a linear or branched alkyl group, it may have a cyclic alkyl group having 3 to 12 carbon atoms as a substituent.
These substituents may be further substituted with the above substituents.

In the general formula (a1-10), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. preferable. The aryl group may have a substituent, and preferred examples of the substituent include 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.

R ¹⁰¹ , R ¹⁰² and R ¹⁰³ can be bonded together to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ¹⁰³ or R ¹⁰² and R ¹⁰³ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like.

Note that in the general formula (a1-10), it is preferable that any one of R ¹⁰¹ and R ¹⁰² be a hydrogen atom or a methyl group.

As the radical polymerizable monomer used for forming the structural unit having a protected carboxyl group represented by the general formula (a1-10), a commercially available one may be used, or it may be synthesized by a known method. Things can also be used. For example, it can be synthesized by the synthesis method described in paragraph numbers 0037 to 0040 of JP2011-212494A.

A first preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a structural unit represented by the following general formula.

(Wherein R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group or Represents an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group; )
When R ¹ and R ² are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferred. When R ¹ and R ² are aryl groups, a phenyl group is preferred. R ¹ and R ² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ³ represents 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, and a single bond is preferred.

A second preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a structural unit of the following general formula.

(Wherein R ¹²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenylene group, and R ¹²² to R ¹²⁸ each independently represents a hydrogen atom or 1 to 4 carbon atoms. Represents an alkyl group of
R ¹²¹ is preferably a hydrogen atom or a methyl group.
L ¹ is preferably a carbonyl group.
R ¹²² to R ¹²⁸ are preferably hydrogen atoms.

As preferred specific examples of the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group, the following structural units can be exemplified. R represents a hydrogen atom or a methyl group.

<<< (a1-2) Structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group >>>
The structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group is a protected phenolic group in which the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below. A structural unit having a hydroxyl group.

<<<<< (a1-2-1) Structural Unit Having Phenolic Hydroxyl Group >>>>
Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene structural unit and a structural unit in a novolac resin. Among these, a structural unit derived from hydroxystyrene or α-methylhydroxystyrene includes: It is preferable from the viewpoint of sensitivity. As the structural unit having a phenolic hydroxyl group, a structural unit represented by the following general formula (a1-20) is also preferable from the viewpoint of sensitivity.

Formula (a1-20)

(In the general formula (a1-20), R ²²⁰ represents a hydrogen atom or a methyl group, R ²²¹ represents a single bond or a divalent linking group, and R ²²² represents a halogen atom or a straight chain of 1 to 5 carbon atoms or Represents a branched alkyl group, a represents an integer of 1 to 5, b represents an integer of 0 to 4, and a + b is 5 or less, and when R ²²² is 2 or more, these R ²²² may be different from each other or the same.)

In the general formula (a1-20), R ²²⁰ represents a hydrogen atom or a methyl group, and is preferably a methyl group.
R ²²¹ represents a single bond or a divalent linking group. A single bond is preferable because the sensitivity can be improved and the transparency of the cured film can be improved. The divalent linking group of R ²²¹ may be exemplified alkylene groups, specific examples R ²²¹ is an alkylene group, a methylene group, an ethylene group, a propylene group, isopropylene group, n- butylene group, isobutylene group, tert -Butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group and the like. Among these, it is preferable that R ²²¹ is a single bond, a methylene group, or an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. A represents an integer of 1 to 5, but a is preferably 1 or 2 and more preferably 1 from the viewpoint of the effects of the present invention and the ease of production. .
Further, the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R ²²¹ is defined as the reference (first position).
R ²²² is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. It is done. Among these, a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of easy production.
B represents 0 or an integer of 1 to 4;

<<<< acid-decomposable group that can be used for the structural unit (a1-2) >>>>
The acid-decomposable group that can be used in the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-decomposable group includes a structure having a protected carboxyl group protected by the acid-decomposable group Similar to the acid-decomposable group that can be used for the unit (a1-1), known ones can be used and are not particularly limited. Among the acid-decomposable groups, a structural unit having a protected phenolic hydroxyl group protected with acetal is a basic physical property of the photosensitive resin composition, particularly sensitivity and pattern shape, storage stability of the photosensitive resin composition, contact This is preferable from the viewpoint of hole formability. Furthermore, among the acid-decomposable groups, the phenolic hydroxyl group is more preferably a protected phenolic hydroxyl group protected in the form of an acetal represented by the general formula (a1-10) from the viewpoint of sensitivity. When the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the general formula (a1-10), the protected phenolic hydroxyl group as a whole is —Ar—O—CR ¹⁰¹ R The structure is ¹⁰² (OR ¹⁰³ ). Ar represents an arylene group.

Preferable examples of the acetal ester structure of the phenolic hydroxyl group include a combination of R ¹⁰¹ = R ¹⁰² = R ¹⁰³ = methyl group, R ¹⁰¹ = R ¹⁰² = methyl group and R ¹⁰³ = benzyl group.

Examples of the radical polymerizable monomer used for forming a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of an acetal include paragraph number 0042 of JP2011-215590A. And the like.
Among these, a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.

Specific examples of the acetal protecting group for the phenolic hydroxyl group include a 1-alkoxyalkyl group, such as a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, and a 1-isobutoxyethyl group. 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) ethyl group, 1 -A benzyloxyethyl group etc. can be mentioned, These can be used individually or in combination of 2 or more types.

As the radical polymerizable monomer used for forming the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-decomposable group, a commercially available one may be used, or a known method may be used. What was synthesize | combined by can also be used. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with another monomer, and then reacted with vinyl ether in the presence of an acid catalyst.

As preferred specific examples of the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group, the following structural units can be exemplified, but the present invention is not limited thereto.

<<< Preferred Aspect of Structural Unit (a1) >>>
When the polymer containing the structural unit (a1) does not substantially contain the structural unit (a2), the structural unit (a1) is 20 to 100 in the polymer containing the structural unit (a1). The mol% is preferable, and 30 to 90 mol% is more preferable.
When the polymer containing the structural unit (a1) contains the following structural unit (a2), the structural unit (a1) is a polymer containing the structural unit (a1) and the structural unit (a2). From the viewpoint of sensitivity, it is preferably 3 to 70 mol%, more preferably 10 to 60 mol%. In particular, when the acid-decomposable group that can be used in the structural unit (a1) is a structural unit having a protected carboxyl group in which the carboxyl group is protected in the form of an acetal, the content is preferably 20 to 50 mol%.

The structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group. Is characterized by being fast. Therefore, when it is desired to develop quickly, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferred. Conversely, when it is desired to delay the development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.
The structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group. Is characterized by being fast. Therefore, when it is desired to develop quickly, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferred. Conversely, when it is desired to delay the development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.

<< (a2) Structural Unit Having Epoxy Group >>
The component (A) has a structural unit (a2) having an epoxy group. The structural unit (a2) having an epoxy group may have at least one epoxy group in one structural unit, and preferably has 1 to 3 epoxy groups in total, and 1 or 2 epoxy groups in total. It is more preferable to have one, and it is still more preferable to have one epoxy group.

Specific examples of the radical polymerizable monomer used for forming the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexyl methacrylate Methyl, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, described in paragraph Nos. 0031 to 0035 of Japanese Patent No. 4168443 Alicyclic And compounds containing epoxy backbone can be cited, the contents of which are hereby incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit (a2) having the epoxy group include a monomer containing a methacrylic ester structure and a monomer containing an acrylic ester structure. preferable.

Among these, preferred are glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, methyl (3-ethyloxetane-3-yl) methacrylate, and methacrylic acid ( 3-ethyloxetane-3-yl) methyl. These structural units can be used individually by 1 type or in combination of 2 or more types.

Preferred examples of the structural unit (a2) having an epoxy group include the following structural units. R represents a hydrogen atom or a methyl group.

<<< Preferred Aspect of Structural Unit (a2) >>>
When the polymer containing the structural unit (a2) does not substantially contain the structural unit (a1), the structural unit (a2) is 5 to 90% in the polymer containing the structural unit (a2). The mol% is preferable, and 20 to 80 mol% is more preferable.
When the polymer containing the structural unit (a2) contains the structural unit (a1), the structural unit (a2) is a polymer containing the structural unit (a1) and the structural unit (a2). From the viewpoint of chemical resistance, it is preferably 3 to 70 mol%, more preferably 10 to 60 mol%.
In the present invention, the structural unit (a2) is preferably contained in an amount of 3 to 70 mol%, more preferably 10 to 60 mol% in all the structural units of the component (A), regardless of any embodiment. The content is preferably 20 to 60 mol%, and most preferably.
Furthermore, it is preferable that the epoxy group which the structural unit (a2) has is not an alicyclic epoxy group.

Within the above numerical range, the transparency and chemical resistance of the cured film obtained from the photosensitive resin composition are improved.

<< (a3) Other structural units >>
In the present invention, the component (A) may have another structural unit (a3) in addition to the structural units (a1) and / or (a2). These structural units may be contained in the polymer component (1) and / or (2). Further, apart from the polymer component (1) or (2), it may have a polymer component having other structural unit (a3) substantially not containing (a1) and (a2). . Apart from the polymer component (1) or (2), in the case of containing a polymer component having other structural unit (a3) substantially not containing (a1) and (a2), The blending amount is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less in all polymer components.

There is no restriction | limiting in particular as a monomer used as another structural unit (a3), For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated Dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds be able to. Moreover, you may have the structural unit which has an acid group so that it may mention later. The monomer which becomes another structural unit (a3) can be used individually or in combination of 2 or more types.

Hereinafter, preferred embodiments of the polymer component of the present invention will be described, but the present invention is not limited thereto.

(First embodiment)
The aspect in which the polymer component (1) further has one or more other structural units (a3).
(Second Embodiment)
The polymer having a structural unit having a group in which the (a1) acid group of the polymer component (2) is protected by an acid-decomposable group further has one or more other structural units (a3). Aspect.
(Third embodiment)
The aspect which the polymer which has a structural unit which has (a2) epoxy group of the polymer component (2) further has 1 type, or 2 or more types of other structural units (a3).

(Fourth embodiment)
In any one of the first to third embodiments, the other structural unit (a3) includes a structural unit containing at least an acid group.

(Fifth embodiment)
In addition to the polymer component (1) or (2), an embodiment having a polymer having another structural unit (a3) substantially not containing (a1) and (a2).

(Sixth embodiment)
A form comprising a combination of two or more of the first to fifth embodiments.
(Seventh embodiment)
An embodiment comprising at least the polymer component (2). In particular, in the first to sixth embodiments, at least the polymer component (2) is included.

The structural unit (a3) specifically includes styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, vinylbenzoic acid. Ethyl, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylic acid Isopropyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate Mention may be made of a structural unit due to theft. In addition, compounds described in paragraph numbers 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.

Further, as other structural unit (a3), styrenes and groups having an aliphatic cyclic skeleton are preferable from the viewpoint of electrical characteristics. Specifically, styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, etc. Can be mentioned.

Furthermore, as other structural unit (a3), (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable. In the structural unit constituting the polymer (A), the content of the structural unit (a3) is preferably 60 mol% or less, more preferably 50 mol% or less, and further preferably 40 mol% or less. As a lower limit, although 0 mol% may be sufficient, it can be set as 1 mol% or more, for example, Furthermore, it can be set as 5 mol% or more. When it is within the above numerical range, various properties of the cured film obtained from the photosensitive resin composition are improved.

The other structural unit (a3) preferably contains an acid group. By containing an acid group, it becomes easy to dissolve in an alkaline developer, and the effects of the present invention are more effectively exhibited. The acid group in the present invention means a proton dissociable group having a pKa of less than 7. The acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
Acid groups used in the present invention include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfones Amide groups, sulfonylimide groups and the like are exemplified, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred.
The structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof. .

In the present invention, it is particularly preferable from the viewpoint of sensitivity to contain a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group.

The structural unit containing an acid group is preferably 1 to 80% by mole, more preferably 1 to 50% by mole, still more preferably 5 to 40% by mole, and particularly preferably 5 to 30% by mole of the structural unit of all polymer components. 5 to 20 mol% is particularly preferable.

In the present invention, in addition to the polymer component (1) or (2), a polymer having other structural unit (a3) without substantially containing (a1) and (a2) may be included. .

Such a polymer is preferably a resin having a carboxyl group in the side chain. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Examples thereof include acidic cellulose derivatives having a carboxyl group, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.

For example, benzyl (meth) acrylate / (meth) acrylic acid copolymer, 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, described in JP-A-7-140654 2-hydroxypropyl (meth) acrylate / polystyrene 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 the like.
In addition, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118 Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used, and the contents thereof are incorporated herein.

SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, manufactured by Sartomer), ARUFON UC-3000, ARUFON UC-3510, ARUFON are commercially available as these polymers. UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), Joncryl 680, Joncryl 682, Joncryl 690, Joncryl 678, JoncrJr 67 Etc.) can also be used.
These other polymers may contain only 1 type, and may contain 2 or more types.

<< (A) Molecular Weight of Polymer >>
The molecular weight of the polymer (A) is a polystyrene-equivalent weight average molecular weight, preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and still more preferably 10,000 to 50,000. 000 range. Various characteristics are favorable in the range of said numerical value. The ratio (dispersity) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.

<< (A) Polymer Production Method >>
Various methods for synthesizing the component (A) are known. To give an example, the component (A) is used to form at least the structural units represented by (a1) and (a3). It can be synthesized by polymerizing a radical polymerizable monomer mixture containing a radical polymerizable monomer in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.

The photosensitive resin composition of the present invention preferably contains the component (A) in a proportion of 50 to 99.9 parts by mass, and in a proportion of 70 to 98 parts by mass with respect to 100 parts by mass of the total solid content. More preferred.

<(B) Photoacid generator>
The photosensitive resin composition of the present invention contains (B) a photoacid generator. As the photoacid generator (also referred to as “component (B)”) used in the present invention, a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid is preferable. The chemical structure is not limited. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. 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 an acid of 2 or less. Most preferred are photoacid generators that generate.

Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation. These photoacid generators can 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 paragraph numbers 0083 to 0088 of JP2011-212494A. It can be illustrated.

Preferred examples of the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following general formula (B1).

General formula (B1)

(In the general formula (B1), R ²¹ represents an alkyl group or an aryl group. A wavy line represents a bond with another group.)

Any group may be substituted, and the alkyl group in R ²¹ may be linear, branched or cyclic. Acceptable substituents are described below.
The alkyl group for R ²¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ²¹ is a bridged type such as an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cyclic alkyl group (7,7-dimethyl-2-oxonorbornyl group). It may be substituted with an alicyclic group, preferably a bicycloalkyl group.
As the aryl group for R ^21, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.

The above compound containing an oxime sulfonate structure represented by the above general formula (B1) is also preferably an oxime sulfonate compound represented by the following general formula (B2).

(In the formula (B2), R ⁴² represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, m4 represents an integer of 0 to 3, and m4 represents 2 or When X is 3, the plurality of X may be the same or different.)

The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group as X is preferably a linear or 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 (B2), m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R ⁴² is a linear alkyl group having 1 to 10 carbon atoms, 7,7- A compound that is a dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.

The compound containing an oxime sulfonate structure represented by the above general formula (B1) is also preferably an oxime sulfonate compound represented by the following general formula (B3).

(In the formula (B3), R ⁴³ has the same meaning as R ⁴² in the formula (B2), and X ¹ is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, cyano Represents a group or a nitro group, and n4 represents an integer of 0 to 5.)

R ⁴³ in the above general formula (B3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group. Perfluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferred, and n-octyl group is particularly preferred.
X ¹ is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
n4 is preferably from 0 to 2, particularly preferably from 0 to 1.

Specific examples of the compound represented by the general formula (B3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino). ) Benzyl cyanide, α- (n-butylsulfonyloxyimino) benzyl cyanide, α- (4-toluenesulfonyloxyimino) benzyl cyanide, α-[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-butylsulfonyloxyimino) -4- Methoxyphenyl] acetonitrile, α-[(4 It can be given toluenesulfonyl) -4-methoxyphenyl] acetonitrile.

Specific examples of preferable oxime sulfonate compounds include the following compounds (i) to (viii), and the like can be used singly or in combination of two or more. Compounds (i) to (viii) can be obtained as commercial products. Moreover, it can also be used in combination with another kind of (B) photo-acid generator.

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

In the general formula (OS-1), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or Represents a heteroaryl group. ^R102 represents an alkyl group or an aryl group.
X ¹⁰¹ represents —O—, —S—, —NH—, —NR ¹⁰⁵ —, —CH ₂ —, —CR ¹⁰⁶ H—, or —CR ¹⁰⁵ R ¹⁰⁷ —, wherein R ¹⁰⁵ to R ¹⁰⁷ are alkyl groups. Or an aryl group.
R ¹²¹ to R ¹²⁴ each 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 sulfo group, a cyano group, Or an aryl group is represented. Two of R ¹²¹ to R ¹²⁴ may be bonded to each other to form a ring.
R ¹²¹ to R ¹²⁴ are preferably a hydrogen atom, a halogen atom and an alkyl group, and an embodiment in which at least two of R ¹²¹ to R ¹²⁴ are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which R ¹²¹ to R ¹²⁴ are all hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the aforementioned functional groups may further have a substituent.

The compound represented by the general formula (OS-1) is more preferably a compound represented by the following general formula (OS-2).

In the general formula (OS-2), R ¹⁰¹ , R ¹⁰² and R ¹²¹ to R ¹²⁴ have the same meanings as in the formula (OS-1), and preferred examples thereof are also the same.
Among these, an embodiment in which R ¹⁰¹ in the general formula (OS-1) and the general formula (OS-2) is a cyano group or an aryl group is more preferable, and is represented by the general formula (OS-2). And R ¹⁰¹ is most preferably a cyano group, a phenyl group, or a naphthyl group.

In the oxime sulfonate compound, the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.

Specific examples of the compound represented by the general formula (OS-1) that can be suitably used in the present invention include compounds described in paragraph numbers 0128 to 0132 of JP2011-221494A (exemplified compounds b-1 to b-34), but the present invention is not limited thereto.

In the present invention, the compound containing the oxime sulfonate structure represented by the above general formula (B1) includes the following general formula (OS-3), the following general formula (OS-4), or the following general formula (OS-5). It is preferable that it is an oxime sulfonate compound represented by these.

(In the general formula (OS-3) to general formula (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represents an alkyl group, an aryl group or a heteroaryl group; R ²³ , R ²⁶ and R ²⁹ Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. X ¹ to X ³ each independently represents an oxygen atom or a sulfur atom, n ¹ to n ³ each independently represents 1 or 2, and m ¹ to m ³ each independently represents an integer of 0 to 6 Represents.)

In the general formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have a substituent.
In the above formulas (OS-3) to (OS-5), the alkyl group in R ²² , R ²⁵ and R ²⁸ is an alkyl group having 1 to 30 carbon atoms which may have a substituent. Is preferred.

In the general formulas (OS-3) to (OS-5), the aryl group in R ²² , R ²⁵ and R ²⁸ is an aryl group having 6 to 30 carbon atoms which may have a substituent. preferable.

In the general formulas (OS-3) to (OS-5), the heteroaryl group in R ¹ is preferably a heteroaryl group having 4 to 30 carbon atoms in total which may have a substituent.

In the general formulas (OS-3) to (OS-5), at least one of the heteroaryl groups in R ²² , R ²⁵ and R ²⁸ may be a heteroaromatic ring, such as a heteroaromatic ring and benzene. The ring may be condensed.

In the general formulas (OS-3) to (OS-5), R ²³ , R ²⁶ and R ²⁹ are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group. preferable.
In the above general formulas (OS-3) to (OS-5), one or two of R ²³ , R ²⁶ and R ²⁹ present in the compound are an alkyl group, an aryl group or a halogen atom. It is more preferable that one is an alkyl group, an aryl group or a halogen atom, and it is particularly preferable that one is an alkyl group and the rest is a hydrogen atom.

The alkyl group for R ²³ , R ²⁶ and R ²⁹ is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 1 carbon atoms which may have a substituent. More preferred is an alkyl group of 6.

The aryl group for R ²³ , R ²⁶ and R ²⁹ is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.

In the general formulas (OS-3) to (OS-5), X ¹ to X ³ each independently represents O or S, and is preferably O.
In the general formulas (OS-3) to (OS-5), the ring containing X ¹ to X ³ as a ring member is a 5-membered ring or a 6-membered ring.
In the general formulas (OS-3) to (OS-5), n ¹ to n ³ each independently represents 1 or 2, and when X ¹ to X ³ are O, n ¹ to n ³ are each independently In addition, when X ¹ to X ³ are S, n ¹ to n ³ are each preferably 2 independently.

In the general formulas (OS-3) to (OS-5), R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group or alkoxysulfonyl group. To express. Among them, R ²⁴ , R ²⁷ and R ³⁰ are preferably each independently an alkyl group or an alkyloxy group.
The alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R ²⁴ , R ²⁷ and R ³⁰ may have a substituent.
In the general formulas (OS-3) to (OS-5), the alkyl group in R ²⁴ , R ²⁷ and R ³⁰ is an alkyl group having 1 to 30 carbon atoms which may have a substituent. It is preferable.

In the general formulas (OS-3) to (OS-5), the alkyloxy group in R ²⁴ , R ²⁷ and R ³⁰ is an alkyloxy group having 1 to 30 carbon atoms which may have a substituent. Preferably there is.

In the general formulas (OS-3) to (OS-5), m ¹ to m ³ each independently represents an integer of 0 to 6, preferably an integer of 0 to 2, preferably 0 or 1. More preferably, it is particularly preferably 0.
In addition, with respect to each of the substituents of (OS-3) to (OS-5) described above, the substitution of (OS-3) to (OS-5) described in paragraph numbers 0092 to 0109 of JP2011-221494A The preferred range of groups is likewise preferred.

The compound containing the oxime sulfonate structure represented by the general formula (B1) is particularly an oxime sulfonate compound represented by any of the following general formulas (OS-6) to (OS-11). preferable.

(In the formulas (OS-6) to (OS-11), R ³⁰¹ to R ³⁰⁶ represent an alkyl group, an aryl group, or a heteroaryl group, R ³⁰⁷ represents a hydrogen atom or a bromine atom, and R ³⁰⁸ to R ³¹⁰ , R ³¹³ , R ³¹⁶ and R ³¹⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group; R ³¹¹ and R ³¹⁴ each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ³¹² , R ³¹⁵ , R ³¹⁷ and R ³¹⁹ each independently represent a hydrogen atom or a methyl group.)

Preferred ranges in the above general formulas (OS-6) to (OS-11) are preferred ranges of (OS-6) to (OS-11) described in paragraph numbers 0110 to 0112 of JP2011-221494A. It is the same.

Specific examples of the oxime sulfonate compounds represented by the general formula (OS-3) to the general formula (OS-5) include compounds described in paragraph numbers 0114 to 0120 of JP2011-221494A. However, the present invention is not limited to these.

In the photosensitive resin composition of the present invention, (B) the photoacid generator is based on 100 parts by mass of all resin components (preferably a solid content, more preferably a total of copolymers) in the photosensitive resin composition. 0.1 to 10 parts by mass is preferably used, and 0.5 to 10 parts by mass is more preferably used. Two or more kinds can be used in combination.

<(C) Alicyclic epoxy compound having a molecular weight of less than 1000>
The photosensitive resin composition of the present invention is characterized by containing an alicyclic epoxy compound having a molecular weight of less than 1000 (hereinafter sometimes simply referred to as “alicyclic epoxy compound”) as a crosslinking agent.
The alicyclic epoxy compound preferably has 1 to 5 alicyclic epoxy groups, more preferably 1 to 3, more preferably 1 or 2.
The alicyclic epoxy group possessed by the alicyclic epoxy compound used in the present invention is preferably an alicyclic epoxy group represented by the following.

The alicyclic epoxy compound is preferably represented by the following formula (1).
Formula (1)

(In the formula (1), n represents an integer of 1 to 4. R ¹ represents an organic group having 1 to 30 carbon atoms.)

R ¹ represents an organic group having 1 to 30 carbon atoms, may be branched or have an unsaturated bond, and may have an aliphatic or aromatic ring structure. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. Moreover, you may have a substituent and substituents may mutually form a bond. R ¹ is an n-valent linking group.

The number of carbon atoms of the organic group represented by R ¹ is preferably 1 to 15, more preferably 1 to 8, and still more preferably 1 to 6. The organic group is at least a hydrocarbon group, a hydrocarbon group, and —O—, —CO—, —S—, and —NR— (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms). A group consisting of one combination is preferred, and a hydrocarbon group or a group consisting of a hydrocarbon group and —O— and / or —CO— is more preferred. The hydrocarbon group is preferably a linear or branched group, and more preferably a linear group. The hydrocarbon group preferably has 1 to 4 carbon atoms. Two or more hydrocarbon groups may be contained in one organic group.

N represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 or 2.

As a preferable aspect of an alicyclic epoxy compound, the compound represented by following formula (2) is illustrated.
Formula (2)

(In the formula (2), R ² represents an organic group having 1 to 15 carbon atoms.)
R ² represents an organic group having 1 to 15 carbon atoms, may be branched or have an unsaturated bond, and may have an aliphatic ring or an aromatic ring structure. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. Moreover, you may have a substituent and substituents may mutually form a bond. R ² is a divalent linking group.

The organic group of R ² preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. The organic group is at least a hydrocarbon group, a hydrocarbon group, and —O—, —CO—, —S—, and —NR— (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms). A group consisting of one combination is preferred, and a hydrocarbon group or a group consisting of a hydrocarbon group and —O— and / or —CO— is more preferred. The hydrocarbon group is preferably a linear or branched group, and more preferably a linear group. The hydrocarbon group preferably has 1 to 4 carbon atoms. Two or more hydrocarbon groups may be contained in one organic group. The hydrocarbon group is preferably an alkylene group.

As a preferable aspect of an alicyclic epoxy compound, the compound represented by following formula (3) is also illustrated.
Formula (3)

(In the formula (3), R ³ represents an organic group having 1 to 15 carbon atoms.)
R ³ represents an organic group having 1 to 15 carbon atoms, may be branched or have an unsaturated bond, and may have an aliphatic or aromatic ring structure. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. Moreover, you may have a substituent and substituents may mutually form a bond. R ³ is a divalent linking group.

The number of carbon atoms in the organic group of R ³ is preferably 1-8, and more preferably 1-6. The organic group is at least a hydrocarbon group, a hydrocarbon group, and —O—, —CO—, —S—, and —NR— (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms). A group consisting of one combination is preferred, and a hydrocarbon group or a group consisting of a hydrocarbon group and —O— and / or —CO— is more preferred. The hydrocarbon group is preferably a linear or branched group, and more preferably a linear group. The hydrocarbon group preferably has 1 to 4 carbon atoms. Two or more hydrocarbon groups may be contained in one organic group. The hydrocarbon group is preferably an alkylene group.

Specific examples of the above formulas (1) to (3) include the following compounds, but the present invention is not particularly limited thereto.

The alicyclic epoxy compound is preferably represented by the following formula (X-1).
Formula (X-1)

(In the formula (X-1), R ⁴ represents an organic group having 1 to 27 carbon atoms, R ⁵ represents a substituent having 1 to 27 carbon atoms, except for one alicyclic epoxy group. The number is 3-30.)

R ⁴ represents an organic group having 1 to 27 carbon atoms, may be branched or have an unsaturated bond, and may have an aliphatic or aromatic ring structure. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. Moreover, you may have a substituent and substituents may mutually form a bond.

The number of carbon atoms in the organic group represented by R ⁴ is preferably 1 to 15, more preferably 1 to 8, and further preferably 1 to 6. The organic group is at least a hydrocarbon group, a hydrocarbon group, and —O—, —CO—, —S—, and —NR— (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms). A group consisting of one combination is preferred, and a hydrocarbon group or a group consisting of a hydrocarbon group and —O— and / or —CO— is more preferred. The hydrocarbon group is preferably a linear or branched group, and more preferably a linear group. The hydrocarbon group preferably has 1 to 4 carbon atoms. Two or more hydrocarbon groups may be contained in one organic group.

Each R ⁵ represents a substituent having 1 to 27 carbon atoms, and may be independently branched, have an unsaturated bond, or have an aliphatic ring or aromatic ring structure. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. Furthermore, they are at least one substituent selected from an epoxy group, an oxetanyl group, an ethylenically unsaturated group, an alkoxysilane group, an isocyanate group, a blocked isocyanate group, a thiol group, a carboxyl group, a hydroxyl group, and a succinic anhydride group. May be substituted.
Two R ^{5 s in} formula (X-1) may be the same or different and are preferably the same.

The carbon number of the substituent of R ⁵ is preferably 1 to 15, more preferably 1 to 8, and further preferably 1 to 6. The substituent is at least one of an epoxy group, a hydroxyl group, a hydrocarbon group, —O—, —CO—, —S—, and —NR— (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms). A group consisting of two combinations is preferred, from a group consisting of a hydroxyl group, a hydrocarbon group, a combination of —O— and / or —CO—, and a combination of an epoxy group, a hydrocarbon group and —O— and / or —CO—. Is more preferred. The epoxy group is preferably an alicyclic epoxy group. Further, the hydrocarbon group is preferably a linear or branched group, and more preferably a linear group. The hydrocarbon group preferably has 1 to 4 carbon atoms. Two or more hydrocarbon groups may be contained in one organic group.

In the formula (X-1), the number of carbon atoms excluding one alicyclic epoxy group, that is, in the six-membered ring containing R ⁴ , 2 R ⁵ , and 3 nitrogen atoms in the formula (X-1) The total number of carbon atoms of the three carbon atoms is preferably 3 to 30, more preferably 5 to 25, and even more preferably 5 to 20.

A preferred embodiment of the alicyclic epoxy compound is exemplified by a compound represented by the following formula (X-2).
Formula (X-2)

(In the formula (X-2), R ⁴ represents an organic group having 1 to 27 carbon atoms, and R ⁵ represents a substituent having 1 to 27 carbon atoms, except for one alicyclic epoxy group. (The number of carbon atoms is 3 to 30.)

R ⁴ has the same meaning as R ⁴ in formula (X-1), and the preferred range is also the same.
R ⁵ has the same meaning as R ⁵ in formula (X-1), and the preferred range is also the same.
Two R ^{4 s in} formula (X-2) may be the same or different and are preferably the same.

In the formula (X-2), the number of carbon atoms excluding one alicyclic epoxy group, that is, in the six-membered ring containing two R ⁴ , R ⁵ , and three nitrogen atoms in the formula (X-2) The total number of carbon atoms of the three carbon atoms is preferably 3 to 30, more preferably 5 to 25, and even more preferably 5 to 20.

As a preferred embodiment of the alicyclic epoxy compound, a compound represented by the following formula (X-3) is also exemplified.
Formula (X-3)

(In formula (X-3), each R ⁴ represents an organic group having 1 to 27 carbon atoms. However, the number of carbon atoms excluding one alicyclic epoxy group is 3 to 30.)

R ⁴ has the same meaning as R ⁴ in formula (X-1), and the preferred range is also the same.
Three R ^{4 s in} formula (X-3) may be the same or different and are preferably the same.

In formula (X-3), the number of carbon atoms excluding one alicyclic epoxy group, that is, in formula (X-3), three R ^{4 s} and three carbons in a six-membered ring containing three nitrogen atoms The total number of carbon atoms is preferably from 3 to 30, more preferably from 5 to 25, and even more preferably from 5 to 20.

Specific examples of the above formulas (X-1) to (X-3) include the following compounds, but the present invention is not particularly limited thereto.

The production method of the alicyclic epoxy compound used in the present invention is not limited. For example, Maruzen KK Publishing, 4th Edition Experimental Chemistry Course 20 Organic Synthesis II, 213-, 1992, Ed. by Alfred Hasfner, The chemistry of heterocyclic compounds-Small Ring Heterocycles part3 oxiranes, John & Wiley and Sons, An Interscience Publication, New York, 1985, Yoshimura, adhesive, Vol. 29 No. 12, 32,1985, Yoshimura, adhesive, Vol. 30, No. 5 42, 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, JP-A-1-100388, Japanese Patent No. 2906245, Japanese Patent No. 2926262, and the like.

The molecular weight of the alicyclic epoxy compound used in the present invention is less than 1000, and preferably less than 500. By setting it as such a range, it exists in the tendency for the effect of this invention to be exhibited more effectively. The lower limit is not particularly defined, but is usually 100 or more.

The addition amount of the alicyclic epoxy compound in the photosensitive resin composition of the present invention is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. The amount is more preferably 5 to 8 parts by mass, and further preferably 1.0 to 5 parts by mass. A plurality of alicyclic epoxy compounds may be used in combination, and in that case, all the alicyclic epoxy compounds are added together to calculate the content.

<(D) Solvent>
The photosensitive resin composition of the present invention contains (D) 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 further optional components described below are dissolved in the solvent (D).
As the solvent (D) used in the photosensitive resin composition of the present invention, known solvents can be used, such as 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 Examples include monoalkyl ether acetates, esters, ketones, amides, lactones and the like. In addition, specific examples of the (D) solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraph numbers 0174 to 0178 of JP2011-221494A, and the contents thereof are described in the present specification. Embedded in the book.

In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added. These solvents can be used alone or in combination of two or more. The solvent that can be used in the present invention is a single type or a combination of two types, more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates. And diethylene glycol dialkyl ethers or esters and butylene glycol alkyl ether acetates are more preferably used in combination.

Component D is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. 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.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be.

The content of the solvent (D) in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass, preferably 60 to 90 parts by mass, per 100 parts by mass of the total resin components in the photosensitive resin composition. More preferably it is.

<Other ingredients>
In addition to the above-mentioned components, other crosslinking agents, alkoxysilane compounds, sensitizers, basic compounds, surfactants and antioxidants are preferably added to the photosensitive resin composition of the present invention as necessary. Can do. Furthermore, the photosensitive resin composition of the present invention includes an acid proliferation agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. Known additives such as can be added.

Other crosslinking agent It is preferable that the photosensitive resin composition of this invention contains other crosslinking agents other than an alicyclic epoxy compound as needed. By adding a crosslinking agent other than the alicyclic epoxy compound, the 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 a crosslinking reaction is caused by heat (excluding the polymer component (A) above). For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, a blocked isocyanate compound, etc. Can be added.
The addition amount of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by mass, and 0.1 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. The amount is more preferably part by mass, and further preferably 0.5 to 20 parts by mass. By adding in this range, a cured film having excellent mechanical strength and solvent resistance can be obtained. A plurality of crosslinking agents may be used in combination. In that case, the content is calculated by adding all the crosslinking agents.

<Compound having two or more epoxy groups or oxetanyl groups in the molecule>
Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like. Can do. Of the aliphatic epoxy resins, chain aliphatic epoxy is preferably used.

These are available as commercial products. Examples thereof include commercially available products described in paragraph number 0189 of JP2011-212494, such as JER157S70, JER157S65, JER828, JER1007K (manufactured by Mitsubishi Chemical Holdings Corporation).
In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation)

The chain aliphatic epoxy that can be used in the present invention has a molecular weight (in the case of a polymer, a weight average molecular weight) of preferably 2000 or less, more preferably 1500 or less, and even more preferably 1000 or less. . As a lower limit, it can be set as 100 or more, for example. In addition, when the weight average molecular weight of a chain aliphatic epoxy compound is not described in a catalog etc., it can estimate by calculation of (epoxy equivalent) x (number of functional groups). Further, the viscosity of the chain aliphatic epoxy at 25 ° C. is preferably 3000 mPa · s or less, more preferably 2000 mPa · s or less, and further preferably 1000 mPa · s or less. The lower limit is not particularly defined, but can be set to 5 mPa · s or more, for example.
The aliphatic epoxy compound used in the present invention is a resin having a linear and / or branched carbon chain and an epoxy group, and in addition to a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a chlorine atom, etc. May be combined. In the present invention, a resin comprising a linear and / or branched carbon chain, a hydrogen atom, and an epoxy group, or a group in which a hydroxyl group is substituted on the resin is particularly preferable. The number of epoxy groups is preferably 1 to 4, and more preferably 2 or 3.
In the present invention, it is also preferable that the cycloaliphatic epoxy compound is not substantially contained. By setting it as such a structure, it exists in the tendency for the effect of this invention to be exhibited more effectively. Here, “substantially not contained” means that it is not added at a level that affects the effects of the present invention, for example, 1% by weight or less of the total solid content.

The chain aliphatic epoxy compound used in the present invention is preferably a resin represented by the following general formula (X-1).
Formula (X-1)

(In general formula (X-1), A is a linear or branched hydrocarbon group, which may have a hydroxyl group as a substituent, and n is an integer of 1 to 4.)
The carbon number of A is preferably 1 to 20, preferably 1 to 15, more preferably 2 to 10, and further preferably 2 to 6. n is an integer of 1 to 4, preferably 2 or 3.

The chain aliphatic epoxy compound used in the present invention is more preferably a resin represented by the following general formula (X-2).
Formula (X-2)

(In the general formula (X-2), B is a linear or branched hydrocarbon group, which may have a hydroxyl group as a substituent, and n is an integer of 1 to 4.)
B preferably has 1 to 18 carbon atoms, more preferably 1 to 13, and more preferably 2 to 8. n is an integer of 1 to 4, preferably 2 or 3.

Examples of the chain aliphatic epoxy that can be preferably used in the present invention include Denacol EX-611 (11,800 mPa · s), EX-612 (11,900 mPa · s), EX-614 (21,200 mPa · s). EX-614B (5,000 mPa · s), EX-622 (11,800 mPa · s), EX-512 (1,300 mPa · s), EX-521 (4,400 mPa · s), EX-411 (800 mPa · s) S), EX-421 (650 mPa · s), EX-313 (150 mPa · s), EX-314 (170 mPa · s), EX-321 (130 mPa · s), EX-211 (20 mPa · s), EX -212 (20 mPa · s), EX-810 (20 mPa · s), EX-811 (20 mPa · s), EX-850 (20 Pa · s), EX-851 (30 mPa · s), EX-821 (40 mPa · s), EX-830 (70 mPa · s), EX-832 (90 mPa · s), EX-841 (110 mPa · s), EX-911 (20 mPa · s), EX-941 (25 mPa · s), EX-920 (20 mPa · s), EX-931 (120 mPa · s), EX-212L (15 mPa · s), EX-214L (15 mPa · s)・ S), EX-321L (800 mPa · s), EX-850L (90 mPa · s), EX-211L (20 mPa · s), EX-946L (50 mPa · s), EX-946L (50 mPa · s), DLC -201 (10 mPa · s), DLC-203 (8 mPa · s), DLC-204 (1,700 mPa · s), DLC-205 15 mPa · s), DLC-206 (20 mPa · s), DLC-301 (60 mPa · s), DLC-402 (150 mPa · s) (manufactured by Nagase Chemtech, the viscosity in parentheses is 25 ° C.), YH- 300 (140 to 160 mPa · s), YH-301 (160 to 220 mPa · s), YH-302 (700 to 1100 mPa · s), YH-315 (700 to 1100 mPa · s), YH-324 (3500 to 5500 mPa · s) s), YH-325 (4000 to 6000 mPa · s) (manufactured by Nippon Steel Chemical Co., Ltd.) and the like.
Among these, it is particularly preferable to contain trimethylolpropane triglycidyl ether or neopentyl glycol diglycidyl ether shown below. Among these, EX-321, EX-321L, EX-211 and EX-211L (manufactured by Nagase Chemtech) fall under this category.

As specific examples of the compound having two or more oxetanyl groups in the molecule, Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX (above, manufactured by Toagosei Co., Ltd.) can be used.

In addition, the compound having an oxetanyl group is preferably used alone or mixed with a compound having an epoxy group.

As other crosslinking agents, alkoxymethyl group-containing crosslinking agents described in paragraphs 0107 to 0108 of JP2012-8223A and compounds having at least one ethylenically unsaturated double bond are also preferably used. The contents of which are incorporated herein by reference. As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated glycoluril is preferable.

In the photosensitive resin composition of the present invention, the content of a compound having 2 or more epoxy groups or oxetanyl groups in the molecule (particularly a chain epoxy compound) is 0.1 to 100 parts by weight with respect to 100 parts by weight of the solid content. The amount is preferably 10 parts by weight, and more preferably 0.5 to 10 parts by weight.

<Block isocyanate compound>
In the photosensitive resin composition of the present invention, a blocked isocyanate compound can also be preferably employed as a crosslinking agent. The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability.
In addition, the blocked isocyanate group in this invention is a group which can produce | generate an isocyanate group with a heat | fever, For example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably. The blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C. to 250 ° C.
Further, the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and is aliphatic, alicyclic or aromatic. Polyisocyanates may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2 2'-diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1 , 4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methylene ditolylene-4,4'-diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate , Isocyanation of hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1,4-xylylene diisocyanate, etc. A compound and a prepolymer type skeleton compound derived from these compounds can be preferably used. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.

Examples of the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.

Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
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 mercaptan compound include alkyl mercaptans and aryl mercaptans.

The blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals, Inc.) ), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above , Manufactured by Asahi Kasei Chemicals Corporation, Death Module B 1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane Co., Ltd.) etc. are preferably used can do.

Alkoxysilane Compound The photosensitive resin composition of the present invention may contain an alkoxysilane compound. When an 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. Can do. As the alkoxysilane compound, a dialkoxysilane compound or a trialkoxysilane compound is preferable, and a trialkoxysilane compound is more preferable. The alkoxy group contained in the alkoxysilane compound preferably has 1 to 5 carbon atoms.
The alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is 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. Preferably, the compound improves the adhesion between the insulating film and the insulating film. Specifically, a known silane coupling agent or the like is also effective.
Examples of silane coupling agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and γ-methacryloxy. Propyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Bis (triethoxysilylpropyl) tetrasulfide. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. Further preferred. These can be used alone or in combination of two or more.

The following compounds can also be preferably employed.

In the above, Ph is a phenyl group.

The alkoxysilane compound in the photosensitive resin composition of this invention is not specifically limited to these, A well-known thing can be used.
The content of the alkoxysilane compound in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, and preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive composition. Is more preferable.

Sensitizer The photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote its decomposition in combination with (B) a photoacid generator. The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.

Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine oleoresin) Di, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, anthraquinone), squaliums (eg, squalium), styryls, base styryls ( For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, 2,3,6,7 -Tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine-11-non).
Among these sensitizers, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.

The addition amount of the sensitizer in the photosensitive resin composition of the present invention is preferably 0 to 1000 parts by mass with respect to 100 parts by mass of the photoacid generator in the photosensitive resin composition. More preferably, it is more preferably 50 to 200 parts by mass.
Two or more kinds can be used in combination.

Basic Compound The photosensitive resin composition of the present invention preferably contains a basic compound.
The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.

Examples of aliphatic amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine. , Dicyclohexylmethylamine, diazabicyclononene, and the like.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.

Examples of the heterocyclic amine 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-oxyquinoline, 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 Such as diazabicyclo [5.3.0] -7-undecene and the like.

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

Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

The basic compounds that can be used in the present invention may be used singly or in combination of two or more. However, it is preferable to use two or more in combination, and it is more preferable to use two in combination. Preferably, two kinds of heterocyclic amines are used in combination.

The content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 3 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition, 0.005 More preferred is 1 part by mass.

Surfactant The photosensitive resin composition of the present invention may contain a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFac (manufactured by DIC Corporation), Florard (Sumitomo 3M) Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone), and the like.
In addition, the surfactant contains the structural unit A and the structural unit B represented by the following general formula (I-1), and is converted to polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A copolymer having a weight average molecular weight (Mw) of 1,000 or more and 10,000 or less can be given as a preferred example.

Formula (I-1)

(In the formula (I-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or C represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is 10 mass% to 80 mass%. A numerical value is represented, q represents a numerical value of 20% by mass or more and 90% by mass or less, r represents an integer of 1 to 18 and s represents an integer of 1 to 10)

L is preferably a branched alkylene group represented by the following general formula (I-2). R ⁴⁰⁵ in the general formula (I-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. A

number

2 or 3 alkyl group is more preferred. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.

Formula (I-2)

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

These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, and 0.001 to 10 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. More preferably, the amount is 0.01 to 3 parts by mass.

Antioxidant The photosensitive resin composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives. Among these, phenol-based antioxidants, amide-based antioxidants, hydrazide-based antioxidants, and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. These may be used individually by 1 type and may mix 2 or more types.
Examples of commercially available phenolic antioxidants include ADK STAB AO-15, ADK STAB AO-18, ADK STAB AO-20, ADK STAB AO-23, ADK STAB AO-30, ADK STAB AO-37, ADK STAB AO-40 and ADK STAB AO. -50, ADK STAB AO-51, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330, ADK STAB AO-412S, ADK STAB AO-503, ADK STAB A-611, ADK STAB A-612, ADK STAB A -613, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB PEP-36Z, ADK STAB HP-1 ADK STAB 2112, ADK STAB 260, ADK STAB 1522, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 13510, ADK STAB 3010, ADK STAB CDA-1, ADK STAB CDA-6, ADK STAB ZS-27, ADK STAB ZS-90 -91 (above, manufactured by ADEKA Corporation), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF, Irganox 1035, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irgafos 168, Irgamod 295 (BAS Co., Ltd.), and the like. Among them, ADK STAB AO-60, ADK STAB AO-80, IRGANOX 1726, IRGANOX 1035, and IRGANOX 1098 can be preferably used.

The content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% by mass. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good.
As additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used in the present invention. You may add to a resin composition.

[Acid multiplication agent]
In the photosensitive resin composition of the present invention, an acid proliferating agent can be used for the purpose of improving sensitivity.
The acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there. In such a compound, since one or more acids increase in one reaction, the reaction proceeds at an accelerated rate as the reaction proceeds. However, the generated acid itself induces self-decomposition, and is generated here. The acid strength is preferably 3 or less as an acid dissociation constant, pKa, and particularly preferably 2 or less.
Specific examples of the acid proliferating agent include paragraph numbers 0203 to 0223 of JP-A-10-1508, paragraphs 0016 to 0055 of JP-A-10-282642, and page 39 of JP-T 9-512498. The compounds described on line 12 to page 47, line 2 can be mentioned, the contents of which are incorporated herein.
Examples of the acid proliferating agent that can be used in the present invention include pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid, which are decomposed by an acid generated from the acid generator. Examples include compounds that generate 3 or less acids.
In particular

Etc.
The content of the acid proliferating agent in the photosensitive composition is 10 to 1,000 parts by mass with respect to 100 parts by mass of the photoacid generator, from the viewpoint of dissolution contrast between the exposed and unexposed parts. It is preferably 20 to 500 parts by mass.

[Development accelerator]
The photosensitive resin composition of the present invention can contain a development accelerator.
As the development accelerator, the description in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.

A development accelerator may be used individually by 1 type, and can also use 2 or more types together.
The addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably 0 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive composition, from the viewpoint of sensitivity and residual film ratio. 1 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is most preferable.
In addition, as other additives, thermal radical generators described in paragraphs 0120 to 0121 of JP2012-8223A, nitrogen-containing compounds and thermal acid generators described in WO2011-133604A1, can be used. Is incorporated herein by reference.

<Method for preparing photosensitive resin composition>
Each component is mixed in a predetermined ratio and by any method, stirred and dissolved to prepare a photosensitive resin composition. For example, a resin composition can be prepared by preparing a solution in which components are dissolved in a solvent in advance and then mixing them in a predetermined ratio. The composition solution prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.

[Method for producing cured film]
Next, the manufacturing method of the cured film of this invention is demonstrated.
The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
(1) The process of apply | coating the photosensitive resin composition of this invention on a board | substrate;
(2) A step of removing the solvent from the applied photosensitive resin composition;
(3) The process of exposing the photosensitive resin composition from which the solvent was removed with actinic rays;
(4) A step of developing the exposed photosensitive resin composition with an aqueous developer;
(5) A post-baking step of thermosetting the developed photosensitive resin composition.
Each step will be described below in order.

In the application step (1), the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent. Before applying the photosensitive resin resin composition to the substrate, it is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning, and it is more preferable to treat the substrate surface with hexamethyldisilazane after substrate cleaning. By performing this treatment, the adhesiveness of the photosensitive resin composition to the substrate tends to be improved. The method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
Examples of the substrate include inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
The resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide compound These substrates which may be mentioned are less if used while the above embodiment, normally, depending on the form of the final product, for example, multi-layered structure such as a TFT element is formed.
The coating method on the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like can be used. Furthermore, it is also possible to apply a so-called pre-wet method as described in JP-A-2009-145395.
The wet film thickness when applied is not particularly limited, and can be applied with a film thickness according to the application, but it is usually used in the range of 0.5 to 10 μm.

(2) In the solvent removal step (2), the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are in the above ranges, the pattern adhesiveness is better 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 through a mask having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to produce a carboxyl group or a phenolic hydroxyl group.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, etc. can be used, and g-line (436 nm), i-line (365 nm), Actinic rays having a wavelength of 300 nm to 450 nm, such as 405 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as “PEB”) can be performed. PEB can promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
However, since the acid-decomposable group in the present invention has low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate a carboxyl group or a phenolic hydroxyl group, PEB is not necessarily performed. A positive image can also be formed by development.

In the developing step (4), a polymer having a liberated carboxyl group or phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
The developer used in the development step preferably contains a basic compound. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. 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 alkaline aqueous solution can also be used as a developer.
Preferred examples of the developer include 0.4% aqueous solution, 0.5% aqueous solution, 0.7% aqueous solution and 2.38% aqueous solution of tetraethylammonium hydroxide.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be either a liquid piling method or a dipping method. After development, washing with running water is usually performed for 30 to 300 seconds to form a desired pattern.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.

In the post-baking step of (5), by heating the obtained positive image, the acid-decomposable group is thermally decomposed to generate a carboxyl group or a phenolic hydroxyl group, and crosslinked with an epoxy group, a crosslinking agent, etc. A cured film can be formed. This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, 30 to 120 minutes for the oven. It is preferable to By proceeding with such a crosslinking reaction, it is possible to form a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like. In addition, when the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
Prior to post-baking, post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process). When middle baking is performed, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Moreover, middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
If the degree of cross-linking is expected to be insufficient due to the characteristics of each material to be selected, the entire surface is re-exposed (post-exposure) with actinic rays to the substrate on which the pattern has been formed prior to post-baking, and then post-baked. An acid is generated from the photoacid generator present in the unexposed portion, and can function as a catalyst for accelerating the cross-linking process, thereby promoting the curing reaction of the film. The preferred exposure amount in the case of including a post-exposure step, preferably 100 ~ 3,000mJ / cm ^2, particularly preferably 100 ~ 500mJ / cm ^2. On the other hand, in cases other than the above, it is preferable not to perform the re-exposure step. In addition to improving productivity, stability at high temperatures and high humidity can be increased.

Furthermore, the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist. In the case where a cured film obtained by thermal curing in a post-baking process is used as a dry etching resist, dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.

[Curing film]
The cured film of the present invention is a cured film 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. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.
With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film physical properties, it is useful for applications of organic EL display devices and liquid crystal display devices.

[Liquid Crystal Display]
The liquid crystal display device of the present invention comprises the cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal displays having various structures. An apparatus can be mentioned.
For example, specific examples of 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, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
Further, the liquid crystal driving methods that can be adopted by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Virtual Alignment) method, IPS (In-Place-Switching) method, FFS (Frings Field Switching) method, OCB (Optical). Compensated Bend) method and the like.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. For example, the organic insulating film (115) of JP-A-2005-284291, -346054 can be used as the organic insulating film (212).
Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.
FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix 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, and the liquid crystal panel includes all pixels disposed between two

glass substrates

14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and can be used as the second interphase insulating film (48) of JP 2011-145686 A or the interphase insulating film (520) of JP 2009-258758 A.

[Organic EL display device]
The organic EL display device of the present invention comprises the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known structures having various structures. Examples thereof include an organic EL display device and a liquid crystal display device.
For example, specific examples of 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, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
FIG. 2 is a conceptual diagram of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 2, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.

Since the photosensitive resin composition of the present invention is excellent in curability and cured film characteristics, a resist pattern formed using the photosensitive resin composition of the present invention as a structural member of a MEMS device can be used as a partition wall or mechanically driven. Used as part of the part. Examples of such MEMS devices include parts such as SAW filters, BAW filters, gyro sensors, display micro shutters, image sensors, electronic paper, inkjet heads, biochips, sealants, and the like. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP-A-2011-107476, JP-A-2010- The partition wall (12) and the planarization film (102) described in FIG. 4 (a) of Japanese Patent No. 9793, the bank layer (221) and the third interlayer insulating film (216b) described in FIG. 10 of Japanese Patent Application Laid-Open No. 2010-27591. ), The second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4A of JP-A-2009-128577, and the flatness described in FIG. 3 of JP-A-2010-182638. It can also be used to form a chemical film (12) and a pixel isolation insulating film (14).

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

In the following synthesis examples, the following symbols represent the following compounds, respectively.
MATHF: 2-tetrahydrofuranyl methacrylate (synthetic product)
MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
MACHOE: 1- (cyclohexyloxy) ethyl methacrylate MATHP: tetrahydro-2H-pyran-2-yl methacrylate GMA: glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries)
MMA: Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
St: Styrene (Wako Pure Chemical Industries, Ltd.)
DCPM: Dicyclopentanyl methacrylate HEMA: Hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.)
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
PGMEA: Methoxypropyl acetate (manufactured by Showa Denko)

<Synthesis of MATHF>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated sodium bicarbonate (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, insolubles were filtered and concentrated under reduced pressure at 40 ° C. or lower to give a residual yellow oily product. Distillation under reduced pressure afforded 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) as a colorless oily substance (yield 80%) at a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg.

<Synthesis Example of Polymer P-1>
PGMEA (89 g) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. MACHOE (amount to be 40 mol% in all monomer components), GMA (amount to be 30 mol% in all monomer components), MAA (amount to be 10 mol% in all monomer components) MMA (amount to be 20 mol% in all monomer components) and V-65 (corresponding to 4 mol% with respect to 100 mol% in total of all monomer components) were dissolved and added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred for 2 hours to complete the reaction. Thereby, a polymer P-1 was obtained. The ratio of the total amount of PGMEA and other components was 60:40. That is, a polymer solution having a solid content concentration of 40% was prepared.
Monomers and the like were changed as shown in the following table, and other polymers were synthesized. In the following table, all solvents used PGMEA and the solid content concentration was 40 parts by mass.

<Adjustment of photosensitive resin composition>
Polymer components, photoacid generators, alicyclic epoxy compounds, other crosslinking agents, basic compounds, alkoxysilane compounds, sensitizers, surfactants, and others so that the solid content ratios shown in the table below are obtained The above components were dissolved and mixed in PGMEA until the solid content concentration became 25%, and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 μm to obtain photosensitive resin compositions of various examples and comparative examples. In addition, the addition amount in a table | surface is a mass part.

Details of the abbreviations indicating each compound used in Examples and Comparative Examples are as follows.

(Polymer component)
P-17: Joncryl 680 (manufactured by BASF)
P-18: Joncryl 67 (BASF)
P-19: ARUFON UC-3910 (manufactured by Toagosei Co., Ltd.)
P-23: SMA-3000P (Cray Valley USA, manufactured by LLC)

(Photoacid generator)
B-1: DTS-105, (triarylsulfonium salt) (manufactured by Midori Chemical Co., Ltd.)
B-2: CGI1397 (manufactured by BASF Japan Ltd.)

B-3: PAI101 (Midori Chemical Co., Ltd.)

B-4: The following compound

B-5: The following compound (synthesized according to the method described in paragraph 0108 of JP-T-2002-528451)

[Synthesis of B-4]
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, reacted at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added and separated, and the organic layer was concentrated, and the crystals were diluted with diisopropyl ether (10 mL). The slurry was reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and a 50 mass% aqueous hydroxylamine solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature. Reacted for hours. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, reslurried with methanol (20 mL), filtered and dried to obtain B-4 (2.3 g).
The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-4 has δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H) , 2.4 (s, 3H), 1.7 (d, 3H).

(Alicyclic epoxy compound)
F-5: Compound 1 below (Daicel Chemical Industries, Celoxide 2021P)

F-6: Compound 2 below (Synthetic product)

F-7: Compound 3 below (Daicel Chemical Industries, Celoxide 2000)

F-11; Compound 4 below (compound shown below)

F-12; the following compound 5 (compound shown below)

F-13; Compound 6 (compound shown below)

(Synthesis of F-6)
It was synthesized according to the method described in Maruzen KK Publishing, 4th edition Experimental Chemistry Course 20 Organic Synthesis II, 213-.

(Synthesis of F-11 to F-13)
The compound was synthesized according to the method described in JP2012-92062A.

(Crosslinking agent other than alicyclic epoxy compound)
F-1: JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation) (bisphenol type epoxy compound)
F-2: Duranate 17B-60P (Asahi Kasei Chemicals Corporation) (isocyanate compound)
F-3: Denacol EX-321L (manufactured by Nagase ChemteX Corporation) (glycidyl ether epoxy compound)
F-4: JER828 (manufactured by Mitsubishi Chemical Holdings Corporation) (bisphenol type epoxy compound)
F-8: Denacol EX-211L (manufactured by Nagase ChemteX Corporation) (glycidyl ether epoxy compound)
F-9: OXT-221 (manufactured by Toagosei Co., Ltd.) (bifunctional oxetane compound)
F-10: (JER1007K (manufactured by Mitsubishi Chemical Holdings Corporation) (bisphenol A type epoxy compound)
F-11: Takenate B-870N (Mitsui Chemicals)

(Alkoxysilane compound)
G-1: γ-glycidoxypropyltrialkoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
G-2: Bis (triethoxysilylpropyl) tetrasulfide (KBE-846, manufactured by Shin-Etsu Chemical Co., Ltd.)
G-3: KBM-3103 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Sensitizer)
E-1: Dibutoxyanthracene having the following structure (manufactured by Kawasaki Kasei Co., Ltd.)

(Basic compound)
S-4: Diazabicyclononene S-5: 2,4,5-triphenylimidazole S-6: N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea

(Surfactant)
W-1: Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by DIC)

(Antioxidant)
J-1: Irganox 1098 (BASF)
J-2: Irganox 1035 (manufactured by BASF)
J-3: ADK STAB AO-60 (manufactured by ADEKA)

<Evaluation of sensitivity>
Each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)) and then pre-baked on a hot plate at 95 ° C. for 140 seconds to volatilize the solvent. A photosensitive resin composition layer having a thickness of 4.0 μm was formed.
Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using MPA 5500CF (extra high pressure mercury lamp) manufactured by Canon Inc. The exposed photosensitive resin composition layer was developed with an alkali developer (0.4 mass% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
The optimum i-line exposure (Eopt) when resolving a 5 μm hole by these operations was taken as the sensitivity. C and above are practical levels.
A: 20mJ / cm ² less B: 20mJ / cm ² or more, 40 mJ / cm ² less than C: 40mJ / cm ² or more, 80 mJ / cm ² less than D: 80mJ / cm ² or more, 160 mJ / cm ² less than E: 160 mJ / cm ² or more

<Evaluation of heat-resistant transparency>
A solution of each photosensitive resin composition was spin-coated on a glass substrate (Eagle 2000 Corning), and then pre-baked on a hot plate at 90 ° C. for 120 seconds to form a coating film having a thickness of 3 μm. The resulting coating film was developed with a 0.4% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds, rinsed with ultrapure water for 45 seconds, and then exposed to PLA-501F manufactured by Canon Inc. Machine (extra-high pressure mercury lamp) so that the integrated dose is 300 mJ / cm ² (illuminance: 20 mW / cm ² ), and then this substrate is heated in an oven at 230 ° C. for 1 hour to form a cured film. Obtained. The obtained cured film was further heated in an oven at 230 ° C. for 2 hours, and the light transmittance was in the range of 400 to 800 nm using a spectrophotometer “150-20 type double beam (manufactured by Hitachi, Ltd.)”. Measured at a wavelength of.
The evaluation criteria are as follows, and B or higher is a practical level. In addition, the value of the minimum light transmittance is converted into a value per 2 μm of film thickness after heating at 230 ° C. for 2 hours.
A: 92% or more B: 87% or more and less than 92% C: 85% or more and less than 87% D: 82% or more and less than 85% E: Less than 82%

<Evaluation of contact hole (CH) uniformity>
Each photosensitive resin composition was spin-coated on a 550 mm × 650 mm glass substrate, pre-baked on a hot plate (95 ° C. × 140 seconds), and then MPA 5500CF (extra-high pressure mercury lamp) manufactured by Canon Inc. was used. It exposed through the predetermined mask. The exposure amount at this time was changed as follows based on the result of sensitivity evaluation.
Sensitivity A: 15 mJ / cm ²
Sensitivity B ... 30mJ / cm ²
Sensitivity C ... 60mJ / cm ²
Sensitivity D ... 120mJ / cm ²
Sensitivity E ... 200mJ / cm ²
Then, it developed with alkaline aqueous solution and formed the contact hole (CH) pattern. Prepare 10 such substrates with CH pattern, 50 points for each substrate, and how much difference there is with respect to the set CH size of 10 μm with optical measuring instrument ZYGO New View 7200 (manufactured by ZYGO corp.) The size was measured. The evaluation criteria are as follows, and D or higher is a practical level.
A: Average CH size difference is 0.2 μm or less B: Average CH size difference is greater than 0.2 μm and 0.4 μm or less C: Average CH size difference is greater than 0.4 μm and 0.6 μm or less D: Average CH size difference greater than 0.6 μm and 0.8 μm or less E: Average CH size difference greater than 0.8 μm and 1.0 μm or less F: Average CH size difference greater than 1.0 μm and 1.2 μm or less G: Average CH size difference of greater than 1.2 μm and 1.4 μm or less H: Average CH size difference of greater than 1.4 μm

As is clear from the above results, the photosensitive resin composition of the present invention was excellent in sensitivity, excellent in heat-resistant transparency and CH uniformity after development, and both were above the practical level. In particular, when F-5 containing an ester bond is used as an alicyclic epoxy compound, it is possible to achieve extremely excellent CH uniformity while maintaining a certain level of sensitivity and transparency after development processing. High significance. In contrast, the photosensitive resin composition of the comparative example had a CH uniformity outside the practical level.

<Example 52>
Example 52 was performed in the same manner as in Example 1, except that the exposure machine was changed from MPA 5500CF manufactured by Canon Inc. to FX-803M (gh-Line stepper) manufactured by Nikon Corporation. The evaluation of sensitivity was the same level as in Example 1.

<Example 53>
Example 53 was performed in the same manner as in Example 1, except that the exposure machine was changed from MPA 5500CF manufactured by Canon Inc. to a 355 nm laser exposure machine, and 355 nm laser exposure was performed. Here, as the 355 nm laser exposure machine, “AEGIS” manufactured by Buoy Technology Co., Ltd. was used (wavelength 355 nm, pulse width 6 nsec), and the exposure amount was measured using “PE10B-V2” manufactured by OPHIR.
The evaluation of sensitivity was the same level as in Example 1.

<Example 54>
In the active matrix liquid crystal display device described in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 54 was obtained. That is, using the photosensitive resin composition of Example 1, a cured film 17 was formed as an interlayer insulating film.
That is, as a pretreatment for improving the wettability of the substrate and the interlayer insulating film 17 in paragraph 0058 of Japanese Patent No. 3321003, the substrate is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and then the photosensitive film of Example 1 is used. After spin-coating the photosensitive resin composition, it was pre-baked on a hot plate at 90 ° C. for 2 minutes to volatilize the solvent, thereby forming a photosensitive resin composition layer having a thickness of 3 μm. Next, the obtained photosensitive resin composition layer was subjected to 40 mJ / cm ² (illuminance: 20 mW / cm ² ) through a hole pattern mask of 10 μmφ using Canon Inc. MPA 5500CF (high pressure mercury lamp). i-line). The exposed photosensitive resin composition layer was developed with an alkali developer (0.4% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds. Subsequently, the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm ² (illuminance: 20 mW / cm ² , i-line), and then the substrate was heated in an oven at 230 ° C. for 30 minutes. Thus, a cured film was obtained.
The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development, and baking.

When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.

<Example 55>
A liquid crystal display device of Example 55 was obtained in the same manner as in Example 54 except that the hexamethyldisilazane (HMDS) treatment was omitted. The obtained liquid crystal display device was a highly reliable liquid crystal display device having good display characteristics without chipping or peeling of the pattern of the cured film.

<Example 56>
A liquid crystal display device of Example 56 was obtained in the same manner as in Example 54 except that the alkaline developer was changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 2.38% tetramethylammonium hydroxide aqueous solution. It was. The obtained liquid crystal display device was a highly reliable liquid crystal display device having good display characteristics without chipping or peeling of the pattern of the cured film.

<Example 57>
A liquid crystal display device of Example 57 was obtained in the same manner as in Example 54 except that the alkaline developer was changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 0.04% KOH aqueous solution. The obtained liquid crystal display device was a highly reliable liquid crystal display device having good display characteristics without chipping or peeling of the pattern of the cured film.

<Example 58>
A liquid crystal display device of Example 58 was obtained in the same manner as in Example 54 except that the step of full exposure after development and rinsing was omitted. The obtained liquid crystal display device showed good display characteristics and was a highly reliable liquid crystal display device.

<Example 59>
The liquid crystal of Example 59 is the same as Example 54 except that a step of heating on a hot plate at 100 ° C. for 3 minutes is added between the entire surface exposure step and the 230 ° C./30 minute heating step in the oven. A display device was obtained. The obtained liquid crystal display device showed good display characteristics and was a highly reliable liquid crystal display device.

<Example 60>
A liquid crystal display device of Example 60 was obtained in the same manner as in Example 54 except that a step of heating on a hot plate at 100 ° C. for 3 minutes was added between the development / rinsing process and the entire surface exposure process. The obtained liquid crystal display device showed good display characteristics and was a highly reliable liquid crystal display device.

<Example 61>
A liquid crystal display device similar to that of Example 54 was obtained by changing only the following coating process. That is, after the photosensitive resin composition of Example 1 was applied by a slit coating method, the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to form a photosensitive resin composition layer having a thickness of 3.0 μm. Formed. The obtained coating film was flat and had a good surface shape without unevenness. Further, the performance as a liquid crystal display device was as good as in Example 54.

<Example 62>
Example 54 was performed in the same manner as in Example 1 except that the exposure machine was changed from MPA 5500CF manufactured by Canon Inc. to a UV-LED light source exposure machine. Further, the performance as a liquid crystal display device was as good as in Example 54.

<Example 63>
A liquid crystal display device similar to that of Example 54 was obtained by changing only the following coating process. That is, after the photosensitive resin composition of Example 1 was applied by a slit and spin method, the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to form a photosensitive resin composition layer having a thickness of 3.0 μm. Formed. The obtained coating film was flat and had a good surface shape without unevenness. Further, the performance as a liquid crystal display device was as good as in Example 54.

<Example 64>
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is used to connect the TFT 1 with an organic EL element formed between TFTs 1 or in a later process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarization film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 16 on a substrate, pre-baking (90 ° C./120 seconds) on a hot plate, and then applying high pressure from above the mask. After irradiating 45 mJ / cm ² (illuminance 20 mW / cm ² ) with i-line (365 nm) using a mercury lamp, a pattern is formed by developing with an alkaline aqueous solution (0.4% TMAH aqueous solution). Using this, the entire surface was exposed so that the integrated irradiation amount was 300 mJ / cm ² (illuminance: 20 mW / cm ² , i-line), and heat treatment was performed at 230 ° C./30 minutes.
The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.

Next, a bottom emission type organic EL element was formed on the obtained flattening film 4. First, a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film 8, the photosensitive resin composition of Example 16 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.

Further, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al was formed on the entire surface above the substrate. The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.

As described above, an active matrix type organic EL display device in which each organic EL element is connected to the TFT 1 for driving it was obtained. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

1: TFT (Thin Film Transistor)
2: Wiring 3: Insulating film 4: Flattened film 5: First electrode 6: Glass substrate 7: Contact hole 8: Insulating film 10: Liquid crystal display device 12: Backlight unit 14, 15: Glass substrate 16: TFT
17: Cured film 18: Contact hole 19: ITO transparent electrode 20: Liquid crystal 22: Color filter

Claims

(A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2):
(1) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a structural unit having an epoxy group,
(2) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit having an epoxy group,
(B) Photoacid generator (C) A photosensitive resin composition containing an alicyclic epoxy compound having a molecular weight of less than 1000, and (D) a solvent.
The photosensitive resin composition according to claim 1, wherein the (C) alicyclic epoxy compound is represented by the following formula (1).
Formula (1)

(In the formula (1), n represents an integer of 1 to 4. R 1 represents an organic group having 1 to 30 carbon atoms.)
The photosensitive resin composition according to claim 2, wherein R 1 represents an organic group having 1 to 15 carbon atoms.
The photosensitive resin composition according to claim 1 or 2, wherein the (C) alicyclic epoxy compound is represented by the following formula (2).
Formula (2)

(In the formula (2), R 2 represents an organic group having 1 to 15 carbon atoms.)
The photosensitive resin composition according to claim 1 or 2, wherein the (C) alicyclic epoxy compound is represented by the following formula (3).
Formula (3)

(In the formula (3), R 3 represents an organic group having 1 to 15 carbon atoms.)
6. The photosensitive resin composition according to claim 1, further comprising a crosslinking agent other than the (C) alicyclic epoxy compound.
The photosensitive resin composition according to claim 1 or 2, wherein the (C) alicyclic epoxy compound is represented by the following formula (X-1).
Formula (X-1)

(In the formula (X-1), R 4 represents an organic group having 1 to 27 carbon atoms. R 5 represents a substituent having 1 to 27 carbon atoms, respectively, except for one alicyclic epoxy group. (The number of carbon atoms is 3 to 30.)
The photosensitive resin composition according to claim 1, wherein the (C) alicyclic epoxy compound is represented by the following formula (X-2).
Formula (X-1)

(In the formula (X-2), R 4 represents an organic group having 1 to 27 carbon atoms, and R 5 represents a substituent having 1 to 27 carbon atoms, except for one alicyclic epoxy group. (The number of carbon atoms is 3 to 30.)
The photosensitive resin composition according to any one of claims 1, 2, 7, and 8, wherein the (C) alicyclic epoxy compound is represented by the following formula (X-3).
Formula (X-1)

(In formula (X-3), each R 4 represents an organic group having 1 to 27 carbon atoms. However, the number of carbon atoms excluding one alicyclic epoxy group is 3 to 30.)
10. The photosensitive resin composition according to claim 1, wherein the acid-decomposable group is a group having a structure protected in the form of an acetal.
The photosensitive resin composition according to any one of claims 1 to 10, wherein any one of the polymer components (A) is a polymer further containing an acid group.
The photosensitive resin composition according to any one of claims 1 to 11, wherein the photoacid generator (B) is an oxime sulfonate compound.
(1) a step of applying the photosensitive resin composition according to any one of claims 1 to 12 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 with actinic radiation,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) A method for producing a cured film, comprising a post-baking step of thermosetting the developed photosensitive resin composition.
The method for forming a cured film according to claim 13, comprising a step of exposing the entire surface of the developed photosensitive resin composition after the developing step and before the post-baking step.
A cured film formed by the method according to claim 13 or 14.
The cured film according to claim 15, which is an interlayer insulating film.
An organic EL display device or a liquid crystal display device having the cured film according to claim 15 or 16.