TW201415161A - Photo-sensitive resin composition, method for manufacturing cured film using the same, cured film, liquid crystal display device, and organic EL display device - Google Patents

Abstract

A photosensitive resin composition which maintains high sensitivity and has excellent chemical resistance is provided. The photosensitive resin composition contains: a polymer component (A) containing a polymer which satisfies at least one of the following (1) and (2): (1) a polymer including (al) a structural unit having a group in which an acid group is protected by an acid-decomposable group and (a2) a structural unit having a crosslinking group; (2) including (a1) a polymer including a structural unit having a group in which an acid group is protected by an acid-decomposable group, and including (a2) a polymer including a structural unit having a crosslinking group; a photo-acid generator (B); an aromatic heterocyclic compound (C) which has a molecular weight of 1000 or less and contains at least one nitrogen atom in an aromatic ring, and contains at least two coordination atoms in an aromatic ring; and a solvent (D).

Description

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

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

In an electronic component such as a thin film transistor (hereinafter referred to as "TFT") type liquid crystal display element, a magnetic head element, an integrated circuit element, or a solid-state imaging element, it is usually provided to insulate between wirings arranged in a layer shape. There is an interlayer insulating film. The material for forming the interlayer insulating film is preferably one having a small number of steps for obtaining a necessary pattern shape and having sufficient flatness. Therefore, a photosensitive resin composition is widely used. For example, JP-A-2011-209681 can be cited as such a photosensitive resin composition.

In the manufacture of electronic components such as the above display devices, a plurality of chemical liquids are used, and it is necessary to have resistance to the chemical liquids. In addition, high panel reliability under high temperature, high humidity, and high pressure conditions is required, and the demand for display devices has been increasing in recent years due to the high definition of display devices.

Further, an aromatic heterocyclic compound may be added as a sensitizer or a photoinitiator in the photosensitive resin composition used to form the interlayer insulating film in the electronic component. However, as a result of research conducted by the inventors of the present application, it is understood that the chemical resistance of the photosensitive resin composition after film hardening is low, and when these photosensitive resin compositions are used, it is easy to be used in the panel reliability test. Produces a situation where the panel is unevenly displayed.

An object of the present invention is to provide a photosensitive resin composition which has high sensitivity and excellent chemical resistance of a cured film, and suppresses panel display unevenness in a panel reliability test. Further, an object of the invention is to provide a method for forming a cured film using such a photosensitive resin composition, a cured film, an organic EL display device, and a liquid crystal display device.

Based on the above, the inventors of the present application conducted active research, and as a result of the research, found that by using a predetermined molecular weight, at least one nitrogen atom is contained in the aromatic ring, and at least two coordinate atoms are contained in the aromatic ring. The aromatic heterocyclic compound not only maintains high sensitivity but also has excellent chemical resistance. The mechanism is not certain, but it is considered that the low molecular weight aromatic heterocyclic compound is easily transferred to the substrate side, and the coordination atom in the aromatic heterocyclic compound interacts with the base substrate, and the inhibition is high. The decomposition product derived from the photosensitive resin composition generated under the conditions of temperature, high humidity, and high pressure enters the base substrate, contributing to improvement in panel reliability. Further, it is presumed that the aromatic heterocyclic compound promotes crosslinking of the cured film and contributes to improvement of chemical resistance.

The means for solving the above problems is the means of the following <1>, and the means of the following <2> to <16> are preferable.

<1> A photosensitive resin composition comprising: (A) a polymer component comprising a polymer satisfying at least one of the following (1) and (2): (1) comprising (a1) having a structural unit of a residue in which an acid group is protected by an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group, (2) including (a1) a residue having an acid group protected by an acid-decomposable group a polymer of the structural unit, and a polymer comprising (a2) a structural unit having a crosslinkable group; (B) a photoacid generator; (C) an aromatic heterocyclic compound; and (D) a solvent; C) The aromatic heterocyclic compound has a molecular weight of 1,000 or less, and the (C) aromatic heterocyclic compound contains at least one nitrogen atom in the aromatic ring and at least two coordinating atoms in the aromatic ring.

The photosensitive resin composition of the above (C), wherein the aromatic heterocyclic compound of the above (C) is a 5-membered ring aromatic heterocyclic compound, a 6-membered ring aromatic heterocyclic compound, and a 5-membered ring. Any one of a polycyclic aromatic heterocyclic compound of at least one of an aromatic heterocyclic structure and a 6-membered cyclic aromatic heterocyclic ring structure.

The photosensitive resin composition as described in <1>, wherein the above-mentioned coordinating atom is any one of a nitrogen atom, a sulfur atom, and an oxygen atom.

The photosensitive resin composition of any one of the above-mentioned (A), the (a2) of the structural unit which has a bridge|crosslinking group. The linking group is at least one selected from the group consisting of an epoxy group, an oxetanyl group, and -NH-CH ₂ -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms).

The photosensitive resin composition as described in any one of the above-mentioned <1>, wherein the acid-decomposable group is a group having a structure protected in the form of an acetal.

The photosensitive resin composition of any one of the above-mentioned (A) is a polymer further containing an acid group.

The photosensitive resin composition of any one of the above-mentioned (B), wherein the photoacid generator of (B) is an oxime sulfonate compound.

The photosensitive resin composition of any one of the above-mentioned (C), wherein the aromatic heterocyclic compound of the above (C) contains two to three coordinating atoms in the aromatic ring.

The photosensitive resin composition of any one of the above-mentioned (C), wherein the aromatic heterocyclic compound of (C) contains at least two nitrogen atoms in an aromatic ring.

The photosensitive resin composition of any one of the above-mentioned (C) aromatic heterocyclic compounds is a single ring, and/or two or three. The condensed ring of the ring.

The photosensitive resin composition as described in any one of the above-mentioned (C) aromatic heterocyclic compound Has a substituent.

<12> A method of forming a cured film, comprising: (1) a coating step of applying the photosensitive resin composition according to any one of <1> to <11> on a substrate; (2) a solvent removing step of removing a solvent from the applied photosensitive resin composition; (3) an exposure step of exposing the solvent-removed photosensitive resin composition by actinic rays; (4) using an aqueous developing solution a developing step of developing the exposed photosensitive resin composition; and (5) a post-baking step of thermally curing the developed photosensitive resin composition.

<13> The method for forming a cured film according to <12>, which comprises the step of subjecting the developed photosensitive resin composition to full exposure after the developing step and before the post-baking step.

<14> A cured film formed by the method according to <12> or <13>.

<15> The cured film according to <14> which is an interlayer insulating film.

<16> An organic EL display device or a liquid crystal display device comprising the cured film according to <14> or <15>.

According to the present invention, it is possible to provide not only high sensitivity but also chemical resistance A photosensitive resin composition excellent in properties, a method for producing a pattern, an organic EL display device, a method for producing a liquid crystal display device, and a cured film.

1,16‧‧‧TFT

2‧‧‧Wiring

3,8‧‧‧Insulation film

4‧‧‧Flat film

5‧‧‧First electrode

6‧‧‧ glass substrate

7, 18‧‧‧ contact holes

10‧‧‧Liquid crystal display device

12‧‧‧Backlight unit

14, 15‧‧‧ glass substrate

17‧‧‧ hardened film

19‧‧‧ITO transparent electrode

20‧‧‧LCD

22‧‧‧Color filters

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

FIG. 2 is a conceptual diagram showing 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, including a planarization film 4.

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

Further, in the expression of the group (atomic group) in the present specification, the description that the substituted or unsubstituted is not described includes not only a substituent but also 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).

Further, the term "(meth)acrylic acid" means acrylic acid and/or methacrylic acid. acid.

The photosensitive resin composition of the present invention (hereinafter sometimes referred to as "the composition of the present invention") is characterized in that (A) contains a polymer satisfying at least one of the following (1) and (2). The polymer component: (1) includes (a1) a structural unit having a residue in which an acid group is protected by an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group; (2) including (a1) a polymer having a structural unit of a residue in which an acid group is protected by an acid-decomposable group, and a polymer comprising (a2) a structural unit having a crosslinkable group; (B) a photoacid generator; (C) an aromatic hybrid a cyclic compound; and (D) a solvent; and the (C) aromatic heterocyclic compound has a molecular weight of 1,000 or less, contains at least one nitrogen atom in the aromatic ring, and contains at least two coordination atoms in the aromatic ring. Further, 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 contains at least one of the following polymers as a polymer component: (1) a structural unit containing (a1) a group having an acid group protected by an acid-decomposable group and (a2) having a crosslinkable group Polymer of a structural unit, and (2) polymerization of a structural unit including (a1) a group having an acid group deprotected by an acid-decomposable group And a polymer comprising (a2) a structural unit having a crosslinkable group. Further, a polymer other than the polymers may be contained. Unless otherwise specified, the (A) polymer component (hereinafter sometimes referred to as "(A) component)" in the present invention means that it is added as needed in addition to the above (1) and/or (2). Other polymerists.

<<Structural unit (a1)>>

Component A includes at least (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group. By including the structural unit (a1) as the component (A), a photosensitive resin composition having an extremely high sensitivity can be obtained.

In the present invention, the "group in which the acid group is protected by the acid-decomposable group" is a group known as an acid group and an acid-decomposable group, and is not particularly limited. The specific acid group is preferably a carboxyl group and a phenolic hydroxyl group. Further, as the acid-decomposable group, a group which is relatively easily decomposed by an acid (for example, an ester structure of a group represented by the formula (A1), a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group can be used. An aldehyde functional group) or a group which is relatively difficult to decompose by an acid (for example, a tertiary alkyl carbonate group such as a tertiary alkyl group such as a third butyl ester group or a tertiary butyl carbonate group such as a third butyl carbonate group).

(a1) The structural unit having a group whose acid group is protected by an acid-decomposable group is preferably a structural unit having a protective carboxyl group protected by an acid-decomposable group or a structure having a protective phenolic hydroxyl group protected by an acid-decomposable group. unit.

Hereinafter, the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group and the structural unit (a1-2) having a protective phenolic hydroxyl group protected by an acid-decomposable group will be sequentially described.

<<<(a1-1) has a carboxyl-protected knot protected by an acid-decomposable group Construction unit>>>

The structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group is a structural unit having a protective carboxyl group which is protected by an acid-decomposable group described below in detail.

The structural unit having a carboxyl group which can be used in the structural unit (a1-1) having a protective carboxyl group protected by an 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 a molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid or an unsaturated tricarboxylic acid; or A structural unit (a1-1-2) having an ethylenically unsaturated group and an acid anhydride-derived structure.

In the following, (a1-1-1) which is used as the structural unit having a carboxyl group, and a structural unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, and (a1-1-2) have both The structural units of the ethylenically unsaturated group and the structure derived from the acid anhydride are separately described.

<<<<(a1-1-1) is derived from a structural unit of an unsaturated carboxylic acid having at least one carboxyl group in a molecule>>>>

As the structural unit (a1-1-1) derived from the unsaturated carboxylic acid having at least one carboxyl group in the molecule, the following may be used as the unsaturated carboxylic acid used in the present invention. 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-(A). Base) propylene methoxyethyl hexahydrophthalic acid, 2-(meth) propylene methoxyethyl-phthalic acid, and the like. Further, examples of the unsaturated dicarboxylic acid include maleic acid, Fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and the like. Further, the unsaturated polycarboxylic acid used to obtain a structural unit having a carboxyl group may also be an acid anhydride thereof. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. Further, the unsaturated polycarboxylic acid may be a mono(2-methylpropenyloxyalkyl)ester of a polyvalent carboxylic acid, and examples thereof include succinic acid mono(2-propenyloxyethyl) ester and dibutyl Acid mono(2-methylpropenyloxyethyl) ester, mono(2-propenyloxyethyl) phthalate, mono(2-methylpropenyloxyethyl) phthalate Ester and the like. Further, the unsaturated polycarboxylic acid may be a mono(meth)acrylate of a di-carboxyl polymer at both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethyl group. Acrylate and the like. Further, as the unsaturated carboxylic acid, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, monoalkyl maleate, monoalkyl fumarate, 4- Carboxy styrene and the like.

In order to form the structural unit (a1-1-1) derived from the unsaturated carboxylic acid having at least one carboxyl group in the molecule, it is preferred to use acrylic acid, methacrylic acid, and 2 in view of developability. -(Meth)propenyloxyethyl-succinic acid, 2-(methyl)propenyloxyethylhexahydrophthalic acid, 2-(methyl)propenyloxyethyl-o-benzene An acid anhydride such as dicarboxylic acid or an unsaturated polycarboxylic acid, or the like, more preferably acrylic acid, methacrylic acid or 2-(meth)acryloxyethyl hexahydrophthalic acid.

The structural unit (a1-1-1) derived from the unsaturated carboxylic acid having at least one carboxyl group in the molecule may be contained alone or in combination of two or more.

<<<<(a1-1-2) Structural unit having both an ethylenically unsaturated group and an acid anhydride-derived structure>>>>

Structural sheet having both an ethylenically unsaturated group and an anhydride-derived structure The unit (a1-1-2) is preferably a unit derived from a monomer obtained by reacting a hydroxyl group present in a structural unit having an ethylenically unsaturated group with an acid anhydride.

As the acid anhydride, a known acid anhydride can be used, and specific examples thereof include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. a dibasic acid anhydride such as chlorendic anhydride; an acid anhydride such as trimellitic anhydride, pyromellitic anhydride, diphenylketone tetracarboxylic anhydride or biphenyltetracarboxylic anhydride. Among these acid anhydrides, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferred from the viewpoint of developability.

The reaction rate of the above acid anhydride to the hydroxyl group is preferably from 10 mol% to 100 mol%, more preferably from 30 mol% to 100 mol%, from the viewpoint of developability.

<<<<Acidolytic Groups Usable in Structural Unit (a1-1)>>>>

The acid-decomposable group which can be used in the structural unit (a1-1) having a carboxyl group which is protected by an acid-decomposable group can be used.

From the viewpoint of the basic physical properties of the photosensitive resin composition, particularly the sensitivity, the pattern shape, the contact hole formation property, and the storage stability of the photosensitive resin composition, among the acid-decomposable groups, the carboxyl group is preferably The protected carboxyl group is protected in the form of an acetal. Further, from the viewpoint of sensitivity, the acid-decomposable group is more preferably a carboxyl group which is a protected carboxyl group protected by an acetal represented by the following formula (a1-10). Further, in the case where the carboxyl group is a protected carboxyl group protected by the form of an acetal represented by the following general formula (a1-10), the entire protective carboxyl group is formed -(C=O)-O-CR ¹⁰¹ R ¹⁰² ( OR ¹⁰³ ) structure.

(In the formula (a1-10), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, wherein R ¹⁰¹ and R ¹⁰² are each a hydrogen atom; R ¹⁰³ represents an alkyl group; R ¹⁰¹ or R ¹⁰² and R ¹⁰³ can be linked to form a cyclic ether.)

In the above formula (a1-10), R ¹⁰¹ to R ¹⁰³ each independently represent a hydrogen atom or an alkyl group, and the alkyl group may be any of a linear chain, a branched chain, and a cyclic group. Here, there is no case where both of R ¹⁰¹ and R ¹⁰² represent a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

In the above 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 is preferably a carbon number of 1 to 12, more preferably a carbon number of 1 to 6, and particularly preferably a carbon number of 1 to 4. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, 2 , 3-dimethyl-2-butyl (thexyl), n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-decyl, and the like.

The above cyclic alkyl group preferably has a carbon number of 3 to 12, more preferably a carbon number of 4 to 8, and particularly preferably a carbon number of 4 to 6. Examples of the above cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, and a ring. Amyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, and the like.

The above alkyl group may have a substituent, and the substituent may, for example, be a halogen atom, an aryl group or an alkoxy group. When a halogen atom is used as a substituent, R ¹⁰¹ , R ¹⁰² and R ^{103 are} a halogenated alkyl group, and when an aryl group is used as a substituent, R ¹⁰¹ , R ¹⁰² and R ^{103 are} aralkyl groups.

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and among these halogen atoms, a fluorine atom or a chlorine atom is preferred.

Further, the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably a carbon number of 6 to 12, and specifically, a phenyl group, an α-methylphenyl group, a naphthyl group or the like may be exemplified by an aryl group. The alkyl group as a whole, that is, an aralkyl group, may, for example, be a benzyl group, an α-methylbenzyl group, a phenethyl group or a naphthylmethyl group.

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

Further, when the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group may be a linear or branched chain. In the case of an alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent.

These substituents may be further substituted by the above substituents.

In the above formula (a1-10), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an aryl group, the aryl group is preferably a carbon number of 6 to 12, more preferably a carbon number of 6 to 10. The aryl group may have a substituent, and the above substituent is preferably an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a cumenyl group, a 1-naphthyl group and the like.

Further, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. To R ¹⁰¹ and R ^102, in the case of a ring structure with R ¹⁰¹ R ¹⁰³ or R ¹⁰² and R ¹⁰³ bonded include, for example: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, tetrahydrofuranyl, adamantane Base and tetrahydropyranyl group and the like.

Further, in the above formula (a1-10), it is preferred that any of R ¹⁰¹ and R ¹⁰² is a hydrogen atom or a methyl group.

The radical polymerizable monomer for forming a structural unit having a protective carboxyl group represented by the above formula (a1-10) can be used commercially, or can be synthesized by a known method. For example, it can be synthesized by the synthesis method described in Paragraph No. 0037 to Paragraph No. 0040 of JP-A-2011-221494.

The first preferred aspect of the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group is a structural unit represented by the following formula (A2').

(wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ represents an alkyl group or an aryl group, and R ¹ or R ² , R ³ can 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 extended aryl group.

When R ¹ and R ² are an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred. In the case where R ¹ and R ² are an aryl group, 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 extended aryl group, preferably a single bond.

A second preferred embodiment of the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group is a structural unit of the following 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 phenyl group; and R ¹²² to R ¹²⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

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 a hydrogen atom.

A preferred specific example of the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group is exemplified by the following structural unit. Further, R represents a hydrogen atom or a methyl group.

<<<(a1-2) Structural unit having a phenolic hydroxyl group protected by an acid-decomposable group>>>

The structural unit (a1-2) having a phenolic hydroxyl group protected by an acid-decomposable group is a structural unit having a phenolic hydroxyl group and a structural unit having a phenolic hydroxyl group protected by an acid-decomposable group described in detail below. .

<<<<(a1-2-1) Structural unit with phenolic hydroxyl group>>>>

The structural unit having a phenolic hydroxyl group may be a structural unit in a hydroxystyrene structural unit or a novolak-based resin, and among these structural units, from the viewpoint of sensitivity, it is preferably derived from hydroxystyrene or α. a structural unit of methyl hydroxystyrene. Further, from the viewpoint of sensitivity, the structural unit having a phenolic hydroxyl group is also preferably a structural unit represented by the following formula (a1-20).

General formula (a1-20)

(In the 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 linear or branched alkyl group having 1 to 5 carbon atoms. A, a represents an integer from 1 to 5, b represents an integer from 0 to 4, and a+b is 5 or less. Further, when two or more R ²²² are present, the R ²²² may be different from each other or the same.

In the above formula (a1-20), R ²²⁰ represents a hydrogen atom or a methyl group, preferably a methyl group.

Further, R ²²¹ represents a single bond or a divalent linking group. In the case of a single bond, the sensitivity can be improved, and the transparency of the cured film can be improved, which is preferable. Specific examples of the divalent linking group of R ²²¹ may be an alkylene group, and R ²²¹ is an alkylene group: methylene, ethyl, propyl, isopropyl, n-butyl, and isobutylene. Stretching the third butyl group, stretching the pentyl group, stretching the isoamyl group, stretching the neopentyl group, and stretching the hexyl group. Among them, R ^{221 is} preferably a single bond, a methylene group or an ethyl group. Further, the divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group and the like. Further, a represents an integer of 1 to 5. However, from the viewpoint of the effects of the present invention or the ease of production, a is preferably 1 or 2, and more preferably a is 1.

Further, when the carbon atom bonded to R ²²¹ is used as a reference (1 position), the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4 position.

R ²²² is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples thereof include a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. Base. Among them, a chlorine atom, a bromine atom, a methyl group or an ethyl group is preferred in terms of ease of production.

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

<<<<Acidolytic Groups Usable in Structural Units (a1-2)>>>>

The above-described acid-decomposable group which can be used in the structural unit (a1-2) having a phenolic hydroxyl group which is protected by an acid-decomposable group, and the above-mentioned structural unit having a protective carboxyl group protected by an acid-decomposable group (a1-1) The acid-decomposable group which can be used in the above is similarly used, and is not particularly limited. The acid-decomposable group preferably has acetal protection from the viewpoint of the basic physical properties of the photosensitive resin composition, particularly the sensitivity or the pattern shape, the storage stability of the photosensitive resin composition, and the formation of contact pores. A structural unit that protects a phenolic hydroxyl group. Further, from the viewpoint of sensitivity, the acid-decomposable group is more preferably a phenolic hydroxyl group protected by a form of an acetal represented by the above formula (a1-10). Further, in the case where the phenolic hydroxyl group is a phenolic hydroxyl group protected in the form of an acetal represented by the above formula (a1-10), the overall formation of the phenolic hydroxyl group is protected - Ar-O-CR ¹⁰¹ R ¹⁰² The structure of (OR ¹⁰³ ). Further, Ar represents an aryl group.

A preferred example of the acetal ester structure of the phenolic hydroxyl group is exemplified by a combination of R ¹⁰¹ = R ¹⁰² = R ¹⁰³ = methyl or R ¹⁰¹ = R ¹⁰² = methyl and R ¹⁰³ = benzyl.

Further, the radical polymerizable monomer for forming a structural unit having a phenolic hydroxyl group having a phenolic hydroxyl group protected by an acetal is exemplified by Paragraph No. 0044 of JP-A-2011-215590. Monomers, etc.

Among these monomers, from the viewpoint of transparency, a 1-alkoxyalkyl protecting agent of 4-hydroxyphenyl methacrylate or a tetrahydropyranyl group of 4-hydroxyphenyl methacrylate is preferred. Protector.

Specific examples of the acetal protecting group of the phenolic hydroxyl group include a 1-alkoxyalkyl group, and examples thereof include 1-ethoxyethyl, 1-methoxyethyl, and 1-n-butoxyethyl. 1-isobutoxyethyl, 1-(2-chloroethoxy)ethyl, 1-(2-ethylhexyloxy)ethyl, 1-n-propoxyethyl, 1-cyclohexyloxy Ethyl ethyl group, 1-(2-cyclohexylethoxy)ethyl group, 1-benzyloxyethyl group, etc., these groups may be used individually or in combination of 2 or more types.

The radical polymerizable monomer for forming the structural unit (a1-2) having a phenolic hydroxyl group which is protected by an acid-decomposable group can be used commercially or by a known method. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with a vinyl ether in the presence of an acid catalyst. The above synthesis allows a monomer having a phenolic hydroxyl group to be previously copolymerized with another monomer and then reacted with a vinyl ether in the presence of an acid catalyst.

A preferred specific example of the structural unit (a1-2) having a phenolic hydroxyl group protected by an acid-decomposable group is exemplified by the following structural unit, but the present invention is not limited to the structural unit.

<<<The preferred aspect of structural unit (a1)>>>

In the case where the polymer containing the structural unit (a1) contains substantially no structural unit (a2), the structural unit (a1) preferably contains 20 mol% to 100% of the polymer containing the structural unit (a1). Molar%, more preferably 30% by mole to 90% by mole.

In the case where the polymer containing the structural unit (a1) contains the following structural unit (a2), the polymer containing the structural unit (a1) and the structural unit (a2) has the above structure in terms of sensitivity. The unit (a1) is preferably from 3 mol% to 70 mol%, more preferably from 10 mol% to 60 mol%. In addition, especially in the above knot In the case where the acid-decomposable group which can be used in the structural unit (a1) is a structural unit having a carboxyl group protected by a form of an acetal, it is preferably 20 mol% to 50 mol%.

The structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group has a feature of rapid development as compared with the above-mentioned structural unit (a1-2) having a phenolic hydroxyl group protected by an acid-decomposable group. Therefore, in the case of rapid development, it is preferably a structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group. On the contrary, in the case where the development is to be slowed down, it is preferred to use a structural unit (a1-2) having a protective phenolic hydroxyl group protected by an acid-decomposable group.

The structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group has a feature of rapid development as compared with the above-mentioned structural unit (a1-2) having a phenolic hydroxyl group protected by an acid-decomposable group. Therefore, in the case of rapid development, it is preferably a structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group. On the contrary, in the case where the development is to be slowed down, it is preferred to use a structural unit (a1-2) having a protective phenolic hydroxyl group protected by an acid-decomposable group.

<<(a2) Structural unit having a crosslinkable group>>

The component (A) includes a structural unit (a2) having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group which undergoes a curing reaction by heat treatment. Examples of the structural unit having a preferred crosslinkable group include those selected from the group consisting of an epoxy group, an oxetanyl group, and -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms). The structural unit of at least one of the group consisting of the ethylenically unsaturated group and the ethylenically unsaturated group is preferably selected from the group consisting of an epoxy group, an oxetanyl group, and -NH-CH ₂ -OR (R is a carbon number) At least one of the groups represented by the alkyl group of 1 to 20). In the photosensitive resin composition of the present invention, the component (A) preferably contains at least one structural unit containing at least one of an epoxy group and an oxetanyl group. More specifically, the following structural unit is mentioned.

<<<(a2-1) Structural unit having an epoxy group and/or oxetanyl group>>>

The above (A) polymer preferably contains a structural unit (structural unit (a2-1)) having an epoxy group and/or an oxetanyl group. The cyclic ether group of the above 3-membered ring is also called an epoxy group, and the cyclic ether group of the 4-membered ring is also called an oxetanyl group.

The structural unit (a2-1) having an epoxy group and/or an oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit, and may have one or more. The epoxy group and one or more oxetanyl groups, two or more epoxy groups, or two or more oxetanyl groups are not particularly limited, and preferably have a total of one to three The epoxy group and/or oxetanyl group is more preferably an epoxy group and/or an oxetanyl group having a total of 1 or 2, and particularly preferably having 1 epoxy group or an oxocyclic group. Butyl.

Specific examples of the radical polymerizable monomer for forming a structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, and α-n-propyl group. Glycidyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxy acrylate Hexyl methyl ester, 3,4-epoxycyclohexyl methyl methacrylate, α-ethyl acrylate-3,4-epoxycyclohexyl methyl ester, o-vinyl Benzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and an alicyclic epoxy skeleton-containing compound described in Paragraph No. 0031 to Paragraph No. 0035 of Japanese Patent No. 4,184,843 Etc., the contents are incorporated into the specification of the present application.

Specific examples of the radical polymerizable monomer for forming a structural unit having an oxetanyl group include an oxygen heterocyclic ring described in Paragraph No. 0011 to Paragraph No. 0016 of JP-A-2001-330953. Butyl (meth) acrylates and the like, which are incorporated in the specification of the present application.

A specific example of the radical polymerizable monomer for forming the above structural unit (a2-1) having an epoxy group and/or an oxetanyl group is preferably a monomer having a methacrylate structure and containing an acrylate. The monomer of the structure.

Among these monomers, preferred are: glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, acrylic acid (3-ethyloxa) Cyclobutane-3-yl)methyl ester, and (3-ethyloxetan-3-yl)methyl methacrylate. These structural units may be used alone or in combination of two or more.

A preferred specific example of the structural unit (a2-1) having an epoxy group and/or an oxetanyl group exemplifies the following structural unit. Further, R represents a hydrogen atom or a methyl group.

<<<(a2-2) Structural unit having an ethylenically unsaturated group>>>

One type of the structural unit (a2) having a crosslinkable group is a structural unit (a2-2) having an ethylenically unsaturated group (hereinafter also referred to as "structural unit (a2-2)"). The structural unit (a2-2) having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group in a side chain, more preferably an ethylenically unsaturated group at the terminal group and having a carbon number of 3 to 16. The structural unit of the side chain is particularly preferably a structural unit having a side chain represented by the following formula (a2-2-1).

(In the formula (a2-2-1), R ³⁰¹ represents a divalent linking group having 1 to 13 carbon atoms, R ³⁰² represents a hydrogen atom or a methyl group, and * represents a structural unit (a2) having a crosslinkable group; The part where the main chain is connected.)

R ³⁰¹ is a divalent linking group having 1 to 13 carbon atoms, and includes an alkenyl group, a cycloalkenyl group, an extended aryl group or a group obtained by combining the groups, and may further contain an ester bond, an ether bond, or a guanamine bond. a bond such as a urethane bond. Further, the divalent linking group may have a substituent such as a hydroxyl group or a carboxyl group at any position. Specific examples of R ³⁰¹ include the following divalent linking groups.

The side chain represented by the above formula (a2-2-1) includes the divalent linking group represented by the above R ³⁰¹ , and is preferably an aliphatic side chain.

In addition, the structural unit having an ethylenically unsaturated group (a2-2) can be referred to the description of Paragraph No. 0072 to Paragraph No. 0090 of JP-A-2011-215580, which is incorporated in the specification of the present application. .

<<<(a2-3) Structural unit of a group represented by -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) >>>

The polymer used in the present invention is also preferably a structural unit (a2-3) having a group represented by -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms). By having the structural unit (a2-3), the hardening reaction can be caused by a slow heat treatment, and a cured film excellent in characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. Further, the alkyl group may be any of a linear, branched or cyclic alkyl group, preferably a linear or branched alkyl group. The structural unit (a2) is more preferably a structural unit having a group represented by the following formula (a2-30).

(In the formula (a2-30), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms.)

R ^{2 is} preferably an alkyl group having 1 to 9 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms. Further, the alkyl group may be any of a linear, branched or cyclic alkyl group, preferably a linear or branched alkyl group.

Specific examples of R ² include a methyl group, an ethyl group, an n-butyl group, an isobutyl group, a cyclohexyl group, and a n-hexyl group. Among them, isobutyl, n-butyl and methyl groups are preferred.

<<<The preferred aspect of structural unit (a2)>>>

In the case where the polymer containing the above structural unit (a2) does not substantially contain the structural unit (a1), the structural unit (a2) preferably contains 5 mol% to 90% of the polymer containing the structural unit (a2). More than 20% of the moles, more preferably 20% by mole to 80% by mole.

In the case where the polymer containing the structural unit (a2) contains the structural unit (a1), the polymer containing the structural unit (a1) and the structural unit (a2) is chemically resistant. The above structural unit (a2) is preferably from 3 mol% to 70 mol%, more preferably from 10 mol% to 60 mol%.

In the present invention, in any of the structural elements of the component (A), it is preferred to contain 3 mol% to 70 mol% of the structural unit (a2), more preferably 10 mol%. ~60% by mole.

When it is in the above numerical range, the cured film obtained from the photosensitive resin composition has good transparency and chemical resistance.

<<(a3) Other structural units>>

In the present invention, the component (A) may include other structural units (a3) other than the structural unit (a1) and/or the structural unit (a2). These structural units may also contain the above polymer component (1) and/or polymer component (2). Further, in addition to the above polymer component (1) or polymer component (2), a polymer component including substantially no structural unit (a1) and structural unit (a2) but including other structural unit (a3) may be contained. . In addition to the above polymer component (1) or polymer component (2), a polymer component including substantially no structural unit (a1) and structural unit (a2) but including other structural unit (a3) is contained. In the polymer component, the amount of the polymer component is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less.

The monomer to be another structural unit (a3) is not particularly limited, and examples thereof include styrene, alkyl (meth)acrylate, cyclic alkyl (meth)acrylate, and aryl (meth)acrylate. Ester, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid , unsaturated dicarboxylic anhydride, other unsaturated compounds. Further, as described later, a structural unit having an acid group may also be included. The monomers which are other structural units (a3) may be used singly or in combination of two or more.

Hereinafter, preferred embodiments of the polymer component of the present invention are listed, but the present invention is not limited to the embodiments.

(First embodiment)

The polymer component (1) further includes one or two or more kinds of other structural units (a3).

(Second embodiment)

The polymer of the polymer component (2) including (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group further includes one or two or more kinds of other structural units (a3).

(Third embodiment)

The polymer of the polymer component (2) including (a2) a structural unit having a crosslinkable group further includes one or two or more kinds of other structural units (a3).

(Fourth embodiment)

In any of the first to third embodiments, the structural unit including at least an acid group is included as the other structural unit (a3).

(Fifth Embodiment)

In addition to the above polymer component (1) or polymer component (2), it further includes a polymer which substantially does not contain the structural unit (a1) and the structural unit (a2) but includes the other structural unit (a3).

(Sixth embodiment)

The form of the combination of two or more types of the above-described first to fifth embodiments is included.

(Seventh embodiment)

At least the aspect of the polymer component (2) is included. In particular, in the first to sixth embodiments described above, at least the aspect of the polymer component (2) is contained.

Specifically, the structural unit (a3) may be exemplified by structural units derived from the following compounds: styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, ethoxylated. Styrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, 4-hydroxybenzoic acid (3-methacryloxypropyl) Ester, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2-hydroxyl (meth)acrylate Ethyl ester, 2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, acrylonitrile, ethylene glycol monoacetate mono(meth)acrylate Wait. In addition, the compound described in Paragraph No. 0021 to Paragraph No. 0024 of JP-A-2004-264623 is mentioned.

Further, from the viewpoint of electrical characteristics, the other structural unit (a3) is preferably a styrene group having an alicyclic skeleton. Specific examples thereof include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth)acrylate, and cyclohexyl (meth)acrylate. Ester, isobornyl (meth)acrylate, benzyl (meth)acrylate, and the like.

Further, from the viewpoint of adhesion, other structural units (a3) are preferred. It is an alkyl (meth)acrylate. Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate, and more preferably methyl (meth)acrylate. . 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 particularly preferably 40 mol% or less. The lower limit value may be 0 mol%, and may be, for example, 1 mol% or more, and may be 5 mol% or more. When it is in the above numerical range, the characteristics of the cured film obtained from the photosensitive resin composition become good.

The other structural unit (a3) preferably contains an acid group. By containing an acid group, it is easy to be dissolved in an alkaline developing solution, and the effect of the present invention is more effectively exerted. The acid group in the present invention means a proton dissociative group having a pKa of less than 7. Usually, a monomer which can form an acid group is used as a structural unit containing an acid group, and an acid group is incorporated into a polymer. The inclusion of such a structural unit containing an acid group in the polymer tends to be easily dissolved in the alkaline developing solution.

The acid group used in the present invention can be exemplified by those derived from a carboxylic acid group, those derived from a sulfonylamino group, those derived from a phosphonic acid group, those derived from a sulfonic acid group, those derived from a phenolic hydroxyl group, and sulfonylamino groups. The sulfonimide group or the like is preferably one derived from a carboxylic acid group and/or derived from a phenolic hydroxyl group.

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, or a structural unit derived from (meth)acrylic acid and/or an ester thereof.

In the present invention, in particular, from the viewpoint of sensitivity, a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group is preferable.

The structural unit containing an acid group is preferably a structural single sheet of all polymer components 1 mol% to 80 mol% of the element, more preferably 1 mol% to 50 mol%, especially preferably 5 mol% to 40 mol%, especially preferably 5 mol% to 30 mol% The best is 5 mol%~20 mol%.

In the present invention, in addition to the polymer component (1) or the polymer component (2), an aggregation including substantially no structural unit (a1) and structural unit (a2) but including other structural unit (a3) may be included. Things.

Such a polymer is preferably a resin having a carboxyl group in a side chain. For example, Japanese Patent Laid-Open No. 59-44615, Japanese Patent Publication No. Sho 54-34327, Japanese Patent Publication No. Sho 58-12577, Japanese Patent Publication No. Sho 54-25957, Japanese Patent Laid-Open No. 59-53836 The methacrylic acid copolymer, the acrylic copolymer, the itaconic acid copolymer, the butenoic acid copolymer, the maleic acid copolymer, and the partial ester described in each of the publications of Japanese Patent Laid-Open Publication No. SHO 59-71048 a maleic acid copolymer or the like, an acidic cellulose derivative having a carboxyl group in a side chain, an acid anhydride added to a polymer having a hydroxyl group, and the like, and further having a (methyl) side chain A propylene fluorenyl polymer is preferred.

For example, benzyl (meth)acrylate / (meth)acrylic acid copolymer, 2-hydroxyethyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic copolymer, Japanese patent 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate described in Kaiping No. 7-140654 Ester/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer , 2-hydroxyethyl methacrylate / poly Styrene macromonomer/benzyl methacrylate/methacrylic acid copolymer.

In addition, Japanese Patent Laid-Open No. Hei 7-207211, Japanese Patent Laid-Open No. Hei 8-259876, Japanese Patent Laid-Open No. Hei 10-300922, Japanese Patent Laid-Open No. Hei 11-140144, and Japanese Patent No. A known polymer compound described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Incorporated into the specification of this application.

These polymers may be contained alone or in combination of two or more.

These polymers can also be used commercially: 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 UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above manufactured by East Asia Synthetic Co., Ltd.), Joncryl 690, Joncryl 678, Joncryl 67, Joncryl 586 (above by BASF ( BASF) manufacturing) and so on.

<<(A) Molecular Weight of Polymer>>

The molecular weight of the (A) polymer is preferably from 1,000 to 200,000, more preferably from 2,000 to 50,000, in terms of polystyrene-equivalent weight average molecular weight. If it is within the above numerical range, the characteristics are good. The ratio (dispersion) of the number average molecular weight to the weight average molecular weight is preferably from 1.0 to 5.0, more preferably from 1.5 to 3.5.

<<(A) Method for producing polymer>>

Further, various methods are also known for the synthesis method of the component (A), and if an example is given, By using a radical polymerization initiator, a radically polymerizable monomer mixture containing at least a radical polymerizable monomer for forming the structural unit represented by the above (a1) and the above (a3) can be organically The polymerization is carried out in a solvent to synthesize. Further, 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 parts by mass to 99.9 parts by mass, more preferably 70 parts by mass to 98 parts by mass, based on 100 parts by mass of all the solid components. (A) ingredient.

<(B) Photoacid generator>

The photosensitive resin composition of the present invention contains (B) a photoacid generator. The photoacid generator (also referred to as "(B) component") used in the present invention is preferably a compound which generates an acid by inducing an actinic ray having a wavelength of 300 nm or more, preferably a wavelength of 300 nm to 450 nm, but Its chemical structure is not limited. In addition, the photoacid generator which does not directly induce the actinic ray having a wavelength of 300 nm or more is a compound which generates an acid by inducing an actinic ray having a wavelength of 300 nm or more by using it together with a sensitizer. It can then be used in combination with a sensitizer. The photoacid generator used in the present invention is preferably a photoacid generator which produces an acid having a pKa of 4 or less, more preferably a photoacid generator which produces an acid having a pKa of 3 or less, and preferably has a pKa of 2 or less. Acid photoacid generator.

Examples of the photoacid generator include trichloromethyl-s-triazine, sulfonium or phosphonium salt, quaternary ammonium salt, diazomethane compound, sulfhydryl sulfonate compound, and sulfonate compound. Wait. Among these compounds, an oxime sulfonate compound is preferably used from the viewpoint of insulating properties. The photoacid generators may be used alone or Two or more types are used in combination. Specific examples of the trichloromethyl-s-triazine, the diarylsulfonium salt, the triarylsulfonium salt, the quaternary ammonium salt, and the diazomethane derivative can be exemplified by Japanese Patent Laid-Open Publication No. 2011-221494. The compound described in paragraph number 0083 to paragraph number 0008.

The oxime sulfonate compound, that is, the compound having an oxime sulfonate structure, is preferably a compound containing an oxime sulfonate structure represented by the following formula (B1).

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

Any group may be substituted, and the alkyl group in R ²¹ may be linear, may be branched, or may be cyclic. The permitted substituents will be described below.

The alkyl group of R ²¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ²¹ may be an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (including a bridged ring such as 7,7-dimethyl-2-oxonorbornyl) The alicyclic group is preferably substituted with a bicycloalkyl group or the like.

The aryl group of R ²¹ is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group. 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 the oxime sulfonate structure represented by the above formula (B1) is also preferably an oxime sulfonate compound represented by the following 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 when m4 is 2 or 3, a plurality of X may be the same It can be 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 formula (B2), it is particularly preferred that m4 is 1, X is a methyl group, the substitution position of X is an ortho position, and R ⁴² is a linear alkyl group having a carbon number of 1 to 10, and 7,7-dimethyl group. a compound of 2-oxo norbornylmethyl or p-tolylmethyl.

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

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

R ⁴³ in the above formula (B3) is preferably: methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, all Fluorine-n-butyl, p-tolyl, 4-chlorophenyl or pentafluorophenyl, particularly preferably n-octyl.

X ^{1 is} preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group.

N4 is preferably 0 to 2, and particularly preferably 0 to 1.

Specific examples of the compound represented by the above formula (B3) include α-(methylsulfonyloxyimino)benzylcarbonitrile and α-(ethylsulfonyloxyimino)benzylcarbonitrile. --(n-propylsulfonyloxyimino)benzylcarbonitrile, α-(n-butylsulfonyloxyimino)benzylcarbonitrile, α-(4-toluenesulfonyloxyimino) Benzonitrile, α-[(methylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(ethylsulfonyloxyimino)-4-methoxybenzene Acetonitrile, α-[(n-propylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(n-butylsulfonyloxyimino)-4-methoxy Phenyl phenyl] acetonitrile, α-[(4-toluenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile.

Specific examples of the preferred oxime sulfonate compound include the following compounds (i) to (viii), and the like, and may be used alone or in combination of two or more. Compound The compound (i) to the compound (viii) can be obtained as a commercial product. Further, it can also be used in combination with other types of (B) photoacid generators.

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

In the above formula (OS-1), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a decyl group, an amine carbaryl group, an amine sulfonyl group, a sulfo group, a cyano group, or the like. Aryl or heteroaryl. R ¹⁰² 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 -, and R ¹⁰⁵ to R ¹⁰⁷ represent an alkyl group or an aromatic group. base.

R ¹²¹ to R ¹²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amine group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, a decylamino group, a sulfo group or a cyano group. Or aryl. 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. Further, it is preferable to exemplify a state in which at least two of R ¹²¹ to R ¹²⁴ are bonded to each other to form an aryl group. Among them, from the viewpoint of sensitivity, it is preferred that all of R ¹²¹ to R ¹²⁴ are hydrogen atoms.

The functional groups described may each further have a substituent.

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

In the above 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 are also the same.

In these preferred embodiments, it is more preferred that the above formula (OS-1) and R ¹⁰¹ in the above formula (OS-2) are in the form of a cyano group or an aryl group, and the above formula (OS) is most preferred. -2) The aspect represented by R ¹⁰¹ being a cyano group, a phenyl group or a naphthyl group.

Further, the steric structure (E, Z, etc.) of the lipid or benzothiazole ring in the above oxime sulfonate compound may be either a mixture or a mixture.

Specific examples of the compound represented by the above formula (OS-1) which can be suitably used in the present invention include the compounds described in Paragraph No. 0128 to Paragraph No. 0132 of JP-A-2011-221494 (exemplified compound b- 1 to the exemplified compound 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 formula (B1) is preferably a compound of the following formula (OS-3), the following formula (OS-4) or the following formula (OS). -5) The oxime sulfonate compound represented.

(In the general formula (OS-3) to (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represent an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ are each independently The ground 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 alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonate. The thiol group, X ¹ to X ³ each independently represents an oxygen atom or a sulfur atom, and n ¹ to n ³ each independently represent 1 or 2, and m ¹ to m ³ each independently represent an integer of 0 to 6.

In the above formula (OS-3) to formula (OS-5), the alkyl group, the aryl group or the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have a substituent.

In the above formula (OS-3) to formula (OS-5), the alkyl group in R ²² , R ²⁵ and R ²⁸ is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent.

Further, in the above formula (OS-3) to formula (OS-5), the aryl group in R ²² , R ²⁵ and R ²⁸ is preferably an aryl group having a total carbon number of 6 to 30 which may have a substituent.

Further, in the above formula (OS-3) to formula (OS-5), the heteroaryl group in R ¹ is preferably a heteroaryl group having a total carbon number of 4 to 30 which may have a substituent.

In the above formula (OS-3) to formula (OS-5), the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may be at least one ring which is a heteroaromatic ring, for example, a heteroaromatic ring and a benzene ring. Can also shrink the ring.

In the above formula (OS-3) to formula (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.

In the above formula (OS-3) to formula (OS-5), two or more of R ²³ , R ²⁶ and R ²⁹ are present in the compound, and preferably one or two are alkyl groups, aryl groups or More preferably, one halogen atom is an alkyl group, an aryl group or a halogen atom, and particularly preferably one is an alkyl group, and the balance is a hydrogen atom.

The alkyl group in R ²³ , R ²⁶ and R ²⁹ is preferably an alkyl group having a total carbon number of 1 to 12 which may have a substituent, and more preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent.

The aryl group in R ²³ , R ²⁶ and R ²⁹ is preferably an aryl group having a total carbon number of 6 to 30 which may have a substituent.

In the above formula (OS-3) to formula (OS-5), X ¹ to X ³ each independently represent O or S, and is preferably O.

In the above formula (OS-3) to formula (OS-5), the ring including X ¹ to X ³ as a ring member is a 5-membered ring or a 6-membered ring.

In the above formula (OS-3) to formula (OS-5), n ¹ to n ³ each independently represent 1 or 2, and when X ¹ to X ³ are 0, n ¹ to n ³ are each independently The ground is preferably 1, and when X ¹ to X ³ are S, n ¹ to n ³ are each independently preferably 2.

In the above formula (OS-3) to formula (OS-5), R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or Alkoxysulfonyl. Wherein R ²⁴ , R ²⁷ and R ³⁰ are each independently preferably an alkyl group or an alkoxy group.

The alkyl group, alkoxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R ²⁴ , R ²⁷ and R ³⁰ may have a substituent.

In the above formula (OS-3) to formula (OS-5), the alkyl group in R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent.

In the above formula (OS-3) to formula (OS-5), the alkoxy group in R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkoxy group having a total carbon number of 1 to 30 which may have a substituent.

Further, in the above formula (OS-3) to formula (OS-5), m ¹ to m ³ each independently represent an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1. , especially good is 0.

Further, regarding the respective substituents of the above (OS-3) to (OS-5), (OS-3) to (OS-, as described in Paragraph No. 0092 to Paragraph No. 0109 of JP-A-2011-221494 The preferred range of the substituent of 5) is also preferably preferred.

In addition, the compound containing the oxime sulfonate structure represented by the above formula (B1) is particularly preferably an oxime sulfonate represented by any one of the following formula (OS-6) to (OS-11). Compound.

(In the formula (OS-6)~(OS-11), R ³⁰¹ to R ³⁰ 6 represent an alkyl group, an aryl group or a heteroaryl group, and R ³⁰⁷ represents a hydrogen atom or a bromine atom, R ³⁰⁸ ~ R ³¹⁰ , R ³¹³ And R ³¹⁶ and R ³¹⁸ each independently represent 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.

The preferred range of the above-mentioned general formula (OS-6) to the general formula (OS-11) and (OS-6) to (OS) described in Paragraph No. 0110 to Paragraph No. 0112 of JP-A-2011-221494 The preferred range of -11) is the same.

Specific examples of the oxime sulfonate compound represented by the above formula (OS-3) to the above formula (OS-5) include those described in paragraph No. 0114 to paragraph number 0120 of JP-A-2011-221494. A compound, but the invention is not limited to the compounds.

In the photosensitive resin composition of the present invention, it is preferred that (B) a photoacid generator is used in an amount of 100 parts by mass based on all the resin components (preferably a solid component, more preferably a total of the copolymer) in the photosensitive resin composition. It is more preferably used in an amount of from 0.1 part by mass to 10 parts by mass, more preferably from 0.5 part by mass to 10 parts by mass. Two or more types may be used in combination.

<(C) Aromatic Heterocyclic Compound>

The composition of the present invention contains (C) an aromatic heterocyclic compound. The (C) aromatic heterocyclic compound has a molecular weight of 1,000 or less, and the (C) aromatic heterocyclic compound contains at least one nitrogen atom in the aromatic ring and at least two coordinating atoms in the aromatic ring. By containing an aromatic heterocyclic compound, not only the sensitivity but also the chemical resistance can be improved. Further, when the cured film formed of the composition of the present invention is used for a display device, panel display unevenness of the display device can be improved.

The molecular weight of the (C) aromatic heterocyclic compound is 1,000 or less, preferably 750 or less, more preferably 500 or less. By setting the molecular weight to a low molecular weight, the molecules are easily moved toward the substrate side. The lower limit is preferably 1 or more, and more preferably 50 or more.

The coordination atom constituting an aromatic heterocyclic ring means that it has a coordination binding energy. The atom of the force may, for example, be a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, and more preferably a nitrogen atom, an oxygen atom or a sulfur atom. (C) The aromatic heterocyclic compound contains at least two coordinating atoms, at least one of which is a nitrogen atom. The coordination atom preferably contains two to three aromatic rings of one molecule of the (C) aromatic heterocyclic compound. At least one of the coordinating atoms is a nitrogen atom, and preferably at least two are nitrogen atoms. Further, it may be a state in which a hydrogen atom is bonded to a coordinating atom. Further, the (C) aromatic heterocyclic compound preferably contains no basic group, and particularly preferably contains no amine group.

The (C) aromatic heterocyclic compound may have a substituent T on the aromatic ring. Examples of the substituent T include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a thioalkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a carboxyl group, an ethyl group, a cyano group, and a halogen. An atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) or the like. These substituents may further have a substituent. However, the (C) aromatic heterocyclic compound used in the present invention is preferably a compound which is unsubstituted or substituted with a methyl group.

Further, from the viewpoint of suppressing the decrease in sensitivity, a substituent having no amine group as an aromatic ring is preferred.

(C) The aromatic heterocyclic compound is not particularly limited as long as it is an aromatic ring, and is preferably a 5-membered cyclic aromatic heterocyclic compound, a 5-membered cyclic aromatic heterocyclic compound, or a 5-membered aromatic heterocyclic ring structure. And a polycyclic aromatic heterocyclic compound of at least one of a 6-membered ring aromatic heterocyclic ring structure.

The polycyclic aromatic heterocyclic compound refers to a compound in which two or more independent aromatic rings are bonded to each other by a bond (for example, bipyridine or the like), or one or more aromatic rings and one or more. Condensation of aliphatic and/or aromatic rings a compound (eg, morphine, etc.). In the present invention, when at least one ring constituting the polycyclic aromatic heterocyclic compound is a 5-membered ring aromatic heterocyclic ring structure or a 6-membered ring aromatic heterocyclic ring structure, the other ring may be any ring, and the other ring may be It is preferably selected from the group consisting of a benzene ring, a 5-membered ring aromatic hetero ring, and a 6-membered ring aromatic hetero ring, and more preferably a benzene ring and a 6-membered ring aromatic hetero ring. The number of rings forming the polycyclic aromatic heterocyclic compound is preferably 2 or 3, more preferably 2 in 1 molecule.

The 5-membered aromatic heterocyclic compound is preferably an imidazole compound, a pyrazole compound, an oxazole compound, an isoxazole compound, a thiazole compound, an isothiazole compound, a triazole compound, or an oxadiazole system. a compound, a thiadiazole-based compound, or the like.

The imidazole-based compound is preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 1-n-propylimidazole, 1-isopropylimidazole, 1-butylimidazole, 1-mercapto-2-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, 1-(heptafluorobutenyl)imidazole, 2-methylimidazole, 4-methylimidazole , 2-phenylimidazole, 4-phenylimidazole, 1-benzylimidazole, 4-methyl-2-phenylimidazole, 1-ethenylimidazole, 1-imidazoleacetic acid, 4-imidazolecarboxylic acid, 4, 5-imidazole dicarboxylic acid or the like.

The pyrazole-based compound is preferably pyrazole, 1-methylpyrazole, 3-methylpyrazole, 4-methylpyrazole, 1-ethylpyrazole, 3-ethylpyrazole, 4-ethyl Pyrazole, 1-phenylpyrazole, 3-phenylpyrazole, 4-phenylpyrazole, 3,5-diisopropylpyrazole, 3-(trifluoromethyl)pyrazole, 4-bromopyrrol Oxazole, 4-chloropyrazole, 3,5-dimethylpyrazole, 1,3,5-trimethylpyrazole, 3,5-dimethyl-1-phenylpyrazole, 3-(4- Tolyl)pyrazole, 3-(4-methoxyphenyl)pyrazole, 3-(4-bromophenyl)pyrazole, 3-methyl-1-phenylpyrazole, 4-bromo-3- Methylpyrazole, 3-(4-bromophenyl) Pyrazole, 3-(4-fluorophenyl)pyrazole, 4-bromo-3,5-dimethylpyrazole, 4-bromo-1-phenylpyrazole, 3-(4-chlorophenyl)pyridinium Azole, 3,5-dimethyl-1-hydroxymethylpyrazole, pyrazole-3-carboxylic acid, pyrazole-4-carboxylic acid, and the like.

The oxazole compound is preferably: oxazole, 2,4-dimethyloxazole, 4-phenyloxazole, 5-phenyloxazole, 2,4-diphenyloxazole, 2,5-di Phenyloxazole, 2,4,5-trimethyloxazole, 5-[3-(trifluoromethyl)phenyl]oxazole, 2-methyl-4,5-diphenyloxazole, 5 Ethoxy-4-methyloxazole, 4-oxazolecarboxylic acid, ethyl 4-oxazolecarboxylic acid, and the like.

The isoxazole-based compound is preferably: isoxazole, 5-methylisoxazole, 3,5-dimethylisoxazole, 4-bromo-3,5-dimethylisoxazole, 3-chloro Methyl-5-methylisoxazole, 4-(chloromethyl)-3,5-dimethylisoxazole, 4-iodo-3,5-dimethylisoxazole, 3-hydroxy-5 -methylisoxazole, 5-methyl-3-isoxazolcarboxylic acid, 5-methylisoxazole-4carboxylic acid, and the like.

The thiazole compound is preferably: thiazole, 2-methylthiazole, 2-ethylthiazole, 2-n-propylthiazole, 2-isopropylthiazole, 2-n-butylthiazole, 2-isobutylthiazole, 2 -phenylthiazole, 4-methylthiazole, 5-methylthiazole, 2,4-dimethylthiazole, 4,5-dimethylthiazole, 2-ethyl-4-methylthiazole, 2-ethyl -4,5-dimethylthiazole, 2-isopropyl-4-methylthiazole, 2-isobutyl-4-methylthiazole, 4-methyl-2-phenylthiazole, 4-methyl- 5-vinylthiazole, 2-isobutyl-4,5-dimethylthiazole, 2-methyl-4,5-diphenylthiazole, 2,4,5-trimethylthiazole, 2-(ortho Tolyl)benzothiazole, 2-(trimethyldecyl)thiazole, 2-bromothiazole, 4-bromothiazole, 5-bromothiazole, 2-bromo-4-methylthiazole, 4-tert-butyl- 2-methylthiazole, 2-second butylthiazole, 2,4-dibromothiazole, 2,5-dibromothiazole, 2,4-dichlorothiazole, 4,5-dimethyl-2-ethyl Thiazole, 4,5-dimethyl-2-isopropylthiazole, 2-ethenylthiazole, 2-ethylindolyl-4,5-dimethylthiazole, etc., 2-ethoxythiazole, 5-hydroxyl Methylthiazole, 2-hydroxy-4-phenylthiazole, 2-methoxythiazole.

The isothiazole compound is preferably isothiazole.

The triazole-based compound is preferably 1,2,3-triazole, 1,2,4-triazole, 3-methyl-1H-1,2,4-triazole or the like.

The oxadiazole-based compound is preferably: 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,5-oxadiazole, 2 -Chloromethyl-5-(4-methylphenyl)-1,3,4-oxadiazole, 3-(chloromethyl)-1,2,4-oxadiazole, 3-(chloromethyl) )-5-phenyl-1,2,4-oxadiazole, 2,5-diphenyl-1,3,4-oxadiazole, 5-methyl-3-phenyl-1,2,4 -oxadiazole, 2-(2-methoxyphenyl)-5-phenyl-1,3,4-oxadiazole, ethyl-1,2,4-oxadiazole-3-carboxylic acid, etc. .

The thiadiazole-based compound is preferably: 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, 1,2,5-thiadiazole, 2 , 5-dimethyl-1,3,4-thiadiazole, 4-phenyl-1,2,3-thiadiazole, 4,5-diphenyl-1,2,3-thiadiazole, 3-bromo-5-chloro-1,2,4-thiadiazole, 2-bromo-5-phenyl-1,3,4-thiadiazole, 2-chloromethyl-5-cyclopropyl-1 , 3,4-thiadiazole, 3,4-dichloro-1,2,5-thiadiazole, 3,5-dichloro-1,2,4-thiadiazole, and the like.

The 6-membered ring aromatic heterocyclic compound is preferably a pyrimidine compound, a pyridazine compound, a pyrazine compound or a triazine compound.

The pyrimidine compound is preferably pyrimidine, 2-chloropyrimidine, 2-bromopyrimidine, 5-bromopyrimidine, 5-bromo-2-chloropyrimidine, 2-chloro-4-methylpyrimidine or 2-chloro-5-ethyl Pyrimidine, 5-bromo-2,4-dichloropyrimidine, 5-bromo-4,6-dichloropyrimidine, 2-chloro-5-n-decylpyrimidine, 2-chloro-4,6-dimethylpyrimidine , 4-chloro-2,6-dimethylpyrimidine, pyrimidine-5-carboxylic acid, 5-bromo-2-hydroxypyrimidine, 5-bromo-2-methoxypyrimidine, 4,6-dihydroxypyrimidine, 4 , 6-dimethoxypyrimidine, 4-hydroxypyrimidine, 2,4,5-trihydroxypyrimidine, and the like.

The pyridazine-based compound is preferably: 3-methylpyridazine, 4-methylpyridazine, 3,6-dichloropyridazine, 3,6-dichloro-4-methylpyridazine, 3,4,6 - chlorotriazine, pyridazine-4-carboxylic acid, pyridazine-4,5-dicarboxylic acid, 3,6-dihydroxy-4-methylpyridazine, 3-methoxypyridazine, and the like.

The pyrazine-based compound is preferably pyrazine, 2-methylpyrazine, 2-ethylpyrazine, 2-n-propylpyrazine, 2-isopropylpyrazine, 2-isobutylpyrazine, 2 -T-butylpyrazine, 2-vinylpyrazine, 2-chloropyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine , 2,3-diethylpyrazine, 2,3-diphenylpyrazine, 2-methyl-3-n-propylpyrazine, 2-ethyl-3-methylpyrazine, 2-isobutyl 3-methylpyrazine, 5-isobutyl-2,3-dimethylpyrazine, 2,3-diethyl-5-methylpyrazine, 3,5-dimethyl-2- Ethylpyrazine, 2,3,5-trimethylpyrazine, 2,3,5,6-tetramethylpyrazine, 2,3-dimethyl-5-isopropylpyrazine, 2,3 -dichloropyrazine, 2,6-dichloropyrazine, 2-ethylindolyl-3-methylpyrazine, 2-methoxypyrazine, 2-ethoxypyrazine, 2-ethoxy- 3-methylpyrazine, 2-ethyl-3-methoxypyrazine, 2-isopropyl-3-methoxypyrazine, 2-isobutyl-3-methoxypyrazine, 2- Ethylpyrazine, 2-ethenyl-3-ethylpyrazine, pyrazinecarboxylic acid, pyrazine-2-carboxylic acid methyl ester, and the like.

The triazine-based compound is preferably: 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, 2,4,6-trichloro-1,3,5- Triazine, 2,4,6-triphenyl-1,3,5-triazine, 2,4,6-tris(trifluoromethyl)-1,3,5-triazine, etc., 2,4- Dimethoxy-1,3,5-triazine.

The polycyclic aromatic heterocyclic compound is preferably a benzimidazole compound, a benzopyrazole compound, a benzoxazole compound, a benzisoxazole compound, a benzothiazole compound, or a benzotriazole. A compound, a benzoxazole-based compound, a benzothiadiazole-based compound, a quinazoline-based compound, a pyridazine-based compound, a phenanthroline-based compound, or a bipyridine-based compound.

Specific examples of the benzimidazole-based compound are preferably benzimidazole, 4-methylbenzimidazole, 5-methylbenzimidazole, 6-methylbenzimidazole, 7-methylbenzimidazole, 4- Ethylbenzimidazole, 5-ethylbenzimidazole, 6-ethylbenzimidazole, 7-ethylbenzimidazole, 4-n-propylbenzimidazole, 5-n-propylbenzimidazole, 6- N-propylbenzimidazole, 7-n-propylbenzimidazole, 4-isopropylbenzimidazole, 5-isopropylbenzimidazole, 6-isopropylbenzimidazole, 7-isopropylbenzo Imidazole, 1-butylbenzimidazole, 2-ethylmercaptobenzimidazole, 2-chlorobenzimidazole, 2-(chloromethyl)benzimidazole, 2,5-dimethylbenzimidazole, 5- Benzimidazolecarboxylic acid, 2-hydroxybenzimidazole, 2-(hydroxymethyl)benzimidazole, 2-(3-hydroxypropyl)benzimidazole, 2-(1-hydroxyethyl)benzimidazole, 5-benzimidazolecarboxylic acid, 2-hydroxybenzimidazole, and the like.

Specific examples of the benzopyrazole compound are preferably 1,2-benzopyrazole, 3-chloro-1H-benzopyrazole and the like.

Specific examples of the benzoxazole-based compound are preferably: benzoxazole, 2-methylbenzoxazole, 5-methylbenzoxazole, 2,6-dichlorobenzoxazole, 2,5 - dimethyl benzoxazole, 5-fluoro-2-methylbenzoxazole, 2,5,6-trimethylbenzoxazole, 2-chlorobenzoxazole, 2-methyl-5 -Phenylbenzoxazole, 2-(2-hydroxyphenyl)benzoxazole, and the like.

Specific examples of the benzoisoxazole-based compound are preferably 1,2-benzisoxazole, 1,2-benzisoxazole-3-acetic acid or the like.

Specific examples of the benzothiazole-based compound are preferably: benzothiazole, 2-methylbenzothiazole, 2-ethylbenzothiazole, 2-n-propylbenzothiazole, 2-isopropylbenzothiazole, 2-n-butylbenzothiazole, 2-phenylbenzothiazole, 2,5-dimethylbenzothiazole, 2,6-dimethylbenzothiazole, 2,5,6-trimethylbenzo Thiazole, 2-chlorobenzothiazole, 2- Chloro-5-chloromethylthiazole, 6-bromo-2-chlorobenzothiazole, 5-bromo-2-methylbenzothiazole, 2,6-dichlorobenzothiazole, 2-fluorobenzothiazole, 5 -Chloro-2-methylbenzothiazole, 5-fluoro-2-methylbenzothiazole, 2-(4-bromophenyl)benzothiazole, 2-ethylmercaptobenzothiazole, 2-hydroxybenzo Thiazole, 5-methoxy-2-methylbenzothiazole, 2-(2-hydroxyphenyl)benzothiazole, benzothiazole-6-carboxylic acid, and the like.

The benzotriazole-based compound is preferably: 1,2,3-benzotriazole, 4-methylbenzotriazole, 1-chlorobenzotriazole, 5-chlorobenzotriazole, 1-methyl -1H-benzotriazole, 2-methyl-2H-benzotriazole, 5-methyl-1H-benzotriazole, 1-(chloromethyl)-1H-benzotriazole, 4-hydroxyl Benzotriazole, 1-(methoxymethyl)-1H-benzotriazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 1H-benzotriazole-1- Methanol, methyl 1,2,3-benzotriazole-5-carboxylate, methyl 1,2,4-benzotriazole-3-carboxylate, 4-methyl-2-phenyl-1, 2,3-triazole-5-carboxylic acid, 1-isopropylbenzotriazole-5-carboxylic acid, 1-aminobenzotriazole, and the like.

The benzoxoxadiazole-based compound is preferably: 2,1,3-benzoxoxadiazole, 4-fluoro-2,1,3-benzoxoxadiazole, 4-chloro-2,1,3-benzene And oxadiazole and so on.

The benzothiadiazole-based compound is preferably: 2,1,3-benzothiadiazole, 4,7-dibromo-2,1,3-benzothiadiazole, 5,6-dibromo-2 , 1,3-benzothiadiazole, 2,1,3-benzothiadiazole-5-carboxylic acid, 2-mercaptobenzothiazole, 6-amino-2-mercaptobenzothiazole, and the like.

The quinazoline compound is preferably quinazoline, 4-chloroquinazoline, 2,4-dichloroquinazoline, 4-hydroxyquinazoline or 5-fluoro-4-hydroxyquinazoline.

The pyridazine-based compound is preferably azine, 6-methylpyridazine, 1-chloropyridazine, 1,4-dichloropyridazine or the like.

The morpholino compound is preferably: 1,10-morpholine, 5-methyl-1,10-morpholine, 2-chloro-1,10-morpholine, 5-chloro-1,10-morpholine, 3,8-dimethyl-1,10-morpholine, 4,7-dimethyl-1,10-morphine Porphyrin, 5,6-dimethyl-1,10-morpholine, 2,9-dibutyl-1,10-morpholine, 4,7-diphenyl-1,10-morpholine, 4,7 -dichloro-1,10-morpholine, 3-bromo-1,10-morpholine, 3,4,7,8-tetramethyl-1,10-morpholine, 4,7-dihydroxy-1, 10-phenoline, 1,10-morpholine-2,9-dicarboxylic acid, and the like.

The bipyridine-based compound is preferably: 2,2'-bipyridine, 2,4'-bipyridine, 4,4'-bipyridine, 5-phenyl-2,2'-bipyridine, 5-phenyl- 2,3'-bipyridyl, 5-phenyl-2,4'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 5,5'-dimethyl-2,2 '-Bipyridine, 6,6'-dimethyl-2,2'-bipyridine, 4,4'-dimercapto-2,2'-bipyridine, 4,4'-dibromo-2,2 '-Bipyridyl, 6,6'-dibromo-2,2'-bipyridine, 4,4'-bis(chloromethyl)-2,2'-bipyridine, 5,5'-dichloro-2 , 2'-bipyridyl, 5-bromo-2,2'-bipyridine, 5-bromo-2,3'-bipyridine, 5-bromo-2,4'-bipyridine, 6-bromo-2,2 '-Bipyridyl, 4,4'-bis(hydroxymethyl)-2,2'-bipyridine, 2,2'-bipyridyl-3,3'-dicarboxylic acid, 2,2'-bipyridine- 4,4'-dicarboxylic acid, 2,2'-bipyridyl-5,5'-dicarboxylic acid, and the like.

Among these compounds, the aromatic heterocyclic compound is preferably: oxazole, 2,4,5-trimethyloxazole, isoxazole, 5-methylisoxazole, thiazole, 5-methylthiazole, or different Thiazole, 1,2,3-triazole, 1,2,4-triazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,5-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, 1,2,5-thiadiazole, Pyrimidine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, 1,2-benzopyrazole, benzoxazole, 5-methylbenzone Oxazole, 1,2-benzisoxazole, benzothiazole, 2,6-dimethylbenzothiazole, 2,1,3-benzoxoxadiazole, 2,1,3-benzothiadiazole 1,2,3-benzotriazole, quinazoline, pyridazine, 1,10-morpholine, 5-methyl-1,10-morpholine, 2,2'-bipyridine, 4,4' -bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 2-mercaptobenzothiazole, 1-aminobenzotriazole, 6-amino-2-mercaptobenzothiazole, Good for: 1,2,3-triazole, 1,2,4- Triazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,5-oxadiazole, 1,2,3-thiazide Diazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, 1,2,5-thiadiazole, pyrimidine, 1,2,3-triazine, 1,2,4- Triazine, 1,3,5-triazine, 1,2-benzopyrazole, 2,1,3-benzoxoxadiazole, 2,1,3-benzothiadiazole, 1,2,3 -benzotriazole, quinazoline, pyridazine, 1,10-morpholine, 5-methyl-1,10-morpholine, 2,2'-bipyridine, 4,4'-bipyridine, 5, 5'-Dimethyl-2,2'-bipyridine.

The amount of the aromatic heterocyclic compound added to the photosensitive resin composition of the present invention is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.01 parts by mass, based on 100 parts by mass of all the solid components of the photosensitive resin composition. ~8 parts by mass, particularly preferably 0.01 parts by mass to 5 parts by mass.

<(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 by dissolving the essential component of the present invention and further optional components described below in (D) a solvent.

The solvent (D) used in the photosensitive resin composition of the present invention may be a known solvent, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, and ethylene glycol monoalkyl ether acetate. Esters, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol Monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, guanamines, lactones, and the like. In addition, as a specific example of the solvent (D) used in the photosensitive resin composition of the present invention, paragraph number 0174 to paragraph of JP-A-2011-221494 can be cited. The solvent described in the number 0178 is incorporated into the specification of the present application.

In addition, if necessary, it may be further added to the solvents: benzyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophor Ketone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, carbonic acid A solvent such as ethylene glycol or propylene carbonate. These solvents may be used alone or in combination of two or more. The solvent which can be used in the present invention is preferably used singly or in combination of two or more, more preferably two kinds, and particularly preferably propylene glycol monoalkyl ether acetate or dialkyl ether or diacetate. It is used in combination with diethylene glycol dialkyl ethers or esters and butanediol alkyl ether acetate.

Further, the component D is preferably a solvent having a boiling point of 130 ° C or more and less than 160 ° C, a solvent having a boiling point of 160 ° C or higher, or a mixture of these solvents.

The solvent having a boiling point of 130 ° C or more and less than 160 ° C can be exemplified by 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 methyl-n-propyl ether (boiling point 131 ° C).

The solvent having a boiling point of 160 ° C or higher can be exemplified by ethyl 3-ethoxypropionate (boiling point: 170 ° C), diethylene glycol methyl ether (boiling point: 176 ° C), and 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), two Diol 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-butanediol diacetate (boiling point 232 ° C).

The content of the solvent (D) in the photosensitive resin composition of the present invention is preferably 50 parts by mass to 95 parts by mass, particularly preferably 60 parts by mass, based on 100 parts by mass of all the resin components in the photosensitive resin composition. 90 parts by mass.

<Other ingredients>

In addition to the above components, the photosensitive resin composition of the present invention may preferably contain (E) an alkoxydecane compound, (F) a crosslinking agent, (G) a sensitizer, and (H) a basic compound. (I) surfactant, (J) antioxidant. Further, an acid proliferating agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a tackifier, and an organic or inorganic precipitate may be added to the photosensitive resin composition of the present invention. A known additive such as a preventive agent.

(E) alkoxydecane compound

The photosensitive resin composition of the present invention is characterized by containing (E) an alkoxydecane compound (also referred to as "(E) component"). When an alkoxy decane compound is used, the adhesiveness of the film formed from the photosensitive resin composition of this invention and a board|substrate can be improved, or the film of the photosensitive resin composition of this invention can be adjusted. The alkoxydecane compound is preferably a dialkoxy decane compound or a trialkoxy decane compound, more preferably a trialkoxy decane compound. The alkoxy group of the alkoxydecane compound preferably has 1 to 5 carbon atoms.

The (E) alkoxydecane compound which can be used in the photosensitive resin composition of the present invention is preferably an inorganic substance which is a base material, for example, an antimony compound such as cerium, cerium oxide or cerium nitride, which improves gold, copper, molybdenum, and the like. Adhesion of metal such as titanium and aluminum to insulating film compound of. Specifically, a known decane coupling agent or the like is also effective.

Examples of the decane coupling agent include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-glycidoxypropyltrialkoxydecane, and γ-glycidyloxy group. Propyl alkyl dialkoxy decane, γ-methyl propylene methoxy propyl trialkoxy decane, γ-methyl propylene methoxy propyl alkyl dialkoxy decane, γ-chloropropyl three Alkoxydecane, γ-mercaptopropyltrialkoxydecane, β-(3,4-epoxycyclohexyl)ethyltrialkoxydecane, vinyltrialkoxydecane. More preferably, these compounds are γ-glycidoxypropyltrialkoxydecane or γ-methacryloxypropyltrialkoxydecane, and particularly preferably γ-glycidoxypropyl III. The alkoxydecane is especially preferably 3-glycidoxypropyltrimethoxydecane. These compounds may be used alone or in combination of two or more.

Further, the following compounds can also be preferably used.

In the above, Ph is a phenyl group.

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

The content of the (E) alkoxydecane compound in the photosensitive resin composition of the present invention is preferably from 0.1 part by mass to 30 parts by mass, more preferably 0.5, based on 100 parts by mass of all the solid components in the photosensitive composition. Parts by mass to 20 parts by mass.

(F) crosslinker

The photosensitive resin composition of the present invention preferably contains a crosslinking agent as needed. The cured film obtained from the photosensitive resin composition of the present invention can form a stronger film by adding a crosslinking agent.

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

The amount of the crosslinking agent added to the photosensitive resin composition of the present invention is preferably from 0.01 part by mass to 50 parts by mass, more preferably from 0.1 part by mass to 30 parts by mass per 100 parts by mass of all the solid components of the photosensitive resin composition. The mass part is preferably from 0.5 part by mass to 20 parts by mass. By adding in this range, a cured film excellent in mechanical strength and solvent resistance is obtained. A plurality of crosslinking agents may be used in combination, and in this case, the total amount of the crosslinking agents is totaled to calculate the content.

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

Specific examples of the compound having two or more epoxy groups in the molecule include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, and a cresol novolak type epoxy resin. Aliphatic epoxy resin, etc.

These compounds are available as commercial products. For example, a commercial item such as JER157S70 and JER157S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), paragraph number 0189 of JP-A-2011-221494.

Other than this, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (above manufactured by ADEKA), NC-2000, NC -3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above manufactured by Eddy Co.), Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-614B, Denacol EX-622, Denacol EX-512, Denacol EX-521, Denacol EX-411, Denacol EX-421, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-211, Denacol EX-212, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931, Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L, Denacol EX-850L, Denacol DLC-201, Denacol DLC-203, Denacol DLC-204, Denacol DLC-205, Denacol DLC-206, Denacol DLC-301, Denacol DLC-402 (above manufactured by Nagase ChemteX), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above by New Day) Iron Chemical Manufacturing), Celloxide 2021P, Celloxide 2081, Celloxide 3000, Celloxide EHPE 3150, Epolead GT400, Celvenus B0134, Celvenus B0177 (Daicel).

These commercially available products may be used alone or in combination of two or more.

Among these compounds, more preferred are: bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, and aliphatic epoxy or aliphatic epoxy resin, particularly preferably Phenolic A type epoxy resin.

Specific examples of the compound having two or more oxetanyl groups in the molecule can be used: Aron Oxetane OXT-121, Aron Oxetane OXT-221, Aron Oxetane OX-SQ, Aron Oxetane PNOX (above manufactured by East Asia Synthetic Co., Ltd.) .

Further, the compound containing an oxetanyl group is preferably used singly or in combination with a compound containing an epoxy group.

Further, the other crosslinking agent may preferably be an alkoxymethyl group-containing crosslinking agent described in Paragraph No. 0107 to Paragraph No. 0108 of JP-A-2012-8223, and having at least one ethylenic property. Compounds of unsaturated double bonds, etc., are incorporated herein by reference. The alkoxymethyl group-containing crosslinking agent is preferably an alkoxymethylated glycoluril.

<Block isocyanate compound>

In the photosensitive resin composition of the present invention, a blocked isocyanate compound can also be preferably used as the crosslinking agent. Block isocyanate compounds as long as they have embedded The compound of the isocyanate group is not particularly limited, and from the viewpoint of curability, a compound having two or more blocked isocyanate groups in one molecule is preferred.

In addition, the block isocyanate group in the present invention means a group which can form an isocyanate group by heat, and for example, a group which reacts with an isocyanate group to protect an isocyanate group is preferably exemplified. Further, the blocked isocyanate group is preferably a group capable of forming an isocyanate group by heat of from 90 ° C to 250 ° C.

Further, the blocked isocyanate compound is not particularly limited as long as it has two isocyanate groups in one molecule, and is preferably an aliphatic, alicyclic or aromatic polyisocyanate, and is suitable, for example. Use: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4- Tetramethylidene 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, Meta-xylene diisocyanate, p-xylene diisocyanate, methylene bis(cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene Isocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methylene xylene-4,4'-diisocyanate, 4,4'-diphenyl Isocyanate compounds such as diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, hydrogenated 1,3-benzyldimethylisocyanate, hydrogenated 1,4-benzyldimethylisocyanate, and derivatives derived therefrom A compound of a prepolymer type skeleton. Among these compounds, particularly preferred is tolylene diisocyanate (tolylene) Diisocyanate, TDI) or diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI).

The parent structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention may be a biuret type, an isocyanurate type, an adduct type or a bifunctional type. Polymer type, etc.

Examples of the block forming the block structure of the above-mentioned blocked isocyanate compound include an anthracene compound, an indoleamine compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a thiol compound, and an imidazole system. a compound, a quinone imine compound, or the like. Among these compounds, a block agent selected from the group consisting of an anthracene compound, an indoleamine compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound is particularly preferred.

Examples of the above hydrazine compound include hydrazine and ketoxime, and specific examples thereof include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketoxime, cyclohexanone oxime, and benzophenone.肟, acetone oxime, etc.

The above-mentioned indoleamine compound can be exemplified by ε-caprolactam, γ-butylide or the like.

The phenol compound may, for example, be phenol, naphthol, cresol, xylenol or halogen-substituted phenol.

The alcohol compound may, for example, be methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether or alkyl lactate.

Examples of the amine compound include a primary amine and a secondary amine, and may also be Any of an aromatic amine, an aliphatic amine, and an alicyclic amine may, for example, be aniline, diphenylamine, ethylenimine or polyethylenimine.

The active methylene compound may, for example, be diethyl malonate, dimethyl malonate, ethyl acetate or ethyl acetate.

The above pyrazole compound can be exemplified by pyrazole, methylpyrazole, dimethylpyrazole and the like.

The above thiol compound can be exemplified by an alkylthiol, an arylthiol or the like.

The blocked isocyanate compound which can be used in the photosensitive resin composition of the present invention can be obtained as a commercial product, and for example, Coronate AP Stable M, Coronate 2503, Coronate 2515, Coronate 2507, Coronate 2513, Coronate 2555 can be preferably used. , Millionate MS-50 (above made by Nippon Polyurethane Industry), Takenate B-830, Takenate B-815N, Takenate B-820NSU, Takenate B-842N, Takenate B- 846N, Takenate B-870N, Takenate B-874N, Takenate B-882N (above manufactured by Mitsui Chemicals Co., Ltd.), Duranate 17B-60PX, Duranate 17B-60P, Duranate TPA-B80X, Duranate TPA-B80E, Duranate MF- B60X, Duranate MF-B60B, Duranate MF-K60X, Duranate MF-K60B, Duranate E402-B80B, Duranate SBN-70D, Duranate SBB-70P, Duranate K6000 (above manufactured by Asahi Kasei Chemicals Co., Ltd.), Desmodur BL1100, Desmodur BL1265 MPA/X, Desmodur BL3575/1, Desmodur BL3272MPA, Desmodur BL3370MPA, Desmodur BL3475BA/SN, Desmodur BL5375MPA, Desmodur VPLS2078/2, Desmodur BL4265SN, Desmodur PL340, Desmodur PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane).

(G) sensitizer

In combination with the (B) photoacid generator, the photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote decomposition thereof. The sensitizer absorbs actinic rays or radiation and becomes an electronically excited state. The sensitizer that is in an electronically excited state is brought into contact with the photoacid generator to cause electron transfer, energy transfer, heat generation, and the like. Thereby, the photoacid generator generates a chemical change to decompose and generate an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength at any wavelength in the wavelength region of 350 nm to 450 nm.

Polynuclear aromatics (eg, pyrene, perylene, extended triphenyl, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxy Base, 9,10-dipropoxypurine, xanthene (eg fluorescein, eosin, erythrosine, rose B) Rhodamine B), rose bengal, xanthone (eg xanthonesone, thioxanthone, dimethylthiazolone, dithionone) ), cyanine (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (eg, merocyanine, carbocyanine (carbomerocyanine) )), rhodacyanine, oxonol, thiazine (eg, thionine, methylene blue) Blue), toluidine blue, acridine (eg acridine orange, chloroflavin, acriflavine), acridone (acridone) ) (eg, acridone, 10-butyl-2-chloroacridone, 10-butylacridone), anthraquinone (eg, hydrazine), squaric acid ylide ( For example: squaric acid ylide, styrenic, basic styryl (eg 2-[2-[4-(dimethylamino)phenyl]vinyl]benzoxazole), Coumarins (eg 7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl -1H, 5H, 11H[1]benzopyrano[6,7,8-ij]quinolizin-11-one).

Among these sensitizers, polynuclear aromatics, acridones, styrenes, basic styrenes, and coumarins are preferred, and polynuclear aromatics are more preferred. Among the polynuclear aromatics, the most preferred is an anthracene derivative.

The amount of the sensitizer added to the photosensitive resin composition of the present invention is preferably from 0 part by mass to 1000 parts by mass, more preferably 10 parts by mass, based on 100 parts by mass of the photoacid generator of the photosensitive resin composition. 500 parts by mass, particularly preferably 50 parts by mass to 200 parts by mass.

Two or more types may be used in combination.

(H) basic compound

The photosensitive resin composition of the present invention may contain (H) a basic compound. (H) The basic compound can be arbitrarily selected from the users of the chemical amplification resist. For example, an aliphatic amine, an aromatic amine, a heterocyclic amine, a quaternary ammonium hydroxide, a quaternary ammonium salt of a carboxylic acid, etc. are mentioned. Specific examples of these compounds include Japanese patents. The compound described in Paragraph No. 0204 to Paragraph No. 0207 of JP-A-2011-221494 is hereby incorporated by reference. Further, thioureas such as N-cyclohexyl-N'-[2-(4-morpholinyl)ethyl]thiourea can also be used.

The basic compound which can be used in the present invention may be used alone or in combination of two or more.

In the case where the other basic compound is contained, the content of the (H) other basic compound in the photosensitive resin composition of the present invention is preferably 0.001 by mass based on 100 parts by mass of all the solid components in the photosensitive resin composition. It is preferably 3 parts by mass, more preferably 0.005 parts by mass to 1 part by mass.

(I) surfactant

The photosensitive resin composition of the present invention may contain (I) a surfactant. (I) The surfactant may be any of an anionic, cationic, nonionic or amphoteric surfactant, and a preferred surfactant is a nonionic surfactant.

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, anthrone series, and fluorine interface. Active agent. In addition, the following product names are listed: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), Eftop (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Megafac (DIC ) (manufacturing), Fluorad (manufactured by Sumitomo 3M), Asahi Guard, Surflon (made by Asahi Glass), PoIyFox (made by OMNOVA), SH-8400 (Toray Dow Corning) (Toray Dow Corning Silicone)) and other series.

Further, the surfactant is exemplified as a copolymer comprising the structural unit A represented by the following formula (I-1) and the structural unit B, and using tetrahydrofuran (THF) as a solvent. The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography in the case of the measurement is 1,000 or more and 10,000 or less.

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

The above L is preferably a branched alkyl group represented by the following formula (I-2). R ⁴⁰⁵ in the formula (I-2) represents an alkyl group having 1 or more and 4 or less carbon atoms, and preferably has a carbon number of 1 or more in terms of compatibility and wettability to a surface to be coated. An alkyl group of 3 or less is more preferably an alkyl group having 2 or 3 carbon atoms. The sum of p and q (p + q) is preferably p + q = 100, that is, 100% by mass.

The weight average molecular weight (Mw) of the above copolymer is more preferably 1,500 or more and 5,000 or less.

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

The amount of the (I) surfactant added to the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, more preferably 0.001 parts by mass, based on 100 parts by mass of all the solid components in the photosensitive resin composition. 10 parts by mass, particularly preferably 0.01 parts by mass to 3 parts by mass.

(J) Antioxidants

The photosensitive resin composition of the present invention may contain an antioxidant. As the antioxidant, a known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or reduction in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.

Examples of such an antioxidant include phosphorus-based antioxidants, guanamines, guanidines, hindered amine-based antioxidants, sulfur-based antioxidants, phenolic antioxidants, ascorbic acid, zinc sulfate, saccharides, nitrites, and sub- Sulfate, thiosulfate, hydroxy Alkylamine derivatives and the like. Among these compounds, a phenolic antioxidant, a guanamine antioxidant, a lanthanoid antioxidant, and a sulfur-based antioxidant are particularly preferable from the viewpoint of coloring and film thickness reduction of the cured film. These compounds may be used alone or in combination of two or more.

Commercial products of phenolic antioxidants include, for example, Adekastab AO-15, Adekastab AO-18, Adekastab AO-20, Adekastab AO-23, Adekastab AO-30, Adekastab AO-37, Adekastab AO-40, Adekastab AO- 50. Adekastab AO-51, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-330, Adekastab AO-412S, Adekastab AO-503, Adekastab A-611, Adekastab A-612, Adekastab A- 613, Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-8W, Adekastab PEP-24G, Adekastab PEP-36, Adekastab PEP-36Z, Adekastab HP-10, Adekastab 2112, Adekastab 260, Adekastab 522A, Adekastab 1178, Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010, Adekastab TPP, Adekastab CDA-1, Adekastab CDA-6, Adekastab ZS-27, Adekastab ZS-90, Adekastab ZS-91 (above manufactured by Eddy Co.) 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 (Manufactured by BASF) . Among them, Adekastab AO-60, Adekastab AO-80, Irganox 1726, Irganox 1035, Irganox 1098 can be suitably used.

The content of the antioxidant is preferably from 0.1% by mass to 10% by mass, more preferably from 0.2% by mass to 5% by mass, even more preferably from 0.5% by mass to 4% by mass based on the total solid content of the photosensitive resin composition. By setting it as this range, the transparency of the formed film is acquired, and the sensitivity at the time of pattern formation also becomes favorable.

In addition, as the additive other than the antioxidant, various ultraviolet absorbers, metal passivators, and the like described in "New Development of Polymer Additives" (Nikkei Kogyo Co., Ltd.) may be added to the photosensitive resin of the present invention. In the composition.

[acid proliferator]

The photosensitive resin composition of the present invention can use an acid multiplier for the purpose of improving sensitivity.

The acid multiplying agent which can be used in the present invention is a compound which can further generate an acid by an acid catalyst reaction and raise the acid concentration in the reaction system, and is a compound which is stably present in the absence of an acid. Since such a compound is increased by one or more acids by one reaction, the reaction proceeds with the progress of the reaction, but since the generated acid itself causes self-decomposition, the strength of the acid generated here is dissociated by acid. The constant and pKa are preferably 3 or less, and particularly preferably 2 or less.

Specific examples of the acid-proliferating agent include paragraph number 0203 to paragraph number 0223 of JP-A-10-1508, paragraph number 0016 to paragraph number 0055 of Japanese Patent Laid-Open No. Hei 10-282642, and Japanese Patent Special Table. The compounds described in Japanese Patent Publication No. Hei 9-512498, page 39, line 12 to page 47, line 2, are incorporated herein by reference.

The acid proliferator which can be used in the present invention can be exemplified by the use of an acid generator. The acid is decomposed by the acid to produce a compound having an acid having a pKa of 3 or less such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid or phenylphosphonic acid.

Specifically, it can be enumerated:

Wait.

The content of the acid-proliferating agent in the photosensitive composition is preferably from 10 parts by mass to 1,000 parts by mass, based on 100 parts by mass of the photo-acid generator, from the viewpoint of the dissolution ratio of the exposed portion and the unexposed portion. The optimum is set to 20 parts by mass to 500 parts by mass.

[development accelerator]

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

The development accelerator can be referred to the description of Paragraph No. 0171 to Paragraph No. 0172 of Japanese Patent Laid-Open No. 2012-042837, which is incorporated herein by reference.

One type of the development accelerator may be used alone or two or more types may be used in combination.

From the viewpoint of the sensitivity and the residual film ratio, the amount of the development accelerator added to the photosensitive resin composition of the present invention is preferably from 0 to 30 mass% per 100 parts by mass of all the solid components of the photosensitive composition. More preferably, it is 0.1 parts by mass~ 20 parts by mass, preferably 0.5 parts by mass to 10 parts by mass.

In addition, as the other additive, the thermal radical generating agent described in Paragraph No. 0120 to Paragraph No. 0121 of JP-A-2012-8223, the nitrogen-containing compound described in WO2011/136074A1, and a thermal acid generator may be used. The content is incorporated into the specification of the present application.

<Method for Preparing Photosensitive Resin Composition>

The components are mixed at a predetermined ratio and by any method, and stirred and dissolved to prepare a photosensitive resin composition. For example, after the components are each dissolved in a solvent to prepare a solution, the solutions are mixed at a predetermined ratio to prepare a resin composition. The composition solution prepared in the above manner can also 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, a method of producing the cured film of the present invention will be described.

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

(1) a step of applying the photosensitive resin composition of the present invention onto a substrate; (2) a step of removing a solvent from the applied photosensitive resin composition; and (3) removing a solvent by an actinic ray pair a step of exposing the photosensitive resin composition; (4) a step of developing the exposed photosensitive resin composition with an aqueous developing solution; (5) post-baking for thermally curing the developed photosensitive resin composition Baking step Step.

Each step will be described in order below.

In the coating step of (1), it is preferred to apply the photosensitive resin composition of the present invention onto a substrate to form a wet film containing a solvent. It is preferred to perform cleaning of the substrate such as alkali cleaning or plasma cleaning before applying the photosensitive resin composition onto the substrate, and it is more preferable to treat the surface of the substrate with hexamethyldiaziridine after the substrate is cleaned. By performing this treatment, the adhesion of the photosensitive resin composition to the substrate tends to be improved. The method of treating the surface of the substrate with hexamethyldioxane is not particularly limited, and examples thereof include a method of exposing the substrate to hexamethyldioxane vapor in advance.

Examples of the substrate include an inorganic substrate, a resin, a resin composite material, and the like.

Examples of the inorganic substrate include glass, quartz, anthrone, and tantalum nitride, and a composite substrate obtained by depositing molybdenum, titanium, aluminum, copper, or the like on the substrate as described above.

Examples of the resin include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, and polyfluorene. , polyether oxime, polyarylate, allyl diol carbonate, polyamine, polyimine, polyamidimide, polyether phthalimide, polybenzazole, polyphenyl sulphide Ether, polycycloolefin, norbornene resin, fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, fluorenone resin, ionic polymer resin, cyanate resin, crosslinked butene A synthetic resin such as a diacid diester, a cyclic polyolefin, an aromatic ether, a maleimide-olefin, a cellulose, or an episulfide compound.

These substrates are rarely used as they are in the above-described form, and a multilayer laminated structure such as a thin film transistor (TFT) element is usually formed by the form of the final product.

The method of applying 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 cast coating method, a slit, and a spin method (slit-and- Spin method) and other methods. Further, a so-called pre-wet method described in Japanese Laid-Open Patent Publication No. 2009-145395 can also be applied.

The wet film thickness at the time of application is not particularly limited, and it can be applied in accordance with the film thickness of the application, and is usually used in the range of 0.5 μm to 10 μm.

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

In the exposure step of (3), the substrate on which the coating film is provided is irradiated with actinic rays through a mask having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. The acid-decomposable group contained in the coating film component is hydrolyzed by the catalytic action of the generated acid to form a carboxyl group or a phenolic hydroxyl group.

The exposure light source by actinic ray can be used: a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generating device, etc., which can be preferably used. G-ray (436 nm), i-ray (365 nm), h-ray (405 nm), etc. have a wavelength of 300 nm An actinic ray at a wavelength of 450 nm or less. Further, the illumination light may be adjusted by a long-wavelength cut filter, a short-wavelength cut filter, or a band pass filter such as a band pass filter as needed.

The exposure device can be used: a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, Various types of exposure machines such as laser exposure.

In the region where the acid catalyst is formed, in order to accelerate the hydrolysis reaction, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as "PEB") may be performed. By PEB, it is possible to promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature in the case of 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.

In particular, the acid-decomposable group in the present invention has a low activation energy due to acid decomposition, and is easily decomposed by an acid derived from an acid generator generated by exposure to produce a carboxyl group or a phenolic hydroxyl group, so that it is not necessary to carry out PEB. A positive image is formed by development.

In the developing step of (4), a polymer having a free carboxyl group or a phenolic hydroxyl group is developed using an alkaline developing solution. A positive image is formed by removing an exposed portion region containing a resin composition having a carboxyl group or a phenolic hydroxyl group which is easily dissolved in an alkaline developing solution.

The developer used in the developing step preferably contains a basic compound. For the basic compound, for example, an alkali metal such as lithium hydroxide, sodium hydroxide or potassium hydroxide can be used. Hydroxides; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogencarbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate; tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline hydroxide Ammonium hydroxides such as choline hydroxide; aqueous solutions such as sodium citrate and sodium metasilicate. Further, an aqueous solution of an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous solution of the above-mentioned alkali as a developing solution.

A preferred developing solution is a 0.4% aqueous solution of tetraethylammonium hydroxide, a 0.5% aqueous solution, a 0.7% aqueous solution, and a 2.38% aqueous solution.

The pH of the developer is preferably from 10.0 to 14.0.

The development time is preferably from 30 seconds to 500 seconds, and the development method may be any one of a puddle method and a dipping method. After development, it is usually carried out by running water for 30 seconds to 300 seconds to form a desired pattern.

After development, a rinsing step can also be performed. In the rinsing step, the developed substrate is cleaned by pure water or the like, and the adhered developer is removed and the development residue is removed. A known method can be used for the rinsing method. For example, spray rinsing, immersion rinsing, etc. are mentioned.

In the post-baking step of (5), the acid-decomposable group is thermally decomposed by heating the obtained positive image to form a carboxyl group or a phenolic hydroxyl group, and cross-linking with a crosslinkable group, a crosslinking agent, or the like. Thereby, a cured film can be formed. Preferably, the heating is performed by a heating means such as a hot plate or an oven at a predetermined temperature, for example, 180 ° C to 250 ° C, for a predetermined period of time, for example, 5 minutes to 90 minutes on a hot plate, if The oven is carried out for 30 minutes to 120 minutes. By doing this cross-linking In response, a more excellent protective film or interlayer insulating film such as heat resistance and hardness can be formed. Further, the transparency can be further improved by performing the heat treatment in a nitrogen atmosphere.

Before baking, it is also possible to perform post-baking after baking at a relatively low temperature (addition of the intermediate baking step). In the case of performing intermediate baking, it is preferred to perform post-baking at a high temperature of 200 ° C or higher after heating at 90 ° C to 150 ° C for 1 minute to 60 minutes. Further, the intermediate baking and the post-baking may be divided into three or more stages to perform heating. The taper angle of the pattern can be adjusted by the intermediate baking and post-baking operations as described above. A known heating method such as a hot plate, an oven, or an infrared heater can be used for the heating.

Further, after performing overall re-exposure (post-exposure) on the patterned substrate by actinic rays before post-baking, post-baking is performed, whereby acid is generated from the photo-acid generator present in the unexposed portion, It functions as a catalyst for promoting the crosslinking step, and promotes the hardening reaction of the film. The preferable exposure amount in the case of including the post-exposure step is preferably from 100 mJ/cm ² to 3,000 mJ/cm ² , particularly preferably from 100 mJ/cm ² to 500 mJ/cm ² .

On the other hand, in the case where the characteristics (transparency, chemical resistance, specific dielectric constant, adhesion to the base substrate, dry etching resistance, etc.) of the cured film are more excellent than the case where the overall re-exposure is performed, The full re-exposure step can also be omitted. Productivity can also be improved by omitting the comprehensive re-exposure step.

Further, the cured film obtained from the photosensitive resin composition of the present invention can also be used as an anti-dry etchant. In the case where the cured film obtained by thermally hardening by the post-baking step is used as an anti-dry etchant, the etching treatment may be performed by ashing, plasma etching, or the like. Dry etching treatment such as ozone etching.

[hardened 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. Further, the cured film of the present invention is preferably a cured film obtained by the method for forming a cured film of the present invention.

According to the photosensitive resin composition of the present invention, an interlayer insulating film which is excellent in insulating properties and has high transparency even when baked at a high temperature is obtained. The interlayer insulating film obtained by using the photosensitive resin composition of the present invention has high transparency and excellent physical properties of the cured film, and thus can be used for an organic EL display device or a liquid crystal display device.

[Liquid Crystal Display Device]

The liquid crystal display device of the present invention is characterized by comprising the cured film of the present invention.

The liquid crystal display device of the present invention is not particularly limited as long as it has a planarizing film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention, and a known liquid crystal display device having various structures can be cited.

Specific examples of the thin film transistor (TFT) included in the liquid crystal display device of the present invention include amorphous germanium-TFT, low-temperature polycrystalline germanium-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.

Further, examples of the liquid crystal driving method that can be employed in the liquid crystal display device of the present invention include a twisted nematic (TN) method, a vertical alignment (VA) method, and an in-plane switching (IPS). Mode, Frings Field Switching (FFS) mode, Optical Compensated Bend (OCB) mode, etc.

In the panel structure, the cured film of the present invention can also be used in a color filter on Allay (COA) type liquid crystal display device, for example, as an organic insulating film of Japanese Laid-Open Patent Publication No. 2005-284291 ( 115) or an organic insulating film (212) of JP-A-2005-346054.

Moreover, the specific alignment of the liquid crystal alignment film which can be taken by the liquid crystal display device of the present invention may be, for example, a rubbing alignment method or a photoalignment method. In addition, the polymer alignment support can be carried out by the Polymer Sustained Alignment (PSA) technique described in JP-A-2003-149647 or JP-A-2011-257734.

Further, the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above applications, and can be used for various purposes. For example, in addition to the planarization film or the interlayer insulating film, a protective film suitable for a color filter or a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device fixed may be provided in the solid-state imaging element. Microlenses and the like on a color filter.

FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel is provided with an element of the TFT 16, and components of the TFT 16 It corresponds to all the pixels disposed between the two glass substrates 14 and 15 to which the polarizing film is attached. On each element formed on the glass substrate, an ITO transparent electrode 19 on which a pixel electrode is formed is wired through a contact hole 18 formed in the cured film 17. A layer of the liquid crystal 20 and a red green blue (RGB) color filter 22 in which a black matrix is disposed are disposed on the ITO transparent electrode 19.

The light source of the backlight is not particularly limited, and a known light source can be used. For example, a multi-color LED such as a white LED, a blue ‧ red ‧ green, a fluorescent lamp (cold cathode tube), an organic EL, or the like can be given.

In addition, the liquid crystal display device can also be made into a three-dimensional (3D) (stereoscopic) type device or a touch panel type device. Further, it can be made into a flexible type, and can be used as the second interphase insulating film (48) of JP-A-2011-145686 or the interphase insulating film (520) of JP-A-2009-258758.

[Organic EL display device]

The organic EL display device of the present invention is characterized by comprising the cured film of the present invention.

The organic EL display device of the present invention is not particularly limited as long as it has a planarizing film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention, and various known organic EL display devices having various structures or Liquid crystal display device.

For example, specific examples of the thin film transistor (TFT) included in the organic EL display device of the present invention include amorphous germanium-TFT and low Warm 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 showing 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, including a planarization film 4.

A bottom gate type TFT 1 is formed on the glass substrate 6 to cover the TFT 1 to form an insulating film 3 containing Si ₃ N ₄ . After the contact hole (not shown) is formed on the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 is formed on the insulating film 3 via the contact hole. The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or in the step described later to the TFT 1.

Further, in order to planarize the unevenness due to the formation of the wiring 2, the planarization layer 4 is formed on the insulating film 3 in a state in which the unevenness caused by the wiring 2 is buried.

A bottom emission type organic EL element is formed on the planarization film 4. That is, on the planarizing film 4, the first electrode 5 including ITO is formed by being connected to the wiring 2 via the contact hole 7. Further, the first electrode 5 corresponds to the anode of the organic EL element.

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

Further, in FIG. 2, a hole transport layer, an organic light-emitting layer, and an electron transport layer are sequentially deposited by vapor deposition through a desired pattern mask, and then a second electrode including Al is formed on the entire upper surface of the substrate. By sealing with a glass plate for sealing by using an ultraviolet curable epoxy resin, it is obtained by connecting to each organic EL element. An active matrix type organic EL display device in which the TFT 1 is driven.

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 microelectromechanical system (MEMS) device is used. It is made into a partition or assembled as part of a mechanically driven part. Examples of such a MEMS element include a surface acoustic wave (SAW) filter, a bulk acoustic wave (BAW) filter, a gyro sensor, and a microshutter for display. , image sensor, electronic paper, inkjet head, biochip, sealant and other parts. More specific examples are exemplified in JP-A-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

The photosensitive resin composition of the present invention is excellent in flatness and transparency, and can be used, for example, in forming a bank layer (16) and planarization described in Fig. 2 of JP-A-2011-107476. The partition (12) and the flattening film (102) described in Fig. 4 (a) of the Japanese Patent Publication No. 2010-9793, and the description of Fig. 10 of Japanese Patent Laid-Open Publication No. 2010-27591 The deposition layer (221) and the third interlayer insulating film (216b), the second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4(a) of JP-A-2009-128577 The flattening film (12) and the pixel separation insulating film (14) described in Fig. 3 of Japanese Laid-Open Patent Publication No. 2010-182638.

Example

The present invention will be further specifically described below by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, "parts" and "%" are quality standards unless otherwise specified.

In the following synthesis examples, the following symbols represent the following compounds, respectively.

MATHF: tetrahydrofuran-2-yl methacrylate (synthetic)

MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

MACHOE: 1-(cyclohexyloxy)ethyl methacrylate (synthetic)

MATHP: tetrahydro-2H-pyran-2-yl methacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

GMA: glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

OXE-30: (3-ethyloxetan-3-yl)methyl methacrylate (Manufactured by Osaka Organic Chemical Industry Co., Ltd.)

NBMA: n-butoxymethyl acrylamide (manufactured by Mitsubishi Rayon Co., Ltd.)

MAA: Methacrylic acid (made by Wako Pure Chemical Industries, Ltd.)

HEMA: 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

MMA: Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

St: Styrene (manufactured by Wako Pure Chemical Industries, Ltd.)

DCPM: Dicyclopentyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.)

V-601: dimethyl-2,2'-azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)

V-65: 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)

MEDG: Diethylene glycol ethyl methyl ether (Manufactured by Toho Chemical Industry Co., Ltd., Hisolve EDM)

PGMEA: methoxypropyl acetate (manufactured by Showa Denko)

<Synthesis of MATHF>

Methacrylic acid (86 g, 1 mol) was previously cooled to 15 ° C, and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution was added dropwise 2-dihydrofuran (71 g, 1 mol, 1.0 eq.). After stirring for 1 hour, saturated sodium hydrogencarbonate (500 mL) was added, and ethyl acetate (500 mL) was evaporated. After ethyl sulfate (500 mL), and dried over magnesium sulfate, the insolubles were filtered, and then concentrated under reduced pressure at 40 ° C. The product was distilled under reduced pressure to obtain 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) having a boiling point (bp.) of 54 to 56 ° C / 3.5 mmHg as a colorless oil (yield 80). %).

Further, the synthesis was carried out in the same manner as the above MATHF except that the MACHOE was changed to a compound corresponding to 2-dihydrofuran.

[Synthesis of Polymer A1]

MEDG (89 g) was placed in a three-necked flask and the temperature was raised to 90 ° C under a nitrogen atmosphere. MAA (in an amount of 9.5 mol% of all monomer components), MATHF (amount of 43 mol% of all monomer components), and GMA (corresponding to 47.5 mol% of all monomer components) were dissolved in the solution. V-65 (corresponding to 100 mol% of all monomer components, equivalent to 4 mol%) was added dropwise over 2 hours. End of drop After stirring for 2 hours, the reaction was completed. Thereby, the polymer A1 was obtained. Further, the ratio of the total amount of MEDG to other components was set to 60:40. Namely, a polymer solution having a solid concentration of 40% was prepared.

The type of the monomer to be used, the polymerization initiator, and the like were changed to be as shown in the following table to synthesize another polymer.

The values of the units not specifically labeled in the above table are in mol%. Further, the value of the polymerization initiator is mol% in the case where the monomer component is made 100 mol%.

The solid content concentration can be calculated by the following formula.

Solid content concentration: monomer weight / (monomer weight + solvent weight) × 100 (unit: mass%)

Further, in the case of using V-601 as a starter, the reaction temperature was set to 90 ° C, and in the case of using V-65 as a starter, the reaction temperature was set to 70 ° C.

<Examples and Comparative Examples>

(1) Preparation of photosensitive resin composition

Each component shown in the following Tables 2 and 3 was dissolved and mixed in a solvent (PGMEA) until a solid content concentration reached 32% to prepare a uniform solution, and then a pore size of 0.1 μm was used. A solution made of a polytetrafluoroethylene filter was filtered, and a solution of the photosensitive resin compositions of the examples and the comparative examples was prepared. Further, the amounts of addition of the respective component amounts in Tables 2 and 3 represent parts by mass.

The details of the abbreviations of the respective compounds used in the examples and the comparative examples are as follows.

<polymer>

A1~A10: polymers synthesized according to the above synthesis examples

A11: Joncryl 67 (manufactured by BASF Corporation)

<Photoacid generator>

B1: a compound of the following structure (synthetic)

B2: a compound of the following structure (synthetic)

B3: a compound of the following structure (synthetic)

B4: CGI-1397 (made by BASF Corporation)

B5: a compound of the following structure (synthesized according to the method described in paragraph 0108 of JP-A-2002-528451)

<Synthesis of B1>

Add aluminum chloride (10.6g) and 2-chloropropionyl chloride (10.1g) to a suspension solution of 2-naphthol (10g) and chlorobenzene (30mL), and heat the mixture to 40 °C to react 2 hour. 4N HCl aqueous solution (60 mL) was added dropwise to the reaction mixture under ice-cooling, and ethyl acetate (50 mL) was added. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 ° C for 1 hour, and then a 2N aqueous HCl solution (60 mL) was added and the mixture was separated, and the organic layer was concentrated, and then the crystals were taken from diisopropyl ether (10 mL). The slurry was further slurried, filtered, and dried to obtain a ketone compound (6.5 g).

Acetic acid (7.3 g) and 50% by weight aqueous hydroxylamine solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (18 mL), and the mixture was heated under reflux for 10 hours. After standing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain a hydrazine compound (2.4 g).

The obtained hydrazine compound (1.8 g) was dissolved in acetone (20 mL), and triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added thereto under ice cooling, and the mixture was heated to room temperature for 1 hour. Water (50 mL) was added to the reaction liquid, and the precipitated crystals were filtered, and then re-slurryed with methanol (20 mL), filtered and dried to obtain B1 (2.3 g).

Further, the ¹ H-NMR spectrum of B1 (300 MHz, CDCl ₃ ) is: 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).

<Synthesis of B2>

2-naphthol (20 g) was dissolved in N,N-dimethylacetamide (150 mL), and potassium carbonate (28.7 g) and ethyl 2-bromooctanoate (52.2 g) were added, and the reaction was carried out at 100 ° C. hour. Water (300 mL) and ethyl acetate (200 mL) were added to the reaction mixture for liquid separation, and the organic layer was concentrated. Then, a 48% by weight aqueous sodium hydroxide solution (23 g), ethanol (50 mL), and water (50 mL) were added. hour. The reaction liquid was poured into a 1N aqueous HCl solution (500 mL), and the precipitated crystals were filtered and washed with water to obtain a crude carboxylic acid, and then 30 g of polyphosphoric acid was added thereto, and the mixture was reacted at 170 ° C for 30 minutes. The reaction solution was poured into water (300 mL), and ethyl acetate (300 mL) was added for liquid separation. After concentration, it was purified by silica gel column chromatography to obtain a ketone compound (10 g).

Sodium acetate (30.6 g), hydroxylamine hydrochloride (25.9 g), and magnesium sulfate (4.5 g) were added to a suspension of the obtained ketone compound (10.0 g) and methanol (100 mL), and the mixture was heated under reflux for 24 hours. After standing to cool, water (150 mL) and ethyl acetate (150 mL) were added for liquid separation, and the organic layer was partitioned with water (80 mL) for 4 times, concentrated, and purified by silica gel column chromatography to obtain a hydrazine compound (5.8 g). ).

The obtained hydrazine (3.1 g) was subjected to sulfonation in the same manner as B1 to obtain B2 (3.2 g).

Further, the ¹ H-NMR spectrum of B2 (300 MHz, CDCl ₃ ) was: δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd , 1H), 7.5 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (dd, 1H), 2.4 (s, 3H), 2.2 (ddt, 1H), 1.9 (ddt, 1H) ), 1.4~1.2 (m, 8H), 0.8 (t, 3H).

<Synthesis of B3>

B3 was synthesized in the same manner as B1 except that phenylsulfonium chloride was used instead of p-toluenesulfonyl chloride in B1.

In addition, the ¹ H-NMR spectrum of B3 (300 MHz, CDCl ₃ ) is: δ = 8.3 (d, 1H), 8.1 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.7-7.5 (m, 4H), 7.4 (dd, 1H), 7.1 (d.1H), 5.6 (q, 1H), 1.7 (d, 3H).

<Aromatic Heterocyclic Compound>

C1: oxazole (made by Wako Pure Chemical Industries Co., Ltd.)

C2: 2,4,5-trimethyloxazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C3: Isoxazole (made by Wako Pure Chemical Industries Co., Ltd.)

C4: 5-methylisoxazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C5: Thiazole (made by Wako Pure Chemical Industries Co., Ltd.)

C6: 5-methylthiazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C7: Isothiazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C8: 1,2,3-triazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C9: 1,2,4-triazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C10: 1,2,3-oxadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C11:1, 2,4-oxadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C12: 1,3,4-oxadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C13: 1,2,5-oxadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C14: 1,2,3-thiadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C15: 1,2,4-thiadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C16: 1,3,4-thiadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C17: 1,2,5-thiadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C18: Pyrimidine (manufactured by Wako Pure Chemical Industries, Ltd.)

C19: 1,2,3-triazine (manufactured by Wako Pure Chemical Industries, Ltd.)

C20: 1,2,4-triazine (manufactured by Wako Pure Chemical Industries, Ltd.)

C21:1,3,5-triazine (manufactured by Wako Pure Chemical Industries, Ltd.)

C22: 1,2-benzopyrazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C23: benzoxazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C24: 5-methylbenzoxazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C25: 1,2-benzisoxazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C26: benzothiazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C27: 2,6-dimethylbenzothiazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C28: 2,1,3-benzooxadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C29: 2,1,3-benzothiadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C30: 1,2,3-benzotriazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C31: quinazoline (manufactured by Wako Pure Chemical Industries, Ltd.)

C32: azine (manufactured by Wako Pure Chemical Industries, Ltd.)

C33: 1,10-morpholine (manufactured by Wako Pure Chemical Industries, Ltd.)

C34: 5-methyl-1,10-morpholine (manufactured by Wako Pure Chemical Industries, Ltd.)

C35: 2,2'-bipyridyl (manufactured by Wako Pure Chemical Industries, Ltd.)

C36: 4,4'-bipyridyl (manufactured by Wako Pure Chemical Industries, Ltd.)

C37: 5,5'-Dimethyl-2,2'-bipyridine (manufactured by Wako Pure Chemical Industries, Ltd.)

C38: 2-mercaptobenzothiazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C39: 1-Aminobenzotriazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C40: 6-Amino-2-mercaptobenzothiazole (manufactured by Wako Pure Chemical Industries, Ltd.)

C41: Pyrrole (manufactured by Wako Pure Chemical Industries, Ltd.)

C42: pyridine (manufactured by Wako Pure Chemical Industries, Ltd.)

C43: 吲哚 (made by Wako Pure Chemical Industries Co., Ltd.)

C44: Heterogeneous (made by Wako Pure Chemical Industries Co., Ltd.)

The structure of C1 to C44 is shown below.

<decane compound>

E1: 3-glycidoxypropyltrimethoxydecane (KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.))

E2: bis(triethoxydecylpropyl)tetrasulfide (KBE-846 (manufactured by Shin-Etsu Chemical Co., Ltd.))

E3: mercaptotrimethoxydecane (KBM-3103 (manufactured by Shin-Etsu Chemical Co., Ltd.))

<sensitizer>

G1: DBA (9,10-dibutoxy oxime, manufactured by Kawasaki Chemical Industry Co., Ltd.)

<alkaline compound>

H1:1,5-diazabicyclo[4,3,0]-5-pinene (manufactured by Tokyo Chemical Industry Co., Ltd.)

H2: a compound of the following structure

<Surfactant>

I1: a compound of the following structure

<crosslinker>

F1: JER157S65 (Mitsubishi Chemical Co., Ltd.)

F2: Duranate 17B-60P (made by Asahi Kasei Chemicals Co., Ltd.)

F3: Desmodur BL4265SN (manufactured by Susei Bayer Aminoate)

<antioxidant>

J1: Irganox 1035FF (antioxidant, manufactured by BASF Corporation)

J2: Irganox 1098 (antioxidant, manufactured by BASF Corporation)

J3: Adekastab AO-60 (antioxidant, manufactured by Eddy Co.)

(2) Evaluation of photosensitive resin composition

(2-1) Evaluation of sensitivity

A glass substrate (EAGLE XG, 0.7 mm thick (manufactured by Corning)) was exposed to hexamethyldioxane (HMDS) vapor for 30 seconds, and each photosensitive resin composition was spin-coated at 90 ° C. The resin was prebaked on a hot plate for 120 seconds to volatilize the solvent to form a photosensitive resin composition layer having a film thickness of 3.0 μm.

Then, the obtained photosensitive resin composition layer was exposed through a predetermined mask using MPA 5500CF (high pressure mercury lamp) manufactured by Canon. Next, the exposed photosensitive resin composition layer was developed by an alkali developer (0.4% tetramethylammonium hydroxide aqueous solution) at 23 ° C / 60 seconds, and then rinsed with ultrapure water for 20 seconds. The optimum i-ray exposure amount (Eopt) when the 5 μm hole was analyzed by these operations was taken as the sensitivity.

A: less than 20mJ/cm ²

B: 20 mJ/cm ² or more and less than 40 mJ/cm ²

C: 40 mJ/cm ² or more and less than 80 mJ/cm ²

D: 80 mJ/cm ² or more and less than 160 mJ/cm ²

E: 160mJ/cm ² or more

(2-2) Evaluation of chemical resistance

The glass substrate was exposed to hexamethyldioxane (HMDS) vapor for 30 seconds, and each photosensitive resin composition was spin-coated on the substrate, and then prebaked on a hot plate at 90 ° C / 120 seconds. The solvent was volatilized to form a photosensitive resin composition layer having a film thickness of 3.0 μm. Then, an ultrahigh pressure mercury lamp was used, and the total exposure amount was 300 mJ/cm ² (energy intensity: 20 mW/cm ² , i-ray), and the substrate was heated in an oven at 230° C./60 minutes. Further, heating was carried out in an oven at 230 ° C for 2 hours.

The film thickness (T1) of the obtained cured film was measured. Next, the substrate on which the cured film was formed was immersed in a solution of dimethyl hydrazine:monoethanolamine=7:3 whose temperature was controlled at 60 ° C for 10 minutes, and then the film thickness (t1) of the cured film after immersion was measured. The film thickness change rate {|t1-T1|/T1}×100 [%] caused by the immersion was calculated.

The smaller the better, A and B are practically problem-free.

A: less than 2%

B: 2% or more and less than 3%

C: 3% or more and less than 4%

D: 4% or more and less than 6%

E: 6% or more

(2-3) Evaluation of display unevenness (panel display unevenness) in the display device

A liquid crystal display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2). In the active matrix liquid crystal display device described in FIG. 1 and FIG. 2 of the Japanese Patent No. 3321003, the cured film 17 is formed as an interlayer insulating film in the following manner to obtain a liquid crystal display device.

That is, the bottom gate type TFT 1 is formed on the glass substrate 6 to form the insulating film 3 containing Si ₃ N ₄ in a state of covering the TFT 1. Then, after a contact hole is formed in the insulating film 3, a wiring 2 (having a height of 1.0 μm) connected to the TFT 1 via the contact hole is formed on the insulating film 3.

Further, in order to planarize the unevenness caused by the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness caused by the wiring 2 is buried. The planarizing film 4 was formed on the insulating film 3, and each of the photosensitive resin compositions of the examples and the comparative examples was spin-coated on a substrate, and prebaked on a hot plate (90 ° C × 2 minutes). After irradiating an i-ray (365 nm) of 25 mJ/cm ² (energy intensity: 20 mW/cm ² ) with a high-pressure mercury lamp on the mask, development was carried out by an aqueous alkali solution to form a pattern, and heat treatment was performed at 230 ° C for 60 minutes. When the photosensitive resin composition was applied, the coating property was good, and the cured film obtained after exposure, development, and firing was not confirmed to have wrinkles or cracks. Further, the average step of the wiring 2 was 500 nm, and the thickness of the produced planarizing film 4 was 2,000 nm.

A driving voltage was applied to the obtained liquid crystal display device, and a gradation test signal was input, and the panel was continuously lit in an environment of 60° C. and 90%, and the gradation display after 1000 hours of lighting was visually observed, and the evaluation criteria were based on the following evaluation criteria. The evaluation showed the presence or absence of the occurrence of unevenness.

A: No unevenness is seen at all (very good)

B: slight unevenness was observed at the edge of the glass substrate, but there was no problem in the display portion (good)

C: Slightly see unevenness in the display section, but it is practical (normal)

D: There is unevenness in the display section (slightly worse)

E: There is a serious unevenness (very bad) in the display section.

As is apparent from the above results, the photosensitive resin composition of the present invention has high sensitivity and excellent chemical resistance of the cured film, and suppresses panel display unevenness in the panel reliability test. On the other hand, it is understood that the photosensitive resin composition of the comparative example does not satisfy all items of sensitivity, chemical resistance, and panel display unevenness.

<Example 74>

Example 74 is the same as in Example 1 except that the exposure machine was changed from MPA 5500CF manufactured by Canon (manufactured by Nikon) to FX-803M (gh-Line, stepper) manufactured by Nikon Co., Ltd. The way to proceed. The evaluation of sensitivity, chemical resistance, and panel display unevenness was the same as in Example 1.

<Example 75>

Example 75 was carried out in the same manner as in Example 1 except that the exposure machine was changed from a MPA 5500CF manufactured by Canon Co., Ltd. to a 355 nm laser exposure machine to perform 355 nm laser exposure. Here, the 355 nm laser exposure machine uses "AEGIS" (wavelength: 355 nm, pulse width: 6 nsec) manufactured by V-Technology Co., Ltd., and uses "PE10B-V2" manufactured by OPHIR to measure the exposure amount. .

The evaluation of sensitivity, chemical resistance, and panel display unevenness was the same as in Example 1.

<Example 76>

Example 76 was carried out in the same manner as in Example 1 except that the exposure machine was changed from the MPA 5500CF manufactured by Canon (manufacturing) to the UV-LED source exposure machine. The evaluation of sensitivity, chemical resistance, and panel display unevenness was the same as in Example 1.

<Example 77>

The same liquid crystal display device was obtained by changing only the following coating process as compared with Example 1. That is, the photosensitive resin of Example 1 was applied by a slit coating method. After the composition, the solvent was removed by heating on a hot plate at 90 ° C / 120 seconds to form a photosensitive resin composition layer having a film thickness of 3.0 μm. The obtained coating film was a flat surface which was flat and had no unevenness. Further, the performance as the liquid crystal display device was also as good as in the first embodiment.

As described above, it is understood that the photosensitive resin composition of the examples has a liquid crystal display device which is excellent in sensitivity and chemical resistance and high in panel reliability regardless of the exposure machine or the coating method.

<Example 78>

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 is formed on the glass substrate 6 to cover the TFT 1 to form an insulating film 3 containing Si ₃ N ₄ . Then, after the contact hole (not shown) is formed on the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 via the contact hole is formed on the insulating film 3. This wiring 2 is for connecting the organic EL element formed in the TFT 1 or in the step described later to the TFT 1.

Further, in order to planarize the unevenness caused by the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness caused by the wiring 2 is buried. The planarizing film 4 was formed on the insulating film 3, and the photosensitive resin composition of Example 16 was spin-coated on a substrate, prebaked on a hot plate (90 ° C / 120 seconds), and then self-masked. After irradiating an i-ray (365 nm) of 45 mJ/cm ² (energy intensity: 20 mW/cm ² ) with a high-pressure mercury lamp, development was carried out by an aqueous alkali solution to form a pattern, and heat treatment was performed at 230 ° C for 30 minutes.

When the photosensitive resin composition was applied, the coating property was good, and no occurrence of wrinkles or cracks was observed on the cured film obtained after exposure, development, and firing. Further, the average step of the wiring 2 was 500 nm, and the thickness of the produced planarizing film 4 was 2,000 nm.

Then, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, the first electrode 5 containing ITO is formed on the planarization film 4 via the contact hole 7 and connected to the wiring 2. Then, the resist is applied and prebaked, and exposed and developed through a mask of a desired pattern. This resist pattern was used as a mask, and pattern processing was performed by wet etching using an ITO etchant. Then, the resist pattern was peeled off at 50 ° C using a resist stripper (Remover 100, manufactured by AZ Electronic Materials Co., Ltd.). The first electrode 5 obtained in the above manner corresponds to the anode of the organic EL element.

Then, an insulating film 8 covering the shape of the periphery of the first electrode 5 is formed. The insulating film 8 was formed on the insulating film 8 by using the photosensitive resin composition of Example 1 in the same manner as described above. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

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

In the above manner, an active matrix organic EL display device in which the TFTs 1 for driving the organic EL elements are connected to each other is obtained. Via the drive circuit When a voltage was applied, it was found that the organic EL display device exhibits excellent display characteristics and high reliability.

10‧‧‧Liquid crystal display device

12‧‧‧Backlight unit

14, 15‧‧‧ glass substrate

16‧‧‧TFT

17‧‧‧ hardened film

18‧‧‧Contact hole

19‧‧‧ITO transparent electrode

20‧‧‧LCD

22‧‧‧Color filters

Claims (20)

A photosensitive resin composition comprising: (A) a polymer component comprising a polymer satisfying at least one of the following (1) and (2): (1) comprising (a1) having an acid group a structural unit of an acid-decomposable group-protected residue, and (a2) a polymer having a structural unit having a crosslinkable group, and (2) a structural unit including (a1) a residue having an acid group protected by an acid-decomposable group And a polymer comprising (a2) a structural unit having a crosslinkable group; (B) a photoacid generator; (C) an aromatic heterocyclic compound; and (D) a solvent, the above (C) aromatic The heterocyclic compound has a molecular weight of 1,000 or less, and the (C) aromatic heterocyclic compound contains at least one nitrogen atom in the aromatic ring and at least two coordinating atoms in the aromatic ring. The photosensitive resin composition according to claim 1, wherein the aromatic heterocyclic compound of the above (C) is a 5-membered cyclic heterocyclic compound, a 6-membered cyclic aromatic heterocyclic compound, and a 5-membered ring. Any one of a polycyclic aromatic heterocyclic compound having at least one of an aromatic heterocyclic structure and a 6-membered cyclic aromatic heterocyclic ring structure. The photosensitive resin composition according to the first or second aspect of the invention, wherein the coordinating atom is any one of a nitrogen atom, a sulfur atom and an oxygen atom. The photosensitive resin composition according to the above-mentioned item (1), wherein the crosslinkable group contained in the structural unit having a crosslinkable group (a2) is At least one selected from the group consisting of an epoxy group, an oxetanyl group, and -NH-CH ₂ -OR, wherein R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The photosensitive resin composition according to the first or second aspect of the invention, wherein the acid-decomposable group is a group having a structure protected in the form of an acetal. The photosensitive resin composition according to the above aspect of the invention, wherein the polymer component of the above (A) is a polymer further containing an acid group. The photosensitive resin composition according to claim 1 or 2, wherein the (B) photoacid generator is an oxime sulfonate compound. The photosensitive resin composition according to claim 1 or 2, wherein the (C) aromatic heterocyclic compound contains two to three coordinating atoms in the aromatic ring. The photosensitive resin composition according to claim 1 or 2, wherein the (C) aromatic heterocyclic compound contains at least two nitrogen atoms in the aromatic ring. The photosensitive resin composition according to claim 1 or 2, wherein the ring of the (C) aromatic heterocyclic compound has a ring of a single ring and/or a ring of two or three rings. . The photosensitive resin composition according to claim 1 or 2, wherein the amine group is not contained as an aromatic ring in the (C) aromatic heterocyclic compound. Has a substituent. The photosensitive resin composition according to claim 1 or 2, wherein the amine group is not contained as a substituent of the aromatic ring in the (C) aromatic heterocyclic compound, and the above-mentioned coordination atom It is any of a nitrogen atom, a sulfur atom, and an oxygen atom. The photosensitive resin composition according to claim 1 or 2, wherein the (C) aromatic heterocyclic compound contains two to three coordinating atoms in the aromatic ring, and the above (C) aromatic The heterocyclic compound is a monocyclic ring and/or a condensed ring of 2 or 3 rings. The photosensitive resin composition according to claim 1 or 2, wherein the aromatic heterocyclic compound of the above (C) contains two to three coordinating atoms in the aromatic ring, and the above-mentioned coordinating atom is Any one of a nitrogen atom, a sulfur atom and an oxygen atom, and the (C) aromatic heterocyclic compound is a monocyclic ring and/or a condensed ring of two or three rings, and the above-mentioned coordinating atom is a nitrogen atom or a sulfur atom. Any of the oxygen atoms. A method for forming a cured film, comprising: (1) a coating step of applying a photosensitive resin composition according to any one of claims 1 to 14 to a substrate; (2) a solvent removing step of removing a solvent from the applied photosensitive resin composition; (3) an exposure step of exposing the solvent-removed photosensitive resin composition by actinic rays; (4) using an aqueous developing solution Exposure of photosensitive resin composition for development And a (5) post-baking step of thermally hardening the developed photosensitive resin composition. The method of forming a cured film according to claim 15, wherein the step of performing total exposure of the developed photosensitive resin composition is performed after the developing step and before the post-baking step. A cured film formed by the method for forming a cured film according to claim 15 of the patent application. The cured film according to claim 17, which is an interlayer insulating film. An organic electroluminescence display device comprising the cured film according to claim 17 of the patent application. A liquid crystal display device comprising the cured film according to item 17 of the patent application.