TW201339750A - Photo-sensitive resin composition, method for manufacturing cured film by using the same, cured film, liquid crystal display and organic EL device - Google Patents

Abstract

A positive photo-sensitive resin composition is provided, wherein photo-sensitivity, a rate of residual film, and a relative dielectric constant thereof are excellent. A photo-sensitive resin composition includes: (A) a polymer component, wherein in one polymer or different polymers are included (a1) a repeat unit containing a residual group in which an acid group is protected by an acid decomposition group, (a2) a repeat unit containing a group selected from an oxiranyl group, an oxetanyl group, or -NH-CH2-OR (R being an alkyl having 1 to 20 carbons), and (a3) a repeat unit which has a carboxyl group at an end of a side chain, and in which an atomic number of a divalent linking group linking a main chain of the polymer and the carboxyl group is equal to or more than 4; (B) a photoacid generator; and (D) a solvent.

Description

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

The present invention relates to a photosensitive resin composition, a method for forming a cured film, a cured film, an organic electroluminescence (EL) display device, and a liquid crystal display device. More specifically, the present invention relates to a positive photosensitive film which is 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. A resin composition and a method for producing a cured film using the same.

In a thin film transistor (hereinafter referred to as a "TFT (Thin Film Transistor)" type liquid crystal display element, an electronic component such as a magnetic head element, an integrated circuit element, or a solid-state imaging element, it is usually arranged between layers of wiring. An interlayer insulating film is provided for insulation. As a material for forming the interlayer insulating film, a material having a small number of steps for obtaining a desired pattern shape and having sufficient flatness is preferable, and thus a photosensitive resin composition is widely used.

Specifically, as a photosensitive resin composition, a composition containing a resin having an acetal structure and/or a ketal structure and an epoxy group structure is known as a photosensitive resin composition (Japanese Patent Laid-Open No. 2004) -264623). However, if the composition is not subjected to post-exposure baking (Post Exposure Bake, PEB), cannot be developed, so the application range is limited. In addition, the composition described in Japanese Laid-Open Patent Publication No. 2004-264623 is excellent in heat resistance and development range, but has low sensitivity and has a problem of residual film properties.

Further, a composition comprising a resin and a photoacid generator containing a repeating unit having a group which decomposes by an action of an acid and generating an alkali-soluble group, and having cross-linking between resins by heating are known. A repeating unit of a functional group (Japanese Patent Laid-Open Publication No. 2009-288343). However, this composition is premised on the use of the double patterning method, and thus the application range is limited. Further, the composition described in Japanese Laid-Open Patent Publication No. 2009-288343 has a problem of residual film properties and relative dielectric constant.

Further, a polymer containing a resin containing a constituent unit having a lactone skeleton or a naphthalene skeleton is known (Japanese Patent Laid-Open Publication No. 2008-95087). The polymer described in Japanese Laid-Open Patent Publication No. 2008-95087 does not exhibit high sensitivity unless an ArF laser is used.

The present invention has an object of solving the above problems, and an object of the invention is to provide a positive photosensitive resin composition having excellent sensitivity, residual film ratio, and relative dielectric constant.

As a result of intensive studies based on the above-mentioned problems, the inventors of the present invention found that by using a polymer having a repeating unit of a long-chain carboxylic acid in combination with a specific two kinds of polymers, it is considered that the activity is considered to be an acid group. This problem can be solved by increasing the sensitivity and the residual film rate caused by a decrease in the glass transition point (Tg) of the film.

The means for solving the above problem is the means of the following [1], and the means of the following [2] to the following [13] are preferable.

[1] A photosensitive resin composition comprising: (A) a polymer component comprising (a1) a repeat of a residue having an acid group protected by an acid-decomposable group in the same polymer or a different polymer a unit (a2) comprising a repeating unit of a crosslinkable group selected from the group consisting of an oxiranyl group, an oxetanyl group, or a -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) And (a3) a repeating unit having a carboxyl group at the terminal of the side chain and having a divalent linking group linking the polymer main chain and the carboxyl group, having a number of atoms of 4 or more; (B) a photoacid generator; and (D) a solvent; and the divalent linking group is selected from -CR ¹ ₂ - (R ¹ represents a hydrogen atom or a methyl group), -O-, -O-SO ₂ -, -OC(O)-, -C (O)-O-, -S-, -C(O)-, an amine group which may have a substituent, a pendant phenyl group which may have a substituent, or a structure of the following (iv) and optionally combined.

(In the formula (iv), z represents an integer of 0 to 5.)

[2] The photosensitive resin composition according to [1], wherein the (A) polymer component has a polymer comprising the repeating unit (a2) and the repeating unit (a3).

[3] The photosensitive resin composition according to [1], wherein the (A) polymer component has the repeating unit (a1), the repeating unit (a2), And a polymer of the repeating unit (a3).

[4] The photosensitive resin composition according to any one of [1] to [3] which is a chemically amplified positive photosensitive resin composition.

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the repeating unit (a3) contains one or more kinds of the formula (i) to the formula (iii) Expressed by Repeat unit.

(In the general formulae (i) to (iii), R ¹ represents a hydrogen atom or a methyl group, L represents a divalent linking group having 4 or more atoms, and R ² represents a halogen atom, a hydroxyl group or a carbon number of 1~ 3 alkyl, n represents an integer from 0 to 4.)

[6] The photosensitive resin composition according to any one of [1] to [5] wherein the repeating unit (a1) is a repeating unit represented by the formula (A2').

(In the formula (A2'), 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. R ¹ or R ² and R ³ may be bonded 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.

[7] The photosensitive resin composition according to any one of [1] to [6] wherein the repeating unit (a2) is a repeating unit represented by the formula (2).

(In the formula (2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having a carbon number of 1 to 20. [8] The photosensitive material according to any one of [1] to [7] The resin composition is characterized in that the repeating unit (a2) is a repeating unit having an oxiranyl group and/or an oxetanyl group.

[9] A method of producing a cured film, comprising: (1) a step of applying the photosensitive resin composition according to any one of [1] to [8] to a substrate; (2) a step of removing the solvent in the applied photosensitive resin composition; (3) a step of performing exposure using actinic radiation; (4) a step of performing development using an aqueous developing solution; and (5) a post-baking step of performing thermal hardening.

[10] The method for producing a cured film according to [9], which is characterized in that, after the developing step and the post-baking step, a step of performing total exposure is included.

[11] A cured film characterized in that it is as described in any one of [1] to [8] The photosensitive resin composition is formed by hardening.

[12] The cured film according to [11], which is characterized in that it is an interlayer insulating film.

[13] A liquid crystal display device comprising the cured film according to [11] or [12].

[14] An organic EL display device comprising the cured film according to [11] or [12].

According to the present invention, it is possible to provide a positive photosensitive resin composition having excellent sensitivity, residual film ratio, and relative dielectric constant, 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‧‧‧TFT (thin film transistor)

2‧‧‧Wiring

3‧‧‧Insulation film

4‧‧‧Flat film

5‧‧‧First electrode

6‧‧‧ glass substrate

7‧‧‧Contact hole

8‧‧‧Insulation film

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

FIG. 1 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, and having a planarization film 4.

FIG. 2 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, and having a cured film 17 as an interlayer insulating film.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be performed based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In the specification of the present application, "~" is used in the sense that the numerical values described before and after are included as the lower limit and the upper limit. Further, the organic EL display device in the present invention means an organic electroluminescence display device (organic electroluminescence device).

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

Further, in the present invention, the term "~ alkali soluble" means by passing a compound (tree The solution of the lipid) was applied to a substrate and heated at 90 ° C for 2 minutes to form a film of a compound (resin) (thickness of 3 μm) for a 0.4% aqueous solution of tetramethylammonium hydroxide at 23 ° C. 0.01 μm/sec or more, "~ alkali-insoluble" means a film of a compound (resin) formed by applying a solution of a compound (resin) to a substrate and heating at 90 ° C for 2 minutes (thickness: 3 μm) The dissolution rate of the 0.4% aqueous solution of tetramethylammonium hydroxide at 23 ° C was less than 0.01 μm / sec.

[Photosensitive Resin Composition]

The photosensitive resin composition of the present invention is characterized by comprising: (A) a polymer component comprising (a1) a repeating unit containing a residue in which an acid group is protected by an acid-decomposable group, in the same polymer or in a different polymer, (a2) a repeating unit containing a group selected from the group consisting of an oxiranyl group, an oxetanyl group, or -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms), and (a3) a repeating unit having a carboxyl group at the terminal of the side chain and having a divalent linking group linking the polymer main chain and the carboxyl group of 4 or more; (B) a photoacid generator; and (D) a solvent.

The component (A) includes (1) a form in which a repeating unit (a1), a repeating unit (a2), and a repeating unit (a3) are copolymerized; (2): a repeating unit (a1) and a repeating unit; a copolymer of (a3), a form of a copolymer of the repeating unit (a2) and the repeating unit (a3), and (3) a polymer comprising the repeating unit (a1), a polymer comprising the repeating unit (a2), and a form of the polymer of the repeating unit (a3); (4) a form of a copolymer of the repeating unit (a1) and the repeating unit (a3), and a polymer comprising the repeating unit (a2); (5): a copolymer of a repeating unit (a2) and a repeating unit (a3), a form of a polymer comprising the repeating unit (a1); and (6) a copolymer of a repeating unit (a1) and a repeating unit (a2) The form of the polymer containing the repeating unit (a3). Among these forms, the forms (1), (3) to (4), and (6) are preferable.

The component (A) may contain a plurality of the above-described forms, and further may include other repeating units (a4).

Hereinafter, each component of the photosensitive resin composition of the present invention will be described.

<(A) component>

The photosensitive resin composition of the present invention (hereinafter also referred to as the photosensitive composition of the present invention or the composition of the present invention) contains a repeating unit (a1) and a repeating unit (a2) in the same polymer or different polymers. And repeating unit (a3) as component (A).

The component (A) may contain other constituent (repeating) units (a4) in addition to the repeating unit (a1) to the repeating unit (a3).

[repeating unit (a1)]

When the component (A) has the constituent unit (a1), a photosensitive resin composition having extremely high sensitivity can be obtained.

The "residue of an acid group protected by an acid-decomposable group" in the present invention is a residue in which a carboxyl group is protected by an acetal, a residue in which an acid group is protected by a ketal, a residue in which an acid group is protected by a tertiary alkyl group, or A residue in which the acid group is protected by a tertiary alkyl carbonate group.

The acid group is preferably a carboxyl group or a phenolic hydroxyl group.

In addition, as the residue which is protected by an acid-decomposable group as an acid group, for example, an ester structure of a group represented by the formula (A1) to be described later, a tetrahydropyranyl ester group or a tetrahydrofuranyl ester group, etc. An acetal or ketal functional group, or a tertiary alkyl ester such as a tert-butyl ester group or a tert-butyl carbonate group Base functional group.

(a1) The constituent unit of the residue having an acid group-protected group containing an acid group preferably contains a structural unit protecting a carboxyl group protected by an acid-decomposable group or a constituent unit containing a protective phenolic hydroxyl group protected by an acid-decomposable group.

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

<<<(a1-1) A constituent unit containing a protected carboxyl group protected by an acid-decomposable group>>>

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

As the structural unit containing a carboxyl group which can be used for the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group, a known structural unit can be used without particular limitation. For example, a constituent 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 both A constituent unit (a1-1-2) having an ethylenically unsaturated group and an acid anhydride-derived structure.

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

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

As the constituent unit (a1-1-1) derived from the unsaturated carboxylic acid having at least one carboxyl group in the molecule, an unsaturated carboxylic acid as exemplified below can be used as the present invention. Unsaturated carboxylic acid. That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Further, examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. Further, the unsaturated polycarboxylic acid used to obtain a structural unit containing 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 butyl. Di(2-methylpropenyloxyethyl) diester, mono(2-propenyloxyethyl) phthalate, mono(2-methylpropenyloxyethyl) phthalate ) esters, etc. 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. Acrylate and the like. Further, as the unsaturated carboxylic acid, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, and 4 may be used. - Carboxystyrene and the like.

Among them, from the viewpoint of developability, in order to form the constituent unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, acrylic acid, methacrylic acid, or As the anhydride or the like of the saturated polycarboxylic acid, acrylic acid or methacrylic acid is more preferably used.

The constituent 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) A constituent unit having both an ethylenically unsaturated group and an acid anhydride-derived structure>>>>

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

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 six. A dibasic acid anhydride such as hydrogen phthalic anhydride or chloric anhydride; an acid anhydride such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride or biphenyltetracarboxylic anhydride. Among these acid anhydrides, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferred from the viewpoint of developability.

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

<<<< can be used to form the acid-decomposable group of unit (a1-1) >>>>

As the acid-decomposable group which can be used for the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group, a positive resist for KrF and a positive resist for ArF can be used. The acid-decomposable group in the agent is known, and is not particularly limited. In the past, as the acid-decomposable group, a group which is relatively easily decomposed by an acid (for example, an acetal-based functional group such as a tetrahydropyranyl group) or a group which is relatively difficult to be decomposed by an acid (for example, a third butyl ester group) is known. a third butyl functional group such as a tert-butyl carbonate group).

Among these acid-decomposable groups, it is preferable to contain a carboxyl group from an acetal from the viewpoint of the basic physical properties of the resist, particularly the sensitivity, the pattern shape, the contact hole formation property, and the storage stability of the photosensitive resin composition. Or a constituent unit that protects a carboxyl group protected by a ketal or a protected carboxyl group protected by a ketal. Further, among the acid-decomposable groups, from the viewpoint of sensitivity, a carboxyl group is more preferably a protected carboxyl group protected by an acetal or a ketal represented by the following formula (a1-1). Further, in the case where the carboxyl group is protected by a acetal or a ketal represented by the following formula (a1-1), the entire protected carboxyl group becomes -(C=O)-O-CR ¹⁰¹ R ¹⁰² ( OR ¹⁰³ ) structure.

(In the formula (a1-1), 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 It can be linked to R ¹⁰³ to form a cyclic ether.)

In the above formula (a1-1), 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 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 (a1-1), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an alkyl group, the alkyl group may be any of a linear chain, a branched chain or a cyclic group.

The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. 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 cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When 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} an aralkyl group.

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 an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an α-methylphenyl group, a naphthyl group, and the like. As a fan The mono-substituted alkyl group, that is, the 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 a carbon number of 1 to 10 as a substituent, and when the alkyl group is linear or branched In the case of an alkyl group, a cycloalkyl group having a carbon number of 3 to 12 may be used as a substituent.

These substituents may also be further substituted by the substituents.

In the above formula (a1-1), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an aryl group, the aryl group preferably has a carbon number of 6 to 12, more preferably a carbon number of 6 to 10. The aryl group may have a substituent, and as the substituent, an alkyl group having 1 to 6 carbon atoms is preferably exemplified. Examples of the aryl group include a phenyl group, a tolyl group, a silyl 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 and form a ring together with the carbon atoms to which they are bonded. Examples of the ring structure when R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ¹⁰³ or R ¹⁰² and R ^{103 are} bonded to each other include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, and an adamantyl group. And tetrahydropyranyl and the like.

Further, in the above formula (a1-1), it is preferred that any of R ¹⁰¹ and R ¹⁰² is a hydrogen atom or a methyl group.

A radically polymerizable monomer for forming a constituent unit containing a protective carboxyl group represented by the above formula (a1-1) may be a commercially available radical polymerizable monomer, or may be synthesized by a known method. A radical polymerizable monomer. For example, as shown below, it can be synthesized by reacting (meth)acrylic acid with a vinyl ether in the presence of an acid catalyst. The reaction can be carried out at the stage of the monomer or after the preparation of the polymer.

In the above scheme, R ¹¹¹ represents a hydrogen atom or an alkyl group which is the same as the alkyl group represented by R ¹⁰¹ to R ¹⁰³ in the above formula (a1-1). As R ¹¹¹ , a hydrogen atom or a methyl group is preferred.

As -CH(R ¹¹² )(R ¹¹³ ), R ¹¹² and R ^{113 have} the same meanings as R ¹⁰² in the above formula (a1-1), and the meaning of R ^{114 is} the same as in the formula (a-1) R ^{101 is the} same, and R ^{115 has} the same meaning as R ¹⁰³ in the above formula (a1-1), and their preferred ranges are also the same.

The synthesis may also be carried out by copolymerizing (meth)acrylic acid with another monomer in advance and then reacting with the vinyl ether in the presence of an acid catalyst.

The first preferred embodiment of the structural unit (a1-1) containing a protective carboxyl group protected by an acid-decomposable group is a constituent unit represented by the 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 may be bonded 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 preferable. When 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.

The second preferred embodiment of the structural unit (a1-1) containing 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; .) a hydrogen atom or a methyl group R ¹²¹ is preferred.

L ¹ is preferably a carbonyl group.

R ¹²² to R ^{128 are} preferably a hydrogen atom.

As a preferable specific example of the structural unit (a1-1) containing the protective carboxyl group protected by the acid-decomposable group, the following structural unit can be exemplified. Further, R represents a hydrogen atom or a methyl group.

<<<(a1-2) A constituent unit containing a protective phenolic hydroxyl group protected by an acid-decomposable group>>>

The constituent unit (a1-2) containing a protective phenolic hydroxyl group protected by an acid-decomposable group is a constituent unit containing a phenolic hydroxyl group and has a constituent unit for protecting a phenolic hydroxyl group protected by an acid-decomposable group, which will be described in detail below. .

<<<<(a1-2-1) constitutive unit containing phenolic hydroxyl group>>>>

Examples of the constituent unit containing the phenolic hydroxyl group include a constituent unit in a hydroxystyrene-based constituent unit or a novolak-based resin. Among these constituent units, from the viewpoint of transparency, it is preferably derived from hydroxystyrene. Or a constituent unit of α-methylhydroxystyrene. Among the constituent units containing a phenolic hydroxyl group, from the viewpoint of transparency and sensitivity, a constituent unit represented by the following formula (a1-2) is preferable.

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

In the above formula (a1-2), 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. When R ²²¹ is a single bond, the sensitivity can be improved, and the transparency of the cured film can be improved, which is preferable. R ²²¹ is a divalent linking group, may be exemplified alkylene group, specific examples of R ²²¹ is alkylene include: methylene, stretching ethyl, propyl stretching, stretch isopropyl, n-butyl extending , isobutyl, tetrabutyl, pentylene, isoamyl, neopentyl, hexyl and the like. Among them, R ²²¹ is preferably a single bond, a methylene group or an extended 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 a 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 new one. Amyl and so on. Among them, a chlorine atom, a bromine atom, a methyl group or an ethyl group is preferable from the viewpoint of easy production.

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

<<<< can be used to form the acid-decomposable group of unit (a1-2) >>>>

The acid-decomposable group which can be used for the structural unit (a1-2) containing a protective phenolic hydroxyl group protected by an acid-decomposable group, and a composition which can be used for the protective carboxyl group which is protected by an acid-decomposable group Similarly to the acid-decomposable group of the unit (a1-1), a known acid-decomposable group can be used, and it is not particularly limited. Among the acid-decomposable groups, the basic physical properties of the resist, particularly the sensitivity, the pattern shape, the storage stability of the photosensitive resin composition, and the formation of contact pores, preferably contain acetal protection. A constituent unit for protecting a phenolic hydroxyl group or a phenolic hydroxyl group protected by a ketal. Further, among the acid-decomposable groups, from the viewpoint of sensitivity, the phenolic hydroxyl group is more preferably protected by a acetal or a ketal represented by the above formula (a1-1). Further, in the case where the phenolic hydroxyl group is protected by a acetal or a ketal represented by the above formula (a1-1), the entire phenolic hydroxyl group is protected to become -Ar-O-CR ^101. The structure of R ¹⁰² (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 group, or R ¹⁰¹ = R ¹⁰² = methyl group and R ¹⁰³ = benzyl group.

In addition, examples of the radical polymerizable monomer for forming a constituent unit for protecting a phenolic hydroxyl group having a phenolic hydroxyl group protected by an acetal or a ketal include a 1-alkoxyalkyl protecting group of hydroxystyrene. , tetrahydropyranyl protecting agent for hydroxystyrene, 1-alkoxyalkyl protecting agent for α-methyl-hydroxystyrene, tetrahydropyranyl protecting agent for α-methyl-hydroxystyrene, 1-alkoxyalkyl protecting agent of 4-hydroxyphenyl acrylate, tetrahydropyranyl protecting agent of 4-hydroxyphenyl methacrylate, 4-hydroxybenzoic acid (1-methylpropenyloxymethyl) a 1-alkoxyalkyl protecting group of an ester, a tetrahydropyranyl protecting group of (1-methylpropenyloxymethyl) 4-hydroxybenzoate, 4-hydroxybenzoic acid (2-A) 1-alkoxyalkyl protecting agent of propylene methoxyethyl ester, tetrahydropyranyl protecting agent of 4-hydroxypropenyloxyethyl 4-hydroxybenzoate, 4-hydroxyl 1-alkoxyalkyl protecting agent of (3-methacryloxypropyl) benzoate, tetrahydropyranyl group of (3-methylpropenyloxypropyl) 4-hydroxybenzoate Protector, 4-hydroxybenzoic acid (3-methyl propyl) 1-alkoxyalkyl protecting group of decyloxy-2-hydroxypropyl) ester, tetrahydropyranyl group of (3-methylpropenyloxy-2-hydroxypropyl) 4-hydroxybenzoate Protector, etc.

Among these radically polymerizable monomers, from the viewpoint of transparency, a 1-alkoxyalkyl protecting agent of 4-hydroxyphenyl methacrylate or a tetrahydrogen of 4-hydroxyphenyl methacrylate is preferable. Pyranyl protecting agent.

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

A commercially available radical polymerizable monomer may be used as the radical polymerizable monomer for forming the structural unit (a1-2) containing a protective phenolic hydroxyl group protected by an acid-decomposable group, or a known one may be used. The free radical polymerizable monomer synthesized by the method. For example, it can be synthesized by reacting a compound containing a phenolic hydroxyl group with a vinyl ether in the presence of an acid catalyst. The synthesis may also be carried out by previously copolymerizing a monomer having a phenolic hydroxyl group with another monomer and then reacting with a vinyl ether in the presence of an acid catalyst.

A preferred specific example of the structural unit (a1-2) containing the protective phenolic hydroxyl group protected by the acid-decomposable group is exemplified by the following constituent units, but the present invention is not limited to these constituent units.

<<<Preferred form of constituent unit (a1)>>>

In the constituent unit constituting the component (A), the content of the constituent unit (a1) is preferably from 1 mol% to 95 mol%, more preferably 10 mol%, from the viewpoint of sensitivity. 80% by mole, and more preferably 20% by mole to 70% by mole, particularly preferably 20% by mole to 50% by mole. Further, in particular, when the acid-decomposable group which can be used in the structural unit (a1) is a constituent unit containing a protective carboxyl group in which a carboxyl group is protected by an acetal or a protective carboxyl group in which a carboxyl group is protected by a ketal, the composition is contained in a composition. The content ratio of the constituent unit (a1) in the constituent unit of the polymer of the unit (a1) is more preferably 20 mol% to 60 mol%, particularly preferably 20 mol% to 50 mol%.

The constituent unit (a1-1) containing a protective carboxyl group protected by an acid-decomposable group has a faster development than the constituent unit (a1-2) containing a protective phenolic hydroxyl group protected by an acid-decomposable group. A feature. Therefore, in the case of rapid development, a constituent unit (a1-1) containing a protective carboxyl group protected by an acid-decomposable group is preferable. Conversely, in the case where the development is to be slowed down, it is preferred to use a constituent unit (a1-2) containing a protective phenolic hydroxyl group protected by an acid-decomposable group.

[repeating unit (a2)]

The repeating unit (a2) is usually used as a crosslinkable group containing an ethylene oxide group, an oxetanyl group, or -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) The unit is incorporated into the resin. The structural unit containing a crosslinkable group is preferably derived from a constituent unit of a compound containing a cyclic ether group, and more preferably a constituent unit derived from a compound containing an oxiranyl group and/or an oxetane group, and further More preferably, it is a repeating unit containing the radical polymerizable monomer represented by any of (3)-(5). These compounds may be used singly or in combination of two or more. Further, it may be a repeating unit represented by the following formula (2).

In the general formulae (3) to (5), X represents a divalent linking group, and examples thereof include an organic group such as -O-, -S-, or -COO- or -OCH ₂ COO-. X is preferably -COO-.

R ⁷ represents a hydrogen atom, a methyl group or a halogen atom, preferably a hydrogen atom or a methyl group.

R ⁸ to R ¹⁵ each independently represent a hydrogen atom or an alkyl group. It preferably represents a hydrogen atom or a methyl group.

n is an integer of 1 to 10, and preferably an integer of 1 to 3.

Specific examples of the radical polymerizable monomer for forming a structural unit containing an oxirane group include glycidyl acrylate, glycidyl methacrylate, and 3,4-epoxybutyl acrylate. , 3,4-epoxybutyl methacrylate, 4,5-epoxypentyl acrylate, 4,5-epoxypentyl methacrylate, 6,7-epoxyheptyl acrylate, A Acrylic 6,7-epoxy (meth) acrylates such as hexyl heptyl ester, 3,4-epoxycyclohexyl methyl acrylate, 3,4-epoxycyclohexyl methacrylate, etc.; o-vinylbenzyl glycidyl ether, m-vinyl Benzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-ethylene Vinylbenzyl glycidyl ethers such as benzyl glycidyl ether; vinyl phenyl glycidyl ethers such as o-vinylphenyl glycidyl ether, m-vinylphenyl glycidyl ether, p-vinylphenyl glycidyl ether class. Preferred are glycidyl acrylate, glycidyl methacrylate, p-vinylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, particularly preferred Glycidyl acrylate, glycidyl methacrylate.

In another aspect, the structural unit containing a crosslinkable group preferably contains a constituent unit of a radical polymerizable monomer represented by the following general formula (6) or (7), and may be used singly or Two or more types are used in combination. The molecular weight of the radically polymerizable monomer represented by the formula (6) or the formula (7) is preferably from 100 to 500, more preferably from 150 to 200.

In the general formulae (6) and (7), X represents a divalent linking group, and examples thereof include an organic group such as -O-, -S-, or -COO- or -OCH ₂ COO-. X is preferably -COO-.

R ⁷ represents a hydrogen atom, a methyl group or a halogen atom, preferably a hydrogen atom or a methyl group.

R ⁸ to R ¹⁵ each independently represent a hydrogen atom or an alkyl group. It preferably represents a hydrogen atom or a methyl group.

n is an integer of 1 to 10, and preferably an integer of 1 to 3.

As an example of such a radically polymerizable monomer for forming a structural unit containing an oxetanyl group, in the specific example of the radically polymerizable monomer containing an oxiranyl group, A compound in which an oxiranyl group is replaced with an oxetanyl group, or an oxetanyl group-containing (meth) acrylate or the like described in paragraphs 0011 to 0016 of JP-A-2001-330953 .

A commercially available radical polymerizable monomer can be used as the radical polymerizable monomer for forming a structural unit containing a crosslinkable group, and a radical polymerizable monomer synthesized by a known method can also be used. For example, an OXE series manufactured by Osaka Organic Chemical Industry Co., Ltd., and the like can be cited.

Preferred specific examples of the constituent unit having a functional group capable of forming a covalent bond with a carboxyl group include the following constituent units.

It is also preferable that the structural unit containing a crosslinkable group is a structural unit (a2-2) containing -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms). By having the constituent unit (a2-2), a hardening reaction can be generated by a gentle heat treatment, and a cured film excellent in various properties can be obtained.

R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 9 carbon atoms, and further More preferably, it is an alkyl group having a carbon number of 1 to 4. Further, the alkyl group may be any of a linear, branched or cyclic alkyl group, preferably a linear or branched alkyl group.

Further, the alkyl group may have a substituent. Examples of the substituent which the alkyl group may have include a halogen atom, an aryl group, and an alkoxy group.

The structural unit (a2-2) containing -NH-CH ₂ -OR preferably contains a structural unit represented by the following formula (2).

(In the formula, 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, 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, but a linear or branched alkyl group is preferred.

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

In the constituent unit constituting the component (A), the content of the constituent unit (a2) is preferably 1 mol% to 95 mol%, more preferably 5 mol% to 70 mol%, still more preferably 10 mol% to 50. More than 20% by mole, and more preferably 20% by mole to 50% by mole, particularly preferably 30% by mole to 50% by mole. When it is within the range of the numerical value, various properties of the cured film obtained from the photosensitive resin composition are good.

[repeating unit (a3)]

The photosensitive composition of the present invention contains a monomer unit (a3) having a carboxyl group at a terminal end of the side chain and constituting a divalent group of a group linking the polymer main chain and the carboxyl group at the terminal of the side chain. The number of atoms of the linking group is 4 or more, and the divalent linking group is selected from -CR ¹ ₂ - (R ¹ represents a hydrogen atom or a methyl group), -O-, -O-SO ₂ -, -OC(O) -, -C(O)-O-, -S-, -C(O)-, an amine group which may have a substituent, a phenyl group which may have a substituent, or a structure of the following (iv) and optionally The basis of the combination.

L is a divalent linking group having 4 or more atoms of a polymer main chain and a carboxyl group, and the number of atoms is preferably 6 or more and 20 or less, and more preferably 8 or more and 12 or less.

The divalent linking group (L) having 4 or more atoms is selected from -CR ¹ ₂ - (R ¹ represents a hydrogen atom or a methyl group), -O-, -O-SO ₂ -, -OC(O)- , -C(O)-O-, -S-, -C(O)-, an amine group which may have a substituent, a phenyl group which may have a substituent, or a structure of the following (iv) and optionally combined Base.

In the formula (iv), z represents an integer of 0 to 5.

z is preferably 2 to 3, and particularly preferably 3.

The amine group is preferably an amine group having a carbon number of 0 to 50, and examples thereof include -NH ₂ , an N-alkylamino group, an N-arylamino group, an N-decylamino group, and an N-sulfonylamine. N-sulfonylamino, N,N-dialkylamino, N,N-diarylamine, N-alkyl-N-arylamine, N,N-disulfonylamino N, N-disulfonylamino) and the like. More specifically, it may, for example, be an N-methylamino group, an N-ethylamino group, an N-propylamino group, an N-isopropylamino group, an N-butylamino group or an N-t-butyl group. Amino, N-hexylamino, N-cyclohexylamino, N-octylamino, N-2-ethylhexylamino, N-decylamino, N-octadecylamino, N -benzylamino, N-phenylamino, N-2-methylphenylamino, N-2-chlorophenylamino, N-2-methoxyphenylamino, N-2- Isopropoxyphenylamino, N-2-(2-ethylhexyl)phenylamino, N-3-chlorophenylamino, N-3-nitrophenylamino, N-3- Cyanophenylamino, N-3-trifluoromethylphenylamino, N-4-methoxyphenylamino, N-4-cyanophenylamino, N-4-trifluoro N-phenylsulfanylphenylamino, N-4-phenylsulfanylphenylamino, N-4-methylsulfanylphenylamino, N-4-dimethyl Aminophenylamino group, N-methyl-N-phenylamino group, N,N-dimethylamino group, N,N-diethylamino group, N,N-dibutylamino group, N,N-diphenylamino, N,N-diethylhydrazino, N,N-dibenridylamino, N,N-(dibutylcarbonyl)amine, N,N- Dimethylsulfonate Amino, N,N-(diethylsulfonyl)amine, N,N-(dibutylsulfonyl)amine, N,N-(diphenylsulfonyl)amine, Morpholinyl, 3,5-dimethylmorpholinyl, oxazolyl, and the like. Among these amine groups, -NH ₂ , N,N-diphenylamino and carbazolyl are preferred.

Examples of the pendant phenyl group include an adjacent phenyl group, an extended phenyl group, and a pendant phenyl group. Among these phenylene groups, an phenyl group or a pendant phenyl group is preferred.

Examples of the substituent which the amine group and the extended phenyl group may have include a halogen atom, an aryl group, and an alkoxy group.

In the present specification, the number of atoms of the divalent linking group means the number of atoms constituting one of the main chains connecting the polymer main chain and the carboxyl group. For example, the following exemplified compound (a3-1) has an atomic number of 8, and the number of atoms of (a3-2) is 8 (it is considered that the number of atoms constituting the main chain is 8 and the number of atoms is 12, but Since the number of atoms which constitutes the smaller number of atoms in the main chain is defined as the number of atoms, the number of atoms is 8, wherein the main chain is a main chain linking the polymer main chain and the carboxyl group), (a3-20) The number of atoms is 8 (the number in the following formula indicates the number of atoms).

The component (a3) preferably contains one or more repeating units represented by the following general formula (i) to formula (iii).

(In the formula (i) to the formula (iii), R ¹ represents a hydrogen atom or a methyl group, and L represents a divalent linking group having 4 or more atoms. In the formula (iii), R ² represents a halogen atom, a hydroxyl group or An alkyl group having a carbon number of 1 to 3, and n represents an integer of 0 to 4.

As an example of L, a group selected from the group of the linking groups shown below is preferable. In the following linking group, "*" indicates a linking site with a polymer main chain and a carboxyl group.

In the formula (iii), R ² is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and preferably a chlorine atom, a bromine atom, a hydroxyl group or a methyl group. n is an integer of 0 to 4, preferably 0.

The repeating unit represented by the above formula (i) to formula (iii) is preferably a repeating unit represented by the following formula (i') to formula (iii').

(In the formula (i ') ~ formula (iii'), R R meaning as in formula (I) of formula ¹ is - (iii) of the same ^1, L ¹ represents an alkylene group having a carbon number of 1 to 4)

L ¹ represents an alkylene group having a carbon number of 1 to 4, preferably an alkylene group having a carbon number of 2 to 3.

Specific examples of the repeating unit (a3) include the following structures, but the present invention It is not limited to the following structure.

Among the specific examples, (a3-1) to (a3-15) are preferable, and (a3-1) to (a3-3), (a3-5), (a3-7), and (a3) are more preferable. 9), and further preferably (a3-2).

In the constituent unit constituting the component (A), the content of the repeating unit (a3) is preferably 0.1 mol% to 50 mol%, more preferably 0.1 mol% to 45 mol%, more preferably 0.1 mol% to 45 mol% of the structural unit of all the resin components. It is preferably 5.0 mol% to 35 mol%. When the content is made 0.1% by mole or more, the effect of high sensitivity and high residual film ratio can be obtained, and when it is 45 mol% or less, it is preferable from the viewpoint of improving developability.

The weight average molecular weight (Mw) of the polymer having the repeating unit (a3) is preferably in the range of 3,000 to 300,000, more preferably 4,000 to 100,000, still more preferably 8,000 to 50,000. When it is set to 3000 or more, the effect of improving the residual film rate can be obtained, and when it is set to 300,000 or less, the effect of high sensitivity can be obtained. Here, the weight average molecular weight is defined by a polystyrene equivalent value of gel permeation chromatography.

[repeating unit (a4)]

The component (A) may contain, in addition to the repeating unit (a1) to the repeating unit (a3), a polymer which is a repeating unit (a4) derived from another monomer. another In addition, the repeating unit (a4) may be copolymerized. As other monomers, hydrogenated hydroxystyrene; halogen-substituted hydroxystyrene, alkoxy-substituted hydroxystyrene or alkyl-substituted hydroxystyrene; styrene; halogen-substituted styrene, alkoxy-substituted styrene, oxime a substituted styrene or an alkyl-substituted styrene; maleic anhydride; an acrylic acid derivative; a methacrylic acid derivative; an N-substituted maleimide or the like, but is not limited to these monomers.

In the constituent unit constituting the component (A), the content of the constituent unit (a4) is preferably 0.01 mol% to 50 mol%, more preferably 0.01 mol% to 33 mol%, still more preferably 5 mol% to 23 Moer%.

In the present invention, among the repeating units constituting the component (A), the repeating unit in which the number of atoms of "L" in the repeating unit represented by the general formula (i) to the formula (iii) is 3 or less It is 3 mol% or less, and it is more preferable that the repeating unit is not substantially contained. By not including substantially, it means that the effect of the present invention is not affected, for example.

[Molecular weight of (A) component]

The weight average molecular weight (Mw) of the component (A) is preferably in the range of 3,000 to 300,000, more preferably 4,000 to 100,000, still more preferably 8,000 to 50,000. When it is set to 3000 or more, the effect of improving the residual film rate can be obtained, and when it is set to 300,000 or less, the effect of high sensitivity can be obtained. Here, the weight average molecular weight is defined by a polystyrene equivalent value of gel permeation chromatography.

<<(A) allocation amount>>

The photosensitive resin composition of the present invention preferably contains 30% by weight or more of the component (A) of the polymer component, more preferably contains 40% by weight or more of the component (A) of the polymer component, and more preferably contains a polymerization. 50% by weight or more of the component (A). By setting it as such a range, the structural unit (a2) is fully present in the composition, and the effect of this invention can exhibit more effectively. The upper limit is not particularly limited and may be 100 wt%.

<<Method for manufacturing component (A)>>

Further, various methods are also known for the synthesis method of the component (A), and by way of example, a radical polymerization initiator can be used to form at least the formation of the (a1) and the (a2). The radically polymerizable monomer mixture of the radical polymerizable monomer constituting the unit represented by the polymerization is synthesized by polymerization in an organic solvent. Further, it can also be synthesized by a so-called polymer reaction. Further, it is also preferred that the component (A) has a carboxyl group at the terminal.

[Synthesis method of resin having carboxyl group at the end]

The resin having a carboxyl group at the terminal can be produced by copolymerizing a corresponding monomer by radical polymerization, anionic polymerization, Group Transfer Polymerization (GTP) or the like. The method for producing the resin having a carboxyl group at the terminal of the present invention is not particularly limited, and examples thereof include the methods (I) to (VIII) described in paragraphs 0099 to 0117 of JP-A-2005-122035.

Among them, the methods of (I) and (II) are preferred.

(I) As a method of using a polymerization initiator having a carboxyl group, a polymerization initiator having a carboxyl group is used as a starter at the time of polymerization.

As an example of a polymerization initiator which is widely used as a carboxyl group, VA-057 (manufactured by Wako Pure Chemical Industries, Ltd.) and V-501 (manufactured by Wako Pure Chemical Industries, Ltd.) can be cited.

The polymerization initiator is preferably 0.05 mol% to 10 mol%, more preferably 0.1 mol% to 5 mol%, based on 100 mol of the polymerizable monomer.

The reaction temperature of the copolymerization reaction is preferably 50 ° C to 100 ° C, more preferably 60 ° C to 100 ° C.

(II) In the method of using a chain transfer agent having a carboxyl group at the time of polymerization, a thiol compound having at least one carboxyl group is used in combination at the time of polymerization. As the thiol compound having at least one carboxyl group, the following examples are given.

The chain transfer agent is preferably formulated in a ratio of from 1/100 mol to 2/3 mol, more preferably from 1/20 mol to 1/3 mol, relative to the starting dose.

The molecular weight is adjusted by the sum of the starting dose and the chain transfer agent, but is preferably 0.05 mol% to 10 mol%, more preferably 0.1 mol% to 5 mol%, based on the total monomers of all monomers. The reaction temperature of the copolymerization reaction is preferably 50 ° C to 100 ° C, more preferably 60 ° C to 95 ° C.

<(B) Photoacid generator>

The photosensitive resin composition of the present invention contains a photoacid generator (B). As the present invention The photoacid generator used in the present invention is preferably a compound which induces an acid by irradiation of an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, but is not limited by its chemical structure. In addition, a photoacid generator that does not directly induce actinic rays having a wavelength of 300 nm or more can be used as a compound which generates an acid by using an actinic ray with a sensitizer and a wavelength of 300 nm or more. The sensitizer is preferably used after combination. The photoacid generator used in the present invention is preferably a photoacid generator which produces an acid having a pKa of 4 or less, and more preferably a photoacid generator which produces an acid having a pKa of 3 or less.

Examples of the photoacid generator include trichloromethyl-s-triazine, sulfonium or iodonium salt, quaternary ammonium salt, diazomethane compound, sulfhydryl sulfonate compound, and sulfonate. An acid ester compound or the like. Among these photoacid generators, an oxime sulfonate compound is preferably used from the viewpoint of insulating properties. These photoacid generators may be used alone or in combination of two or more.

Specific examples of these photoacid generators include the following examples.

Trichloromethyl-s-triazines are 2-(3-chlorophenyl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-bis ( 4,6-trichloromethyl)-s-triazine, 2-(4-methylthiophenyl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-methoxy -β-styryl)-bis(4,6-trichloromethyl)-s-triazine, 2-piperidinyl-bis(4,6-trichloromethyl)-s-triazine, 2-[2- (furan-2-yl)vinyl]-bis(4,6-trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-bis (4 ,6-trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-bis(4,6-trichloromethyl)- a s-triazine, or a 2-(4-methoxynaphthyl)-bis(4,6-trichloromethyl)-s-triazine; the diaryliodonium salt is diphenyliodonium trifluoroacetate Salt, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, phenyl , 4-(2'-hydroxy-1'-tetradecyloxy)phenyliodonium trifluoromethanesulfonate, 4-(2'-hydroxy-1'-tetradecyloxy)phenyliodonium hexafluorophosphate Phthalate, phenyl, 4-(2'-hydroxy-1'-tetradecyloxy)phenyliodonium-p-toluenesulfonate, etc.; The triarylsulfonium salts are triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxybenzene Diphenylphosphonium trifluoroacetate, 4-phenylthiophenyldiphenylphosphonium trifluoromethanesulfonate, or 4-phenylthiophenyldiphenylphosphonium trifluoroacetate; quaternary ammonium salt The class is tetramethylammonium butyl tris(2,6-difluorophenyl)borate, tetramethylammonium hexyltris(p-chlorophenyl)borate, tetramethylammonium hexyltris(3-trifluoromethyl) Phenyl)borate, benzyldimethylphenylammonium butyl tris(2,6-difluorophenyl)borate, benzyldimethylphenylammonium hexyltris(p-chlorophenyl)borate, benzyl Dimethylphenylammonium hexyltris(3-trifluoromethylphenyl)borate; etc.; diazomethane derivative is bis(cyclohexylsulfonyl)diazomethane, bis(t-butylsulfonyl) Diazomethane, bis(p-toluenesulfonyl)diazomethane, etc.; ruthenium sulfinate derivative is trifluoromethylsulfonyloxybicyclo[2.2.1]hept-5-enedicarboxyfluorene Amine, amber quinone imine triflate, phthalimide triflate, N-hydroxynaphthalene Methanesulfonate imide, N- hydroxy-5-norbornene-2,3-dicarboxy-propane sulfonate (PEI) and the like; oxime sulfonate compound is a compound shown below.

As the oxime sulfonate compound, that is, a compound having an oxime sulfonate residue, a compound containing an oxime sulfonate residue represented by the following formula (b1) is preferably exemplified.

(In the formula (b1), R ⁵ represents an alkyl group or an aryl group.)

Any group may be substituted, and the alkyl group in R ⁵ may be linear, branched or cyclic. The substituents allowed are explained below.

The alkyl group of R ⁵ is preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group. The alkyl group of R ⁵ 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 bridge such as 7,7-dimethyl-2-oxonorbornyl group). A cyclic alicyclic group, preferably a bicycloalkyl group, etc., is substituted.

The aryl group of R ⁵ 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 ⁵ may be substituted by a lower alkyl group, an alkoxy group or a halogen atom.

As the compound containing the oxime sulfonate residue represented by the formula (b1), an oxime sulfonate represented by the formula (OS-3), the formula (OS-4) or the formula (OS-5) is preferred. Compound.

(In the formula (OS-3) to (OS-5), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, and R ² each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ⁶ respectively Independently, it represents a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, and m represents an integer of 0-6. )

In the formula (OS-3) to the formula (OS-5), the alkyl group, the aryl group or the heteroaryl group in R ¹ may have a substituent.

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

Examples of the substituent which the alkyl group in R ¹ may have include a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group.

Examples of the alkyl group in R ¹ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, and an n-octyl group. N-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl, benzyl.

Further, in the above formula (OS-3) to formula (OS-5), as the aryl group in R ¹ , an aryl group having a total carbon number of 6 to 30 which may have a substituent is preferable.

Examples of the substituent which the aryl group in R ¹ may have include a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an amine group. A carbonyl group, a sulfonic acid group, an aminosulfonyl group, an alkoxysulfonyl group.

Examples of the aryl group in R ¹ include a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, and a p-phenoxyphenyl group.

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

Examples of the substituent which the heteroaryl group in R ¹ may have include a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an amine. A carbonyl group, a sulfonic acid group, an aminosulfonyl group, an alkoxysulfonyl group.

In the above formula (OS-3) to formula (OS-5), the heteroaryl group in R ¹ may be a heteroaromatic ring as long as at least one ring, and for example, a heteroaromatic ring and a benzene ring may be condensed.

The heteroaryl group in R ¹ may, for example, be selected from the group consisting of a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzimidazole ring. A group in which one hydrogen atom is removed from the ring in the group.

In the above formula (OS-3) to formula (OS-5), R ² is 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), it is preferred that one or two of two or more R ² present in the compound are an alkyl group, an aryl group or a halogen atom, and more preferably 1 The one is an alkyl group, an aryl group or a halogen atom, and particularly preferably one is an alkyl group and the remainder is a hydrogen atom.

In the formula (OS-3) to formula (OS-5), the alkyl group or the aryl group in R ² may have a substituent.

The substituent which the alkyl group or the aryl group in R ² may have is the same as the substituent which the alkyl group or the aryl group in R ¹ may have.

The alkyl group in R ² is preferably an alkyl group having a total carbon number of 1 to 12, and more preferably an alkyl group having a total carbon number of 1 to 6 which may have a substituent.

As the alkyl group in R ² , a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a second butyl group, a n-hexyl group, an allyl group, a chloromethyl group or a bromomethyl group are preferable. Methoxymethyl, benzyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl, still more preferably methyl, ethyl , n-propyl, n-butyl, n-hexyl, particularly preferably methyl.

As the aryl group in R ² , an aryl group having a total carbon number of 6 to 30 which may have a substituent is preferable.

Specific examples of the aryl group in R ² are a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, and a p-phenoxyphenyl group.

Examples of the halogen atom in R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Among these halogen atoms, a chlorine atom or a bromine atom is preferred.

In the formula (OS-3) to formula (OS-5), X represents O or S, preferably O.

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

In the formula (OS-3) to formula (OS-5), n represents 1 or 2. When X is 0, n is preferably 1, and when X is S, n is preferably 2.

In the above formula (OS-3) to formula (OS-5), the alkyl group and the alkoxy group in R ⁶ may have a substituent.

In the above formula (OS-3) to formula (OS-5), as the alkyl group in R ⁶ , an alkyl group having a total carbon number of 1 to 30 which may have a substituent is preferable.

Examples of the substituent which the alkyl group in R ⁶ may have include a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group.

As the alkyl group in R ⁶ , a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, an n-octyl group, and a fluorenyl group are preferable. Base, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl, benzyl.

In the above formula (OS-3) to formula (OS-5), the alkoxy group in R ⁶ is preferably an alkoxy group having a total carbon number of 1 to 30 which may have a substituent.

Examples of the substituent which the alkoxy group in R ⁶ may have include a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group.

As the alkoxy group in R ⁶ , a methoxy group, an ethoxy group, a butoxy group, a hexyloxy group, a phenoxyethoxy group, a trichloromethoxy group, or an ethoxyethyloxy group is preferable.

In the above formula (OS-3) to formula (OS-5), examples of the aminosulfonyl group in R ⁶ include a methylaminosulfonyl group, a dimethylaminosulfonyl group, and a phenyl group. Aminosulfonyl, methylphenylaminosulfonyl, aminosulfonyl.

In the above formula (OS-3) to formula (OS-5), examples of the alkoxysulfonyl group in R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, and a propoxy sulfonate. Mercapto, butoxysulfonyl.

Further, in the above formula (OS-3) to formula (OS-5), m represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

Further, the compound containing the oxime sulfonate residue represented by the formula (b1) is particularly preferably an oxime sulfonate represented by any one of the following formulas (OS-6) to (OS-11). Compound.

(In the formula (OS-6)~(OS-11), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, R ⁷ represents a hydrogen atom or a bromine atom, and R ⁸ represents a hydrogen atom, and the carbon number is 1-8. Alkyl, halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl or chlorophenyl, R ⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, R ¹⁰ Represents a hydrogen atom or a methyl group.)

The same as in the formula (OS-6) ~ formula (OS-11) R ¹ with the meaning of the formula - (OS-5) R of the formula (OS-3) ^1, a preferred embodiment is also the same.

R ⁷ in the formula (OS-6) represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.

R ⁸ in the formula (OS-6)~(OS-11) represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, or a methoxy group. The group, a phenyl group or a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms. Particularly preferred is a methyl group.

R ⁹ in the formula (OS-8) and the formula (OS-9) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and preferably a hydrogen atom.

R ¹⁰ in the formula (OS-8)~(OS-11) represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

Further, in the oxime sulfonate compound, regarding the steric structure (E, Z) of ruthenium, It may be either a stereostructure or a mixture.

Specific examples of the oxime sulfonate compound represented by the above formula (OS-3) to formula (OS-5) include the following exemplified compounds, but the present invention is not limited to these exemplified compounds.

As the compound containing the oxime sulfonate residue represented by the formula (b1), a compound represented by the formula (OS-1) is also preferable.

(In the formula (OS-1), R ¹ 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, an aromatic group. Or a heteroaryl group. R ² represents an alkyl group or an aryl group.)

X represents -O -, - S -, - NH -, - NR 5 -, - CH 2 -, - CR 6 H-, ^{or, -CR 6 R 7 -, R} 5 ~ R 7 represents an alkyl group, or aryl base.

R ²¹ to R ²⁴ 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 ²¹ to R ²⁴ may be bonded to each other to form a ring.

R ²¹ to R ^{24 are} preferably a hydrogen atom, a halogen atom or an alkyl group, and a form in which at least two of R ²¹ to R ²⁴ are bonded to each other to form an aryl group is also preferable. Among them, from the viewpoint of sensitivity, it is preferred that R ²¹ to R ²⁴ are each a hydrogen atom.

The functional groups described may each further have a substituent.

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

(OS-2) ^{of, R 1, R 2, 2} , R 21 ~ R the same meaning as the formula R ²¹ ~ R ²⁴ are respectively the formula R (OS-1) is ^1, R ^24, Further, preferred examples of The same is true.

Among these compounds, R ¹ in the formula (OS-1) and the formula (OS-2) is more preferably a form of a cyano group or an aryl group, most preferably represented by the formula (OS-2), and R ¹ is a cyanide. The form of a phenyl group or a naphthyl group.

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

In the following, specific examples (exemplified compound b-1 to exemplary compound b-34) of the compound represented by the formula (OS-1) which can be suitably used in the present invention are shown, but the present invention is not limited thereto. Further, Me represents a methyl group, Et represents an ethyl group, Bn represents a benzyl group, and Ph represents a phenyl group.

Among the above compounds, b-9, b-16, b-31, and b-33 are preferable from the viewpoint of the coexistence of sensitivity and stability.

The compound containing the oxime sulfonate residue represented by the formula (b1) may also be an oxime sulfonate compound represented by the following formula (b2).

(In the formula (b2), R ⁵ represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group or a halogen atom, m represents an integer of 0 to 3, and when m is 2 or 3, a plurality of X may be the same , can also be different.)

The alkyl group of X is preferably a linear alkyl group or a branched alkyl group having 1 to 4 carbon atoms.

The alkoxy group of X is preferably a linear alkoxy group having a carbon number of 1 to 4 or a branched alkoxy group.

As the halogen atom of X, a chlorine atom or a fluorine atom is preferred.

m is preferably 0 or 1.

In the formula (b2), m is preferably 1, X is a methyl group, the substitution position of X is an ortho position, and R ⁵ is a linear alkyl group having a carbon number of 1 to 10, and 7,7-dimethyl-2. - a compound of oxo norbornylmethyl or p-tolylmethylhydrazino.

The compound containing the oxime sulfonate residue represented by the formula (b1) may also be an oxime sulfonate compound represented by the formula (b3).

(In the formula (b3), the same meaning as R in the formula (b1) ⁵ to R ^5, X 'represents a halogen atom, hydroxyl, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 , cyano or nitro, L represents an integer from 0 to 5.)

As R ⁵ in the formula (b3), methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro-positive are preferable. Butyl, p-tolyl, 4-chlorophenyl or pentafluorophenyl, particularly preferably n-octyl.

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

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

Specific examples of the compound represented by the formula (b3) include α-(methylsulfonyloxyimino)benzyl cyanide and α-(ethylsulfonyloxyimino)benzyl cyanide. , α-(n-propylsulfonyloxyimino)benzyl cyanide, α-(n-butylsulfonyloxyimino)benzyl cyanide, α-(4-toluenesulfonyloxyimino) Benzyl cyanide, α-[(methylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(ethylsulfonyloxyimino)-4-methoxy Phenyl]acetonitrile, α-[(n-propylsulfonyloxyimino)-4-methoxyphenyl] Acetonitrile, α-[(n-butylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(4-toluenesulfonyloxyimino)-4-methoxybenzene Base] acetonitrile.

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

In the photosensitive resin composition of the present invention, the photoacid generator (B) is preferably used in an amount of 0.1 part by weight to 10 parts by weight, more preferably 0.5 part by weight to 10 parts by weight, per 100 parts by weight of the resin component.

<(C) component>

The photosensitive resin composition of the present invention preferably contains (C) a polymer containing at least a crosslinking group.

The component (C) is preferably an addition polymerization type resin, and more preferably a polymer containing a constituent unit derived from (meth)acrylic acid and/or an ester thereof. Further, it may have a constituent unit other than the constituent unit derived from (meth)acrylic acid and/or an ester thereof, for example, a constituent unit derived from styrene or derived from A constituent unit of a vinyl compound or the like.

The component (C) preferably contains 50 mol% or more of a constituent unit derived from (meth)acrylic acid and/or an ester thereof, and more preferably contains 90 mol% or more of the total amount of the component (C). The constituent unit of the methyl methacrylate and/or its ester is particularly preferably a polymer containing only a constituent unit derived from (meth)acrylic acid and/or an ester thereof.

In addition, "the constituent unit derived from (meth)acrylic acid and/or its ester" is also referred to as "acrylic constituent unit". Further, "(meth)acrylic acid" means "methacrylic acid and/or acrylic acid".

The component (C) may further comprise (c1) a constituent unit containing a residue in which the acid group is protected by an acid-decomposable group. When the component (C) contains (c1), the sensitivity is improved, and the component (C) contains (c2), and the permanent film property is improved. Further, the component (C) preferably does not substantially contain a constituent unit having -NH-CH ₂ -OR (R is an alkyl group). With such a configuration, the effects of the present invention tend to be more effectively exhibited. Here, the term "substantially not included" means that it is not added to the level which affects the effect of the present invention, and is, for example, 3 mol% or less of the total constituent unit of the component (C), and further 1 mol%. the following.

As the component (C1) (C1), the same group as the constituent unit>> of the residue in which the acid group is protected by the acid-decomposable group can be used. In the constituent unit constituting the copolymer (C), the content of the constituent unit (c1) is preferably 0 mol% to 95 mol%, more preferably 5 mol%, from the viewpoint of sensitivity. ~90% by mole, particularly preferably 20% by mole to 70% by mole.

As the component (C2) of the component (C), the same group as the constituent unit >> containing the crosslinking group in the above <<(a3) can be used. The preferred embodiment is also the same. In the constituent unit constituting the copolymer (C), the content of the constituent unit (c2) is preferably 0 mol% to 95 mol%, more preferably 5 mol%, from the viewpoint of sensitivity. ~90% by mole, particularly preferably 30% by mole to 70% by mole.

The component (C) may have other constituent units (c3) in addition to (c1), (c2), and (a2). The monomer to be another constituent unit (c3) is not particularly limited. The same base as the "repeating unit (a3)" and the other constituent unit of <<(a4) can be suitably used. The preferred embodiment is also the same. The preferred range is also the same.

<<Molecular weight of (C) component>>

The molecular weight of the component (C) 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 range of the numerical value, various 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.

<<Manufacturing method of (C) component>>

Various methods are also known for the synthesis method of the component (C), and if an example is given, the content can be represented by the above (c1) and (c2) by using a radical polymerization initiator. The radically polymerizable monomer mixture of the radical polymerizable monomer of the constituent unit is synthesized by polymerization in an organic solvent. Further, it can also be synthesized by a so-called polymer reaction.

Similarly to the component (A), a carboxyl group at the terminal is also preferable.

As an example of the component (C), a copolymer of 3,4-epoxycyclohexylmethyl methacrylate/acrylic acid/hydroxystyrene/methyl methacrylate (mol ratio of 30/40/15/) is exemplified. 15, Mw is 7000); glycidyl methacrylate / methacrylic acid / styrene / dicyclopentanyl methacrylate copolymer (Morby is 70/10/10/10, Mw is 15000); Glycidyl glycidyl ether / (3-ethyl-3-oxetanyl)methyl methacrylate / maleic acid / cyclohexyl methacrylate copolymer (Morby ratio 25/25/ 30/20, Mw is 27000); 1-ethoxyethyl methacrylate/methacrylic acid/methacrylic acid (3-ethyloxalate) Cyclobutane-3-yl)methyl ester/2-hydroxyethyl methacrylate/methyl methacrylate copolymer (mol ratio 38/7/35/15/5, Mw 35000); methacrylic acid 1-cyclohexyloxyethyl ester/methacrylic acid/methoxypolyethylene glycol methacrylate (Blemmer PME-400 (Blemma PME-400), Nippon Oil (share) copolymer (Morbi is 70/15/15, Mw is 45000); Acrylic (3-ethyl-3-oxetanyl)methyl ester/methacrylic acid/N-phenyl maleimide copolymer (Moerby It is 30/30/40 and Mw is 57000).

The content of the component (C) is preferably 0 wt% to 80 wt%, more preferably 8 wt% to 70 wt%, still more preferably 30 wt% to 65 wt%, particularly preferably 30 wt% to 50 wt% of the total polymer component. . When two or more types of (C) components are contained, the total amount thereof becomes the above range.

<ratio of each constituent unit to total polymer component>

The photosensitive resin composition of the present invention preferably has 99% by weight or more of the polymer component as the component (A) or the component (C).

Further, in the present invention, the proportion of the constituent unit (a2) in the total polymer component is preferably from 1 mol% to 50 mol%, more preferably from 10 mol% to 50 mol%, still more preferably 15 mol%. ~50% by mole. Further, in the present invention, the proportion of the crosslinking group in the total polymer component is preferably from 1 mol% to 40 mol%, more preferably from 10 mol% to 35 mol%, still more preferably from 15 mol% to 30 Moer%.

In particular, in the present invention, it is preferred that 10 mol% or more of the total polymer component contained in the positive photosensitive composition is a constituent unit (a2) having -NH-CH ₂ -OR (R is an alkyl group), More than 20 mol% of the total polymer component is a crosslinking group.

Further, in the present invention, the ratio of the crosslinkable group in the total polymer component to the total amount of the constituent unit (a2) is preferably 10 mol% to 70 mol%, more preferably 40 mol% to 60 mol%. . By setting it as such a range, the effect of this invention is exhibited more effectively.

<(D) Solvent>

The photosensitive resin composition of the present invention usually contains (D) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution obtained by dissolving an essential component, a preferred component, and an optional component in a solvent (D).

As the solvent (D) used in the photosensitive resin composition of the present invention, a known solvent can be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, and ethylene glycol monoalkanes. Ethyl acetate, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, propylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, diethylene glycol monoalkyl ether acetate And dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, guanamines, lactones, and the like.

The (D) solvent used in the photosensitive resin composition of the present invention may, for example, be (D-1) ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether or ethylene glycol. Ethylene glycol monoalkyl ethers such as monobutyl ether; (D-2) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether; 3) ethylene glycol monomethyl ether acetate such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate; -4) propylene glycol monomethyl ether such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether; (D-5) propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether , propylene glycol monoalkyl ether such as diethylene glycol monoethyl ether; (D-6) propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc. Ethyl ether acetates; (D-7) diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether; (D-8) diethylene glycol single Diethylene glycol monoalkyl ether acetates such as methyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate; (D-9 Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether Dipropylene glycol dialkyl ether; (D-10) dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, etc. Ether acetate; (D-11) lactate such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate (D-12) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, N-propyl acrylate, isopropyl propionate, n-butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate , an aliphatic carboxylic acid ester such as isobutyl butyrate; (D-13) ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutanoate, Ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropane Ethyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3 butyrate Other esters such as -methoxybutyl ester, ethyl acetate methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate; (D-14) methyl ethyl ketone, methyl propyl ketone, a ketone such as methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone or cyclohexanone; (D-15) N-methylformamide, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. Amines; (D-16) lactones such as γ-butyrolactone.

Further, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether may be further added to these solvents as needed. , isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, A solvent such as ethylene carbonate 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 are used in combination, and further, propylene glycol monoalkyl ether acetate and diethylene glycol dialkyl ether are more preferably used in combination.

The content of the solvent (D) in the photosensitive resin composition of the present invention is preferably 50 parts by weight to 3,000 parts by weight, more preferably 100 parts by weight to 2,000 parts by weight, still more preferably 150 parts by weight to 100 parts by weight of the resin component. 1,500 parts by weight.

In the positive photosensitive resin composition of the present invention, a crosslinking agent, an adhesion improving agent, a basic compound, a surfactant, a plasticizer, a thermal radical generating agent, and an antioxidant may be added in addition to the above components. And known additives such as a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic anti-precipitation agent.

<(E) adhesion improver>

The photosensitive resin composition of the present invention may contain (E) a adhesion improving agent. The (E) adhesion improver which can be used in the photosensitive resin composition of the present invention is an inorganic substance which is promoted as a substrate, for example, a ruthenium compound such as ruthenium, iridium oxide or ruthenium nitride, and adhesion between a metal such as gold, copper or aluminum and an insulating film. compound of. Specific examples thereof include a decane coupling agent, a thiol compound, and the like. The decane coupling agent which is the (E) adhesion improving agent used in the present invention is not particularly limited as long as it is a modification of the interface, and a known decane coupling agent can be used.

Preferred examples of the decane coupling agent include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-glycidoxypropyltrialkoxydecane, and γ-. Glycidoxypropyl dialkoxy decane, γ-methyl propylene methoxy propyl trialkoxy decane, γ-methyl propylene methoxy propyl dialkoxy decane, γ-chloropropyl three Alkoxydecane, γ-mercaptopropyltrialkoxydecane, β-(3,4-epoxycyclohexyl)ethyltrialkoxydecane, vinyltrialkoxydecane. Among these decane coupling agents, γ-glycidoxypropyl trialkoxy decane or γ-methacryloxypropyl trialkoxy decane is more preferable, and γ-glycidoxypropyl group is more preferable. Trialkoxydecane. These adhesion improving agents may be used alone or in combination of two or more. These adhesion improvers are effective for improving the adhesion to the substrate, and are also effective for adjusting the taper angle with the substrate.

The content of the (E) adhesion improving agent in the photosensitive resin composition of the present invention is preferably 0.1 parts by weight to 20 parts by weight, and more preferably 0.5 parts by weight to 10 parts by weight, based on 100 parts by weight of the resin component.

<(G) Basic Compound>

The photosensitive resin composition of the present invention may contain (G) a basic compound. The (G) basic compound can be arbitrarily selected from the basic compounds used in 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.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and bicyclol. Hexylamine, dicyclohexylmethylamine, and the like.

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

Examples of the heterocyclic amine include pyridine, 2-methylpyridine, and 4-methylpyridine. 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-hydroxyquinoline , pyrazine, pyrazole, pyridazine, anthracene, pyrrolidine, acridine, pyridazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.3.0]-7-undecene.

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

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

The basic compound which can be used in the present invention may be used singly or in combination of two or more kinds, and it is preferred to use two or more kinds in combination, and it is more preferred to use two kinds in combination, and it is more preferred to use two kinds of heterocyclic amines in combination.

The content of the (G) basic compound in the photosensitive resin composition of the present invention is preferably 0.001 part by weight to 1 part by weight, more preferably 0.005 part by weight to 0.2 part by weight, per 100 parts by weight of the resin component.

<(H) surfactant]

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

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, polyoxyethylene glycols, higher fatty acid diesters, and fluorenone. Fluorine surfactant. In addition, the following product names are listed: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), and Eftop (Japan Electronic Materials Co., Ltd. (JEMCO)) Manufacture), Megafac (Mega) (made by Di sheng (DIC)), Fluorad (made by Sumitomo 3M (share)), Asahi Guard (Asahi Kasuga), Surflon (Savron) (Asako (share) ) Manufacturing), PolyFox (made by OMNOVA) and other series.

In addition, as a surfactant, a copolymer containing a structural unit A and a structural unit B represented by the following formula (1) and having tetrahydrofuran (THF) as a solvent is exemplified. The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography is 1,000 or more and 10,000 or less.

(In the formula (1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkyl group having 1 or more and 4 or less carbon atoms, and R ⁴ represents a hydrogen atom or a carbon number of 1 In the above alkyl group, 4 or less, L represents an alkylene group having 3 or more and 6 or less carbon atoms, p and q are weight percentages indicating a polymerization ratio, and p is a numerical value of 10% by weight or more and 80% by weight or less, and q is a value. a numerical value of 20 wt% or more and 90 wt% or less, r represents an integer of 1 or more and 18 or less, and n represents an integer of 1 or more and 10 or less.) The L is preferably a branched alkyl represented by the following formula (2) base. R ⁵ in the formula (2) is an alkyl group having 1 or more and 4 or less carbon atoms, and from the viewpoint of compatibility and wettability to a surface to be coated, an alkane having 1 or more and 3 or less carbon atoms is preferable. The base 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, which is 100 wt%.

The weight average molecular weight (Mw) of the 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 (H) surfactant added to the photosensitive resin composition of the present invention is preferably 10 parts by weight or less, more preferably 0.01 parts by weight to 10 parts by weight, still more preferably 0.01 parts by weight to 100 parts by weight of the resin component. 1 part by weight.

<(I) plasticizer>

The photosensitive resin composition of the present invention may contain (I) a plasticizer. Examples of the (I) plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, and glycerin. Dimethyl glycerin phthalate, dibutyl tartrate, dioctyl adipate, triethylene glycerol, and the like.

The amount of the (I) plasticizer added to the photosensitive resin composition of the present invention is preferably 0.1 parts by weight to 30 parts by weight, more preferably 1 part by weight to 10 parts by weight, per 100 parts by weight of the resin component.

<(J) Thermal Radical Producer>

The photosensitive resin composition of the present invention may contain (J) a thermal radical generating agent, and when it contains an ethylenically unsaturated compound having a compound having at least one ethylenically unsaturated double bond as described above, it is preferably contained (J). a thermal radical generator. As the thermal radical generator in the present invention, a known thermal radical generator can be used.

The thermal radical generating agent is a compound which generates a radical by thermal energy and starts or promotes a polymerization reaction of the polymerizable compound. By adding a thermal radical generator, the obtained cured film sometimes becomes stronger, and heat resistance and solvent resistance are improved.

Preferred examples of the thermal radical generator include aromatic ketones and sulfonium salts. , organic peroxide, thio compound, hexaarylbiimidazole compound, ketoxime compound, borate compound, azinium compound, metallocene compound, active ester compound, compound having a carbon halogen bond, An azo compound, a bibenzyl compound or the like. (J) The thermal radical generating agent may be used singly or in combination of two or more.

When the (A) polymer is 100 parts by weight, the amount of the (J) thermal radical generating agent in the photosensitive resin composition of the present invention is preferably 0.01 parts by weight to 50%. The parts by weight are more preferably 0.1 part by weight to 20 parts by weight, most preferably 0.5 part by weight to 10 parts by weight.

<(K)Antioxidant>

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

Examples of such an antioxidant include phosphorus-based antioxidants, hydrazines, hindered amine-based antioxidants, sulfur-based antioxidants, phenolic antioxidants, ascorbic acid, zinc sulfate, saccharides, nitrites, and sulfites. , thiosulfate, hydroxylamine derivatives, and the like. Among these antioxidants, a phenol-based antioxidant is particularly preferable from the viewpoint of coloring and film thickness reduction of the cured film. These antioxidants may be used alone or in combination of two or more.

As a commercial item of a phenolic antioxidant, Adekastab AO-60 (Adi Costab AO-60), Adekastab AO-80 (Adi Costab AO-80) (The above, Adico ( ADEKA) (manufactured by the company), Irganox 1098 (Ilagana Knox 1098) (manufactured by Ciba Japan (stock)).

The content of the (K) antioxidant is preferably 0.1% by mass to 6% by mass, more preferably 0.2% by mass to 5% by mass, and particularly preferably 0.5% by mass based on the total solid content of the photosensitive resin composition. %~4% by mass. When it is set in this range, the film formed can obtain sufficient transparency, and the sensitivity at the time of pattern formation also becomes favorable.

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

<(L) Crosslinker>

The photosensitive resin composition of the present invention preferably contains a crosslinking agent (L) as needed. As the crosslinking agent (L), for example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, a crosslinking agent containing an alkoxymethyl group, and at least one ethylene may be added. A compound of a sexually unsaturated double bond. By adding a crosslinking agent (L), the cured film can be made into a stronger film. The following compounds may be added as a crosslinking agent.

<Compound having two or more epoxy 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 novolak type epoxy resin, and a cresol novolak type ring. Oxygen resin, aliphatic epoxy resin, and the like.

These compounds are available as commercial products. For example, examples of the bisphenol A type epoxy resin include JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, and JER1010 (above, Japan Epoxy Resins (share)). EPICLON 860 (Epilon 860), EPICLON 1050 (Epiclon 1050), EPICLON 1051 (Epiclon 1051), EPICLON 1055 (Epiclon 1055) (above, manufactured by Di Ai Sheng (share)), etc., as bisphenol F-type epoxy Examples of the resin include JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, manufactured by Nippon Epoxy Co., Ltd.), EPICLON 830 (Epicon 830), and EPICLON 835 (Epicon 835) (above, Di Aisheng (share) ))), LCE-21, RE-602S (above, As a phenol novolac type epoxy resin, JER152, JER154, JER157S65, JER157S70 (above, manufactured by Nippon Epoxy Resin Co., Ltd.), EPICLON N-740 (Epilon N -740), EPICLON N-770 (Epiclon N-770), EPICLON N-775 (Epilon N-775) (above, manufactured by Di Aisheng (share)), etc., as cresol novolak type epoxy resin Examples include EPICLON N-660 (Epiclon N-660), EPICLON N-665 (Epilon N-665), EPICLON N-670 (Epiclon N-670), EPICLON N-673 (Epiclon) N-673), EPICLON N-680 (Epiclon N-680), EPICLON N-690 (Epiclon N-690), EPICLON N-695 (Epicon N-695) (above, Di Aisheng (share (manufacturing), EOCN-1020 (above, manufactured by Nippon Kayaku Co., Ltd.), etc., as the aliphatic epoxy resin, ADEKA RESIN EP-4080S (Adico resin EP-4080S), ADEKA RESIN EP-4085S ( Adico Resin EP-4085S), ADEKA RESIN EP-4088S (Adico Resin EP-4088S) (above, manufactured by Eddy Co., Ltd.), Celloxide 2021P (West Roxie 2021P), Celloxide2081 (Western Samuel 2081), Celloxide2083 ( West Roxie 2083), Celloxide2085 (West Roxie 2085), EHPE3150, EPOLEAD PB 3600 (Apollo PB 3600), EPOLEAD PB 4700 (Apollo PB 4700) (above, Daicel Chemical) Industrial (share) manufacturing, etc. In addition, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4010S ), ADEKA RESIN EP-4011S (Adico Resin EP-4011S) (above, manufactured by Eddy Co., Ltd.), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN- 502 (above, manufactured by Aidike (share)), etc. These compounds may be used alone or in combination of two or more.

Among these compounds, preferred examples of the compound include a bisphenol A epoxy resin, a bisphenol F epoxy resin, an aliphatic epoxy resin, and a phenol novolak epoxy resin. Cresol novolac type epoxy resin. A bisphenol A type epoxy resin, a phenol novolak type epoxy resin, and an aliphatic epoxy resin are particularly preferable.

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

Specific examples of the compound having two or more oxetanyl groups in the molecule include OXT-121, OXT-221, OX-SQ, and PNOX (above, manufactured by Toagosei Co., Ltd.).

When the total amount of the resin component is 100 parts by weight, the compound having an epoxy group or oxetanyl group is preferably added in an amount of from 1 part by weight to 50 parts by weight, more preferably 3 parts by weight, based on the photosensitive resin composition. ~30 parts by weight.

<Alkoxymethyl group-containing crosslinking agent>

The alkoxymethyl group-containing crosslinking agent is preferably an alkoxymethylated melamine, an alkoxymethylated benzoguanamine, an alkoxymethylated glycoluril or an alkoxymethylated urea. These cross-linking agents are each obtained by converting a methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril or methylolated urea to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. In particular, a methoxymethyl group is particularly preferred. Among these crosslinkable compounds, preferred examples of the crosslinkable compound include alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril, which are transparent. From the viewpoint, alkoxymethylated glycoluril is particularly preferred.

These alkoxymethyl group-containing crosslinking agents are commercially available, and for example, Cymel 300 (Semmel 300), Cymel 301 (Semmel 301), Cymel 303 (Semmel 303), Cymel 370 (race) can be preferably used. Meier 370), Cymel325 (Semmel 325), Cymel327 (Semmel 327), Cymel701 (Semmel 701), Cymel266 (Semmel 266), Cymel267 (Semel 267), Cymel238 (Semel) 238), Cymel1141 (Semel 1141), Cymel272 (Semel 272), Cymel 202 (Semel 202), Cymel 1156 (Semel 1156), Cymel 1158 (Semel 1158), Cymel 1123 (Semel 1123), Cymel 1170 (Semel 1170), Cymel 1174 (Semel 1174), Cymel UFR65 (Semmel UFR65) (above, Mitsui Cyanamid) Manufactured by the company), Nikalac MX-750 (Nikarak MX-750), Nikalac MX-032 (Nikarak MX-032), Nikalac MX-706 (Nikarak MX-706), Nikalac MX-708 (Ni Karak MX-708), Nikalac MX-40 (Nikarak MX-40), Nikalac MX-31 (Nikarak MX-31), Nikalac MX-270 (Nikarak MX-270), Nikalac MX-280 (Nikarak MX-280), Nikalac MX-290 (Nikarak MX-290), Nikalac MS-11 (Nikarak MS-11), Nikalac MW-30HM (Nikarak MW-30HM), Nikalac MW -100LM (Nikarak MW-100LM), Nikalac MW-390 (Nikarak MW-390) (above, manufactured by Sanwa Chemical Co., Ltd.).

When a crosslinking agent containing an alkoxymethyl group is used for the photosensitive resin composition of the present invention with respect to 100 parts by weight of the resin component, the amount of the crosslinking agent containing an alkoxymethyl group is preferably 0.05 to 50% by weight. It is more preferably 0.5 to 10 parts by weight. By adding in this range, it is possible to obtain a preferable alkali solubility at the time of development and an excellent solvent resistance of the film after curing.

<Compound having at least one ethylenically unsaturated double bond>

As the compound having at least one ethylenically unsaturated double bond, a monofunctional (meth) acrylate, a difunctional (meth) acrylate, a trifunctional or higher (meth) acrylate or the like (methyl) can be preferably used. Acrylate compound.

Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth)acrylate, carbitol (meth)acrylate, isobornyl (meth)acrylate, and (meth)acrylic acid 3. - methoxybutyl ester, 2-(methyl) propylene methoxyethyl 2-hydroxypropyl phthalate, and the like.

Examples of the difunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexane diol di(meth) acrylate, and 1,9-nonanediol bis (methyl). Acrylate, polypropylene glycol Di(meth)acrylate, tetraethylene glycol di(meth)acrylate, bisphenoxyethanoloxime diacrylate, and the like.

Examples of the trifunctional or higher (meth) acrylate include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and tris((meth)acryloxyethyl) Phosphate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.

These compounds having at least one ethylenically unsaturated double bond may be used alone or in combination of two or more.

The use ratio of the compound having at least one ethylenically unsaturated double bond in the photosensitive resin composition of the present invention is preferably 50 parts by weight or less, and more preferably 30 parts by weight or less, based on 100 parts by weight of the resin component. By containing a compound having at least one ethylenically unsaturated double bond in such a ratio, heat resistance, surface hardness, and the like of the insulating film obtained from the photosensitive resin composition of the present invention can be improved. When a compound having at least one ethylenically unsaturated double bond is added, it is preferred to add (J) a thermal radical generator.

The positive photosensitive resin composition of the present invention preferably contains the photoacid generator (B) in an amount of at least 0.1% by mass to 10% by mass based on the total solid content, and is 40 in total. The resin (A) is contained in the range of % by mass to 95% by mass. Furthermore, it is more preferable to contain the resin (A) in a total range of 40% by mass to 95% by mass, and the photoacid generator (B) in a range of 0.1% by mass to 10% by mass based on the total solid content, and The crosslinking agent (D) is contained in the range of 3 to 40% by mass.

<sensitizer>

The photosensitive resin composition of the present invention preferably contains a sensitizer in combination with the photoacid generator (B) to promote decomposition of the photoacid generator. The sensitizer absorbs actinic rays or radiation and becomes an electronically excited state. a sensitizer that becomes an electronically excited state is in contact with a photoacid generator Electron movement, energy movement, heat, etc. Thereby, the photoacid generator undergoes 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 in any of the wavelength bands of 350 nm to 450 nm.

Polynuclear aromatics (eg, ruthenium, osmium, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10) -dipropoxypurine), xanthones (eg luciferin, eosin, erythrosine, rose red B, rose bengal), xanthones (eg xanthones, thioxanthone) , dimethyl thioxanthone, diethyl thia fluorenone), cyanines (such as thiacarbocyanine, oxacarbocyanine), procyanidins (such as procyanidins, carbonyls) Anthocyanins), rhodamines, oxaphthalocyanines, thiazides (such as thioindigo, methylene blue, toluidine blue), acridines (such as acridine orange, chlorferrin, acridine yellow), acridine Ketones (eg acridone, 10-butyl-2-chloroacridone), terpenoids (eg hydrazine), squaraines (eg squaraine), styryls, basic styrenics ( For example, 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] Quinazine-11-one).

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

(Method of forming a cured film)

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

The method for forming a cured film of the present invention is characterized by comprising the following steps (1) to (5).

(1) a step of applying the photosensitive resin composition of the present invention to a substrate; (2) a step of removing a solvent from the applied photosensitive resin composition; (3) a step of performing exposure using actinic rays; (4) a step of performing development using an aqueous developing solution; (5) A step of performing thermal hardening (post-baking step).

Each step will be described in order below.

In the step (1), the photosensitive resin composition of the present invention is applied (usually applied) to a substrate to form a wet film containing a solvent.

If a step of completely irradiating the actinic ray is added before the heating step, the acid generated by the irradiation of the actinic ray can be utilized to promote the crosslinking reaction.

Next, a method of forming a cured film using the positive photosensitive resin composition of the present invention will be specifically described.

In the solvent removal step of (2), the solvent is removed from the applied film by depressurization (vacuum) and/or heating to form a dried film on the substrate.

In the exposure step of (3), the obtained coating film is irradiated with actinic rays having a wavelength of 300 nm or more and 450 nm or less. In this step, (B) the photoacid generator decomposes and generates an acid. The acid generated by the acid-decomposable gene contained in the component (A) is hydrolyzed to form a carboxyl group or a phenolic hydroxyl group. By irradiating the obtained film with actinic rays, the photoacid generator decomposes and generates an acid. The acid dissociation gene hydrolysis reaction in the structural unit represented by the general formula (A2') contained in the resin (A) is dissociated by the catalytic action of the generated acid to form a carboxyl group. Then, by performing development using an alkaline developing solution, the exposed portion including the resin having a carboxyl group which is easily dissolved in the alkaline developing solution is removed to form a positive image.

The reaction formula of this hydrolysis reaction is shown below.

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 as needed. The formation of a carboxyl group or a phenolic hydroxyl group derived from an acid-decomposable group can be promoted by PEB.

The acid-decomposable group in the monomer unit represented by the formula (1) in the present invention has low activation energy due to acid decomposition, is easily decomposed by an acid derived from a photoacid generator generated by exposure, and generates a carboxyl group or Since the phenolic hydroxyl group is not necessarily PEB, it can be formed into a positive image by development.

Further, PEB can also be carried out at a relatively low temperature, whereby hydrolysis of the acid-decomposable group is promoted without causing a crosslinking reaction. The temperature at the time of 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 80° C. or lower.

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

In the step of post-baking in (5), by heating the obtained positive image, the acid-decomposable group in the monomer unit (a1) can be thermally decomposed to form a carboxyl group or a phenolic hydroxyl group, and The crosslinking group of the monomer unit (a2) is crosslinked, whereby a cured film can be formed. The heating is preferably carried out to a high temperature of 150 ° C or higher, more preferably to 180 ° C to 250 ° C, and particularly preferably to 200 ° C to 250 ° C. The heating time can be appropriately set depending on the heating temperature and the like, but is preferably in the range of 10 minutes to 90 minutes.

If a step of completely irradiating the developing pattern with actinic rays, preferably ultraviolet rays, is added before the post-baking step, the acid generated by irradiating the actinic rays can be utilized to promote the crosslinking reaction.

Next, a method of forming a cured film using the photosensitive resin composition of the present invention will be specifically described.

<Method for Preparing Photosensitive Resin Composition>

Mixing the ingredients in a prescribed ratio and in an arbitrary manner, followed by stirring The photosensitive resin composition was prepared by dissolving. For example, a resin composition may be prepared by dissolving each component in a solvent in advance to prepare a solution, and then mixing these components in a predetermined ratio. The composition solution prepared as described above may be used after being filtered using a filter having a pore size of 0.2 μm or the like.

<Application step and solvent removal step>

The photosensitive resin composition is applied to a predetermined substrate, and the solvent is removed by pressure reduction and/or heating (prebaking), whereby a desired dried coating film can be formed. In the production of the liquid crystal display device, for example, a polarizing plate is provided, and a black matrix layer, a color filter layer, and a transparent conductive circuit layer are provided as needed. The method of applying the photosensitive resin composition to the substrate is not particularly limited, and for example, a method such as a slit coating method, a spray method, a roll coating method, or a spin coating method can be used. Among them, a slit coating method is preferred from the viewpoint of being suitable for a large substrate. When it manufactures with a large substrate, productivity is high, and it is preferable. Here, the large-sized substrate refers to a substrate having a size of 1 m or more on each side.

In addition, (2) the heating condition of the solvent removal step is that the acid-decomposable group is decomposed in the monomer unit (a1) in the resin component in the unexposed portion, and the resin component is not soluble in the alkaline developing solution. The range varies depending on the type of each component or the blending ratio, but it is preferably heated at 80 ° C to 130 ° C for about 30 seconds to 120 seconds.

<Exposure step and development step (pattern formation method)>

In the exposure step, the substrate provided with the coating film is irradiated with actinic rays through a mask having a predetermined pattern. After the exposure step, heat treatment (PEB) is performed as needed, and then, in the development step, the exposed portion region is removed using an alkaline developer to form an image pattern.

In the exposure using actinic rays, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generating device, or the like can be used, and g rays can be preferably used. (436 nm), i-ray (365 nm), An actinic ray having a wavelength of 300 nm or more and 450 nm or less, such as h-ray (405 nm). Further, the illumination light may be adjusted by a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter as needed.

It is preferred that the developer used in the developing step contains a basic compound. As the basic compound, for example, an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide; an alkali metal carbonate such as sodium carbonate or potassium carbonate; or an alkali metal such as sodium bicarbonate or potassium bicarbonate can be used. Bicarbonate; ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or choline hydroxide; aqueous solution of sodium citrate or sodium metasilicate. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution of the base may be used as the developer.

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

The development time is preferably from 30 seconds to 180 seconds, and the development method may be any one of a puddle development method and a dipping method. After development, a running water rinse of 30 seconds to 90 seconds can be performed to form a desired pattern.

<Post-baking step (cross-linking step)>

Use a heating device 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 60 minutes on a hot plate, or 30 minutes to 90 minutes for an oven. In a minute, the pattern corresponding to the unexposed area obtained by the development is heat-treated, whereby the acid-decomposable group in the resin component is decomposed to generate a carboxyl group or a phenolic hydroxyl group, and then reacted with the crosslinkable group. By crosslinking, a protective film or an interlayer insulating film excellent in heat resistance, hardness, and the like can be formed. Further, when the heat treatment is performed, it can also be carried out under a nitrogen atmosphere, thereby improving transparency.

Further, it is preferred that after the heat treatment, the substrate on which the pattern is formed is re-exposed by actinic rays, and then post-baking (re-exposure/post-baking) is performed, thereby being present from the unexposed portion. The component (B) in the middle produces an acid and functions as a catalyst for promoting the crosslinking step.

That is, the method of forming the cured film of the present invention is preferably between the developing step and the post-baking step, and includes a re-exposure step of performing re-exposure using actinic rays. The exposure in the re-exposure step may be carried out by the same method as the exposure step, and in the re-exposure step, it is preferable to comprehensively form the side of the substrate on which the film is formed by the photosensitive resin composition of the present invention. exposure.

The preferred exposure amount of the re-exposure step is from 100 mJ/cm ² to 1,000 mJ/cm ² .

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 can be obtained. The interlayer insulating film obtained by using the photosensitive resin composition of the present invention has high transparency and is excellent in physical properties of a cured film, and thus is useful for use in an organic EL display device or a liquid crystal display device.

The organic EL display device or 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 using the photosensitive resin composition of the present invention, and various structures are known. Various organic EL display devices or liquid crystal display devices.

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 in various applications. For example, in addition to the planarization film or the interlayer insulating film, a protective film for a color filter or a spacer for maintaining the thickness of the liquid crystal layer in the liquid crystal display device to be fixed, or A microlens or the like provided on a color filter in the solid-state imaging element.

FIG. 1 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, and having a planarization film 4.

A bottom gate type TFT 1 is formed on the glass substrate 6, and an insulating film 3 containing Si ₃ N ₄ is formed in a state of covering the TFT 1. 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 a wire for connecting the organic EL element formed between the TFTs 1 or in the subsequent step and 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 generated by the wiring 2 is buried.

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

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

Further, although not shown in FIG. 1, the hole transport layer, the organic light-emitting layer, and the electron transport layer are provided by sequentially performing vapor deposition through a desired pattern mask, and then Al is formed on the entire upper surface of the substrate. The second electrode is then sealed by bonding with a glass plate for sealing and an ultraviolet curable epoxy resin, and an active matrix type organic body obtained by connecting TFT1 for driving the organic EL elements to drive them is obtained. EL display device.

FIG. 2 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 a liquid crystal panel is provided with elements of the TFT 16, and elements of the TFT 16 are disposed between two glass substrates 14 and a glass substrate 15 to which a polarizing film is attached. All pixels correspond. Among the elements 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 an RGB color filter 22 in which a black matrix is disposed are provided on the ITO transparent electrode 19.

Specific examples of the TFT (Thin-Film Transistor) included in the organic EL display device and the liquid crystal display device of the present invention include amorphous germanium-TFT and low-temperature polysilicon-TFT. Oxide semiconductor TFT or the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.

Further, examples of the liquid crystal driving method which 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 a coplanar switching (In-Plane Switching, IPS). ), Fringes Field Switching (FFS) mode, Optically Compensated Bend (OCB) mode, etc.

In addition, as a specific alignment method of the liquid crystal alignment film which can be used for the liquid crystal display device of the present invention, a rubbing alignment method, a light alignment method, and the like can be given. Further, the polymer alignment support can be obtained by the Polymer Sustained Alignment (PSA) technique described in JP-A-2003-149647 or JP-A-2011-257734.

Example

Hereinafter, the present invention will be more specifically described 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.

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

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

MAEVE: 1-ethoxyethyl methacrylate

MATHF: tetrahydro-2H-furan-2-yl methacrylate

MATHP: tetrahydro-2H-pyran-2-yl methacrylate

NBMA: n-butoxymethyl acrylamide (NBMA, manufactured by Tokyo Chemical Industry Co., Ltd.)

GMA: glycidyl methacrylate

St: Styrene

MMA: Methyl methacrylate

MAA: Methacrylic acid

EDM: Diethylene glycol ethyl methyl ether (manufactured by Toho Chemical Industry, Hisolve EDM)

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

DCPM: methacrylic acid (tricyclo[5.2.1.0 ^2,6 ]decane-8-yl) ester

(a3-1)~(a3-3), (a3-5)~(a3-7), (a3-9), (a3-10), (a3-14), (a3-16) are as follows Compound.

(x-1), (x-2), (x-3), and (x-4) are the following compounds.

<Synthesis of Polymer C-2>

Diethylene glycol ethyl methyl ether (manufactured by Toho Chemical Industries, Hisolve EDM, 36 g) was added as a solvent to a three-necked flask, and the temperature was raised to 70 ° C under a nitrogen atmosphere. Glycidyl methacrylate 34.7 g (244 mmol), methyl methacrylate 1.63 g (16.3 mmol), Light Acrylate HO-a-HH (light acrylate HO-a-HH) under a nitrogen stream A mixed solution of 7.04 g, 26.06 mmol of styrene and 4.07 g of styrene (39.08 mmol) was heated to 70 °C. While stirring the mixed solution, a radical polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd., 3.64 g) and diethylene glycol ethyl methyl ether (35.6 g) were added dropwise over 2.5 hours. a mixed solution. After completion of the dropwise addition, the mixture was reacted at 70 ° C for 5 hours to obtain a diethylene glycol ethyl methyl ether solution (solid content concentration: 40 wt%) of the binder a-1. The obtained polymer C-2 had a weight average molecular weight of 9,000.

<Synthesis of MATHF>

Methacrylic acid (86 g, 1 mol) was first cooled to 15 ° C, then 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 extracted with ethyl acetate (500 mL), dried over magnesium sulfate, and then filtered, and then concentrated under reduced pressure at 40 ° C. The yellow oil of the residue was distilled under reduced pressure to give tetrahydro-2H-furan-2-yl methacrylate as a colorless oil (bp.) 54 ° C to 56 ° C / 3.5 mmHg fraction (MATHF) 125 g (yield 80%).

<Synthesis of Polymer A-1>

Diethylene glycol ethyl methyl ether (manufactured by Toho Chemical Industries, Hisolve EDM, 43 g) was added as a solvent to a three-necked flask, and the temperature was raised to 90 ° C under a nitrogen atmosphere. 1-Ethyl methacrylate (MAEVE, 20.61 g) and n-butoxymethyl acrylamide (NBMA, manufactured by Tokyo Chemical Industry, 14.58 g) as a monomer component were added dropwise to the solution over 2 hours. , Light Acrylate HO-a-HH (light acrylate HO-a-HH) (manufactured by Kyoeisha, 19.81 g), styrene (St., manufactured by Wako Pure Chemical Industries, Ltd., 3.39 g), and dimethyl-2,2'-azobis(2-methylacetate) as a polymerization initiator (V-601) , manufactured by Wako Pure Chemical Industries, 6.00 g, 8 mol% relative to the monomer, diethylene glycol ethyl methyl ether (manufactured by Toho Chemical Industries, Hisolve EDM, 43 g), and They dissolve. After the completion of the dropwise addition, the mixture was stirred for 2 hours. Further, V-601 (1.5 g, 2 mol% based on the monomer) was added to the solution, and the mixture was further stirred for 2 hours, and then the reaction was terminated. Thus, the polymer A-1 was obtained. The weight average molecular weight was 16,000.

The monomer type and the like were changed as shown in the following table, and the polymer A-2 to the polymer A-24, the polymer A'-1 to the polymer A'-5, and the polymer C-1 were synthesized in the same manner. Polymer C-3~Polymer C-5.

(Preparation of photosensitive resin composition)

[Example 1]

The components were dissolved and mixed so as to have a solid content ratio as described in the table, and filtered through a filter made of polytetrafluoroethylene having a diameter of 0.2 μm to obtain a photosensitive resin composition of Example 1. Further, the solvent used was a mixed solvent of propylene glycol monomethyl ether acetate / diethylene glycol ethyl methyl ether / 1,3-butylene glycol diacetate = 60 / 37 / 3 (weight ratio), and the viscosity became 5 mPa. s way to adjust.

[Example 2 to Example 36, Comparative Example 1 to Comparative Example 5]

The same procedure as in Example 1 was carried out except that each of the compounds used in Example 1 was changed to the compounds described in Tables 4 to 7.

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

B-1: PAG-103 (manufactured by BASF)

B-2: PAI-101 (manufactured by Ciba Specialty Chemicals)

B-3: Structure shown below (hereinafter, a synthesis example will be described)

B-4: Structure shown below (hereinafter, a synthesis example will be described)

<Synthesis of B-3>

The compound (α-(methylsulfonyloxyimino)-2-phenylacetonitrile) represented by B-3 was synthesized as follows.

[Synthesis of [α-(hydroxyimino)-2-phenylacetonitrile]

5.85 g of phenylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed in tetrahydrofuran: 50 ml (manufactured by Wako Pure Chemical Industries, Ltd.), and then placed in an ice bath to cool the reaction liquid to 5 ° C or lower. Then, 11.6 g of SM-28 (sodium methoxide 28% in methanol, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the mixture was stirred for 30 minutes in an ice bath to carry out a reaction. Then, while maintaining the internal temperature at 20 ° C or lower, 7.03 g of isoamyl nitrite (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and after the completion of the dropwise addition, the reaction solution was allowed to react at room temperature for 1 hour. The obtained reaction liquid was placed in 150 mL of water in which 1 g of sodium hydroxide was dissolved and completely dissolved, and then 100 ml of ethyl acetate was added to carry out liquid separation to obtain about 180 ml of an aqueous layer having a target substance. Further, 100 ml of ethyl acetate was again added, and the aqueous layer was made acidic with a pH of 3 or less by using concentrated hydrochloric acid, and then the product was extracted and concentrated. If hexane is used The obtained crude crystals were washed, and then 4.6 g of α-(hydroxyimino)-2-phenylacetonitrile was obtained in a yield of 63%.

[Synthesis of [α-(methylsulfonyloxyimino)-2-phenylacetonitrile (Compound B-3)]

11.5 g of α-(hydroxyimino)-2-phenylacetonitrile was dissolved in tetrahydrofuran: 100 ml (manufactured by Wako Pure Chemical Industries, Ltd.), and then placed in an ice bath to cool the reaction liquid to 5 ° C or lower. Then, 9.9 g of methane sulfonium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and then the internal temperature was kept below 20 ° C while adding 9.55 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.), followed by stirring in an ice bath. The reaction was carried out in 1 hour.

The obtained reaction liquid was added to 500 mL of water, and stirred at room temperature for one hour. When the obtained powdery precipitate was filtered and dried, α-(methylsulfonyloxyimino)-2-phenylacetonitrile (Compound B-5) 16 g was obtained in a yield of 90%. . H-NMR spectroscopy of the compound showed the product to be a mixture of oxime structural isomers (syn/anti) with a ratio of syn:anti = 25/75.

<Synthesis of B-4>

Α-(p-Toluenesulfonyloxyimino)phenylacetonitrile (Compound B-4) was synthesized according to the method described in Paragraph No. [0108] of JP-A-2002-528451.

B-5: Structure shown below (hereinafter, a synthesis example will be described)

B-6: Structure shown below (hereinafter, a synthesis example will be described)

B-7: Structure shown below (hereinafter, a synthesis example will be described)

B-8: Structure shown below (hereinafter, a synthesis example will be described)

<Synthesis of B-5>

1-1. Synthesis of synthetic intermediate B-5A

2-Aminobenzenethiol: 31.3 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in toluene: 100 mL (manufactured by Wako Pure Chemical Industries, Ltd.) at room temperature (25 ° C). Then, phenylacetonitrile chloride: 40.6 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the obtained solution, and the mixture was stirred at room temperature for 1 hour, followed by stirring at 100 ° C for 2 hours to carry out a reaction. 500 mL of water was added to the obtained reaction liquid to dissolve the precipitated salt, and the toluene oil fraction was extracted, and the extract was concentrated by a rotary evaporator to obtain a synthetic intermediate B-5A.

1-2. Synthesis of B-5

2.25 g of the synthetic intermediate B-5A obtained in the above manner was mixed in tetrahydrofuran: 10 mL (manufactured by Wako Pure Chemical Industries, Ltd.), and placed in an ice bath to cool the reaction liquid to 5 ° C or lower. Then, tetramethylammonium hydroxide: 4.37 g (25 mass% methanol solution, manufactured by Alfa Acer Co., Ltd.) was added dropwise to the reaction liquid, and the mixture was stirred under an ice bath for 0.5 hour to carry out a reaction. Further, while maintaining the internal temperature at 20 ° C or lower, isoamyl nitrite: 7.03 g was added dropwise, and after the completion of the dropwise addition, the reaction liquid was allowed to warm to room temperature, and then stirred for one hour.

Then, after cooling the reaction liquid to below 5 ° C, p-toluenesulfonyl chloride (1.9 g) was charged. (manufactured by Tokyo Chemical Industry Co., Ltd.), while stirring at 10 ° C or lower for 1 hour. Thereafter, 80 mL of water was introduced and stirred at 0 ° C for 1 hour. After filtering the obtained precipitate, 60 mL of isopropyl alcohol (IPA) was added, and the mixture was heated to 50 ° C, and stirred for 1 hour, and filtered while being hot, and dried to obtain B-5 (the structure). 1.8 g.

The ¹ H-NMR spectrum of the obtained B-5 (300 MHz, Deuterated Dimethyl Sulfoxide ((D3C) 2S=O)) was δ=8.2~8.17 (m, 1H), 8.03 ~8.00 (m, 1H), 7.95 to 7.9 (m, 2H), 7.6 to 7.45 (m, 9H), 2.45 (s, 3H).

From the results of the ¹ H-NMR measurement, it was inferred that the obtained B-5 was a single geometric isomer.

<Synthesis of B-6>

Add aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and heat the mixture to 40 ° C. 2 hours. Under ice cooling, a 4 N aqueous HCl solution (60 mL) was added dropwise, and then ethyl acetate (50 mL) was added to carry out liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, and after reacting at 40 ° C for 1 hour, 2 N aqueous HCl solution (60 mL) was added to carry out liquid separation, and the organic layer was concentrated, and then diisopropyl ether (10 mL) was used. The crystals were reslurryed, then filtered and dried to obtain a ketone compound (6.5 g).

To a suspension solution of the obtained ketone compound (3.0 g) and methanol (30 mL), acetic acid (7.3 g) and a 50% by mass aqueous hydroxylamine solution (8.0 g) were added, and the mixture was heated under reflux. 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 under ice cooling, and the mixture was warmed to room temperature and then reacted. hour. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, and then used. The alcohol (20 mL) was repulped, then filtered and dried to obtain 2.3 g of B-6 (the structure).

Furthermore, the ¹ H-NMR spectrum of B-6 (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 B-7>

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 at 100 ° C. Reaction for 2 hours. Water (300 mL) and ethyl acetate (200 mL) were added to the reaction mixture for liquid separation, and the organic layer was concentrated, and then a 48% by mass aqueous sodium hydroxide solution (23 g), ethanol (50 mL), and water ( 50 mL) and react for 2 hours. The reaction liquid was poured into a 1 N aqueous HCl solution (500 mL), and the precipitated crystals were filtered and washed with water to obtain a crude carboxylic acid product. Then, 30 g of polyphosphoric acid was added and reacted at 170 ° C for 30 minutes. The reaction solution was poured into water (300 mL), and ethyl acetate (300 mL) was added to carry out liquid separation. The organic layer was concentrated and 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 separated by water for 8 times with 80 mL of water, and concentrated, and then purified by silica gel column chromatography. A hydrazine compound (5.8 g) was obtained.

For the obtained hydrazine (3.1 g), sulfonation was carried out in the same manner as B-6 to obtain 3.2 g of B-7 (the structure).

Furthermore, the ¹ H-NMR spectrum of B-7 (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), 7.5 (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 B-8>

B-8 (the structure) was synthesized in the same manner as B-6 except that phenylsulfonium chloride was used instead of p-toluenesulfonyl chloride in B-6.

Furthermore, the ¹ H-NMR spectrum of B-8 (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).

B-9: TPS-1000 (manufactured by Midori Kagaku Co., Ltd.)

NQD: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2- Condensate of naphthoquinonediazide-5-sulfonyl chloride (2.0 mol)

E-1: DBA (9,10-dibutoxy oxime, manufactured by Kawasaki Chemicals Co., Ltd.)

E-2: NBCA (Black Gold Chemical (Stock) Manufacturing)

F-1: JER157S65 (trade name, phenol novolak type epoxy resin, Japan Epoxy Resins (share))

F-2: Nikalac MW-100LM (Nikarak MW-100LM) (manufactured by Sanwa Chemical Co., Ltd.)

F-3: EX-111 (manufactured by Nagase ChemteX)

F-4: EX-212L (manufactured by Changchun Chemical Co., Ltd.)

F-5: Kayarad DPHA (Kayad DPHA) (manufactured by Nippon Kayaku Co., Ltd.)

G-1: KBM-403 (trade name, 3-glycidoxypropyltrimethoxydecane, structure shown below, manufactured by Shin-Etsu Chemical Co., Ltd.)

G-2: KBE-403 (trade name, 3-glycidoxypropyl triethoxy decane, manufactured by Shin-Etsu Chemical Co., Ltd.)

G-3: KBE-1003 (trade name, vinyl triethoxy decane, manufactured by Shin-Etsu Chemical Co., Ltd.)

G-4: KBM-502 (trade name, 3-methacryloxypropyldimethoxydecane, Shin-Etsu Chemical Industry Co., Ltd.

G-5: KBM-5103 (trade name, 3-acryloxypropyltrimethoxydecane, manufactured by Shin-Etsu Chemical Co., Ltd.)

G-6: KBM-803 (trade name, 3-mercaptopropyltrimethoxydecane, manufactured by Shin-Etsu Chemical Co., Ltd.)

G-7: KBM-903 (trade name, 3-aminopropyltrimethoxydecane, manufactured by Shin-Etsu Chemical Co., Ltd.)

H-1:1,5-diazabicyclo[4.3.0]-5-decene

H-2: triphenylimidazole

H-3: The following structure

I-1: a perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula

I-2: Anthrone-based surfactant SH-8400 (Dow Corning Toray Silicone)

Each of the photosensitive resin compositions of the examples and the comparative examples obtained in the above manner was subjected to the following evaluations.

<Evaluation of sensitivity>

Each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737 (Corning 1737), 0.7 mm thick (manufactured by Corning)), and prebaked on a hot plate at 95 ° C / 140 seconds. On the other hand, the solvent was volatilized to form a photosensitive resin composition layer having a film thickness of 4.0 μm.

Then, the obtained photosensitive resin composition layer was exposed through a predetermined mask using a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon. Then, the photosensitive composition layer after exposure was developed with an alkaline developer (0.4 wt% aqueous solution of tetramethylammonium hydroxide) at 23 ° C / 60 seconds, and then rinsed with ultrapure water for 20 seconds.

The optimum i-ray exposure amount (Eopt) when analyzing the line and space of 1:1 to 9 μm by these operations is set as the sensitivity. Furthermore, the evaluation criteria are as follows. 3~5 is a practical level without problems.

5: less than 40 mJ/cm ²

4:40 mJ/cm ² or more, less than 60 mJ/cm ²

3:60 mJ/cm ² or more, less than 80 mJ/cm ²

2:80 mJ/cm ² or more, less than 150 mJ/cm ²

1:150 mJ/cm ² or more

<Evaluation of residual film rate>

The film thickness of the unexposed portion after development was measured, and the ratio with respect to the film thickness after application (thickness of the unexposed portion after development, film thickness after coating × 100 (%)) was determined, and thus the following The residual film rate at the time of development was evaluated by the reference.

5:98% or more

4: 95% or more, less than 98%

3:90% or more, less than 95%

2:80% or more, less than 90%

1: less than 80%

<Evaluation of relative dielectric constant>

The photosensitive resin composition solution was slit-coated on a bare wafer (N-type low resistance) (manufactured by SUMCO Co., Ltd.), and then prebaked on a hot plate at 90 ° C for 2 minutes to form a film thickness of 3.0. A photosensitive resin composition layer of μm. The obtained photosensitive resin composition was exposed in such a manner that the cumulative irradiation amount became 300 mJ/cm ² (illuminance: 20 mW/cm ² ) by using a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon Co., Ltd. Then, the substrate was heated at 220 ° C for 1 hour in an oven to thereby obtain a cured film.

CVmap92A (manufactured by Four Dimensions Inc.) was used for the cured film, and the relative dielectric constant was measured at a measurement frequency of 1 MHz, and evaluated according to the following criteria. It can be said that when the value is small, the relative dielectric constant of the cured film is good.

5: under 3.5

4: 3.5 or more, less than 3.7

3:3.7 or above, less than 3.9

2:3.9 or more, less than 4.2

1:4.2 or more

As shown in the table, since the photosensitive resin composition of the example contains the repeating unit (a3), the photosensitive resin composition layer becomes soft. Therefore, it is understood that it is easy to be dissolved in the developer, and excellent sensitivity, excellent residual film ratio, and excellent relative dielectric constant are exhibited regardless of the substrate and the exposure machine, and the shape of the formed pattern is also excellent. On the other hand, it is understood that the sensitivity, residual film property, and relative dielectric constant of the comparative example containing no repeating unit (a3) are inferior compared with the examples.

[Example 100]

In Example 100, the photosensitive resin composition of Example 24 was used, and the substrate was changed from a glass substrate (Corning 1737 (Corning 1737), 0.7 mm thick (manufactured by Corning)) to a 6 inch silicon wafer. In the same manner as in the evaluation of the photosensitive resin composition of Example 1, the sensitivity, the residual film property, and the relative dielectric constant were evaluated, and the results were all evaluated as 5.

[Example 101]

For the same solid component as in Example 100, a mixture of propylene glycol monomethyl ether acetate / diethylene glycol ethyl methyl ether / 1,3-butylene glycol diacetate = 60 / 37 / 3 (weight ratio) was used. Solvent and change the viscosity to 35 mPa. The evaluation was carried out in the same manner as in Example 100 except that the coating was adjusted in the manner of s. In the same manner as the evaluation of the photosensitive resin composition of Example 1, the sensitivity, the residual film property, and the relative dielectric constant were evaluated, and the results were all evaluated as 5.

[Example 102]

Using the photosensitive resin composition of Example 100, the exposure machine was changed from a PLA-501F exposure machine manufactured by Canon (Stock) to an FX-803M manufactured by Nikon (Stock). In the same manner as in the evaluation of the photosensitive resin composition of Example 1, the sensitivity, the residual film property, and the relative dielectric constant were measured in the same manner as in the evaluation of the photosensitive resin composition of Example 1 (g-line stepper). Evaluation, the results were evaluated as 5.

[Example 103]

Using the photosensitive resin composition of Example 100, the exposure machine was changed from a PLA-501F exposure machine manufactured by Canon Co., Ltd. to a 355 nm laser exposure machine to perform laser exposure at 355 nm, and other examples were given. The evaluation by the photosensitive resin composition of 1 evaluated the sensitivity similarly.

Furthermore, as a 355 nm laser exposure machine, "AEGIS" (wavelength 355 nm, pulse width 6 nsec) manufactured by V-Technology Co., Ltd. is used, and the exposure amount is OPHIR. "PE10B-V2" manufactured by Phil) was measured and the result was evaluated as 5. In the same manner as in the evaluation of the photosensitive resin composition of Example 1, the residual film properties and the relative dielectric constant were evaluated, and the results were all evaluated as 5.

[Example 104]

Using the photosensitive resin composition of Example 100, the exposure machine was changed from a PLA-501F exposure machine manufactured by Canon Co., Ltd. to an ultraviolet (Ultraviolet, UV)-LED light source exposure machine, and the same as Example 1 Evaluation of the photosensitive resin composition The sensitivity was evaluated in the same manner, and as a result, it was evaluated as 5. In the same manner as in the evaluation of the photosensitive resin composition of Example 1, the residual film properties and the relative dielectric constant were evaluated, and the results were all evaluated as 5.

[Example 200]

An organic EL display using a thin film transistor (TFT) was produced by the following method Device (see Figure 1).

A bottom gate type TFT 1 is formed on the glass substrate 6, and an insulating film 3 containing Si ₃ N ₄ is formed in a state of covering the TFT 1. 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 is formed on the insulating film 3 via the contact hole. This wiring 2 is a wire for connecting the organic EL element formed between the TFTs 1 or in the subsequent step and 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 formation of the planarizing film 4 on the insulating film 3 was carried out by spin-coating the photosensitive resin composition of Example 16 on a substrate, prebaking on a hot plate (90 ° C × 2 minutes), and then using a high pressure mercury lamp. The mask was irradiated with i-rays (365 nm) of 45 mJ/cm ² (illuminance of 20 mW/cm ² ), developed with an alkaline aqueous solution to form a pattern, and heat-treated at 230 ° C for 60 minutes.

When the photosensitive resin composition was applied, the coating property was good, and no wrinkles or cracks were observed in 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 flattening film 4 produced 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 connected to the wiring 2 via the contact hole 7 to be formed on the planarization film 4. Thereafter, the resist is applied, prebaked, exposed through a mask of a desired pattern, and then developed. This resist pattern was used as a mask, and pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was peeled off at 50 ° C using a resist stripper (Remover 100 (release agent 100), manufactured by AZ Electronic Materials Co., Ltd.). The first electrode 5 obtained in the manner described is equivalent to organic The anode of the EL element.

Then, an insulating film 8 covering the shape of the periphery of the first electrode 5 is formed. The photosensitive resin composition of Example 100 was used for the insulating film 8, and the insulating film 8 was formed 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, in the vacuum vapor deposition apparatus, a hole transport layer, an organic light-emitting layer, and an electron transport layer are provided by sequentially performing vapor deposition through a desired pattern mask. Then, a second electrode containing Al is formed on the entire upper surface of the substrate. The obtained substrate was taken out from the vapor deposition machine and sealed by bonding with a UV-curable epoxy resin using a sealing glass plate.

As described above, an active matrix type organic EL display device in which the TFTs 1 for driving the organic EL elements are connected to each other is obtained. As a result of applying a voltage via the drive circuit, it is understood that the organic EL display device exhibits excellent display characteristics and high reliability.

[Example 201]

In the active matrix liquid crystal display device described in FIG. 1 of Japanese Patent No. 3,321,003, a cured film 17 is formed as an interlayer insulating film in the following manner, and a liquid crystal display device of Example 201 is obtained.

In other words, using the photosensitive resin composition of Example 100, the cured film 17 was formed as an interlayer insulating film in the same manner as the method of forming the planarizing film 4 of the organic EL display device of Example 200.

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

1‧‧‧TFT (thin film transistor)

2‧‧‧Wiring

3‧‧‧Insulation film

4‧‧‧Flat film

5‧‧‧First electrode

6‧‧‧ glass substrate

7‧‧‧Contact hole

8‧‧‧Insulation film

Claims (18)

A photosensitive resin composition comprising: (A) a polymer component comprising (a1) a repeating unit having a residue in which an acid group is protected by an acid-decomposable group, in the same polymer or in a different polymer, ( A2) a repeating unit containing a crosslinkable group selected from the group consisting of an oxiranyl group, an oxetanyl group, or -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms), and A3) a repeating unit having a carboxyl group at the terminal of the side chain and having a divalent linking group linking the polymer main chain and the carboxyl group, having a number of atoms of 4 or more; (B) a photoacid generator; and (D) a solvent; And the divalent linking group is selected from -CR ¹ ₂ - (R ¹ represents a hydrogen atom or a methyl group), -O-, -O-SO ₂ -, -OC(O)-, -C(O) -O-, -S-, -C(O)-, an amine group which may have a substituent, a pendant phenyl group which may have a substituent, or a structure of the following (iv) and optionally combined; In the formula (iv), z represents an integer of 0 to 5. The photosensitive resin composition according to claim 1, wherein the (A) polymer component has a polymer comprising the repeating unit (a2) and the repeating unit (a3). The photosensitive resin composition according to claim 1 or 2, wherein the (A) polymer component has the repeating unit (a1), the repeating unit (a2), and the Repeat the polymer of unit (a3). The photosensitive resin composition according to claim 1 or 2, which is a chemically amplified positive photosensitive resin composition. The photosensitive resin composition according to the first or second aspect, wherein the repeating unit (a3) contains one or more repeating units represented by the general formula (i) to the general formula (iii). In the general formulae (i) to (iii), R ¹ represents a hydrogen atom or a methyl group, L represents a divalent linking group having 4 or more atoms, and R ² represents a halogen atom, a hydroxyl group or a carbon number of 1 to 3 The alkyl group, n represents an integer from 0 to 4. The photosensitive resin composition according to claim 1 or 2, wherein the repeating unit (a1) is a repeating unit represented by the formula (A2'), In the formula (A2'), 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 and R ³ may be bonded 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. The photosensitive resin composition according to claim 1 or 2, wherein the repeating unit (a2) is a repeating unit represented by the formula (2), In the formula (2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms. The photosensitive resin composition according to claim 1 or 2, wherein the repeating unit (a2) is a repeating unit having an oxiranyl group and/or an oxetanyl group. The photosensitive resin composition according to claim 1 or 2, wherein the repeating unit (a1) is a repeating unit represented by the formula (A2'), and the repeating unit (a2) is a repeating unit represented by the formula (2), wherein the repeating unit (a3) contains one or more repeating units represented by the formula (i) to the formula (iii). In the formula (A2'), 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 and R ³ may be bonded 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. In the formula (2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms. In the general formulae (i) to (iii), R ¹ represents a hydrogen atom or a methyl group, L represents a divalent linking group having 4 or more atoms, and R ² represents a halogen atom, a hydroxyl group or a carbon number of 1 to 3 The alkyl group, n represents an integer from 0 to 4. The photosensitive resin composition according to claim 1 or 2, wherein the repeating unit (a1) is a repeating unit represented by the formula (A2'), and the repeating unit (a2) is a repeating unit having an oxirane group and/or an oxetanyl group, the repeating unit (a3) comprising one or more repeating units represented by the formulae (i) to (iii), In the formula (A2'), 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 and R ³ may be bonded 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. In the general formulae (i) to (iii), R ¹ represents a hydrogen atom or a methyl group, L represents a divalent linking group having 4 or more atoms, and R ² represents a halogen atom, a hydroxyl group or a carbon number of 1 to 3 The alkyl group, n represents an integer from 0 to 4. The photosensitive resin composition according to claim 1 or 2, wherein the (A) polymer component has the repeating unit (a1), the repeating unit (a2), and the a polymer of the repeating unit (a3) which is a repeating unit represented by the formula (A2'), and the repeating unit (a2) is a repeating unit represented by the formula (2), The repeating unit (a3) contains one or more repeating units represented by the general formula (i) to the general formula (iii). In the formula (A2'), 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 and R ³ may be bonded 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. In the formula (2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms. In the general formulae (i) to (iii), R ¹ represents a hydrogen atom or a methyl group, L represents a divalent linking group having 4 or more atoms, and R ² represents a halogen atom, a hydroxyl group or a carbon number of 1 to 3 The alkyl group, n represents an integer from 0 to 4. The photosensitive resin composition according to claim 1 or 2, wherein the (A) polymer component has the repeating unit (a1), the repeating unit (a2), and the The polymer of the repeating unit (a3) which is a repeating unit represented by the formula (A2') having an oxirane group and/or an oxo group a repeating unit of a butyl group, the repeating unit (a3) comprising one or more repeating units represented by the formula (i) to the formula (iii), In the formula (A2'), 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 and R ³ may be bonded 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. In the general formulae (i) to (iii), R ¹ represents a hydrogen atom or a methyl group, L represents a divalent linking group having 4 or more atoms, and R ² represents a halogen atom, a hydroxyl group or a carbon number of 1 to 3 The alkyl group, n represents an integer from 0 to 4. A method for producing a cured film, comprising: (1) a step of applying a photosensitive resin composition as described in claim 1 or 2 to a substrate; and (2) applying sensitization from the application a step of removing the solvent in the resin composition; (3) a step of performing exposure using actinic radiation; (4) a step of performing development using an aqueous developing solution; (5) A post-baking step of performing thermal hardening. The method for producing a cured film according to claim 13, wherein the step of performing full exposure is performed after the developing step and before the post-baking step. A cured film obtained by curing a photosensitive resin composition according to the first or second aspect of the invention. The cured film according to claim 15, which is an interlayer insulating film. A liquid crystal display device comprising the cured film according to claim 15 of the patent application. An organic electroluminescence display device comprising the cured film according to claim 15 of the patent application.