TWI566034B - Photo-sensitive resin composition, method for manufacturing cured film, cured film, organic el device and liquid crystal display - Google Patents

Description

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

The present invention relates to a photosensitive resin composition, a method for producing 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.

An interlayer insulating film is provided in an organic EL display device, a liquid crystal display device, or the like from the viewpoint of improving brightness and reducing power consumption. A photosensitive resin composition is widely used for the formation of the interlayer insulating film. In order to efficiently manufacture an organic EL display device or a liquid crystal display device, the sensitivity of the photosensitive resin composition is required to be high.

In addition, since the interlayer insulating film is exposed to various chemical solutions, resistance to chemicals (chemical resistance) is required. Further, in recent years, various metals (Mo or Ti) have been used in wiring or substrates, and adhesion to these metals is required.

As a photosensitive resin composition having high sensitivity, for example, a tool is known. A photosensitive composition of an acrylic resin having an acetal structure or a ketal structure (Japanese Patent Laid-Open Publication No. 2011-221494). However, a photosensitive resin composition having a sufficiently high sensitivity and a strong adhesion to a metal (Mo or Ti) and excellent chemical resistance is not known.

An object of the present invention is to provide a photosensitive resin composition which satisfies the required performance required for a photosensitive resin composition in recent years, that is, high sensitivity and high chemical resistance. And high metal adhesion.

As a result of intensive studies to solve the above problems, the present inventors have found that the above-mentioned problem is solved by adding a vinyl ether group-containing compound to a photosensitive resin composition, and the vinyl ether group-containing compound has a molecule in the molecule. 1 to 4 vinyl ether groups, having an alkylene oxide group and/or a hydroxyl group, and having a molecular weight of 80 to 1,000.

Specifically, the above problem is preferably solved by means <2> to <11> by the following means <1>.

<1> A photosensitive resin composition comprising: (A) a polymer component satisfying at least one of the following (1) and (2), (1) having (a1) an acid group-containing acid group decomposable a constituent unit of the base-protected residue, and (a2) at least copolymerization of a constituent unit containing an epoxy group, an oxetanyl group, or -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) (2) an acrylic polymer having (a1) a constituent unit containing a residue in which an acid group is protected by an acid-decomposable group, and having (a2) an epoxy group or an oxetane An acrylic polymer having a constituent unit of -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms); (B) a photoacid generator; (C) a compound containing a vinyl ether group; And (D) a solvent; and the (C) vinyl ether group-containing compound has one to four vinyl ether groups in the molecule, and has an alkylene oxide group and/or a hydroxyl group, and has a molecular weight of 80 to 1,000.

<2> The photosensitive resin composition according to <1>, wherein (C) the vinyl ether group-containing compound has one to two vinyl ether groups.

<3> The photosensitive resin composition according to <1>, wherein the (C) vinyl ether group-containing compound contains only a carbon atom, a hydrogen atom, and an oxygen atom.

The photosensitive resin composition of any one of the above-mentioned structural unit (a1) is a structural unit containing the residue whose carboxyl group is protected by the acetal form.

The photosensitive resin composition of any one of the above-mentioned structural unit (a1) is a structural unit represented by the following formula (A2').

Formula (A2')

In the formula, 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, R ³ represents an alkyl group or an aryl group, and R ¹ or R ² is 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.

<6> A method for producing a cured film, comprising: (1) a step of applying the photosensitive resin composition according to any one of <1> to <5> 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.

<7> The method for producing a cured film according to <6>, which comprises the step of performing total exposure after the developing step and the post-baking step.

<8> A cured film formed by curing the photosensitive resin composition according to any one of <1> to <5>.

<9> The cured film according to <8>, which is an interlayer insulating film.

<10> A liquid crystal display device or an organic EL display device, which includes A cured film as described in <8> or <9>.

<11> An adhesion improving agent which is an adhesion improving agent for a photosensitive resin composition and a molybdenum substrate, the adhesion improving agent comprising: one to four vinyl ether groups in the molecule and having an alkylene oxide A vinyl ether compound having a molecular weight of from 80 to 1000 and/or a hydroxyl group.

According to the present invention, it is possible to provide a photosensitive resin composition which satisfies high sensitivity, high chemical resistance, and high metal adhesion.

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 addition, in the specification of the present application, "~" is used in the meaning of including the numerical values described before and after the lower limit and the upper limit.

[Photosensitive Resin Composition]

The photosensitive resin composition of the present invention is characterized by comprising (A) a polymer component satisfying at least one of the following (1) and (2), (B) a photoacid generator, and (C) a vinyl group. An ether group-based compound and (D) a solvent, and the (C) vinyl ether group-containing compound has one to four vinyl ether groups in the molecule, and has an alkylene oxide group and/or a hydroxyl group, and a molecular weight It is 80~1000.

(1) A constituent unit having (a1) a residue having an acid group protected by an acid-decomposable group, and (a2) containing an epoxy group, an oxetanyl group, or -NH-CH ₂ -OR (R is An acrylic polymer obtained by copolymerizing at least a constituent unit having an alkyl group having 1 to 20 carbon atoms, and (2) an acrylic polymer having (a1) a constituent unit containing a residue having an acid group decomposed by an acid-decomposable group And an acrylic polymer having (a2) a constituent unit containing an epoxy group, an oxetanyl group, or -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms).

By using such a photosensitive resin composition, it is possible to provide an interlayer insulating film which is excellent in sensitivity, chemical resistance, and adhesion to metal.

The photosensitive resin composition of the present invention is a positive photosensitive resin composition. Further, the photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition).

Hereinafter, a preferred embodiment of each component will be sequentially described with respect to the photosensitive resin composition of the present invention.

<(A) component>

The photosensitive resin composition of the present invention contains (A) a polymer component satisfying at least one of the following (1) and the following (2) as the component (A).

(1) A constituent unit having (a1) a residue having an acid group protected by an acid-decomposable group, and (a2) containing an epoxy group, an oxetanyl group, or -NH-CH ₂ -OR (R is An acrylic polymer obtained by copolymerizing at least a constituent unit having an alkyl group having 1 to 20 carbon atoms; (2) an acrylic polymer having (a1) a constituent unit containing a residue having an acid group deprotected by an acid-decomposable group And an acrylic polymer having (a2) a constituent unit containing an epoxy group, an oxetanyl group, or -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms).

Here, the embodiment of the above (1) is an embodiment comprising at least one type of acrylic polymer having (a1) a constituent unit of a residue having an acid group-protected group which is protected by an acid-decomposable group. And (a2) a structural unit containing an epoxy group, an oxetanyl group, or -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms). The acrylic polymer may further contain other repeating units. Further, the constituent unit (a1) or the constituent unit (a2) may be contained in two or more types.

The embodiment (2) is an embodiment comprising at least two kinds of acrylic polymers, and at least one of the acrylic polymers has a constituent unit (a1), and at least one of the other acrylic polymers has at least one of The unit (a2) is constructed.

Further, in the embodiment (2), the acrylic polymer containing the constituent unit (a1) may further contain a constituent unit (a2) or another constituent unit. Similarly, the acrylic polymer containing the constituent unit (a2) may contain the constituent unit (a1) or other constituent unit. In this case, it becomes satisfied (1) and (2) The implementation of both. In the present specification, the term "component A" unless otherwise specified is meant to include any of the above-mentioned acrylic polymer components.

In a preferred first embodiment of the present invention, two or more acrylic polymers are contained as the component (A), and at least one of the acrylic polymers has at least one residue having an acid group-protected group. In the acrylic polymer of the constituent unit of the group, at least one of the other acrylic polymers is an acrylic polymer having at least a constituent unit containing a crosslinkable group. From the viewpoint of the degree of freedom in molecular design, it is more preferred that the acrylic polymer having at least a constituent unit having a residue having an acid group-protected group derived from an acid-decomposable group substantially does not contain a constituent unit (a2), and has at least The acrylic polymer having a structural unit containing a crosslinkable group does not substantially contain a constituent unit (a1). Here, the term "substantially absent" means, for example, a ratio of 3 mol% or less to the total constituent unit, and further 1 mol% or less.

In a preferred second embodiment of the present invention, an embodiment in which the acrylic polymer containing the structural unit (a1) contains the structural unit (a2) is exemplified as a viewpoint of compatibility.

Further, as the third embodiment, an embodiment in which the acrylic polymer of the first embodiment and the acrylic polymer of the second embodiment coexist as the acrylic polymer component (A) may be considered.

The component (A) 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, based on the total constituent unit in the polymer. A constituent unit derived from (meth)acrylic acid and/or an ester thereof, particularly preferably a polymerization comprising only constituent units derived from (meth)acrylic acid and/or an ester thereof Things.

In addition, the "constituting 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 (A) is preferably alkali-insoluble, and is preferably a resin which becomes alkali-soluble when the acid-decomposable group of the structural unit (a1) is decomposed. Here, the acid-decomposable group means a functional group which is decomposable in the presence of an acid. In other words, the constituent unit protecting the carboxyl group having a carboxyl group protected by an acid-decomposable group is decomposed by protecting the genetic acid to form a carboxyl group, and the constituent unit protecting the phenolic hydroxyl group having a phenolic hydroxyl group protected by an acid-decomposable group is borrowed. It is decomposed by protecting the acid, so that a phenolic hydroxyl group can be produced. In the present invention, the term "alkali-soluble" means a coating of the compound (resin) formed by applying a solution of the compound (resin) to a substrate and heating at 90 ° C for 2 minutes. The film (thickness: 3 μm) has a dissolution rate of 0.4 μm/sec or more in a 0.4% aqueous solution of tetramethylammonium hydroxide at 23° C. The term “alkali-insoluble” means coating a solution of the compound (resin). The coating film (thickness: 3 μm) of the compound (resin) formed on the substrate and heated at 90 ° C for 2 minutes was not more than 0.01 μm for the dissolution rate of 0.4% aqueous solution of tetramethylammonium hydroxide at 23 ° C. second.

The (A) copolymer may have another constituent unit containing a carboxyl group to be described later, a structure derived from a carboxylic anhydride, and/or a phenolic hydroxyl group. However, when an acidic group is introduced, it is preferred to introduce the entire (A) copolymer in an alkali-insoluble state.

<<(a1) A constituent unit of a residue having an acid group protected by an acid-decomposable group>>

The structural unit (a1) in the present invention preferably includes a constituent unit containing a protective 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 of a carboxyl group-containing constituent unit having a protective carboxyl group protected by an acid-decomposable group as 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 is used as the structural unit containing a carboxyl group, is derived from a constituent unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, and (a1-1-2) Structure of ethylenically unsaturated groups and structures derived from acid anhydrides The units are described separately.

<<<<(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 unsaturated carboxylic acid used in the present invention. . That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, 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 also be a mono(meth)acrylate of a di-carboxyl polymer at both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethyl group. Acrylate and the like. Further, as the unsaturated carboxylic acid, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, and 4 may be used. - Carboxystyrene and the like.

In order to form the structural unit (a1-1-1) derived from the unsaturated carboxylic acid having at least one carboxyl group in the molecule, it is preferred to use acrylic acid, methacrylic acid, or An anhydride or the like of an unsaturated polycarboxylic acid, more preferably Use acrylic or methacrylic acid.

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 obtained by reacting a hydroxyl group present in a constituent unit containing an ethylenically unsaturated group with an acid anhydride. Monomer 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 hexahydrophthalic acid. A dibasic acid anhydride such as formic anhydride or chloric anhydride; an acid anhydride such as trimellitic anhydride, pyromellitic anhydride, diphenylketonetetracarboxylic anhydride or biphenyltetracarboxylic anhydride. Among these acid anhydrides, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferred from the viewpoint of developability.

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

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

The acid-decomposable group which can be used for the above-mentioned structural unit (a1-1) having a protective carboxyl group which is protected by an acid-decomposable group can be used as an acid-decomposable group, and is not particularly limited. In the past, as an 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) is known, or it is difficult. A group decomposed by an acid (for example, a third butyl group functional group such as a tert-butyl ester group or a tert-butyl carbonate group).

Among these acid-decomposable groups, the basic physical properties of the photosensitive resin composition, particularly the sensitivity, the pattern shape, the formation of contact holes, and the storage stability of the photosensitive resin composition are preferred. A constituent unit of a protected carboxyl group in which a carboxyl group is protected by an acetal form. Further, among the acid-decomposable groups, from the viewpoint of sensitivity, the carboxyl group is more preferably a protected carboxyl group protected by an acetal represented by the following formula (a1-1). Further, in the case where the carboxyl group is protected by a carboxy group protected by an acetal 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, and a case where both R ¹⁰¹ and R ¹⁰² are a hydrogen atom are excluded. R ¹⁰³ represents an alkyl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be bonded 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 linear, branched or cyclic.

The linear or branched alkyl group is preferably a carbon number of 1 to 12, more preferably a carbon number of 1 to 6, and still more preferably a carbon number of 1 to 4. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, 2,3-Dimethyl-2-butyl (thexyl), n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-decyl, and the like.

The cyclic alkyl group is preferably a carbon number of 3 to 12, more preferably a carbon number of 4 to 8, and still more preferably a carbon number of 4 to 6. 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 the whole alkyl group substituted with an aryl group, that is, an aralkyl group, a benzyl group, an α-methylbenzyl group, a phenethyl group, a naphthylmethyl group or the like can be exemplified.

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

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

These substituents may also be further substituted by the above 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 cumyl 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 these bonded carbon atoms. 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 preferred embodiment of the structural unit (a1-1) containing a protective carboxyl group protected by an acid-decomposable group is a structural unit represented by the formula (A2').

Formula (A2')

In the formula, 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, R ³ represents an alkyl group or an aryl group, and R ¹ or R ² is 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 preferred. 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.

A radically polymerizable monomer for forming a structural 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.

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 structural unit (a1-2) containing a protective phenolic hydroxyl group protected by an acid-decomposable group is a structural unit having a phenolic hydroxyl group as follows: a structural unit containing a phenolic hydroxyl group is protected by an acid-decomposable group 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 of a hydroxystyrene-based constituent unit or a novolac-based resin. Among these constituent units, from the viewpoint of transparency, it is preferably derived from hydroxybenzene. A constituent unit of ethylene or 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 preferred.

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 linear or branched alkane having 1 to 5 carbon atoms. Base, a represents an integer from 1 to 5, b represents an integer from 0 to 4, and a+b is 5 or less. Furthermore, when there are two or more R ^222s , these R ^222s 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 , stretching isobutyl, stretching tert-butyl, stretching pentyl, stretching isoamyl, stretching neopentyl, stretching hexyl and the like. Among them, R ^{221 is} preferably a single bond, a methylene group or an ethyl group. Further, the above-mentioned 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 viewpoint of 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, and an isopenic group. Base, neopentyl and so on. Among them, a chlorine atom, a bromine atom, a methyl group or an ethyl group is preferred 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 the phenolic hydroxyl group which is protected by the acid-decomposable group, and the constituent unit (a1) which can be used for the above-mentioned protective carboxyl group which is protected by the acid-decomposable group Similarly to the above-described acid-decomposable group, 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 photosensitive resin composition, particularly the sensitivity, the pattern shape, the storage stability of the photosensitive resin composition, and the formation of contact pores are preferably contained. A constituent unit that protects the phenolic hydroxyl group by acetal protection.

Further, among the acid-decomposable groups, the phenolic hydroxyl group is more preferably protected by a phenolic hydroxyl group protected by the acetal represented by the above formula (a1-1) from the viewpoint of sensitivity. Further, in the case where the phenolic hydroxyl group is protected by a phenolic hydroxyl group protected by the acetal represented by the above formula (a1-1), the entirety of the protective phenolic hydroxyl group becomes -Ar-O-CR ¹⁰¹ R ^102. The structure of (OR ¹⁰³ ). Further, Ar represents an aryl group.

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

In addition, as a radically polymerizable monomer which forms a structural unit which protects a phenolic hydroxyl group which has a phenolic hydroxyl group and is protected by the acetal, it is set, for example, in the paragraph 0042 of Unexamined-Japanese-Patent No. 2011-215590. Recorded free radicals Synergistic monomers, etc.

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

Specific examples of the acetal 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-butoxyethyl group. , 1-isobutoxyethyl, 1-(2-chloroethoxy)ethyl, 1-(2-ethylhexyloxy)ethyl, 1-n-propoxyethyl, 1-cyclohexyl An oxyethyl group, a 1-(2-cyclohexylethoxy)ethyl group, a 1-benzyloxyethyl group, etc. may be used alone or in combination of two or more.

A commercially available radical polymerizable monomer can be used as the radical polymerizable monomer for forming the structural unit (a1-2) containing the phenolic hydroxyl group which is protected by the acid-decomposable group, and a known one can 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. In the above synthesis, a monomer having a phenolic hydroxyl group may be copolymerized with another monomer in advance, and then reacted 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 embodiment of the constituent unit (a1)>>>

When the polymer containing the above-mentioned structural unit (a1) does not substantially contain the constituent unit (a2), in the polymer containing the constituent unit (a1), the constituent unit (a1) is preferably 5 mol% to 90 mol. % of ear, more preferably 20% by mole to 80% by mole.

When the polymer containing the above-mentioned structural unit (a1) contains the above-mentioned structural unit (a2), the constituent unit is contained in the polymer containing the structural unit (a1) and the structural unit (a2) from the viewpoint of sensitivity. (a1) is preferably 3 mol% to 70% Molar%, more preferably 10% by mole to 60% by mole. Further, in particular, when the acid-decomposable group which can be used in the above-mentioned structural unit (a1) is a constituent unit containing a protective carboxyl group in which a carboxyl group is protected by an acetal, it is more preferably 10 mol% to 40 mol%.

Further, in the present invention, in any of the embodiments, the total structural unit of the component (A) preferably contains 3 mol% to 70 mol% of the constituent unit (a1), more preferably 10 mol. The constituent unit (a1) of the ear %~60 mol%.

The constituent unit (a1-1) containing the protective carboxyl group protected by the acid-decomposable group has a feature of faster development than the structural unit (a1-2) containing the protective phenolic hydroxyl group protected by the acid-decomposable group. . Therefore, in the case of rapid development, it is preferably a constituent unit (a1-1) containing a protective carboxyl group protected by an acid-decomposable group. On the other hand, 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.

<<(a2) constituent unit containing a crosslinking group>>

The component (A) has a structural unit (a2) containing a crosslinking group. The crosslinking group is not particularly limited as long as it is a group which undergoes a curing reaction by heat treatment. Examples of the preferred constituent unit containing a crosslinking group include an epoxy group, an oxetanyl group, and -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms). And a constituent unit of at least one of the group consisting of ethylenically unsaturated groups.

In the photosensitive resin composition of the present invention, the component (A) preferably contains at least one of an epoxy group and an oxetanyl group, and particularly preferably the component (A) contains an oxygen-containing component. a constituent unit of a cyclobutyl group. More specifically, the following are mentioned.

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

The (A) copolymer preferably contains a structural unit (constituting unit (a2-1)) having an epoxy group and/or an oxetanyl group. The cyclic ether group of the above 3-membered ring is also referred to as an epoxy group, and the cyclic ether group of the 4-membered ring is also referred to as an oxetanyl group. The constituent unit (a2-1) having an epoxy group and/or an oxetanyl group is preferably a constituent unit having an alicyclic epoxy group and/or an oxetanyl group, and more preferably has an oxa compound. a constituent unit of a cyclobutyl group.

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

Specific examples of the radical polymerizable monomer for forming a constituent unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, and α-positive propylene. Glycidyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxy acrylate Cyclohexyl methyl ester, 3,4-epoxycyclohexylmethyl methacrylate, α-ethyl acrylate-3,4-epoxycyclohexyl methyl ester, o-vinylbenzyl glycidyl ether, m-vinyl benzyl Glycidyl ether, p-vinylbenzyl shrinkage A glycerol ether, a compound containing an alicyclic epoxy group structure described in paragraphs 0031 to 0035 of Japanese Patent No. 4,184,843, and the like.

Specific examples of the radical polymerizable monomer for forming a structural unit having an oxetanyl group include an oxygen heterocyclic ring described in paragraphs 0011 to 0016 of JP-A-2001-330953. Butyl (meth) acrylate and the like.

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

Among these monomers, a more preferred monomer is an alicyclic epoxy group-containing compound described in paragraphs 0034 to 0035 of Japanese Patent No. 4,164,843, and Japanese Patent Laid-Open Publication No. 2001-330953 The (meth) acrylate having an oxetanyl group described in paragraphs 0011 to 0016, and a particularly preferred monomer having oxygen as described in paragraphs 0011 to 0016 of JP-A-2001-330953 Heterocyclic butyl (meth) acrylate. Among these, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and acrylic acid (3-ethyloxetane) are preferred. Alkyl-3-yl)methyl ester, and (3-ethyloxetane-3-yl)methyl methacrylate, most preferably acrylic acid (3-ethyloxetan-3-yl) Methyl ester, and (3-ethyloxetane-3-yl)methyl methacrylate. These constituent units may be used alone or in combination of two or more.

As the constituent unit (a2-1) having an epoxy group and/or an oxetanyl group, the paragraph number 0053 of JP-A-2011-215590 can be referred to. ~ Paragraph number 0055.

Preferred examples of the structural unit (a2-1) having an epoxy group and/or an oxetanyl group include the following constituent units. Further, R represents a hydrogen atom or a methyl group.

In the present invention, from the viewpoint of sensitivity, an oxetanyl group is preferred. Further, from the viewpoint of transmittance (transparency), an alicyclic epoxy group and an oxetanyl group are preferred. As described above, in the present invention, the epoxy group and/or the oxetanyl group are preferably an alicyclic epoxy group and an oxetanyl group, and particularly preferably an oxetanyl group.

<<<(a2-2) constituent unit having -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms)>>>

The copolymer used in the present invention is also preferably a structural unit (a2-2) having -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms). By containing the constituent unit (a2-2), the heat treatment which can be relaxed can cause a hardening reaction, and a cured film excellent in various properties can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. Further, the alkyl group may be any of a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group. The constituent unit (a2) is more preferably a constituent unit having a group represented by the following general formula (1).

In the above 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 is preferably a linear or branched alkyl group.

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

<<<Preferred embodiment of the constituent unit (a2)>>>

When the polymer containing the above-mentioned structural unit (a2) does not substantially contain the constituent unit (a1), in the polymer containing the constituent unit (a2), the constituent unit (a2) is preferably 5 mol% to 90 mol. % of ear, more preferably 20% by mole to 80% by mole.

When the polymer containing the above-mentioned structural unit (a2) contains the above-mentioned structural unit (a1), the constituent unit is contained in the polymer containing the structural unit (a1) and the structural unit (a2) from the viewpoint of sensitivity. (a1) is preferably from 3 mol% to 70 mol%, more preferably from 10 mol% to 60 mol%.

Further, in the present invention, in any of the constituent units of the component (A), it is preferable to contain 3 mol% to 70 mol% of the constituent unit (a2), and more preferably 10 mol. The constituent unit (a2) of the ear %~60 mol%.

When it is in the range of the above numerical values, the transparency of the cured film obtained from the photosensitive resin composition and the indium tin oxide (ITO) sputtering resistance are improved.

<<(a3) Other constituent units>>

In the present invention, the component (A) may have other constituent units (a3) in addition to the constituent unit (a1) and the constituent unit (a2). The monomer to be another constituent unit (a3) is not particularly limited. Examples thereof include styrenes, alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, aryl (meth)acrylates, unsaturated dicarboxylic acid diesters, and bicyclic unsaturated compounds. And a maleimide compound, an unsaturated aromatic compound, a conjugated diene compound, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated dicarboxylic anhydride, and other unsaturated compound.

Specifically, a constituent unit formed of the following compounds: styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, ethoxylated styrene, methoxy Styrene, ethoxystyrene, chlorostyrene, methyl benzoate, ethyl vinyl benzoate, 4-hydroxypropenyl propyl 4-hydroxybenzoate, (methyl Acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, tert-butyl (meth) acrylate, (methyl) ) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol Monoethyl acetate mono(meth) acrylate, and the like. In addition, the compound described in paragraphs 0021 to 0024 of JP-A-2004-264623 may be mentioned.

Among them, from the viewpoint of film strength, it is preferably another constituent unit (a3) having a group which reacts with the constituent unit (a2) or a further added crosslinking agent by (final) heat treatment.

Specifically, a group having an alcoholic hydroxyl group is preferred, and 2-hydroxyethyl methacrylate is particularly preferred. The ratio of the other constituent unit (a3) having a group which reacts with the crosslinking agent constituting the unit (a2) or the additional crosslinking agent by the (final) heat treatment is preferably 1 mol% with respect to the entire (A) component. ~50% by mole, more preferably 5% by mole to 40% by mole, and particularly preferably 10% by mole to 30% by mole.

Further, from the viewpoint of sensitivity, the component (A) preferably contains 1 mol% to 50 mol% of a constituent unit containing an unprotected carboxyl group or contains no relative to the entire (A) component. The constituent unit of the protected phenolic hydroxyl group is more preferably a structural unit containing 3 mol% to 40 mol%, and particularly preferably the above-mentioned constituent unit containing 5 mol% to 20 mol%. The constituent unit containing the unprotected carboxyl group or the phenolic hydroxyl group may, for example, be a monomer having a known acidic group. Among them, a hydroxystyrene or (meth)acrylic acid is preferred, and methacrylic acid is more preferred.

The monomers which are the other constituent units (a3) described above may be used singly or in combination of two or more kinds.

Further, as the other structural unit (a3), from the viewpoint of electrical properties, a styrene type or a group having an aliphatic cyclic skeleton is preferable. Specifically, it can be enumerated: Styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, (methyl) Benzyl acrylate and the like.

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

In the above-mentioned embodiment, the component (A) may have a component (a3) component, and may be used in combination.

In the present invention, it is preferred to include a constituent unit containing a carboxyl group or a phenolic hydroxyl group protected by an acetal form, and a constituent unit containing an unprotected carboxyl group or a phenolic hydroxyl group.

In the photosensitive resin composition of the present invention, the polymer component (A) preferably accounts for 80% by weight or more, more preferably 90% by weight or more, of the components other than the solvent.

<<(A) Molecular Weight of Copolymer>>

The molecular weight of the (A) copolymer 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 in the range of the above numerical value, the sensitivity and ITO adaptability are good.

The ratio (dispersion) of the number average molecular weight to the weight average molecular weight is preferably from 1.0 to 5.0, more preferably from 1.5 to 3.5.

<<(A) Method for producing copolymer>>

Further, various methods are also known for the synthesis method of the component (A). As an example, a radical polymerizable monomer containing at least a radical polymerizable monomer which is a constituent unit represented by the above (a1) and the above (a2) can be used by using a radical polymerization initiator. The body mixture is synthesized by polymerization in an organic solvent. Further, it can also be synthesized by a so-called polymer reaction.

Specific examples of the copolymer (A) include 1-ethoxyethyl methacrylate/methacrylic acid/(3-ethyloxetan-3-yl)methyl methacrylate/A 2-Hydroxyethyl acrylate copolymer (45/8/35/12), 1-ethoxyethyl methacrylate/methacrylic acid/glycidyl methacrylate/allyl methacrylate/methyl Dicyclopentyl acrylate/styrene copolymer (35/10/30/5/15/15), 1-cyclohexyloxyethyl methacrylate/methacrylic acid/glycidyl methacrylate/methacrylic acid 2-Hydroxyethyl ester/styrene copolymer (40/8/35/12/5), tetrahydrofuran-2-yl methacrylate/methacrylic acid/methacrylic acid (3-ethyloxetane- 3-yl)methyl ester/glycidyl methacrylate/2-hydroxyethyl methacrylate/styrene copolymer (35/10/15/15/15/10), 1-ethoxy methacrylate Ester/methacrylic acid/(3-ethyloxetan-3-yl)methyl methacrylate/N-methoxymethylpropenylamine/2-hydroxyethyl methacrylate copolymer (40 /5/40/5/10), tetrahydropyran-2-yl methacrylate/methacrylic acid/methacrylic acid (3-ethyloxocycle) Butan-3-yl)methyl ester / 2-hydroxyethyl methacrylate / dicyclopentanyl methacrylate copolymer (42/11/25/18/4).

Specific examples of the polymer (A') and the polymer (A") include: 1-Ethoxyethyl methacrylate/methacrylic acid/2-hydroxyethyl methacrylate/benzyl methacrylate copolymer (60/10/10/20) and methacrylic acid (3-ethyloxy) Combination of heterocyclobutane-3-yl)methyl ester/methacrylic acid/2-hydroxyethyl methacrylate/benzyl methacrylate copolymer (60/10/10/20), tetrahydropyridyl methacrylate喃-2-yl ester / methacrylic acid / 2-hydroxyethyl methacrylate / dicyclopentyl methacrylate copolymer (65/5/10/20) and glycidyl methacrylate / N-methoxy A combination of methacrylamide/methacrylic acid/dicyclopentanyl methacrylate/styrene copolymer (50/15/5/15/15).

<(B) Photoacid generator>

The photoacid generator used in the present invention is preferably a compound having an induction wavelength of 300 nm or more, preferably an actinic ray having a wavelength of 300 nm to 450 nm, to generate an acid, but is not limited by its chemical structure. In addition, a photoacid generator which does not directly induce an actinic ray having a wavelength of 300 nm or more can be used as a compound which generates an acid by using an actinic ray having a wavelength of 300 nm or more and a sensitizer. 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.

From the viewpoint of sensitivity, the component (B) is preferably an onium salt compound or an oxime sulfonate compound. Among these, from the viewpoint of electrical characteristics, an oxime sulfonate is more preferable.

Examples of the photoacid generator include trichloromethyl-s-triazines, phosphonium salts or phosphonium salts, quaternary ammonium salts, diazomethane compounds, and sulfilimine sulfonate compounds. And oxime sulfonate compounds. 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.

As trichloromethyl-s-triazines: 2-(3-chlorophenyl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-double (4,6-trichloromethyl)-s-triazine, 2-(4-methylthiophenyl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-methoxy Benzyl-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 diarylsulfonium salt is diphenylsulfonium trifluoroacetate, Diphenylphosphonium trifluoromethanesulfonate, 4-methoxyphenylphenylphosphonium trifluoromethanesulfonate, 4-methoxyphenylphenylphosphonium trifluoroacetate, phenyl, 4-(2 '-Hydroxy-1'-tetradecyloxyphenylphenyl trifluoromethanesulfonate, 4-(2'-hydroxy-1'-tetradecyloxy)phenylphosphonium hexafluoroantimonate, phenyl, 4-(2'-hydroxy-1'-tetradecyloxy)phenylindole-p-toluenesulfonate; the triarylsulfonium salt is triphenylsulfonium Trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylphosphonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylphosphonium trifluoroacetate, 4-phenylthiophenyldiphenylphosphonium trifluoromethanesulfonate, or 4-phenylthiophenyldiphenylphosphonium trifluoroacetate, triphenylsulfonium 4-methoxyphenylsulfonate, etc. ; The quaternary ammonium salts are tetramethylammonium butyl tris(2,6-difluorophenyl)borate, tetramethylammonium hexyltris(p-chlorophenyl)borate, tetramethylammonium hexyltris(3- Trifluoromethylphenyl)borate, benzyldimethylphenylammonium butyl tris(2,6-difluorophenyl)borate, benzyldimethylphenylammonium hexyltris(p-chlorophenyl) Borate, benzyldimethylphenylammonium hexyltris(3-trifluoromethylphenyl)borate, etc.; diazomethane derivative is bis(cyclohexylsulfonyl)diazomethane, double (third Sulfhydrazinyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, etc.; sulfhydrazine sulfonate derivative is trifluoromethylsulfonyloxybicyclo[2.2.1]hept-5-ene Dicarboxy quinone imine, amber quinone imine triflate, phthalimide triflate, N-hydroxynaphthyl imine methane sulfonate, N-hydroxyl -5-norbornene-2,3-dicarboxyindolide propane sulfonate; the oxime sulfonate compound is a compound shown below.

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

In the formula (B1), R ²¹ represents an alkyl group, an aryl group, a fluorinated alkyl group, or a fluorinated aryl group. The wavy line indicates the bond with other bases.

Any group may be substituted, and the alkyl group in R ²¹ may be linear, branched or cyclic. The substituents allowed are explained below.

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

The aryl group of R ²¹ is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group. The aryl group of R ²¹ may be substituted by a lower alkyl group, an alkoxy group or a halogen atom.

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

In the formula (B2), R ⁴² represents an alkyl group, an aryl group, a fluorinated alkyl group, a fluorinated aryl group, X represents an alkyl group, an alkoxy group or a halogen atom, and m4 represents an integer of 0 to 3, when m4 is 2 or At 3 o'clock, multiple Xs may be the same or different.

The preferred range of R ⁴² is the same as the preferred range of the above R ²¹ .

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

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

The halogen atom as X is preferably a chlorine atom or a fluorine atom.

M4 is preferably 0 or 1.

In the above formula (B2), it is particularly preferred that m4 is 1, X is a methyl group, the substitution position of X is an ortho position, and R ⁴² is a linear alkyl group having a carbon number of 1 to 10, and 7,7-dimethyl group. a compound of 2-oxo norbornylmethyl or p-tolylmethyl.

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

In the formula (B3), R ^{43 has} the same meaning as R ⁴² in the formula (b1), and X ¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a cyano group. Or nitro, n4 represents an integer from 0 to 5.

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

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

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

Specific examples of the compound represented by the above formula (B3) include α-(methylsulfonyloxyimino)benzyl cyanide and α-(ethylsulfonyloxyimino)benzylidene. Cyanogen, α-(n-propylsulfonyloxyimino)benzyl cyanide, α-(n-butylsulfonyloxyimino)benzyl cyanide, α-(4-toluenesulfonyloxy) Amino)benzyl cyanide, α-[(methylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(ethylsulfonyloxyimino)-4-methyl Oxyphenyl]acetonitrile, α-[(n-propylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(n-butylsulfonyloxyimino)-4 -Methoxyphenyl]acetonitrile, α-[(4-toluenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile.

Specific examples of the preferred 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 can also be used in combination with other types of (B) photoacid generators.

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

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

X ¹⁰¹ represents -O-, -S-, -NH-, -NR ¹⁰⁵ -, -CH ₂ -, -CR ¹⁰⁶ H-, or -CR ¹⁰⁵ R ¹⁰⁷ -, and R ¹⁰⁵ to R ¹⁰⁷ represent an alkyl group or an aromatic group. base.

R ¹²¹ to R ¹²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amine group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, a decylamino group, a sulfo group or a cyano group. Or aryl. Two of R ¹²¹ to R ¹²⁴ may be bonded to each other to form a ring.

R ¹²¹ to R ^{124 are} preferably a hydrogen atom, a halogen atom or an alkyl group, and an embodiment in which at least two of R ¹²¹ to R ¹²⁴ are bonded to each other to form an aryl group is also preferable. Among them, from the viewpoint of sensitivity, an embodiment in which R ¹²¹ to R ¹²⁴ are each a hydrogen atom is preferred.

The functional groups described may each further have a substituent.

Preferred examples of the compound represented by the above formula (OS-1) include the formulas described in paragraphs 0194 to 0202 of JP-A-2011-221496, and the exemplified compounds thereof.

In the present invention, the compound containing the oxime sulfonate structure represented by the above formula (B1) is preferably a compound of the following formula (OS-3) or the following formula (OS-4) or The oxime sulfonate compound represented by the formula (OS-5).

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

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

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

The alkyl group in R ²² , R ²⁵ and R ²⁸ is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, n-pentyl or hexyl. Base, n-octyl, n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl, benzyl.

Examples of the substituent which the alkyl group in R ²² , R ²⁵ and R ²⁸ may have include a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, and an aryloxycarbonyl group. , aminocarbonyl.

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

As the aryl group in R ²² , R ²⁵ and R ²⁸ , preferred are phenyl, p-methylphenyl, p-chlorophenyl, pentachlorophenyl, pentafluorophenyl, o-methoxyphenyl, p-benzene. Oxyphenyl.

Examples of the substituent which the aryl group in R ²² , R ²⁵ and R ²⁸ may have include a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, and an aromatic group. An oxycarbonyl group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, an alkoxysulfonyl group.

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

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

Examples of the heteroaryl group in R ²² , R ²⁵ and R ²⁸ include a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and the like which may have a substituent. A group in which a hydrogen atom is removed from a ring of a group consisting of benzimidazole rings.

Examples of the substituent which the heteroaryl group in R ²² , R ²⁵ and R ²⁸ 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, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, an alkoxysulfonyl group.

In the above formula (OS-3) to formula (OS-5), R ²³ , R ²⁶ and R ^{29 are} preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.

In the above formula (OS-3) to formula (OS-5), it is preferred that two or more of R ²³ , R ²⁶ and R ²⁹ are present in the compound, and one or two of them are an alkyl group or an aryl group. Or a halogen atom, more preferably 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 above formula (OS-3) to formula (OS-5), the alkyl group or the aryl group in R ²³ , R ²⁶ and R ²⁹ may have a substituent. Here, as the substituent which the alkyl group or the aryl group in R ²³ , R ²⁶ and R ²⁹ may have, the same as the substituent which the alkyl group or the aryl group in the above R ²² , R ²⁵ and R ²⁸ may have may be exemplified. Base.

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

The alkyl group in R ²³ , R ²⁶ and R ²⁹ is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl or allyl. , chloromethyl, bromomethyl, methoxymethyl, benzyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl Further, it is more preferably a methyl group, an ethyl group, a n-propyl group, a n-butyl group or a n-hexyl group, and particularly preferably a methyl group.

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

The aryl group in R ²³ , R ²⁶ and R ²⁹ is specifically a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group or a p-phenyloxy group. Phenyl group.

Examples of the halogen atom in R ²³ , R ²⁶ and R ²⁹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Among these, a chlorine atom and a bromine atom are preferable.

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

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

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

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

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

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

The alkyl group in R ²⁴ , R ²⁷ and R ³⁰ is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, n-pentyl or hexyl. Base, n-octyl, n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl, benzyl.

Examples of the substituent which the alkyl group in R ²⁴ , R ²⁷ and R ³⁰ may have include a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, and an aryloxycarbonyl group. , aminocarbonyl.

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

Further, as a preferable range or an exemplary compound of the general formula (OS-3) to the general formula (OS-5), the description of Paragraph No. 0171 to Paragraph No. 0200 of JP-A-2011-227449 can be referred to.

In the photosensitive resin composition of the present invention, (B) photoacid is produced with respect to all the resin components (preferably a solid component, more preferably the above (A) copolymer) in the photosensitive resin composition. The agent is preferably used in an amount of from 0.1 part by mass to 10 parts by mass, more preferably from 0.5 part by mass to 10 parts by mass. Two or more types may be used in combination.

The photosensitive resin composition of the present invention may also contain 1,2-quinonediazide The substance acts as a photoacid generator for inducing actinic radiation. Although the 1,2-quinonediazide compound generates a carboxyl group by a stepwise photochemical reaction, its quantum yield must be 1 or less.

<(C) Compound containing a vinyl ether group>

The photosensitive resin composition of the present invention contains (C) a vinyl ether group-containing compound (hereinafter also referred to as a vinyl ether compound). The vinyl ether compound used in the present invention has one to four vinyl ether groups in the molecule, and has an alkylene oxide group and/or a hydroxyl group, and has a molecular weight of 80 to 1,000. By adding such a compound, the effect of the present invention tends to be more effectively exhibited.

The (C) vinyl ether compound used in the present invention has one to four vinyl ether groups in the molecule, preferably one to two, and particularly preferably two. When the number of vinyl ether groups is 5 or more, the adhesion of the substrate is deteriorated, and the effects of the present invention are not exhibited.

The (C) vinyl ether compound used in the present invention has an alkylene oxide group or a hydroxyl group, and more preferably has an alkylene oxide group.

The epoxyalkyl group is not particularly limited, and examples thereof include an epoxyalkyl group having 2 to 10 carbon atoms. Specific examples thereof include a chain alkylene oxide group such as an oxirane group or an oxypropylene group, and a cyclic epoxyalkyl group such as an epoxy group or an oxetanyl group.

Among them, an oxiranyl group or an oxetanyl group is preferred.

The molecular weight of the (C) vinyl ether compound used in the present invention is from 80 to 1,000, preferably from 100 to 500, more preferably from 100 to 300.

The (C) vinyl ether compound used in the present invention preferably contains only a carbon atom, an oxygen atom and a hydrogen atom.

Further, the (C) vinyl ether compound used in the present invention may contain a cyclic structure, but preferably contains only a linear or branched structure.

The (C) vinyl ether compound used in the present invention preferably has at least two cationic polymerizable groups.

In the photosensitive resin composition of the present invention, the vinyl ethers can be used, and the following vinyl ethers can be used as a commercial product, and the following vinyl ethers can be obtained from Maruzen Petrochemical Co., Ltd. class. (Hydroxyvinyl ethers): 2-hydroxyethyl vinyl ether, hydroxypentyl vinyl ether, hydroxyhexyl vinyl ether, triethylene glycol monovinyl ether, cyclohexane dimethanol monovinyl ether, three Cyclodecanediol monovinyl ether, tricyclodecane dimethylol monovinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether; (monovinyl ether): methoxy Ethyl vinyl ether, ethoxyethyl vinyl ether, methyl diethylene glycol vinyl ether, methyl triethylene glycol vinyl ether, ethyl triethylene glycol vinyl ether; (divinyl Ethers: diethylene glycol divinyl ether, triethylene glycol divinyl ether; (trivinyl ether): pentaerythritol trivinyl ether; (heterofunctional vinyl ethers): ethyl oxalate Cyclobutane methanol vinyl ether, diethylene glycol monovinyl monoglycidyl ether, butanediol monovinyl monoglycidyl ether, cyclohexyl dimethanol vinyl ether glycidyl ether, butanediol monovinyl ether Monoacrylate, butanediol monovinyl ether monomethacrylate, cyclohexane dimethanol monovinyl ether monoacrylate.

Among the above-mentioned vinyl ethers, as the compound which can sufficiently exhibit the effects of the present invention, divinyl ethers and heterofunctional vinyl ethers are preferable, and specifically, two of them can be suitably used. Ethylene glycol divinyl ether, triethylene glycol divinyl ether, cyclohexyl dimethanol divinyl ether, tricyclodecane divinyl ether, trimethylolpropane trivinyl ether, ethyl oxalate Cyclobutane methanol vinyl ether, diethylene glycol monovinyl monoglycidyl ether, cyclohexyl dimethanol vinyl ether glycidyl ether, butanediol monovinyl ether monoacrylate, of which the best is two Diol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, ethyl oxetane methanol vinyl ether, diethylene glycol monovinyl monoglycidyl ether.

In the present invention, the amount of the vinyl ether compound to be used for the effect of the total solid content is 0.1% by mass to 15% by mass, preferably 0.2% by mass to 12.5% by mass, more preferably 0.5% by mass to 5.0% by mass. Furthermore, it is more preferably 1% by mass or more and 5% by mass or less, and particularly preferably 1.5% by mass to 5% by mass or less.

<(D) Solvent>

The photosensitive resin composition of the present invention contains (D) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution containing the above-mentioned (A) component to (D) component as an essential component, and (E) component (I) which will be described later as a preferable component. A component and a solution in which any of the components described below are dissolved in the 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 ether acetate, propylene glycol monoalkyl ether, propylene glycol II Alkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers Classes, dipropylene glycol monoalkyl ether acetates, esters, ketones, guanamines, lactones, and the like.

For the solvent (D) used in the photosensitive resin composition of the present invention, for example, the description of Paragraph No. 0166 to Paragraph No. 0169 of JP-A-2011-215580 can be referred to.

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, more preferably two, and more preferably propylene glycol monoalkyl ether acetate or dialkyl ether or diacetate. With diethylene glycol dialkyl ethers, or esters and butanediol alkyl ether acetates, it is preferred to use propylene glycol monomethyl ether acetate and diethylene glycol ethyl methyl ether in combination.

Further, the component D is preferably a solvent having a boiling point of 130 ° C or higher and less than 160 ° C, a solvent having a boiling point of 160 ° C or higher, or a mixture of these, more preferably a solvent having a boiling point of 130 ° C or higher and less than 160 ° C. a solvent having a boiling point of 160 ° C or higher and 200 ° C or lower, or a mixture thereof, more preferably a solvent having a boiling point of 130 ° C or higher and less than 160 ° C, a solvent having a boiling point of 160 ° C or higher, less than 200 ° C, and a boiling point of A mixture of solvents above 200 ° C and below 260 ° C.

The solvent having a boiling point of 130 ° C or higher and less than 160 ° C can be exemplified by propylene glycol monomethyl ether acetate (boiling point: 146 ° C), propylene glycol monoethyl ether acetate (boiling point: 158 ° C), propylene glycol methyl-n-butyl Ether (boiling point 155 ° C), propylene glycol methyl-n-propyl ether (boiling point 131 ° C).

The solvent having a boiling point of 160 ° C or higher and less than 200 ° C can be exemplified by ethyl 3-ethoxypropionate (boiling point: 170 ° C), diethylene glycol methyl ethyl ether (boiling point: 176 ° C), and propylene glycol. Monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate (boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butyl Diol diacetate (boiling point 232 ° C).

The solvent having a boiling point of 160 ° C or higher and less than 260 ° C can be exemplified by diethylene glycol monoethyl ether acetate (boiling point: 220 ° C) and 1,3-butylene glycol diacetate (boiling point: 232 ° C). .

The content of the solvent (D) in the photosensitive resin composition of the present invention is more than 100 parts by mass of all the resin components (preferably the solid content, more preferably the copolymer (A)) in the photosensitive resin composition. The amount is preferably from 50 parts by mass to 3,000 parts by mass, more preferably from 100 parts by mass to 2,000 parts by mass, further preferably from 150 parts by mass to 1,500 parts by mass, particularly preferably from 150 parts by mass to 900 parts by mass.

<Other ingredients>

In the positive photosensitive resin composition of the present invention, in addition to the components (A), (B), (C) and (D), (E) a sensitizer may be preferably added ( F) a crosslinking agent, (G) a adhesion improving agent, (H) a basic compound, and (I) a surfactant. Further, in the positive photosensitive resin composition of the present invention, a plasticizer, a thermal radical generator, an antioxidant, a thermal acid generator, an ultraviolet absorber, a tackifier, a development accelerator, and an organic or Known additives such as inorganic anti-precipitation agents Additives.

(E) sensitizer

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

Polynuclear aromatics (eg, ruthenium, osmium, tert-triphenyl, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10- Dipropoxy fluorene), xanthene (such as fluorescein, blush, erythrosine, Rhodamine B, Rose Bengal) ), xanthone (such as xanthone, thioxanthone, dimethylthiazinone, diethyl thianonanone), cyanine (such as thiacarbocyanine, oxacarbonyl) Cyanine), anthocyanins (eg, anthocyanins, carbonyl anthocyanins), rhodamines, oxaphthalenes, thiazines (eg, thiazide, methylene blue, toluidine blue), Acridines (eg acridine orange, chloroflavin, acriflavine), acridone (eg acridone, 10-butyl-2-chloroacridone), anthraquinones (eg hydrazine) , succinic acid ylide (such as squaric acid ylide), styryl, basic styrenic (such as 2-[2-[4-(dimethylamino)phenyl]vinyl]benzene And oxazole), coumarins (eg 7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, 2,3,6,7-tetrahydro-9- Base-1H, 5H, 11H[1 Benzopyran [6,7,8-ij]quinolizin-11-one).

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

The amount of the sensitizer added to the photosensitive resin composition of the present invention is preferably from 0 part by weight to 1000 parts by weight, more preferably 10 parts by weight, per 100 parts by weight of the photoacid generator of the photosensitive resin composition. It is 500 parts by weight, and more preferably 50 parts by weight to 200 parts by weight. Two or more types may be used in combination.

(F) crosslinker

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

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

Among these crosslinking agents, a compound having two or more epoxy groups or oxetanyl groups in the molecule is preferred, and an epoxy resin is particularly preferred.

The amount of the crosslinking agent added to the photosensitive resin composition of the present invention is preferably from 0.01 part by weight to 50 parts by weight, more preferably from 0.5 part by weight to 30 parts by weight per 100 parts by weight of the total solid content of the photosensitive resin composition. The parts by weight are further preferably 2 parts by weight to 10 parts by weight. Mechanical strength and resistance can be obtained by adding in this range A cured film excellent in solvent properties. A plurality of crosslinking agents may be used in combination, and in this case, all the crosslinking agents are combined to calculate the content.

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

Specific examples of the compound having two or more epoxy groups in the molecule include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol 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, bisphenol A type epoxy resins are JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, Japan Epoxy Resins (share)), EPICLON860, EPICLON1050 EPICLON 1051, EPICLON 1055 (above, DIC (manufactured by DIC)), bisphenol F-type epoxy resin is JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, manufactured by Nippon Epoxy Co., Ltd.) , EPICLON 830, EPICLON 835 (above, manufactured by Di Ai Sheng (share)), LCE-21, RE-602S (above, manufactured by Nippon Chemical Co., Ltd.), etc., phenol novolak type epoxy resin is JER152, JER154, JER157S70, JER157S65 (The above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by Di Ai Sheng (share)), etc., cresol novolak type epoxy resin is EPICLON N -660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, Di Aisheng (share) manufacturing), EOCN-1020 (to In the case of Nippon Chemical Co., Ltd., the aliphatic epoxy resin is ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (above, manufactured by ADEKA). Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE 3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (above, manufactured by Daicel Chemical Industry Co., Ltd.) and the like.

Other than this, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (above, manufactured by Eddy Co., Ltd.), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by Eddy Co., Ltd.), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX- 512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX- 850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (manufactured by Changchun Huacheng), YH-300, YH-301, YH-302, YH -315, YH-324, YH-325 (above Nippon Steel Chemical Manufacturing).

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

Among these compounds, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, and an aliphatic epoxy resin can be more preferably exemplified, and a bisphenol A type ring can be particularly preferably exemplified. Oxygen resin.

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

<Alkoxymethyl group-containing crosslinking agent>

As the crosslinking group containing an alkoxymethyl group, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril and alkoxymethylated urea are preferred. Wait. 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, it is preferably a methoxymethyl group.

Among these alkoxymethyl group-containing crosslinking agents, preferred examples of the crosslinking agent include alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycine. From the viewpoint of transparency, urea is particularly preferably an alkoxymethylated glycoluril.

These alkoxymethyl group-containing crosslinking agents are commercially available, and for example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272 can be preferably used. 202, 1156, 1158, 1123, 1170, 1174, UFR 65, 300 (above, manufactured by Mitsui Cyanamid (share)), Nikalac MX-750, Nikalac MX-032, Nikalac MX-706, Nikalac MX- 708, Nikalac MX-40, Nikalac MX-31, Nikalac MX-270, Nikalac MX-280, Nikalac MX-290, Nikalac MS-11, Nikalac MW-30HM, Nikalac MW-100LM, Nikalac MW-390 (above, manufactured by Sanwa Chemical Co., Ltd.).

a 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 can be preferably used. Base) 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.

When a compound having at least one ethylenically unsaturated double bond is added, it is preferred to add a thermal radical generating agent to be described later.

(G) adhesion improver

The photosensitive resin composition of the present invention may contain a (G) adhesion improver. The (G) 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 (G) adhesion improving agent used in the present invention is not particularly limited as long as it is intended to modify 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 alkyl dialkoxy decane, γ-methyl propylene methoxy propyl trialkoxy decane, γ-methyl propylene methoxy propyl alkyl dialkoxy decane, γ - chloropropyl trialkoxydecane, γ-mercaptopropyltrialkoxydecane, β-(3,4-epoxycyclohexyl)ethyltrialkoxydecane, vinyltrialkoxydecane. More preferably, it is γ-glycidoxypropyltrialkoxydecane or γ-methacryloxypropyltrialkoxydecane, and more preferably γ-glycidoxypropyltri The alkoxydecane, and more preferably 3-glycidoxypropyltrimethoxydecane. These decane coupling agents may be used alone or in combination of two or more. These decane coupling agents are effective for improving the adhesion to the substrate, and are also effective for adjusting the taper of the substrate.

The content of the (G) adhesion improving agent in the photosensitive resin composition of the present invention is preferably 100 parts by mass based on the total solid content in the photosensitive resin composition. 0.1 parts by mass to 30 parts by mass, more preferably 0.5 parts by mass to 10 parts by mass.

(H) basic compound

The photosensitive resin composition of the present invention may contain a (H) basic compound. The (H) 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, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, and 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, piperidine, piperazine, morpholine, 4-methylmorpholine, 1 , 5-diazabicyclo[4.3.0]-5-pinene, 1,8-diazabicyclo[5.3.0]-7-undecene, and the like.

Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, 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 alone or in combination of two or more. It is preferred to use two or more kinds in combination, more preferably two kinds, and more preferably two kinds of heterocyclic amines.

The content of the (H) basic compound in the photosensitive resin composition of the present invention is preferably 0.001 part by mass to 1 part by mass, more preferably 0.005 part by mass, based on 100 parts by mass of the total solid content of the photosensitive resin composition. Parts ~ 0.2 parts by mass.

(I) surfactant

The photosensitive resin composition of the present invention may further contain (I) a surfactant. As the (I) 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 alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, anthrone series, and fluorine. Is a surfactant. In addition, the following trade names are listed: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), Eftop (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Megafac (Di Aisheng (share) ) Manufacturing), Fluorad (manufactured by Sumitomo 3M (share)), Asahi Guard, Surflon (made by Asahi Glass), PolyFox (made by OMNOVA), SH-8400 (Dow Corning) Toray Silicone)) and other series.

Further, as the surfactant, a compound described in Paragraph No. 0185 to Paragraph No. 0188 of JP-A-2011-215580 can also be used.

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

The amount of the (I) surfactant added to the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, more preferably 0.001 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive resin composition. 50 parts by mass, more preferably 0.01 parts by mass to 10 parts by mass, still more preferably 0.01 parts by mass to 3 parts by mass, particularly preferably 0.01 parts by mass to 1 part by mass.

Antioxidants

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

Examples of such an antioxidant include phosphorus-based antioxidants, 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, a phenolic 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.

Commercially available as a phenolic antioxidant, such as Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, Adekastab manufactured by Adico (stock) AO-80, Adekastab AO-330, sumilizer GM manufactured by Sumitomo Chemical Co., Ltd. Sumilizer GS, sumilizer MDP-S, sumilizer BBM-S, sumilizer WX-R, sumilizer GA-80, IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1098, IRGANOX1135, IRGANOX1330, IRGANOX1726, IRGANOX1425WL manufactured by Ciba Japan , IRGANOX1520L, IRGANOX245, IRGANOX259, IRGANOX3114, IRGANOX565, IRGAMOD295, Yoshinox BHT, Yoshinox BB, Yoshinox 2246G, Yoshinox 425, Yoshinox 250, Yoshinox 930, Yoshinox SS, Yoshinox TT, Yoshinox 917 manufactured by API Corporation (shares) , Yoshinox 314, etc.

Among them, Adekastab AO-60, Adekastab AO-80 (above, manufactured by Eddy Co., Ltd.), and Irganox 1098 (manufactured by Nippon Ciba (share)) are preferred.

The content of the antioxidant is preferably from 0.1% by mass to 10% by mass, more preferably from 0.2% by mass to 5% by mass, even more preferably from 0.5% by mass to 4% by mass based on the total solid content of the photosensitive resin composition. By setting it as this range, the 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.

[thermal radical generator]

The photosensitive resin composition of the present invention may further contain a thermal radical generating agent, and contains a compound having at least one ethylenically unsaturated double bond as described above. In the case of an ethylenically unsaturated compound, it is preferred to contain a thermal radical generating agent.

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, phosphonium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, and sulfonium compounds. a metallocene compound, an active ester compound, a compound having a carbon halogen bond, an azo compound, a bibenzyl compound, or the like.

The thermal radical generating agent may be used alone or in combination of two or more.

The content of the thermal radical generating agent in the photosensitive resin composition of the present invention is preferably 0.01 parts by weight to 50% when the total content of the component (A) is 100 parts by weight. 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.

[thermal acid generator]

In the present invention, a thermal acid generator may be used in order to improve film properties and the like at the time of low-temperature curing.

The thermal acid generator which can be used in the present invention is a compound which generates an acid by heat, and usually has a thermal decomposition point of 130 ° C to 250 ° C, preferably 150 ° C to 220 ° C. The compound of the range is, for example, a compound which generates a low nucleophilic acid such as a sulfonic acid, a carboxylic acid or a disulfonyl sulfenimide by heating.

The acid produced by the thermal acid generator is preferably a sulfonic acid having a pKa of 2 or less, or a substituted alkyl or aryl carboxylic acid having an electron withdrawing group, and a substituted electron-substituted group. Sulfonyl imine and the like. Examples of the electron withdrawing group include a halogen atom such as a fluorine atom, a halogenated alkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.

Further, in the present invention, it is also preferred to use a sulfonate which does not substantially generate an acid by irradiation of exposure light, and which generates an acid by heat.

The acid which is not substantially generated by the irradiation of the exposure light can be determined by infrared (Infrared, IR) spectroscopy or nuclear magnetic resonance (NMR) spectroscopy before and after exposure of the compound, and is determined by no change in the spectrum.

The molecular weight of the sulfonate is preferably from 230 to 1,000, more preferably from 230 to 800.

As the sulfonic acid ester which can be used in the present invention, a commercially available sulfonic acid ester can be used, and a sulfonic acid ester synthesized by a known method can also be used. The sulfonate can be synthesized, for example, by reacting sulfonium chloride or a sulfonic acid anhydride with a corresponding polyol under basic conditions.

When the total content of the component (A) is 100 parts by weight, the content of the thermal acid generator in the photosensitive resin composition is preferably from 0.5 part by weight to 20 parts by weight, more preferably from 1 part by weight to 15 parts by weight. .

[acid proliferator]

In order to increase the sensitivity, an acid proliferating agent can be used as the photosensitive resin composition of the present invention.

The acid proliferator which can be used in the present invention can be further reacted by an acid catalyst reaction A compound which generates an acid and increases the acid concentration in the reaction system, and is a compound which is stably present in the absence of an acid. Since such a compound is increased by one or more kinds of acids by one reaction, the reaction proceeds with the progress of the reaction, but the generated acid itself induces self-decomposition, and thus the strength of the acid generated here is an acid dissociation constant. The pKa is preferably 3 or less, and particularly preferably 2 or less.

Specific examples of the acid-proliferating agent include paragraphs 0203 to 0223 of JP-A-10-1508, paragraphs 0016 to 0055 of Japanese Patent Laid-Open No. Hei 10-282642, and Japanese Patent Laid-Open No. 9 -512498, page 39, line 12 to page 47, line 2, compounds.

Specifically, the following compounds etc. are mentioned.

The acid proliferator which can be used in the present invention is decomposed by an acid generated from an acid generator, and produces dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and benzene. A compound such as a phosphinic acid having an pKa of 3 or less.

The content of the acid multiplying agent in the photosensitive resin composition is preferably from 10 parts by weight to 1,000 parts by weight based on 100 parts by weight of the photoacid generator from the viewpoint of the dissolution ratio of the exposed portion and the unexposed portion. More preferably set to 20 parts by weight~ 500 parts by weight.

[development accelerator]

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

As the development accelerator, any compound having a development promoting effect can be used, but a compound having a structure selected from at least one of a group consisting of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group is preferred, and more preferably The compound having a carboxyl group or a phenolic hydroxyl group is preferably a compound having a phenolic hydroxyl group.

Further, the molecular weight of the (M) development accelerator is preferably from 100 to 2,000, more preferably from 100 to 1,000, most preferably from 100 to 800.

As an example of the development accelerator, examples of the development accelerator having an alkylene oxide include polyethylene glycol, monomethyl ether of polyethylene glycol, dimethyl ether of polyethylene glycol, and polyethylene glycol glyceride. , polypropylene glycol glyceride, polypropylene glycol diglyceride, polytetramethylene glycol, polyethylene glycol-bisphenol A ether, polypropylene glycol-bisphenol A ether, alkyl ether of polyoxyethylene, alkyl ester of polyoxyethylene The compound described in Japanese Laid-Open Patent Publication No. Hei 9-222724, and the like.

Examples of the development accelerator having a carboxyl group include maleic acid, fumaric acid, acetylenecarboxylic acid, 1,4-cyclohexanedicarboxylic acid, suberic acid, and adipic acid. Citric acid, malic acid, and the like. In addition, it is described in Japanese Laid-Open Patent Publication No. 2000-66406, Japanese Patent Application Publication No. Hei 9-6001, Japanese Patent Application Laid-Open No. Hei No. Hei. compound of.

As a development accelerator having a phenolic hydroxyl group, a Japanese patent is exemplified. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Hei. No. Hei. No. Hei. No. Hei. The compound described in JP-A-2007-121766, JP-A-H09-297396, and JP-A-2003-43679. Among these, a phenol compound having a benzene ring number of 2 to 10 is suitable, and a phenol compound having a benzene ring number of 2 to 5 is more preferable. As a particularly preferable compound, a phenolic compound disclosed as a dissolution promoter in JP-A-10-133366 can be mentioned.

The development accelerator may be used alone or in combination of two or more.

From the viewpoint of the sensitivity and the residual film ratio, when the component (A) is 100 parts by mass, the amount of the development accelerator in the photosensitive resin composition of the present invention is preferably from 0 to 30 mass%. The portion is more preferably 0.1 part by mass to 20 parts by mass, most preferably 0.5 part by mass to 10 parts by mass.

[Method for producing cured film]

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

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

(1) a step of applying the positive photosensitive resin composition of the present invention to a substrate; (2) a step of removing a solvent from a positive photosensitive resin composition to be applied; and (3) exposing with an actinic ray a step of (4) developing with an aqueous developing solution; (5) A post-baking step of performing thermal hardening.

Each step will be described in order below.

In the application step of (1), it is preferred to apply the positive photosensitive resin composition of the present invention to a substrate to form a wet film containing a solvent. When a metal substrate, particularly a molybdenum substrate, is used, the photosensitive composition of the present invention can exhibit particularly high adhesion. This is based on the addition of a vinyl ether compound.

In the solvent removal step of (2), the solvent is removed from the applied film by pressure reduction (vacuum) and/or heating to form a dried coating 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. (A) The catalytic action of an acid generated by an acid-decomposable gene contained in the copolymer is hydrolyzed to form a carboxyl group or a phenolic hydroxyl group.

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") is performed. The formation of a carboxyl group or a phenolic hydroxyl group derived from an acid-decomposable group can be promoted by PEB. 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 100° C. or lower.

The acid-decomposable group in the structural unit represented by the formula (a1-1) in the present invention has low activation energy due to acid decomposition, is easily decomposed by an acid derived from an acid generator generated by exposure, and generates a carboxyl group or Since the phenolic hydroxyl group is not necessarily subjected to PEB, a positive image can be formed by development. However, in the method for producing a cured film of the present invention, the photosensitive resin composition of the present invention is used after (5) Baking step The resulting cured film reduces heat flow. Therefore, when the cured film obtained by the method for producing a cured film of the present invention is used as a resist for a substrate, for example, even if the cured film of the present invention is heated together with the substrate, the resolution of the pattern hardly occurs. deterioration. In the present specification, the term "heat flow" means heating the cured film by a cross-sectional shape of the patterned cured film formed by the exposure and development steps (preferably 180 ° C or higher, more preferably 200). Deformation at °C~240°C), deterioration in size, taper angle, etc.

In the developing step of (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 post-baking step of (5), by heating the obtained positive image, the acid-decomposable group in the constituent unit (a1) can be thermally decomposed to form a carboxyl group or a phenolic hydroxyl group, and the constituent unit The crosslinking group (a2), the crosslinking agent, and the like are 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 240 ° 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 120 minutes.

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

Further, the cured film obtained from the photosensitive resin composition of the present invention is also Can be used as a dry etching resist.

When the cured film obtained by thermally hardening the post-baking step of (5) is used as a dry etching resist, dry etching treatment such as ashing, plasma etching, or ozone etching may be performed as an etching treatment.

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>

The necessary components of (A) to (D) are mixed at a predetermined ratio and in an arbitrary manner, and then stirred and dissolved to prepare a photosensitive resin composition. For example, the (A) component to the (C) component may be dissolved in the solvent (D) to prepare a solution, and these may be mixed in a predetermined ratio to prepare a resin composition. 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, a black matrix layer, a color filter layer, and a transparent conductive circuit layer may be provided as needed. The method of applying the photosensitive resin composition to the substrate is not particularly limited. In the present invention, it is preferred to apply a photosensitive resin composition onto the substrate. The coating method on 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, From the viewpoint of being suitable for a large substrate, a slit coating method is preferred. When it is manufactured by 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 and 5 m or less on each side.

Further, (2) the heating condition of the solvent removal step is that the acid-decomposable group is decomposed in the constituent unit (a1) in the component (A) in the unexposed portion, and the component (A) is not soluble in the alkaline development. The range in the liquid varies depending on the type of each component or the mixing 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 ultra-high 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 can be preferably used. An actinic ray having a wavelength of 300 nm or more and 450 nm or less, such as g-ray (436 nm), i-ray (365 nm), and 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; or an alkali metal carbonate such as sodium carbonate or potassium carbonate; Alkali metal bicarbonate such as sodium bicarbonate or potassium 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 above-mentioned alkali may be used as the developing solution.

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.

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

<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 90 minutes on a hot plate, and 30 minutes to 120 minutes for an oven. In a minute, the pattern corresponding to the unexposed area obtained by development is heat-treated, whereby the crosslinking reaction proceeds, whereby 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.

It can also be post-baked after baking at a relatively low temperature before post-baking. Bake (addition of the middle baking step). When the intermediate baking is performed, it is preferably heated at 90 ° C to 150 ° C for 1 minute to 60 minutes, and then post-baked at a high temperature of 200 ° C or higher. Further, the intermediate baking and the post-baking may be divided into three or more stages to perform heating. With this intermediate baking and post-baking design, the taper angle of the pattern can be adjusted. These heating can be carried out by a known heating method such as a hot plate, an oven, or an infrared heater.

Furthermore, it is preferred to re-expose the patterned substrate with actinic rays before the heat treatment, and then perform post-baking (re-exposure/post-baking), thereby being self-existing in the unexposed portion ( The B) component 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 a developing step and a post-baking step, including 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 above-described exposure step. However, in the above-described re-exposure step, it is preferred to perform the film on the side of the substrate on which the photosensitive resin composition of the present invention is formed. Full exposure.

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

[hardened film]

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

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

According to the photosensitive resin composition of the present invention, an interlayer insulating film which is excellent in insulation 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.

[Organic EL display device, liquid crystal display device]

The organic EL display device and the liquid crystal display device of the present invention are characterized by comprising the cured film of the present invention.

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 known structures using various structures are exemplified. 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 which is suitably used 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 solid-state imaging element A microlens or the like disposed on a color filter.

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

Further, although not shown in FIG. 1, the hole transport layer, the organic light-emitting layer, and the electron transport layer are sequentially formed by vapor deposition through a desired pattern mask, and then formed on the entire upper surface of the substrate. The second electrode of Al is sealed by bonding with a UV-curable epoxy resin using a glass plate for sealing, and an active matrix type obtained by connecting TFTs 1 for driving the organic EL elements. Organic 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 the liquid crystal panel is disposed and disposed on two glass substrates to which a polarizing film is attached. The elements of the TFT 16 corresponding to all the pixels between the board 14 and the glass substrate 15. Among the elements formed on the glass substrate, an ITO transparent electrode 19 on which a pixel electrode is formed is wired by 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.

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

StOEVE: 4-(1-ethoxyethoxy)styrene

IBMAA: Isobutoxymethyl acrylamide (made by Tokyo Chemical Industry Co., Ltd.)

GMA: glycidyl methacrylate

OXE-30: (3-ethyloxetan-3-yl)methyl methacrylate (Osaka has Machine chemical industry (shares) manufacturing)

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

THFFMA: tetrahydrofurfuryl methacrylate

St: Styrene

MMA: Methyl methacrylate

MAA: Methacrylic acid

AA: Acrylic

StCOOEVE: ethyl vinyl ether protector of styrene carboxylic acid

DCPM: Dicyclopentyl Methacrylate

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

<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). After drying over magnesium sulfate, the insolubles were filtered, and then concentrated under reduced pressure at 40 ° C or less. The yellow oil was distilled under reduced pressure to obtain a tetrahydro-2H-furan-2-yl methacrylate (MATHF) having a boiling point (bp.) of 54 ° C to 56 ° C / 3.5 mmHg as a colorless oil. (Yield 80%).

<Synthesis of Polymer A-1>

The polymer A-1 as the copolymer (A) was synthesized as follows.

Add phenothiazine (0.5 parts) to ethyl vinyl ether (144.2 parts, 2 molar equivalents), and add methacrylic acid (86.1 parts, 1 mol) while cooling to 10 ° C or less in the reaction system. After the ear equivalent), it was stirred at room temperature (25 ° C) for 4 hours. After adding pyridinium p-toluenesulfonate (5.0 parts), the mixture was stirred at room temperature for 2 hours and then allowed to stand at room temperature overnight. Sodium hydrogencarbonate (5 parts) and sodium sulfate (5 parts) were added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour. The insoluble material was filtered and concentrated under reduced pressure at 40 ° C or less. Distillation under reduced pressure gave 1-ethoxyethyl methacrylate (MAEVE, 134.0 parts) as a colorless oil (bp.) 43 ° C - 45 ° C / 7 mmHg fraction.

The obtained 1-ethoxyethyl methacrylate (63.28 parts (0.4 mole equivalent)), GMA (42.65 parts (0.3 mole equivalent)), MAA (8.61 parts (0.1 mole) was obtained under a nitrogen stream. Equivalent)), a mixed solution of HEMA (26.03 parts (0.2 mole equivalent)) and EDM (110.8 parts) was heated to 80 °C. While stirring the mixed solution, a mixed solution of a radical polymerization initiator V-601 (trade name, manufactured by Wako Pure Chemical Industries, Ltd., 4 parts) and EDM (100.0 parts) was added dropwise over 2.5 hours. After completion of the dropwise addition, the mixture was reacted at 80 ° C for 4 hours, whereby an EDM solution of polymer A-1 (solid content concentration: 40%) was obtained.

The weight average molecular weight of the obtained polymer A-1 as measured by Gel Permeation Chromatography (GPC) was 15,000.

<Synthesis of other polymers>

In addition to changing the amount of each monomer used and its usage, it is recorded in the following table. A polymer as the copolymer (A) was synthesized in the same manner as in the synthesis of the polymer A-1, except for the carrier.

<Photoacid generator>

B-1: Irgacure PAG-103 (trade name, structure shown below, manufactured by BASF)

B-2: PAI-101 (trade name, structure shown below, manufactured by Midori Kagaku Co., Ltd.)

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-9: N-hydroxynaphthyldimethylimine mesylate

B-10: TPS-1000 (trade name, structure shown below, manufactured by Green Chemical Co., Ltd.)

<Synthesis of B-3>

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

Synthesis of α-(hydroxyimino)-2-phenylacetonitrile

Mixing 5.85 g of phenylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) into tetrahydrofuran Silane: 50 ml (manufactured by Wako Pure Chemical Industries, Ltd.), and then placed in an ice bath to cool the reaction solution to below 5 °C. Then, 11.6 g of SM-28 (sodium methoxide 28% methanol solution, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the mixture was stirred under ice bath for 30 minutes to carry out a reaction. Then, 7.03 g of isoamyl nitrite (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise while maintaining the internal temperature at 20 ° C or lower. 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 thereto to carry out liquid separation, thereby obtaining about 180 ml of an aqueous layer having a target substance. Further, 100 ml of ethyl acetate was added again, 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. When the obtained crude crystals were washed with hexane, 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 9.55 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added while maintaining the internal temperature at 20 ° C or lower, 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, 16 g of α-(methylsulfonyloxyimino)-2-phenylacetonitrile (Compound B-3) was obtained in a yield of 90%. The H-NMR spectrum of the compound showed the product to be a hydrazine structural isomer (cis/reverse A mixture of (syn/anti)) having 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.

<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, the reaction liquid was cooled to 5 ° C or lower, and then p-toluenesulfonium chloride (1.9 g) (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged, and the mixture was stirred for 1 hour while maintaining the temperature at 10 ° C or lower. Thereafter, 80 mL of water was added, and the mixture was stirred at 0 ° C for 1 hour. After the obtained precipitate was filtered, 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 1.8 g of B-5 (structure described above).

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

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

<Synthesis of B-6>

To a suspension solution of 2-naphthol (10 g) and chlorobenzene (30 mL), aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added, and the mixture was heated to 40 ° C and reacted for 2 hours. . Under ice cooling, a 4N aqueous HCl solution (60 mL) was added dropwise, and then ethyl acetate (50 mL) was added and partitioned. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 ° C for 1 hour, and then a 2N aqueous HCl solution (60 mL) was added and the mixture was separated, and the organic layer was concentrated, and then crystallised from diisopropyl ether (10 mL) It was reslurryed, and 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 50% by mass aqueous hydroxylamine solution (8.0 g) were added and added. Heat 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 thereto under ice cooling, and the mixture was heated to room temperature and reacted for 1 hour. . Water (50 mL) was added to the reaction liquid, and the precipitated crystals were filtered, and then re-slurryed with methanol (20 mL), and then filtered and dried to obtain 2.3 g of B-6 (the above structure).

Further, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-6 was 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).

<vinyl ether compound>

C-1: Diethylene glycol divinyl ether (manufactured by ISP Japan, RAPI-CURE DVE2)

C-2: Ethyl oxetane methanol vinyl ether (manufactured by Maruz Petrochemical Co., EOXTVE)

C-3: (Hydroxyhexyl) vinyl ether (Machine Petrochemical Manufacturing, HHVE)

C-4: pentaerythritol trivinyl ether (synthesized according to Sint. Svoistva Monomerov, Sb. Rab. Konf. Vysokomol. Soedin., 12th, 1962, p. 264, 265-266)

C'-1: cyclohexyl dimethanol divinyl ether (manufactured by Maruz Petrochemical, CHDMDVE)

C'-2: ethyl vinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)

C'-4: a polymer synthesized by the following synthesis method

<c'-4>

The styrene-containing polyhydroxystyrene resin (100 g) was dissolved in methanol (400 g) and pure water (40 g), and purified by an ion exchange resin, and then concentrated to obtain γ-butyl so that the concentration became about 30%. After the lactone was adjusted, it was concentrated again in order to remove residual methanol and water.

Acetic acid (0.1 g) was added to the resin solution (333 g), and the mixture was stirred at an internal temperature of 100 ° C to 110 ° C, and then cyclohexyldivinyl ether (9.5 g) was added dropwise. After reacting for 20 hours, pyridine (4 g) was added dropwise, and the mixture was stirred at room temperature for 1 hour, and then 2-heptanone (300 g) was added and dissolved.

The solution is then washed several times with a solution of methanol/water. The 2-heptanone layer was separated and then concentrated to remove residual methanol/water.

The obtained vinyl ether-containing polymer had a molecular weight of 85,000.

<sensitizer>

E-1: NBCA (structure described below, manufactured by Heijin Huacheng (share))

E-2: DBA (trade name, 9,10-dibutoxy oxime, manufactured by Kawasaki Chemicals Co., Ltd.)

<crosslinker>

F-1: JER157S65 (trade name, phenol novolac type epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd.)

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

F-3: Trimethylolpropane triacrylate (made by East Asia Synthetic)

<Close Agent>

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

G-2: KBM-5103 (trade name, 3-acryloxypropyltrimethoxydecane, manufactured by Shin-Etsu Chemical Co., Ltd.)

<alkaline compound>

H-1:1,5-diazabicyclo[4.3.0]-5-pinene (manufactured by Tokyo Chemical Industry Co., Ltd.)

H-2: triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Surfactant>

I-1: Fluorine-based surfactant (Ftergent FTX-218, Neos)

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

<Other additives>

AO-60: hindered phenol Adekastab AO-60 (made by Eddy)

BC-90: Nofmer BC-90 (manufactured by Nippon Oil & Fats Co., Ltd.)

SE-1: Suberic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

PA-1:

[Adjustment of photosensitive resin composition]

Each component was made into propylene glycol monomethyl ether acetate: diethylene glycol ethyl methyl ether: dipropylene glycol methyl ether acetate in the form of the composition of the following table, and the solid content was 15 mass %. The mixture was dissolved and mixed in a mixed solvent of 46:46:8, and then filtered through a filter made of polytetrafluoroethylene having a diameter of 0.2 μm to obtain photosensitive resin compositions of the examples and the comparative examples, respectively.

<Evaluation of sensitivity>

After coating each photosensitive resin composition in a slit on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)) which was subjected to a surface treatment for 1 minute under hexamethyldioxane vapor, The solvent was volatilized by prebaking at 95 ° C / 150 seconds on a hot plate 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 9 μm hole pattern 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 alkali developer (0.4% by mass aqueous solution of tetramethylammonium hydroxide) at 24 ° C / 50 seconds, and then rinsed with ultrapure water for 20 seconds.

The optimum exposure amount (Eopt) when a hole pattern of 9 μm was formed by these operations was taken as the sensitivity. Furthermore, the evaluation criteria are as follows. The smaller the value, the better, the practical range is 1~3. The results are shown in the following table.

1: less than 60mJ/cm ²

2: 60 mJ/cm ² or more, less than 90 mJ/cm ²

3: 90 mJ/cm ² or more, less than 120 mJ/cm ²

4: 120 mJ/cm ² or more, less than 150 mJ/cm ²

5:150mJ/cm ² or more

<Evaluation of chemical resistance>

Each photosensitive resin composition was applied to a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), and then dried at 95 ° C / 120 on a hot plate. The solvent was volatilized by prebaking in seconds to form a photosensitive resin composition layer having a film thickness of 3.0 μm. The film was exposed to 300 mJ using an ultrahigh pressure mercury lamp, and further heated at 240 ° C for 40 minutes in an oven to form a cured film.

The film thickness (T ¹ ) of the obtained cured film was measured. Further, after the substrate on which the cured film was formed was immersed in a solution of dimethyl hydrazine:monoethanolamine=7:3 controlled to a temperature of 60 ° C for 10 minutes, the film thickness (t ¹ ) of the cured film after immersion was performed. The measurement was performed, and the film thickness change rate {|t ¹ -T ¹ |/T ¹ } × 100 [%] by the immersion was calculated. The results are shown in the following table.

The smaller the film thickness change rate, the better, and 1, 2, and 3 are practically problem-free levels.

1: less than 2%

2:2% or more, less than 3%

3:3% or more, less than 4%

4:4% or more, less than 6%

5:6% or more

<Evaluation of substrate adhesion>

After each slit of the photosensitive resin composition was applied onto a molybdenum substrate, it was prebaked on a hot plate at 95° C./120 seconds to volatilize the solvent to form a photosensitive resin composition layer having a film thickness of 0.4 μm. .

After treatment with an alkaline developer (0.4% by mass aqueous solution of tetramethylammonium hydroxide) at 24 ° C / 50 seconds, it was rinsed with ultrapure water for 20 seconds.

Thereafter, after irradiating 500 mJ/cm ² of light at a wavelength of 365 nm using an ultrahigh pressure mercury lamp, it was heated at 240 ° C for 40 minutes in an oven to obtain a cured film.

For the cured film, the adhesion was evaluated in accordance with the cross-cut test of JIS K5600.

1: No peeling on any of the grids, the edges of the cut are completely smooth.

2: No peeling on any of the grids, but floating on the edge of the cut.

3: Peeling off to 1~2

4: Peeling off to 3~4

5: peeling off to 5 or more

<evaluation of patterns>

The composition of each of the examples and the comparative examples was subjected to slit coating of each photosensitive resin composition on a tantalum wafer substrate which was subjected to surface treatment for one minute under hexamethyldiazepine vapor, and then on a hot plate. The solvent was volatilized by prebaking at 95 ° C / 120 seconds to form a photosensitive resin composition layer having a film thickness of 4.0 μm.

Then, the obtained photosensitive resin composition layer was exposed to 9 μm with an optimum exposure amount (Eopt) of each composition using an NSR-2205i14E2F exposure machine (i-ray stepper) manufactured by Nikon Co., Ltd. Hole pattern shape. Then, the photosensitive composition layer after exposure was developed with an alkali developer (0.4% by mass aqueous solution of tetramethylammonium hydroxide) at 24 ° C / 50 seconds, and then rinsed with ultrapure water for 20 seconds. After irradiating 500 mJ/cm ² of light at a wavelength of 365 nm using an ultrahigh pressure mercury lamp, it was heated at 140 ° C for 20 minutes in an oven, then heated at 180 ° C for 20 minutes, and further heated at 230 ° C for 60 minutes to obtain a cured film. The hole pattern was observed using an electron microscope.

A hole pattern is clearly formed in any of the embodiments. The comparative example also formed a pattern of holes.

[Example 30]

An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 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 planarization film 4 on the insulating film 3 was formed by spin-coating the photosensitive resin composition of Example 16 on a substrate, and pre-baking (90 ° C × 2 minutes) on a hot plate, 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 produced planarizing film 4 was 2,000 nm.

Then, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, the first electrode 5 including ITO is connected to the first via the contact hole 7 Line 2 is formed on the planarization film 4. Thereafter, the resist is applied, pre-baked, 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, manufactured by AZ Electronic Materials Co., Ltd.). The first electrode 5 obtained in the above manner corresponds to the anode of the organic EL element.

Then, an insulating film 8 covering the shape of the periphery of the first electrode 5 is formed. The photosensitive resin composition of Example 4 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, vapor deposition is sequentially performed through a desired pattern mask to provide a hole transport layer, an organic light-emitting layer, and an electron transport layer. 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 glass plate for sealing and an ultraviolet curable epoxy resin.

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 31]

In the active matrix liquid crystal display device described in FIG. 1 of Japanese Patent No. 3321003, the cured film 17 is formed as interlayer insulation in the following manner. A film was obtained to obtain a liquid crystal display device of Example 31.

In the same manner as the method of forming the planarizing film 4 of the organic EL display device of the above-described Example 30, the cured film 17 was used as the interlayer insulating film.

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 (13)

A photosensitive resin composition comprising: (A) a polymer component satisfying at least one of the following (1) and (2), (1) having (a1) an acid group-containing acid group-protected group; a constituent unit of the residue, and (a2) a constituent unit containing an epoxy group, an oxetanyl group, or -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) at least copolymerized (acrylic polymer) (2) an acrylic polymer having (a1) a constituent unit containing a residue in which an acid group is protected by an acid-decomposable group, and having (a2) an epoxy group, an oxetanyl group, or An acrylic polymer having a constituent unit of -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms); (B) a photoacid generator; (C) a compound containing a vinyl ether group; and (D) a solvent; wherein the (C) vinyl ether group-containing compound contains only a carbon atom, a hydrogen atom, and an oxygen atom, and has 1 to 4 vinyl ether groups in the molecule, and has an alkylene oxide group and/or Hydroxyl group with a molecular weight of 80 to 1000. The photosensitive resin composition according to claim 1, wherein the (C) vinyl ether group-containing compound has one to two vinyl ether groups. The photosensitive resin composition according to the first or second aspect of the invention, wherein the structural unit (a1) is a constituent unit containing a residue in which a carboxyl group is protected by an acetal form. The photosensitive resin composition according to the first or second aspect of the invention, wherein the structural unit (a1) is a constituent unit represented by the following formula (A2'): In the formula, 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, R ³ represents an alkyl group or an aryl group, and R ¹ or R ² is 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 the first or second aspect of the invention, wherein the structural unit (a1) is a constituent unit containing a residue in which a carboxyl group is protected by an acetal form. The photosensitive resin composition according to claim 1 or 2, wherein the structural unit (a1) is a constituent unit represented by the following formula (A2'): Formula (A2') In the formula, 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, R ³ represents an alkyl group or an aryl group, and R ¹ or R ² is 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 5, wherein the structural unit (a1) is a component having a carboxyl group protected by an acetal form and represented by the following formula (A2'). : In the formula, 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, R ³ represents an alkyl group or an aryl group, and R ¹ or R ² is 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. 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; (2) a step of removing a solvent from a photosensitive resin composition to be applied; 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. The method for producing a cured film according to claim 8, wherein the step of performing total exposure is performed after the developing step and before the post-baking step. A cured film formed by curing a photosensitive resin composition according to the first or second aspect of the invention. The cured film according to claim 10, which is an interlayer insulating film. A liquid crystal display device comprising the cured film according to claim 10 of the patent application. An organic electroluminescence display device comprising the cured film according to claim 10 of the patent application.