JP2016160393A - Curable resin composition, cured film for display element, method for forming the same, and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition which can form a cured film excellent in adhesiveness and transparency, and is excellent in preservation stability, wherein a cured film for a display element in this invention is excellent in adhesiveness and transparency, and accordingly can be suitably used as an interlayer insulation film, a protective film, a spacer and the like of the display element.SOLUTION: A curable resin composition contains [A] a polymer having a group represented by formula (1A) and a structural unit containing a carboxyl group; and [B] a basin compound.SELECTED DRAWING: None

Description

  The present invention relates to a curable resin composition, a cured film for a display element, a method for forming the same, and a display element.

  For display elements such as liquid crystal display elements and organic EL, an interlayer insulating film for maintaining insulation between wirings arranged in layers, a protective film for suppressing deterioration and damage of electronic components including touch panels, A cured film such as a spacer for providing a liquid crystal layer or the like with a constant film thickness is provided. Such a cured film is required to have excellent transparency in addition to excellent adhesion to a substrate, a transparent conductive film, wiring, and the like.

  In the formation of such a cured film, a curable resin composition is used from the viewpoints that the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained. As such a curable resin composition, since a high surface hardness is obtained, those containing a polymer having an ethylenically unsaturated bond in the side chain have been studied, and this polymer has a carboxyl group. Those obtained by reacting an epoxy group-containing unsaturated compound with a polymer and those obtained by reacting an isocyanate group-containing unsaturated compound with a polymer having a carboxyl group and a hydroxyl group are known (Japanese Patent Laid-Open No. 11-1990). 174464 and JP-A-2002-20442).

  Under such circumstances, recently, there has been a further increase in demand for the performance of the cured film, particularly adhesion, and the above-mentioned conventional curable resin composition cannot satisfy the demand. In addition, the conventional curable resin composition is also required to improve its storage stability from the viewpoint of process stability.

JP-A-11-174464 JP 2002-20442 A

  The present invention has been made based on the circumstances as described above, and an object thereof is to provide a curable resin composition that can form a cured film having excellent adhesion and transparency and is excellent in storage stability. It is.

  Invention made | formed in order to solve the said subject is the hardening | curing containing the polymer which has [A] group represented by following formula (1A), and the structural unit containing a carboxyl group, and [B] a basic compound. It is an adhesive resin composition.

(In Formula (1A), R ¹ , R ² and R ³ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. Among R ¹ , R ² and R ³ May be bonded to each other to form a ring structure having 3 to 20 ring members together with the carbon atom to which they are bonded, and R ⁴ is (a) a (n + 1) -valent carbon atom having 1 to 20 carbon atoms. A hydrogen group, (b) a group containing at least one selected from the group consisting of an oxygen atom, a sulfur atom, —SO— and —SO ₂ — between carbon-carbon of the hydrocarbon group, or (c) ( a) A part or all of the hydrogen atoms of the hydrocarbon group and (b) group are selected from the group consisting of a halogen atom, a cyano group, a nitro group, a carboxyl group, a sulfino group, a mercapto group, and an alkoxy group having 1 to 12 carbon atoms. is at least one substituted with a group selected .R ⁵ is a single If or -COO- in which .n, when it .n is 2 or more integer from 1 to 6, a plurality of R ¹ may be the same or different, even if a plurality of R ² may be the same or different The plurality of R ³ may be the same or different, and * indicates the site to be bound.)
Another invention made to solve the above problems is a cured film for a display element as an interlayer insulating film, a protective film or a spacer formed from the curable resin composition.

  Still another invention made in order to solve the above-mentioned problems is a step of forming a coating film on a substrate, a step of irradiating at least a part of the coating film, and a coating film irradiated with the radiation. It is a method for forming a cured film for a display element, comprising a step and a step of heating the developed coating film, wherein the coating film is formed from the curable resin composition.

  Yet another invention made to solve the above-described problems is a display element comprising the display element cured film.

  The curable resin composition of the present invention can form a cured film having excellent adhesion and transparency, and is excellent in storage stability. Since the cured film for a display element of the present invention is excellent in adhesion and transparency as described above, it can be suitably used as an interlayer insulating film, a protective film, a spacer or the like of the display element. Therefore, these can be suitably used for the manufacturing process of a display element such as a liquid crystal device.

<Curable resin composition>
The curable resin composition of the present invention contains a [A] polymer and a [B] basic compound. The curable composition includes, as suitable components, [C] a polymerizable compound having an ethylenically unsaturated bond (hereinafter also referred to as “[C] polymerizable compound”), [D] a radical polymerization initiator, [E]. Copolymerized with an acid generator and / or a monomer comprising an epoxy group-containing unsaturated compound and at least one selected from the group consisting of [F] unsaturated carboxylic acids and unsaturated carboxylic anhydrides. A polymer (hereinafter also referred to as “[F] polymer”) may be contained, and other optional components may be contained as long as the effects of the present invention are not impaired.

  The curable resin composition can function as a thermosetting resin composition because the (meth) acryloyl group of the structural unit (1) of the polymer [A] can be polymerized by heating. Moreover, the curable resin composition may function as a radiation curable resin composition by containing a radiation sensitive radical polymerization initiator and / or a radiation sensitive acid generator, as will be described later. it can. Examples of radiation include electromagnetic waves such as visible light, ultraviolet light, far ultraviolet light, and X-rays; and charged particle beams such as electron beams and α rays.

Hereinafter, each component will be described.
<[A] polymer>
[A] The polymer is a polymer having a group represented by the following formula (1A) and a structural unit containing a carboxyl group.

In formula (1A), R ¹ , R ² and R ³ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. Two or more of R ¹ , R ² and R ³ may be bonded to each other to form a ring structure having 3 to 20 ring members together with the carbon atom to which they are bonded. R ⁴ represents (a) an (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, (b) an oxygen atom, a sulfur atom, —SO— and —SO ₂ between carbon and carbon of the hydrocarbon group. A group containing at least one selected from the group consisting of-, or (c) a halogen atom, a cyano group, a nitro group, or a carboxyl group, part or all of the hydrogen atoms of the (a) hydrocarbon group and (b) group , A sulfino group, a mercapto group, and a group substituted with at least one selected from the group consisting of alkoxy groups having 1 to 12 carbon atoms. R ⁵ is a single bond or —COO—. n is an integer of 1-6. When n is 2 or more, the plurality of R ¹ may be the same or different, the plurality of R ² may be the same or different, and the plurality of R ³ may be the same or different. * Indicates a binding site.
[A] The polymer may have one or more of each structural unit.

  The said curable resin composition is excellent in the adhesiveness and transparency of a cured film, and storage stability by containing a [A] polymer. Moreover, it is excellent in the radiation sensitivity at the time of setting it as a radiation curable resin composition so that it may mention later. The reason why the curable resin composition has the above-described configuration provides the above-described effect is not necessarily clear, but can be inferred as follows, for example. That is, the [A] polymer has the structural unit (1) as a structural unit containing an ethylenically unsaturated bond in the side chain. Unlike the case of the conventional curable resin composition, this structural unit (1) has a hydroxyl group generated by a reaction between a carboxyl group and an epoxy group, an imino group generated by a reaction between a hydroxyl group and an isocyanate group, and the like. Not done. As a result, it is considered that the adhesion of the cured film is improved, for example, by suppressing the penetration of the alkaline aqueous solution between the patterns in the development process. In addition, since the structural unit (1) of the polymer [A] does not have a hydroxy group, an imino group or the like, the alteration during heating, which is considered to be caused by these groups, is suppressed, and the transparency of the cured film is improved. To do. Furthermore, since the condensation of the hydroxyl group, imino group and the like with the carboxyl group of the structural unit (2) does not occur, it is considered that the storage stability is improved. In the case of a radiation curable resin composition, it is considered that the activity of radicals and acids is increased by having no hydroxy group, imino group or the like in the vicinity of an ethylenically unsaturated bond, and as a result, radiation sensitivity is improved. More improved.

Hereinafter, each structural unit will be described.
[Structural unit (1)]
The structural unit (1) is represented by the following formula (1).

The formula ^(1), R 1, ^{R 2} and ^{R 3} are each independently a monovalent hydrocarbon group having a hydrogen atom or a C 1-20. Two or more of R ¹ , R ² and R ³ may be bonded to each other to form a ring structure having 3 to 20 ring members together with the carbon atom to which they are bonded. R ⁴ represents (a) an (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, (b) an oxygen atom, a sulfur atom, —SO— and —SO ₂ between carbon and carbon of the hydrocarbon group. A group containing at least one selected from the group consisting of-, or (c) a halogen atom, a cyano group, a nitro group, or a carboxyl group, part or all of the hydrogen atoms of the (a) hydrocarbon group and (b) group , A sulfino group, a mercapto group, and a group substituted with at least one selected from the group consisting of alkoxy groups having 1 to 12 carbon atoms. n is an integer of 1-6. When n is 2 or more, the plurality of R ¹ may be the same or different, the plurality of R ² may be the same or different, and the plurality of R ³ may be the same or different. R ⁵ is a single bond or —COO— *. * Indicates a site binding to ^{R 4.} R ⁶ is a hydrogen atom, a methyl group or a fluorinated methyl group.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ , R ² and R ³ include, for example, a monovalent chain hydrocarbon group having 1 to 20 carbon atoms and a carbon number of 3 to 20 Examples thereof include a monovalent alicyclic hydrocarbon group and a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

Examples of the monovalent chain hydrocarbon group include alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, and t-butyl group. Group;
An alkenyl group such as an ethenyl group, a propenyl group, a butenyl group;
Alkynyl groups such as ethynyl group, propenyl group, butenyl group and the like can be mentioned.

Examples of the monovalent alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an adamantyl group;
Examples include cycloalkenyl groups such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, and a norbornenyl group.

Examples of monovalent aromatic hydrocarbon groups include aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, and anthryl groups;
Examples thereof include aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group and anthrylmethyl group.

Examples of the ring structure having 3 to 20 ring members formed by combining two or more of R ¹ , R ² and R ³ together with the carbon atom to which they are bonded include, for example, a cyclopropene structure, a cyclobutene structure, and a cyclopentene structure And cycloalkene structures such as a cyclohexene structure, a cyclooctene structure, and a norbornene structure.

R ¹ , R ² and R ³ are preferably a hydrogen atom or a monovalent chain hydrocarbon group, more preferably a hydrogen atom or an alkyl group, still more preferably a hydrogen atom, a methyl group or an ethyl group, and particularly preferably a hydrogen atom. preferable.

Examples of (a) (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴ include those exemplified as monovalent hydrocarbon groups represented by R ¹ , R ² and R ^3. From the above, groups from which n hydrogen atoms have been removed are exemplified.

Examples of the group containing an oxygen atom between carbon and carbon of (b) (a) hydrocarbon group represented by R ⁴ include a hydrocarbon group exemplified as R ¹ , R ^2, and R ³ as an oxygen atom. And a group obtained by removing (n + 1) hydrogen atoms from an ether formed by one bond.

Examples of the group containing a sulfur atom between carbon-carbon of the hydrocarbon group (b) (a) represented by R ⁴ include hydrocarbon groups exemplified as R ¹ , R ² and R ³ with 2 A group obtained by removing (n + 1) hydrogen atoms from a thioether formed by two bonds.

Examples of the group (b) (a) represented by R ⁴ that includes —SO— between the carbon-carbon of the hydrocarbon group include hydrocarbon groups exemplified as R ¹ , R ^2, and R ³ , —SO—. And a group obtained by removing (n + 1) hydrogen atoms from a sulfoxide compound formed by bonding two sulfur atoms.

Examples of the group containing —SO ₂ — between the carbon-carbon of the hydrocarbon group (b) (a) represented by R ⁴ include hydrocarbon groups exemplified as R ¹ , R ² and R ^3. _And a group obtained by removing (n + 1) hydrogen atoms from a sulfone compound formed by bonding two to 2-sulfur atoms.

  As a C1-C12 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group etc. are mentioned, for example.

Examples of the halogen atom in the group (c) represented by R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Sulfino group means a -SO ₂ H.

R ⁴ is preferably (a) a hydrocarbon group or (b) group, more preferably a group in which (n + 1) hydrogen atoms have been removed from alkane, cycloalkane, arene, or cycloalkylalkyl ether, and it has 2 to 6 carbon atoms. More preferably a group in which (n + 1) hydrogen atoms have been removed from a C 3-15 cycloalkane, a C 6-18 arene, and a C 5-20 cycloalkyl alkyl ether, an ethane group, cyclohexane Particularly preferred are groups in which (n + 1) hydrogen atoms have been removed from adamantane, benzene and adamantyl ethyl ether.

  n is preferably an integer of 1 to 3, and more preferably 1 or 2, from the viewpoint of the ease of synthesis of the monomer that gives the structural unit (I). When n is a curable and radiation curable resin composition From the viewpoint of further improving the radiation sensitivity, 2 is more preferable.

As R ⁵ , R ⁴ is selected from the group consisting of a chain hydrocarbon group, an alicyclic hydrocarbon group, and an oxygen atom, a sulfur atom, —SO— and —SO ₂ — between the carbon and carbon of these groups. A group comprising at least one kind, and a part or all of hydrogen atoms of the above group from a group consisting of a halogen atom, a cyano group, a nitro group, a carboxyl group, a sulfino group, a mercapto group, and an alkoxy group having 1 to 12 carbon atoms When it is a group substituted with at least one selected, -COO- * is preferred.

Examples of the fluorinated methyl group represented by R ⁶ include a fluoromethyl group, a difluoromethyl group, and a trifluoromethyl group. Of these, a trifluoromethyl group is preferred.

R ⁶ is preferably a methyl group from the viewpoint of the copolymerizability of the monomer giving the structural unit (I).

  Examples of the structural unit (I) include structural units represented by the following formulas (1-1) to (1-12) (hereinafter also referred to as “structural units (I-1) to (I-12)”). Etc.

In the formulas (1-1) to (1-12), R ⁶ has the same meaning as the formula (1).

  Among these, the structural units (1-1) to (1-7) are preferable.

  [A] The method for incorporating the structural unit (1) into the polymer is not particularly limited. For example, as shown in the following scheme, by polymerization using a monomer represented by the following formula (i), By synthesizing a polymer in which the structural unit (1 ′) represented by the formula (1 ′) is incorporated, this polymer is subjected to dehydrohalogenation reaction in the presence of a base such as triethylamine, for example. The method etc. which produce | generate an unsaturated double bond and form the structural unit (1) represented by following formula (1) are mentioned.

In said scheme, R < ¹ > -R < ⁶ > and n are synonymous with the said Formula (1). X is a halogen atom.

  The halogen atom represented by X is preferably a chlorine atom or a bromine atom, more preferably a chlorine atom, from the viewpoint of increasing the yield of the dehydrohalogenation reaction.

  The monomer represented by the above formula (i) is, for example, a compound having a (meth) acryloyl group and a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, and a β-halo such as 3-chloropropionic acid chloride. -A carboxylic acid halide can be synthesized by a dehydrohalogenation condensation reaction in a solvent such as methylene chloride in the presence of a base such as pyridine.

As a content rate of the said structural unit (1), 5 mol%-90 mol% are preferable as a preparation ratio with respect to all the monomers used for the synthesis | combination of a [A] polymer, and 10 mol%-70 mol% are more. Preferably, 15 mol%-40 mol% are more preferable. By making the said content rate into the said range, the radiation sensitivity at the time of setting it as the adhesiveness and transparency of a cured film, storage stability, and a radiation-curable resin composition can be improved more.
[Structural unit (2)]
The structural unit (2) is a structural unit containing a carboxyl group. The said curable resin composition can exhibit alkali developability because the [A] polymer has a structural unit (2).

  Examples of the monomer that gives the structural unit (2) include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids, and anhydrides of unsaturated dicarboxylic acids. And mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends, an unsaturated polycyclic compound having a carboxyl group, and an anhydride thereof.

  Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.

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

  Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include, for example, maleic acid mono [(meth) acryloyloxyethyl] ester, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] and the like.

  As an anhydride of unsaturated dicarboxylic acid, the anhydride of the compound illustrated as said dicarboxylic acid, etc. are mentioned, for example.

  Examples of the mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends include ω-carboxypolycaprolactone mono (meth) acrylate.

  Examples of unsaturated polycyclic compounds having a carboxyl group and anhydrides thereof include 5-carboxybicyclo [2.2.1] hept-2-ene and 5,6-dicarboxybicyclo [2.2.1]. Hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5- Carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2. 2.1] hept-2-ene anhydride and the like.

Moreover, as a monomer which provides the said structural unit (2), the compound formed by protecting carboxyl groups, such as the said carboxylic acid, can also be used. Examples of the protected carboxyl group in the above compound include groups in which a hydrogen atom of a carboxyl group is substituted with —C (R ^a ) (R ^b ) (OR ^c ) (R ^a and R ^b are each independently, A hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ^c is a monovalent hydrocarbon group having 1 to 20 carbon atoms). Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ^a , R ^b and R ^c are the same as the monovalent hydrocarbon groups exemplified as the above R ¹ , R ² and R ³ . Groups and the like. Among these, as R ^a and R ^c , an alkyl group is preferable. R ^b is preferably a hydrogen atom.

  Examples of the compound formed by protecting the carboxyl group such as carboxylic acid include 1-butoxyethyl (meth) acrylate, 1-ethoxyethyl (meth) acrylate, 1-ethoxybutyl (meth) acrylate and the like.

  Among these, from the viewpoints of copolymerization and availability of the monomer that gives the structural unit (2), and solubility of the [A] polymer in an aqueous alkali solution, unsaturated monocarboxylic acid, unsaturated monocarboxylic acid A compound obtained by protecting the carboxyl group of carboxylic acid is preferred, and methacrylic acid and 1-butoxyethyl methacrylate are more preferred.

The content ratio of the structural unit (2) is preferably 5 mol% to 50 mol%, more preferably 10 mol% to 40 mol%, as a charging ratio with respect to all monomers used for the synthesis of the polymer [A]. Preferably, 15 mol%-35 mol% are more preferable. By making the said content rate into the said range, the alkali developability of the said curable resin composition can be made more moderate.
[Structural unit (3)]
The structural unit (3) is a structural unit other than the structural unit (1) and the structural unit (2) and does not include any of a hydroxyl group, an amino group, and an imino group. [A] When the polymer has the structural unit (3), the storage stability of the curable resin composition can be further improved.

  Examples of the monomer that gives the structural unit (3) include methacrylic acid alkyl ester, methacrylic acid cycloalkyl ester, acrylic acid alkyl ester, acrylic acid cycloalkyl ester, methacrylic acid aromatic ester, acrylic acid aromatic ester, and the like. Unsaturated dicarboxylic acid diesters, bicyclo unsaturated compounds, N-maleimide compounds, unsaturated aromatic compounds, conjugated dienes, tetrahydrofuran skeletons, furan skeletons, tetrahydropyran skeletons or pyran skeletons, and other compounds Examples thereof include unsaturated compounds that do not have any of a hydroxyl group, an amino group, and an imino group.

  Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, Examples include tridecyl methacrylate and n-stearyl methacrylate.

Examples of the methacrylic acid cycloalkyl ester include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, and tricyclomethacrylate [5.2.1]. .0 ^2,6] decan-8-yl oxy ethyl, and isobornyl methacrylate.

  Examples of the alkyl acrylate ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, n-lauryl acrylate, Examples include tridecyl acrylate and n-stearyl acrylate.

Examples of the cycloalkyl acrylate include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, and tricyclo [5.2. 1.0 ^2,6 ] decan-8-yloxyethyl, isobornyl acrylate, and the like.

  Examples of the methacrylic acid aromatic ester include methacrylic acid aryl esters such as phenyl methacrylate and naphthyl methacrylate; methacrylic acid aralkyl esters such as benzyl methacrylate and phenethyl methacrylate.

  Examples of the acrylic acid aromatic ester include acrylic acid aryl esters such as phenyl acrylate and naphthyl acrylate; acrylic acid aralkyl esters such as benzyl acrylate and phenethyl acrylate.

  Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like.

  Examples of the bicyclo unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2.1]. Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 .1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 -Cyclohexyloxycarbonyl bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [2 2.1] Hept- - ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, and the like.

  Examples of N-maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N-succinimidyl-3-maleimidobenzoate, and N-succinimidyl-4-maleimidobuty Rate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.

  Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene.

  Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

  Examples of the unsaturated compound having a tetrahydrofuran skeleton include tetrahydrofurfuryl methacrylate, 2-methacryloyloxy-tetrahydrofurfuryl propionate, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like.

  Examples of unsaturated compounds containing a furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-ene- 2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2- Yl-hex-1-en-3-one, 2-furan-2-yl-1-methyl-ethyl ester of acrylic acid, 6- (2-furyl) -6-methyl-1-hepten-3-one, etc. Can be mentioned.

  Examples of the unsaturated compound containing a tetrahydropyran skeleton include tetrahydropyran-2-ylmethyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) oct-1-en-3-one, 2- Examples include methacrylic acid tetrahydropyran-2-yl ester, 1- (tetrahydropyran-2-oxy) butyl-3-en-2-one, and the like.

  Examples of unsaturated compounds containing a pyran skeleton include 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyran and 4- (1,5-dioxa-6-oxo. -7-octenyl) -6-methyl-2-pyran and the like.

  Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

  Among these, from the viewpoint of the copolymerizability of the monomer that gives the structural unit (3), alkyl methacrylates and unsaturated aromatic compounds are preferable, and methyl methacrylate and styrene are more preferable.

As a content rate of the said structural unit (3), as a preparation ratio with respect to all the monomers used for the synthesis | combination of a [A] polymer, 0 mol%-80 mol% are preferable, and 20 mol%-75 mol% are more. 40 mol% to 70 mol% is more preferable. By making the said content rate into the said range, the storage stability of the said curable resin composition can further be improved.
[Other structural units]
Examples of other structural units include structural units containing a hydroxy group, an amino group, or an imino group. The content ratio of other structural units is preferably 20 mol% or less, more preferably 5 mol% or less, and even more preferably 0 mol%, as a charge ratio with respect to all monomers used for the synthesis of the polymer [A]. .

[A] The content of the polymer is preferably 30% by mass or more, more preferably 35% by mass to 95% by mass, and more preferably 40% by mass to 70% by mass with respect to the total solid content of the curable resin composition. Is more preferable.
<[A] Polymer Synthesis Method>
[A] As described above, the polymer is a monomer that gives the structural unit (1) by a dehydrohalogenation reaction after the polymerization reaction, such as the monomer represented by the above formula (i), A monomer that gives the structural unit (II), a monomer that gives the structural unit (3), if necessary, is polymerized in a solvent using a radical polymerization initiator, and the resulting polymer is dehalogenated. It can be synthesized by hydrogenation reaction to form the structural unit (1).

  Examples of the solvent include alcohol, chain ether, cyclic ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether propionate, aromatic Group hydrocarbons, ketones, other esters and the like.

  Examples of the alcohol include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol and the like.

  Examples of the chain ether include diethyl ether, dipropyl ether, dibutyl ether, anisole, diphenyl ether and the like.

  Examples of the cyclic ether include tetrahydrofuran and tetrahydropyran.

  Examples of the glycol ether include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.

  Examples of the ethylene glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate.

  Examples of the diethylene glycol alkyl ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.

  Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like.

  Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate and the like.

  Examples of the propylene glycol monoalkyl ether propionate include propylene monoglycol methyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate and the like. .

  Examples of the aromatic hydrocarbon include toluene and xylene.

  Examples of the ketone include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and the like.

  Examples of other esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, hydroxyacetic acid Methyl, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, Methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, Methyl poxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propylbutoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionate Propyl acid, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxypropionic acid Ethyl, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-metho Butyl cypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxy Examples include propyl propionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

  As the solvent, other esters are preferable, and methyl 3-methoxypropionate is preferable. One or two or more of the solvents may be used.

  Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-). 2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), dimethyl-2,2′-azobis (2-methylpropionate), 2,2′-azobis (4-methoxy-) 2,4-dimethylvaleronitrile) and the like.

  Of these, 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile) are preferable.

  The amount of the radical polymerization initiator used is preferably from 1 mol% to 10 mol%, more preferably from 2 mol% to 8 mol%, based on a total of 100 mol of monomers used for polymerization. As the radical polymerization initiator, one kind or two or more kinds may be used.

In the polymerization reaction, a molecular weight modifier can be used to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide;
mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid;
Xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide;
Examples include terpinolene and α-methylstyrene dimer.

  The amount of the molecular weight modifier used is appropriately selected according to the molecular weight of the desired [A] polymer, but 0.1 mol% to 10 mol with respect to 100 mol% of the total monomers used for polymerization. % Is preferable, and 0.5 mol% to 5 mol% is more preferable. One or more molecular weight regulators may be used.

  As superposition | polymerization temperature, it is 0 to 150 degreeC normally, and 50 to 120 degreeC is preferable.

  The polymerization time is usually 10 minutes to 20 hours, preferably 30 minutes to 6 hours.

  As the solvent used in the dehydrohalogenation reaction after the polymerization reaction, those exemplified as the solvent that can be used in the polymerization can be used, but it is preferable to use the solvent used in the polymerization as it is. That is, it is preferable to perform a dehydrohalogenation reaction by adding a base to the polymerization reaction solution.

Examples of the base used in the dehydrohalogenation reaction include amines such as diethylamine, dipropylamine, trimethylamine, triethylamine, tripropylamine, pyrrolidine, piperidine, pyridine, and triethanolamine:
Metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide;
Metal carbonates such as sodium carbonate, potassium carbonate, calcium carbonate;
Metal hydrogen carbonates such as sodium hydrogen carbonate, potassium hydrogen carbonate, calcium hydrogen carbonate;
Examples thereof include metal alkoxides such as sodium methoxide and potassium t-butoxide.

  The amount of the base used in the dehydrohalogenation reaction is preferably 1 mol to 10 mol, more preferably 1.5 mol to 7 mol, and more preferably 2 mol to 5 mol with respect to 1 mol of desorbed hydrogen halide. Further preferred.

  As temperature of dehydrohalogenation reaction, it is 0 degreeC-150 degreeC normally, and 50 degreeC-100 degreeC is preferable.

  The time for the dehydrohalogenation reaction is usually 10 minutes to 20 hours, preferably 30 minutes to 6 hours.

  [A] As a polystyrene conversion weight average molecular weight (Mw) of a polymer, 2.00-100,000 are preferable, 3,000-50,000 are more preferable, 5,000-20,000 are further more preferable. [A] By making Mw of a polymer into the said range, the adhesiveness of a cured film can be improved more and the radiation sensitivity at the time of setting it as a radiation curable resin composition can be improved more.

[A] The molecular weight distribution (Mw / Mn) of the polymer is preferably 5.0 or less, and more preferably 3.0 or less. [A] By making Mw / Mn of a polymer below the above upper limit, the pattern shape of a cured film can be made more favorable.
<[B] Basic compound>
[B] Examples of basic compounds include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, carboxylic acid quaternary ammonium salts, and the like. By including a basic compound in the curable resin composition, curability can be promoted and adhesion of the resulting cured film can be improved. Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, and di-n. -Propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine, dicyclohexylmethylamine and the like.

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

Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,8-diazabicyclo [5,3,0] -7 Undesen,
Biimidazole compounds are mentioned. Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2 ′. -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5 5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-bi Examples include imidazole.

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

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

It is preferable that content of the basic compound in the said curable resin composition shall be 0.001-20 mass parts with respect to 100 mass parts of [A] polymers, and shall be 0.005-10 mass parts. Is more preferable. By making content of a basic compound into the said range, while being able to accelerate | stimulate sclerosis | hardenability without impairing the storage stability of curable resin composition, the adhesiveness of the obtained cured film can also be improved.
<[C] polymerizable compound>
[C] The polymerizable compound is a polymerizable compound having an ethylenically unsaturated bond. The curable resin composition further includes a [C] polymerizable compound, so that when a negative pattern is formed, the adhesion of the cured film can be further improved. In the case of forming, the thermal stability of the pattern shape can be improved. [C] The polymerizable compound can be cured by heating, but can be more effectively cured by containing a radical polymerization initiator described later.

  Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group, and a styryl group.

  [C] The number of ethylenically unsaturated bonds of the polymerizable compound may be one or plural. The number of ethylenically unsaturated bonds is preferably 2 or more, more preferably 3 or more from the viewpoint of improving the adhesion of the cured film, and 10 or less is preferable and 6 or less is more preferable from the viewpoint of enhancing storage stability. preferable.

  [C] Examples of the polymerizable compound include monofunctional acrylates, polyfunctional acrylates, and other polymerizable compounds.

  Examples of the monofunctional acrylate include ω-carboxypolycaprolactone mono (meth) acrylate and ethylene glycol mono (meth) acrylate.

  Examples of the polyfunctional acrylate include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, Cyclodecane dimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenoxyethanol full orange (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, 2-hydroxy- 3- (meth) acryloyloxypropyl methacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( Acrylate), dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tri (2- (meth) acryloyloxy Ethyl) phosphate, ethylene oxide-modified dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, succinic acid-modified dipentaerythritol pentaacrylate, linear alkylene group and alicyclic structure, and two or more isocyanates A urethane (meth) acrylate obtained by reacting a compound having a group with a compound having one or more hydroxyl groups in the molecule and having 3 to 5 (meth) acryloyloxy groups. Polyfunctional (meth) acrylate compound of the rate compounds and the like.

  Examples of other polymerizable compounds include 2- (2'-vinyloxyethoxy) ethyl (meth) acrylate and the like.

[C] Examples of commercially available polymerizable compounds include Aronix M-400, M-402, M-405, M-450, M-520, M-1310, M-1600 and M. -1960, M-7100, M-8030, M-8060, M-8100, M-8100, M-8530, M-8560, M-9050, Aronix TO-756, TO-1450, TO -1382 (above, Toagosei Co., Ltd.);
KAYARAD DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, MAX-3510 (above, Nippon Kayaku Co., Ltd.);
Viscoat 295, 300, 360, 802, GPT, 3PA, 400 (above, Osaka Organic Chemical Industries);
As a urethane acrylate compound, New Frontier R-1150 (Daiichi Kogyo Seiyaku Co., Ltd.);
KAYARAD DPHA-40H, KAYARAD DPEA-12, HUX-5000 (above, Nippon Kayaku Co., Ltd.);
UN-9000H (Negami Kogyo Co.);
Aronix M-5300, M-5600, M-5700, M-210, M-220, M-240, M-270, M-6200, M-305, M-309, M M-310, M-315 (above, Toagosei Co., Ltd.);
KAYARAD HDDA, KAYARAD HX-220, HX-620, R-526, R-167, R-604, R-684, R-551, R-712, UX-2201, UX-2301 UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (above, Nippon Kayaku Co., Ltd.);
Art Resin UN-9000PEP, UN-9200A, UN-7600, UN-333, UN-1003, UN-1255, UN-6060PTM, UN-6060P, SH-500B Company);
Viscoat 260, 312 and 335HP (Osaka Organic Organic Chemical Industry Co., Ltd.) are listed.

  [C] The polymerizable compound is preferably a polyfunctional acrylate, such as dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, trimethylolpropane triacrylate, tripentaerythritol heptaacrylate, tripentaerythritol. Octaacrylate and succinic acid-modified dipentaerythritol pentaacrylate are more preferred.

[C] The content of the polymerizable compound is preferably 20 parts by mass or more and 200 parts by mass or less, and more preferably 40 parts by mass or more and 160 parts by mass or less with respect to 100 parts by mass of the polymer [A]. In the curable resin composition, the content of the [C] polymerizable compound is set in the above range, so that the adhesiveness of the cured film in the case of the negative pattern formation described above and the pattern shape in the case of the positive pattern formation are obtained. Thermal stability can be further increased.
<[D] radical polymerization initiator>
[D] The radical polymerization initiator is a component that generates an active species capable of initiating radical polymerization of a compound having polymerizability. The said curable resin composition can improve the adhesiveness of a cured film more by containing a [D] radical polymerization initiator. [D] Examples of radical polymerization initiators include [D1] a heat-sensitive radical polymerization initiator that decomposes by heating to generate radicals, and [D2] a radiation-sensitive radical polymerization initiator that generates radicals by irradiation with radiation. Is mentioned. In the curable resin composition, the content of the [D] radical polymerization initiator may be a low molecular compound as described later, or a form incorporated as a part of the [A] polymer or the like. It may be a form. [D] One or more radical polymerization initiators may be contained.
[[D1] Thermosensitive radical polymerization initiator]
[D1] The heat-sensitive radical polymerization initiator is a compound that decomposes by heating to generate radicals. The said curable resin composition can function as a thermosetting resin composition, if it contains a [D1] thermosensitive radical polymerization initiator.

[D1] Examples of the heat-sensitive radical polymerization initiator include azobisisobutyronitrile (AIBN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), and 2,2′-azobis. Azo radical initiators such as (2-cyclopropylpropionitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate; benzoyl peroxide, t -Peroxide radical initiators such as butyl hydroperoxide and cumene hydroperoxide.
[[D2] Radiation sensitive radical polymerization initiator]
[D2] The radiation-sensitive radical polymerization initiator is a compound that generates radicals upon irradiation with radiation. When the curable resin composition contains [D2] a radiation sensitive radical polymerization initiator, it can function as a radiation curable resin composition, and [A] polymer and [C] polymerizable compound are generated by the generated radicals. And the like are polymerized to exhibit negative radiation sensitive characteristics. The curable resin composition can further improve the radiation sensitivity by containing [D2] a radiation-sensitive radical polymerization initiator.

  [D2] Examples of the radiation-sensitive radical polymerization initiator include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, thioxanthone compounds, and the like.

  Examples of the O-acyloxime compound include 1- [4- (phenylthio) -2- (O-benzoyloxime)], 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime). )], Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl- 9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like.

  Examples of acetophenone compounds include α-aminoketone compounds and α-hydroxyketone compounds.

  Examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4 -Morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and the like.

  Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone can be mentioned.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4 -Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5 '-Tetraphenyl-1,2'-biimidazole and the like, and 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole Imidazole is preferred.

  Examples of the thioxanthone compound include thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone and the like.

  Among these, O-acyloxime compounds, acetophenone compounds, and thioxanthone compounds are preferable, O-acyloxime compounds, α-aminoketone compounds, and thioxanthone compounds are more preferable, and ethanone-1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2,4-diethyl More preferred is thioxanthone.

[D] The content of the radical polymerization initiator is preferably 1 part by mass or more and 40 parts by mass or less, and more preferably 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the polymer [A]. [D] By making content of a radical polymerization initiator into the said range, the said curable resin composition can improve the adhesiveness of a cured film more, and in the case of a radiation curable resin composition, it is radiation. Sensitivity can be further increased.
<[E] acid generator>
[E] The acid generator is a compound that generates an acid. Examples of the acid generated include carboxylic acid and sulfonic acid. The said curable resin composition can improve characteristics, such as heat resistance of a cured film, hardness, by containing an [E] acid generator. [E] Examples of the acid generator include [E1] a heat-sensitive acid generator that generates an acid by heating, and [E2] a radiation-sensitive acid generator that generates an acid by irradiation with radiation. The content of the [E] acid generator in the curable resin composition may be a low molecular compound as described later or a form incorporated as a part of the [A] polymer or the like. Form may be sufficient. The curable resin composition may contain one or more [E] acid generators.
[[E1] Thermosensitive acid generator]
[E1] The heat-sensitive acid generator is a compound that generates an acid by heating. The said curable resin composition can function as a thermosetting resin composition, when a [E1] thermosensitive acid generator is contained.

[E1] Examples of the heat-sensitive acid generator include onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts, and phosphonium salts. [E1] Specific examples of the heat-sensitive acid generator compound include those similar to those exemplified as the component [E] described in JP 2010-134442 A.
[[E2] Radiation sensitive acid generator]
[E2] The radiation-sensitive acid generator is a compound that generates an acid upon irradiation with radiation. The curable resin composition can function as a radiation curable resin composition when it contains [E2] a radiation sensitive acid generator. The said curable resin composition can improve a radiation sensitivity more by containing a [E2] radiation sensitive acid generator.

  [E2] Examples of the acid generator include quinonediazide compounds, oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds.

  A quinonediazide compound generates a carboxylic acid upon irradiation with radiation. The curable resin composition contains a quinonediazide compound as an [E2] acid generator, so that the generated carboxylic acid enhances the solubility of the irradiated portion in the alkali developer, thereby positive radiation sensitive. The characteristic can be exhibited.

  As the quinonediazide compound, for example, a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used.

  Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nuclei.

  Examples of trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone.

  Examples of tetrahydroxybenzophenone include 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3 , 4,2′-tetrahydroxy-4′-methylbenzophenone, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone, and the like.

  Examples of pentahydroxybenzophenone include 2,3,4,2 ', 6'-pentahydroxybenzophenone.

  Examples of hexahydroxybenzophenone include 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone and 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone.

  Examples of the (polyhydroxyphenyl) alkane include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tri (p-hydroxy). Phenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-) 4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl) -4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiin Down -5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl -7,2 ', 4'-trihydroxy flavan like.

  As other mother nucleus, for example, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- {3- (1- [4 -Hydroxyphenyl] -1-methylethyl) -4,6-dihydroxyphenyl} -1-methylethyl] -3- [1- {3- (1- [4-hydroxyphenyl] -1-methylethyl) -4 , 6-dihydroxyphenyl} -1-methylethyl] benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene, and the like.

  Among these mother nuclei, 2,3,4,4′-tetrahydroxybenzophenone, 1,1,1-tri (p-hydroxyphenyl) ethane, 4,4 ′-[1- [4- [1- [ 4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferred.

  As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable. Examples of 1,2-naphthoquinonediazide sulfonic acid chloride include 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, and the like. Of these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferred.

  The synthesis of the quinonediazide compound can be performed by a known condensation reaction. In this condensation reaction, 1,2-naphthoquinonediazide sulfone corresponding to preferably 30 mol% to 85 mol%, more preferably 50 mol% to 70 mol%, based on the number of OH groups in the phenolic compound or alcoholic compound. Acid halides can be used.

  Examples of the quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, such as 2,3,4-triaminobenzophenone-1,2-naphthoquinonediazide. -4-sulfonic acid amide and the like are also preferably used.

  [E2] When the acid generator is other than a quinonediazide compound, such as an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, a carboxylic acid ester compound, etc. The resin composition can usually exhibit negative radiation sensitive characteristics by reacting and curing the [F] polymer, which will be described later, by the action of the generated acid.

  Examples of the oxime sulfonate compound include (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)- (2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)- (2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile and the like.

  Examples of the onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, and pyridinium salts. Specific examples of preferred onium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluorochlorosulfonate, Phenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl diphenylsulfonium p-toluenesulfonate, 4,7-di-n- Butoxynaphthyltetrahydrothiophenium trifluorolo Tan sulfonate, 4- (phenylthio) phenyl diphenyl sulfonium tris (pentafluoroethyl) trifluoro phosphate, 4- (phenylthio) phenyl diphenyl sulfonium hexafluorophosphate and the like.

  Examples of the N-sulfonyloxyimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoro And methylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide and N- (trifluoromethylsulfonyloxy) naphthylimide.

  Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Specific examples of preferred halogen-containing compounds include 1,10-dibromo-n-decane, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, phenyl-bis (trichloromethyl) -s-triazine. S-triazine derivatives such as 4-methoxyphenyl-bis (trichloromethyl) -s-triazine, styryl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine, and the like.

  Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (phenylsulfonyl) diazomethane.

  Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Specific examples of preferred sulfone compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis (phenacylsulfonyl) methane.

  Examples of the sulfonic acid ester compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Specific examples of preferred sulfonic acid compounds include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, and o-nitrobenzyl p-toluene sulfonate.

  Examples of the carboxylic acid ester compound include carboxylic acid o-nitrobenzyl ester.

[E] The content of the acid generator is preferably 5 parts by mass or more and 100 parts by mass or less, and more preferably 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polymer [A]. [E] By making content of an acid generator into the said range, the said curable resin composition can improve the adhesiveness of a cured film more, and in the case of a radiation curable resin composition, radiation sensitivity is improved. It can be further increased.
<[F] polymer>
[F] The polymer is at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter also referred to as “(F1) compound”), and an epoxy group-containing unsaturated compound (hereinafter referred to as “F”). (F2) also referred to as “compound”). The said curable resin composition can improve the adhesiveness of a cured film more by containing a [F] polymer, and can improve solvent resistance and hardness. [F] The polymer can be cured by heating, but can be cured more effectively by containing [D] radical polymerization initiator and / or [E] acid generator.
[F] As specific examples of the polymer, the same polymers as those exemplified in JP-A-4-352101, JP-A-2005-227525, JP-A-2010-134422 and the like can be used. .

[F] The content of the polymer is preferably from 10 parts by weight to 3,000 parts by weight, more preferably from 50 parts by weight to 1,500 parts by weight, based on 100 parts by weight of the polymer [A]. 150 parts by mass or more and 800 parts by mass or less are more preferable. The said curable resin composition can raise the hardness of a cured film more by making content of a [F] polymer into the said range.
<Other optional components>
Examples of other optional components include a compound having a cyclic ether group, an adhesion aid, metal oxide particles, a surfactant, and a curing agent. The said curable resin composition may contain the said other arbitrary component 1 type, or 2 or more types, and may contain each component 1 type or 2 types or more.
[Compound having a cyclic ether group]
The compound having a cyclic ether group is a compound having an epoxy group (except for those corresponding to the above [F] polymer). The curable resin composition can further improve the heat resistance, surface hardness, and film thickness uniformity of the cured film by containing a compound having a cyclic ether group.

  Examples of the epoxy group include an oxiranyl group and an oxetanyl group. The epoxy compound may have one or more epoxy groups.

  As specific examples of the compound having a cyclic ether group, the same polymers as those exemplified in JP 2014-066764 A can be used.

As content of the compound which has a cyclic ether group, 100 mass parts or less are preferable with respect to 100 mass parts of [A] polymers, 75 mass parts or less are more preferable, and 50 mass parts or less are still more preferable. The said curable resin composition can further improve the heat resistance of a cured film, surface hardness, and film thickness uniformity by making content of the compound which has a cyclic ether group into the said range.
[Adhesion aid]
The adhesion assistant is for further improving the adhesion between the cured film obtained from the curable resin composition and the substrate. As such an adhesion assistant, a functional silane coupling agent is preferable. Examples of the functional silane coupling agent include those having a reactive group such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. Examples of such functional silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycol. Sidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned.

The content of the adhesion assistant is preferably 20 parts by mass or less and more preferably 10 parts by mass or less with respect to 100 parts by mass of the [A] polymer. By setting the content of the adhesion assistant to 20 parts by mass or less, it is possible to suppress the occurrence of development residue in the development process.
[Metal oxide particles]
When an insulating film is formed from the curable resin composition, the metal oxide particles can control an increase in relative dielectric constant while maintaining the electric insulation of the insulating film. The metal oxide particles can also be used for the purpose of controlling the refractive index of the insulating film, controlling the transparency of the insulating film, suppressing cracks by alleviating curing shrinkage, and improving the surface hardness of the insulating film.

  The metal oxide particles are, for example, oxide particles of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium, and hafnium. The metal oxide particles may be single oxide particles or composite oxide particles.

  Examples of the single oxide include silica, alumina, zirconia, titania, and ceria.

  Examples of the composite oxide include barium titanate, strontium titanate, ATO (antimoy-tin oxide), ITO (indium-tin oxide), and IZO (indium-zinc oxide).

  Among these, oxide particles of silicon, zirconium, titanium, zinc, and barium are preferable, and silica particles, zirconia particles, titania particles, and barium titanate (BaTiO3) are more preferable. As a commercial item of metal oxide particles, for example, “Nanotech (registered trademark)” manufactured by CI Kasei Co., Ltd. can be used.

  The shape of the metal oxide particles is not particularly limited, and may be spherical or indeterminate, and may be hollow particles, porous particles, core / shell particles, or the like.

  The volume average particle diameter of the metal oxide particles is a value obtained by a dynamic light scattering method, preferably 5 nm to 200 nm, more preferably 5 nm to 100 nm, and still more preferably 10 nm to 80 nm. If the volume average particle size of the metal oxide particles is less than 5 nm, the hardness of the insulating film obtained using the curable resin composition may be lowered, and the intended relative dielectric constant may not be exhibited. On the other hand, if the volume average particle diameter exceeds 200 nm, the haze of the insulating film may increase and the transmittance may decrease, and the smoothness of the insulating film may deteriorate.

As content of a metal oxide particle, 0.01 mass part or more and 20 mass parts or less are preferable with respect to [A] polymer, and 1 mass part or more and 10 mass parts or less are more preferable. If the content of the metal oxide particles is less than 0.01 parts by mass, the relative dielectric constant of the insulating film may not be controlled within a desired range. On the other hand, when the compounding amount of the metal oxide particles exceeds 20 parts by mass, the applicability and the film curability may be lowered, and the haze of the insulating film may be increased.
[Surfactant]
A surfactant improves the applicability of the curable resin composition. As this surfactant, a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant are preferable. By containing the surfactant, the surface smoothness of the coating film can be improved, and as a result, the film thickness uniformity of the cured film formed from the radiation-sensitive resin composition can be further improved.

  As specific examples of the surfactant, polymers similar to those exemplified in JP-A-4-352101, JP-A-2005-227525, JP-A-2010-134422 and the like can be used.

As content of surfactant, 10 mass parts or less are preferable with respect to 100 mass parts of [A] polymers, 5 mass parts or less are more preferable, and 3 mass parts or less are further more preferable. By making content of surfactant into 10 mass parts or less, the applicability | paintability of the said curable resin composition can further be improved.
[Curing agent]
As a hardening | curing agent, the hardening | curing agent as described in Unexamined-Japanese-Patent No. 2012-88459 can be used, for example.
[solvent]
As the solvent that can be used for the preparation of the curable resin composition, a solvent that uniformly dissolves or disperses other components in the curable resin composition and does not react with the other components is preferably used. Examples of such solvents include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, Aromatic hydrocarbons, ketones, other esters and the like can be mentioned. As the solvent, the solvents described in JP2011-232632 can be used.
<Method for preparing curable resin composition>
The curable resin composition includes [A] polymer and [B] basic compound, [C] polymerizable compound, [D] radical polymerization initiator, [E] acid generator, [F] as required. The polymer and other optional components are uniformly mixed and preferably prepared by filtering with a membrane filter of about 0.2 μm. The curable resin composition is preferably used in the form of a solution after being dissolved in an appropriate solvent.

Since the said curable resin composition can form the cured film excellent in adhesiveness and transparency, it can be used suitably for formation of the cured film for display elements as an interlayer insulation film, a protective film, or a spacer, for example.
<Curing film for display element>
The cured film for display elements of the present invention is formed from the curable resin composition. Since the display element cured film is formed from the curable resin composition, it has excellent adhesion and transparency. For example, the display element cured film is suitably used for an interlayer insulating film, a protective film, a spacer, and the like of the display element. it can. Although it does not specifically limit as the formation method of the said cured film for display elements, It is preferable to apply the formation method of the cured film for display elements demonstrated below.
<Method for forming cured film for display element>
The method for forming a cured film for a display element of the present invention is as follows.
A step of forming a coating film on the substrate (hereinafter also referred to as “coating layer forming step”), a step of irradiating at least a part of the coating film (hereinafter also referred to as “irradiation step”), and radiation irradiation. It has the process (henceforth a "development process") which develops a coating film, and the process (henceforth a "heating process") which heats the developed coating film. In the formation method, the coating film is formed from the curable resin composition. The curable resin composition is preferably a radiation curable resin composition containing the above-mentioned [D2] radiation sensitive radical polymerization initiator and / or [E2] radiation sensitive acid generator.
[Coating film forming process]
In this step, the curable resin composition is applied to the substrate surface, and a coating film is formed by removing the solvent preferably by pre-baking. Examples of the substrate used in this step include a glass substrate, a silicon wafer, a plastic substrate, and a substrate on which various metals are formed. Examples of the plastic substrate include a substrate mainly composed of a plastic such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide.

As a method for applying the curable resin composition, for example, an appropriate method such as spraying, roll coating, spin coating (spin coating), slit die coating, bar coating, or ink jet may be employed. it can. Among these coating methods, spin coating, bar coating, and slit die coating are preferable. As prebaking conditions, although it changes also with the kind of content component of the said curable resin composition, content, etc., it can be set as about 30 second-about 10 minutes at 60 to 120 degreeC, for example. The film thickness of the coating film is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and further preferably 0.1 μm to 4 μm as a value after pre-baking.
[Irradiation process]
In this step, the coating film formed in the coating film forming step is irradiated with radiation through a mask having a predetermined pattern. Examples of radiation at this time include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.

Examples of ultraviolet rays include g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet light include a KrF excimer laser. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include an electron beam. Among these radiations, ultraviolet rays are preferable, and among the ultraviolet rays, radiation containing g-line and / or i-line is particularly preferable. The exposure ^{amount, 30J / m 2 ~1,500J / m} 2 is preferred.
[Development process]
In this step, a desired pattern can be formed by developing the coating film irradiated with radiation in the irradiation step. An alkaline aqueous solution can be used as the developer used in the development process. Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, Dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3, 0] -5-nonane and the like. As the developer, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent or a surfactant such as methanol or ethanol to the alkaline aqueous solution, or various organic solvents so as to dissolve a coating film formed from the curable resin composition. Those containing a small amount of a solvent can be used. Furthermore, as a developing method, for example, a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time varies depending on the composition of the curable resin composition, but can be, for example, 30 seconds to 120 seconds.

After the development step, the patterned coating film is rinsed by running water washing, and subsequently irradiated with a high-pressure mercury lamp or the like (post-exposure) to remain in the coating film [D2] It is preferable to perform a decomposition treatment of a radiation sensitive radical polymerization initiator, [E2] a radiation sensitive acid generator or the like. The exposure amount in the post-exposure is preferably about 2,000 J / m ^{2 to} 5,000 J / m ² .
[Heating process]
In this step, the coating film is cured by heating (post-baking) the coating film using a heating device such as a hot plate or an oven for baking the coating film developed in the development step. Moreover, as heating temperature, 100 to 300 degreeC is preferable, 120 to 280 degreeC is more preferable, 150 to 250 degreeC is further more preferable. As heating time, although it changes with kinds of heating apparatus, 5 minutes-300 minutes are preferable, 10 minutes-180 minutes are more preferable, and 20 minutes-120 minutes are further more preferable.

According to the method for forming a cured film for the display element, since the pattern is formed by exposure, development and heating using the radiation sensitivity of the curable resin composition, curing having excellent adhesion and transparency is achieved. A film pattern can be easily formed.
<Display element>
The display element of the present invention includes the cured film for display element. Examples of the display element include a liquid crystal display element and an organic EL element. In such a display element, the cured film is provided as, for example, an interlayer insulating film, a protective film, or a spacer.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.
[Mw and Mn]
In the following synthesis examples, Mw and Mw / Mn of the [A] polymer were measured by gel permeation chromatography (GPC) using the following measuring apparatus and measurement conditions.

Measuring device: “GPC-101” from Showa Denko
Measurement condition:
GPC columns: “GPC-KF-801”, “GPC-KF-802”, “GPC-KF-803” and “GPC-KF-804” manufactured by Showa Denko KK were used in combination.

Mobile phase: Tetrahydrofuran <Synthesis of compounds>
[Synthesis Example 1] (Synthesis of Compound (HC-1))
In a 5 L reactor equipped with a stirrer and a dropping funnel, 65.1 g (0.5 mol) of 2-hydroxyethyl methacrylate, 59.3 g (0.75 mol) of pyridine and 500 mL of methylene chloride were charged, and the reactor was purged with nitrogen. While cooling to 0 ° C., 76.18 g (0.6 mol) of 3-chloropropionic acid chloride was dropped from the dropping funnel, and the mixture was reacted at 0 ° C. with stirring for 2 hours. The obtained reaction solution was washed successively with aqueous sodium hydrogen carbonate solution and saturated brine, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 83.4 g of a compound represented by the following formula (HC-1). (Yield 76%).

[Synthesis Example 2] (Synthesis of Compound (HC-2))
In a 5 L reactor equipped with a stirrer and a dropping funnel, 67.1 g (0.5 mol) of 4-hydroxy-α-methylstyrene, 59.3 g (0.75 mol) of pyridine and 500 mL of methylene chloride were charged, and the reaction was conducted under nitrogen. While the inside of the vessel was cooled to 0 ° C., 76.18 g (0.6 mol) of 3-chloropropionic acid chloride was dropped from the dropping funnel, and then reacted at 0 ° C. with stirring for 2 hours. The obtained reaction solution was washed successively with aqueous sodium hydrogen carbonate solution and saturated brine, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 80.0 g of a compound represented by the following formula (HC-2). (Yield 71%).

[Synthesis Example 3] (Synthesis of Compound (HC-3))
A 5 L reactor equipped with a stirrer and a dropping funnel was charged with 80.1 g (0.5 mol) of 2,3-dihydroxypropyl methacrylate, 118.7 g (1.5 mol) of pyridine and 500 mL of methylene chloride, and the reactor was added under nitrogen. While the inside was cooled to 0 ° C., 152.4 g (1.2 mol) of 3-chloropropionic acid chloride was dropped from the dropping funnel, and then reacted at 0 ° C. with stirring for 2 hours. The obtained reaction solution was washed successively with aqueous sodium hydrogen carbonate solution and saturated brine, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 106.3 g of a compound represented by the following formula (HC-3). (Yield 62%).

[Synthesis Example 4] (Synthesis of Compound HC-4)
In a 5 L reactor equipped with a stirrer and a dropping funnel, 103,4 g (0.5 mol) of (3,4-dihydroxycyclohexyl) methyl methacrylate, 118.7 g (1.5 mol) of pyridine and 500 mL of methylene chloride were charged, and nitrogen was added. While the reactor was cooled to 0 ° C., 152.4 g (1.2 mol) of 3-chloropropionic acid chloride was dropped from the dropping funnel, and then reacted at 0 ° C. with stirring for 2 hours. The obtained reaction mixture was washed successively with aqueous sodium hydrogen carbonate solution and saturated brine, concentrated under reduced pressure, and purified by silica gel column chromatography to give 125.5 g of a compound represented by the following formula (HC-4). (Yield 64%).

[Synthesis Example 5] (Synthesis of Compound (HC-5))
In a 5 L reactor equipped with a stirrer and a dropping funnel, 118.2 g (0.5 mol) of 3-hydroxy-1-adamantyl methacrylate, 59.3 g (0.75 mol) of pyridine and 500 mL of methylene chloride were charged and reacted under nitrogen. While the inside of the vessel was cooled to 0 ° C., 76.18 g (0.6 mol) of 3-chloropropionic acid chloride was dropped from the dropping funnel, and then reacted at 0 ° C. with stirring for 2 hours. The obtained reaction mixture was washed successively with aqueous sodium hydrogen carbonate solution and saturated brine, concentrated under reduced pressure, and purified by silica gel column chromatography to give 117.2 g of a compound represented by the following formula (HC-5). (Yield 72%).

[Synthesis Example 6] (Synthesis of Compound (HC-6))
In a 5 L reactor equipped with a stirrer and a dropping funnel, 140.2 g (0.5 mol) of 3- (2-hydroxyethoxy) -adamantyl methacrylate, 59.3 g (0.75 mol) of pyridine and 500 mL of methylene chloride were charged, and nitrogen was added. Then, while cooling the inside of the reactor to 0 ° C., 76.18 g (0.6 mol) of 3-chloropropionic acid chloride was dropped from the dropping funnel, and then reacted at 0 ° C. with stirring for 2 hours. The obtained reaction mixture was washed successively with aqueous sodium hydrogen carbonate solution and saturated brine, concentrated under reduced pressure, and purified by silica gel column chromatography to give 128.5 g of a compound represented by the following formula (HC-6). (Yield 69%).

[Synthesis Example 7] (Synthesis of Compound (HC-7))
In a 5 L reactor equipped with a stirrer and a dropping funnel, 89.1 g (0.5 mol) of 4-hydroxyphenyl methacrylate, 59.3 g (0.75 mol) of pyridine and 500 mL of methylene chloride were charged, and the reactor was purged with nitrogen. While cooling to 0 ° C., 76.18 g (0.6 mol) of 3-chloropropionic acid chloride was dropped from the dropping funnel, and the mixture was reacted at 0 ° C. with stirring for 2 hours. The obtained reaction solution was washed successively with aqueous sodium hydrogen carbonate solution and saturated brine, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 105.1 g of a compound represented by the following formula (HC-7). (Yield 78%).

<[A] Synthesis of polymer>
[Synthesis Example 8] (Synthesis of Polymer (A-1))
Compound (HC-1) 36.6 g (20 mol%), methacrylic acid 17.8 g (25 mol%) and methyl methacrylate 45.6 g (55 mol%) were converted into 140 g of methyl 3-methoxypropionate. After dissolution, 14.4 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to prepare a monomer solution. Next, a 500 mL three-necked flask containing 60 g of methyl 3-methoxypropionate was purged with nitrogen for 30 minutes and then heated to 70 ° C. with stirring. The monomer solution prepared above was added to the dropping funnel over 2 hours. And dripped. The dripping start was set as the polymerization reaction start time, and the polymerization reaction was carried out for 4 hours. Thereafter, the temperature of the polymerization reaction solution was set to 90 ° C. and stirred for 30 minutes. Thereafter, the temperature of the polymerization reaction solution was set to 70 ° C., 77.9 mL of triethylamine was added, and the mixture was stirred at 70 ° C. for 3 hours. After cooling to room temperature, 55.9 mL of 12N aqueous hydrochloric acid was added and stirred for 30 minutes, and then ethyl acetate was added to separate the layers. After washing the organic phase with distilled water, the recovered organic phase is concentrated and diluted with methyl 3-methoxypropionate ((B-1) as the [B] solvent) to obtain the polymer (A-1). A polymer solution containing 40% by mass was obtained. Mw of the polymer (A-1) was 7,000.
[Synthesis Example 9 to Synthesis Example 19]
Each polymer was synthesized in the same manner as in Synthesis Example 8 except that the types and amounts of monomers shown in Table 1 were used. Table 1 shows the Mw and Mw / Mn of each synthesized polymer. “-” Indicates that the corresponding monomer was not used. In Synthesis Examples 16 and 19, when 1-butoxyethyl methacrylate obtained by protecting the carboxyl group is used as the compound that gives the structural unit (II), the obtained [A] polymer is deprotected and has a carboxyl group. Is generated.

[Synthesis Example 20] (Synthesis of polymer (a-1))
In a flask equipped with a condenser and a stirrer, 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate ((B-1) as a solvent [B]) Prepared the department. Next, after 40 parts by mass of methacrylic acid and 60 parts by mass of methyl methacrylate were charged and purged with nitrogen, stirring was started gently. The temperature of the polymerization reaction solution was raised to 70 ° C., and this temperature was maintained for 5 hours. Then, 30 parts by mass of glycidyl methacrylate and 3 parts by mass of tetrabutylammonium bromide were added, and the mixture was further reacted at 90 ° C. for 10 hours. A polymer solution containing 40% by mass of a-1) was obtained. Mw of the polymer (a-1) was 10,000.
[Synthesis Example 21] (Synthesis of polymer (F-1))
In a flask equipped with a condenser and a stirrer, 8 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether ((B-2) as a solvent [B]) Further, 13 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of α-methyl-p-hydroxystyrene, 10 parts by weight of styrene, 12 parts by weight of tetrahydrofurfuryl methacrylate, 15 parts by weight of N-cyclohexylmaleimide and After adding 10 parts by mass of n-lauryl methacrylate and substituting with nitrogen, the temperature of the solution is raised to 70 ° C. while gently stirring, and this temperature is maintained for 5 hours to polymerize to obtain a polymer (F-1 ) Was obtained. The solid content concentration of this solution was 31.9% by mass. Mw of the polymer (F-1) was 8,000, and the molecular weight distribution (Mw / Mn) was 2.3.
[Synthesis Example 22] (Synthesis of polymer (F-2))
A flask equipped with a condenser and a stirrer was charged with 5 parts by mass of 2,2′-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate ((B-3) as a [B] solvent), and 7 parts by weight of methacrylic acid, 18 parts by weight of tricyclo [5.2.2.6.6] decan-8-yl methacrylate, 15 parts by weight of styrene, 40 parts by weight of 3-methacryloxypropyltriethoxysilane and glycidyl methacrylate 20 After adding part by mass and purging with nitrogen, the temperature of the solution is raised to 80 ° C. while gently stirring, and polymerization is carried out while maintaining this temperature for 5 hours to obtain a solution containing the polymer (F-2). Obtained. The solid content concentration of this solution was 28.8% by mass. Mw of this polymer (F-2) was 12,000, and the molecular weight distribution (Mw / Mn) was 2.2.
[Synthesis Example 23] (Synthesis of polymer (F-3))
A flask equipped with a condenser and a stirrer was charged with 5 parts by mass of 2,2′-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate, and further 7 parts by mass of methacrylic acid, tricyclomethacrylate [5.2. 1.02.6] After adding 28 parts by mass of decan-8-yl, 25 parts by mass of styrene, and 40 parts by mass of glycidyl methacrylate, the temperature of the solution was raised to 80 ° C. while gently stirring, The solution containing the polymer (F-3) was obtained by polymerization while maintaining this temperature for 5 hours. The solid content concentration of this solution was 28.8% by mass. Mw of this polymer (F-3) was 10,000, and the molecular weight distribution (Mw / Mn) was 2.2.
[Synthesis Example 24] (Synthesis of polymer (F-4))
A flask equipped with a condenser and a stirrer was charged with 5 parts by mass of 2,2′-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate, and further 7 parts by mass of methacrylic acid, tricyclomethacrylate [5.2. 1.0 ^2.6 ] 28 parts by mass of decan-8-yl, 25 parts by mass of styrene and 40 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate were added, and the temperature of the solution was changed while gently stirring the solution. Was raised to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a solution containing the polymer (F-4). The solid content concentration of this solution was 28.8% by mass. Mw of this polymer (F-4) was 11,000, and the molecular weight distribution (Mw / Mn) was 2.1.
<Preparation of curable resin composition>
[B] basic compound, [C] polymerizable compound, [D] radical polymerization initiator and [E] acid generator used for the preparation of the curable resin composition are shown below.
[[B] Basic compound]
B-1: Triethylamine B-2: Pyridine B-3: 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole [[ C] Polymerizable compound]
C-1: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (“KAYARAD DPHA” from Nippon Kayaku Co., Ltd.)
C-2: Succinic acid-modified pentaerythritol triacrylate (“Aronix TO-756” manufactured by Toagosei Co., Ltd.)
C-3: Trimethylolpropane triacrylate C-4: Mixture of tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate (“Biscoat 802” from Osaka Organic Chemical Industry Co., Ltd.)
C-5: Succinic acid-modified dipentaerythritol pentaacrylate (“Aronix M-520” manufactured by Toagosei Co., Ltd.)
[[D] radical polymerization initiator]
D-1: 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (“Irgacure 907” from BASF)
D-2: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (“Irgacure OXE02” from BASF)
D-3: 2,4-diethylthioxanthone [[E] acid generator]
E-1: 4,4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonate [implementation] Example 1]
100 parts by mass of (A-1) as the [A] polymer synthesized in Synthesis Example 8 above, 0.005 parts by mass of (B-1) as the basic compound, and [C] as the polymerizable compound (C-1) 50 parts by mass and [D] 10 parts by mass of (D-1) radical polymerization initiator are dissolved in propylene glycol monomethyl ether acetate and filtered through a membrane filter having a pore size of 0.2 μm. A curable resin composition (J-1) was prepared.
[Examples 2-18 and Comparative Examples 1-2]
The curable resin compositions (J-2) to (J-18) were operated in the same manner as in Example 1 except that the raw materials were mixed so as to contain the components of the types and contents shown in Table 2 below. And (CJ-1) to (CJ-2) were prepared. “-” In Table 2 indicates that the corresponding component was not used.
<Evaluation>
About the prepared curable resin composition, the adhesiveness and transparency of a cured film, storage stability, and radiation sensitivity were evaluated according to the following method.
[Adhesion of cured film]
The adhesion of the cured film was evaluated for the cured film pattern after exposure. Specifically, first, a curable resin composition was applied onto a glass substrate using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. . Subsequently, 700 (J / m 2) was passed through a mask for forming a pattern of 10 μm line and space (one to one) using an exposure machine (“MPA-600FA (ghi line mixing)” manufactured by Canon Inc.). ). Thereafter, development was performed by a puddle method at 25 ° C. for 80 seconds using a 0.5 mass% tetramethylammonium hydroxide aqueous solution. Next, running water was washed with ultrapure water for 1 minute, and then dried to form a pattern on the glass substrate. The substrate after development was observed with an optical microscope to confirm the presence or absence of pattern peeling. The pattern adhesion was evaluated according to the following criteria.

When there is almost no peeling of the pattern: “○”
If the pattern is slightly peeled: “△”
When the pattern is peeled off and almost no pattern remains on the substrate: “×”
[Transparency of cured film]
A coating film having a thickness of 3.0 μm was formed on the silicon substrate using the curable resin composition. This silicon substrate was heated in a clean oven at 220 ° C. for 1 hour to form a cured film. About this cured film, the transmittance | permeability in wavelength 400nm was measured using the spectrophotometer ("150-20 type double beam" of Hitachi, Ltd.). Tables 2 and 3 show the transmittance (%) values. Transparency can be evaluated as good when the transmittance is 90% or more and poor when it is less than 90%.
[Evaluation of storage stability]
The curable resin composition was left in an oven at 40 ° C. for 1 week. The initial viscosity (1) and the viscosity after standing for one week (2) were measured, and the viscosity change rate (%) was calculated from | Viscosity (2) −Viscosity (1) | × 100 / Viscosity (1). . | Viscosity (2) −Viscosity (1) | means the absolute value of the difference between the viscosity (2) and the viscosity (1). The viscosity change rate (%) is shown in Table 2. Storage stability can be evaluated as good when the rate of viscosity change is 5% or less, and poor when it exceeds 5%.
[Radiation sensitivity]
A curable resin composition was applied onto a glass substrate using a spinner and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Next, using an exposure machine ("MPA-600FA (ghi line mixing)" manufactured by Canon Inc.), the exposure dose is applied as a variable via a mask having a 10 μm line-and-space (one-to-one) pattern. The membrane was irradiated with radiation. Then, it developed by the piling method for 80 seconds at 25 degreeC with 0.5 mass% tetramethylammonium hydroxide aqueous solution. Next, the substrate was washed with running ultrapure water for 1 minute and then dried to form a pattern on the glass substrate. At this time, the exposure amount necessary for completely dissolving the 10 μm space pattern was examined. Table 2 shows the exposure value (J / m ² ). The radiation sensitivity can be evaluated as good when the exposure value is 350 (J / m ² ) or less.

  As is clear from the results in Table 2, the curable resin compositions of the examples were excellent in adhesion and transparency of the cured film, storage stability, and radiation sensitivity when used as a radiation curable resin composition. . On the other hand, the curable resin composition of the comparative example did not give good results for all of these performances.

The curable resin composition of the present invention can form a cured film having excellent adhesion and transparency, and is excellent in storage stability. Since the cured film for display elements of the present invention is excellent in adhesion and transparency, it can be suitably used as an interlayer insulating film, protective film, spacer, etc. for display elements. Therefore, these can be suitably used in the manufacturing process of display elements such as liquid crystal devices.

Claims (12)

[A] A curable resin composition comprising a polymer having a group represented by the following formula (1A) and a structural unit containing a carboxyl group, and [B] a basic compound.
(In Formula (1A), R ¹ , R ² and R ³ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. Among R ¹ , R ² and R ³ May be bonded to each other to form a ring structure having 3 to 20 ring members together with the carbon atom to which they are bonded, and R ⁴ is (a) a (n + 1) -valent carbon atom having 1 to 20 carbon atoms. A hydrogen group, (b) a group containing at least one selected from the group consisting of an oxygen atom, a sulfur atom, —SO— and —SO ₂ — between carbon-carbon of the hydrocarbon group, or (c) ( a) A part or all of the hydrogen atoms of the hydrocarbon group and (b) group are selected from the group consisting of a halogen atom, a cyano group, a nitro group, a carboxyl group, a sulfino group, a mercapto group, and an alkoxy group having 1 to 12 carbon atoms. is at least one substituted with a group selected .R ⁵ is a single If or -COO- in which .n, when it .n is 2 or more integer from 1 to 6, a plurality of R ¹ may be the same or different, even if a plurality of R ² may be the same or different The plurality of R ³ may be the same or different, and * indicates the site to be bound.) The curing according to claim 1, wherein the polymer [A] is a polymer having a structural unit represented by the following formula (1) containing a group represented by the formula (1A) and a structural unit containing a carboxyl group. Resin composition.
(In formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and n have the same definition as in formula (1A). R ⁶ is a hydrogen atom, a methyl group or a fluorinated methyl group. .)   [C] The curable resin composition according to claim 1 or 2, further comprising a polymerizable compound having an ethylenically unsaturated bond.   The curable resin composition according to any one of claims 1 to 3, further comprising at least one selected from the group consisting of a radical polymerization initiator and an acid generator.   The curable resin composition of Claim 4 containing the said radical polymerization initiator.   The curable resin composition according to claim 5, wherein the radical polymerization initiator is radiation sensitive.   The curable resin composition of Claim 4 containing the said acid generator.   The curable resin composition according to claim 7, wherein the acid generator is radiation sensitive.   The curable resin composition of any one of Claims 1-8 used for formation of the cured film for display elements as an interlayer insulation film, a protective film, or a spacer.   The cured film for display elements as an interlayer insulation film, a protective film, or a spacer formed from the curable resin composition according to claim 9. Forming a coating film on the substrate;
Irradiating at least a part of the coating film with radiation,
A step of developing the coating film irradiated with the radiation, and a step of heating the developed coating film,
The formation method of the cured film for display elements which forms the said coating film with the curable resin composition of Claim 6 or Claim 8. A display element provided with the cured film for display elements of Claim 10.