TWI649339B - Curable resin composition, cured film for display element, method for forming cured film for display element, and display element - Google Patents

Abstract

The present invention is a curable resin composition containing a polymer and a solvent, the polymer having a structural unit represented by the following formula (1) and a structural unit containing a carboxyl group. In Formula (1), R ¹ , R ² and R ³ are a hydrogen atom or a monovalent hydrocarbon group. R ⁴ is (a) a (n + 1) -valent hydrocarbon group, and (b) the carbon-carbon between (a) a hydrocarbon group is selected from the group consisting of an oxygen atom, a sulfur atom, -SO-, and -SO _2- At least one kind of group, or a part or all of the hydrogen atoms of (c) (a) hydrocarbon group and (b) group are selected from the group consisting of halogen atom, cyano, nitro, carboxyl, sulfinyl, thiol, and A group substituted with at least one of the alkoxy groups. R ⁵ is a single bond or -COO- *.

Description

Curable resin composition, cured film for display element, display element Method for forming cured film and display element

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

A display element such as a liquid crystal display element or organic electroluminescence (EL) is provided with a hardened film: an interlayer insulating film for maintaining the insulation of the wiring rooms arranged in a layered manner; Touch panel) is a protective film for deterioration or damage of electronic components, and a spacer for fixing a liquid crystal layer or the like to a fixed film thickness. Such a cured film is required to have excellent adhesion to a substrate, a transparent conductive film, wiring, and the like, as well as excellent transparency.

In the formation of the cured film, a curable resin composition is used from the viewpoint that the number of steps for obtaining a desired pattern shape is small and sufficient flatness can be obtained. As such a curable resin composition, a high surface hardness can be obtained In terms of a polymer containing an ethylenically unsaturated bond in a side chain, a polymer obtained by reacting an unsaturated compound containing an epoxy group with a polymer having a carboxyl group has been known as the polymer. It is obtained by reacting an isocyanate group-containing unsaturated compound with a polymer having a carboxyl group and a hydroxyl group (see Japanese Patent Laid-Open No. 11-174464 and Japanese Patent Laid-Open No. 2002-20442).

Among them, recently, the requirements for the properties of the cured film, especially the adhesion, have been further increased, and the existing curable resin composition cannot meet the requirements. In addition, from the viewpoint of process stability, improvement of storage stability is also required for the conventional curable resin composition.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 11-174464

[Patent Document 2] Japanese Patent Laid-Open No. 2002-20442

The present invention is based on the above-mentioned circumstances, and an object thereof is to provide a curable resin composition which can form a cured film having excellent adhesion and transparency and has excellent storage stability.

An invention made in order to solve the problems is a curable resin composition containing a polymer (hereinafter also referred to as "[A] polymer") and a solvent (hereinafter also referred to as "[A] polymer"). (Referred to as "[B] solvent"), the polymer has a structural unit represented by the following formula (1) (hereinafter also referred to as "structural unit (I)") and an acidic group-containing structural unit (hereinafter also referred to as (Referred to as "structural unit (II)").

(In formula (1), 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. And together with the carbon atoms to which they are bonded, form a ring structure with 3 to 20 member rings; R ⁴ is (a) a (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, (b) a hydrocarbon group in (a) The carbon-carbon group contains at least one group selected from the group consisting of an oxygen atom, a sulfur atom, -SO-, and -SO _2- , or a group of (c) (a) a hydrocarbon group and (b) A group in which a part or all of the hydrogen atom is substituted with at least one selected from the group consisting of a halogen atom, a cyano group, a nitro group, a carboxyl group, a sulfinyl group, a mercapto group, and an alkoxy group having 1 to 12 carbon atoms. ; N is an integer from 1 to 6; when n is 2 or more, multiple R ¹ may be the same or different, multiple R ² may be the same or different, multiple R ³ may be the same or different; R ⁵ is a single bond Or -COO- *; * indicates a site bonded to R ⁴ ; R ⁶ is a hydrogen atom, a methyl group, or a fluorinated methyl group)

Another invention made in order to solve the problem is a cured film for a display element as an interlayer insulating film, a protective film, or a spacer, which is made of the curable resin The composition is formed.

In order to solve the problem, still another invention is a method for forming a cured film for a display element, which includes a step of forming a coating film on a substrate; a step of irradiating at least a part of the coating film with radiation; The step of developing the coating film irradiated with radiation, and the step of heating the developed coating film, and forming the coating film from the curable resin composition.

Another invention made in order to solve the said problem is a display element including the said hardened film for display elements.

The curable resin composition of the present invention can form a cured film having excellent adhesion and transparency, and has excellent storage stability. Since the cured film for display elements of the present invention is excellent in adhesiveness and transparency as described above, it can be suitably used as an interlayer insulating film, a protective film, a spacer, and the like of a 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 [B] a solvent. The curable composition may contain [C] a polymerizable compound having an ethylenically unsaturated bond (as Hereinafter also referred to as "[C] polymerizable compound"), [D] radical polymerization initiator, [E] acid generator, and / or [F] selected from unsaturated carboxylic acid and unsaturated carboxylic anhydride As a preferred component, a polymer (hereinafter also referred to as a "[F] polymer") obtained by copolymerizing at least one of the group consisting of an epoxy-containing unsaturated compound monomer may be used without any damage. And other arbitrary components are included in the range of the effect of this invention.

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

Each component is explained below.

<[A] polymer>

[A] The polymer is a polymer having a structural unit (I) and a structural unit (II). [A] The polymer preferably has a structure that is a structural unit other than the structural unit (I) and the structural unit (II) and does not contain any of a hydroxyl group, an amine group, and an imine group in addition to the structural unit. The unit (III) may contain other structural units other than the structural unit (I) to the structural unit (III) as long as the effect of the present invention is not impaired. [A] The polymer may contain one type or two or more types of each structural unit.

By containing the [A] polymer, the cured film of the curable resin composition is excellent in adhesion and transparency, and has excellent storage stability. In addition, as described later, In the case of a radiation-curable resin composition, the radiation sensitivity is excellent. The reason why the curable resin composition has the above-mentioned effect is not necessarily clear, but it can be estimated as follows, for example. That is, the [A] polymer has a structural unit (I) as a structural unit containing an ethylenically unsaturated bond in a side chain. The structural unit (I) is different from the case of the conventional curable resin composition, and does not have a hydroxyl group generated by a reaction of a carboxyl group and an epoxy group, or an imine formed by a reaction of a hydroxyl group and an isocyanate group. Base etc. As a result, it is considered that the adhesion of the cured film is improved by, for example, suppressing the penetration of the alkaline aqueous solution between the patterns in the development step. In addition, since the structural unit (I) of the [A] polymer does not have a hydroxyl group, an imine group, or the like, it is thought that deterioration due to heating caused by these groups is suppressed, and the transparency of the cured film is improved. Furthermore, it is thought that the above-mentioned hydroxyl group, imide group, and the like do not cause condensation and the like with the carboxyl group and the like of the structural unit (II), so that storage stability is improved. When a radiation-curable resin composition is produced, it is considered that since there is no hydroxyl group, imine group, etc. near the ethylenically unsaturated bond, the activity of radicals or acids is increased, and as a result, radiation sensitivity is further improved.

Each structural unit will be described below.

[Construction unit (I)]

The structural unit (I) is represented by the following formula (1).

[Chemical 2]

In the formula (1), 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 and form a ring structure with 3 to 20 member rings together with the carbon atoms to which they are bonded. R ⁴ is (a) a (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and (b) the carbon-carbon between (a) the hydrocarbon group is selected from the group consisting of an oxygen atom, a sulfur atom, -SO-, and -SO ₂ -At least one type of group in the group or a part or all of the hydrogen atoms of (c) (a) hydrocarbon group and (b) group are selected from the group consisting of halogen atom, cyano group, nitro group, carboxyl group, A group substituted with at least one of a group consisting of a sulfonic acid group, a mercapto group, and an alkoxy group having 1 to 12 carbon atoms. n is an integer from 1 to 6. When n is 2 or more, a plurality of R ¹ may be the same or different, a plurality of R ² may be the same or different, and a plurality of R ³ may be the same or different. R ⁵ is a single bond or -COO- *. * Indicates a site to which R ^{4 is} bonded. 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 a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, and a monovalent alicyclic group having 3 to 20 carbon atoms. A hydrocarbon group, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the like.

Examples of the monovalent chain hydrocarbon group include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, and t-butyl; vinyl, propenyl, Alkenyl such as butenyl; alkynyl such as ethynyl, propynyl, butynyl and the like.

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

Examples of the monovalent aromatic hydrocarbon group include aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, and anthracenyl; benzyl, phenethyl, naphthylmethyl, and anthrylmethyl And so on.

Examples of the ring structure of R ¹ , R ² and R ³ having two or more member rings having 3 to 20 members bonded together with the carbon atom to which they are bonded include, for example, a cyclopropene structure, a cyclobutene structure, Cyclopentene structure, cyclohexene structure, cyclooctene structure, norbornene structure and other cycloolefin structures.

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

Examples of the (a) (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴ include the group exemplified as the monovalent hydrocarbon group represented by R ¹ , R ^2, and R ³ . A hydrogen atom.

Examples of the (b) group containing an oxygen atom between the carbon and carbon of the (a) hydrocarbon group represented by R ⁴ include ^two of the hydrocarbon groups exemplified as R ¹ , R ^2, and R ³ bonded to an oxygen atom. The resulting ether is a group obtained by removing (n + 1) hydrogen atoms.

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

Examples of the (b) group containing -SO- between the carbon-carbon of (a) a hydrocarbon group represented by R ⁴ include ^two of the hydrocarbon groups exemplified as R ¹ , R ^2, and R ³ and -SO- A group obtained by removing an (n + 1) hydrogen atom from a fluorene compound in which a sulfur atom is bonded.

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

Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy, ethoxy, propoxy, butoxy, and pentyloxy.

Examples of the halogen atom of the (c) group represented by R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The sulfinic group refers to -SO ₂ H.

R ⁴ is preferably (a) a hydrocarbon group and (b) group, more preferably a group obtained by removing (n + 1) hydrogen atoms from an alkane, a cycloalkane, an arene (arene), and a cycloalkylalkyl ether, and furthermore It is preferred to remove (n + 1) hydrogen atoms from alkanes having 2 to 6 carbon atoms, naphthenes having 3 to 15 carbon atoms, aromatics having 6 to 18 carbon atoms and cycloalkyl alkyl ethers having 5 to 20 carbon atoms. The formed group is particularly preferably a group obtained by removing (n + 1) hydrogen atoms from an ethane group, cyclohexane, adamantane, benzene, and adamantyl ethyl ether.

From the viewpoint of providing ease of synthesis of the monomer of the structural unit (I), n is preferably an integer of 1 to 3, and more preferably 1 or 2. In order to further improve the hardenability and produce a radiation-curable resin composition, From the viewpoint of the radiation sensitivity, n is more preferably 2.

R ⁴ is a chain hydrocarbon group, an alicyclic hydrocarbon group, and a group containing at least one selected from the group consisting of an oxygen atom, a sulfur atom, -SO- and -SO ₂ -between the carbon and carbon of these groups, And at least part of or all of the hydrogen atoms of the group are selected from the group consisting of a halogen atom, a cyano group, a nitro group, a carboxyl group, a sulfinyl group, a mercapto group, and an alkoxy group having 1 to 12 carbon atoms. In the case of one substituted group, R ⁵ is preferably -COO- *.

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

From the viewpoint of providing copolymerization of the monomer of the structural unit (I), R ⁶ is preferably a methyl group.

The structural unit (I) can be exemplified by the structural units represented by the following formulae (1-1) to (1-12) (hereinafter also referred to as "structural units (I-1) to (I-12) ")Wait.

[Chemical 3]

In the formulae (1-1) to (1-12), R ⁶ is synonymous with the formula (1).

Among these, the structural unit (I-1) to the structural unit (I-7) are preferred.

The method for incorporating the structural unit (I) into the [A] polymer is not particularly limited, For example, as shown in the following scheme, a polymerization unit using a monomer represented by the following formula (i) is synthesized to incorporate a structural unit (I ') represented by the following formula (1'). ), And the polymer is subjected to a dehydrohalogenation reaction in the presence of a base such as triethylamine to generate an ethylenically unsaturated double bond, thereby forming a structural unit represented by the following formula (1) (I).

In the scheme, R ¹ to R ⁶ and n are synonymous with the formula (1). X is a halogen atom.

From the viewpoint of improving the yield of the dehydrohalogenation reaction, the halogen atom represented by X is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

The monomer represented by the formula (i) can be synthesized, for example, by using a compound having a (meth) acrylfluorenyl group and a hydroxyl group, such as 2-hydroxyethyl (meth) acrylate, and 3-chloropropylammonium Β-halo-carboxamidines such as chlorine in the presence of bases such as pyridine, The dehydrohalogenation condensation reaction is performed in a solvent such as alkane.

The content ratio of the structural unit (I) is based on the input ratio of all monomers used in the synthesis of the [A] polymer, and is preferably 5 mol% to 90 mol%, and more preferably 10 mol. % To 70 mol%, more preferably 15 to 40 mol%. By setting the content ratio to the range, it is possible to further improve the adhesion and transparency of the cured film, storage stability, and radiation sensitivity when the radiation-curable resin composition is made.

[Construction unit (II)]

The structural unit (II) is a structural unit containing an acidic group. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfo group, and a fluoroalcohol-containing group. Among them, a carboxyl group is particularly preferred. When the [A] polymer has the structural unit (II), the curable resin composition can exhibit alkali developability and function as an alkali-soluble resin.

Examples of the monomer providing the structural unit (II) include unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, poly [(meth) acrylfluorenyloxyalkyl] ester of polycarboxylic acid, and unsaturated dicarboxylic acid. An anhydride of a carboxylic acid, a mono (meth) acrylate having a polymer having a carboxyl group and a hydroxyl group at both ends, an unsaturated polycyclic compound having a carboxyl group, an anhydride thereof, and the like.

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

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

Examples of the mono [(meth) acrylfluorenyloxyalkyl] ester of a polycarboxylic acid include maleic acid mono [(meth) acrylfluorenyloxyethyl] ester, and succinic acid mono [2 -(A Propyl) acrylfluorenyloxyethyl] ester, phthalate mono [2- (meth) acrylfluorenyloxyethyl] ester, and the like.

Examples of the anhydride of the unsaturated dicarboxylic acid include anhydrides of the compounds exemplified as the dicarboxylic acid.

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

Examples of unsaturated polycyclic compounds having a carboxyl group and their anhydrides include 5-carboxybicyclo [2.2.1] hept-2-ene, 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 (II), you may use the compound which protected the carboxyl group, such as the said carboxylic acid. Examples of the protected carboxyl group in the compound include a group 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 carbon A monovalent hydrocarbon group having a number of 1 to 20. R ^c is a monovalent hydrocarbon group having a carbon number of 1 to 20) and the like. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ^a , R ^b and R ^c include the same groups as the monovalent hydrocarbon group exemplified as the R ¹ , R ² and R ³ . Among them, R ^a and R ^{c are} preferably an alkyl group. R ^b is preferably a hydrogen atom.

Examples of the compound obtained by protecting the carboxyl group such as the carboxylic acid include 1-butoxyethyl (meth) acrylate, 1-ethoxyethyl (meth) acrylate, and 1-ethyl (meth) acrylate Oxybutyl etc.

Among them, the copolymerization of the monomers providing the structural unit (II) and the ease of obtaining From the viewpoint of the solubility and the solubility of the [A] polymer in an alkaline aqueous solution, an unsaturated monocarboxylic acid and a compound that protects the carboxyl group of the unsaturated monocarboxylic acid are preferred, and methacrylic acid and methyl are more preferred. 1-butoxyethyl acrylate.

The content ratio of the structural unit (II) is preferably 5 mol% to 50 mol%, and more preferably 10 mol, based on the input ratio of all monomers used in the synthesis of the [A] polymer. % To 40 mol%, more preferably 15 to 35 mol%. By setting the content ratio to the range, the alkali developability of the curable resin composition can be set to a more appropriate property.

[Construction unit (III)]

The structural unit (III) is a structural unit other than the structural unit (I) and the structural unit (II), and is a structural unit that does not contain any of a hydroxyl group, an amine group, and an imine group. When the [A] polymer has the structural unit (III), the storage stability of the curable resin composition can be further improved.

Examples of the monomer providing the structural unit (III) include alkyl methacrylate, cycloalkyl methacrylate, alkyl acrylate, cycloalkyl acrylate, aromatic methacrylate, and aromatic acrylic Examples of the ester include the following compounds and the like, which do not have any of a hydroxyl group, an amine group, and an imine group: unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, and N-maleimide diimide compounds , Unsaturated aromatic compounds, conjugated dienes, unsaturated compounds having a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton or a pyran skeleton, other unsaturated compounds, and the like.

Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, second butyl methacrylate, and methacrylic acid. Tert-butyl enoate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, and the like.

Examples of the cycloalkyl methacrylate include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, Tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethyl methacrylate, isobornyl methacrylate and the like.

Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, n-butyl acrylate, second butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, and n-lauryl acrylate. , Tridecyl acrylate, n-stearyl acrylate, etc.

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

Examples of aromatic methacrylic esters include aryl methacrylates such as phenyl methacrylate and naphthyl methacrylate; aromatic methacrylates such as benzyl methacrylate and phenethyl methacrylate. Alkyl esters, etc.

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

Examples of the unsaturated dicarboxylic acid diesters include diethyl maleate, diethyl fumarate, and diethyl itaconic acid.

Examples of the bicyclic 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-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxy Carbonylcarbonyl bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] Hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc.

Examples of the N-cis-butene difluorene imine compound include N-phenyl-cis-butene difluorene imine, N-cyclohexyl-cis-butene difluorene imine, N-benzyl-cis butene difluorene, N- (4-hydroxyphenyl) cis-butenediamidoimide, N-succinimidylimido-3-cisbutenediamidoiminobenzoate, N-succinimidylimino-4-cis Butene difluorene imide butyrate, N-succinimide imino-6-cis butene diimide hexanoate, N-succinimide 3-maleimide dipropionate Esters, N- (9-acridyl) cis-butenediamidine, 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-methacrylfluorenyloxy-propionate tetrahydrofurfuryl ester, and 3- (meth) acrylfluorenyloxytetrahydrofuran. -2-ketone, etc.

Examples of the unsaturated compound containing a furan skeleton include 2-methyl-5- (3- Furanyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-en-2-one, 1-furan-2-butyl-3- Methoxy-3-en-2-one, 6- (2-furanyl) -2-methyl-1-hexene-3-one, 6-furan-2-yl-hex-1-ene-3 -Ketone, 2-furan-2-yl-1-methyl-ethyl acrylate, 6- (2-furanyl) -6-methyl-1-hepten-3-one, and the like.

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

Examples of unsaturated compounds containing a pyran skeleton include 4- (1,4-dioxo-5-oxo-6-heptenyl) -6-methyl-2-pyran, 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 providing copolymerization of the monomers of the structural unit (III), alkyl methacrylate and unsaturated aromatic compounds are preferred, and methyl methacrylate and styrene are more preferred.

The content ratio of the structural unit (III) is based on the input ratio of all monomers used in the synthesis of the [A] polymer, and is preferably 0 mol% to 80 mol%, and more preferably 20 mol. % To 75 mol%, more preferably 40 to 70 mol%. By setting the content ratio to the range, the storage stability of the curable resin composition can be further improved.

[Other structural units]

Examples of the other structural unit include a structural unit containing a hydroxyl group, an amine group, or an imine group. The content ratio of the other structural units is preferably 20 mol% or less, more preferably 5 mol% or less, and still more preferably 0 mol, based on the input ratio of all monomers used in the synthesis of the [A] polymer. ear%.

The content of the [A] polymer is preferably 30% by mass or more, more preferably 35% by mass to 95% by mass, and still more preferably 40% by mass to 70% by mass with respect to the total solid content of the curable resin composition. .

<[A] Synthesis method of polymer>

[A] The polymer can be synthesized as described by, for example, using a radical polymerization initiator in a solvent, and dehalogenating the monomer as represented by the formula (i) after the polymerization reaction. Hydrogen reacts to polymerize the monomers that provide structural unit (I), monomers that provide structural unit (II), and monomers that provide structural unit (III) as needed, and polymerize the resulting polymer by dehydrohalogenation to form a structure Unit (I).

Examples of the solvent include alcohols, chain ethers, cyclic ethers, glycol ethers, glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, and propylene glycol monoalkyl ether acetates. Esters, propylene glycol monoalkyl ether propionates, aromatic hydrocarbons, ketones, other esters, and the like.

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

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

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 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, and propylene glycol monobutyl ether.

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

Examples of the propylene glycol monoalkyl ether propionate include propylene glycol monomethyl 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, and 4-hydroxy-4-methyl-2-pentanone.

Examples of other esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, and 2-hydroxy-2-methyl Ethyl propionate, methyl glycolate, ethyl glycolate, butyl glycolate, 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 propoxyacetate, Ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, 2 -Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 -Ethyl ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2 -Propyl butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3 -Butyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate , Methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate , Ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and the like.

The solvent is preferably another ester, and more preferably methyl 3-methoxypropionate. These solvents can be used alone or in combination of two or more.

Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), and 2,2'-azo Bis- (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.

Among them, 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethyl Valeronitrile).

The use amount of the radical polymerization initiator is preferably 1 mol% to 10 mol%, and more preferably 2 mol% to 8 mol% with respect to 100 mol of the monomers used in the polymerization in total. As the radical polymerization initiator, one kind or two or more kinds can be used.

In the polymerization reaction, a molecular weight modifier can be used in order to adjust the molecular weight. Examples of molecular weight regulators include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, and thioglycolic acid. Thiols; xanthates such as dimethyl xanthate and diisopropyl xanthate; terpineolene and α -methylstyrene dimers.

The use amount of the molecular weight modifier can be appropriately selected according to the desired molecular weight of the [A] polymer, but is preferably 0.1 mol% to 10 mol% relative to the total of 100 mol% of the monomers used in the polymerization. More preferably, it is 0.5 to 5 mol%. The molecular weight adjuster can be used alone or in combination of two or more.

The polymerization temperature is usually 0 ° C to 150 ° C, and preferably 50 ° C to 120 ° C. The polymerization time is usually 10 minutes to 20 hours, and preferably 30 minutes to 6 hours.

As the solvent used in the dehydrohalogenation reaction after the polymerization reaction, a solvent exemplified as a solvent usable in the polymerization can be used, and the solvent used in the polymerization is preferably used directly. That is, it is preferable to add a base to the polymerization reaction liquid and perform a dehydrohalogenation reaction.

Examples of the base used in the dehydrohalogenation reaction include: Diethylamine, dipropylamine, trimethylamine, triethylamine, tripropylamine, pyrrolidine, pyridine, pyridine, triethanolamine and other amines; sodium hydroxide, potassium hydroxide, calcium hydroxide and other metal hydroxides; sodium carbonate , Potassium carbonate, calcium carbonate and other metal carbonates; sodium bicarbonate, potassium bicarbonate, calcium bicarbonate and other metal bicarbonates; sodium methoxide, potassium tert-butoxide and other metal alkoxides.

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 still more preferably 2 mol to 5 mol, relative to 1 mol of the desorbed hydrogen halide. ear.

The temperature of the dehydrohalogenation reaction is usually 0 ° C to 150 ° C, and preferably 50 ° C to 100 ° C.

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

[A] The polystyrene-equivalent weight average molecular weight (Mw) of the polymer is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, and still more preferably 5,000 to 20,000. By setting the Mw of the [A] polymer to the above range, the adhesiveness of the cured film can be further improved, and the radiation sensitivity when the radiation-curable resin composition is made can be further improved.

[A] The molecular weight distribution (Mw / Mn) of the polymer is preferably 5.0 or less, and more preferably 3.0 or less. By setting the Mw / Mn of the [A] polymer to be equal to or lower than the upper limit, the pattern shape of the cured film can be further improved.

<[B] Solvent>

[B] The solvent can be used as long as it dissolves the contained component uniformly and does not react with the contained component. Examples of the [B] solvent include the same solvents as those exemplified as the solvent used in the polymerization of the polymer [A], and the like. [B] One or more solvents can be used.

[B] The solvent is preferably propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether ester, or the like from the viewpoints of solubility, dispersibility of solid content, and coatability of the curable resin composition. Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ether, cyclohexanone, 2-heptanone, 3-heptane Ketone, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, isobutyl acetate, n-pentyl formate , Isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, more preferably methyl 3-methoxypropionate, diethylene glycol Alcohol methyl ether, 3-methoxybutyl acetate. [B] The solvent also preferably contains both the solvent and the high-boiling-point solvent. Examples of the high boiling point solvent include benzyl ether, di-n-hexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl acetate, and ethyl benzoate. Esters, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethyl carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate, and the like.

[B] The content of the solvent is not particularly limited, but from the viewpoints of coatability and storage stability of the curable resin composition, it is preferably from 20% by mass to 90% by mass, and more preferably from 40% by mass. ~ 80% by mass.

<[C] polymerizable compound>

[C] The polymerizable compound is a polymerizable compound having an ethylenically unsaturated bond. The curable resin composition further contains a [C] polymerizable compound, which can further improve the adhesion of the cured film when forming a negative pattern, and can improve the thermal stability of the pattern shape when forming a positive pattern. The [C] polymerizable compound may be hardened by heating, but can be more effectively hardened by containing a [D] radical polymerization initiator described later.

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

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

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

Examples of the monofunctional acrylate include ω-carboxy polycaprolactone mono (meth) acrylate, ethylene glycol mono (meth) acrylate, and the like.

Examples of the polyfunctional acrylate include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and Ethylene glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenoxy Jiyi Alcohol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, 2-hydroxy-3- (meth) acrylic acid oxypropyl methacrylate, trimethylol Propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol seven (Meth) acrylate, tripentaerythritol octa (meth) acrylate, tris (2- (meth) acryloxyethyl) phosphate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid Modified pentaerythritol triacrylate, succinic acid modified dipentaerythritol pentaacrylate, a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, and having one or more hydroxyl groups in the molecule, and A polyfunctional (meth) acrylate compound such as a (meth) acrylic acid urethane obtained by reacting a compound having 3 to 5 (meth) acrylic fluorenyloxy groups.

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

[C] Examples of commercially available polymerizable compounds include: Aronix M-400, Aronix M-402, Aronix M-405, and Aronix M-450, Aronix M-520, Aronix M-1310, Aronix M-1600, Aronix M-1960, Aronix M-7100, Aronix M-8030, Aronix M-8060, Aronix M-8100, Aronix M-8530, Aronix M-8560, Aronix M-9050, Aronix TO-756, Aronix TO-1450, Aronix TO-1382 (Above, East Asia Synthesis); KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD MAX-3510 (above, Nippon Kayakusho); Viscoat 295, Viscoat 300, Biscott ( Viscoat 360, Viscoat 802, Viscoat GPT, Viscoat 3PA, Viscoat 400 (above, Osaka Organic Chemical Industry Co., Ltd.); as acrylic amino New frontier R-1150 (First Industrial Pharmaceutical Company) of ester compounds; KAYARAD DPHA-40H, KAYARAD DPEA-12, HUX-5000 (Above, Nippon Kayakusho); UN-9000H (Kanekami Corporation); Aronix M-5300, Aronix M-5600, Aronix M-5700, Yarrow Aronix M-210, Aronix M-220, Aronix M-240, Aronix M-270, Aronix M-6200, Yarrow Aronix M-305, Aronix M-30 9. Aronix M-310, Aronix M-315 (above, East Asia Synthesis); KAYARAD HDDA, KAYARAD HX-220, card Kayarad HX-620, Kayarad R-526, Kayarad R-167, Kayarad R-604, Kayarad R-684, Kayarad R-551, Kaya KAYARAD R-712, UX-22201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU -4001 (above, Nippon Kayakusho); Art Resin UN-9000PEP, Art Resin UN-9200A, Art Resin UN-7600, Art Resin ) UN-333, Art Resin UN-1003, Art Resin UN-1255, Art Resin UN-6060PTM, Art Resin UN-6060P, Asia Special resin (Art Resin) SH-500B (above, Genjo Industrial Co.); Viscoat 260, Viscoat 312, Viscoat 335HP (above, Osaka Organic Chemical Industry Co., Ltd.) .

[C] The polymerizable compound is preferably a polyfunctional acrylate, and more preferably dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, trimethylolpropane triacrylate, and tripentaerythritol seven Acrylate, tripentaerythritol octaacrylate, succinic acid modified dipentaerythritol pentaacrylate.

The content of the [C] polymerizable compound with respect to 100 parts by mass of the [A] polymer 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. By setting the content of the [C] polymerizable compound to the range, the curable resin composition can further improve the adhesion of the cured film when the negative pattern is formed and the pattern shape when the positive pattern is formed. Thermal stability.

<[D] radical polymerization initiator>

[D] The radical polymerization initiator is a component that generates active species that can initiate radical polymerization of a polymerizable compound. When the curable resin composition contains a [D] radical polymerization initiator, the adhesion of the cured film can be further improved. Examples of the [D] radical polymerization initiator include: [D1] thermosensitive radical polymerization initiator which is decomposed by heating to generate radicals, and [D2] radiation which generates radicals by irradiation of radiation. Radical polymerization initiators, etc. The contained form of the [D] radical polymerization initiator in the curable resin composition may be a form of a low-molecular compound as described below, a form incorporated as part of the [A] polymer, and the like Both forms. It may contain 1 type or 2 or more types of [D] radical polymerization initiators.

[[D1] Thermosensitive radical polymerization initiator]

[D1] The thermosensitive radical polymerization initiator is a compound that is decomposed by heating and generates radicals. When the said curable resin composition contains a [D1] thermosensitive radical polymerization initiator, it can function as a thermosetting resin composition.

[D1] Thermosensitive radical polymerization initiators include, for example, azobisisobutyronitrile (AIBN), 2,2'-azobis (4-methoxy-2,4-dimethylpentane) Nitrile), 2,2'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'- Azo radical initiators such as azobisisobutyrate; peroxide radical initiators such as benzamyl peroxide, t-butyl hydroperoxide, and cumene hydroperoxide.

[[D2] Radiation-sensitive Radical Polymerization Initiator]

[D2] Radiation-sensitive radical polymerization initiator is produced by irradiation of radiation Free radical generating compounds. If the curable resin composition contains a [D2] radiation-sensitive radical polymerization initiator, it can function as a radiation curable resin composition, and the [A] polymer, [C] polymerizable compound, etc. Polymerizes the free radicals, thereby exerting negative radiation-sensitive properties. By including the [D2] radiation-sensitive radical polymerization initiator in the curable resin composition, the radiation sensitivity can be further improved.

[D2] The radiation-sensitive radical polymerization initiator includes, for example, an O-fluorenyl oxime compound, an acetophenone compound, a biimidazole compound, and a thia anthrone compound.

Examples of the O-fluorenyl oxime compound include 1- [4- (phenylthio) -2- (O-benzylidene oxime)], 1,2-octanedione 1- [4- (phenylthio ) -2- (O-benzylideneoxime)], ethyl ketone-1- [9-ethyl-6- (2-methylbenzylidene) -9H-oxazol-3-yl] -1 -(O-ethylamidoxime), 1- [9-ethyl-6-benzylidene-9.H.-oxazol-3-yl] -octane-1-oneoxime-O-acetic acid Ester, 1- [9-ethyl-6- (2-methylbenzyl) -9.H.-oxazol-3-yl] -ethane-1-one oxime-O-benzoate , 1- [9-n-butyl-6- (2-ethylbenzylidene) -9.H.-oxazol-3-yl] -ethane-1-oneoxime-O-benzoate Ethyl ketone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofurylbenzyl) -9.H.-oxazol-3-yl] -1- (O-acetamidine Oxime), ethyl ketone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzyl) -9.H.-oxazol-3-yl] -1 -(O-ethylamidoxime), ethyl ketone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzyl) -9.H.-oxazol-3-yl ] -1- (O-acetylamoxime), ethyl ketone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxa Cyclopentyl) methoxybenzylidene} -9.H.-oxazol-3-yl] -1- (O-acetamidooxime) and the like.

Examples of the acetophenone compound include an α -amino ketone compound and an α -hydroxy ketone compound.

Examples of the α -amino ketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butane-1-one and 2-dimethylamino- 2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one, 2-methyl-1- (4-methylthiophenyl) 2-morpholinylpropan-1-one and the like.

Examples of the α -hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropane-1-one and 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-ketone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone.

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, etc., preferably 2,2'-bis (2,4-dichlorophenyl) -4,4', 5, 5'-tetraphenyl-1,2'-biimidazole.

Examples of the xanthone compound include xanthone, 2,4-diethylxanthone, 2-isopropylxanthone, 2,4-diisopropylxanthone, 2 -Chlorothanthone and the like.

Among these, an O-fluorenyl oxime compound, an acetophenone compound, and a thia anthrone compound are preferable, an O-fluorenyl oxime compound, an α -amino ketone compound, and a thia anthrone compound are more preferable, and an ethyl ketone is more preferable -1- [9-ethyl-6- (2-methylbenzylidene) -9H-oxazol-3-yl] -1- (O-acetamidooxime), 2-methyl-1- (4-methylthiophenyl) -2-morpholinylpropane-1-one, 2,4-diethylthiaxanthone.

The content of the [D] radical polymerization initiator relative to 100 parts by mass of the [A] polymer 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. By setting the content of the [D] radical polymerization initiator to Within the above range, the curable resin composition can further improve the adhesion of the cured film, and in the case of a radiation curable resin composition, can further improve the radiation sensitivity.

<[E] acid generator>

[E] An acid generator is a compound that generates an acid. Examples of the generated acid include carboxylic acid and sulfonic acid. By including the [E] acid generator in the curable resin composition, properties such as heat resistance and hardness of the cured film can be improved. Examples of the [E] acid generator include a [E1] thermosensitive acid generator that generates an acid by heating, and a [E2] radiation-sensitive acid generator that generates an acid by irradiation of radiation. The content of the [E] acid generator in the curable resin composition may be a form of a low-molecular compound as described below, a form incorporated as a part of the [A] polymer, or the like. form. The said curable resin composition may contain 1 type or 2 or more types of [E] acid generator.

[[E1] Thermosensitive acid generator]

[E1] The thermosensitive acid generator is a compound that generates an acid by heating. When the said curable resin composition contains a [E1] thermosensitive acid generator, it can function as a thermosetting resin composition.

[E1] Examples of the thermosensitive acid generator include onium salts such as sulfonium salts, benzothiazolium salts, ammonium salts, and sulfonium salts. [E1] Specific examples of the thermosensitive acid generator compound include the same compounds as those exemplified as the [E] component described in Japanese Patent Laid-Open No. 2010-134442.

[[E2] Radioactive acid generator]

[E2] A radiation-sensitive acid generator is an acid that is generated by radiation. 组合。 The compound. When the said curable resin composition contains a [E2] radiation-sensitive acid generator, it can function as a radiation-curable resin composition. By containing the [E2] radiation-sensitive acid generator, the curable resin composition can further improve radiation sensitivity.

[E2] Examples of the acid generator include quinonediazide compounds, oxime sulfonate compounds, onium salts, sulfonylimine compounds, halogen-containing compounds, diazomethane compounds, sulfonium compounds, sulfonate compounds, and carboxylates. Ester compounds, etc.

A quinonediazide compound generates a carboxylic acid by irradiation of radiation. When the curable resin composition contains a quinonediazide compound as an [E2] acid generator, the generated carboxylic acid improves the solubility of the radiation irradiated portion in the alkaline developer, thereby exhibiting positive radiation sensitivity. characteristic.

As the quinonediazide compound, for example, a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as a "mother core") and 1,2-naphthoquinonediazidesulfonium halide can be used.

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

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

Examples of the 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'-methoxydi Benzophenone and so on.

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

Examples of hexahydroxybenzophenone include: 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxydione Benzophenone and so on.

Examples of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris ( P-hydroxyphenyl) 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] ethylene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1, 1'-spirobiindene-5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan and the like.

Examples of other mother cores include 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.

The mother core is preferably 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tris (p-hydroxyphenyl) ethane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol.

The 1,2-naphthoquinonediazidesulfonium halide is preferably 1,2-naphthoquinonediazidesulfonyl chloride. Examples of the 1,2-naphthoquinonediazidesulfonyl chloride include 1,2-naphthoquinonediazide-4-sulfonyl chloride, and 1,2-naphthoquinonediazide-5-sulfonyl chloride. Among these, 1,2-naphthoquinonediazide-5-sulfonyl chloride is preferred.

The synthesis of the quinonediazide compound can be performed by a known condensation reaction. In the condensation reaction, with respect to the number of OH groups in the phenolic compound or the alcoholic compound, The 1,2-naphthoquinonediazidesulfonium halide equivalent to preferably 30 mol% to 85 mol%, more preferably 50 mol% to 70 mol% can be used.

In addition, as the quinonediazide compound, 1,2-naphthoquinonediazidesulfonamides obtained by changing the ester bond of the mother nucleus just exemplified to the amidine bond can be suitably used. For example, 2,3,4 -Triaminobenzophenone-1,2-naphthoquinonediazide-4-sulfonamide and the like.

The [E2] acid generator is other than a quinonediazide compound, for example, an oxime sulfonate compound, an onium salt, a sulfonylimide compound, a halogen-containing compound, a diazomethane compound, a sulfonium compound, a sulfonate compound, In the case of a carboxylic acid ester compound and the like, the above-mentioned curable resin composition can react with and harden the [F] polymer and the like described later by the action of an acid generated, and thus can generally exhibit negative radiation-sensitive properties. .

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

Examples of onium salt compounds include sulfonium salts, sulfonium salts, sulfonium salts, diazonium salts, and pyridinium salts. Specific examples of preferred onium salts include diphenylsulfonium triflate, diphenylsulfonium p-toluenesulfonate, diphenylsulfonium hexafluoroantimonate, diphenylsulfonium hexafluorophosphate, Diphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-tert-butylphenyl. Diphenylsulfonium triflate, 4-tert-butylphenyl. Diphenylphosphonium p-toluenesulfonate, 4,7-di-n-butyl Oxynaphthyl tetrahydrothienium trifluoromethanesulfonate, 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, 4- (phenylthio) phenyldi Phenylphosphonium hexafluorophosphate.

Examples of the N-sulfonyloxyfluorenimine compound include N- (trifluoromethylsulfonyloxy) succinimine, N- (trifluoromethylsulfonyloxy) phthalimide Fluorenimine, N- (trifluoromethylsulfonyloxy) diphenylcis-butenedifluorenimine, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5 -Ene-2,3-dicarboxyfluorenimine, N- (trifluoromethylsulfonyloxy) naphthylfluorenimine.

Examples of the halogen-containing compound include a halogenated alkyl group-containing hydrocarbon compound and a halogenated alkyl group-containing heterocyclic compound. Specific examples of preferred halogen-containing compounds include 1,10-dibromo-n-decane, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, and phenyl- Bis (trichloromethyl) -mesytriazine, 4-methoxyphenyl-bis (trichloromethyl) -mesytriazine, styryl-bis (trichloromethyl) -mesytriazine, naphthyl -Bis (trichloromethyl) -mesytriazine derivatives and the like.

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

Examples of the fluorene compound include a β -ketofluorene compound, a β -sulfonylfluorene compound, and an α -diazo compound of these compounds. Specific examples of the preferred sulfonium compound include 4-tribenzylfluorenylmethylfluorene, mesitylbenzylfluorenylmethylfluorene, bis (benzylfluorenylmethylsulfonyl) methane, and the like.

Examples of the sulfonate compound include alkylsulfonates, haloalkylsulfonates, arylsulfonates, and iminosulfonates. Specific examples of preferred sulfonate compounds include benzoin tosylate, pyrogallol tris (trifluoromethanesulfonic acid) Ester), o-nitrobenzyl triflate, o-nitrobenzyl p-toluenesulfonate.

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

The content of the [E] acid generator relative to 100 parts by mass of the [A] polymer is preferably 5 parts by mass or more and 100 parts by mass, and more preferably 10 parts by mass or more and 50 parts by mass or less. By setting the content of the [E] acid generator within the above range, the curable resin composition can further improve the adhesion of the cured film, and can further improve the radiation curable resin composition. Radiosensitivity.

<[F] Polymer>

[F] The polymer is a polymer containing at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (hereinafter also referred to as "(F1) compound"), and an epoxy-containing polymer A monomer of an unsaturated compound (hereinafter also referred to as a "(F2) compound") is copolymerized. By containing the [F] polymer in the curable resin composition, the adhesiveness of the cured film can be further improved, and the solvent resistance and hardness can be improved. The [F] polymer can be hardened by heating, but it can be more effectively hardened by containing a [D] radical polymerization initiator and / or an [E] acid generator.

In the synthesis of the [F] polymer, an unsaturated compound (hereinafter also referred to as a "(F3) compound") other than the (F1) compound and the (F2) compound can be copolymerized. These compounds can be used alone or in combination of two or more.

Each compound will be described below.

[(F1) Compound]

The (F1) compound is at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. (F1) Compounds include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids Carboxylic acids, anhydrides of unsaturated dicarboxylic acids, mono [(meth) acrylfluorenyloxyalkyl] esters of polycarboxylic acids, mono (meth) acrylates of polymers having carboxyl and hydroxyl groups at both ends, Unsaturated polycyclic compounds having a carboxyl group, and anhydrides thereof. These compounds include the same compounds as those exemplified as the monomers that provide the structural unit (II) of the [A] polymer, and the like.

Among these, from the viewpoints of copolymerization reactivity and availability, and the solubility of the [F] polymer in an alkaline aqueous solution, preferred are monocarboxylic and dicarboxylic anhydrides, and more preferred are acrylic acid, methacrylic acid, Maleic anhydride is more preferably methacrylic acid.

The content ratio of the structural unit derived from the (F1) compound is preferably 1% to 40% by mass, and more preferably 2% by mass based on the input ratio of all monomers used in the synthesis of the [F] polymer. % To 30% by mass, and more preferably 3 to 20% by mass. By setting the content ratio to the range, the solubility of the [F] polymer in the alkaline aqueous solution can be optimized, and the developability of the curable resin composition can be further improved.

[(F2) compound]

The (F2) compound is an epoxy-containing unsaturated compound. The (F2) compound has radical polymerizability and usually has both an epoxy group and an ethylenically unsaturated bond. Examples of the epoxy group include an oxetanyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure).

Examples of the unsaturated compound having an oxetanyl group include glycidyl acrylate, glycidyl methacrylate, α -ethyl acrylate, α -n-propyl acrylate, and α -n-butyl acrylate. Glycidyl acrylate, -3,4-epoxybutyl acrylate, -3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, -6,7 methacrylate -Epoxyheptyl, α -ethylhexyl-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate and the like.

Examples of the unsaturated compound having an oxetanyl group include 3- (propenyloxymethyl) oxetane and 3- (propenyloxymethyl) -2-methyloxane Butane, 3- (propenyloxymethyl) -3-ethyloxetane, 3- (propenyloxymethyl) -2-trifluoromethyloxetane, 3 -(Propenyloxymethyl) -2-pentafluoroethyloxetane, 3- (propenyloxymethyl) -2-phenyloxetane, 3- (propenefluorene Methoxymethyl) -2,2-difluorooxetane, 3- (propenyloxymethyl) -2,2,4-trifluorooxetane, 3- (propenefluorene) Ethoxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-propenyloxyethyl) oxetane, 3- (2-propenylfluorenyl) (Oxyethyl) -2-ethyloxetane, 3- (2-propenyloxyethyl) -3-ethyloxetane, 3- (2-propenyloxy) (Ethyl) -2-trifluoromethyloxetane, 3- (2-propenyloxyethyl) -2-pentafluoroethyloxetane, 3- (2-propenyloxetyl (Oxyethyl) -2-phenyloxetane, 3- (2-propenyloxyethyl) -2,2-difluorooxetane, 3- (2-propenyloxetyl Oxyethyl Acryl) -2,2,4-trifluorooxetane, 3- (2-propenyloxyethyl) -2,2,4,4-tetrafluorooxetane, etc. ; 3- (methacrylfluorenyloxymethyl) oxetane, 3- (methacrylfluorenyloxymethyl) -2-methyloxetane, 3- (methacryl Fluorenyloxymethyl) -3-ethyloxetane, 3- (methacrylfluorenyloxymethyl) -2-trifluoromethyloxetane, 3- (methacrylfluorenyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacrylfluorenyloxymethyl) -2-phenyloxetane, 3- (methacrylfluorenyloxymethyl) -2,2-difluorooxetane, 3- (methacrylfluorenyloxymethyl) -2,2,4-trifluorooxe Cyclobutane, 3- (methacrylfluorenyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-methacrylfluorenyloxyethyl) oxy Heterocyclobutane, 3- (2-methylpropenyloxyethyl) -2-ethyloxetane, 3- (2-methpropenyloxyethyl) -3-ethyl Oxetane, 3- (2-methacrylfluorenyloxyethyl) -2-trifluoromethyloxetane, 3- (2-methacrylfluorenyloxyethyl) 2-pentafluoroethyloxetane, 3- (2-methacrylfluorenyloxyethyl) -2-phenyloxetane, 3- (2-methacrylfluorenyloxy) Ethyl) -2,2-difluorooxetane, 3- (2-methylpropenyloxyethyl) -2,2,4-trifluorooxetane, 3- ( 2-methacrylfluorenyloxyethyl) -2,2,4,4-tetrafluorooxetane and other methacrylates.

Among these, from the viewpoint of improving the copolymerization reactivity and the curability of the curable resin composition, glycidyl methacrylate, -6,7-epoxyheptyl methacrylate, and o-vinyl group are preferred. Benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, more preferably glycidyl methacrylate, methyl 3,4-epoxycyclohexyl acrylate.

The content ratio of the structural unit derived from the (F2) compound is preferably 5% to 70% by mass, and more preferably 10% by mass based on the input ratio of all monomers used in the synthesis of the [F] polymer. % To 60% by mass, and more preferably 15% to 50% by mass. By setting the content ratio to the range, it is possible to further improve High solvent resistance and hardness.

[(F3) Compound]

The (F3) compound is an unsaturated compound other than the (F1) compound and the (F2) compound. The (F3) compound is not particularly limited as long as it is a radically polymerizable unsaturated compound. Examples of the (F3) compound include alkyl methacrylate, cycloalkyl methacrylate, methacrylate having a hydroxyl group, alkyl acrylate, cycloalkyl acrylate, acrylate having a hydroxyl group, and methyl Aromatic acrylic acid, aromatic acrylic acid, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, N-cis butylene diimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan Unsaturated compounds having a skeleton, a tetrahydropyran skeleton, a pyran skeleton or a skeleton represented by the following formula (2), unsaturated compounds containing a phenolic hydroxyl group represented by the following formula (3), and hydrolyzable silane groups Unsaturated compounds, other unsaturated compounds, etc.

In the formula (2), R ⁷ is a hydrogen atom or a methyl group. m is an integer of 1 or more.

[Chemical 6]

In the formula (3), R ⁸ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁹ to R ¹³ are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms. Y is a single bond, -COO-, or -CONH-. p is an integer from 0 to 3. Among them, at least one of R ⁹ to R ¹³ is a hydroxyl group.

Alkyl methacrylate, cycloalkyl methacrylate, alkyl acrylate, cycloalkyl acrylate, aromatic methacrylate, aromatic acrylate, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound , N-cis-butene difluorene imine compound, unsaturated aromatic compound, conjugated diene, unsaturated compound having tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton or pyran skeleton, and other compounds include The same compounds as the compounds exemplified as the compound providing the structural unit (III) of the [A] polymer, and the like.

Examples of the methacrylate having a hydroxyl group include hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, and diethylene glycol monoester. Methacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethyl glucoside, 4-hydroxyphenyl methacrylate, and the like.

Examples of the acrylate having a hydroxyl group include hydroxymethyl acrylate, acrylic 2-hydroxyethyl enoate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, diethylene glycol monoacrylate, 2,3-dihydroxypropyl acrylate, 2-propenyloxyethyl glucoside , 4-hydroxyphenyl acrylate and the like.

Examples of unsaturated compounds containing a skeleton represented by the formula (2) include polyethylene glycol (n = 2 to 10) mono (meth) acrylate, and polypropylene glycol (n = 2 to 10) mono (methyl) Group) acrylate and the like.

Examples of the phenolic hydroxyl group-containing unsaturated compound represented by the formula (3) include compounds represented by the following formulae (4) to (8) based on the definitions of Y and p.

In the formula (4), q is an integer of 1 to 3. R ⁸ to R ^{13 are} synonymous with the formula (3).

[Chemical 8]

In the formula (5), R ⁸ to R ^{13 are} synonymous with the formula (3).

In the formula (6), r is an integer of 1 to 3. R ⁸ to R ^{13 are} synonymous with the formula (3).

In the formula (7), R ⁸ to R ^{13 are} synonymous with the formula (3).

[Chemical 11]

In the formula (8), R ⁸ to R ^{13 are} synonymous with the formula (3).

Examples of the unsaturated compound having a hydrolyzable silane group include 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, and 3-methacrylfluorene Oxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropylsilane, 3-methacryloxypropyltripropyl Trichlorosilane, 4-methacryloxybutyltrimethoxysilane, 4-methacryloxybutyltriethoxysilane, 2-acryloxyethyltrimethoxysilane, 2- Propylene ethoxyethyltriethoxysilane, 3-propylene ethoxypropyltrimethoxysilane, 3-propylene ethoxypropyltriethoxysilane, 3-propylene ethoxypropyltripropyl Silane, 3-propenyloxypropyltrichlorosilane, 4-propenyloxybutyltrimethoxysilane, 4-propenyloxybutyltriethoxysilane, and the like.

Among them, an alkyl methacrylate, a cycloalkyl methacrylate, an N-cis butylene diimide compound, a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, or the formula is preferable. Unsaturated compounds of the skeleton represented by (2), phenolic hydroxyl-containing unsaturated compounds represented by the formula (3), unsaturated aromatic compounds, cycloalkyl acrylates, and unsaturated hydrolysable silane groups Compound. Among them, styrene, tert-butyl methacrylate, n-lauryl methacrylate, and tricyclic methacrylate are more preferred in terms of copolymerization reactivity and the solubility of the [F] polymer in an alkaline aqueous solution. 5.2.1.0 ^2,6 ] Decane-8-yl ester, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylcis butylene diimide, N-cyclohexylcis butene Diamidine, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (n = 2 ~ 10) mono (meth) acrylate, 3- (meth) propenyloxytetrahydrofuran-2- Ketone, 4-hydroxybenzyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, o-hydroxystyrene, p-hydroxystyrene, α -methyl-p-hydroxystyrene, more preferably α -Methyl-p-hydroxystyrene, styrene, tetrahydrofurfuryl methacrylate, N-cyclohexyl cis butene diamidine, n-lauryl methacrylate, tricyclic methacrylate [5.2.1.0 ^2,6 ] decane-8-yl ester, 3-methacryloxypropyltriethoxysilane.

The content ratio of the structural unit derived from the (F3) compound is preferably 10% to 90% by mass, and more preferably 30% by mass relative to the input ratio of all monomers used in the synthesis of the [F] polymer. % To 80% by mass, and more preferably 40% to 65% by mass. By setting the content ratio to the range, the developability of the curable resin composition and the solvent resistance of the cured film can be further improved.

<[F] Synthesis method of polymer>

[F] The polymer can be synthesized by, as in the polymerization of the synthesized [A] polymer, using a radical polymerization initiator in a solvent to make the (F1) compound and (F2) compound, And (F3) compound etc., as needed, are polymerized.

[F] The Mw of the polymer is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, and even more preferably 5,000 to 20,000. By setting the Mw of the [F] polymer to the above range, the curable resin composition can further improve developability, and when the radiation curable resin composition is made, the radiation can be further improved. Sensitivity.

The content of the [F] polymer is preferably 10 parts by mass or more and 3,000 parts by mass relative to 100 parts by mass of the [A] polymer, more preferably 50 parts by mass or more and 1,500 parts by mass or less, and still more preferably 150 parts by mass More than 800 parts by mass. By setting the content of the [F] polymer to the above range, the curable resin composition can further increase the hardness of the cured film.

<Other optional ingredients>

Examples of other optional components include epoxy compounds, adhesion aids, metal oxide particles, surfactants, and hardeners. The said curable resin composition may contain one or two or more of said other arbitrary components, and may contain one or two or more of each of them.

[Epoxy compound]

The epoxy compound is a compound having an epoxy group (except for compounds corresponding to the [F] polymer). The curable resin composition can further improve the heat resistance, surface hardness, and film thickness uniformity of the cured film by containing an epoxy compound.

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

Examples of the compound having one epoxy group include glycidyl (meth) acrylate, glycidyl α -ethylacrylate, glycidyl α -n-propylacrylate, glycidyl α -n-butylacrylate, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxybutyl α -ethylacrylate, 6,7-epoxyheptyl (meth) acrylate, α -ethylacrylic acid 6.7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-methyl-3- (meth) acryloxy Methyloxetane, 3-ethyl-3- (meth) acryloxymethyloxetane, phenyl glycidyl ether, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyldiethoxysilane, and the like.

Examples of the compound having two or more epoxy groups include 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, and 2- (3,4-cyclo Oxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3 , 4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-form Cyclohexanecarboxylic acid ester, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, bis (3,4-epoxycyclohexyl) of ethylene glycol Methyl) ether, ethyl bis (3,4-epoxycyclohexanecarboxylate); bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenation Bisphenol-type diglycidyl ethers such as bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether; 1,4-butanediol diglycidyl ether, 1,6 -Polyglycidyl polyol such as hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether Ethers; polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyols such as ethylene glycol, propylene glycol, and glycerol; phenol novolacs Epoxy resin; cresol novolac epoxy resin; Polyphenol epoxy resins; diglycidyl esters of aliphatic long-chain dibasic acids; glycidyl esters of higher fatty acids; aliphatic polyglycidyl ethers; epoxidized soybean oil, epoxidized linseed oil, etc.

Commercially available products of compounds having two or more epoxy groups include, for example, Epikote 1001, Epikote 1002, and Epicote as bisphenol A novolac epoxy resins. Epikote 1003, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote 828 (Above, Japan Epoxy Resins), etc .; Epikote 807 (above, Japan Epoxy Resins), etc. as bisphenol F type epoxy resin; etc., as phenol novolac type ring Epoxyte 152, Epikote 154, Epikote 157S65 (above, Japan Epoxy Resin), EPPN201, EPPN202 (above, Japan Chemical Co.) Etc .; as cresol novolac epoxy resin EOCN102, EOCN103S, EOCN104S, 1020, 1025, 1027 (above, Nippon Kayaku Co., Ltd.), Epikote 180S75 (Japan Epoxy Co., Ltd.), etc .; Epikote 1032H60, Epikote XY-4000 (above, Japanese epoxy resin) Fat company), etc .; Cycyclic aliphatic epoxy resins CY-175, CY-177, CY-179, Araldite CY-182, Araldite 192, 184 (above, Ciba specialty chemicals), ERL-4234, 4299, 4221, 4206 (above, UCC), Shodain 509 (Showa Denko), Epiclon 200, Epiclon 400 ( Above, DIC Corporation), Epikote 871, Epikote 872 (above, Japan Epoxy Resin Company), ED-5661, ED-5662 (above, Celanese (Celanese Coating Co.), etc .; Epolight 100MF (Kyoeisha Chemical Co., Ltd.) as an aliphatic polyglycidyl ether; Epiol TMP (Nippon Oil & Fats Co., Ltd.).

The content of the epoxy compound is preferably 100 parts by mass or less with respect to 100 parts by mass of the [A] polymer, more preferably 75 parts by mass or less, and still more preferably 50 parts by mass or less. By setting the content of the epoxy compound to the above range, the curable resin composition can further improve the heat resistance, surface hardness, and film thickness uniformity of the cured film.

[Adhesion aid]

The adhesion auxiliary agent is used to further improve the adhesion between the cured film obtained from the curable resin composition and a substrate or the like. Such an adhesion promoter is preferably a functional silane coupling agent. Examples of the functional silane coupling agent include a coupling agent having a reactive group such as a carboxyl group, a methacryl group, an isocyanate group, and an epoxy group. Examples of such a functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

The content of the adhesion aid is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, based on 100 parts by mass of the [A] polymer. By setting the content of the adhesion aid to 20 parts by mass or less, it is possible to suppress generation of development residue in the development step.

[Metal oxide particles]

When the metal oxide particles form an insulating film from the curable resin composition, the electrical insulating properties of the insulating film can be maintained, and an increase in the relative dielectric constant can be suppressed. The metal oxide particles can also be used for the following purposes: control of the refractive index of the insulating film, control of the transparency of the insulating film, suppression of cracks due to relaxation hardening shrinkage, and reduction of the surface hardness of the insulating film. improve.

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

Examples of the single oxide include silicon dioxide, aluminum oxide, zirconia, titanium dioxide, and cerium oxide.

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

Among these, oxide particles of silicon, zirconium, titanium, zinc, and barium are preferable, and silicon dioxide particles, zirconia particles, titanium dioxide particles, and barium titanate (BaTiO ₃ ) are more preferable. As a commercially available product of metal oxide particles, for example, "Nanotec (registered trademark)" of CIKasei Co., Ltd. can be used.

The shape of the metal oxide particles is not particularly limited, and may be spherical or indefinite, and may also be hollow particles, porous particles, or nuclei. Shell-type particles, etc.

The volume average particle diameter of the metal oxide particles is preferably 5 nm to 200 nm, more preferably 5 nm to 100 nm, and even more preferably 10 nm to 80 nm, as a value obtained by a dynamic light scattering method. When the volume average particle diameter of the metal oxide particles is less than 5 nm, there is a concern that the hardness of the insulating film obtained by using the curable resin composition may decrease, and that the required relative dielectric constant may not be developed. On the other hand, if the volume average particle diameter exceeds 200 nm, there is a concern that the haze of the insulating film increases and the transmittance decreases, and the smoothness of the insulating film may deteriorate.

The content of the metal oxide particles is preferably 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the [A] polymer, and more preferably 1 part by mass or more and 10 parts by mass or less. When the content of the metal oxide particles is less than 0.01 parts by mass, there is a concern that the relative dielectric constant of the insulating film cannot be controlled within a desired range. On the other hand, when the compounding quantity of a metal oxide particle exceeds 20 mass parts, there exists a possibility that coating property or film hardenability may fall, and the haze of an insulating film may become high.

[Surfactant]

The surfactant is a compound that improves the coatability of the curable resin composition. The surfactant is preferably a fluorine-based surfactant, a silicone-based surfactant, or a non-ionic surfactant.

Examples of the fluorine-based surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, and 1,1,2,2-tetrafluorooctylhexyl Ether, octaethylene glycol di (1,1,2,2-tetrafluoro Butyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol Bis (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8,8,9,9,10,10 -Decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc. In addition, there may be mentioned: sodium fluoroalkylbenzenesulfonate; fluoroalkyloxyethyl ether; fluoroalkyl Ammonium iodide, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol; perfluoroalkyl alkoxylates; fluorine-based alkyl esters, etc.

Examples of commercially available products of the fluorine-based surfactant include: "BM-1000", "BM-1100" (above, BM Chemie), "Megafac F142D", and "Megaf ( Megafac) F172 "," Megafac F173 "," Megafac F183 "," Megafac F178 "," Megafac F191 "," Megafac F471 "( Above, Dainippon Ink Chemical Industry Co., Ltd.), "Fluorad FC-170C", "Fluorad FC-171", "Fluorad FC-430", "Flod (Fluorad) FC-431 "(above, Sumitomo 3M)," Surflon S-112 "," Surflon S-113 "," Surflon S-131 " , "Surflon S-141", "Surflon S-145", "Surflon S-382", "Surflon SC-101", " "Surflon SC-102", "Surflon SC-103", "Surflon SC-104", "Surflon SC-105", "Saflon (Surflon SC-106 "(above, Asahi Glass Co., Ltd.)," Eftop EF301 "," Aifu (Eftop) EF303 "," aifo extension (Eftop) EF352 "(above, new Akita Kasei Corporation) Wait.

Examples of commercially available silicone surfactants include "DC3PA", "DC7PA", "FS-1265", "SF-8428", "SH11PA", "SH21PA", "SH28PA", "SH29PA", "SH30PA", "SH-190", "SH-193", "SZ-6032" (above, toray dowcorning silicone company), "TSF-4440", "TSF-4300", " TSF-4445 "," TSF-4446 "," TSF-4460 "," TSF-4452 "(above, GE Toshiba Silicone Corporation), etc.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, Polyoxyethylene aryl ethers such as polyethylene oxide nonylphenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate, polyoxyethylene distearate; (meth) acrylic copolymer Category, etc.

Examples of commercially available nonionic surfactants include "Polyflow No. 57", "Polyflow No. 95" (above, Kyoeisha Chemical Co., Ltd.), and the like.

The content of the surfactant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 3 parts by mass or less based on 100 parts by mass of the [A] polymer. By setting the content of the surfactant to 10 parts by mass or less, The coating property of the curable resin composition is improved.

[hardener]

As the hardener, for example, the hardener described in Japanese Patent Laid-Open No. 2012-88459 can be used.

<Preparation method of curable resin composition>

The curable resin composition can be prepared by: [A] polymer and [B] solvent, [C] polymerizable compound as needed, [D] radical polymerization initiator, [E] acid The generator, the [F] polymer, and other optional components are uniformly mixed, and it is preferably filtered through a membrane filter of about 0.2 μm. The curable resin composition is preferably used in the form of a solution by dissolving in a suitable solvent.

Since the said curable resin composition can form the hardened film excellent in adhesiveness and transparency, it can be used suitably for formation of the hardened film for display elements, for example as an interlayer insulation film, a protective film, or a spacer.

<Cured film for display elements>

The cured film for a display element of the present invention is formed of the curable resin composition. Since the cured film for a display element is formed of the curable resin composition, it has excellent adhesion and transparency, and can be suitably used for, for example, an interlayer insulating film, a protective film, a spacer, and the like of a display element. The method for forming the cured film for a display element is not particularly limited, but it is preferable to apply the method for forming a cured film for a display element described below.

<Method for Forming Cured Film for Display Elements>

The method for forming a cured film for a display element of the present invention includes a step of forming a coating film on a substrate (hereinafter also referred to as a "coating film forming step"), A step of irradiating at least a part of the coating film with radiation (hereinafter also referred to as "irradiation step"), a step of developing a coating film irradiated with radiation (hereinafter also referred to as "development step"), and a developed coating film A step of heating (hereinafter also referred to as a "heating step"). In the forming method, the coating film is formed from the curable resin composition. The curable resin composition is preferably a radiation curable resin composition obtained by containing the [D2] radiation-sensitive radical polymerization initiator and / or [E2] radiation-sensitive acid generator or the like.

[Coating film formation step]

In this step, the surface of the substrate is coated with the curable resin composition, and a solvent is preferably removed by performing a prebake to form a coating film. Examples of the substrate used in this step include a glass substrate, a silicon wafer, a plastic substrate, and a substrate having various metals formed on the surface of these substrates. Examples of the plastic substrate include a substrate mainly composed of plastics such as polyethylene terephthalate (PET), polybutylene terephthalate, polyether fluorene, polycarbonate, and polyimide. .

The coating method of the curable resin composition may be, for example, a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an inkjet method. And other suitable methods. The coating method is preferably a spin coating method, a bar coating method, or a slit die coating method. The pre-baking conditions differ depending on the type, content, and the like of the components contained in the curable resin composition, but they may be performed at 60 ° C. to 120 ° C. for about 30 seconds to 10 minutes, for example. The film thickness of the coating film is a value after pre-baking, preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and further It is preferably 0.1 μm to 4 μm.

[Irradiation procedure]

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 the radiation at this time include ultraviolet rays, extreme ultraviolet rays, X-rays, and charged particle beams.

Examples of the ultraviolet rays include g-rays (wavelength 436 nm) and i-rays (wavelength 365 nm). Examples of the far ultraviolet rays include KrF excimer lasers. Examples of the X-ray include synchrotron radiation. Examples of the charged particle beam include an electron beam. Among these radiations, ultraviolet rays are preferable, and among ultraviolet rays, radiations including g rays and / or i rays are particularly preferable. The exposure amount is preferably 30 J / m ² to 1,500 J / m ² .

[Developing steps]

In this step, a coating film irradiated with radiation in the irradiation step may be developed to form a desired pattern. As the developing solution used in the developing process, an alkaline aqueous solution can be used. Examples of the base include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, and di-n-propylamine , Triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, pyridine, 1,8-diazabicyclo [5.4.0 ] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonane and the like. In addition, the developing solution may be an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution, or it may be contained for dissolving a coating film formed of the curable resin composition. A small amount of a developing solution of various organic solvents. Further, as the development method, for example, a liquid coating method, a dipping method, a shaking dipping method, or the like can be used. Spray method and other methods. The development time varies depending on the composition of the curable resin composition, but it can be set to, for example, 30 seconds to 120 seconds.

After the developing step, it is preferable to perform a process of subjecting the patterned coating film to a rinsing treatment using flowing water cleaning, and then comprehensively irradiating (post-exposure) radiation from a high-pressure mercury lamp or the like, so that the remaining in the coating film [D2] The radiation-sensitive radical polymerization initiator, [E2] the radiation-sensitive acid generator, and the like decompose. The exposure amount at the time of post exposure is preferably about 2,000 J / m ² to 5,000 J / m ² .

[Heating step]

In this step, the coating film is heated (post-baking treatment) by using a heating device such as a hot plate or an oven for sintering the coating film developed in the developing step, thereby curing the coating film. . The heating temperature is preferably 100 ° C to 300 ° C, more preferably 120 ° C to 280 ° C, and even more preferably 150 ° C to 250 ° C. The heating time varies depending on the type of heating equipment, but is preferably 5 minutes to 300 minutes, more preferably 10 minutes to 180 minutes, and even more preferably 20 minutes to 120 minutes.

According to the method for forming a cured film for a display element, the curable resin composition is a method for forming a pattern by exposing radiation, developing, and heating by using a radiation-sensitive radiation. Therefore, an excellent adhesiveness and transparency can be easily formed. Hardened film pattern.

<Display element>

A display element of the present invention includes the cured film for a display element. Examples of the display element include a liquid crystal display element and an organic EL element. Such a display element includes a cured film as, for example, an interlayer insulating film, a protective film, and a spacer.

[Example]

Hereinafter, the present invention will be specifically described based on examples, but the present 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 measurement devices and measurement conditions.

Measuring device: "GPC-101" by Showa Denko Corporation

Measurement conditions:

GPC column: "GPC-KF-801", "GPC-KF-802", "GPC-KF-803", and "GPC-KF-804" used by Showa Denko Corporation.

Mobile phase: tetrahydrofuran

<Synthesis of Compound>

[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 dichloromethane were charged, and the reaction was carried out under nitrogen. The inside of the apparatus was cooled to 0 ° C, and 76.18 g (0.6 mol) of 3-chloropropanyl chloride was added dropwise from a dropping funnel, and then the reaction was carried out at 0 ° C with stirring for 2 hours. The obtained reaction solution was sequentially washed with an aqueous solution of sodium bicarbonate and saturated brine, and then 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) ( 76% yield).

[Chemical 12]

[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 dichloromethane were charged. The inside of the reactor was cooled to 0 ° C, while 76.18 g (0.6 mol) of 3-chloropropanidine chloride was added dropwise from a dropping funnel, and then the reaction was carried out at 0 ° C with stirring for 2 hours. The obtained reaction solution was sequentially washed with an aqueous sodium hydrogen carbonate solution and saturated brine, and then 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) ( 71% yield).

[Synthesis Example 3] (Synthesis of Compound (HC-3))

In a 5 L reactor equipped with a stirrer and a dropping funnel, 80.1 g (0.5 mol) of 2,3-dihydroxypropyl methacrylate, 118.7 g (1.5 mol) of pyridine, and 500 mL of dichloromethane were charged. While cooling the inside of the reactor to 0 ° C., 152.4 g (1.2 mol) of 3-chloropropanidine chloride was added dropwise from a dropping funnel, and then the reaction was carried out at 0 ° C. with stirring for 2 hours. For the obtained reaction solution, an aqueous sodium hydrogen carbonate solution and a saturated food were used in this order. After washing with brine, the solution was concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 106.3 g (yield 62%) of a compound represented by the following formula (HC-3).

[Synthesis Example 4] (Synthesis of Compound (HC-4))

In a 5 L reactor equipped with a stirrer and a dropping funnel, 107.2 g (0.5 mol) of methyl (3,4-dihydroxycyclohexyl) methacrylate, 118.7 g (1.5 mol) of pyridine and 500 mL of dichloromethane were charged. While cooling the inside of the reactor to 0 ° C. under nitrogen, 152.4 g (1.2 mol) of 3-chloropropanidine chloride was added dropwise from a dropping funnel, and then the reaction was carried out at 0 ° C. with stirring for 2 hours. The obtained reaction solution was sequentially washed with an aqueous sodium hydrogen carbonate solution and saturated brine, and then concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 125.5 g of a compound represented by the following formula (HC-4) ( 64% yield).

[Synthesis Example 5] (Synthesis of Compound (HC-5))

In a 5L reactor equipped with a stirrer and a dropping funnel, methacrylic acid was charged. 118.2 g (0.5 mol) of 3-hydroxy-1-adamantyl acid, 59.3 g (0.75 mol) of pyridine, and 500 mL of dichloromethane. The reactor was cooled to 0 ° C under nitrogen while the reactor was added dropwise. 76.18 g (0.6 mol) of 3-chloropropanyl chloride was added dropwise, and the mixture was reacted at 0 ° C with stirring for 2 hours. The obtained reaction solution was sequentially washed with an aqueous solution of sodium bicarbonate and saturated brine, and then concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 117.2 g of a compound represented by the following formula (HC-5) ( 72% yield).

[Synthesis Example 6] (Synthesis of Compound (HC-6))

In a 5L 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 dichloride were charged. In 500 mL of methane, 76.18 g (0.6 mol) of 3-chloropropanyl chloride was added dropwise from a dropping funnel while cooling the inside of the reactor to 0 ° C. under nitrogen, and then reacted at 0 ° C. with stirring for 2 hours. The obtained reaction solution was sequentially washed with an aqueous solution of sodium bicarbonate and saturated brine, and then concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 128.5 g of a compound represented by the following formula (HC-6) ( Yield 69%).

[Chemical 17]

[Synthesis Example 7] (Synthesis of Compound (HC-7))

In a 5L 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 dichloromethane were charged. While the inside of the reactor was cooled to 0 ° C, 76.18 g (0.6 mol) of 3-chloropropanyl chloride was added dropwise from a dropping funnel, and the reaction was carried out at 0 ° C with stirring for 2 hours. The obtained reaction solution was sequentially washed with an aqueous sodium hydrogen carbonate solution and saturated brine, and then 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))

36.6 g (20 mole%) of the synthesized compound (HC-1), 17.8 g (25 mole%) of methacrylic acid, and 45.6 g (55 mole%) of methyl methacrylate were dissolved in 140 g of 3 To a methyl methoxypropionate, 14.4 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was added to prepare a monomer solution. Then, 60 g of 3-methoxypropionic acid was added. After the methyl ether 500 mL three-necked flask was purged with nitrogen for 30 minutes, it was heated to 70 ° C. while stirring, and the prepared monomer solution was added dropwise using a dropping funnel for 2 hours. The start of the dropwise addition was set as the start time of the polymerization reaction, and the polymerization reaction was performed for 4 hours. After that, the temperature of the polymerization reaction liquid was set to 90 ° C. and stirred for 30 minutes. After that, the temperature of the polymerization reaction solution was set to 70 ° C, 77.9 mL of triethylamine was added, and the temperature was maintained at 70 ° C and stirred for 3 hours. After cooling to room temperature, 55.9 mL of 12N hydrochloric acid water was added, and after stirring for 30 minutes, ethyl acetate was added to carry out liquid separation. After the organic phase was washed with distilled water, the recovered organic phase was concentrated and diluted with methyl 3-methoxypropionate ((B-1) as a [B] solvent), thereby obtaining a polymer containing 40% by mass Polymer solution of (A-1). The 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 monomers of the kinds and amounts used in Table 1 below were used. The Mw and Mw / Mn of each synthesized polymer are shown in Table 1. In addition, "-" indicates that no eligible monomer was used. In Synthesis Example 16 and Synthesis Example 19, when 1-butoxyethyl methacrylate obtained by protecting a carboxyl group was used as a compound providing a structural unit (II), in the obtained [A] polymer, Deprotection to form a carboxyl group.

[Synthesis Example 20] (Synthesis of polymer (a-1))

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and methyl 3-methoxypropionate (as a solvent of [B] (B-1)) 200 parts by mass. Next, 40 parts by mass of methacrylic acid and 60 parts by mass of methyl methacrylate were introduced and replaced with nitrogen, and then, stirring was started slowly. The temperature of the polymerization reaction solution The temperature was raised to 70 ° C, and the 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 further reacted at 90 ° C for 10 hours. A polymer solution of a mass% polymer (a-1). The Mw of the polymer (a-1) was 10,000.

[Synthesis Example 21] (Synthesis of Polymer (F-1))

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and diethylene glycol methyl ether ((B as a solvent of [B] -2)) 220 parts by mass, further added 13 parts by mass of methacrylic acid, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of α -methyl-p-hydroxystyrene, 10 parts by mass of styrene, and four parts of methacrylic acid 12 parts by mass of hydrogen furfuryl ester, 15 parts by mass of N-cyclohexyl cis butylene diimide and 10 parts by mass of n-lauryl methacrylate. After nitrogen substitution, slowly stir and raise the temperature of the solution to 70 The temperature was maintained at 5 ° C. for 5 hours and polymerization was performed, thereby obtaining a solution containing a polymer (F-1). The solid content concentration of the solution was 31.9% by mass. The polymer (F-1) had an Mw of 8,000 and a molecular weight distribution (Mw / Mn) of 2.3.

[Synthesis Example 22] (Synthesis of Polymer (F-2))

In a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate ((B-3) as the [B] solvent) were charged. 7 parts by mass of methacrylic acid, 18 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl ester, 15 parts by mass of styrene, and 3-methacryloxypropyl After 40 parts by mass of triethoxysilane and 20 parts by mass of glycidyl methacrylate, after nitrogen substitution, the solution was slowly stirred and the temperature of the solution was raised to 80 ° C, and the temperature was maintained for 5 hours to perform polymerization. A solution containing the polymer (F-2) was obtained. The solid content concentration of the solution was 28.8% by mass. The polymer (F-2) had a Mw of 12,000 and a molecular weight distribution (Mw / Mn) of 2.2.

[Synthesis Example 23] (Synthesis of polymer (F-3))

In a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate were added, and 7 parts by mass of methacrylic acid and methacrylic acid were further added. 28 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl ester, 25 parts by mass of styrene, and 40 parts by mass of glycidyl methacrylate. After nitrogen substitution, the solution was slowly stirred and the temperature of the solution was increased. The temperature was raised to 80 ° C, and the temperature was maintained for 5 hours to perform polymerization, thereby obtaining a solution containing the polymer (F-3). The solid content concentration of the solution was 28.8% by mass. The polymer (F-3) had an Mw of 10,000 and a molecular weight distribution (Mw / Mn) of 2.2.

[Synthesis Example 24] (Synthesis of Polymer (F-4))

In a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate were added, and 7 parts by mass of methacrylic acid and methacrylic acid were further added. After 28 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl ester, 25 parts by mass of styrene, and 40 parts by mass of 3,4-epoxycyclohexyl methyl methacrylate, after nitrogen substitution, The solution was slowly stirred and the temperature of the solution was raised to 80 ° C, and the temperature was maintained for 5 hours to perform polymerization, thereby obtaining a solution containing the polymer (F-4). The solid content concentration of the solution was 28.8% by mass. The polymer (F-4) had a Mw of 11,000 and a molecular weight distribution (Mw / Mn) of 2.1.

<Preparation of curable resin composition>

The [B] solvent, [C] polymerizable compound, [D] radical polymerization initiator, and [E] acid generator used in the preparation of the curable resin composition are shown below.

[[B] Solvent]

B-1: methyl 3-methoxypropionate

B-2: Diethylene glycol methyl ether

B-3: 3-methoxybutyl acetate

[[C] Polymerizable compound]

C-1: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate ("KAYARAD DPHA" of Nippon Kayaku Co., Ltd.)

C-2: Succinic acid-modified pentaerythritol triacrylate ("Aronix TO-756" of Toa Synthesis Corporation)

C-3: Trimethylolpropane triacrylate

C-4: Mixture of tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate ("Viscoat 802" of Osaka Organic Chemical Industry Co., Ltd.)

C-5: Succinic acid-modified dipentaerythritol pentaacrylate ("Aronix M-520" of Toa Synthesis Corporation)

[[D] radical polymerization initiator]

D-1: 2-methyl-1- (4-methylthiophenyl) -2-morpholinylpropane-1-one ("Irgacure 907" by BASF)

D-2: Ethyl ketone-1- [9-ethyl-6- (2-methylbenzylidene) -9H-oxazol-3-yl] -1- (O-acetamidooxime) (BASF Company's "Irgacure OXE02")

D-3: 2,4-Diethylthiaxanthone

[[E] Acid generator]

E-1: 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol-1,2-naphthoquinone di Azide-5-sulfonate

[Example 1]

A solution containing 100 parts by mass of (A-1) as the [A] polymer synthesized in the aforementioned Synthesis Example 8 and 150 parts by mass of (B-1) as the solvent of [B], and ( B-1) 200 parts by mass of (C-1) as a [C] polymerizable compound and 10 parts by mass of (D-1) as a [D] radical polymerization initiator were mixed, and a pore diameter of 0.2 μm was used. The thin-film filter was filtered to prepare a curable resin composition (J-1).

[Example 2 to Example 25 and Comparative Example 1 to Comparative Example 3]

A curable resin composition (J-2) was prepared in the same manner as in Example 1 except that the raw materials were mixed so as to contain the respective components of the types and contents shown in Tables 2 and 3 below. Hardening resin composition (J-25) and hardening resin composition (CJ-1) to hardening resin composition (CJ-3). "-" In Table 3 indicates that no eligible component was used.

<Evaluation>

About the prepared curable resin composition, the adhesiveness and transparency of the cured film, storage stability, and radiation sensitivity were evaluated according to the following methods.

[Adhesiveness of hardened film]

The adhesiveness of the cured film was evaluated after the retardation of the cured film pattern. Specifically, first, a curable resin composition was applied to a glass substrate using a spin coater, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a film thickness of 3.0 μm. Next, using an exposure machine ("MPA-600FA (ghi-ray hybrid)" by Canon), a mask for pattern formation with a space of 10 μm between lines and space (1: 1) was used at 700 (J / m ² ) Exposure. Thereafter, a 0.5% by mass tetramethylammonium hydroxide aqueous solution was used for development for 80 seconds at 25 ° C. by a liquid coating method. Subsequently, the glass was washed with flowing water for 1 minute with ultrapure water, and then dried to form a pattern on the glass substrate. The developed substrate was observed with an optical microscope, and the presence or absence of pattern peeling was confirmed. The adhesion of the pattern was evaluated according to the following judgment criteria.

Hardly found pattern peeling: "○"

Slightly found pattern peeling: "△"

When the pattern is peeled off and there is almost no pattern left on the substrate: "×"

[Transparency of hardened film]

A coating film having a thickness of 3.0 μm was formed on a silicon substrate using a curable resin composition. The silicon substrate was heated at 220 ° C. for 1 hour in a clean oven to form a cured film. With respect to the cured film, a transmittance at a wavelength of 400 nm was measured using a spectrophotometer ("150-20 type dual beam" by Hitachi, Ltd.). The values of the transmittance (%) are shown in Tables 2 and 3. Regarding transparency, when the transmittance is 90% or more, it can be evaluated as good, and when it is less than 90%, it can be evaluated as poor.

[Evaluation of storage stability]

The curable resin composition was left in an oven at 40 ° C for one week. Measure the initial viscosity (1) and the viscosity (2) after standing for 1 week, according to | viscosity (2)-viscosity (1) | × 100 / Viscosity (1) to calculate the viscosity change rate (%). | Viscosity (2)-Viscosity (1) | refers to the absolute value of the difference between viscosity (2) and viscosity (1). The values of the viscosity change rate (%) are shown in Tables 2 and 3. Regarding storage stability, a case where the viscosity change rate is 5% or less can be evaluated as good, and a case where it exceeds 5% can be evaluated as poor.

[Radiation sensitivity]

After the curable resin composition was coated on a glass substrate using a spin coater, it was pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a film thickness of 3.0 μm. Next, an exposure machine ("MPA-600FA (ghi-ray hybrid) from Canon") was used, and a mask having a line and space (1: 1) pattern of 10 μm was separated, and the exposure amount was set as a variable to coat the coating film. Expose radiation. Thereafter, development was performed for 80 seconds at 25 ° C. by a liquid coating method using a 0.5% by mass tetramethylammonium hydroxide aqueous solution. Then, the pattern was formed on a glass substrate by running-water washing with ultrapure water for 1 minute and then drying. At this time, investigate the space of 10 μm. The amount of exposure required to completely dissolve the pattern. The values of the exposure amount (J / m ² ) are shown in Tables 2 and 3. The radiation sensitivity can be evaluated as good when the exposure amount is 500 (J / m ² ) or less.

[table 3]

From the results of Tables 2 and 3, it is clear that the curable resin composition of the examples has excellent adhesion and transparency of the cured film, storage stability, and excellent radiation sensitivity when the radiation-curable resin composition is formed. In contrast, the curable resin composition of the comparative example did not obtain good results with respect to all of these properties.

[Industrial availability]

The curable resin composition of the present invention can form a cured film having excellent adhesion and transparency, and has excellent 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, a protective film, a spacer, and the like of a display element. Therefore, these can be suitably used in the manufacturing process of a display element, such as a liquid crystal device.

Claims (11)

A curable resin composition containing a polymer and a solvent, the polymer having a structural unit represented by the following formula (1) and a structural unit containing an acidic group, In formula (1), 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 and Forms a ring structure with 3 to 20 member rings together with the carbon atoms to which they are bonded; R ⁴ is (a) a (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, (b) a (a) hydrocarbon group The carbon-to-carbon group contains at least one group selected from the group consisting of an oxygen atom, a sulfur atom, -SO- and -SO _2- , or a hydrogen possessed by the (c) (a) hydrocarbon group and (b) group. Some or all of the atoms are substituted with at least one member selected from the group consisting of a halogen atom, a cyano group, a nitro group, a carboxyl group, a sulfinyl group, a mercapto group, and an alkoxy group having 1 to 12 carbon atoms; n is an integer from 1 to 6; when n is 2 or more, multiple R ¹ may be the same or different, multiple R ² may be the same or different, multiple R ³ may be the same or different; R ⁵ is -COO- *; * Indicates a site bonded to R ⁴ ; R ⁶ is a hydrogen atom, a methyl group, or a fluorinated methyl group; wherein, when n is 1, R ⁴ is (d) (n + 1) having a carbon number of 1 to 20 ) Valent cyclic hydrocarbon group, (e) contains at least one selected from the group consisting of oxygen atom, sulfur atom, -SO- and -SO ₂ -between carbons and carbons of (d) cyclic hydrocarbon group. (F) contains at least 1 selected from the group consisting of a sulfur atom, -SO- and -SO ₂ -between the carbon-carbon of the (n + 1) -valent chain hydrocarbon group having 1 to 20 carbon atoms. Part of or all of the hydrogen atoms of (g) (d) cyclic hydrocarbon group, (e) group and (f) group are selected from halogen atom, cyano, nitro, carboxyl, and sulfinic acid. A group substituted with at least one of the group consisting of a group, a mercapto group and an alkoxy group having 1 to 12 carbon atoms. The curable resin composition according to item 1 of the patent application scope, further comprising: a polymerizable compound having an ethylenically unsaturated bond. The curable resin composition according to claim 1 or claim 2, further comprising: at least one selected from the group consisting of a radical polymerization initiator and an acid generator. The curable resin composition according to item 3 of the scope of patent application, which contains the radical polymerization initiator. The curable resin composition according to item 4 of the scope of patent application, wherein the radical polymerization initiator is radiation-sensitive. The curable resin composition according to item 3 of the scope of patent application, which contains the acid generator. The curable resin composition according to item 6 of the scope of patent application, wherein the acid generator is radiation-sensitive. The curable resin composition according to item 1 or 2 of the scope of patent application, which is used for forming a cured film for a display element as an interlayer insulating film, a protective film, or a spacer. A cured film for a display element, which serves as an interlayer insulating film, a protective film, or a spacer, and is formed of a curable resin composition as described in item 8 of the scope of patent application. A method for forming a cured film for a display element, comprising: a step of forming a coating film on a substrate; a step of irradiating at least a portion of the coating film with radiation; a step of developing a coating film irradiated with the radiation; and A step of heating the developed coating film; and forming the coating film from a curable resin composition according to item 5 or 7 of the scope of patent application. A display element includes the cured film for a display element according to item 9 of the scope of patent application.