TW201534628A - Curable resin composition, cured film for display device, method for forming cured film for display device, and display device - Google Patents

Abstract

The invention provides a curable resin composition containing a polymer and a solvent, and the polymer has a structural unit represented by the following formula (1) and a structural unit containing a carboxyl group. In the formula (1), R1, R2 and R3 represent a hydrogen atom or a monovalent hydrocarbon group. R4 represents (a) an (n+1) valent hydrocarbon group, (b) a group containing at least one selected from the group consisting of an oxygen atom, a sulfur atom, -SO- and -SO2- between carbon-carbon of the hydrocarbon group (a), or (c) a group formed by substituting a portion or all of hydrogen atoms owned by the hydrocarbon group (a) and the group (b) with at least one selected from the group consisting of a halogen atom, a cyano group, a nitro group, a carboxyl group, a sulfino group, a mercapto group and an alkoxy group. R5 represents 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 of forming the cured film for a display element, and a display element.

In a display element such as a liquid crystal display element or an organic electroluminescence (EL), a cured film is provided which is used to hold an insulating interlayer insulating film between wirings arranged in a layer shape, and to suppress a touch panel ( The touch panel is a protective film for deteriorating or damaging the electronic component, a spacer for setting a liquid crystal layer or the like as a fixed film thickness, or the like. In addition to the excellent adhesion to a substrate, a transparent conductive film, wiring, etc., such a cured film is also required to have excellent transparency.

In the formation of the cured film, a curable resin composition is used from the viewpoint of obtaining a small number of steps for obtaining a desired pattern shape and obtaining sufficient flatness. As such a curable resin composition, a high surface hardness can be obtained. In the meantime, a polymer having an ethylenically unsaturated bond in a side chain has been studied, and as the polymer, it is known to react an epoxy group-containing unsaturated compound with a polymer having a carboxyl group. The unsaturated compound containing an isocyanate group is reacted with a polymer having a carboxyl group and a hydroxyl group (refer to Japanese Laid-Open Patent Publication No. Hei 11-174464 and JP-A-2002-20442).

Among them, the demand for the properties, particularly the adhesion, of the cured film has recently been further improved, and the conventional curable resin composition cannot satisfy the above requirements. Further, from the viewpoint of process stability, improvement in storage stability is also required for the conventional curable resin composition.

[Prior Art Literature] [Patent Literature]

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

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

The present invention has been made in view of the above, and it is an object of the invention to provide a curable resin composition which is excellent in adhesion and transparency and which has excellent storage stability.

The invention to solve the above problem is a curable resin composition containing a polymer (hereinafter also referred to as "[A] polymer") and a solvent (hereinafter also The polymer has a structural unit represented by the following formula (1) (hereinafter also referred to as "structural unit (I)") and a structural unit containing an acidic group (hereinafter also referred to as "[B] solvent"). It is called "structural unit (II)").

(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; and 2 or more of R ¹ , R ² and R ³ may be bonded to each other; And together with the carbon atom to which they are bonded, form a ring structure having a ring number of 3 to 20; R ⁴ is (a) a (n+1)-valent hydrocarbon group having 1 to 20 carbon atoms, and (b) a (a) hydrocarbon group. The carbon-carbon contains at least one group selected from the group consisting of an oxygen atom, a sulfur atom, -SO-, and -SO ₂ -, or (c) a (a) hydrocarbon group and (b) group. a part or all of a 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 sulfinic acid group, a fluorenyl group, and an alkoxy group having 1 to 12 carbon atoms. n is an integer of 1 to 6; when n is 2 or more, a plurality of R ^{1 's} may be the same or different, and a plurality of R ^{2 's} may be the same or different, and a plurality of R ^{3 's} 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 for solving the above 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.

Still another invention for solving the above problem is a method of forming a cured film for a display element, comprising: a step of forming a coating film on a substrate; and a step of irradiating at least a portion of the coating film with radiation; a step of developing a coating film irradiated with radiation; and a step of heating the developed coating film, and forming the coating film from the curable resin composition.

Still another invention to solve the above problem is a display element including the cured film for the display element.

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

<Curable resin composition>

The curable resin composition of the present invention contains the [A] polymer and the [B] solvent. The curable composition may contain [C] a polymerizable compound having an ethylenically unsaturated bond ( Also referred to as "[C] polymerizable compound"), [D] radical polymerization initiator, [E] acid generator, and/or [F] are selected to be selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. A polymer obtained by copolymerizing at least one of the groups of the epoxy group-containing unsaturated compound (hereinafter also referred to as "[F] polymer") as a preferred component may be used as a preferred component. And other arbitrary components are contained in the range of the effect of this invention.

In the curable resin composition, since the (meth)acrylonyl group of the structural unit (I) of the [A] polymer can be polymerized by heating, it can function as a thermosetting resin composition. In addition, 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 will be described later. Examples of the radiation include electromagnetic waves such as visible light, ultraviolet light, far ultraviolet light, and X-ray, and charged particle beams such as an electron beam and an α beam.

Each component will be described below.

<[A]polymer>

The [A] polymer is a polymer having a structural unit (I) and a structural unit (II). The polymer [A] preferably has a structural unit other than the structural unit (I) and the structural unit (II) in addition to the structural unit, and does not contain any of a hydroxyl group, an amine group, and an imine group. The unit (III) may contain other structural units other than the structural unit (I) to the structural unit (III) within a range that does not impair the effects of the present invention. The [A] 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 is excellent in storage stability. In addition, as will be described later When the radiation curable resin composition is formed, the radiation sensitivity is excellent. The reason why the curable resin composition has the above-described effects by the above-described configuration is not necessarily clear, but 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 conventional curable resin composition in that it does not have a hydroxyl group formed 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. As a result, it is considered that the adhesion of the cured film is improved by, for example, suppressing penetration of the aqueous alkaline solution into the pattern in the developing step. Further, the structural unit (I) of the [A] polymer does not have a hydroxyl group, an imine group or the like, and it is considered that the deterioration at the time of heating by these groups is suppressed, and the transparency of the cured film is improved. Further, it is considered that the condensation of the hydroxyl group, the imine group, and the like with the carboxyl group of the structural unit (II) or the like is not caused, so that the storage stability is improved. In the case of the radiation curable resin composition, it is considered that the activity of the radical or the acid is increased because the hydroxyl group or the imine group is not present in the vicinity of the ethylenically unsaturated bond or the like, and as a result, the radiation sensitivity is further improved.

Each structural unit will be described below.

[Structural 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 each independently represent 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 atom to which they are bonded form a ring structure having a ring number of 3 to 20. R ⁴ is (a) a (n+1)-valent hydrocarbon group having 1 to 20 carbon atoms, and (b) a carbon-carbon intercalation between (a) a hydrocarbon group selected from an oxygen atom, a sulfur atom, -SO-, and -SO ₂ - at least one of the groups in the group, or (c) the (a) hydrocarbon group and a part or all of the hydrogen atoms of the (b) group are selected from the group consisting of a halogen atom, a cyano group, a nitro group, a carboxyl group, and a sub A group obtained by substituting at least one of a group consisting of a sulfonic acid group, a fluorenyl 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 's} may be the same or different, and a plurality of R ^{2 's} may be the same or different, and a plurality of R ^{3 's} may be the same or different. R ⁵ is a single bond or -COO-*. * indicates the part bonded to R ⁴ . R ⁶ is a hydrogen atom, a methyl group or a fluorinated methyl group.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ , R ² and R ³ include a monovalent chain hydrocarbon group having 1 to 20 carbon atoms and a monovalent alicyclic ring having 3 to 20 carbon atoms. A hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

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

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

Examples of the monovalent aromatic hydrocarbon group include an aryl group such as a phenyl group, a tolyl group, a xylyl group, a mesityl group, a naphthyl group or a fluorenyl group; a benzyl group, a phenethyl group, a naphthylmethyl group, and a decylmethyl group; Isoarylalkyl and the like.

Ring structure R ^1, R ² and R ³ bonded to each other two or more are formed and they are bonded together with the carbon atom number of 3 to 20-membered ring include for example: structure cyclopropene, cyclobutene structure, a cyclopentene structure, a cyclohexene structure, a cyclooctene structure, a cycloolefin structure such as a norbornene structure, and the like.

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

(a) The (n+1)-valent hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴ may, for example, be removed from the group exemplified as the monovalent hydrocarbon group represented by R ¹ , R ² and R ³ . A group of hydrogen atoms and the like.

(b) The group having an oxygen atom between the carbon-carbon of the (a) hydrocarbon group represented by R ⁴ is, for example, ^two of the hydrocarbon groups exemplified as R ¹ , R ² and R ³ bonded to an oxygen atom. A group obtained by removing (n+1) hydrogen atoms from the obtained ether.

R ⁴ represented by (b) in (a) hydrocarbon group of a carbon - group between carbon containing a sulfur atom, for example, include: since as R ^1, hydrocarbon groups R ² and R ³ are exemplified in two sulfur atoms bonded A group obtained by removing (n+1) hydrogen atoms from the obtained thioether.

R ⁴ represented by (b) in (a) hydrocarbon group of a carbon - carbon content between the -SO- group include for example: from a hydrocarbon group R ^1, R ² and R ³ in the illustrated embodiment with two -SO- A group obtained by removing (n+1) hydrogen atoms from an anthracene compound in which a sulfur atom is bonded.

R ⁴ represented by (b) in (a) hydrocarbon group of a carbon - containing between carbon -SO ₂ -, for example, include a base: a hydrocarbon group from R ^1, R ² and R ³ in the illustrated embodiment with two -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 a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group.

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

R ⁴ is preferably a (a) hydrocarbon group or a (b) group, and more preferably a group obtained by removing (n+1) hydrogen atoms from an alkane, a cycloalkane, an aromatic hydrocarbon or a cycloalkyl alkyl ether, and further Preferably, (n+1) hydrogen atoms are removed from an alkane having 2 to 6 carbon atoms, a cycloalkane having 3 to 15 carbon atoms, an aromatic hydrocarbon having 6 to 18 carbon atoms, and a cycloalkyl alkyl ether having 5 to 20 carbon atoms. The group formed is particularly preferably a group obtained by removing (n+1) hydrogen atoms from an ethane group, cyclohexane, adamantane, benzene or adamantyl ethyl ether.

From the viewpoint of the ease of the synthesis of the monomer of the structural unit (I), n is preferably an integer of from 1 to 3, more preferably 1 or 2, and further improves the curability and the composition for forming a radiation curable resin. From the viewpoint of the radiation sensitivity, n is more preferably 2.

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

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

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

For the structural unit (I), for example, a structural unit represented by the following formula (1-1) to formula (1-12) (hereinafter also referred to as "structural unit (I-1) to structural unit (I-12)) ")Wait.

[Chemical 3]

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

Among them, the structural unit (I-1) to the structural unit (I-7) are preferable.

The method of incorporating the structural unit (1) into the [A] polymer is not particularly limited. For example, as shown in the following scheme, a structural unit represented by the following formula (1') is synthesized by polymerization using a monomer represented by the following formula (i). The polymer is subjected to dehydrohalogenation reaction in the presence of a base such as triethylamine to form 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.

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

The monomer represented by the formula (i) can be synthesized, for example, by reacting a compound having a (meth)acrylonyl group and a hydroxyl group such as 2-hydroxyethyl (meth)acrylate with 3-chloropropionate. a β-halo-carboxyindole halide such as chlorine in the presence of a base such as pyridine in dichloro The dehydrohalogenation condensation reaction is carried out in a solvent such as an alkane.

The content ratio of the structural unit (I) is preferably from 5 mol% to 90 mol%, more preferably 10 mol%, based on the ratio of the total monomers used in the synthesis of the [A] polymer. %~70% by mole, further preferably 15% by mole to 40% by mole. By setting the content ratio to the above range, the adhesion and transparency of the cured film, the storage stability, and the radiation sensitivity when the radiation curable resin composition is formed can be further improved.

[Structural 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 preferable. The [A] polymer has a structural unit (II), and the curable resin composition exhibits alkali developability and functions as an alkali-soluble resin.

Examples of the monomer which provides the structural unit (II) include an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, a mono[(meth)acryloyloxyalkyl]ester of a polyvalent carboxylic acid, and an unsaturated second. An anhydride of a carboxylic acid, a mono(meth)acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals, 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, crotonic acid, and the like.

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)acrylenyloxyalkyl]ester of a polyvalent carboxylic acid include maleic acid mono[(meth)acryloyloxyethyl]ester, succinic acid mono [2] - (A Base) acryloyloxyethyl]ester, mono[2-(methyl)propenyloxyethyl] phthalate, and the like.

The anhydride of the unsaturated dicarboxylic acid is, for example, an anhydride of the compound exemplified as the dicarboxylic acid.

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

Examples of the unsaturated polycyclic compound having a carboxyl group and an anhydride thereof include 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, and 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.

Further, a compound obtained by protecting the carboxyl group of the carboxylic acid or the like may be used as the monomer which provides the structural unit (II). The protected carboxyl group in the compound may, for example, be a group in which a hydrogen atom of a carboxyl group is substituted by -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 of 1 to 20, R ^c is a monovalent hydrocarbon group having 1 to 20 carbon atoms, 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 above 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 which protects the carboxyl group of the carboxylic acid or the like include 1-butoxyethyl (meth)acrylate, 1-ethoxyethyl (meth)acrylate, and 1-ethyl (meth)acrylate. Oxybutyl acrylate and the like.

Among them, the copolymerization of the monomer of the structural unit (II) is provided and it is easy to obtain. From the viewpoint of the solubility of the [A] polymer in the aqueous alkaline solution, it is preferably an unsaturated monocarboxylic acid or a compound which protects the carboxyl group of the unsaturated monocarboxylic acid, and more preferably methacrylic acid or methyl group. 1-butoxyethyl acrylate.

The content ratio of the structural unit (II) is preferably from 5 mol% to 50 mol%, more preferably 10 mol%, based on the ratio of the total monomers used in the synthesis of the [A] polymer. %~40% by mole, further preferably 15% by mole to 355% by mole. By setting the content ratio to the above range, the alkali developability of the curable resin composition can be set to a more appropriate property.

[Structural 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 which does not contain any of a hydroxyl group, an amine group and an imine group. By the structural unit (III) of the [A] polymer, the storage stability of the curable resin composition can be further improved.

Examples of the monomer which provides the structural unit (III) include alkyl methacrylate, cycloalkyl methacrylate, alkyl acrylate, cycloalkyl acrylate, aromatic methacrylate, and acrylic acid aromatic. Examples of the esters and the like include the following compounds and the like, and do not have any of a hydroxyl group, an amine group, and an imine group: an unsaturated dicarboxylic acid diester, a bicyclic unsaturated compound, and an N-maleimide compound. An unsaturated aromatic compound, a conjugated diene, an unsaturated compound having a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton or a pyran skeleton, or another unsaturated compound.

Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, second butyl methacrylate, and methyl propyl acrylate. Tert-butyl olefinate, 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, and tricyclo [5.2.1.0 ^2,6 ]decane-8-yl methacrylate. Tricyclo [ 0.45.1.0 ^2,6 ]decane-8-yloxyethyl methacrylate, isobornyl methacrylate, and the like.

The alkyl acrylate may, for example, be methyl acrylate, ethyl acrylate, n-butyl acrylate, second butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate or n-lauryl acrylate. , tridecyl acrylate, n-stearyl acrylate, and the like.

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

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

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

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

Examples of the bicyclic unsaturated compound include bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2- Alkene, 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 Alkylcarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(tert-butoxycarbonyl)bicyclo[2.2.1] Hept-2-ene, 5,6-di(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene, and the like.

Examples of the N-maleimide compound include N-phenyl maleimide, N-cyclohexyl maleimide, and N-benzyl maleimide. N-(4-hydroxyphenyl)maleimide, N-succinimido-3-synyleneimide benzoate, N-succinimide-4-cis Butenylimine butyrate, N-succinimide-6-methyleneimide hexanoate, N-succinimide-3-oxenimide propionic acid Ester, N-(9-acridinyl) maleimide, and the like.

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

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

Examples of the unsaturated compound having a tetrahydrofuran skeleton include tetrahydrofurfuryl methacrylate, 2-methylpropenyloxy-tetrahydrofurfuryl propionate, and 3-(methyl)propenyloxytetrahydrofuran. 2-ketone and the like.

Examples of the unsaturated compound containing a furan skeleton include 2-methyl-5-(3- Furyl)-1-penten-3-one, decyl (meth) acrylate, 1-furan-2-butyl-3-en-2-one, 1-furan-2-butyl-3- Methoxy-3-en-2-one, 6-(2-furyl)-2-methyl-1-hexen-3-one, 6-furan-2-yl-hex-1-ene-3 a ketone, 2-furan-2-yl-1-methyl-ethyl acrylate, 6-(2-furyl)-6-methyl-1-hepten-3-one, and the like.

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

Examples of the unsaturated compound containing a pyran skeleton include 4-(1,4-dioxa-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 the other unsaturated compound include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Among them, from the viewpoint of providing copolymerizability of the monomer of the structural unit (III), an alkyl methacrylate or an unsaturated aromatic compound is preferable, and methyl methacrylate or styrene is more preferable.

The content ratio of the structural unit (III) is preferably from 0 mol% to 80 mol%, more preferably 20 mol%, based on the ratio of the total monomers used in the synthesis of the [A] polymer. % to 75 mol%, further preferably 40 mol% to 70 mol%. By setting the content ratio to the above 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 imido group. The content ratio of the other structural unit is preferably 20 mol% or less, more preferably 5 mol% or less, and further preferably 0 mol%, based on the ratio of the total of the 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, even more preferably 40% by mass to 70% by mass based on the total solid content of the curable resin composition. .

<[A] Synthesis Method of Polymer>

The [A] polymer can be synthesized as described above by, for example, using a radical polymerization initiator in a solvent, and dehalogenating after polymerization as in the monomer represented by the formula (i). The hydrogen reacts to provide a monomer of the structural unit (I), a monomer which provides the structural unit (II), a monomer which provides the structural unit (III), and the like, and the resulting polymer is subjected to a dehydrohalogenation reaction to form a structure. Unit (I).

Examples of the solvent include an alcohol, a chain ether, a cyclic ether, a glycol ether, an ethylene glycol alkyl ether acetate, a diethylene glycol alkyl ether, a propylene glycol monoalkyl ether, and a propylene glycol monoalkyl ether acetate. Ester, propylene glycol monoalkyl ether propionate, aromatic hydrocarbon, ketone, 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, tetrahydropyran, and the like.

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

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

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

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, and propylene glycol monobutyl ether propionate.

Examples of the aromatic hydrocarbons include toluene, xylene, and the like.

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

Examples of the 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 propyl propionate, methyl hydroxyacetate, ethyl hydroxyacetate, 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, more preferably methyl 3-methoxypropionate. These solvents may 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, preferred is 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethyl Valeronitrile).

The amount of the radical polymerization initiator to be used is preferably from 1 mol% to 10 mol%, more preferably from 2 mol% to 8 mol%, based on 100 mols of the monomers used in the polymerization. One type or two or more types of radical polymerization initiators can be used.

In the polymerization reaction, a molecular weight modifier can be used in order to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid, and the like. Mercaptans; xanthogens such as dimethyl xanthate, diisopropyl xanthogen disulfide; terpinolene, α-methylstyrene dimer, and the like.

The amount of the molecular weight modifier to be used may be appropriately selected depending on the molecular weight of the desired [A] polymer, but is preferably 100 mol%, preferably 0.1 mol% to 10 mol%, based on the total of the monomers used in the polymerization. More preferably, it is 0.5 mol% - 5 mol%. One type or two or more types of molecular weight modifiers can be used.

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

The solvent used for the dehydrohalogenation reaction after the polymerization reaction can be exemplified as the solvent which can be used for the polymerization, and it is preferred to use the solvent used in the polymerization as it is. That is, it is preferred to add a base to the polymerization reaction liquid and carry out a dehydrohalogenation reaction.

Examples of the base used in the dehydrohalogenation reaction include, for example: Amines such as diethylamine, dipropylamine, trimethylamine, triethylamine, tripropylamine, pyrrolidine, acridine, pyridine, triethanolamine; metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide; sodium carbonate a metal carbonate such as potassium carbonate or calcium carbonate; a metal hydrogencarbonate such as sodium hydrogencarbonate, potassium hydrogencarbonate or calcium hydrogencarbonate; a metal alkoxide such as sodium methoxide or potassium t-butoxide; and the like.

The amount of the base used in the dehydrohalogenation reaction is preferably from 1 mole to 10 moles, more preferably from 1.5 moles to 7 moles, and even more preferably from 2 moles to 5 moles, relative to the liberated hydrogen halide of 1 mole. ear.

The temperature at which the dehydrohalogenation reaction is carried out is usually from 0 ° C to 150 ° C, preferably from 50 ° C to 100 ° C.

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

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

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

<[B]solvent>

The solvent [B] can be used as long as it dissolves the component in a homogeneous manner and does not react with the component. The solvent of the [B] solvent is the same as the solvent exemplified as the solvent used for the polymerization of the synthetic [A] polymer. [B] The solvent may be used alone or in combination of two or more.

The solvent [B] is preferably propylene glycol monomethyl ether, propylene glycol monoethyl ether or ethylene glycol monomethyl ether acetate, from the viewpoints of solubility, dispersibility of a solid component, 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-glycol 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-amyl formate , isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, more preferably methyl 3-methoxypropionate, diethylene Alcohol methyl ether, 3-methoxybutyl acetate. Further, the [B] solvent 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 benzoic acid B. Ester, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethyl carbonate, propyl carbonate, ethylene glycol monophenyl ether acetate, and the like.

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

<[C] polymerizable compound>

The [C] polymerizable compound is a polymerizable compound having an ethylenically unsaturated bond. The curable resin composition further contains a [C] polymerizable compound, and the adhesion of the cured film can be further improved when a negative pattern is formed, and the thermal stability of the pattern shape can be improved when a positive pattern is formed. The [C] polymerizable compound may be cured by heating, but it may be more effectively cured 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)acryl fluorenyl group, and a styryl group.

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

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

Examples of the monofunctional acrylate include ω-carboxypolycaprolactone 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 four. Ethylene glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, bisphenoxy Base B Alcohol bis(meth) acrylate, dimethylol tricyclodecane di(meth) acrylate, 2-hydroxy-3-(methyl) propylene methoxy propyl methacrylate, trimethylol Propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol (Meth) acrylate, tripentaerythritol octa (meth) acrylate, tris(2-(methyl) propylene methoxyethyl) phosphate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid a modified pentaerythritol triacrylate, a succinic acid-modified dipentaerythritol pentaacrylate, a compound having a linear alkyl group and an alicyclic structure and having two or more isocyanate groups, and one or more hydroxyl groups in the molecule; A polyfunctional (meth) acrylate compound such as a (meth)acrylic acid urethane obtained by reacting a compound having three to five (meth) acryloxy groups.

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

[C] Commercial products of the polymerizable compound include, for example, 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 Synthetic Company); KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD MAX-3510 (above, Nippon Kayaku Co., Ltd.); Viscoat 295, Viscoat 300, Biscott ( Viscoat 360, Viscoat 802, Viscoat GPT, Viscoat 3PA, Viscoat 400 (above, Osaka Organic Chemical Industry Co., Ltd.); New boundary of acid ester compounds R-1150 (New Frontier R-1150) (First Industrial Pharmaceutical Company); KAYARAD DPHA-40H, KAYARAD DPEA-12, HUX-5000 (above, Nippon Chemical Pharmaceutical Co., Ltd.); UN-9000H (Guanshang Industrial Co., Ltd.); 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 Synthetic Company); 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-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU -4001 (above, Nippon Kayaku Co., Ltd.); Art Resin UN-9000PEP, 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 Art Resin SH-500B (above, Gensei Industrial Co., Ltd.); Viscoat 260, Viscoat 312, Viscoat 335HP (above, Osaka Organic Chemical Industry Co., Ltd.), etc. .

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

The content of the [C] polymerizable compound is preferably 20 parts by mass or more and 200 parts by mass or less, and more preferably 40 parts by mass or more and 160 parts by mass or less with respect to 100 parts by mass of the [A] polymer. When the content of the [C] polymerizable compound is in the above 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 Starter>

The [D] radical polymerization initiator is a component which produces an active species which can initiate radical polymerization of a polymerizable compound. The curable resin composition can further improve the adhesion of the cured film by containing a [D] radical polymerization initiator. [D] The radical polymerization initiator may, for example, be a [D1] thermosensitive radical polymerization initiator which decomposes by heating and generates a radical, and a [D2] radiation which generates a radical by irradiation of radiation. A free radical polymerization initiator or the like. The form of the [D] radical polymerization initiator in the curable resin composition may be a form of a low molecular compound as described later, a form incorporated as a part of [A] a polymer, or the like. The form of both. One or two or more kinds of [D] radical polymerization initiators may be contained.

[[D1] Thermotropic Radical Polymerization Starter]

[D1] A thermosensitive radical polymerization initiator is a compound which decomposes by heating and generates a radical. When the curable resin composition contains a [D1] thermosensitive radical polymerization initiator, it can function as a thermosetting resin composition.

[D1] The thermosensitive radical polymerization initiator may, for example, be azobisisobutyronitrile (AIBN) or 2,2'-azobis(4-methoxy-2,4-dimethylpentane). Nitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-couple An azo radical initiator such as nitrogen diisobutyrate; a peroxide radical initiator such as benzammonium peroxide, t-butyl hydroperoxide or cumene hydroperoxide.

[[D2] Radiation-induced Radical Polymerization Starter]

[D2] Radiation-induced linear radical polymerization initiator is produced by irradiation of radiation A free radical compound. When the curable resin composition contains a [D2] radiation-sensitive radical polymerization initiator, it can function as a radiation curable resin composition, and [A] a polymer or a [C] polymerizable compound can be produced. The radicals are polymerized, thereby exerting a negative-type radiation linear characteristic. The curable resin composition can further improve the radiation sensitivity by containing a [D2] radiation-sensitive radical polymerization initiator.

[D2] The radiation-sensitive linear radical polymerization initiator may, for example, be an O-indenyl hydrazine compound, an acetophenone compound, a biimidazole compound or a thioxanthone compound.

Examples of the O-indenyl ruthenium compound include 1-[4-(phenylthio)-2-(O-benzoguanidinopurine)], 1,2-octanedione 1-[4-(phenylthio). )-2-(O-benzylidene hydrazide)], ethyl ketone-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1 -(O-acetylindenyl), 1-[9-ethyl-6-benzylidenyl-9.H.-oxazol-3-yl]-octane-1-one oxime-O-acetic acid Ester, 1-[9-ethyl-6-(2-methylbenzhydryl)-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-one oxime-O-benzoate Ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylbenzoguanidino)-9.H.-oxazol-3-yl]-1-(O-acetamidine) Ketone), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzylidene)-9.H.-carbazol-3-yl]-1 -(O-acetinyl), ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzylidene)-9.H.-carbazol-3-yl ]-1-(O-acetamidoxime), ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxa) Cyclopentyl)methoxybenzylidene}-9.H.-carbazol-3-yl]-1-(O-ethylindenyl) and the like.

Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound.

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

The α-hydroxyketone compound may, for example, be 1-phenyl-2-hydroxy-2-methylpropan-1-one or 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane- 1-ketone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl 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 thioxanthone compound include thioxanthone, 2,4-diethylthiaxanone, 2-isopropylthioxanthone, 2,4-diisopropylthiaxanone, and 2 - Chlorothione and the like.

Among them, an O-indenyl hydrazine compound, an acetophenone compound, and a thioxanthone compound are preferable, and an O-indenyl hydrazine compound, an α-amino ketone compound, a thioxanthone compound, and more preferably an ketone. -1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-ethylindenyl), 2-methyl-1- (4-Methylthiophenyl)-2-morpholinylpropan-1-one, 2,4-diethylthiaxanone.

The content of the [D] radical polymerization initiator is preferably 1 part by mass or more and 40 parts by mass or less, and more preferably 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the [A] polymer. By setting the content of the [D] radical polymerization initiator In the above range, the curable resin composition can further improve the adhesion of the cured film, and when it is a radiation curable resin composition, the radiation sensitivity can be further improved.

<[E]acid generator>

The [E] acid generator is a compound that produces an acid. Examples of the acid to be produced include a carboxylic acid, a sulfonic acid, and the like. The curable resin composition can improve characteristics such as heat resistance and hardness of the cured film by containing an [E] acid generator. The [E] acid generator may, for example, be an [E1] thermosensitive acid generator that generates an acid by heating, or an [E2] sensitizing radioactive acid generator that generates an acid by irradiation with radiation. The form of the [E] acid generator in the curable resin composition may be a form of a low molecular compound as described later, a form incorporated as a part of [A] a polymer, or the like, and both of them. form. The curable resin composition may contain one or more kinds of [E] acid generators.

[[E1] sensible acid generator]

[E1] A sensible acid generator is a compound which generates an acid by heating. When the curable resin composition contains the [E1] sensible acid generator, it can function as a thermosetting resin composition.

[E1] The thermosensitive acid generator may, for example, be an onium salt such as a phosphonium salt or a benzothiazolium salt, an ammonium salt or a phosphonium salt. Specific examples of the sensible acid generator compound include the same compounds as those exemplified as the component [E] described in JP-A-2010-134442.

[[E2] Radiation-sensitive acid generator]

[E2] The radiation-sensitive linear acid generator is acidized by irradiation of radiation. Compound. When the curable resin composition contains a [E2] sensitizing radioactive acid generator, it can function as a radiation curable resin composition. The curable resin composition can further improve the radiation sensitivity by containing the [E2] sensitizing radioactive acid generator.

Examples of the [E2] acid generator include a quinonediazide compound, an oxime sulfonate compound, a sulfonium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a hydrazine compound, a sulfonate compound, and a carboxy group. An acid ester compound or the like.

The quinonediazide compound generates a carboxylic acid by irradiation with radiation. When the curable resin composition contains a quinonediazide compound as an [E2] acid generator, the carboxylic acid produced increases the solubility of the radiation-irradiated portion in the alkaline developer, thereby exerting a positive-type radiation. characteristic.

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

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

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

Examples of the hexahydroxybenzophenone include 2,4,6,3',4',5'-hexahydroxybenzophenone, 3,4,5,3',4',5'-hexahydroxydiene. Benzophenone and the like.

Examples of the (polyhydroxyphenyl)alkane include bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, tris(p-hydroxyphenyl)methane, 1,1,1-tri ( p-Hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3,4-trihydroxyphenyl)propane, 1,1,3-tri 2,5-Dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl] Phenyl]ethylidene]bisphenol, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl-1, 1'-spirobi-5,6,7,5',6'-hexanol, 2,2,4-trimethyl-7,2',4'-trihydroxyflavan and the like.

Other parent cores include, for example, 2-methyl-2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxychroman, 1-[1-{3-( 1-[4-hydroxyphenyl]-1-methylethyl)-4,6-dihydroxyphenyl}-1-methylethyl]-3-[1-{3-(1-[4- Hydroxyphenyl]-1-methylethyl)-4,6-dihydroxyphenyl}-1-methylethyl]benzene, 4,6-bis{1-(4-hydroxyphenyl)-1- Methyl ethyl}-1,3-dihydroxybenzene and the like.

Preferred in the mother nucleus are 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tris(p-hydroxyphenyl)ethane, 4,4'-[1-[4- [1-[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol.

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

The synthesis of the quinonediazide compound can be carried out by a known condensation reaction. In the condensation reaction, relative to the number of OH groups in the phenolic compound or the alcoholic compound, A 1,2-naphthoquinonediazidesulfonium halide corresponding to preferably from 30 mol% to 85 mol%, more preferably from 50 mol% to 70 mol%, may be used.

Further, as the quinonediazide compound, 1,2-naphthoquinonediazidesulfonamide which is obtained by changing the ester bond of the parent nucleus just described to a guanamine bond, for example, 2, 3, 4 can be suitably used. - Triaminobenzophenone-1,2-naphthoquinonediazide-4-sulfonamide and the like.

The [E2] acid generator is other than the quinonediazide compound, for example, an oxime sulfonate compound, a sulfonium salt, a sulfonium imide compound, a halogen-containing compound, a diazomethane compound, a hydrazine compound, a sulfonate compound, In the case of a carboxylic acid ester compound or the like, the curable resin composition is reacted and hardened by a [F] polymer or the like which will be described later by the action of an acid generated, whereby a negative-type radiation characteristic can be exhibited normally. .

The oxime sulfonate compound may, for example, be (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile or (5-octylsulfonate). Hydroxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophene-2-ylidene)-(2 -methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyl) Oxyimido)-(4-methoxyphenyl)acetonitrile and the like.

Examples of the onium salt compound include a phosphonium salt, a phosphonium salt, a phosphonium salt, a diazonium salt, and a pyridinium salt. Specific examples of preferred onium salts include diphenylsulfonium trifluoromethanesulfonate, diphenylsulfonium p-toluenesulfonate, diphenylphosphonium hexafluoroantimonate, and diphenylphosphonium hexafluorophosphate. Diphenylphosphonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-tert-butylphenyl. Diphenylsulfonium trifluoromethanesulfonate, 4-tert-butylphenyl. Diphenylphosphonium p-toluenesulfonate, 4,7-di-n-butyl Oxynaphthyltetrahydrothiophene trifluoromethanesulfonate, 4-(phenylthio)phenyldiphenylphosphonium tris(pentafluoroethyl)trifluorophosphate, 4-(phenylthio)phenyldi Phenylphosphonium hexafluorophosphate.

Examples of the N-sulfonyloxyquinone imine compound include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalic acid. Yttrium imine, N-(trifluoromethylsulfonyloxy)diphenylmethylene iodide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5 - ene-2,3-dicarboxy quinone imine, N-(trifluoromethylsulfonyloxy)naphthyl quinone imine.

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)-s-triazine, 4-methoxyphenyl-bis(trichloromethyl)-s-triazine, styryl-bis(trichloromethyl)-s-triazine, naphthyl a s-triazine derivative such as bis(trichloromethyl)-s-triazine.

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

Examples of the ruthenium compound include a β-ketooxime compound, a β-sulfonylhydrazine compound, and an α-diazo compound of these compounds. Specific examples of the preferable ruthenium compound include 4-trityl hydrazine methyl hydrazine, mesitylene benzyl hydrazine methyl hydrazine, bis(benzhydrylmethylsulfonyl) methane, and the like.

Examples of the sulfonate compound include alkylsulfonates, haloalkylsulfonates, arylsulfonates, and imidosulfonates. Specific examples of preferred sulfonate compounds include benzoin tosylate and pyrogallol tris(trifluoromethanesulfonic acid Ester), o-nitrobenzyl trifluoromethanesulfonate, 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 is preferably 5 parts by mass or more and 100 parts by mass or less, and more preferably 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the [A] polymer. When the content of the [E] acid generator is in the above range, the curable resin composition can further improve the adhesion of the cured film, and when it is a radiation curable resin composition, it can be further improved. Radiation sensitivity.

<[F]polymer>

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

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

Each compound will be described below.

[(F1) compound]

The compound (F1) is at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. (F1) compounds can be enumerated: unsaturated monocarboxylic acid, unsaturated two a monocarboxylic acid, an anhydride of an unsaturated dicarboxylic acid, a mono[(meth)acryloyloxyalkyl]ester of a polyvalent carboxylic acid, a mono(meth)acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals, An unsaturated polycyclic compound having a carboxyl group, an anhydride thereof, and the like. Examples of the compound include the same compounds as those exemplified as the monomer which provides the structural unit (II) of the [A] polymer.

Among them, from the viewpoints of copolymerization reactivity and availability, and [F] solubility of the polymer in an aqueous alkaline solution, an anhydride of a monocarboxylic acid or a dicarboxylic acid is preferable, and acrylic acid or methacrylic acid is more preferable. Maleic anhydride is further preferably methacrylic acid.

The content ratio of the structural unit derived from the (F1) compound is preferably from 1% by mass to 40% by mass, and more preferably 2% by mass based on the total ratio of the monomers used in the synthesis of the [F] polymer. From 3% to 30% by mass, more preferably from 3% by mass to 20% by mass. By setting the content ratio to the above 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 group-containing unsaturated compound. The (F2) compound has a radical polymerizable property and usually has both an epoxy group and an ethylenically unsaturated bond. The epoxy group may, for example, be an oxyheteropropyl group (1,2-epoxy structure) or an oxetanyl group (1,3-epoxy structure).

Examples of the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, and α-ethyl methacrylate. Glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, acrylic acid-6, 7-epoxyheptyl ester, -6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, meta-vinyl Benzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, and the like.

Examples of the unsaturated compound having an oxetanyl group include 3-(acrylenyloxymethyl)oxetane and 3-(acrylenyloxymethyl)-2-methyloxocycle. Butane, 3-(acrylenyloxymethyl)-3-ethyloxetane, 3-(acrylenyloxymethyl)-2-trifluoromethyloxetane, 3 -(Propylmethyloxymethyl)-2-pentafluoroethyloxetane, 3-(acrylenyloxymethyl)-2-phenyloxetane, 3-(acrylofluorene Benzyloxymethyl)-2,2-difluorooxetane, 3-(acrylenyloxymethyl)-2,2,4-trifluorooxetane, 3-(acrylofluorene -oxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(2-propenylmethoxyethyl)oxetane, 3-(2-propenylfluorenyl) Oxyethyl)-2-ethyloxetane, 3-(2-propenylmethoxyethyl)-3-ethyloxetane, 3-(2-propenyloxy) Ethyl)-2-trifluoromethyloxetane, 3-(2-propenyloxyethyl)-2-pentafluoroethyloxetane, 3-(2-propenylfluorenyl) Oxyethyl)-2-phenyloxetane, 3-(2-propenylmethoxyethyl)-2,2-difluorooxetane, 3-(2-propenylfluorenyl) Oxygen B Acrylates such as -2,2,4-trifluorooxetane, 3-(2-propenylmethoxyethyl)-2,2,4,4-tetrafluorooxetane 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-2-methyloxetane, 3-(methacryl) Mercaptooxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 3-(methacryloyloxymethyl)-2,2-difluorooxetane, 3-(methylpropenyloxymethyl)-2,2,4-trifluoroox Cyclobutane, 3-(methacryloyloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(2-methylpropenyloxyethyl)oxy Heterocyclobutane, 3-(2-methylpropenyloxyethyl)-2-ethyloxetane, 3-(2-methylpropenyloxyethyl)-3-ethyl Oxycyclobutane, 3-(2-methylpropenyloxyethyl)-2-trifluoromethyloxetane, 3-(2-methylpropenyloxyethyl) -2-pentafluoroethyloxetane, 3-(2-methylpropenyloxyethyl)-2-phenyloxetane, 3-(2-methylpropenyloxy) Benzyl)-2,2-difluorooxetane, 3-(2-methylpropenyloxyethyl)-2,2,4-trifluorooxetane, 3-( A methacrylate such as 2-methylpropenyl methoxyethyl)-2,2,4,4-tetrafluorooxetane or the like.

Among them, from the viewpoint of improving the copolymerization reactivity and the curability of the curable resin composition, glycidyl methacrylate, -6,7-epoxyheptyl methacrylate, ortho-vinyl group is preferable. Benzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl 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 from 5% by mass to 70% by mass, and more preferably 10% by mass based on the total ratio of the monomers used in the synthesis of the [F] polymer. % to 60% by mass, more preferably 15% by mass to 50% by mass. Further, by setting the content ratio to the range Solvent resistance and hardness of high-hardening film.

[(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 radical 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 group. Acrylic acid aromatic ester, acrylic acid aromatic ester, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, N-maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan An unsaturated compound having a skeleton, a tetrahydropyran skeleton, a pyran skeleton or a skeleton represented by the following formula (2), a phenolic hydroxyl group-containing unsaturated compound represented by the following formula (3), and a hydrolyzable alkyl group Unsaturated compounds, other unsaturated compounds, and the like.

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 An N-maleimide compound, an unsaturated aromatic compound, a conjugated diene, an unsaturated compound having a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton or a pyran skeleton, and other compounds may, for example, be The same compound or the like as the compound exemplified as the compound of the structural unit (III) which provides the [A] polymer.

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

Examples of the acrylate having a hydroxyl group include hydroxymethyl acrylate and C. 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 the unsaturated compound containing the skeleton represented by the formula (2) include polyethylene glycol (n=2 to 10) mono(meth)acrylate and polypropylene glycol (n=2 to 10) single (A). Base) acrylate and the like.

The phenolic hydroxyl group-containing unsaturated compound represented by the formula (3) includes a compound represented by the following formula (4) to formula (8), and the like, depending on the definition 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).

[化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).

[11]

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

Examples of the unsaturated compound having a hydrolyzable decyl group include 2-methylpropenyloxyethyltrimethoxydecane, 2-methylpropenyloxyethyltriethoxydecane, and 3-methylpropene oxime. Oxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-methylpropenyloxypropyltripropylnonane, 3-methylpropenyloxypropyl Trichlorodecane, 4-methylpropenyloxybutyltrimethoxydecane, 4-methylpropenyloxybutyltriethoxydecane, 2-propenyloxyethyltrimethoxydecane, 2- Propylene methoxyethyl triethoxy decane, 3-propenyl methoxy propyl trimethoxy decane, 3-propenyl methoxy propyl triethoxy decane, 3-propenyl methoxy propyl tripropyl Decane, 3-propenyloxypropyltrichlorodecane, 4-propenyloxybutyltrimethoxydecane, 4-propenyloxybutyltriethoxydecane, and the like.

Among them, an alkyl methacrylate, a cycloalkyl methacrylate, an N-maleimide compound, a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton or the above formula is preferable. (2) an unsaturated compound of a skeleton represented by the above, a phenolic hydroxyl group-containing unsaturated compound represented by the formula (3), an unsaturated aromatic compound, a cycloalkyl acrylate, or an unsaturated group having a hydrolyzable alkyl group Compound. Among them, styrene, tert-butyl methacrylate, n-lauryl methacrylate, and trimethyl methacrylate are more preferable in terms of copolymerization reactivity and solubility of the [F] polymer in an aqueous alkaline solution [ 5.2.1.0 ^2,6 ]decane-8-yl ester, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenyl maleimide, N-cyclohexyl-n-butene Diimine, tetrahydrofurfuryl (meth)acrylate, polyethylene glycol (n=2~10) mono(meth)acrylate, 3-(methyl)propenyloxytetrahydrofuran-2- Ketone, 4-hydroxybenzyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, o-hydroxystyrene, p-hydroxystyrene, α-methyl-p-hydroxystyrene, further preferably α -Methyl-p-hydroxystyrene, styrene, tetrahydrofurfuryl methacrylate, N-cyclohexylmethylene iodide, n-lauryl methacrylate, trimethyl methacrylate [5.2.1.0 ^2,6 ]decane-8-yl ester, 3-methylpropenyloxypropyltriethoxydecane.

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

<[F] Method for synthesizing polymer>

[F] The polymer can be synthesized by the same method as the polymerization of the synthetic [A] polymer, using a radical polymerization initiator in a solvent to cause the (F1) compound and the (F2) compound, And polymerization is carried out as needed (F3) compound or the like.

The Mw of the [F] polymer is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, still more preferably 5,000 to 20,000. When the Mw of the [F] polymer is in the above range, the curable resin composition can further improve the developability, and when the radiation curable resin composition is formed, 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 or less, more preferably 50 parts by mass or more and 1,500 parts by mass or less, and still more preferably 150 parts by mass, based on 100 parts by mass of the [A] polymer. More than 800 parts by mass or less. 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 an epoxy compound, an adhesion aid, metal oxide particles, a surfactant, and a curing agent. The curable resin composition may contain one or two or more of the other optional components, or may contain one or two or more of the respective components.

[epoxy compound]

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

Examples of the epoxy group include an oxacyclopropyl group, an oxetanyl group, and the like. 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-ethyl acrylate, glycidyl α-n-propyl acrylate, and glycidyl α-n-butyl acrylate. 3,4-epoxybutyl (meth)acrylate, 3,4-epoxybutyl α-ethyl acrylate, 6,7-epoxyheptyl (meth)acrylate, α-ethyl acrylate 6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, methylene Glycidyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-methyl-3-(methyl)propenyloxymethyloxetane, 3-ethyl-3-(methyl) Propylene methoxymethyl oxetane, phenyl glycidyl ether, γ-glycidoxypropyltrimethoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane , γ-glycidoxypropyl diethoxy decane, and the like.

Examples of the compound having two or more epoxy groups include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, and 2-(3,4-ring). 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'-A Dicyclo(3,4-epoxycyclohexyl), cyclohexane carboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol Methyl)ether, exoethyl bis(3,4-epoxycyclohexanecarboxylate); bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenation Bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, bisphenol type diglycidyl ether; 1,4-butanediol diglycidyl ether, 1,6 Polyglycidol of a polyol such as hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether a polyglycidyl ether of a polyether polyol obtained by adding one or more alkylene oxides to an aliphatic polyol such as ethylene glycol, propylene glycol or glycerin; a phenol novolac; Epoxy resin; cresol novolac type epoxy resin; Polyphenol type epoxy resin; diglycidyl ester of aliphatic long-chain dibasic acid; glycidyl ester of higher fatty acid; aliphatic polyglycidyl ether; epoxidized soybean oil, epoxidized linseed oil, and the like.

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

The content of the epoxy compound is preferably 100 parts by mass or less, more preferably 75 parts by mass or less, and still more preferably 50 parts by mass or less based on 100 parts by mass of the [A] polymer. 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.

[Adhesive Aid]

The adhesion aid is used to further improve the adhesion between the cured film obtained from the curable resin composition and the substrate. Such an adhesion aid is preferably a functional decane coupling agent. The functional decane coupling agent may, for example, be a coupling agent having a reactive group such as a carboxyl group, a methacryl group, an isocyanate group or an epoxy group. Examples of such a functional decane coupling agent include trimethoxydecyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, and vinyl trimethoxy decane. Γ- Isocyanate propyl triethoxy decane, γ-glycidoxy propyl trimethoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 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, the occurrence of development residue in the development step can be suppressed.

[Metal oxide particles]

When the metal oxide particles form an insulating film from the curable resin composition, electrical insulation of the insulating film can be maintained and an increase in relative dielectric constant can be suppressed. The metal oxide particles can also be used for the purpose of controlling the refractive index of the insulating film, controlling the transparency of the insulating film, suppressing the crack due to the relaxation hardening shrinkage, and the surface hardness of the insulating film. improve.

The metal oxide particles are, for example, oxide particles of cerium, aluminum, zirconium, titanium, zinc, indium, tin, antimony, cerium, lanthanum, cerium, or lanthanum. The metal oxide particles may be a single oxide particle or a composite oxide particle.

The single oxide may, for example, be cerium oxide, aluminum oxide, zirconium oxide, titanium oxide or cerium oxide.

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

Among them, oxide particles of cerium, zirconium, titanium, zinc, and cerium are preferable, and cerium oxide particles, zirconia particles, titania particles, and barium titanate (BaTiO ₃ ) are more preferable. As a commercial item of the metal oxide particles, for example, "Nanotec (registered trademark)" of CIKasei Co., Ltd., or the like can be used.

The shape of the metal oxide particles is not particularly limited, and may be a spherical shape or an indefinite shape, and may be a hollow particle, a porous particle, or a core. Shell particles, etc.

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

The content of the metal oxide particles is preferably 0.01 parts by mass or more and 20 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the [A] polymer. 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 amount of the metal oxide particles exceeds 20 parts by mass, the coating property or the hardenability of the film may be lowered, and the haze of the insulating film may be increased.

[Surfactant]

The surfactant is a compound which improves the coatability of the curable resin composition. The surfactant is preferably a fluorine-based surfactant, an anthrone-based surfactant, or a nonionic 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 bis(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., furthermore: sodium fluoroalkylbenzenesulfonate; fluoroalkyloxyethyl ether; fluoroalkyl Ammonium iodide, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethylene; perfluoroalkyl alkoxylate; fluoroalkyl ester.

Commercial products of the fluorine-based surfactant include, for example, "BM-1000", "BM-1100" (above, BM Chemie), "Megafac F142D", and "Mega" ( 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", "Frode (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, Shafu "Surflon SC-106" (above, Asahi Glass), "Eftop EF301", "Ipho (Eftop) EF303 "," aifo extension (Eftop) EF352 "(above, new Akita Kasei Corporation) Wait.

Commercial products of an anthrone-based surfactant include, for example, "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 Ketone Co., Ltd.) and the like.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene nonylphenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; (meth)acrylic copolymerization Things and so on.

Commercial products of the nonionic surfactants include "Polyflow No. 57" and "Polyflow No. 95" (above, Kyoeisha Chemical Co., Ltd.).

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. Further, by setting the content of the surfactant to 10 parts by mass or less, further The coatability of the curable resin composition is improved.

[hardener]

As the curing agent, for example, a curing agent described in JP-A-2012-88459 can be used.

<Preparation method of curable resin composition>

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

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

<hardened 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 is excellent in adhesion and transparency, and can be suitably used, for example, as an interlayer insulating film, a protective film, a spacer, or the like of a display element. The method for forming the cured film for a display element is not particularly limited, but a method of forming a cured film for a display element as described below is preferably applied.

<Method of Forming Cured Film for Display Element>

The method for forming a cured film for a display element of the present invention has a step of forming a coating film on a substrate (hereinafter also referred to as "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 the radiation-coated coating film (hereinafter also referred to as "development step"), and a developed coating film The step of heating (hereinafter also referred to as "heating step"). In the forming method, the coating film is formed of the curable resin composition. The curable resin composition is preferably a radiation curable resin composition obtained by containing the [D2] radiation-induced radical polymerization initiator and/or [E2] radiation-sensitive acid generator.

[Coating film forming step]

In this step, the curable resin composition is applied onto the surface of the substrate, and it is preferable to remove the solvent by prebake to form a coating film. Examples of the substrate used in this step include a glass substrate, a tantalum wafer, a plastic substrate, and a substrate in which various metals are formed on the surface of these substrates. Examples of the plastic substrate include a substrate mainly composed of a plastic such as polyethylene terephthalate (PET), polybutylene terephthalate, polyether oxime, polycarbonate, or polyimide. .

The coating method of the curable resin composition can 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. Among the coating methods, a spin coating method, a bar coating method, and a slit die coating method are preferable. The pre-baking conditions vary depending on the type and content of the component contained in the curable resin composition, and may be, for example, about 60 to 10 minutes at 60 to 120 ° C. The film thickness of the coating film is preferably from 0.1 μm to 8 μm, more preferably from 0.1 μm to 6 μm, based on the value after prebaking, and further It is preferably 0.1 μm to 4 μm.

[Irradiation step]

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, far ultraviolet rays, X-rays, charged particle beams, and the like.

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

[Development Step]

In this step, the coating film irradiated with radiation in the irradiation step can be developed to form a desired pattern. An alkaline aqueous solution can be used as the developing solution used in the development treatment. Examples of the base include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, and di-n-propylamine. , triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, acridine, 1,8-diazabicyclo[5.4.0 7-undecene, 1,5-diazabicyclo[4.3.0]-5-decane, 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 containing a coating film formed of the curable resin composition. A small amount of developer of various organic solvents. Further, the developing method can be, for example, a liquid coating method, a dipping method, a shaking dipping method, or the like. Spray method and other methods. The development time varies depending on the composition of the curable resin composition, but may be, for example, 30 seconds to 120 seconds.

After the development step, it is preferable to perform a treatment of subjecting the patterned coating film to a rinsing treatment by running water washing, and then comprehensively irradiating (post-exposure) radiation derived from a high-pressure mercury lamp or the like, thereby remaining in the coating film. [D2] Decomposition of a radiation-sensitive linear radical polymerization initiator, an [E2] radiation-sensitive acid generator, and the like. 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 which is simmered by the coating film developed in the developing step, thereby performing hardening of the coating film. . Further, the heating temperature is preferably from 100 ° C to 300 ° C, more preferably from 120 ° C to 280 ° C, still more preferably from 150 ° C to 250 ° C. The heating time varies depending on the type of the heating device, and is preferably from 5 minutes to 300 minutes, more preferably from 10 minutes to 180 minutes, still more preferably from 20 minutes to 120 minutes.

According to the method for forming a cured film for a display element, the curable resin composition is formed by patterning by exposure, development, and heating by radiation, so that adhesion and transparency can be easily formed. Hardened film pattern.

<display element>

The display element of the present invention includes the cured film for the display element. The display element may be a liquid crystal display element, an organic EL element, or the like. Such a display element is provided with a cured film as, for example, an interlayer insulating film, a protective film, and a spacer.

[Examples]

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited by 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 apparatus and measurement conditions.

Measuring device: "GPC-101" of Showa Denko Co., Ltd.

Measurement conditions: GPC column: "GPC-KF-801", "GPC-KF-802", "GPC-KF-803", and "GPC-KF-804" of Showa Denko Co., Ltd. were used.

Mobile phase: tetrahydrofuran

<Synthesis of Compounds> [Synthesis Example 1] (Synthesis of Compound (HC-1))

65.1 g (0.5 mol) of 2-hydroxyethyl methacrylate, 59.3 g (0.75 mol) of pyridine, and 500 mL of dichloromethane were placed in a 5 L reactor equipped with a stirrer and a dropping funnel, and the reaction was carried out under nitrogen. After cooling to 0 ° C, 76.18 g (0.6 mol) of 3-chloropropionyl chloride was added dropwise from the dropping funnel, followed by a reaction under stirring at 0 ° C for 2 hours. The obtained reaction liquid was washed with a sodium hydrogencarbonate aqueous solution and a saturated aqueous sodium chloride solution, 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). Yield 76%).

[化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 placed under nitrogen. The inside of the reactor was cooled to 0 ° C, and 76.18 g (0.6 mol) of 3-chloropropionyl chloride was added dropwise from the dropping funnel, followed by a reaction under stirring at 0 ° C for 2 hours. The obtained reaction liquid was washed with a sodium hydrogencarbonate aqueous solution and a saturated aqueous sodium chloride solution, and then concentrated under reduced pressure, and purified by silica gel column chromatography to obtain a compound represented by the following formula (HC-2): 80.0 g ( Yield 71%).

[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 placed under nitrogen. While cooling the inside of the reactor to 0 ° C, 152.4 g (1.2 mol) of 3-chloropropionyl chloride was added dropwise from the dropping funnel, followed by a reaction under stirring at 0 ° C for 2 hours. The obtained reaction solution is sequentially subjected to an aqueous solution of sodium hydrogencarbonate and a saturated food. The salt water was washed, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 106.3 g (yield: 62%) of the compound of the 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 methacrylic acid (3,4-dihydroxycyclohexyl)methyl ester, 118.7 g (1.5 mol) of pyridine, and 500 mL of dichloromethane were placed. Under a nitrogen atmosphere, while cooling the reactor to 0 ° C, 152.4 g (1.2 mol) of 3-chloropropionyl chloride was added dropwise from the dropping funnel, followed by a reaction under stirring at 0 ° C for 2 hours. The obtained reaction liquid was washed with a sodium hydrogencarbonate aqueous solution and a saturated aqueous sodium chloride solution, and then concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 125.5 g of the compound represented by the following formula (HC-4). Yield 64%).

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

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

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

In a 5 L reactor equipped with a stirrer and a dropping funnel, 140.2 g (0.5 mol) of 3-(2-hydroxyethoxy)-adamantyl methacrylate, 59.3 g (0.75 mol) of pyridine and dichloride were charged. After 500 mL of methane, 76.18 g (0.6 mol) of 3-chloropropionyl chloride was added dropwise from the dropping funnel while cooling the reactor to 0 ° C under nitrogen, and then reacted at 0 ° C for 2 hours with stirring. The obtained reaction liquid was washed with a sodium hydrogencarbonate aqueous solution and a saturated aqueous sodium chloride solution, 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%).

[化17]

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

In a 5 L reactor equipped with a stirrer and a dropping funnel, 89.1 g (0.5 mol) of 4-hydroxyphenyl methacrylate, 59.3 g (0.75 mol) of pyridine, and 500 mL of dichloromethane were placed under nitrogen. The inside of the reactor was cooled to 0 ° C, and 76.18 g (0.6 mol) of 3-chloropropionyl chloride was added dropwise from the dropping funnel, followed by a reaction under stirring at 0 ° C for 2 hours. The obtained reaction liquid was washed with a sodium hydrogencarbonate aqueous solution and a saturated aqueous sodium chloride solution, 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 Polymers> [Synthesis Example 8] (Synthesis of Polymer (A-1))

36.6 g (20 mol%) of the synthesized compound (HC-1), 17.8 g (25 mol%) of methacrylic acid, and 45.6 g (55 mol%) of methyl methacrylate were dissolved in 140 g of 3 To the 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 to the addition. The 500 mL three-necked flask of the methyl ester was purged with nitrogen for 30 minutes, and then heated to 70 ° C while stirring, and the prepared monomer solution was added dropwise by a dropping funnel for 2 hours. The start of the dropwise addition was set to the start time of the polymerization reaction, and the polymerization reaction was carried out for 4 hours. Thereafter, the temperature of the polymerization reaction solution was set to 90 ° C, and the mixture was stirred for 30 minutes. Then, the temperature of the polymerization reaction liquid was 70 ° C, 77.9 mL of triethylamine was added, and the mixture was stirred at a temperature of 70 ° C 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 and liquid-separated. After washing the organic phase with distilled water, the recovered organic phase was concentrated and diluted with methyl 3-methoxypropionate ((B-1) as a solvent of [B]), thereby obtaining a polymer containing 40% by mass. A 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 the monomers of the types and amounts used in the following Table 1 were used. The Mw and Mw/Mn of each of the synthesized polymers are shown together in Table 1. In addition, "-" indicates that no eligible monomers were used. In Synthesis Example 16 and Synthesis Example 19, when 1-butoxyethyl methacrylate obtained by protecting a carboxyl group is used as a compound which provides the structural unit (II), in the obtained [A] polymer, Deprotection produces 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 solvent of [B]) (B-1)) 200 parts by mass. Then, 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 After the temperature was raised to 70 ° C and the temperature was maintained for 5 hours, 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 to obtain 40%. Polymer solution of 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 (as a solvent of [B] (B) -2)) 220 parts by mass, further adding 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 methacrylic acid 12 parts by mass of hydroquinone ester, 15 parts by mass of N-cyclohexylmethyleneimine and 10 parts by mass of n-lauryl methacrylate, after nitrogen substitution, slowly stirring and raising the temperature of the solution to 70 °C, the temperature was maintained for 5 hours and polymerization was carried out, thereby obtaining a solution containing the 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 a solvent of [B]) were charged. Further, 7 parts by mass of methacrylic acid, 18 parts by mass of tricyclo [5.2.1.0 ^2,6 ]decane-8-yl methacrylate, 15 parts by mass of styrene, and 3-methylpropenyloxypropyl group were added. 40 parts by mass of triethoxy decane and 20 parts by mass of glycidyl methacrylate, after nitrogen substitution, the mixture was slowly stirred and the temperature of the solution was raised to 80 ° C, and the temperature was maintained for 5 hours to carry out 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, slowly stirring and the temperature of the solution The temperature was raised to 80 ° C, the temperature was maintained for 5 hours, and polymerization was carried out, whereby a solution containing the polymer (F-3) was obtained. The solid content concentration of the solution was 28.8% by mass. The polymer (F-3) had a 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. 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-epoxycyclohexylmethyl methacrylate, after nitrogen substitution, The mixture was slowly stirred and the temperature of the solution was raised to 80 ° C, the temperature was maintained for 5 hours, and polymerization was carried out, whereby a solution containing the polymer (F-4) was obtained. 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, the [C] polymerizable compound, the [D] radical polymerization initiator, and the [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" by Nippon Kayaku Co., Ltd.)

C-2: Succinic acid-modified pentaerythritol triacrylate (Aronix TO-756 of East Asia Synthesis Co., Ltd.)

C-3: Trimethylolpropane triacrylate

C-4: a mixture of tripentaerythritol octaacrylate and tripentaerythritol hepta acrylate ("Viscoat 802" by Osaka Organic Chemical Industry Co., Ltd.)

C-5: Succinic acid-modified dipentaerythritol pentaacrylate ("Aronix M-520" by East Asian Synthetic Company)

[[D] radical polymerization initiator]

D-1: 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one (BASF company "Irgacure 907")

D-2: Ethylketone-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-ethylindenyl) (BASF The company's "Irgacure OXE02")

D-3: 2,4-diethylthiaxanthone

[[E]acid generator]

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

[Example 1]

100 parts by mass of (A-1) as the [A] polymer synthesized in the synthesis example 8 and 150 parts by mass of (B-1) as the solvent of [B], as the solvent of [B] ( B-1) 200 parts by mass, (C-1) 50 parts by mass of the [C] polymerizable compound, and (D-1) 10 parts by mass as a [D] radical polymerization initiator, using a pore size of 0.2 μm The membrane filter was filtered to prepare a curable resin composition (J-1).

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

The curable resin composition (J-2) was hardened in the same manner as in Example 1 except that the respective materials were mixed in such a manner as to include the types and contents shown in Tables 2 and 3 below. Resin composition (J-25) and curable resin composition (CJ-1) to curable resin composition (CJ-3). The "-" in Table 3 indicates that the eligible ingredients were not used.

<evaluation>

With respect to the curable resin composition prepared as described above, the adhesion and transparency of the cured film, storage stability, and radiation sensitivity were evaluated in accordance with the following methods.

[Adhesion of hardened film]

The adhesion of the cured film was evaluated after the exposure delay of the cured film pattern. Specifically, first, a curable resin composition was applied onto 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. Then, using an exposure machine (Canon's "MPA-600FA (ghi ray mixing)"), a 10 μm line and space (1:1) pattern forming mask was used, at 700 (J/m ² ). The exposure is exposed. Thereafter, development was carried out by a coating method at 25 ° C for 80 seconds using a 0.5% by mass aqueous solution of tetramethylammonium hydroxide. Then, it was washed with ultrapure water for 1 minute, and then dried to form a pattern on the glass substrate. The substrate after development was observed with an optical microscope, and the presence or absence of pattern peeling was confirmed. The adhesion of the pattern was evaluated based on the following criteria.

Almost no pattern peeling was found: "○"

Slightly found the pattern peeling: "△"

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

[Transparency of cured film]

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

[Evaluation of preservation stability]

The curable resin composition was allowed to stand in an oven at 40 ° C for 1 week. Determine the initial viscosity (1) and the viscosity after leaving for 1 week (2), according to | viscosity (2) - viscosity (1) | × 100 / Viscosity (1) was used to calculate the viscosity change rate (%). | Viscosity (2) - Viscosity (1) | is the absolute value of the difference between viscosity (2) and viscosity (1). The values of the viscosity change rate (%) are shown in Table 2 and Table 3. The storage stability can be evaluated as good when the viscosity change rate is 5% or less, and can be evaluated as bad when it exceeds 5%.

[radiation sensitivity]

After applying a curable resin composition on a glass substrate using a spin coater, it was prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film having a film thickness of 3.0 μm. Then, using an exposure machine ("MPA-600FA (ghi ray mixing)" of Canon Inc.), a mask having a line and space (1:1) pattern of 10 μm was interposed, and the exposure amount was set as a variable to the coating film. Irradiation of radiation. Thereafter, development was carried out by a coating method at 25 ° C for 80 seconds using a 0.5% by mass aqueous solution of tetramethylammonium hydroxide. Then, it was washed with ultrapure water for 1 minute, and then dried to form a pattern on the glass substrate. At this time, investigate the space of 10μm. The amount of exposure required for the pattern to completely dissolve. The values of the exposure amount (J/m ² ) are shown in Table 2 and Table 3. The radiation sensitivity can be evaluated as good when the exposure amount is 500 (J/m ² ) or less.

[table 3]

According to the results of Tables 2 and 3, the curable resin composition of the examples is excellent in adhesion and transparency of the cured film, storage stability, and radiation sensitivity when the radiation curable resin composition is formed. On the other hand, the curable resin composition of the comparative example did not give good results with respect to all of these properties.

[Industrial availability]

The curable resin composition of the present invention can form a cured film excellent in adhesion and transparency, and is excellent in storage stability. Since the cured film for a display element of the present invention is excellent in adhesion and transparency, it can be suitably used as an interlayer insulating film, a protective film, a spacer, or 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 having a structural unit represented by the following formula (1) and a structural unit containing an acidic group, and a solvent; In the formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; and 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, a ring structure having a ring number of 3 to 20 is formed; R ⁴ is (a) a (n+1)-valent hydrocarbon group having 1 to 20 carbon atoms, and (b) a hydrocarbon group at (a) The carbon-carbon contains at least one group selected from the group consisting of an oxygen atom, a sulfur atom, -SO-, and -SO ₂ -, or (c) a (a) hydrocarbon group and a hydrogen group (b) a part or all of an atom substituted with at least one selected from the group consisting of a halogen atom, a cyano group, a nitro group, a carboxyl group, a sulfinic acid group, a fluorenyl group, and an alkoxy group having 1 to 12 carbon atoms; n is an integer of 1 to 6; when n is 2 or more, a plurality of R ^{1 's} may be the same or different, and a plurality of R ^{2 's} may be the same or different, and a plurality of R ^{3 's} may be the same or different; R ⁵ is a single bond or -COO-*;* represents a site bonded to R ⁴ ; R ⁶ is a hydrogen atom, a methyl group or a fluorinated methyl group. The curable resin composition according to claim 1, which further comprises a polymerizable compound having an ethylenically unsaturated bond. The composition of the curable resin as described in claim 1 or 2 And 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 claim 3, which contains the radical polymerization initiator. The curable resin composition according to claim 4, wherein the radical polymerization initiator is radiation sensitive. The curable resin composition according to claim 3, which contains the acid generator. The curable resin composition according to claim 6, wherein the acid generator is radiation sensitive. The curable resin composition according to claim 1 or 2, which is used for forming a cured film for a display element as an interlayer insulating film, a protective film or a separator. A cured film for a display element which is formed as an interlayer insulating film, a protective film or a spacer, and which is formed of a curable resin composition as described in claim 8 of the patent application. A method of 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; and a step of developing a coating film irradiated with the radiation; a step of heating the developed coating film; The coating film is formed of a curable resin composition as described in claim 5 or 7. A display element comprising the cured film for a display element according to claim 9 of the patent application.