JP2011132503A - Resin composition and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition capable of forming a coating film with a small amount of unevenness. <P>SOLUTION: The resin composition containing a resin, a polymerizable compound, a compound expressed by formula (F) (wherein L<SP>1</SP>is a 2-8C divalent aliphatic hydrocarbon group, L<SP>2</SP>and L<SP>3</SP>are each independently 2-8C trivalent aliphatic hydrocarbon group, R<SP>1</SP>and R<SP>2</SP>are independently 1-8C monovalent aliphatic hydrocarbon group, at least three hydrogen atoms of the aliphatic hydrocarbon group are substituted with fluorine atoms, m and n are each independently an integer of 0 or more and 22 or less, and m+n is 3 or more and 22 or less) and a solvent can form the coating film with a small amount of unevenness. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin composition, a coating film and a pattern obtained from the resin composition, and a display device including the coating film and / or pattern.

  A transparent film such as a pixel pattern or a coat layer of a color filter used in a display device (for example, a liquid crystal display device) is usually formed using a resin composition (particularly a photosensitive resin composition). In the production of a coat layer and a pattern of a display device, a resin composition is usually applied onto a substrate by a spin coating method, a slit & spin method, or the like. Therefore, there is a demand for a resin composition that can form a uniform coating film with little unevenness. Conventionally, as a photosensitive resin composition, what contains resin, a polymeric compound, a photoinitiator, and a solvent is known, for example (patent document 1 etc.).

JP 2008-181087 A

  However, conventionally known resin compositions may not always be sufficiently satisfied with respect to unevenness during coating. The subject of this invention is providing the resin composition which can form a coating film with few nonuniformity.

The present invention includes the following inventions.
[1] A resin composition comprising a resin, a polymerizable compound, a compound represented by formula (F), and a solvent.

In the formula (F), L ¹ represents a divalent C _2-8 aliphatic hydrocarbon group.
L ² and L ³ each independently represents a trivalent C _2-8 aliphatic hydrocarbon group.
R ¹ and R ² each independently represents a monovalent C _1-8 aliphatic hydrocarbon group, and at least three hydrogen atoms of the aliphatic hydrocarbon group are substituted with fluorine atoms.
m and n each independently represent an integer of 0 or more and 22 or less. However, m + n is 3 or more and 22 or less.

[2] The resin composition according to [1], wherein R ¹ and R ² are each independently a group represented by the formula (f1).
_{-C p H 2p -C q F 2q} + 1 (f1)
[In Formula (f1), p and q each independently represents an integer of 1 or more and 4 or less. ]

[3] The resin composition according to [1] or [2], wherein R ¹ and R ² are linear C _1-8 aliphatic hydrocarbon groups.

[4] The resin composition according to [2] or [3], wherein q in the formula (f1) is 4.

[5] The resin composition according to any one of [1] to [4], wherein the compound represented by the formula (F) is a compound represented by the formula (F1-1).

[In formula (F1-1), m and n have the same meaning as described above. ].

[6] The resin composition according to any one of [1] to [5], wherein m + n is 3 or more and 6 or less.

[7] A structural unit derived from at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a carbon-carbon double bond, and a cyclic ether structure The resin composition according to any one of [1] to [6], which is a copolymer containing a structural unit derived from a monomer (b) having a structure different from that of the monomer (a).

[8] The [7], wherein the monomer (b) is at least one selected from the group consisting of a compound represented by the formula (b1-1) and a compound represented by the formula (b1-2). Resin composition.

In formulas (b1-1) and (b1-2), R ³ represents a hydrogen atom or a C _1-4 aliphatic hydrocarbon group, and the hydrogen atom of the aliphatic hydrocarbon group is substituted with a hydroxy group. It may be.
L ⁴ represents a single bond or a C _1-6 aliphatic hydrocarbon group, and —CH ₂ — of the aliphatic hydrocarbon group may be substituted with —O—, —S— or —NH—. .
R ³ and L ⁴ in formula (b1-1) may be the same as or different from R ³ and L ^{4 in} formula (b1-2), respectively.

[9] The resin composition according to any one of [1] to [8], further including a polymerization initiator.

[10] The resin composition according to [9], wherein the polymerization initiator is a polymerization initiator containing a biimidazole compound.

[11] A coating film formed using the resin composition according to any one of [1] to [10].

[12] A pattern formed using the resin composition according to [9] or [10].

[13] A liquid crystal display device comprising at least one selected from the group consisting of the coating film according to [11] and the pattern according to [12].

[14] An organic EL display device comprising at least one selected from the group consisting of the coating film according to [11] and the pattern according to [12].

  The resin composition of the present invention containing the compound represented by the formula (F) can form a coating film with less unevenness. Therefore, it is suitable for manufacturing a coat layer and a pixel pattern of a large display device.

  The resin composition of the present invention comprises a resin (A), a polymerizable compound (B), a compound represented by formula (F) (hereinafter referred to as “compound represented by formula (F)” as “compound (F)”. The compound represented by other formulas may also be abbreviated in the same manner.) And a solvent (H), and in some cases, a polymerization initiator (C) and a polymerization initiation assistant (D ), Polyfunctional thiol (E) and other additives (G). As long as there is no notice in particular, said each component may be used individually by 1 type, and may use 2 or more types together. Hereinafter, each component contained in the resin composition of this invention is demonstrated in order.

<Resin (A)>
The resin (A) is preferably soluble in a developer (particularly preferably an alkali developer). Examples of the resin soluble in the alkali developer include at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride; and a carbon-carbon double bond. And a monomer (x) different from the monomer (a). As the monomer (a) and the monomer (x), one type may be used alone, or two or more types may be used in combination. These will be described in order below.

As the monomer (a), for example,
(Meth) acrylic acid, crotonic acid, cinnamic acid, o-, m-, p-vinylbenzoic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl) ], Ω-carboxypolycaprolactone mono (meth) acrylate, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept Unsaturation such as 2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene Monocarboxylic acids;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid, methyl-5-norbornene-2,3-dicarboxylic acid;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);
Etc.

  In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  From the viewpoints of copolymerization reactivity and alkali solubility, the monomer (a) is preferably at least one compound selected from the group consisting of (meth) acrylic acid and maleic anhydride, more preferably Methacrylic acid.

  The monomer (x) preferably includes a monomer (b) having a carbon-carbon double bond and a cyclic ether structure. A monomer (b) may be used individually by 1 type, and may use 2 or more types together. As the monomer (b), a monomer (b1) having an epoxy structure (that is, an oxirane structure), a monomer (b2) having an oxetane structure, and a monomer having a tetrahydrofuran structure (that is, oxolane structure) ( b3) and the like. Among these, the monomer (b1) having an epoxy structure and the monomer (b2) having an oxetane structure are preferable, and the monomer (b1) having an epoxy structure is more preferable.

The epoxy structure
(1) a structure having a monocyclic oxirane ring (ie, a structure obtained by epoxidizing an alkene) (hereinafter abbreviated as “structure (1)”), and (2) an alicyclic hydrocarbon ring and an oxirane ring condensed. It can be classified into a structure (a structure represented by the following formula (b1-0)) (hereinafter abbreviated as “structure (2)”).

[W ⁰ represents a ring of an alicyclic hydrocarbon in the formula (b1-0). ]

Furthermore, structure (2)
(2-1) An alicyclic hydrocarbon ring having a single ring (in the structure represented by the formula (b1-0), W ⁰ is a monocyclic alicyclic hydrocarbon ring) ( Hereinafter abbreviated as “structure (2-1)”), and
(2-2) Polycyclic ring of alicyclic hydrocarbon (in the structure represented by formula (b1-0), W ⁰ is a bridged ring) (hereinafter referred to as “structure (2-2 ) ")
Can be classified. Among these, the structure (2) is preferable and the structure (2-2) is more preferable.

Examples of the monomer (b1) having the structure (1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, and JP-A-7-248625. Examples include monomers represented by the formula (b1-3) described in the publication {in the formula (b1-3), R ^{4 to} R ⁶ are each independently a hydrogen atom or a C _1-10 alkyl group. Represents. m1 represents an integer of 1 to 5. }. In the present specification and claims, “C _xy ” means “the number of carbon atoms is x or more and y or less”.

  Examples of the monomer (b1-3) having the structure (1) include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and α-methyl-o-vinylbenzyl glycidyl ether. , Α-methyl-m-vinylbenzylglycidyl ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5 -Bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2 , 3,6-Tris (glycidyloxymethyl) styre , 3,4,5-tris (glycidyloxy) styrene, and 2,4,6-tris (glycidyloxy-methyl) styrene and the like.

  Examples of the monomer (b1) having the structure (2-1) include 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 2,3-epoxycyclohexyl. Methyl (meth) acrylate, 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; Daicel Chemical Industries, Ltd.) ))).

  The monomer (b1) having the structure (2-2) may have a carbon-carbon double bond in a polycyclic aliphatic hydrocarbon group, and in a side chain bonded to the ring. You may have. Examples of the polycycle include a norbornane ring and a tricyclodecane ring. Among these, a tricyclodecane ring is preferable.

  As the monomer (b1) having the structure (2-2), for example, epoxy norbornyl (meth) acrylate {for example, 3,4-epoxynorbornyl (meth) acrylate}, represented by the formula (b1-1) And a monomer represented by the formula (b1-2).

In formulas (b1-1) and (b1-2), R ³ represents a hydrogen atom or a C _1-4 aliphatic hydrocarbon group, and the hydrogen atom of the aliphatic hydrocarbon group is substituted with a hydroxy group. It may be.
L ⁴ represents a single bond or a divalent C _1-6 aliphatic hydrocarbon group, and —CH ₂ — of the aliphatic hydrocarbon group is substituted with —O—, —S— or —NH—. May be. R ³ and L ⁴ in formula (b1-1) may be the same as or different from R ³ and L ^{4 in} formula (b1-2), respectively. Similarly, symbols common to other formulas in the present specification may be the same or different from each other. Here, such as "- - CH ₂ aliphatic hydrocarbon group substituted by -O- or the like", "apparently, -CH ₂ aliphatic hydrocarbon group - is replaced by -O- such And the like are not meant to mean “a group obtained by synthesizing an aliphatic hydrocarbon group and then substituting —CH ₂ — with —O—” or the like. Expressions such as “aliphatic hydrocarbon group in which a hydrogen atom is substituted with a fluorine atom” have the same meaning.

Examples of the aliphatic hydrocarbon group which may be substituted with the hydroxy group of R ³ include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, and a hydroxymethyl group. 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like. R ³ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Examples of the divalent aliphatic hydrocarbon group which may be substituted with L ⁴ —O— or the like include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, and butane. -1,4-diyl group, butane-1,3-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, methyleneoxy group (—CH ₂ —O—), ethyleneoxy group {— (CH ₂ ) ₂ —O—}, propanediyloxy group {— (CH ₂ ) ₃ —O—, etc.}, methylenesulfanediyl group (—CH ₂ —S—), ethylenesulfanediyl group {— (CH ₂ ) ₂ —S—}, propanediylsulfanediyl group {— (CH ₂ ) ₃ —S— etc.}, methyleneimino group (—CH ₂ —NH—), ethyleneimino group {— (CH ₂ ) ₂ -NH-}, pro Panjii Louis amino group {- (CH _{2) 3} -N - etc.} and the like. L ⁴ is preferably a single bond, a methylene group, an ethylene group, a methyleneoxy group, an ethyleneoxy group, an ethylenesulfanediyl group, or an ethyleneimino group, and more preferably a single bond or an ethyleneoxy group.

  A monomer (b1-1) and a monomer (b1-2) may be used individually by 1 type, respectively, and may use 2 or more types together, respectively. Furthermore, you may use the mixture of a monomer (b1-1) and a monomer (b1-2). When these mixtures are used, the molar ratio of monomer (b1-1): monomer (b1-2) is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10. More preferably, it is 20:80 to 80:20.

  A preferred monomer (b1-1) is represented by any one of formulas (b1-1-1) to (b1-1-15). Among these, monomer (b1-1-1), monomer (b1-1-3), monomer (b1-1-5), monomer (b1-1-7), single amount Body (b1-1-9) and monomer (b1-1-11) to monomer (b1-1-15) are more preferable, monomer (b1-1-1), monomer ( More preferred are b1-1-7), monomer (b1-1-9), and monomer (b1-1-15).

  A preferred monomer (b1-2) is represented by any one of formulas (b1-2-1) to (b1-2-15). Among these, monomer (b1-2-1), monomer (b1-2-3), monomer (b1-2-5), monomer (b1-2-7), single amount Body (b1-2-9) and monomer (b1-2-11) to monomer (b1-2-15) are more preferable, and monomer (b1-2-1), monomer ( More preferred are b1-2-7), monomer (b1-2-9), and monomer (b1-2-15).

  Examples of the monomer (b2) having an oxetane structure include 3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) acryloxymethyloxetane, and 3-ethyl-3- (meth) acryloxy. Methyloxetane, 3-methyl-3- [1- (meth) acryloxy] methyloxetane, 3-ethyl-3- [1- (meth) acryloxy] methyloxetane, 3-methyl-3- [1- (meth) acryloxy ] Ethyl oxetane, 3-ethyl-3- [1- (meth) acryloxy] ethyl oxetane, 2-phenyl-3- (meth) acryloxymethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxymethyl oxetane 2-pentafluoroethyl-3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) Acryloxyethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 2-phenyl-3- (meth) acryloxyethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxyethyl oxetane or 2 -Pentafluoroethyl-3- (meth) acryloxyethyl oxetane, 3- (meth) acryloxy oxetane, etc. are mentioned. Among these, 3-ethyl-3- (meth) acryloxymethyl oxetane is preferable.

  Examples of the monomer (b3) having a tetrahydrofuran structure include tetrahydrofurfuryl (meth) acrylate, tetrahydrofurylmethoxyethyl (meth) acrylate, tetrahydrofurylmethoxypropyl (meth) acrylate, and the like.

  The monomer (x) may contain a monomer (c) different from the monomer (a) and the monomer (b). Examples of the monomer (c) include carboxylic acid esters having a carbon-carbon double bond, amides having a carbon-carbon double bond, and a polymerizable unsaturated bond (carbon-carbon double bond in the side chain). Aromatic compounds having a bond or triple bond), substituted vinyl compounds, N-substituted maleimides, dienes, polycyclic unsaturated compounds, and the like. A monomer (c) may be used individually by 1 type, and may use 2 or more types together.

As the monomer (c), for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, isobornyl ( Meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (sometimes referred to by the common name “dicyclopentanyl (meth) acrylate” in the art) 4-tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate, 5-tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate , Phenyl (meth) acrylate, aminoethyl (meth) acrylate, diethyl maleate, fumaric acid Ethyl, unsaturated carboxylic acid esters such as itaconic acid diethyl;
Carboxylic acid vinyl esters such as vinyl acetate or vinyl propionate;
Amides having a carbon-carbon double bond such as dimethyl (meth) acrylamide and isopropyl (meth) acrylamide;
An aromatic compound having a polymerizable unsaturated bond in the side chain, such as styrene, α-methylstyrene, vinyltoluene, p-methoxystyrene;
Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile or α-chloro (meth) acrylonitrile;
Halogenated vinyl compounds such as chloroethylene, dichloroethylene, trichloroethylene, fluoroethylene, difluoroethylene, trifluoroethylene, tetrafluoroethylene;
N-substituted maleimides such as N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide;
Dienes such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [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-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2] 2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2 -Polycyclic unsaturated compounds such as ene;
Etc.

  Among the monomers (c), benzyl acrylate, styrene, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, and bicyclo [2.2.1] hept-2-ene are preferable.

  As the monomer (x), only either the monomer (b) or the monomer (c) may be used, or both of them may be used. The monomer (x) preferably contains the monomer (b). That is, the monomer (x) is preferably only the monomer (b) or both the monomer (b) and the monomer (c), more preferably the monomer (b). Only. The copolymer containing the monomer (b) improves the heat resistance, light resistance, solvent resistance, and mechanical properties of the coating film or pattern obtained from the resin composition.

  When the resin (A) is a copolymer of the monomer (a) and the monomer (b), the structural unit derived from the monomer (a) among all the structural units of the copolymer is: It is preferably 2 to 98 mol% (more preferably 5 to 60 mol%, still more preferably 10 to 50 mol%), and the structural unit derived from the monomer (b) is preferably 2 to 98 mol% ( More preferably, it is 40-95 mol%, More preferably, it is 50-90 mol%. If it is this range, there exists a tendency for the storage stability and developability of a resin composition, the residual film rate of a coating film or a pattern, and solvent resistance to become favorable.

  When the resin (A) is a copolymer of the monomer (a) and the monomer (c), the structural unit derived from the monomer (a) is 2 in all the structural units of the copolymer. It is preferably -98 mol%, and the structural unit derived from the monomer (c) is preferably 2-98 mol%. If it is this range, there exists a tendency for storage stability and heat resistance to become favorable. More preferably, in all the structural units of the copolymer of the monomer (a) and the monomer (c), the structural unit derived from the monomer (a) is 5 to 50 mol%, The structural unit derived from the body (c) is 50 to 95 mol%. Within this range, the developability and the remaining film rate tend to be good.

  When the resin (A) is a copolymer of the monomer (a), the monomer (b), and the monomer (c), the monomer (a) in all the structural units of the copolymer The derived structural unit is 2 to 97 mol%, the structural unit derived from the monomer (b) is 2 to 97 mol%, and the structural unit derived from the monomer (c) is 1 to 96 mol%. It is preferable that If it is this range, there exists a tendency for storage stability, heat resistance, and mechanical strength to become favorable. More preferably, among all structural units of the copolymer of monomer (a), monomer (b) and monomer (c), the structural unit derived from monomer (a) is 10 to 50 mol. %, The structural unit derived from the monomer (b) is 20 to 80 mol%, and the structural unit derived from the monomer (c) is 10 to 70 mol%. If it is this range, there exists a tendency for developability, a residual film rate, and solvent resistance to also become favorable.

  Resin (A) is, for example, a method described in the document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document Can be produced by polymerizing monomers with reference to the literature cited in the above. More specifically, a predetermined amount of monomer (a), monomer (b) and / or monomer (c), a polymerization initiator and a solvent are charged into a reaction vessel, and in the absence of nitrogen-substituted oxygen. The copolymer can be produced by stirring, heating and keeping warm. What is necessary is just to adjust suitably the preparation method and reaction temperature of this copolymerization, considering the production equipment, the calorific value by superposition | polymerization, etc.

  For the obtained copolymer, the solution after the reaction may be used as it is. In particular, if the solvent (H) described later is used as the polymerization solvent, it can be used as it is in the resin composition without removing the solvent from the copolymer solution after polymerization, and the production process can be simplified. Further, the copolymer solution may be concentrated or diluted. Further, a copolymer taken out as a solid (powder) by a method such as reprecipitation may be used.

  The resin (A) may further have a structural unit (d) having a carbon-carbon double bond in the side chain. The structural unit (d) preferably has a 1-alkyl-1-ethenecarbonyl group, more preferably a (meth) acryloyl group at the end, as represented by the formula (d1) or the formula (d2).

In formula (d1) and formula (d2), R ⁷ and R ⁸ each independently represent a hydrogen atom or a C _1-6 alkyl group (preferably a hydrogen atom or a methyl group). In addition, * mark in a formula (d1) and a formula (d2) represents the coupling | bonding position in a structural unit (d1) and a structural unit (d2), respectively. The same applies to other chemical formulas.

The structural unit (d) having a carbon-carbon double bond in the side chain is obtained by copolymerizing the monomer (a) and the monomer (b) and / or monomer (c). A carboxy group or a carbonyloxycarbonyl group (carboxylic acid anhydride structure) derived from (a) is subjected to a carbon-carbon double bond and a cyclic ether structure in the same manner as in, for example, the method described in JP-A-2005-189574. Monomer (b), preferably a monomer (b1) having a carbon-carbon double bond and an epoxy structure {for example, a monomer represented by formula (b1-4) or formula (b1-5)} [In formula (b1-4) or formula (b1-5), R ⁸ is the same as defined above.
].

  Specifically, the structural unit (d) having a carbon-carbon double bond in the side chain can be formed as follows. Monomer (a), and monomer (b) and / or monomer (c) were copolymerized, and then the atmosphere in the reaction vessel was replaced with nitrogen to air, and the monomer used for copolymerization 5-80 mol% of monomer (b) is added with respect to the amount of (a). Next, 0.001 to 5% by mass of a reaction catalyst (for example, trisdimethylaminomethylphenol) based on the total amount of the monomer (a) used for the copolymer and the monomer (b) used for the addition reaction And 0.001-5 mass% polymerization inhibitor (for example, hydroquinone etc.) is added, and it is made to react at 60-130 degreeC for 1 to 10 hours. As in the case of copolymerization, in this addition reaction, the charging method and the reaction temperature may be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the addition reaction, and the like.

  In this addition reaction, the amount of monomer (b) used in the addition reaction is preferably 10 to 75 mol%, more preferably 15 to 70, based on the amount of monomer (a) used in the copolymerization. Mol%. Within this range, storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity tend to be good.

  As the copolymer containing the structural unit (d) having a carbon-carbon double bond in the side chain, the solution after the reaction may be used as it is, or it may be concentrated or diluted. Further, a copolymer taken out as a solid (powder) by a method such as reprecipitation may be used.

The acid value of the resin (A) is preferably 50 to 150 (mgKOH / g), more preferably 60 to 135 (mgKOH / g), and still more preferably 70 to 135 (mgKOH / g). If it is this range, the solubility with respect to a developing solution will improve, and it will become easy to melt | dissolve an unexposed part.
Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the polymer having an acidic group, and is usually obtained by titration using an aqueous potassium hydroxide solution. Can do.

  The weight average molecular weight of the resin (A) is preferably 2,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 3,000 to 30,000. If it is this range, the applicability | paintability of a resin composition will be favorable, and there exists a tendency for a high developing speed to be obtained, maintaining the residual film rate at the time of image development. The weight average molecular weight is determined by gel permeation chromatography using polystyrene as a standard.

  The molecular weight distribution {that is, weight average molecular weight (Mw) / number average molecular weight (Mn)} of the resin (A) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. Within this range, the developability tends to be excellent.

  The content of the resin (A) in the resin composition is preferably 5 to 90% by mass (more preferably 10 to 70% by mass) in the solid content of the resin composition. If it is this range, the solubility to a developing solution will be enough and it will become difficult to generate | occur | produce a development residue on the board | substrate of a non-exposed part (non-pixel part). Further, during development, the exposed portion (pixel portion) is not easily reduced in film thickness, and the remaining film ratio tends to increase. In the present specification, the “solid content of the composition” means “the total of each component of the resin composition excluding the solvent”. This solid content can be measured by known means such as gas chromatography or liquid chromatography.

<Polymerizable compound (B)>
Examples of the polymerizable compound (B) include compounds having a polymerizable carbon-carbon unsaturated bond. The polymerizable compound (B) is preferably a polymerizable compound having three or more carbon-carbon unsaturated bonds (hereinafter referred to as “trifunctional or higher functional polymerizable compound”).

  Examples of the trifunctional or higher functional polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, and ethoxylated trimethylolpropane tri. (Meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate , Tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meta Acrylate, tripentaerythritol octa (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, tripentaerythritol hepta (meta ) Reaction product of acrylate and acid anhydride, caprolactone-modified trimethylolpropane tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone Modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol Ruhexa (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol hepta (meth) acrylate, Caprolactone-modified tripentaerythritol octa (meth) acrylate, reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride, caprolactone modification Examples include a reaction product of tripentaerythritol hepta (meth) acrylate and an acid anhydride.

  Among these, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are preferable. Pentaerythritol hexa (meth) acrylate is more preferred.

  The content of the polymerizable compound (B) is preferably 5 to 75% by mass, more preferably 10 to 70% by mass, and further preferably 15 to 65% by mass in the total of the resin (A) and the polymerizable compound (B). %. If it is this range, hardening will fully occur, the film thickness will be prevented from decreasing before and after development, and it will be difficult for the pattern to be undercut, and the pattern will tend to have good adhesion. Moreover, if it is this range, there exists a tendency for the sensitivity of a resin composition, the intensity | strength of a coating film and a pattern, smoothness, heat resistance, and chemical resistance to become favorable.

<Polymerization initiator (C)>
The resin composition of the present invention may contain a polymerization initiator (C), preferably a photopolymerization initiator (C), if necessary. The polymerization initiator (C) is a compound that generates an active radical or an acid by heating or light irradiation and starts polymerization, and a known polymerization initiator can be used.

  Examples of the polymerization initiator (C) include biimidazole compounds, acetophenone compounds, triazine compounds, acylphosphine oxide compounds, oxime compounds, benzoin compounds, and benzophenone compounds. Among these, a biimidazole compound, an acetophenone compound, an oxime compound, and a triazine compound are preferable, and a biimidazole compound excellent in sensitivity is more preferable.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4,4. ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis (2-chlorophenyl) -4,4' , 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′- Bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxyphenyl) biimidazole (for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204) And an imidazole compound in which the phenyl group at the 4,4 ′, 5,5 ′ position is substituted with an alkoxycarbonyl group (—COOR) (for example, see JP-A-7-10913). .

  Among these, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole {particularly 2,2′-bis (2-chlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole}, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′- Bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole is preferred.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2- Methylpropan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, 1-hydroxy Cyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2 -(2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2 (3-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-propylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,3-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,4-Dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-chlorobenzyl) 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-chlorobenzyl) 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-bromobenzyl) 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methoxybenzyl) 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1- (4- Morpholinophenyl) -butanone, 2- (4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-methoxybenzyl) -2-dimethylamino-1 -(4-morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromo-4-methoxybenzyl) ) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one oligomers, and the like. .

  As triazine compounds, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl)- 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methyl) Phenyl) etheni ] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Examples of the oxime compound include O-acyloxime compounds, and specific examples thereof include 1- (4-phenylsulfanyl-phenyl) -butane-1,2-dione 2-oxime-O-benzoate, 1- (4-Phenylsulfanyl-phenyl) -octane-1,2-dione 2-oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1-O-acetate, 1- [9-ethyl-6- (2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl) -9H-carbazole-3- Yl] ethanone 1-O-acetate and the like.

  Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.

  Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl). ) Benzophenone, 2,4,6-trimethylbenzophenone and the like.

  Further, as a polymerization initiator (C), 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound and the like are used. Also good.

  Further, as the polymerization initiator (C), a polymerization initiator having a group capable of causing chain transfer as described in JP-T-2002-544205 may be used. The polymerization initiator having a group capable of causing chain transfer can be used for copolymerization of the resin (A) and incorporated into the resin (A) as a structural unit.

  Examples of the polymerization initiator having a group capable of causing chain transfer include polymerization initiators represented by the formulas (C1) to (C6).

  When using a polymerization initiator (C), the content is preferably 0.1 to 40 parts by mass, more preferably 1 with respect to 100 parts by mass in total of the resin (A) and the polymerizable compound (B). -30 mass parts. If it is this range, a resin composition will become highly sensitive with respect to light and a heat | fever, and there exists a tendency for the intensity | strength and smoothness of the coating film and pattern which were formed using this resin composition to become favorable.

<Polymerization initiation aid (D)>
The resin composition of the present invention may contain a polymerization initiation assistant (D) as necessary. The polymerization initiation assistant (D) is usually used in combination with the polymerization initiator (C), and is used to accelerate the polymerization initiated by the polymerization initiator (C).

  When using a polymerization initiation assistant (D), the content is preferably 0.01 to 50 parts by mass, more preferably 100 parts by mass in total of the resin (A) and the polymerizable compound (B). 0.1 to 40 parts by mass. If the polymerization initiation aid (D) within this range is used, the sensitivity of the resulting resin composition to light and heat is further increased, and the productivity of coating films and patterns formed using this resin composition tends to be improved. is there.

  Examples of the polymerization initiation aid (D) include amine compounds, thioxanthone compounds, and carboxylic acid compounds.

  Examples of amine compounds include aliphatic amines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethylamino 2-ethylhexyl benzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4′-bis (diethylamino) benzophenone, etc. And aromatic amines. Moreover, as an amine compound, you may use commercial items, such as brand name "EAB-F" (Hodogaya Chemical Co., Ltd. product).

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Carboxylic acid compounds include (phenylthio) acetic acid, (methylphenylthio) acetic acid, (ethylphenylthio) acetic acid, (methylethylphenylthio) acetic acid, (dimethylphenylthio) acetic acid, (methoxyphenylthio) acetic acid, (dimethoxyphenyl) Aromatic heteroacetic acids such as thio) acetic acid, (chlorophenylthio) acetic acid, (dichlorophenylthio) acetic acid, N-phenylglycine, phenoxyacetic acid, (naphthylthio) acetic acid, N-naphthylglycine, and naphthoxyacetic acid.

  As the polymerization initiation assistant (D), a compound represented by the formula (D1) may be used.

In formula (D1), W ¹ represents a C _6-12 aromatic ring, and the hydrogen atom of the aromatic ring may be substituted with a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.). L ⁵ represents —O— or —S—. R ⁹ represents a linear, branched or cyclic C _1-6 aliphatic hydrocarbon group.
R ¹⁰ represents a linear, branched or cyclic C _1-12 aliphatic hydrocarbon group or a C _6-12 aromatic hydrocarbon group, and the aliphatic hydrocarbon group and the aromatic carbon group The hydrogen atom of the hydrogen group may be substituted with a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.).

Examples of the aromatic ring of W ¹ include benzene ring, methylbenzene ring, dimethylbenzene ring, ethylbenzene ring, propylbenzene ring, butylbenzene ring, pentylbenzene ring, hexylbenzene ring, cyclohexylbenzene ring, naphthalene ring, and phenylbenzene ring. Can be mentioned. Examples of the halogenated aromatic ring for W ¹ include a chlorobenzene ring, a dichlorobenzene ring, a bromobenzene ring, a dibromobenzene ring, a chlorophenylbenzene ring, a bromophenylbenzene ring, a chloronaphthalene ring, and a bromonaphthalene ring. W ¹ is preferably a benzene ring (phenylene group) or a naphthalene ring (naphthylene group).

Examples of the aliphatic hydrocarbon group for R ⁹ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, 2-butyl group, 2-methylpropyl group, tert-butyl group, pentyl group, 2-pentyl group, Examples thereof include 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, hexyl group, cyclopentyl group, cyclohexyl group and the like. R ⁹ is preferably a methyl group.

As the aliphatic hydrocarbon group for R ¹⁰ , in addition to the groups listed for R ⁹ , heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, cycloheptyl group, methylcyclohexyl group, hexylcyclohexyl group , Norbornyl group, adamantyl group and the like. Examples of the halogenated aliphatic hydrocarbon group for R ¹⁰ include a trifluoromethyl group, a 1-chlorobutyl group, a 2-chlorobutyl group, a 3-chlorobutyl group, a 1-bromohexyl group, and a 2-bromododecyl group. Examples of the aromatic hydrocarbon group represented by R ¹⁰ include phenyl group, methylphenyl group, dimethylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, cyclohexylphenyl group, and naphthyl group. And biphenylyl group. Examples of the halogenated aromatic hydrocarbon group for R ¹⁰ include a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a dibromophenyl group, a chlorophenylphenyl group, a bromophenylphenyl group, a chloronaphthyl group, and a bromonaphthyl group. R ¹⁰ is preferably a phenyl group, a biphenylyl group, or a naphthyl group.

  Examples of the polymerization initiation assistant (D1) include 2-benzoylmethylene-3-methylnaphtho [2,1-d] thiazoline, 2-benzoylmethylene-3-methylnaphtho [1,2-d] thiazoline, 2-benzoylmethylene. -3-methylnaphtho [2,3-d] thiazoline, 2- (2-naphthoylmethylene) -3-methylbenzothiazoline, 2- (1-naphthoylmethylene) -3-methylbenzothiazoline, 2- (2- Naphthoylmethylene) -3-methyl-5-phenylbenzothiazoline, 2- (1-naphthoylmethylene) -3-methyl-5-phenylbenzothiazoline, 2- (2-naphthoylmethylene) -3-methyl-5 -Fluorobenzothiazoline, 2- (1-naphthoylmethylene) -3-methyl-5-fluorobenzothiazoline, 2- (2-naphtho Ylmethylene) -3-methyl-5-chlorobenzothiazoline, 2- (1-naphthoylmethylene) -3-methyl-5-chlorobenzothiazoline, 2- (2-naphthoylmethylene) -3-methyl-5-bromo Benzothiazoline, 2- (1-naphthoylmethylene) -3-methyl-5-bromobenzothiazoline, 2- (4-phenylbenzoylmethylene) -3-methylbenzothiazoline, 2- (4-phenylbenzoylmethylene) -3 -Methyl-5-phenylbenzothiazoline, 2- (2-naphthoylmethylene) -3-methylnaphtho [2,1-d] thiazoline, 2- (2-naphthoylmethylene) -3-methylnaphtho [1,2-d ] Thiazoline, 2- (4-phenylbenzoylmethylene) -3-methylnaphtho [2,1-d] thiazoline, 2- (4-phenyl) Nylbenzoylmethylene) -3-methylnaphtho [1,2-d] thiazoline, 2- (p-fluorobenzoylmethylene) -3-methylnaphtho [2,1-d] thiazoline, 2- (p-fluorobenzoylmethylene) -3 -Methylnaphtho [1,2-d] thiazoline, 2-benzoylmethylene-3-methylnaphtho [2,1-d] oxazoline, 2-benzoylmethylene-3-methylnaphtho [1,2-d] oxazoline, 2-benzoylmethylene- 3-methylnaphtho [2,3-d] oxazoline, 2- (2-naphthoylmethylene) -3-methylbenzoxazoline, 2- (1-naphthoylmethylene) -3-methylbenzoxazoline, 2- (2-naphtho Ylmethylene) -3-methyl-5-phenylbenzoxazoline, 2- (1-naphthoylmethylene) -3-methyl-5-phenylbenzoxazoline, 2- (2-naphthoylmethylene) -3-methyl-5-fluorobenzoxazoline, 2- (1-naphthoylmethylene) -3-methyl-5-fluorobenzoxazoline 2- (2-naphthoylmethylene) -3-methyl-5-chlorobenzoxazoline, 2- (1-naphthoylmethylene) -3-methyl-5-chlorobenzoxazoline, 2- (2-naphthoylmethylene) -3-methyl-5-bromobenzoxazoline, 2- (1-naphthoylmethylene) -3-methyl-5-bromobenzoxazoline, 2- (4-phenylbenzoylmethylene) -3-methylbenzoxazoline, 2- ( 4-phenylbenzoylmethylene) -3-methyl-5-phenylbenzoxazoline, 2- (2-naphthoyl) Methylene) -3-methylnaphtho [2,1-d] oxazoline, 2- (2-naphthoylmethylene) -3-methylnaphtho [1,2-d] oxazoline, 2- (4-phenylbenzoylmethylene) -3-methylnaphtho [2,1-d] oxazoline, 2- (4-phenylbenzoylmethylene) -3-methylnaphtho [1,2-d] oxazoline, 2- (p-fluorobenzoylmethylene) -3-methylnaphtho [2,1-d Oxazoline, 2- (p-fluorobenzoylmethylene) -3-methylnaphtho [1,2-d] oxazoline, and the like.

  Among those described above, 2- (2-naphthoylmethylene) -3-methylbenzothiazoline represented by the formula (D1-1), 2-benzoylmethylene-3-methylnaphtho represented by the formula (D1-2) [ 1,2-d] thiazoline and 2- (4-phenylbenzoylmethylene) -3-methylnaphtho [1,2-d] thiazoline represented by the formula (D1-3) are preferable.

  The resin composition containing the polymerization initiation assistant (D1) is highly sensitive and tends to improve the productivity of the coating film and pattern. Since the polymerization initiation assistant (D1) is discolored by the action of light or heat, the visible light transmittance of the coating film or pattern can be improved by using it.

  The content of the polymerization initiation assistant (D1) is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 65% by mass or more, in the content of the polymerization initiation assistant (D). Is 100 mass% or less. When the polymerization initiation aid (D1) is used in an amount within this range, the visible light transmittance of the coating film is increased.

  Moreover, you may use the compound represented by a formula (D2) or a formula (D3) as a polymerization start adjuvant (D).

In formula (D2) or formula (D3), W ² and W ³ each independently represent a C _6-12 aromatic ring or a heterocyclic ring, and the hydrogen atom of the aromatic ring and the heterocyclic ring is substituted with a halogen atom May be. L ⁶ and L ⁷ each independently represent —O— or —S— (preferably —S—). R ¹¹ and R ¹² each independently represents a linear, branched or cyclic C _1-12 aliphatic hydrocarbon group, or a C _6-12 aromatic hydrocarbon group, The hydrogen atom of the hydrogen group and the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group or a C _1-6 alkoxy group.

Examples of the aromatic ring and heterocyclic ring of W ² and W ³ include a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, an imidazole ring, a pyridine ring, a pyrimidine ring, and a pyrazine ring, and combinations thereof (for example, naphthalene ring, Benzofuran ring, benzimidazole ring, etc.). Examples of the halogenated aromatic ring of W ² and W ³ include chlorobenzene ring, dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, chloronaphthalene ring, bromonaphthalene ring, etc. Can be mentioned. W ² and W ³ are each independently preferably a benzene ring or a naphthalene ring.

Examples of the aliphatic hydrocarbon group, halogenated aliphatic hydrocarbon group, aromatic hydrocarbon group, and halogenated aromatic hydrocarbon group for R ¹¹ and R ¹² include those listed for R ¹⁰ . Examples of the aliphatic hydrocarbon group substituted with the hydroxy group of R ¹¹ or R ¹² include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group. Examples of the aromatic hydrocarbon group substituted with the hydroxy group of R ¹¹ or R ¹² include a hydroxyphenyl group and a hydroxynaphthyl group. Examples of the aliphatic hydrocarbon group substituted with the alkoxy group of R ¹¹ or R ¹² include methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, butoxymethyl group, ethoxyethyl group, ethoxypropyl group, propoxybutyl Groups and the like. Examples of the aromatic hydrocarbon group substituted with the alkoxy group of R ¹¹ or R ¹² include a methoxyphenyl group and an ethoxynaphthyl group. R ¹¹ and R ¹² are each independently preferably a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group.

As the polymerization initiation assistant (D2) or (D3), for example,
Dialkoxynaphthalenes such as dimethoxynaphthalene, diethoxynaphthalene, dipropoxynaphthalene, diisopropoxynaphthalene, dibutoxynaphthalene;
Dimethoxyanthracene, diethoxyanthracene, dipropoxyanthracene, diisopropoxyanthracene, dibutoxyanthracene, dipentaoxyanthracene, dihexaoxyanthracene, methoxyethoxyanthracene, methoxypropoxyanthracene, methoxyisopropoxyanthracene, methoxybutoxyanthracene, ethoxypropoxyanthracene Dialkoxyanthracenes such as ethoxyisopropoxyanthracene, ethoxybutoxyanthracene, propoxyisopropoxyanthracene, propoxybutoxyanthracene, isopropoxybutoxyanthracene;
Dialkoxytetracenes such as dimethoxytetracene, diethoxytetracene, dipropoxytetracene, diisopropoxytetracene, dibutoxytetracene;
Etc.

<Multifunctional thiol (E)>
The resin composition of this invention may contain the polyfunctional thiol (E) as needed.
Here, “polyfunctional thiol” means “compound having two or more sulfanyl groups in the molecule”. Among the polyfunctional thiols (E), a compound having two or more sulfanyl groups bonded to the carbon atom of the aliphatic hydrocarbon group is preferable because the sensitivity of the resin composition is improved.

  Examples of the polyfunctional thiol (E) include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bis (3-sulfanylpropionate), butanediol bis (2-sulfanyl acetate), ethylene glycol bis (2-sulfanyl acetate), trimethylolpropane tris (2-sulfanyl acetate), butanediol bis (3-sulfanylpropionate), trimethylolpropane tris (3-sulfanylpropionate), trimethylolpropane tris (2- Sulfanyl acetate), pentaerythritol tetrakis (3-sulfanylpropionate), pentaerythritol tetrakis (2-sulfanyl acetate), trishydroxyethyltris ( - sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), 1,4-bis (3-sulfanyl butyryloxy) include butane and the like.

  When using polyfunctional thiol (E), the content is preferably 0.5 to 100 parts by mass, more preferably 1 to 90 parts by mass with respect to 100 parts by mass of the polymerization initiator (C). If polyfunctional thiol (E) is used in an amount within this range, the sensitivity tends to be high and the developability tends to be good. Moreover, it is preferable to use polyfunctional thiol (E) in combination with the biimidazole compound which is a polymerization initiator (C). If this combination is used, the sensitivity tends to increase.

<Compound (F)>
One of the characteristics of the resin composition of the present invention is that it contains a compound represented by the formula (F). By using the compound (F), a uniform coating film or pattern with little unevenness can be produced. The resin composition of the present invention can also form a coating film having high heat resistance.
Hereinafter, the groups in the formula (F) will be described in order.

In the formula (F), L ¹ represents a divalent C _2-8 aliphatic hydrocarbon group. L ¹ includes ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, 2-methylpropane-1,3-diyl group, butane-1,4-diyl group, 2,2 -Dimethylpropane-1,3-diyl group, butane-1,3-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, cyclohexane-1,4-diyl group, heptane-1 , 7-diyl group, octane-1,8-diyl group and the like. Among these, 2,2-dimethylpropane-1,3-diyl group is preferable.

In formula (F), L ² and L ³ each independently represents a trivalent C _2-8 aliphatic hydrocarbon group.
Examples of L ² and L ³ include groups represented by formula (f2-1) to formula (f2-11), and among these, a group represented by formula (f2-1) is preferable. In addition, * mark in a following formula represents a bond position, and it couple | bonds with the oxygen atom in Formula (F) at this position.

In formula (F), R ¹ and R ² each independently represents a monovalent C _1-8 aliphatic hydrocarbon group, and at least three of the hydrogen atoms of the aliphatic hydrocarbon group are fluorine atoms. Has been replaced. As R ¹ and R ² , for example,
A linear aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group, wherein at least three hydrogen atoms are substituted with fluorine atoms (For example, a trifluoromethyl group);
2-methylethyl group, 2-methylpropyl group, 2,2-dimethylethyl group, 2-butyl group, 2-pentyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1, A branched aliphatic hydrocarbon group such as 2-dimethylpropyl group or 2,2-dimethylpropyl group in which at least three hydrogen atoms are substituted with fluorine atoms (for example, 2-trifluoromethylpropyl group) );
A cyclic aliphatic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group or an ethylcyclohexyl group in which at least three hydrogen atoms are substituted with fluorine atoms (for example, a pentafluoroethylcyclohexyl group);
Is mentioned. Among these, a linear thing is preferable and the ethyl group, propyl group, butyl group, and hexyl group which have an at least 3 fluorine atom are more preferable.

R ¹ and R ² are each independently preferably a group represented by the formula (f1):
_{-C p H 2p -C q F 2q} + 1 (f1)

In formula (f1), p and q each independently represent an integer of 1 or more and 4 or less. p is preferably 1 or 2, more preferably 2. q is preferably 3 or 4, more preferably 4. Moreover, it is preferable that group represented by a formula (f1) is linear. Among the groups represented by the formula (f1), 2,2,3,3,4,4,5,5,5-nonafluoropentyl group {n-CF ₃ (CF ₂ ) ₃ CH ₂ —}, 3 , 3,4,4,5,5,6,6,6- nonafluorohexyl group _{{n-CF 3 (CF 2} ) 3 (CH 2) 2 -}, 4,4,5,5,6,6 , 7,7,7- nonafluorobutyl heptyl _{{n-CF 3 (CF 2} ) 3 (CH 2) 3 -}, 5,5,6,6,7,7,8,8,8- nonafluorobutyl octyl The group {n—CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₄ —} is preferred, and the 3,3,4,4,5,5,6,6,6-nonafluorohexyl group is more preferred.

  In formula (F), m and n each independently represent an integer of 0 or more, preferably 1 or more, more preferably 2 or more, and 22 or less, preferably 10 or less, more preferably 6 or less. . However, m + n is 3 or more, preferably 4 or more, 22 or less, preferably 10 or less, more preferably 6 or less.

The compound (F) is preferably represented by the formula (F1) [in the formula (F1), m, n, p and q have the same meaning as described above. Description of the group represented by _{-C p H 2p -C q F 2q} + 1 is the same as described for the group represented by formula (f1). ].

Among the compounds (F1), compounds represented by the formula (F1-1) to the formula (F1-3) are preferable, the compound (F1-1) is more preferable, and the compound (F1-) in which m + n is 3 or more and 6 or less. 1) is more preferable. [In Formula (F1-1) to Formula (F1-3), m and n have the same meaning as described above. -C ₄ F ₉ in the formula (F1-1) is preferably linear. ]

  The content of the compound (F) is preferably 0.001 to 0.15% by mass in the solid content of the resin composition. More preferably, it is 0.01-0.1 mass%, More preferably, it is 0.02-0.1 mass%. When the content of the compound (F) is within this range, a uniform coating film is easily obtained.

Compound (F) can be produced by various reaction routes. For example, a preferred compound (F1) is obtained by an etherification reaction using a compound represented by the formula (f3) and a compound represented by the formula (f4) (that is, 2,2-dimethyl-1,3-propanediol). Can be manufactured. Further, a preferred compound (F1) is commercially available from Omninova as PolyFox ^™ PF-7002.

<Other additives (G)>
The resin composition of this invention may contain the other additive (G) as needed.
Other additives (G) include, for example, colorants, pigment dispersants, fillers, polymer compounds different from the resin (A), adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer Agents, leveling agents and the like.

Examples of the colorant include compounds classified as pigments according to a color index (published by The Society of Dyers and Colorists). Specifically, for example,
C. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. Black pigments such as CI Pigment Black 1 and 7;
Etc. In the present specification, “CI Pigment Yellow” or the like is described only for the first pigment, and only the number is described for the same described pigment.

  A surfactant can be used as the pigment dispersant. Surfactants can be electrically classified into cationic, anionic, nonionic, and amphoteric, and compounds can be classified into ester, amine, acrylic, silicone, and the like. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. It is done. Commercially available surfactants such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (registered trademark) (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Geneca Corporation), EFKA (manufactured by CIBA), Ajisper (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (manufactured by BYK Chemie) and the like can also be used.

Examples of the filler include glass, silica, and alumina.
Examples of the polymer compound include epoxy resins (for example, ortho-cresol novolac type epoxy resins), curable resins such as maleimide resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane, and the like. A thermoplastic resin etc. are mentioned.

  Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxy. Silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. It is.

  Examples of the antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3). , 5-Di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2 , 4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, 3,9-bis [2- {3- (3-tert-butyl-4- Hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2′-methylene (6-tert-butyl-4-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 4,4′-thiobis (2-tert-butyl-5-methylphenol) ), 2,2′-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′- Thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine -2,4,6 (1H, 3H, 5H) -trione, 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', a "- Mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl -4-methylphenol etc. Moreover, antioxidant is marketed by brand names, such as "IRGANOX3114", from Ciba Japan.

  Examples of the ultraviolet absorber include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, octyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-). 2H-benzotriazol-2-yl) phenyl] propionate, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethyl) Phenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- (2,4-bis-butyloxyphenyl) 1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1- Phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. Can be mentioned.

  Examples of the light stabilizer include a polymer composed of succinic acid and (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl) ethanol; N, N ′, N ″, N ′ ″ Tetrakis (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) triazin-2-yl) -4,7-diazadecane-1,10 A diamine; a reaction product of decandioic acid, bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester and 1,1-dimethylethyl hydroperoxide; bis ( 1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate; 2,4-bis [ N-Bu Til-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine; bis (1, 2,2,6,6-pentamethyl-4-piperidinyl) sebacate; methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and the like.

  Examples of the chain transfer agent include dodecanethiol and 2,4-diphenyl-4-methyl-1-pentene.

  Examples of the leveling agent include silicone leveling agents. A silicone type leveling agent is a leveling agent which has a siloxane bond in a molecule | numerator. Examples of silicone leveling agents include straight silicone oils such as dimethyl silicone oil and methylphenyl silicone oil; modified silicone oils such as polyether-modified silicone oil (in which an organic group is introduced into the main chain or side chain of the polysiloxane skeleton) ); A silicone resin composed of a three-dimensional polymer formed by a polysiloxane bond, and the like. Among these, a modified silicone oil (preferably a polyether-modified silicone oil) is preferable. Specifically, DC3PA, SH7PA, DC11PA, SH21PA, SH21PA, SH29PA, SH29PA, SH30PA, SH8400 (polyether-modified silicone oil), Shin-Etsu Chemical (commercially available from Toray Dow Corning Co., Ltd.) KP321, KP322, KP323, KP324, KP326, KP340, KP341, TSF400, TSF401, TSF410, TSF4300, TSF4445, TSF4446, commercially available from Momentive Performance Materials Japan LLC. Examples include TSF4452 and TSF4460.

  When a leveling agent is added as the additive (G), the content of the leveling agent is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass in the solid content of the resin composition. % To 0.1% by mass, and more preferably 0.005% to 0.05% by mass. By containing the leveling agent in the above range, the flatness of the coating film can be improved.

<Solvent (H)>
As the solvent (H), those which uniformly dissolve or disperse each component such as the resin (A) and do not react with each component are suitable. From the viewpoints of coating properties and drying properties, an organic solvent having a boiling point of 100 ° C to 200 ° C is preferable. As the solvent (H), for example, the following can be used.

Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether;
Alkylene glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxypentyl acetate .

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether, propylene glycol ethyl propyl ether;
Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate.

Butanediol monoalkyl ethers such as methoxybutanol, ethoxybutanol, propoxybutanol, butoxybutanol;
Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, butoxybutyl acetate;
Butanediol monoalkyl ether propionates such as methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate, butoxybutyl propionate.

Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol methyl ethyl ether;
Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol methyl ethyl ether.

Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone;

  Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxyethyl acetate, hydroxy Butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3-methylbutane Methyl acetate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxyacetate, propoxy Ethyl acetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2- Butyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxy Propyl propionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3- Methyl toxipropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxy Esters such as butyl propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

Cyclic ethers such as tetrahydrofuran and pyran;
Cyclic esters such as γ-butyrolactone.

  Among these, alkylene glycol alkyl ether acetates (more preferably propylene glycol monomethyl ether acetate), ketones (more preferably cyclohexanone), butanediol monoalkyl ether acetates (more preferably methoxybutyl acetate), butanediol mono Alkyl ethers (more preferably methoxybutanol), diethylene glycol dialkyl ethers (more preferably diethylene glycol ethyl methyl ether), and esters (more preferably ethyl 3-ethoxypropionate and methyl 3-methoxypropionate) are preferred.

  The content of the solvent (H) is preferably 50% by mass or more, more preferably 60% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less in the resin composition.

<Coating film, pattern, display device>
The coating film of the present invention is obtained by applying the resin composition to a substrate (for example, a substrate made of glass, silicon, metal, plastic, or the like, or a substrate on which a resin layer or an inorganic compound layer is formed). Alternatively, the coating film can be formed by photopolymerization. There is no particular limitation on the coating method for forming the coating film, and a known method such as a spin coating method can be used.

  The pattern of the present invention can be formed by applying the resin composition of the present invention in a pattern using, for example, an inkjet device, and then performing thermal polymerization or photopolymerization. Moreover, if the photosensitive resin composition of this invention containing a photoinitiator (C) is used, a pattern can be formed also by the photolithographic method. In the photolithographic method, a pattern is usually formed through application of a photosensitive resin composition, solvent removal, heating before exposure (pre-baking), exposure, development, heating after development (post-baking), and each step.

  The coating film and pattern of the present invention include, for example, a transparent film that is a component such as a color filter or an array substrate of a display device, a coloring pattern of a color filter, a photo spacer, an overcoat, an insulating film, a protrusion for controlling liquid crystal alignment, a micro Suitable for lenses, coat layers and the like. Since the coating film and pattern of this invention show sufficient adhesiveness with respect to a board | substrate, they are especially useful as a coating film or pattern formed on this board | substrate. Preferred examples of the display device include a liquid crystal display device and an organic EL display device.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples, and appropriate modifications are made within a range that can meet the above and the following purposes. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.
In the following, “%” and “parts” in the component amounts are “% by mass” and “parts by mass” unless otherwise specified.

1. Synthesis of Resin (A) Nitrogen was flowed at 0.02 L / min into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, and 130 parts of 3-methoxybutyl acetate and 3-methoxy-1 -Put 110 parts of butanol and heat to 80 ° C with stirring. Next, 40 parts of methacrylic acid, a mixture of monomer (b1-1-1) and monomer (b1-2-1) {monomer (b1-1-1) in the mixture: monomer (b1- 2-1) molar ratio = 50: 50} 360 parts, and a mixed solution prepared by dissolving 36 parts by weight of azobisdimethylvaleronitrile in 210 parts of 3-methoxybutyl acetate and 170 parts of 3-methoxy-1-butanol. The solution was added dropwise over a period of time and aged for 3 hours, and then cooled to room temperature to obtain a copolymer solution having a solid content of 43.1% and an acid value of 60 mg-KOH / g. This copolymer is referred to as “resin (A1)”. The weight average molecular weight (Mw) of the obtained resin (A1) was 7800, and the molecular weight distribution (Mw / Mn) was 1.95.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained resin (A1) were measured using the GPC method under the following conditions.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector; RI
Standard: Polystyrene

2. Preparation of Resin Composition The following components were mixed in the amounts shown in Table 1 to obtain resin compositions 1-6.
Resin (A): Resin (A1) solution (in Table 1, the number of parts of resin (A1) converted to solid content is shown)
Polymerizable compound (B): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (C): 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (B-CIM; Hodogaya Chemical Co., Ltd.) Made)
Polymerization initiation assistant (D): 2- (2-naphthoylmethylene) -3-methylbenzothiazoline Multifunctional thiol (E): Pentaerythritol tetrakis (3-sulfanylpropionate) (PEMP; SC Organic Chemical Co., Ltd.) Made)
Compound (F): PolyFox ^™ PF-7002 represented by the formula (F1-1-1) (Omnova, m ′ + n′≈4 to 5 in the formula (F1-1-1))
Other additives (G)
(G1): Ortho-cresol novolac type epoxy resin (Sumiepoxy ESCN-195XL-80; manufactured by Sumitomo Chemical Co., Ltd.)
(G2): IRGANOX 3114 (Ciba Japan)
(G3): 3-aminopropyltrimethoxysilane (KBM-903; manufactured by Shin-Etsu Chemical Co., Ltd.)
(G4): Polyether-modified silicone oil (SH8400 manufactured by Toray Dow Corning Co., Ltd.)
Solvent (H)
(H1): ethyl 3-ethoxypropionate (H2): 3-methoxy-1-butanol (H3): 3-methoxybutyl acetate (H4): propylene glycol monomethyl ether acetate (H5): diethylene glycol ethyl methyl ether

3. Evaluation of Resin Composition The coating film unevenness (striation and haze unevenness) obtained from the above compositions 1 to 7 was evaluated as follows.
Moreover, the heat resistance of the coating film obtained from each of the composition 4 and the composition 6 was evaluated as follows.

(1) Evaluation of striation In order to evaluate the striation of the coating film obtained from the compositions 1 to 7, a colored pattern is first formed on the silicon substrate using the colored resin composition having the composition shown in Table 2, and then A coating film was formed on the silicon substrate on which the colored pattern was formed using Compositions 1-7. Here, the striation means a radial unevenness of the coating film derived from the steps of the colored pattern.

A 4-inch silicon substrate was sequentially washed with a neutral detergent, water and 2-propanol and then dried. On this silicon substrate, the colored resin composition was spin-coated so that the film thickness after post-baking was 3.0 μm. Next, the spin-coated colored resin composition layer was pre-baked at 90 ° C. for 3 minutes in a clean oven. After cooling, the gap between the substrate coated with the colored resin composition layer and the quartz glass photomask is set to 100 μm, and exposure is performed using an exposure machine (TME-150RSK; manufactured by Topcon Corporation, light source: ultrahigh pressure mercury lamp). The exposure was performed at an exposure amount of 100 mJ / cm ² (based on 365 nm) in an atmosphere. In addition, the exposure to the colored resin composition layer at this time was performed by passing the radiated light from the ultrahigh pressure mercury lamp through an optical filter (UV-35; manufactured by Asahi Techno Glass Co., Ltd.). In addition, a photomask having a pattern (having 10 mm square square light-transmitting portions and having a square interval of 100 mm) formed on the same plane was used as a photomask. After exposure, the colored resin composition layer exposed with an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide was developed by immersing at 23 ° C. for 80 seconds, washed with water, Post-baking was performed in an oven at 220 ° C. for 20 minutes to form a 10 mm square colored pattern on the silicon substrate.

Compositions 1 to 6 were applied to a silicon substrate on which a colored pattern was formed under the condition that the film thickness after curing was 2.0 μm using a spin coater. Thereafter, the degree of vacuum was reduced to 1.0 Torr (about 1.3 × 10 ² Pa) with a vacuum dryer (VCD Microtech Co., Ltd.), and the film was dried. Subsequently, it prebaked for 2 minutes on the hotplate set at 90 degreeC, and the coating film was formed. After cooling, the surface of the coating film was irradiated with a Na lamp, and then the surface of the coating film was visually confirmed. On the substrate, when no striation was observed, it was evaluated as good (◯), and when it was observed, it was evaluated as defective (×). The results are shown in Table 3.

(2) Moyamura evaluation In the same manner as the striation evaluation, a coating film was formed on the silicon substrate on which a colored pattern was not formed using compositions 1 to 7, and the coating film surface was illuminated with a Na lamp. Then, the coating film surface was confirmed visually. When uneven (uneven) unevenness is not recognized on the coating film, it is good (◯). When haze-like unevenness was observed, it was evaluated as defective (x). The results are shown in Table 3.

(3) Evaluation of heat resistance A 2-inch square glass substrate (Eagle 2000; manufactured by Corning) was sequentially washed with a neutral detergent, water and 2-propanol, and then dried. Composition 4 or composition 6 was applied onto this glass substrate by a spin coating method, baked in a clean oven at 100 ° C. for 3 minutes, and subsequently baked at 220 ° C. for 20 minutes to form a coating film. The coating film thus formed was heated in a clean oven at 240 ° C. for 4 hours, and before and after that, the transmittance (%) at a wavelength of 400 nm of the coating film was measured with a microspectrophotometer (OSP-SP200; manufactured by OLYMPUS). Measured and determined transmittance retention from equation (i):
Transmittance retention rate (%)
= 100 × transmittance after heating (%) / transmittance before heating (%) (i)

  The results are shown in Table 3. When the transmittance retention is 90% or more, it can be determined that the heat resistance of the coating film is good.

  From the result shown to Tables 1-3, the compositions 1-4 and 7 containing a compound (F) can form a coating film with few nonuniformity with respect to the compositions 5 and 6 which do not contain a compound (F). I understand. Moreover, the coating film obtained from the composition 4 has better transmittance retention than the coating film obtained from the composition 6, and is excellent in heat resistance.

  The resin composition of the present invention containing the compound (F) has good coatability and can form a coating film and a pattern with little unevenness. Therefore, if the resin composition of the present invention is used, a high-quality display device can be manufactured with a high yield. In particular, the resin composition of the present invention is suitable for producing a coat layer and a pixel pattern of a large display device.

Claims (14)

A resin composition comprising a resin, a polymerizable compound, a compound represented by formula (F), and a solvent.

[In Formula (F), L ¹ represents a divalent C _2-8 aliphatic hydrocarbon group.
L ² and L ³ each independently represents a trivalent C _2-8 aliphatic hydrocarbon group.
R ¹ and R ² each independently represents a monovalent C _1-8 aliphatic hydrocarbon group, and at least three hydrogen atoms of the aliphatic hydrocarbon group are substituted with fluorine atoms.
m and n each independently represent an integer of 0 or more and 22 or less. However, m + n is 3 or more and 22 or less. ] The resin composition according to claim ^1, wherein R ¹ and R ² are each independently a group represented by the formula (f1).
_{-C p H 2p -C q F 2q} + 1 (f1)
[In Formula (f1), p and q each independently represents an integer of 1 or more and 4 or less. ] The resin composition according to claim 1 or 2, wherein R ¹ and R ² are linear C _1-8 aliphatic hydrocarbon groups.   The resin composition according to claim 2 or 3, wherein q is 4. The resin composition according to any one of claims 1 to 4, wherein the compound represented by the formula (F) is a compound represented by the formula (F1-1).

[In formula (F1-1), m and n have the same meaning as described above. ]   m + n is 3-6, The resin composition in any one of Claims 1-5.   The resin is a single unit having a structural unit derived from at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a carbon-carbon double bond, and a cyclic ether structure. The resin composition according to any one of claims 1 to 6, which is a copolymer comprising a structural unit derived from a monomer (b) {but different from the monomer (a)}. The resin composition according to claim 7, wherein the monomer (b) is at least one selected from the group consisting of a compound represented by the formula (b1-1) and a compound represented by the formula (b1-2). object.

[In Formula (b1-1) and Formula (b1-2), R ³ represents a hydrogen atom or a C _1-4 aliphatic hydrocarbon group, and the hydrogen atom of the aliphatic hydrocarbon group is substituted with a hydroxy group. May be.
L ⁴ represents a single bond or a C _1-6 aliphatic hydrocarbon group, and —CH ₂ — of the aliphatic hydrocarbon group may be substituted with —O—, —S— or —NH—. .
R ³ and L ⁴ in formula (b1-1) may be the same as or different from R ³ and L ^{4 in} formula (b1-2), respectively. ]   Furthermore, the resin composition in any one of Claims 1-8 containing a polymerization initiator.   The resin composition according to claim 9, wherein the polymerization initiator is a polymerization initiator containing a biimidazole compound.   The coating film formed using the resin composition in any one of Claims 1-10.   The pattern formed using the resin composition of Claim 9 or 10.   A liquid crystal display device comprising at least one selected from the group consisting of the coating film according to claim 11 and the pattern according to claim 12.   An organic EL display device comprising at least one selected from the group consisting of the coating film according to claim 11 and the pattern according to claim 12.