KR20180096524A - Resin composition and cured film - Google Patents

Abstract

A resin composition of the present invention includes a resin, a polymerizable compound, and a polymerization initiator, wherein the polymerizable compound comprises a polymerizable compound having a fluorene skeleton. The content of the polymerizable compound having a fluorene skeleton is preferably more than 10 mass% to the total amount of the polymerizable compound. According to the present invention, the developing ability of the resin composition can be improved and the refractive index of obtained films can be improved.

Description

RESIN COMPOSITION AND CURED FILM [0001]

The present invention relates to a resin composition and a cured film.

In recent liquid crystal displays, a resin composition capable of forming a pattern by development is used for a color filter or the like. As such a resin composition, JP 2011-165396 discloses a photosensitive composition containing 9.4% by mass of a compound represented by the following formula as a polymerizable compound in a polymerizable compound.

The present invention includes the following inventions.

[1] A resin composition comprising a resin, a polymerizable compound and a polymerization initiator,

Wherein the polymerizable compound comprises a polymerizable compound having a fluorene skeleton,

The content of the polymerizable compound having a fluorene skeleton is more than 10% by mass based on the total amount of the polymerizable compounds.

[2] The resin composition according to [1], wherein the polymerizable compound having a fluorene skeleton is a compound represented by the formula (VI).

[In the formula (VI), L ¹ independently represents an alkanediyl group having 1 to 16 carbon atoms which may have a single bond or a substituent, and the methylene group contained in the alkanediyl group may be substituted with an oxygen atom. Provided that the methylene group to which the oxygen atom is bonded is not replaced with an oxygen atom.

And R < ¹¹ > independently represent a hydrogen atom or a methyl group.

[3] The resin composition according to any one of [1] to [4], wherein the resin comprises a constituent unit (Aa) having a cyclic ether structure of 2 to 4 carbon atoms, wherein the constituent unit (Aa) is derived from a monomer having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized [ 1] or [2].

[4] The resin composition according to any one of [1] to [3], wherein the resin is a resin containing a structural unit having a carbazole ring.

[5] A cured film formed from the resin composition according to any one of [1] to [4].

In the present specification, the compounds exemplified as respective components may be used singly or in combination of plural species unless otherwise specified.

[Resin composition]

The resin composition of the present invention comprises a resin (hereinafter referred to as resin (A)), a polymerizable compound (hereinafter referred to as polymerizable compound (C)) and a polymerization initiator (hereinafter referred to as polymerization initiator (D)). ). The polymerizable compound (C) includes a polymerizable compound having a fluorene skeleton.

The resin composition may further contain a solvent (hereinafter referred to as a solvent (E)). The resin composition of the present invention may further contain other components such as a leveling agent (hereinafter referred to as leveling agent B), an antioxidant (hereinafter referred to as antioxidant F), a curing agent And a hardening agent (G)). Examples of the curing agent (G) include polyvalent carboxylic acid (hereinafter referred to as polyvalent carboxylic acid (G1)) and imidazole compound (hereinafter referred to as imidazole compound (G2)).

<Polymerizable compound>

The polymerizable compound (C) includes a polymerizable compound having a fluorene skeleton (hereinafter, referred to as a polymerizable compound (C1)), which reacts with heat or by the action of a polymerization initiator (D). The content of the polymerizable compound (C1) is more than 10% by mass, preferably not less than 12% by mass, more preferably not less than 15% by mass, relative to the total amount of the polymerizable compound (C) 20 mass% or more, and more preferably 40 mass% or more. The polymerizable compound (C1) is usually 100 mass% or less based on the total amount of the polymerizable compound (C). By including the polymerizable compound (C1) at such a content, the developability of the resin composition can be improved. Incorporation of the polymerizable compound (C1) at such a content can improve the refractive index of the obtained film.

The polymerizable compound (C) may contain other polymerizable compounds other than the polymerizable compound (C1). As the other polymerizable compound, a compound having an ethylenically unsaturated bond can be enumerated, preferably a (meth) acrylic compound, more preferably at least an acryloyl group and a methacryloyl group And a compound having one kind of group. In the present specification, "(meth) acrylic acid" refers to at least one compound selected from the group consisting of acrylic acid and methacrylic acid. The expressions such as "(meth) acryloyl" and "(meth) acrylate" have the same meaning.

[1] The polymerizable compound (C1)

The polymerizable compound (C1) is a compound having a fluorene skeleton, and is preferably a compound represented by the formula (VI).

[In the formula (VI), L ¹ independently represents an alkanediyl group having 1 to 16 carbon atoms which may have a single bond or a substituent, and the methylene group contained in the alkanediyl group may be substituted with an oxygen atom. Provided that the methylene group to which the oxygen atom is bonded is not replaced with an oxygen atom.

And R &lt; ¹¹ &gt; independently represent a hydrogen atom or a methyl group.

Examples of the compound represented by the formula (VI) include compounds represented by the formulas (VI-1) to (VI-3).

[In the formula (VI-3), R ^12a and R ^12b independently represent a hydrogen atom or a methyl group, and m and n are an integer of 0 or more. Provided that when m and n are 0, at least one of R ^12a and R ^12b is a methyl group.

As the compound represented by the formula (VI), a compound represented by the formula (VIa) is more preferable.

[In the formula (VIa), L ^2a and L ^2b independently represent an alkanediyl group having 1 to 6 carbon atoms which may be substituted.

m and n independently represent an integer of 0 to 8; Provided that m + n is 0 to 16;

When m and n are each 2 or more, a plurality of L ^2a and L ^2b may be the same or different.

With the proviso that in m L ^2a and n L ^2b , the total number of carbon atoms thereof is 0-30.

R ^13a and R ^13b independently represent a hydrogen atom or a methyl group.

[2] (meth) acrylic compound

Examples of the (meth) acrylic compound having one (meth) acryloyl group include (meth) acrylic acid alkyl ester, phenoxylated polyethylene glycol ester of (meth) acrylic acid, alkoxylated polyethylene glycol ester of (meth) acrylic acid, isobornyl Hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxybutyl And tetrahydrofurfuryl (meth) acrylate.

Examples of the (meth) acrylic compound having two (meth) acryloyl groups include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, Acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, propylene oxide-modified neopentyl glycol di (meth) acrylate, ethylene oxide-modified neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A Pentyl glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, and the like.

Examples of the (meth) acrylic compound having three or more (meth) acryloyl groups include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (Meth) acrylate, ethylene oxide modified trimethylol propane tri (meth) acrylate, propylene oxide modified trimethylol propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta , Tripentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (metha) acrylate, tripentaerythritol penta (metha) acrylate, tripentaerythritol hexa (metha) acrylate, tripentaerythritol hepta , Tripentaerythritol octa (meth) acrylate, pentaerythritol tri (meth) acrylate (Meth) acrylate and acid anhydride, a reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, a reaction product of tripentaerythritol hepta (meth) acrylate and acid anhydride, caprolactone-modified trimethylolpropane tri (meth) Caprolactone modified tetra (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipenta Caprolactone-modified tetrapenta (meta) acrylate, caprolactone-modified dipentaerythritol hexa (metha) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta Tripentaerythritol hexa (meth) acrylate, caprolactone (Meth) acrylate, caprolactone-modified tripentaerythritol octa (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride, caprolactone-modified dipentaerythritol penta ) Acrylate and an acid anhydride, a reaction product of caprolactone-modified tripentaerythritol hepta (meth) acrylate and an acid anhydride, and the like.

As the (meth) acrylic compound, a (meth) acrylic compound having three or more (meth) acryloyl groups is preferable, and dipentaerythritol hexa (meth) acrylate is more preferable.

The content of the polymerizable compound (C) is preferably 20 to 200 parts by mass, more preferably 30 to 150 parts by mass, per 100 parts by mass of the resin (A). When the content of the polymerizable compound (C) is within the above range, the chemical resistance and the mechanical strength of the resulting film can be improved.

&Lt; Resin (A) >

The resin (A) is not limited as long as it is a curable resin, but it is preferable that the resin (A) is an alkali-soluble resin. The resin (A) contains at least one structural unit selected from the group consisting of a structural unit having a cyclic ether structure of 2 to 4 carbon atoms (hereinafter referred to as structural unit (Aa)) and an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. (Hereinafter referred to as &quot; structural unit (Ac) &quot;). The resin (A) preferably contains a constituent unit containing a condensed ring (hereinafter referred to as a constituent unit (Ab)). The resin (A) may have a constituent unit other than the constituent unit (Aa), (Ab) and (Ac) (hereinafter referred to as a constituent unit (Ad)).

The resin (A) may contain two or more kinds of the structural unit (Aa) and the structural unit (Ab).

[1] Structural unit (Aa)

The constituent unit (Aa) can be derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one kind selected from the group consisting of oxirane rings, oxetane rings and tetrahydrofuran rings) . A constituent unit derived from an unsaturated compound having a cyclic ether structure of 2 to 4 carbon atoms can be obtained by obtaining a copolymer using the unsaturated compound as a monomer. Or a compound having a cyclic ether structure of 2 to 4 carbon atoms to the other structural unit (hereinafter referred to as structural unit (Aa ')).

Examples of the unsaturated compound for deriving the constituent unit (Aa) include monomers having an oxiranyl group and an ethylenic unsaturated bond (hereinafter referred to as monomer (Aa1)), oxetanyl groups and monomers having an ethylenic unsaturated bond ( (Hereinafter referred to as monomer (Aa2)), and a monomer having a tetrahydrofuryl group and an ethylenic unsaturated bond (hereinafter referred to as monomer (Aa3)).

The monomer (Aa1) is, for example, a monomer having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter referred to as a monomer (Aa1-1)) and an unsaturated alicyclic hydrocarbon having an epoxidized (Hereinafter referred to as &quot; monomer (Aa1-2) &quot;). As the monomer for deriving the constituent unit (Aa), it is preferable that the monomer (Aa1) is used because it is possible to further increase the reliability of the obtained film, such as heat resistance and chemical resistance. Further, from the viewpoint of excellent storage stability of the resin composition, the monomer (Aa1-2) is more preferable.

Examples of the monomer (Aa1-1) include glycidyl (meth) acrylate,? -Methyl glycidyl (meth) acrylate,? -Ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, Vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5- Styrenes such as 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, (Glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) .

Examples of the monomer (Aa1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e. G., Celloxide 2000; Daicel), 3,4-epoxycyclohexylmethyl Acrylate (for example, cyclomer A400 manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (e.g., , A compound represented by the formula (I) and a compound represented by the formula (II).

[In the formulas (I) and (II), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group.

X ^b1 and X ^b2 represent a single bond, * -R ^b3- , * -R ^b3 -O-, * -R ^b3 -S- or * -R ^b3 -NH-.

R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms.

* Stands for a binding hand with O.]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.

Examples of the alkyl group in which the hydrogen atom is substituted by a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, 1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group.

R ^b1 and R ^b2 are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane- A 6-diyl group and the like.

X ^b1 and X ^b2 are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O-, * -CH ₂ CH ₂ -O- and more preferably a single bond, * - CH ₂ CH ₂ -O-. * Represents the binding hand with O.

Examples of the compound represented by the formula (I) include compounds represented by any one of the formulas (I-1) to (I-15), preferably the compounds represented by the formulas (I- ), Formula (I-5), Formula (I-7), Formula (I-9) and Formula (I-11) to Formula (I-15) (I-1), formula (I-7), formula (I-9) and formula (I-15).

Examples of the compound represented by the formula (II) include compounds represented by any one of the formulas (II-1) to (II-15), preferably the compounds represented by the formulas (II- ), Formula (II-5), Formula (II-7), Formula (II-9) and Formula (II-11) to Formula (II-15) (II-1), (II-7), (II-9) and (II-15).

The compound represented by formula (I) and the compound represented by formula (II) may be used alone or in combination of two or more. When these compounds are used in combination, the content ratio of the compound [compound represented by formula (I): compound represented by formula (II)] is preferably 5:95 to 95: 5, more preferably 20: 80 to 80:20. For example, a mixture containing 50:50 of the compound represented by the formula (I-1) and the compound represented by the formula (II-1) (commercially available product "E-DCPA" ) Can be used.

As the monomer (Aa2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. As the monomer (Aa2), 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3 Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3- 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

As the monomer (Aa3), a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is preferable. Examples of the monomer (Aa3) include tetrahydrofurfuryl acrylate (for example, Viscot V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

As the constituent unit (Aa), it is preferable that the monomer (Aa1-2) is used in view of the storage stability of the resin composition, the chemical resistance of the obtained film, the heat resistance and the mechanical strength and also the superior follow- (Aa-1) or (Aa-2) is more preferable. The structural unit represented by the formula (Aa-1) is derived from the compound represented by the formula (I), and the structural unit represented by the formula (Aa-2) is derived from the compound represented by the formula (II).

[Wherein R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group do.

X ^b1 and X ^b2 represent a single bond, * -R ^b3- , * -R ^b3 -O-, * -R ^b3 -S- or * -R ^b3 -NH-.

R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms.

* Stands for a binding hand with O.]

[2] Structural unit (Ab)

The structural unit (Ab) having a condensed ring can be derived from an unsaturated compound having a condensed ring. Examples of the condensed rings include a naphthalene ring, an anthracene ring, a carbazole ring and the like, among which a carbazole ring is preferable. The constituent unit having a carbazole ring is a constituent unit derived from an unsaturated compound having a carbazole ring. A constituent unit derived from an unsaturated compound having a carbazole ring can be obtained by obtaining a copolymer using the unsaturated compound as a monomer. Or by reacting a compound (Ab ") having a carbazole ring with another structural unit (Ab ').

By having the constituent unit (Ab) having a carbazole ring, it is possible to form a film having high followability with respect to the shape of the base substrate. Also, by having the structural unit (Ab) having a carbazole ring, the refractive index of the resulting film can be improved.

The unsaturated compound which derives the constituent unit (Ab) is preferably a compound represented by the formula (III).

[In the formula (III), R ¹ represents a hydrogen atom, a methyl group or a hydroxymethyl group.

R ² to R ⁹ independently represent a hydrogen atom, a halogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is an alkoxy group or an aryl group Or may be substituted.

X represents a single bond, an alkanediyl group having a carbon number of 1 or more, or a straight or branched chain group represented by the following formula (V).

(In the formula (V), 1 represents an integer of 0 or more, and m represents an integer of 1 or more.)]

Examples of the compound represented by the formula (III) include N-vinylcarbazole, N-allylcarbazole, N- (meth) acryloylcarbazole, 2- (9- (Meth) acrylate, 2- (9-carbazolyl) ethoxyethyl (meth) acrylate, 2- (Meth) acrylate, and N-vinylcarbazole, N-allylcarbazole and 2- (9-carbazolyl) ethyl (meth) acrylate .

[3] Structural unit (Ac)

As the structural unit (Ac), a structural unit derived from a compound belonging to the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter referred to as "structural unit (Ac1)") can be mentioned.

Examples of the compound belonging to the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m- and p-vinylbenzoic acid;

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, Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- 5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept- [2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , Unsaturated dicarboxylic anhydrides such as dimethyl tetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-eno anhydride; Unsaturated mono [(meth) acryloyloxyalkyl] unsaturated monocarboxylic acid such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] ester;

and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule such as? - (hydroxymethyl) acrylic acid.

[4] Construction unit (Ad)

As the constituent unit (Ad), for example, the following compounds:

(Meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate such as cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan- (Hereinafter referred to as "tricyclodecyl (meth) acrylate"), tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (Meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, , Allyl (meth) acrylate, propargyl (meth) acrylate, Methacrylate, phenyl (meth) acrylate, benzyl (meth) (meth) acrylic acid esters such as acrylate; (Meth) acrylic acid esters having a hydroxy group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] Non-cyclounsaturated compounds such as 2-ene;

Dicarbonyl such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate and N-succinimidyl- Meade derivatives;

(Meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, vinyl acetate (meth) acrylate, , 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

[5] Percentage of each constituent unit

Examples of the resin (A) include the following resins [K1] to [K4].

Resin [K1]: a copolymer composed of a constituent unit (Aa) and a constituent unit (Ac);

Resin [K2]: a copolymer composed of a constituent unit (Ab) and a constituent unit (Ac);

Resin [K3]: a copolymer composed of a constituent unit (Aa), a constituent unit (Ab) and a constituent unit (Ac);

Resin [K4]: Copolymer composed of a constituent unit (Aa), a constituent unit (Ab), a constituent unit (Ac) and a constituent unit (Ad).

Resin (A) is preferably resin [K1] and resin [K3].

In the resin [K1], the ratio of each constituent unit is preferably such that the total constituent units constituting the resin [K1]

A constituent unit (Aa); 50 to 99 mol%

A constituent unit (Ac); , More preferably 1 to 50 mol%

A constituent unit (Aa); 60 to 95 mol%

A constituent unit (Ac); And more preferably 5 to 40 mol%.

When the ratio of the constituent unit constituting the resin [K1] is within the above range, a film having excellent storage stability of the resin composition, chemical resistance of the obtained film, heat resistance and mechanical strength, It is preferable from the viewpoint of being able to do.

The resin [K1] can be synthesized by a method described in, for example, "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Publishing Co., Ltd., 1st Edition, 1st Edition, March 1, 1972) It can be produced with reference to the cited documents.

Specifically, a predetermined amount of the constituent unit (Aa) and the constituent unit (Ac), a polymerization initiator and a solvent are placed in a reaction vessel, and oxygen is replaced by, for example, nitrogen, , Heating and keeping warm. The polymerization initiator, solvent and the like to be used herein are not particularly limited and those generally used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutylonitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like) and organic peroxides such as benzoyl peroxide ). Examples of the solvent include any of those described below that are soluble in the respective monomers and used in the resin composition.

The obtained resin may be a solution after the reaction as it is, or a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by re-precipitation or the like. In particular, by using the solvent used for the resin composition of the present invention as the polymerization solvent, the solution after the reaction can be used as it is for the production of the resin composition, so that the production process of the resin composition can be simplified.

In the resin [K2], the ratio of the respective constitutional units is such that, among all the constitutional units constituting the resin [K2]

A structural unit (Ab); 50 to 99 mol%

A constituent unit (Ac); , More preferably 1 to 50 mol%

A structural unit (Ab); 60 to 90 mol%

A constituent unit (Ac); And more preferably 5 to 40 mol%.

In the resin [K3], the proportion of each constituent unit is preferably selected from among all the constituent units constituting the resin [K3]

A constituent unit (Aa); 1 to 90 mol%

A structural unit (Ab); 1 to 98 mol%

A constituent unit (Ac); , More preferably 1 to 50 mol%

A constituent unit (Aa); 3 to 70 mol%

A structural unit (Ab); 20 to 90 mol%

A constituent unit (Ac); More preferably 3 to 40 mol%

A constituent unit (Aa); 3 to 70 mol%

A structural unit (Ab); 50 to 90 mol%

A constituent unit (Ac); And more preferably 3 to 40 mol%.

In the resin [K4], the ratio of the respective constitutional units is such that, among all the constitutional units constituting the resin [K4]

A constituent unit (Aa); 1 to 70 mol%

A structural unit (Ab); 5 to 90 mol%

A constituent unit (Ac); 1 to 50 mol%

A constituent unit (Ad); , More preferably 1 to 40 mol%

A constituent unit (Aa); 3 to 50 mol%

A structural unit (Ab); 10 to 90 mol%

A constituent unit (Ac); 5 to 35 mol%

A constituent unit (Ad); More preferably 1 to 30 mol%

A constituent unit (Aa); 3 to 50 mol%

A structural unit (Ab); 50 to 90 mol%

A constituent unit (Ac); 5 to 35 mol%

A constituent unit (Ad); More preferably 1 to 30 mol%.

When the ratio of the constituent units of the resins [K2] to [K4] is within the above range, it is preferable from the viewpoint of the storage stability of the resin composition, the chemical resistance of the obtained film, the heat resistance and the mechanical strength, Do. Resins [K2] to [K4] can be produced by the same method as Resin [K1].

The weight average molecular weight (Mw) of the resin (A) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 20,000, and particularly preferably 5,000 to 10,000. When the weight average molecular weight (Mw) of the resin (A) is within the above range, the coating property of the resin composition tends to be good.

The dispersion degree (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin (A) is preferably 1.1 to 6.0, more preferably 1.2 to 4.0. When the degree of dispersion is within the above range, the resulting cured film tends to have excellent chemical resistance.

The acid value of the resin (A) is preferably 30 mgKOH / g or more and 180 mgKOH / g or less, more preferably 40 mgKOH / g or more and 150 mgKOH / g or less, still more preferably 50 Mg-KOH / g and not more than 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin, and can be obtained by titration using an aqueous potassium hydroxide solution. When the acid value of the resin (A) is within the above range, the resulting cured film tends to have excellent adhesion with the substrate.

The content of the resin (A) is preferably 30 to 90 mass%, more preferably 35 to 80 mass%, and even more preferably 40 to 70 mass%, based on the solid content of the resin composition of the present invention. When the content of the resin (A) is within the above range, the resin composition is excellent in developability, and the cured film obtained is excellent in heat resistance and tends to have excellent adhesion with the substrate and chemical resistance. Here, the solid content of the resin composition refers to the amount obtained by subtracting the content of the solvent (E) from the total amount of the resin composition of the present invention.

&Lt; Polymerization initiator (D) >

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical or acid by the action of light or heat and capable of initiating polymerization of the polymerizable compound (C), and a known polymerization initiator can be used . As the polymerization initiator (D), a polymerization initiator containing at least one member selected from the group consisting of an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound and a imidazole compound is preferable, A polymerization initiator comprising an acyloxime compound is more preferable. These polymerization initiators tend to have a high sensitivity and a high transmittance in the visible light region.

The O-acyloxime compound is a compound having a structure represented by the formula (D1).

Herein, * denotes a combined hand.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- Ethyl-6- (2-methylbenzyl) -9H-carbazol-3-yl] ethan- 1-imine, N- acetoxy- (3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan- 1-imine, N- acetoxy- 1- [ Carbamoyl) -9H-carbazol-3-yl] -3-cyclopentylpropan- 1-imine, N-benzoyloxy- 3-yl] -3-cyclopentylpropan-1-one-2-imine. A commercially available product such as Irgacure (registered trademark) OXE01, OXE02 (manufactured by BASF Corporation) and N-1919 (manufactured by ADEKA Corporation) may be used.

The alkylphenone compound is a compound having a structure represented by formula (D2-1) or a structure represented by formula (D2-2). Of these structures, the benzene ring may have a substituent.

Examples of the compound having a structure represented by the formula (D2-1) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- (4-morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) Phenyl] butan-1-one. IRGACURE (registered trademark) 369, 907 and 379 (manufactured by BASF Co., Ltd.) and the like may be used. A polymerization initiator having a group capable of chain transfer described in JP-A-2002-544205 may also be used. Examples of the compound having a partial structure represented by the formula (D2-2) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2- 2-methyl-1- (4-isopropenylphenyl) propane-1-one, On oligomers,?,? - diethoxyacetophenone, and benzyldimethyl ketal. From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by the formula (D2-1).

Examples of the triazine compound include 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, (Trichloromethyl) -6- [2- (5-methylfuran-2- (4-methoxystyryl) -1,3,5-triazine, Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. A commercially available product such as Irgacure 819 (manufactured by BASF Japan Co., Ltd.) may be used.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A 6-75372 and JP-A 6-75373), 2 (2-chlorophenyl) -4,4 ', 5' -tetra (alkoxyphenyl) biimidazole, 2,2'-bis , 5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra , Japanese Unexamined Patent Publication (Kokai) No. 48-38403, Japanese Unexamined Patent Publication (Kokai) No. 62-174204, and the like), a ratio in which the phenyl group at the 4,4 ', 5,5'- position is substituted by a carboalkoxy group Imidazole compounds (see, for example, Japanese Patent Application Laid-Open No. 7-10913, etc.).

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, camphorquinone, etc .; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These can be used in combination with a polymerization initiator (hereinafter referred to as polymerization initiator (H)) (especially amines) to be described later.

The polymerization initiator (D) may be an acid generating system. As the acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p- 4-acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate , Diphenyl iodonium hexafluoroantimonate, and the like, and nitrobenzyl tosylate and benzoin tosylate.

When the resin composition of the present invention contains the polymerizable compound (C) and the polymerization initiator (D), the content of the polymerization initiator (D) is preferably 100 parts by mass or less per 100 parts by mass of the total content of the resin (A) Preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 15 parts by mass, and even more preferably from 1 to 8 parts by mass. When the content of the polymerization initiator (D) is within the above range, the visible light transmittance of the resulting cured film tends to be high.

&Lt; Polymerization initiator (H) >

The polymerization initiator (H) is a compound or a sensitizer used in combination with the polymerization initiator (D) and used for promoting polymerization of the polymerizable compound (C) initiated by polymerization initiator (D).

Examples of the polymerization initiator (H) include a thiazoline compound, an amine compound, an alkoxy anthracene compound, a thioxanthone compound, and a carboxylic acid compound.

Examples of the thiazoline compound include compounds represented by the formulas (H1-1) to (H1-3) and compounds described in Japanese Patent Application Laid-Open No. 2008-65319.

Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4-dimethylamino benzoic acid 2 (Ethylhexyl), N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'- Bis (ethylmethylamino) benzophenone, and the like, among which 4,4'-bis (diethylamino) benzophenone is preferable. And commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may be used.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10- Anthracene, and 2-ethyl-9,10-dibutoxyanthracene.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Santon et al.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, Phenylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

When the resin composition of the present invention contains the polymerizable compound (C), the polymerization initiator (D) and the polymerization initiator (H), the content of the polymerization initiator (H) ) Is preferably from 0.1 to 30 parts by mass, and more preferably from 0.2 to 10 parts by mass, based on 100 parts by mass of the total content. When the amount of the polymerization initiator (H) is within the above range, there is a tendency that the sensitivity becomes higher when the pattern is formed.

&Lt; Leveling agent (B) >

Examples of the leveling agent (B) include a silicone surfactant, a fluorine surfactant, and a silicon surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specific examples thereof include Toray Silicone DC3PA, Copper SH7PA, Copper DC11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA and Copper SH8400 (trade names, manufactured by Toray Dow Corning), KP321, KP322, KP323, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (produced by Momentive Performance Materials Japan Joint-Industrial Company).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specific examples thereof include Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Corporation), Megapack (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper F554 (Manufactured by Mitsubishi Materials Electronics Co., Ltd.), RS-718-K (manufactured by DIC Corporation), FTOP (registered trademark) EF301, EF303, EF351, Surflon (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Co., Ltd.).

Examples of the silicon-containing surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megapac (registered trademark) R08, Copolymer BL20, Copolymer F475, Copolymer F477 and Copolymer F443 (manufactured by DIC Corporation).

When the leveling agent (B) is contained, the content thereof is preferably 0.001 mass% or more and 0.2 mass% or less, more preferably 0.002 mass% or more and 0.1 mass% or less, relative to the total amount of the resin composition, Is 0.005 mass% or more and 0.07 mass% or less.

&Lt; Antioxidant (F) >

Examples of the antioxidant (F) include a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant and an amine-based antioxidant. Among them, a phenol-based antioxidant is preferable in that the obtained film is less colored.

Examples of the phenolic antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4- methylphenyl acrylate, 2- [1- Tert-butyl-4-hydroxyphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 3,9-bis [2- {3- Methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis (6-tert- Methylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert- (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-tri (3H, 5H) -triene, 3,3 ', 3 ", 5,5', 5" -hexa-tert- Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6- Butyl-4-methylphenol and 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) Tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphpepine. A commercially available phenol-based antioxidant may be used (Trade names, all manufactured by Sumitomo Chemical Co., Ltd.), Irganox (registered trademark) 1010, 1076, 1330 and 3114 (all manufactured by BASF Corporation).

Examples of the sulfur-based antioxidant include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, And pentaerythrityl tetrakis (3-laurylthiopropionate). As the sulfur-based antioxidant, a commercially available product may be used. Examples of commercially available sulfur-based antioxidants include Smilizer (registered trademark) TPL-R and TP-D (all manufactured by Sumitomo Chemical Co., Ltd.).

Examples of the phosphorus antioxidant include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) 3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane diphosphite. As the phosphorus antioxidant, a commercially available product may be used. Examples of commercially available phosphorus antioxidants include Irgafos (registered trademark) 168, 12 and 38 (all manufactured by BASF Corporation), Adecastab 329K, Adecastab PEP36 (all above ) Manufactured by ADEKA).

Examples of the amine antioxidant include N, N'-di-sec-butyl-p-phenylenediamine, N, N'-di- p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine and N, N'-bis (2-naphthyl) -p-phenylenediamine. As the amine antioxidant, a commercially available product may be used. Examples of commercially available amine antioxidants include Smilizer (registered trademark) BPA, BPA-M1 and 4ML (all manufactured by Sumitomo Chemical Co., Ltd.).

When the resin composition of the present invention contains the antioxidant (F), the content thereof is preferably 0.1 part by mass or more and 5 parts by mass or less, more preferably 0.1 parts by mass or more, per 100 parts by mass of the total content of the resin (A) More preferably not less than 0.5 parts by mass and not more than 3 parts by mass. When the content of the antioxidant (F) is within the above range, the obtained film tends to have excellent heat resistance and pencil hardness.

&Lt; Curing agent (G) >

<Sugar carboxylic acid (G1)>

The polyvalent carboxylic acid (G1) is at least one compound selected from the group consisting of polyvalent carboxylic anhydrides and polyvalent carboxylic acids. The polyvalent carboxylic acid is a compound having two or more carboxyl groups, and the polyvalent carboxylic acid anhydride is an anhydride of a polyvalent carboxylic acid. The molecular weight of the polyvalent carboxylic acid (G1) is preferably 3000 or less, more preferably 1,000 or less.

Examples of the polyvalent carboxylic acid anhydride include maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhydride, 2-dodecylsuccinic anhydride, 2- (2-octa- Chain polycarboxylic anhydrides such as succinic anhydride, 2- (2,4,6-trimethylnona-3-enyl) succinic anhydride, tricarvalylic anhydride and 1,2,3,4-butanetetracarboxylic dianhydride; Tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, norbornene dicar 2.2.1] heptane-2,3-dicarboxylic anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, bicyclo [2.2.1] hepta- Alicyclic polycarboxylic anhydrides such as 2,2-dimethylene-2,3-dicarboxylic anhydride, methylbicyclo [2.2.1] hepta-5-ene-2,3-dicarboxylic anhydride and cyclopentane tetracarboxylic dianhydride ; Vinyl phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid 2 Glycerin tris (anhydrotrimellitate), glycerin bis (anhydrotrimellitate) monoacetate, 1,3,3a, 4,5,9b-hexahydro-pentaerythritol monohydrate, anhydride, ethylene glycol bis (anhydrotrimellitate) Aromatic tetracarboxylic anhydrides such as 5- (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione; . (Trade name) (hereinafter referred to as ADEKA), Rikaside (registered trademark) -HH, copper-TH, copper-MH, copper MH-700 (Manufactured by Sumitomo Chemical Co., Ltd.), Epikinia 126, Copper YH-306, Copper DX-126 (made by Oil Shell Epoxy Co., Ltd.)

Examples of the polyvalent carboxylic acid include chain polycarboxylic acids such as oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, and polyvalent carboxylic acids derived from a chain polyvalent carboxylic acid anhydride; Alicyclic polycarboxylic acids such as cyclohexanedicarboxylic acid, and polycarboxylic acids derived from alicyclic polycarboxylic anhydride; Aromatic polycarboxylic acids such as isophthalic acid, terephthalic acid, 1,4,5,8-naphthalenetetracarboxylic acid, and polyvalent carboxylic acids derived from aromatic polycarboxylic anhydrides; And the like.

Among them, a chain carboxylic anhydride and an alicyclic polycarboxylic acid anhydride are preferable, and an alicyclic polycarboxylic anhydride is more preferable because heat resistance of the resulting film is excellent, and in particular, transparency in a visible light region is not easily lowered.

When the resin composition of the present invention contains a polyvalent carboxylic acid (G1), its content is preferably from 1 to 30 parts by mass, more preferably from 1 to 30 parts by mass, based on 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C) More preferably 2 to 20 parts by mass, and still more preferably 2 to 15 parts by mass. When the content of the polyvalent carboxylic acid (G1) is within the above range, the obtained film is excellent in heat resistance and adhesion.

&Lt; Imidazole compound (G2) >

The imidazole compound (G2) is not particularly limited as long as it is a compound having an imidazole skeleton, and examples thereof include compounds known as epoxy curing agents. Among them, a compound represented by the formula (G2-1) is preferable.

Of the formula (G2-1), R ³¹ represents an alkyl group, a phenyl group, a benzyl group or a cyano alkyl group having 2 - 5 carbon atoms of 1 to 20 carbon atoms.

R ³² to R ³⁴ independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a nitro group or an acyl group having 1 to 20 carbon atoms, and the alkyl group and the hydrogen atom contained in the phenyl group, Or may be substituted by a hydroxy group.]

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isobutyl, butyl, tert-butyl, hexyl, Practical skill can be given.

Examples of the cyanoalkyl group having 2 to 5 carbon atoms include a cyanomethyl group, a cyanoethyl group, a cyanopropyl group, a cyanobutyl group and a cyanopentyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

Examples of the acyl group having 1 to 20 carbon atoms include a formyl group, an acetyl group, a propionyl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pivaloyl group, a lauroyl group, a myristoyl group, .

Examples of the imidazole compound (G2) include 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-ethylimidazole, Phenylimidazole, 2-phenyl-2-hydroxymethylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl Benzimidazole, 1-benzyl-5-hydroxymethylimidazole, 2- (p-hydroxyphenyl) imidazole, 1-cyanomethyl- 2-ethyl-4-cyanoethyl) -2-hydroxymethylimidazole, 2,4-diphenylimidazole, 1-cyanomethyl- Methylimidazole, 1-cyanomethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole. Among them, 1-benzyl-4-phenylimidazole, 2-ethyl-4-methylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole are preferable.

When the resin composition of the present invention contains the imidazole compound (G2), its content is preferably 0.1 part by mass or more and 25 parts by mass or more per 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C) More preferably 0.2 parts by mass or more and 15 parts by mass or less, and still more preferably 0.5 parts by mass or more and 5 parts by mass or less. When the content of the imidazole compound (G2) is within the above range, the obtained film tends to have excellent transparency in the visible light region.

&Lt; Solvent (E) >

The resin composition of the present invention may contain a solvent (E). The solvent (E) is not particularly limited and includes solvents commonly used in the art. For example, an ester solvent (a solvent containing -COO- in the molecule and containing no -O-), an ether solvent (a solvent containing -O- and no -COO- in the molecule), an ether ester (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not including -COO-), alcohol solvent (containing OH in the molecule, O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, Butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetone and? -Butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1 , 4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole and methyl anisole .

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Methoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Methyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, propyleneglycol monomethyl ether acetate, Ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether And the like Le acetate and diethylene glycol monobutyl ether acetate.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, Cyclohexanone, isophorone, and the like.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

Among these solvents, an organic solvent having a boiling point of 100 占 폚 or more and 200 占 폚 or less at 1 atm is preferable from the viewpoint of coatability and drying property. As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethylene glycol ethyl methyl ether, cyclohexanone, methoxybutanol and methoxybutyl acetate are preferable , Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, methoxybutanol and methoxybutyl acetate are more preferable.

The content of the solvent (E) in the resin composition of the present invention is preferably 60 to 95 mass%, more preferably 70 to 95 mass%, based on the total amount of the resin composition. In other words, the solid content of the resin composition of the present invention is preferably 5 to 40% by mass, and more preferably 5 to 30% by mass. When the content of the solvent (E) is in the above range, there is a tendency to improve the followability of the film obtained by applying the resin composition to the shape of the base substrate.

&Lt; Other components >

The resin composition of the present invention may contain additives known in the art, such as fillers, other polymer compounds, ultraviolet absorbers, chain transfer agents, adhesion promoters, colorants, and pigment dispersants, if necessary.

When the resin composition of the present invention is filled in a quartz cell having an optical path length of 1 cm and the transmittance is measured under a condition of a measurement wavelength of 400 to 700 nm using a spectrophotometer, the average transmittance is preferably 70 % Or more, and more preferably 80% or more.

When a film is formed using the resin composition of the present invention, the average transmittance of the film is preferably 90% or more, and more preferably 95% or more. The average transmittance is an average value when a film having a thickness of 2 占 퐉 after heat curing (100 to 250 占 폚, 5 minutes to 3 hours) is measured using a spectrophotometer under the condition of a measurement wavelength of 400 to 700 nm . Thereby, it is possible to provide a film having excellent transparency in the visible light region.

&Lt; Production method of resin composition >

The resin composition of the present invention is a resin composition comprising a resin (A), a polymerizable compound (C) and a polymerization initiator (D), and optionally a solvent (E), a polymerization initiator (H), a leveling agent (F), a curing agent (G) and other components in a known manner. After mixing, it is preferable to perform filtration with a filter having a pore diameter of about 0.05 to 1.0 mu m.

&Lt; Process for producing a cured film &

The cured film can be produced by applying the resin composition of the present invention on a substrate, and drying and heating. A cured film having a pattern can be produced by the following steps.

Step (1): a step of applying the resin composition of the present invention to a substrate,

Step (2): a step of forming a composition layer by vacuum drying and / or heat drying the resin composition after application,

Step (2a): a step of exposing the composition layer through a photomask,

Step (2b): a step of developing the composition layer after exposure,

Step (3a): Step of heating the composition layer after development.

Step (1) is a step of applying the resin composition of the present invention to a substrate (base substrate). The substrate may be glass, metal, plastic, or the like, and a color filter, an insulating film, a conductive film, a driving circuit, or the like may be formed on the substrate. The application onto the substrate is preferably performed using a coating apparatus such as a spin coater, a slit & spin coater, a slit coater, an ink jet, a roll coater or a dip coater.

Step (2) is a step of forming a composition layer by vacuum drying and / or heat drying the resin composition after application. By carrying out this process, volatile components such as a solvent in the resin composition are removed. The reduced-pressure drying is preferably carried out at a temperature of 20 to 25 캜 under a pressure of 50 to 150 Pa. (Pre-baking) may be performed before or after the reduced-pressure drying. The heating and drying is carried out usually using a heating apparatus such as an oven or a hot plate. The temperature for the heat drying is preferably 30 to 120 占 폚, more preferably 50 to 110 占 폚. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

The step (2a) is a step of exposing the composition layer formed by the step (2) through a photomask. In the photomask, a light shielding portion is used corresponding to a portion of the composition layer to be removed. The shape of the light shielding portion is not particularly limited and can be selected in accordance with the intended use. As a light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, a light having a wavelength of less than 350 nm is cut using a filter that cuts the wavelength region, or a band-pass filter for extracting light in the vicinity of 436 nm, around 408 nm, and around 365 nm, Or may be selectively taken out. Examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp. It is preferable to use an exposure apparatus such as a mask aligner or a stepper to uniformly irradiate the entire surface of the exposure surface with a parallel light beam or precisely align the photomask with the composition layer.

Step (2b) is a step of developing the composition layer after exposure. The exposed composition layer is brought into contact with a developing solution and developed, whereby the unexposed portion of the composition layer is dissolved and removed in the developing solution to form a composition layer having a pattern on the substrate. As the developing solution, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide or the like is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. In addition, the developer may contain a surfactant. The developing method may be any of paddle method, dipping method and spray method. Further, the substrate may be inclined at an arbitrary angle during development. It is preferable to rinse after development.

Step (3a) is a step of heating the composition layer after development, that is, a so-called post-baking step. By heating in the same manner as in the conventionally known post-baking step, the composition layer having a pattern is cured, and a film having a pattern is formed on the substrate. Since the resin composition of the present invention used for pattern formation has excellent developability, unintentional peeling of the composition layer does not occur at the time of development, and a clear pattern can be formed. The film thickness of the film having the pattern is preferably 0.3 占 퐉 to 10 占 퐉, and more preferably 0.5 占 퐉 to 5 占 퐉. With such a film thickness, the developing property can be further improved.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples. In the examples, &quot;% &quot; and &quot; part (s) &quot; are by mass% and part by mass unless otherwise specified.

[Examples 1 to 11, Comparative Example 1]

&Lt; Preparation of Resin Composition >

The resin (A), the polymerizable compound (C) and the polymerization initiator (D) shown in Table 1 were contained in the ratios shown in Table 1, and the solvent (E), propylene glycol monomethyl ether acetate Were mixed to prepare a resin composition. In Table 1 and Table 2, the number of each component represents the mass part in terms of solid content.

The components in Table 1 and Table 2 are as follows.

Resin (a1): The resin obtained in Synthetic Example 1,

Resin (a2): The resin obtained in Synthetic Example 2,

Compound (c1): A compound represented by the formula (VI-3) (OGSOL (registered trademark) EA-0200, Osaka Gas Chemical Co., Ltd.)

Compound (c2): A bifunctional acrylate compound having fluorene skeleton (OGSOL (registered trademark) EA-0300; manufactured by Osaka Gas Chemical Co., Ltd.)

Compound (c3): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Yakuza Co., Ltd.)

Initiator (d1): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF).

(Synthesis Example 1: Preparation of resin (a1)) [

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, a nitrogen gas was flowed in an appropriate amount, and the flask was purged with nitrogen atmosphere. 280 parts of propylene glycol monomethyl ether acetate was added and heated to 80 DEG C with stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan- (Product name: E-DCPA, manufactured by Daicel Chemical Industries, Ltd.) and 125 parts of propylene glycol monomethyl ether acetate were added dropwise over 5 hours.

On the other hand, a mixed solution obtained by dissolving 33 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was held at the same temperature for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (a1)) having a B-type viscosity (23 캜) of 125 mPas and a solid content of 35.1%. The weight average molecular weight (Mw) of the obtained copolymer was 9200, the degree of dispersion was 2.08, and the acid value in terms of solid content was 77 mg-KOH / g. The resin (a1) has the following constitutional units.

(Synthesis Example 2: preparation of resin (a2)) [

A flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with a nitrogen stream in a nitrogen atmosphere, 324 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85 DEG C with stirring. Then, 60 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan- (Trade name: E-DCPA, manufactured by Daicel Chemical Industries, Ltd.), 210 parts of 9-vinylcarbazole and 190 parts of propylene glycol monomethyl ether acetate was added dropwise over 4 hours. On the other hand, a mixed solution obtained by dissolving 31 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 155 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropwise addition, the mixture was held at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer (resin (a1)) having a B-type viscosity (23 캜) of 163 mPas and a solid content of 31.8%. The obtained resin (a1) had a weight average molecular weight (Mw) of 7900, a dispersion degree (Mw / Mn) of 1.99 and an acid value in terms of solid content of 107 mg-KOH / g. The resin (a2) has the following constitutional units.

&Lt; Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn) >

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained resin were measured by the GPC method under the following conditions.

Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GEL G2000HXL

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0 mL / min

Test liquid Solid content concentration: 0.001 to 0.01 mass%

Injection volume: 50 μL

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500 and A-500 (manufactured by TOSOH CORPORATION)

The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in terms of polystyrene obtained as described above was referred to as dispersion degree.

&Lt; Preparation of cured film &

A glass substrate (Eagle XG; manufactured by Corning) having an aspect ratio of 2 inches was sequentially washed with a neutral detergent, water and isopropanol, and then dried. On this substrate, the resin compositions of Examples 1 to 11 and Comparative Example 1 were each spin-coated so as to have a film thickness of 1.0 mu m after post-baking. Subsequently, the mixture was vacuum-dried by a vacuum dryer (manufactured by VCD Microtech Co., Ltd.) under the conditions of a rotary pump revolution of 1000 rpm, a booster pump revolution of 700 rpm, and a room temperature of 25 캜 until the vacuum degree reached 66 Pa Thereby forming a resin composition layer. After cooling, 100 mJ / cm &lt; 2 &gt; of the resin composition layer and the quartz glass photomask on the substrate were set at an interval of 100 mu m using an exposure machine (TME-150RSK; (Based on 365 nm). This light irradiation was carried out by passing the radiation from the ultra-high pressure mercury lamp through an optical filter (UV-31; manufactured by Asahi Techno Glass Co., Ltd.). As the photomask, a photomask for forming a 1: 1 line-and-space pattern having a line width of 100 mu m was used. After the light irradiation, the resin composition layer was immersed in a 1% aqueous solution of tetramethylammonium hydroxide at 23 캜 for 60 seconds and developed. After washing with water, post-baking was performed in an oven at 230 캜 for 15 minutes to obtain a 1: A cured film having a pattern of one line and space was formed.

&Lt; Evaluation of pattern formation property &

The cured film formed was observed using a microscope (magnification: 500x; VF-7510; Quot; A &quot; when a 1: 1 line and space pattern was formed with a line width of 100 mu m, and &quot; C &quot; The results are shown in Tables 1 and 2.

In the case of using the resin compositions of Examples 1 to 11, a cured film having a 1: 1 line-and-space pattern with a line width of 100 μm could be formed on a glass substrate. In the resin composition of Comparative Example, The layer was peeled off, and a pattern could not be formed on the glass substrate.

According to the present invention, it is possible to provide a resin composition capable of forming a cured film having a pattern on a glass substrate. The cured film can be suitably used for a display device or the like.

Claims (5)

A resin, a polymerizable compound and a polymerization initiator,
Wherein the polymerizable compound comprises a polymerizable compound having a fluorene skeleton,
The content of the polymerizable compound having a fluorene skeleton is more than 10% by mass based on the total amount of the polymerizable compounds. The method according to claim 1,
Wherein the polymerizable compound having a fluorene skeleton is a compound represented by the formula (VI).

[In the formula (VI), L ¹ independently represents an alkanediyl group having 1 to 16 carbon atoms which may have a single bond or a substituent, and the methylene group contained in the alkanediyl group may be substituted with an oxygen atom. Provided that the methylene group to which the oxygen atom is bonded is not replaced with an oxygen atom.
And R &lt; ¹¹ &gt; independently represent a hydrogen atom or a methyl group. 3. The method according to claim 1 or 2,
Wherein the resin comprises a constituent unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms and the constituent unit (Aa) is derived from a monomer having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized. The method according to claim 1,
Wherein the resin is a resin comprising a constituent unit having a carbazole ring. A cured film formed from the resin composition according to claim 1.