JP7046638B2 - Resin compositions, membranes and copolymers - Google Patents

Description

The present invention relates to resin compositions, membranes and copolymers.

In recent liquid crystal display devices, a resin composition is used to form a film such as an overcoat. As such a resin composition, a resin composition containing a copolymer obtained by polymerizing methacrylic acid and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate is known (). Patent Document 1).

Japanese Unexamined Patent Publication No. 2006-171160

The present invention provides a resin composition capable of forming a film having high followability to the shape of a base substrate, a film formed by the resin composition, and a copolymer that can be used in the resin composition. The purpose is.

The present invention includes the following inventions.
[1] Contains resin (A) and solvent,
The resin (A) includes a structural unit (Aa) derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms and a structural unit (Ab) having a carbazole ring which may have a substituent. A resin composition which is a copolymer containing.

[2] The resin composition according to [1], wherein the structural unit (Aa) has a structure in which an unsaturated alicyclic hydrocarbon is epoxidized.

［式（Ａａ－１）及び式（Ａａ－２）中、Ｒ^ｂ１及びＲ^ｂ２は、水素原子又は炭素数１～４のアルキル基を表し、該アルキル基に含まれる水素原子は、ヒドロキシ基で置換されていてもよい。
Ｘ^ｂ１及びＸ^ｂ２は、単結合、＊－Ｒ^ｂ３－、＊－Ｒ^ｂ３－Ｏ－、＊－Ｒ^ｂ３－Ｓ－又は＊－Ｒ^ｂ３－ＮＨ－を表す。
Ｒ^ｂ３は、炭素数１～６のアルカンジイル基を表す。
＊は、Ｏとの結合手を表す。］ [3] The structure in which the unsaturated alicyclic hydrocarbon is epoxidized is selected from the group consisting of the structural unit represented by the formula (Aa-1) and the structural unit represented by the formula (Aa-2). The resin composition according to [2], which comprises at least one of them.

[In the formula (Aa-1) and the formula (Aa-2), 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 is a hydroxy group. It may be replaced.
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.
* Represents a bond with O. ]

[4] The resin (A) includes a structural unit (Aa), a structural unit (Ab), and a structural unit (Ac1) derived from a compound belonging to the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride. The resin composition according to any one of [1] to [3], which is a copolymer composed of.

［式（Ａｂ－１）中、Ｒ^１は、水素原子、メチル基、またはヒドロキシメチル基を表す。
Ｒ^２～Ｒ^９は、互いに独立に、水素原子、ハロゲン原子、炭素数１～２０の飽和炭化水素基又は炭素数６～２０のアリール基を表し、該飽和炭化水素基に含まれる水素原子は、アルコキシ基又はアリール基で置換されていてもよい。
Ｘは、単結合、炭素数１以上のアルカンジイル基、もしくは直鎖状又は分枝鎖状の下記の式（Ｖ）で表される基を表す。

（式（Ｖ）中、前記ｌは、０以上の整数を表す。ｍは、１以上の整数を表す。）］ [5] The resin composition according to any one of [1] to [4], wherein the structural unit (Ab) is a structural unit represented by the formula (Ab-1).

[In formula (Ab-1), R ¹ represents a hydrogen atom, a methyl group, or a hydroxymethyl group.
^R2 to R9 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 , May be substituted with an alkoxy group or an aryl group.
X represents a single bond, an alkanediyl group having one or more carbon atoms, or a linear or branched group represented by the following formula (V).

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

[6] The resin composition according to any one of [1] to [5], which comprises a polymerization initiator.

[7] A film formed from the resin composition according to any one of [1] to [6].

[8] A copolymer containing a structural unit (Aa) derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms and a structural unit (Ab) having a carbazole ring which may have a substituent. Combined.

According to the resin composition of the present invention, it is possible to form a film having high followability to the shape of the underlying substrate.

It is sectional drawing which shows typically the state which the line pattern on the glass substrate and the film are laminated.

In the present specification, the compounds exemplified as each component may be used alone or in combination of a plurality of kinds unless otherwise specified.

[Resin composition]
The resin composition of the present invention contains a resin (hereinafter referred to as resin (A)) and a solvent (hereinafter referred to as solvent (E)), and the resin (A) is a cyclic ether having 2 to 4 carbon atoms. A structural unit (Aa) having a structure (hereinafter referred to as “constituent unit (Aa)”) and a structural unit (Ab) having a carbazole ring which may have a substituent (hereinafter referred to as “constituent unit (Ab)”). It is a copolymer containing (referred to as). Since the resin (A) is a copolymer containing a structural unit (Aa) and a structural unit (Ab), the resin composition of the present invention can form a film having high followability to the shape of the underlying substrate. can.

The resin composition of the present invention may contain a polymerizable compound (hereinafter, referred to as a polymerizable compound (C)). When the polymerizable compound (C) is contained, it is preferable to also contain a polymerization initiator (hereinafter, referred to as a polymerization initiator (D)). Further, the resin composition of the present invention has other components, for example, a polymerization initiation aid (hereinafter referred to as a polymerization initiation aid (H)), a leveling agent (hereinafter referred to as a leveling agent (B)), and the like. It may contain an antioxidant (hereinafter referred to as an antioxidant (F)), a curing agent (hereinafter referred to as a curing agent (G)) and the like. Examples of the curing agent (G) include polyvalent carboxylic acid (hereinafter referred to as polyvalent carboxylic acid (G1)), imidazole compound (hereinafter referred to as imidazole compound (G2)), and the like.

<Resin (A)>
The resin (A) is a copolymer containing a structural unit (Aa) and a structural unit (Ab).
The copolymer is further copolymerizable with the constituent unit (Aa) or (Ab), and is referred to as a constituent unit other than the constituent units (Aa) and (Ab) (hereinafter referred to as a constituent unit (Ac)). ) May be further included. In addition, in this specification, "(meth) acrylic acid" represents at least one compound selected from the group consisting of acrylic acid and methacrylic acid. Notations such as "(meth) acryloyl" and "(meth) acrylate" have the same meaning. The resin (A) may contain two or more kinds of the constituent unit (Aa) and the constituent unit (Ab), respectively.

[1] Structural unit (Aa)
The structural 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 selected from the group consisting of an oxylan ring, an oxetane ring and a tetrahydrofuran ring). The structural unit derived from the unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms can be obtained by producing a copolymer using the unsaturated compound as a monomer. Alternatively, it can also be obtained by reacting another structural unit (hereinafter referred to as a structural unit (Aa')) with a compound having a cyclic ether structure having 2 to 4 carbon atoms.

The unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms, which leads to the structural unit (Aa), is, for example, a monomer having an oxylanyl group and an ethylenically unsaturated bond (hereinafter referred to as a monomer (Aa1)). ), A monomer having an oxetanyl group and an ethylenically unsaturated bond (hereinafter referred to as a monomer (Aa2)), and a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as a monomer). It is referred to as a monomer (Aa3)).

The monomer (Aa1) is referred to as, 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 a monomer having an epoxidized structure of an unsaturated alicyclic hydrocarbon (hereinafter referred to as a monomer (Aa1-2)). The monomer (Aa1) is preferable as the monomer that leads to the structural unit (Aa) in that the reliability of the obtained film such as heat resistance and chemical resistance can be further improved. Further, the monomer (Aa1-2) is more preferable in that the storage stability of the resin composition is excellent.

Examples of the monomer (Aa1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, and m-vinylbenzyl glycidyl. Ether, p-vinylbenzyl styrene ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxy) Methyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxy) Methyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4 6-Tris (glycidyloxymethyl) styrene and the like can be mentioned.

Examples of the monomer (Aa1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, seroxide 2000; manufactured by Daicel Co., Ltd.), and 3,4-epoxycyclohexylmethyl (meth) acrylate. (For example, Cyclomer A400; manufactured by Dycel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Dycel Co., Ltd.), the compound represented by the formula (I) and the formula. Examples thereof include the compound represented by (II).

[In the formula (I) and the formula (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 is substituted with a hydroxy group. May be good.
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.
* Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like.
Alkyl groups in which the hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group and 1-hydroxy. Examples thereof include -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.

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

The alkanediyl group includes a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-. Examples include 1,6-diyl group.

Examples of X ^b1 and X ^b2 are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O-, and * -CH ₂ CH ₂ -O-, and more preferably a single bond, * -CH ₂ . CH ₂ -O- can be mentioned. * Represents a bond with O.

Examples of the compound represented by the formula (I) include compounds represented by any of the formulas (I-1) to (I-15), preferably formulas (I-1) and (I). -3), the compound represented by the formula (I-5), the formula (I-7), the formula (I-9) or the formula (I-11) to the formula (I-15) can be mentioned, and more preferably. Examples thereof include compounds represented by the formula (I-1), the formula (I-7), the formula (I-9) or the formula (I-15).

Examples of the compound represented by the formula (II) include compounds represented by any of the formulas (II-1) to (II-15), preferably formulas (II-1) and (II). -3), the compound represented by the formula (II-5), the formula (II-7), the formula (II-9) or the formula (II-11) to the formula (II-15) can be mentioned, and more preferably. Examples thereof include compounds represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of two or more. When these are used in combination, their content ratios [compound represented by formula (I): compound represented by formula (II)] are based on a molar basis, preferably 5:95 to 95: 5, more preferably 20. : 80 to 80:20. For example, a mixture containing a compound represented by the formula (I-1) and a compound represented by the formula (II-1) at a ratio of 50:50 (commercially available, trade name "E-DCPA" (Co., Ltd.). (Made by Daicel) is available).

As the monomer (Aa2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of the monomer (Aa2) include 3-methyl-3-methacrylloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, and 3-ethyl-3-acryloyl. Oxymethyloxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, etc. Be done.

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, Viscort V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate and the like.

［式（Ａａ－１）及び式（Ａａ－２）中、Ｒ^b１及びＲ^b２は、水素原子又は炭素数１～４のアルキル基を表し、該アルキル基に含まれる水素原子は、ヒドロキシ基で置換されていてもよい。
Ｘ^b１及びＸ^b２は、単結合、＊－Ｒ^b３－、＊－Ｒ^b３－Ｏ－、＊－Ｒ^b３－Ｓ－又は＊－Ｒ^b３－ＮＨ－を表す。
Ｒ^b３は、炭素数１～６のアルカンジイル基を表す。
＊は、Ｏとの結合手を表す。］ As the structural unit (Aa), it is excellent in storage stability of the resin composition, chemical resistance of the obtained film, heat resistance and mechanical strength, and further excellent followability of the shape of the underlying substrate can be obtained. It is preferably a structural unit derived from the monomer (Aa1-2), and more preferably a structural unit represented by the formula (Aa-1) or the formula (Aa-2). 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). Be taken.

[In the formula (Aa-1) and the formula (Aa-2), 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 is a hydroxy group. It may be replaced.
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.
* Represents a bond with O. ]

[2] Structural unit (Ab)
The building block (Ab) can be derived from an unsaturated compound having a carbazole ring, which may have a substituent. The structural unit derived from the unsaturated compound can be obtained by producing a copolymer using the unsaturated compound as a monomer.
Alternatively, it can also be obtained by reacting another structural unit (Ab') with a compound (Ab'') having a carbazole ring which may have a substituent.
Since the resin (A) has the structural unit (Ab), it is possible to form a film having high followability to the shape of the underlying substrate. Further, by having the structural unit (Ab), the refractive index of the obtained film can be improved.

［式（ＩＩＩ）中、Ｒ^１は、水素原子、メチル基、またはヒドロキシメチル基を表す。
Ｒ^２～Ｒ^９は、互いに独立に、水素原子、ハロゲン原子、炭素数１～２０の飽和炭化水素基又は炭素数６～２０のアリール基を表し、該飽和炭化水素基に含まれる水素原子は、アルコキシ基又はアリール基で置換されていてもよい。
Ｘは、単結合、炭素数１以上のアルカンジイル基、もしくは直鎖状又は分枝鎖状の下記の式（Ｖ）で表される基を表す。

（式（Ｖ）中、前記ｌは、０以上の整数を表す。ｍは、１以上の整数を表す。）］ The unsaturated compound that leads to the structural unit (Ab) is preferably a compound represented by the formula (III).

[In formula (III), R ¹ represents a hydrogen atom, a methyl group, or a hydroxymethyl group.
^R2 to R9 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 , May be substituted with an alkoxy group or an aryl group.
X represents a single bond, an alkanediyl group having one or more carbon atoms, or a linear or branched group represented by the following formula (V).

(In the formula (V), l represents an integer of 0 or more. 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-carbazolyl) ethyl (meth) acrylate, and 2- (9-carbazolyl). Examples thereof include ethoxyethyl (meth) acrylate, 2- (9-carbazolyl) -2-methylethyl (meth) acrylate, 2- (9-carbazolyl) -1-methylethyl (meth) acrylate and the like. Of these, N-vinylcarbazole, N-allylcarbazole, and 2- (9-carbazolyl) ethyl (meth) acrylate are preferable.

[3] Structural unit (Ac)
Examples of the structural unit (Ac) include a structural unit derived from a compound belonging to the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (hereinafter referred to as “constituent unit (Ac1)”). 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, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, 1,4-cyclohexendicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] A bicyclounsaturated compound containing a carboxy group such as hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, Citraconic acid anhydride, Itaconic acid anhydride, 3-Vinylphthalic acid anhydride, 4-Vinylphthalic acid anhydride, 3,4,5,6-Tetrahydrophthalic acid anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic acid anhydride, dimethyltetrahydrophthalic acid anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydrate; Meta) acryloyloxyethyl], mono [2- (meth) acryloyloxyethyl] and other divalent or higher polyvalent carboxylic acid unsaturated mono [(meth) acryloyloxyalkyl] esters;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.

Examples of the structural unit (Ac) other than the structural unit (Ac1) (hereinafter referred to as “constituent unit (Ac2)”) include the following compounds:
Methyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2- Methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (in the art, it is commonly referred to as "dicyclopentanyl (meth) acrylate". Also referred to as "tricyclodecyl (meth) acrylate"), tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate (as a common name in the art). It is called "dicyclopentenyl (meth) acrylate"), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate. , Phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate and other (meth) acrylic acid esters;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid;
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] Bicyclounsaturated compounds such as hept-2-ene;
Dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate;
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, vinyl acetate, 1,3- Examples thereof include structural units derived from butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like. The resin (A) preferably has a structural unit (Ac1).

[4] The ratio resin (A) of each constituent unit is the following resin [K1] or [K2].
Resin [K1]: A copolymer composed of a structural unit (Aa) and a structural unit (Ab);
Resin [K2]: A copolymer composed of a structural unit (Aa), a structural unit (Ab) and a structural unit (Ac).
The resin (A) is preferably the resin [K2]. Further, among the resin [K2], it is preferable that the constituent unit (Ac) includes the constituent unit (Ac1), and the resin composed of the constituent unit (Aa), the constituent unit (Ab), and the constituent unit (Ac1) is formed. preferable.
When the resin (A) contains the constituent unit (Ac1), the content thereof is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, based on all the constituent units constituting the resin (A).

In the resin [K1], the ratio of each constituent unit is the ratio of all the constituent units constituting the resin [K1].
Constituent unit (Aa); 5-95 mol%,
Constituent unit (Ab); preferably 5 to 95 mol%.
Constituent unit (Aa); 10-70 mol%,
Constituent unit (Ab); 30-90 mol%, more preferably.

When the ratio of the constituent units constituting the resin [K1] is within the above range, the storage stability of the resin composition, the chemical resistance of the obtained film, the heat resistance and the mechanical strength are excellent, and the shape of the underlying substrate is further improved. It is preferable in that a film having high followability to the resin can be formed.

The resin [K1] is, for example, the method described in the document "Experimental Method for Polymer Synthesis" (published by Takayuki Otsu, published by Kagaku-Dojin Co., Ltd., 1st edition, 1st print, published on March 1, 1972). It can be manufactured with reference to the cited documents described in the literature.
Specifically, a predetermined amount of the structural unit (Aa) and the structural unit (Ab), a polymerization initiator, a solvent and the like are placed in the reaction vessel, and for example, oxygen is replaced with nitrogen to create a deoxidized atmosphere. Examples thereof include a method of heating and keeping warm while stirring. The polymerization initiator, solvent and the like are not particularly limited, and those usually used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). The solvent may be any solvent as long as it dissolves each monomer, and examples thereof include the solvents described below used in the resin composition.

When preparing the resin composition of the present invention, the resin solution obtained by the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) may be used by a method such as reprecipitation. ) May be used. In particular, by using the solvent contained in the resin composition of the present invention as the polymerization solvent, the solution after the reaction can be used as it is in the production of the resin composition, which simplifies the production process of the resin composition. be able to.

In the resin [K2], the ratio of each structural unit is the structural unit (Aa); 1 to 90 mol%, among all the structural units constituting the resin [K2].
Constituent unit (Ab); 5-98 mol%,
Constituent unit (Ac); preferably 1 to 50 mol%.
Constituent unit (Aa); 3-80 mol%,
Constituent unit (Ab); 17-90 mol%,
Constituent unit (Ac); 3-40 mol%,
Is more preferable
Constituent unit (Aa); 3-80 mol%,
Constituent unit (Ab); 50-90 mol%,
Constituent unit (Ac); 3-40 mol%,
Is more preferable.

When only the constituent unit (Ac1) is included as the constituent unit (Ac) in the resin [K2].
Constituent unit (Aa); 1-70 mol%,
Constituent unit (Ab); 5 to 90 mol%,
Constituent unit (Ac1); preferably 1 to 50 mol%.
Constituent unit (Aa); 3-50 mol%,
Constituent unit (Ab); 20-90 mol%,
Constituent unit (Ac1); more preferably 5-40 mol%.
Constituent unit (Aa); 3-50 mol%,
Constituent unit (Ab); 50-90 mol%,
Constituent unit (Ac1); more preferably 5-40 mol%.

When only the constituent unit (Ac2) is included as the constituent unit (Ac) in the resin [K2].
Constituent unit (Aa); 1-90 mol%,
Constituent unit (Ab); 5-98 mol%,
Constituent unit (Ac2); preferably 1 to 50 mol%.
Constituent unit (Aa); 3 to 70 mol%,
Constituent unit (Ab); 20-90 mol%,
Constituent unit (Ac2); more preferably 3-40 mol%.
Constituent unit (Aa); 3 to 70 mol%,
Constituent unit (Ab); 50-90 mol%,
Constituent unit (Ac2); more preferably 3-40 mol%.

When both the constituent unit (Ac1) and the constituent unit (Ac2) are included in the resin [K2] as the constituent unit (Ac).
Constituent unit (Aa); 1-70 mol%,
Constituent unit (Ab); 5 to 90 mol%,
Constituent unit (Ac1); 1-50 mol%,
Constituent unit (Ac2); preferably 1-40 mol%
Constituent unit (Aa); 3-50 mol%,
Constituent unit (Ab); 10-90 mol%,
Constituent unit (Ac1); 5-35 mol%,
Constituent unit (Ac2); more preferably 1-30 mol%.
Constituent unit (Aa); 3-50 mol%,
Constituent unit (Ab); 50-90 mol%,
Constituent unit (Ac1); 5-35 mol%,
Constituent unit (Ac2); more preferably 1-30 mol%.

When the ratio of the constituent units of the resin [K2] is within the above range, the storage stability of the resin composition, the chemical resistance of the obtained film, the heat resistance and the mechanical strength are excellent, and the shape of the underlying substrate is followed. It is preferable in that a film having high properties can be obtained. The resin [K2] can be produced by the same method as the resin [K1].

The polystyrene-equivalent weight average molecular weight (Mw) of the resin (A) 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. Is between 5,000 and 10,000. When the weight average molecular weight (Mw) of the resin (A) is within the above range, the coatability of the resin composition tends to be good.

The dispersity [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 obtained film tends to have excellent chemical resistance.

When the resin (A) contains a structural unit (Ac1), its acid value is preferably 30 mg-KOH / g or more and 180 mg-KOH / g or less, more preferably 40 mg-KOH / g or more and 150 mg-KOH / g or less. More preferably, it is 50 mg-KOH / g or more and 135 mg-KOH / g or less. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained by titrating with an aqueous potassium hydroxide solution. When the acid value of the resin (A) is within the above range, the obtained film tends to have excellent adhesion to the substrate.

When the resin composition of the present invention contains components other than the resin (A) and the solvent (E), the content of the resin (A) is preferably 30 to 99 with respect to the solid content of the resin composition of the present invention. It is by mass, more preferably 35 to 80% by mass, and even more preferably 40 to 70% by mass. When the content of the resin (A) is within the above range, the obtained film tends to have excellent heat resistance, adhesion to the substrate, and chemical resistance. Here, the solid content of the resin composition means an amount obtained by subtracting the content of the solvent (E) from the total amount of the resin composition of the present invention.

<Polymerizable compound (C)>
The polymerizable compound (C) is a monomer that reacts by heat or the action of the polymerization initiator (D), and examples of the monomer include compounds having an ethylenically unsaturated bond, and a (meth) acrylic compound is preferable. , And more preferably a compound having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group.

As the (meth) acrylic compound having one (meth) acryloyl group, a compound similar to the monomer leading to the structural unit (Aa), the structural unit (Ab) and the structural unit (Ac) of the resin (A) can be used. Can be mentioned.

Examples of the (meth) acrylic compound having two (meth) acryloyl groups include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, and 1,6-hexanediol di (meth). Acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, bisphenol A bis (acryloyloxyethyl) ether, ethylene oxide-modified bisphenol A di (meth) acrylate, propylene oxide-modified neopentyl glycol di (meth) acrylate, ethylene oxide-modified neopentyl glycol di (meth) acrylate, 3-methylpentanediol di Examples thereof include (meth) acrylate.

Examples of the (meth) acrylic compound having three or more (meth) acryloyl groups include trimethylolpropanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanuratetri (meth) acrylate, and the like. Ethylene oxide-modified trimethylol propanetri (meth) acrylate, propylene oxide-modified trimethylol propanetri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri. Pentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri (meth) Reaction product of acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, reaction product of tripentaerythritol hepta (meth) acrylate and acid anhydride, caprolactone-modified trimethyl propantri (Meta) 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 ) Acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tri Pentaerythritol hepta (meth) acrylate, caprolactone-modified tripentaerythritol octa (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride reaction product, caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride Reactant with acrylate, caprolactone-modified tripentaerythritol hepta (meth) acrylate Examples thereof include a reaction product of acid anhydride and acid anhydride.

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

When the resin composition of the present invention contains the polymerizable compound (C), the content thereof is preferably 20 to 200 parts by mass, more preferably 30 to 150 parts by mass with respect to 100 parts by mass of the resin (A). be. When the content of the polymerizable compound (C) is within the above range, the chemical resistance and mechanical strength of the obtained film can be improved.

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

The O-acyloxime compound is a compound having a structure represented by the formula (D1).
Hereinafter, * represents a bond.

Examples of the O-acyloxym compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-. 1-on-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-on-2-imine, N-acetoxy-1- [9-ethyl-6- (9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4) -Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropane-1 -On-2-Imine can be mentioned. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (all 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 the formula (D2-1) or a structure represented by the formula (D2-2). In 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-1-one and 2-dimethylamino-1-(. 4-Molholinophenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1- On is mentioned. Commercially available products such as Irgacure (registered trademark) 369, 907 and 379 (all manufactured by BASF Corporation) may be used. Further, a polymerization initiator having a group capable of causing chain transfer, which is described in JP-A-2002-544205, may be used. Examples of the compound having a structure represented by the formula (D2-2) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (4). 2-Hydroxyethoxy) Phenyl] Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, α, α-di Examples thereof include ethoxyacetophenone and benzyldimethylketal. In terms 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 and 2,4-bis (trichloromethyl) -6- (4-methoxy). Naftil) -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- (fran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2) -Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine Be done.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products such as Irgacure 819 (manufactured by BASF Japan Ltd.) may be used.

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, JP-A-6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4, 4', 5,5'-Tetraphenyl biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole 2-Chlorophenyl) -4,4', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxy) Phenyl) Biimidazole (see, for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), the phenyl group at the 4,4', 5,5'-position is substituted with a carboalkoxy group. Examples thereof include biimidazole compounds (see, for example, JP-A-7-10913).

Further, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, o-methyl benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl- Benzoyl compounds such as 4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthlenquinone, Kinon compounds such as 2-ethylanthraquinone and camphorquinone; examples thereof include 10-butyl-2-chloroacrydone, benzyl, methyl phenylglycoxylate, and titanosen compounds. These can be used in combination with the polymerization initiation aid (H) (particularly an amine compound) described later.

As the polymerization initiator (D), an acid generator can also be used. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethyl. Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyltosylate, benzoin Tosilate can be mentioned.

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 the total content of the resin (A) and the polymerizable compound (C). The amount is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 1 to 8 parts by mass with respect to 100 parts by mass. When the content of the polymerization initiator (D) is within the above range, the visible light transmittance of the obtained pattern tends to be high.

<Polymerization initiation aid (H)>
The polymerization initiator (H) is a compound or a sensitizer used to promote the polymerization of the polymerizable compound (C) initiated by the polymerization initiator (D) together with the polymerization initiator (D). Is.

Examples of the polymerization initiation aid (H) include thiazolin compounds, amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds and the like.

Examples of the thiazolin compound include compounds represented by formulas (H1-1) to (H1-3), compounds described in JP-A-2008-65319, and the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4-. 2-Ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis ( Ethylmethylamino) benzophenone and the like can be mentioned, with 4,4'-bis (diethylamino) benzophenone being preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical 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, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene and the like can be mentioned.

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

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, and N. -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.

When the resin composition of the present invention contains a polymerizable compound (C), a polymerization initiator (D) and a polymerization initiator (H), the content of the polymerization initiator (H) is polymerized with the resin (A). The total content of the sex compound (C) is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass. When the amount of the polymerization initiation aid (H) is within the above range, the sensitivity tends to be higher when forming a pattern.

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

Examples of the silicone-based surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324. , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan GK) and the like. ..

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafuck (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F554. R30, RS-718-K (manufactured by DIC Co., Ltd.), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, Examples thereof include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).

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

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

<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 phenolic antioxidant is preferable because the resulting film is less colored.

Examples of the phenolic antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate and 2- [1- (2-hydroxy). -3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 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'-methylenebis (6-tert-butyl-4-methyl) Phenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert-butyl-5-methylphenol), 2,2'-thiobis (6- tert-Butyl-4-methylphenol), 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 "-(mecitylene-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 and 6- [3-( 3-tert-Butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosfepine As the phenol-based antioxidant, a commercially available product may be used. Examples of the commercially available phenol-based antioxidant include Sumilyzer (registered trademark) BHT, GM, GS, GP (all of the above). Examples thereof include Sumitomo Chemical Co., Ltd.) and Irganox (registered trademark) 1010, 1076, 1330, 3114 (all manufactured by BASF Co., Ltd.).

Examples of the sulfur-based antioxidant include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, disstearyl 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 Sumilyzer (registered trademark) TPL-R and TP-D (all manufactured by Sumitomo Chemical Co., Ltd.).

Examples of the phosphorus-based antioxidant include trioctyl phosphite, trilauryl phosphite, tridecylphosphite, tris (nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra (tridecyl) -1,1, and so on. Examples thereof include 3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphite. As the phosphorus-based antioxidant, a commercially available product may be used. Examples of commercially available phosphorus-based antioxidants include Irgaphos (registered trademark) 168, 12, 38 (all manufactured by BASF Corporation), ADEKA STAB 329K, and ADEKA STAB PEP36 (all manufactured by ADEKA Corporation). Can be mentioned.

Examples of the amine-based antioxidant include N, N'-di-sec-butyl-p-phenylenediamine, N, N'-di-isopropyl-p-phenylenediamine, and N, N'-dicyclohexyl-p-phenylene. Examples thereof include diamine, N, N'-diphenyl-p-phenylenediamine and N, N'-bis (2-naphthyl) -p-phenylenediamine. As the amine-based antioxidant, a commercially available product may be used. Examples of commercially available amine-based antioxidants include Sumilyzer (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 with respect to 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). It is 5 parts by mass or more, more preferably 0.5 parts by mass or more and 3 parts by mass or less. When the content of the antioxidant (F) is within the above range, the obtained film tends to be excellent in heat resistance and pencil hardness.

<Curing agent (G)>

<Polyvalent carboxylic acid (G1)>
The polyvalent carboxylic acid (G1) is at least one compound selected from the group consisting of polyvalent carboxylic acid anhydride and polyvalent carboxylic acid. The polyvalent carboxylic acid is a compound having two or more carboxy groups, and the polyvalent carboxylic acid anhydride is an anhydride of the polyvalent carboxylic acid. The molecular weight of the polyvalent carboxylic acid (G1) is preferably 3000 or less, more preferably 1000 or less.

Examples of the polyvalent carboxylic acid anhydride include maleic anhydride, succinic anhydride, glutaric acid anhydride, citraconic acid anhydride, itaconic acid anhydride, 2-dodecylsuccinic acid anhydride, and 2- (2-octa). -3-enyl) succinic anhydride, 2- (2,4,6-trimethylnona-3-enyl) succinic anhydride, tricarballylic acid anhydride, 1,2,3,4-butanetetracarboxylic acid di Chain polyvalent carboxylic acid anhydride such as anhydride; 3,4,5,6-tetrahydrophthalic acid anhydride, 1,2,3,6-tetrahydrophthalic acid anhydride, dimethyltetrahydrophthalic acid anhydride, hexahydro Phthrate Anhydride, 4-Methylhexahydrophthalic Anhydride, Norbornendicarboxylic Acid Anhydride, Methylbicyclo [2.2.1] Heptane-2,3-Dicarboxylic Acid Anhydride, Bicyclo [2.2.1] Heptane -2,3-dicarboxylic acid anhydride, bicyclo [2.2.1] hepta-5-en-2,3-dicarboxylic acid anhydride, methylbicyclo [2.2.1] hepta-5-en-2, Alicyclic polyvalent carboxylic acid anhydrides such as 3-dicarboxylic acid anhydride, cyclopentanetetracarboxylic acid dianhydride; phthalic anhydride, 3-vinylphthalic acid anhydride, 4-vinylphthalic acid anhydride, pyromellitic acid anhydride , Trimellitic hydride, benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic hydride, ethylene glycol bis (anhydrotrimeritate), glycerintris (anhydro) (Trimeritate), Glycerinbis (Anhydrotrimeritate) Monoacetate, 1,3,3a, 4,5,9b-Hexahydro-5- (Tetrahydro-2,5-dioxo-3-franyl) Naft [1, 2-c] Aromatic polyvalent carboxylic acid anhydrides such as furan-1,3-dione; Adeka Hardna (registered trademark) -EH-700 (trade name (same below), manufactured by ADEKA Corporation), Ricacid (registered trademark) -HH, -TH, -MH, MH-700 (New Japan Rika Co., Ltd.) ), Epikinia 126, YH-306, DX-126 (manufactured by Yuka Shell Epoxy Co., Ltd.) and the like.

Examples of the polyvalent carboxylic acid include chain polyvalent carboxylic acids such as oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, and polyvalent carboxylic acid that leads to chain polyvalent carboxylic acid anhydride. Acids; alicyclic polyvalent carboxylic acids such as cyclohexanedicarboxylic acid, polyvalent carboxylic acids that lead to alicyclic polyvalent carboxylic acid anhydrides; isophthalic acid, terephthalic acid, 1,4,5,8-naphthalenetetracarboxylic acid, Fragrant polyvalent carboxylic acids Fragrant polycarboxylic acids such as polyvalent carboxylic acids that lead to anhydrides; and the like.

Among them, chain carboxylic acid anhydrides and alicyclic polyvalent carboxylic acid anhydrides are preferable, and alicyclic polyvalents are preferable because the obtained film has excellent heat resistance and the transparency in the visible light region does not easily decrease. Carboxylic acid anhydrides are more preferred.

When the resin composition of the present invention contains a polyvalent carboxylic acid (G1), the content thereof is preferably 1 to 1 to 100 parts by mass with respect to a total content of 100 parts by mass of the resin (A) and the polymerizable compound (C). It is 30 parts by mass, more preferably 2 to 20 parts by mass, and even 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.

<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. Of these, the compound represented by the formula (G2-1) is preferable.

[In the formula (2), R ³¹ represents an alkyl group having 1 to 20 carbon atoms, a phenyl group, a benzyl group or a cyanoalkyl group having 2 to 5 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 phenyl group. The hydrogen atom contained in may be substituted with a hydroxy group. ]

Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isobutyl group, a butyl group, a tert-butyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and a heptadecyl group. , Undecyl group.
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 isobutylyl group, a valeryl group, an isovaleryl group, a pivaloyl group, a lauroyl group, a myritoyl group and a stearoyl group.

Examples of the imidazole compound (G2) include 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, 5-hydroxymethyl-4-methylimidazole and 2-ethylimidazole. , 2-Undecylimidazole, 2-Heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-hydroxymethyl-2-phenylimidazole, 2-phenylimidazole, 2-phenyl-2- Hydroxymethylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl-4-phenylimidazole, 1-benzyl-5-hydroxymethylimidazole, 2- (p-hydroxyphenyl) imidazole, 1-cyanomethyl-2-methylimidazole , 1- (2-cyanoethyl) -2-hydroxymethylimidazole, 2,4-diphenylimidazole, 1-cyanomethyl-2-undecylimidazole, 1-cyanomethyl-2-ethyl-4-methylimidazole, 1-cyanomethyl-2 -Phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole can be mentioned. Of these, 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), the content thereof is preferably 0.1% by mass with respect to 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). More than 25 parts by mass, more preferably 0.2 parts by mass or more and 15 parts by mass or less, 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 in the above range, the obtained film tends to have excellent transparency in the visible light region.

<Solvent (E)>
The resin composition of the present invention contains a solvent (E). The solvent (E) is not particularly limited, and examples thereof include solvents usually used in the art. For example, an ester solvent (solvent containing -COO- in the molecule and not containing -O-), an ether solvent (solvent containing -O- in the molecule and not containing -COO-), an ether ester solvent (intramolecular). Solvent containing -COO- and -O-), Ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule, -O-,- CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

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 monomethyl ether, and propylene glycol monoethyl ether. , 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 Examples thereof include ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol and methyl anisol.

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, 3-ethoxy. Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl Examples thereof include ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. And so on.

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

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 the above solvents, an organic solvent having a boiling point of 100 ° C. or higher and 200 ° C. or lower 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, and propylene glycol monomethyl ether. More preferred are acetate, propylene glycol monomethyl ether, ethylene glycol ethylmethyl ether, methoxybutanol and methoxybutyl acetate.

The content of the solvent (E) in the resin composition of the present invention is preferably 60 to 95% by mass, more preferably 70 to 95% by 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, more preferably 5 to 30% by mass. When the content of the solvent (E) is in the above range, the followability of the film obtained by applying the resin composition to the shape of the underlying substrate tends to be improved.

<Other ingredients>
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, etc., if necessary. good.

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 the condition of a measurement wavelength of 400 to 700 nm using a spectrophotometer, the average transmittance is preferable. It is 70% or more, more preferably 80% or more.

When a film is formed from the resin composition of the present invention, the average transmittance of the film is preferably 90% or more, more preferably 95% or more. This average transmittance was measured under the conditions of a measurement wavelength of 400 to 700 nm using a spectrophotometer for a film having a thickness of 2 μm after heat curing (100 to 250 ° C., 5 minutes to 3 hours). The average value of the cases. This makes it possible to provide a film having excellent transparency in the visible light region.

<Manufacturing method of resin composition>
The resin composition of the present invention comprises a resin (A) and a solvent (E), as well as a polymerizable compound (C), a polymerization initiator (D), a polymerization initiator (H), and a leveling agent used as needed. It can be produced by mixing (B), an antioxidant (F), a curing agent (G) and other components by a known method. After mixing, it is preferable to filter with a filter having a pore size of about 0.05 to 1.0 μm.

<Membrane manufacturing method>
The film can be produced by applying the resin composition of the present invention on a substrate, drying the film, and then heating the film. More specifically, the method for producing a film of the present invention includes the following steps (1) to (3).
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 drying the resin composition after coating under reduced pressure and / or heating and drying.
Step (3): A step of heating the composition layer.

When the resin composition of the present invention contains the polymerizable compound (C) and the polymerization initiator (D), a film having a pattern can be produced by performing 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 drying the resin composition after coating under reduced pressure and / or heating and drying.
Step (2a): A step of exposing the composition layer via a photomask,
Step (2b): A step of developing the composition layer after exposure,
Step (3a): A step of heating the composition layer after development.

The step (1) is a step of applying the resin composition of the present invention to a substrate (base substrate). Examples of the substrate include glass, metal, plastic, and the like, and a color filter, an insulating film, a conductive film, and / or a drive circuit may be formed on the substrate. The coating on the substrate is preferably performed using a coating device such as a spin coater, a slit & spin coater, a slit coater, an inkjet, a roll coater, and a dip coater.

The step (2) is a step of drying the resin composition after coating under reduced pressure and / or heating and drying to form a composition layer. By performing this step, volatile components such as a solvent in the resin composition are removed. The vacuum drying is preferably performed under a pressure of 50 to 150 Pa in a temperature range of 20 to 25 ° C. Heat drying (pre-baking) may be performed before or after vacuum drying. Heat drying is usually performed using a heating device such as an oven or a hot plate. The heat-drying temperature is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

The step (3) is a step (post-baking) of heating the composition layer. Heating is usually performed using a heating device such as an oven or a hot plate. The heating temperature is preferably 130 to 270 ° C, more preferably 150 to 260 ° C, and even more preferably 200 to 250 ° C. When the heating temperature is 200 to 250 ° C., it is possible to prevent unnecessary solvent from remaining in the film. The heating time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

The step (2a) is a step of exposing the composition layer formed by the step (2) via a photomask. As the photomask, a photomask having a light-shielding portion formed corresponding to a portion of the composition layer to be removed is used. The shape of the light-shielding portion is not particularly limited and can be selected according to the intended use. As the light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light less than 350 nm is cut by using a filter that cuts this wavelength range, and light near 436 nm, 408 nm, and 365 nm is selectively extracted by using a bandpass filter that extracts these wavelength ranges. You may do it. Examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp and the like.
It is preferable to use an exposure device such as a mask aligner or a stepper because it is possible to uniformly irradiate the entire exposed surface with parallel rays and accurately align the photomask with the composition layer.

The step (2b) is a step of developing the composition layer after exposure. By bringing the exposed composition layer into contact with a developing solution for development, the unexposed portion of the composition layer is dissolved in the developing solution and removed, and a composition layer having a pattern is formed on the substrate. As the developing solution, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate and tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant. The developing method may be any of a paddle method, a dipping method, a spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.

The step (3a) is a step of heating the composition layer after development. By heating in the same manner as in the above step (3), the composition layer having a pattern is cured, and a film having a pattern is formed on the substrate.

The film thus obtained is excellent in followability to the shape of the underlying substrate, and is therefore useful as a color filter substrate used in, for example, a liquid crystal display device, an organic EL display device, or electronic paper. This makes it possible to manufacture a display device having a high quality film. Even in a color filter substrate having an uneven shape of a colored pattern on the surface, a film having excellent followability to the uneven shape can be obtained by forming an overcoat layer with the resin composition of the present invention.

The film thickness of the overcoat layer (the film thickness from the surface of the convex portion when the surface to be coated has an uneven shape) is preferably 0.5 μm or more and 5 μm or less, and more preferably 0.5 μm or more and 3 μm or less. The resin composition of the present invention has an uneven shape when the surface to be coated has an uneven shape, for example, the width of the concave portion is 1 to 500 μm, and the height from the surface of the concave portion to the surface of the convex portion is 0.1 to 20 μm. It can be used for a base substrate having the above. In particular, for such a base substrate, it is possible to obtain a film having excellent followability to the shape of the base substrate.

[Copolymer]
The copolymer of the present invention is a resin (A) containing a structural unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms and a structural unit (Ab) having a carbazole ring. The above description of the resin (A) contained in the resin composition is applied to the copolymer of the present invention.

Hereinafter, the present invention will be described in more detail by way of examples. Unless otherwise specified, "%" and "part" in the example are mass% and parts by mass.

[Example 1, Comparative Example 1]
<Preparation of resin composition>
A resin composition was prepared by mixing the resin (A) shown in Table 1 and the propylene glycol monomethyl ether acetate as the solvent (E) so as to have the solid content concentration shown in Table 1. In Table 1, the number of copies of each component represents the mass part in terms of solid content.

Each component in Table 1 is as follows.
Resin (a1): Resin obtained by Synthesis Example 1 Resin (a2): Resin obtained by Synthesis Example 2.

(Synthesis Example 1: Preparation of resin (a1))
An appropriate amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 324 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85 ° C. with stirring. Then 60 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^2, ]. ⁶ ] 30 parts of a mixture of decane-9-ylacrylate (trade name "E-DCPA", manufactured by Daicel Corporation)), 210 parts of 9-vinylcarbazole, and 190 parts of propylene glycol monomethyl ether acetate over 4 hours. And dropped. On the other hand, a mixed solution prepared 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 dropping, the mixture was kept at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer (resin (a1)) solution having a B-type viscosity (23 ° C.) of 163 mPas and a solid content of 31.8%. The obtained resin (a1) had a weight average molecular weight (Mw) of 7900, a dispersity (Mw / Mn) of 1.99, and an acid value in terms of solid content of 107 mg-KOH / g. The resin (a1) has the following structural units.

(Synthesis Example 2: Preparation of Resin (a2))
Nitrogen was sufficiently flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, 140 parts of diethylene glycol ethylmethyl ether was added, and the mixture was heated to 70 ° C. with stirring. Next, 40 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.2.1.02 ² ]. ^{, 6} ] A solution prepared by dissolving 360 parts of a mixture of decane-9-ylacrylate (trade name "E-DCPA", manufactured by Daicel Co., Ltd.) in 190 parts of diethylene glycol ethylmethyl ether was prepared, and this solution was prepared. Was dropped into a flask kept at 70 ° C. for 4 hours using a dropping pump.

On the other hand, a solution prepared by dissolving 30 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 240 parts of diethylene glycol ethylmethyl ether was placed in a flask over 5 hours using another dropping pump. Dropped. After the dropping of the polymerization initiator solution was completed, the mixture was kept at 70 ° C. for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (a2)) having a solid content of 42%. The obtained resin (a2) had a weight average molecular weight (Mw) of 7800, a dispersity (Mw / Mn) of 2.0, and an acid value in terms of solid content of 61 mg-KOH / g. The resin (a2) has the following structural units.

<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 using the GPC method under the following conditions.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Flow velocity: 1.0 mL / min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector: RI
Calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained above was defined as the degree of dispersion.

<Manufacturing of evaluation board>
A 2-inch square glass substrate (Eagle XG; manufactured by Corning Inc.) was washed successively with a neutral detergent, water and isopropanol, and then dried. A commercially available photosensitive resin composition was spin-coated on this substrate so that the film thickness after post-baking was 2.0 μm. Next, a resin composition layer was formed by prebaking at 100 ° C. for 3 minutes in a clean oven. After allowing to cool, the distance between the resin composition layer on the substrate and the quartz glass photomask is set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd., light source; ultrahigh pressure mercury lamp) is used in an atmospheric atmosphere. , 100 mJ / cm ² exposure (based on 365 nm). This light irradiation was performed by passing the synchrotron radiation from the ultrahigh 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 20 μm was used. The resin composition layer after light irradiation is developed by immersing it in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 60 seconds, washed with water, and then in an oven. In the middle, post-baking was performed at 230 ° C. for 15 minutes to prepare an evaluation substrate having a 1: 1 line-and-space pattern (having 10 lines and 10 spaces each) with a line width of 20 μm.

<Preparation of membrane>
The resin (a1) or the resin (a2) was subjected to spin coating under the condition that the film thickness after post-baking (the film thickness from the line pattern surface on the evaluation substrate) was 1.0 μm on the evaluation substrate. The solution was applied. After that, the rotary pump was dried under a vacuum dryer (manufactured by VCD Microtech Co., Ltd.) at a rotary pump rotation speed of 1000 rpm, a booster pump rotation speed of 700 rpm, and a room temperature of 25 ° C. A film was formed by post-baking at ° C. in an oven for 15 minutes.

<Followability evaluation>
The film thickness Fa of the line pattern 2b on the evaluation substrate was measured using a contact type film thickness measuring device (DEKTAK6M; manufactured by ULVAC, Inc.). As shown in a schematic cross-sectional view in FIG. 1, the maximum film from the substrate surface of the line pattern 2b in a state where the 1: 1 line and space pattern 2 (space 2a, line 2b) on the substrate 1 and the film 3 are laminated. The thickness Fc and the minimum film thickness Fb from the substrate surface of the space pattern were measured, and F was calculated according to the following formula. It can be said that the smaller F is, the better the followability to the base pattern. The results are shown in Table 1.
F = 1- (Fc-Fb) / Fa

According to the present invention, it is possible to provide a resin composition capable of forming a film having excellent followability to the shape of a base substrate. Since the film obtained from the resin composition has excellent followability to the shape of the underlying substrate, it can be suitably used for a display device or the like.

1 glass substrate, 2 line and space pattern, 2a space, 2b line, 3 film.

Claims (7)

Contains resin (A) and solvent
The resin (A) includes a structural unit (Aa) derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms and a structural unit (Ab) having a carbazole ring which may have a substituent. , A copolymer composed of a structural unit (Ac1) derived from a compound belonging to the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides .
The structural unit (Aa) has a structure in which unsaturated alicyclic hydrocarbons are epoxidized.
The structural unit (Ab) is a resin composition which is a structural unit represented by the formula (Ab-1) .

[In formula (Ab-1), R ¹ represents a hydrogen atom, a methyl group, or a hydroxymethyl group.
R2 to R9 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} , May be substituted with an alkoxy group or an aryl group.
X represents a single bond, an alkanediyl group having one or more carbon atoms, or a linear or branched group represented by the following formula (V).

(In the formula (V), l represents an integer of 0 or more. M represents an integer of 1 or more.)] The structure in which the unsaturated alicyclic hydrocarbon is epoxidized is at least one selected from the group consisting of the structural unit represented by the formula (Aa-1) and the structural unit represented by the formula (Aa-2). The resin composition according to claim 1 , which comprises a seed.

[In the formula (Aa-1) and the formula (Aa-2), 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 is a hydroxy group. It may be replaced.
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.
* Represents a bond with O. ] The resin composition according to claim 1 or 2, wherein the structural unit (Ac1) is a structural unit derived from acrylic acid or methacrylic acid. The resin composition according to any one of claims 1 to 3 , which comprises a polymerization initiator. A film formed from the resin composition according to any one of claims 1 to 4 . A structural unit (Aa) derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms, a structural unit (Ab) having a carbazole ring which may have a substituent , an unsaturated carboxylic acid and an unsaturated carboxylic acid. It is composed of a structural unit (Ac1) derived from a compound belonging to the group consisting of saturated carboxylic acid anhydrides.
The structural unit (Aa) has a structure in which unsaturated alicyclic hydrocarbons are epoxidized.
The structural unit (Ab) is a copolymer which is a structural unit represented by the formula (Ab-1) .

[In formula (Ab-1), R ¹ represents a hydrogen atom, a methyl group, or a hydroxymethyl group.
R2 to R9 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} , May be substituted with an alkoxy group or an aryl group.
X represents a single bond, an alkanediyl group having one or more carbon atoms, or a linear or branched group represented by the following formula (V).

(In the formula (V), l represents an integer of 0 or more. M represents an integer of 1 or more.)] The copolymer according to claim 6, wherein the structural unit (Ac1) is a structural unit derived from acrylic acid or methacrylic acid.

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