JP2017160372A - Polymerizable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable resin composition which has high sensitivity to light having a wavelength of 400 nm or more, and has small dissociation between a width of a mask to be used and a width of a pattern to be obtained when the pattern is formed.SOLUTION: A polymerizable resin composition contains a resin (A), a polymerizable compound (B), a polymerization initiator (C), a polymerization initiation assistant (C-1) and a solvent (D). The resin (A) is a resin containing a structural unit derived from a compound having an alicyclic epoxy group or an oxetanyl group and an unsaturated bond. The polymerization initiation assistant (C-1) is a compound represented by formula (V-1) or formula (V-2).SELECTED DRAWING: None

Description

  The present invention relates to a polymerizable resin composition.

In a display device such as a liquid crystal display device and a touch panel, and a lighting device, a structure having an arbitrary shape, that is, a patterned coating film (hereinafter referred to as a “pattern”) is formed at an arbitrary place by photolithography using a polymerizable resin composition. Is often formed). For example, it has been proposed to form a photo spacer between the color filter and the substrate by the photolithography. The light emitted from the mercury lamp used as the light source for photolithography usually has a high intensity spectrum at wavelengths such as around 436 nm, around 408 nm, around 365 nm, around 315 nm, and the like.
As an exposure machine used in the actual process, a proximity exposure machine or a stepper is often used. In recent years, a proximity exposure machine cuts light with a short wavelength of less than 350 nm. In many steppers, light having a wavelength of around 408 nm or around 365 nm is often used.
So far, a polymerizable resin composition having curability has been proposed even if an exposure machine that does not emit light having a short wavelength of less than 350 nm has been proposed. As such a polymerizable resin composition, polymerization is possible. Compositions containing 4,4′-bis (diethylamino) benzophenone (Patent Document 1, Patent Document 2 and Patent Document 3) and compositions containing 9,10-dibutoxyanthracene (Patent Document 4) as initiation assistants Are known.

JP-A-10-177108 JP 2005-208360 A JP 2006-133378 A JP 2009-139932 A

In recent years, there has been a demand for polymerizable resin compositions that can be cured with light having a longer wavelength.
For example, when performing backside exposure in pattern formation on a flexible substrate, the exposure is through a film. At this time, since some polymer films absorb light having a wavelength of less than 400 nm, it is necessary to perform photocuring using light having a wavelength of 408 nm or 436 nm. In addition, the case where the exposure light source is an LED has been increasing in recent years, and in this case, it is necessary to perform photocuring using light having a wavelength of 408 nm. Therefore, there is a demand for a polymerizable resin composition that has high sensitivity to light having a wavelength of 400 nm or more and is photocured.
However, the above-described polymerizable resin composition has insufficient sensitivity to light having a wavelength of 400 nm or more.
Further, when a pattern is formed from the above polymerizable resin composition using a mask, the width of the pattern to be obtained is likely to be thicker than the width of the mask to be used, and the width of the mask to be used and the width of the pattern to be obtained Separation was likely to increase. For this reason, there are problems that it is difficult to form a fine pattern and a desired shape cannot be obtained.
An object of the present invention is to provide a polymerizable resin composition having high sensitivity to light having a wavelength of 400 nm or more, and having a small separation between the width of a mask to be used and the width of the resulting pattern when forming a pattern. It is to provide.

［式（Ｖ−２）は、Ｘ¹およびＸ^２からなる群より選ばれる少なくとも一つを有し、Ｘ¹およびＸ^２は、芳香環を表す。
式（Ｖ−１）中のＲ^１およびＲ^２と、式（Ｖ−２）中のＲ^３およびＲ^４は、それぞれ独立に、置換基を有していてもよい炭素数１〜１２の飽和炭化水素基または置換基を有していてもよい炭素数６〜１２のアリール基を表す。］ As a result of intensive studies on new means that can solve the above-mentioned problems, the present inventors have found that the polymerizable resin composition of the present invention can solve the above-mentioned problems, and have reached the present invention.
That is, the present invention provides a polymerizable resin composition containing the following resin (A), polymerizable compound (B), polymerization initiator (C), the following polymerization initiation assistant (C-1) and solvent (D). To do.
Resin (A): Resin polymerization initiation assistant (C-1) containing a structural unit derived from a compound having an alicyclic epoxy group or oxetanyl group and an unsaturated bond: represented by the following formula (V-1) And at least one selected from the group consisting of compounds represented by the following formula (V-2)

[Formula (V-2) has at least one selected from the group consisting of X ¹ and ^{X 2,} X ¹ and ^{X 2} represents an aromatic ring.
R ¹ and R ^{2 in} Formula (V-1) and R ³ and R ⁴ in Formula (V-2) are each independently a saturated group having 1 to 12 carbon atoms that may have a substituent. An aryl group having 6 to 12 carbon atoms which may have a hydrocarbon group or a substituent. ]

Moreover, this invention is the coating film formed from the said polymeric resin composition.
Moreover, this invention is a display apparatus containing the said coating film.
Moreover, this invention is an illuminating device containing the said coating film.

  According to the present invention, there is provided a polymerizable resin composition having high sensitivity to light having a wavelength of 400 nm or more and having a small separation between the width of a mask to be used and the width of a pattern to be obtained when forming a pattern. be able to.

Hereinafter, the present invention will be described in detail.
In the present specification, “(meth) acryloyloxy” represents “methacryloyloxy” or “acryloyloxy”, “(meth) acrylate” represents “methacrylate” or “acrylate”, and “( “Meth) acryl” means “methacryl” or “acryl”.
The “alicyclic epoxy group” means a group obtained by removing at least one hydrogen atom from an alicyclic epoxy compound, and the alicyclic epoxy compound is obtained by epoxidizing an alicyclic unsaturated hydrocarbon. Represents a compound.
Moreover, in this specification, a pattern represents the patterned coating film, and the coating film of this invention includes the pattern and the coating film which is not patterned.

The polymerizable resin composition of the present invention is
It is a polymerizable resin composition containing the following resin (A), a polymerizable compound (B), a polymerization initiator (C), the following polymerization initiation assistant (C-1) and a solvent (D).
Resin (A): Resin polymerization initiation assistant (C-1) containing a structural unit derived from a compound having an alicyclic epoxy group or oxetanyl group and an unsaturated bond: represented by the following formula (V-1) And at least one selected from the group consisting of compounds represented by the following formula (V-2)

[Formula (V-2) has at least one selected from the group consisting of X ¹ and ^{X 2,} X ¹ and ^{X 2} represents an aromatic ring.
R ¹ and R ^{2 in} Formula (V-1) and R ³ and R ⁴ in Formula (V-2) are each independently a saturated group having 1 to 12 carbon atoms that may have a substituent. An aryl group having 6 to 12 carbon atoms which may have a hydrocarbon group or a substituent. ]

The resin (A) used in the polymerizable resin composition of the present invention is a resin containing a structural unit derived from a compound having an alicyclic epoxy group or oxetanyl group and an unsaturated bond.
Examples of the resin (A) include the following resin (A-1) and the following resin (A-2).
Resin (A-1): a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter referred to as (a)), an alicyclic epoxy group or oxetanyl Resin resin (A-2) consisting only of a structural unit derived from a group having a group and an unsaturated bond (hereinafter referred to as (b)): It can be polymerized with (a) and (b), and A structural unit derived from a compound having no cyclic epoxy group and no oxetanyl group (hereinafter referred to as (c)), a structural unit derived from (a), and a structural unit derived from (b). Resin (However, (c) is different from (a).)

Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid;
Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
And anhydrides of the aforementioned unsaturated dicarboxylic acids.
As (a), acrylic acid, methacrylic acid, or maleic anhydride is preferable from the viewpoint of copolymerization reactivity and alkali solubility. Said (a) may be used individually or may be used together 2 or more types.

  Among the compounds (b), examples of the compound having an alicyclic epoxy group and an unsaturated bond include vinylcyclohexene monooxide 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.). ), 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.) , Compounds represented by the following formula (I), compounds represented by the following formula (II), and the like.

[R ⁵ in Formula (I) and R ⁶ in Formula (II) each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and are included in the alkyl group having 1 to 4 carbon atoms. At least one of the hydrogen atoms may be substituted with a hydroxyl group.
Y ¹ in formula (I) and Y ² in formula (II) each independently represent an alkylene group having 1 to 6 carbon atoms, and at least one contained in the alkylene group having 1 to 6 carbon atoms The carbon atom may be substituted with a heteroatom.
m is 0 or 1. ]

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁵ and R ⁶ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Etc.
At least one hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms may be substituted with a hydroxyl group. Examples of the alkyl group substituted with a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like can be mentioned.
R ⁵ and R ⁶ are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Examples of the alkylene group having 1 to 6 carbon atoms represented by Y ¹ and Y ² include a methylene group, an ethylene group, and a propylene group.
At least one carbon atom contained in the alkylene group having 1 to 6 carbon atoms may be substituted with a hetero atom. Examples of the alkylene group substituted with a hetero atom include an oxymethylene group, an oxyethylene group, Examples thereof include an oxypropylene group, a thiomethylene group, a thioethylene group, a thiopropylene group, an azamethylene group, an azaethylene group, and an azapropylene group.
Y ¹ and Y ² are preferably a methylene group, an ethylene group, an oxymethylene group, or an oxyethylene group, and more preferably an oxyethylene group.

In the formula (I) and the formula (II), a compound in which m is 0 or a compound in which m is 1 and Y ¹ and Y ² are oxyethylene groups is preferable.

  Examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15), preferably the formula (I-1) and the formula (I-3). , Formula (I-5), formula (I-7), formula (I-9), or a compound represented by formula (I-11) to formula (I-15), more preferably formula (I -1), a compound represented by formula (I-7), formula (I-9), or formula (I-15).

  Examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (II-15), preferably the formula (II-1) and the formula (II-3). , Formula (II-5), formula (II-7), formula (II-9), or a compound represented by formula (II-11) to formula (II-15), more preferably formula (II) -1), a compound represented by formula (II-7), formula (II-9), or formula (II-15).

  As the compound having an alicyclic epoxy group and an unsaturated bond, a compound having an alicyclic epoxy group and a (meth) acryloyloxy group is preferable in that the storage stability of the polymerizable resin composition is better. The compound represented by formula (I) or formula (II) is more preferred.

The compounds having an alicyclic epoxy group and an unsaturated bond may be used alone or in combination of two or more.
When a compound represented by formula (I) and a compound represented by formula (II) are used in combination as a compound having an alicyclic epoxy group and an unsaturated bond, the content ratio (represented by formula (I) The compound represented by formula (II)) is in a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and still more preferably 20:80 to 80:20.

  Of the compounds (b), the compound having an oxetanyl group and an unsaturated bond is preferably a compound having an oxetanyl group and a (meth) acryloyloxy group, such as 3-methyl-3-methacryloyloxymethyloxetane. 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3 -Acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, etc. are mentioned.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-hydroxyethyl (meth). (Meth) acrylic acid alkyl esters such as acrylate and 2-hydroxypropyl (meth) acrylate;
Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, dicyclopenta Nyl (meth) acrylate)), (meth) acrylic acid cyclic alkyl esters such as dicyclopentanyloxyethyl (meth) acrylate and isoboronyl (meth) acrylate;
(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
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-carboxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1 ] Hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5,6- Di (hydroxymethyl) bicyclo [2.2.1] hept-2-e 5,6-di (2′-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6 -Diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2 .1] Hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6- Ethylbicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride), 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxy Carbonyl bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (tert-butoxycarbonyl) bicyclo [2.2. 1] alicyclic unsaturated compounds such as hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -N-substituted maleimides such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrenes such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1 , 3-butadiene, isoprene, and other vinyl compounds such as 2,3-dimethyl-1,3-butadiene.
As the above (c), styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, or bicyclo [2.2.1] hept-2 is preferable because of good polymerization reactivity and alkali solubility. -Ene is preferred.
Said (c) may be used independently or may be used together 2 or more types.

In the resin (A-1) and the resin (A-2), the content of the structural unit derived from (a) and the content of the structural unit derived from (b) are the structural unit derived from (a) ( The total number of moles of structural units derived from b) is preferably within the following ranges, respectively (100 mole%):
Structural unit derived from (a); 5 to 60 mol%
Structural unit derived from (b); 40-95 mol%
The following range is more preferable.
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (b); 50-90 mol%

  In the resin (A-2), the content of the structural unit derived from (c) is relative to the total number of moles (100 parts by mole) of the structural unit derived from (a) and the structural unit derived from (b). It is preferably more than 0 mol part and 300 mol parts or less, more preferably more than 0 mol parts and 280 mol parts or less.

  In the resin (A-1) and the resin (A-2), when the ratio of the structural units derived from the respective monomers is in the above range, the storage stability of the polymerizable resin composition, the polymerizable resin composition From the above, the developability when forming a pattern, and the solvent resistance, heat resistance and mechanical strength of the resulting coating film tend to be better.

Resin (A) is, for example, a method described in the document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and the document Can be produced with reference to the cited references described in 1.
For example, a predetermined amount of a compound such as (a), (b), or (c) above, a polymerization initiator, a solvent, etc. is placed in a reaction vessel, and oxygen in the atmosphere is replaced with nitrogen to remove the compound. Examples thereof include a method of heating and keeping warm under stirring in an oxygen atmosphere. In addition, when manufacturing the below-mentioned polymerization composition, you may use the solution after reaction containing resin (A) as it is, you may use what concentrated or diluted this solution, methods, such as reprecipitation The resin (A) taken out as a solid (powder) may be used.

Examples of the polymerization initiator include azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.), organic peroxides (benzoyl peroxide, etc.) Etc.
As a solvent, what is necessary is just to melt | dissolve each compound, For example, the solvent illustrated by the solvent (F) of the below-mentioned polymerizable resin composition is mentioned.

  The weight average molecular weight in terms of polystyrene of the resin (A) is that the exposed portion is less likely to be reduced during development when forming a pattern from the polymerizable resin composition, and the non-exposed portion is easily removed by development. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000.

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (A) is preferably 1.1 to 6 in terms of excellent developability when forming a pattern from the polymerizable resin composition. 0.0, more preferably 1.2 to 4.0. The weight average molecular weight and molecular weight distribution can be measured by GPC (gel permeation chromatography).

  As content of resin (A) in the polymeric resin composition of this invention, Preferably it is 5-95 mass% with respect to 100 mass% of total amounts of resin (A) and polymeric compound (B), More preferably It is 20-80 mass%, More preferably, it is 30-70 mass%. If the content of the resin (A) is in the above range, there is a tendency to obtain a polymerizable resin composition having higher sensitivity to light having a wavelength of 400 nm, and a pattern is formed from the polymerizable resin composition. When developing, there is a tendency that the developability, adhesion of the resulting coating film, solvent resistance, smoothness, reliability and mechanical strength become better.

The polymerizable resin composition of the present invention may contain the following resin (X) in addition to the resin (A).
Resin (X): Resin having a structural unit derived from (a) and a structural unit derived from (c) (however, the structural unit derived from (b) is not included).

In resin (X), the ratio of the structural unit derived from each monomer is the total number of moles (100 moles) of the structural unit derived from (a) and the structural unit derived from (c) constituting the resin (X). %) Is preferably in the following range,
Structural unit derived from (a); 2 to 40 mol%
Structural unit derived from (c); 60-98 mol%
The following range is more preferable.
Structural unit derived from (a); 5-35 mol%
Structural unit derived from (c); 65 to 95 mol%
When the ratio of the structural unit of the resin (X) is in the above range, the storage stability of the polymerizable resin composition, the developability when forming a pattern from the polymerizable resin composition, and the resulting coating film The solvent resistance tends to be better.

Resin (X) is, for example, a method described in the document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and the document Can be produced with reference to the cited references described in 1.
For example, a predetermined amount of a compound such as (a) and (c), a polymerization initiator, a solvent, and the like are put in a reaction vessel, and oxygen in the atmosphere is replaced with nitrogen to obtain a deoxygenated atmosphere. Examples of the method include heating and heat retention. In addition, when adding resin (X) at the time of manufacture of the below-mentioned polymerization composition, you may use the solution after reaction containing resin (X) as it is, or you may use what concentrated or diluted this solution. The resin (X) taken out as a solid (powder) by a method such as reprecipitation may be used.
As a polymerization initiator and a solvent, the same thing as the polymerization disclosure agent and solvent used at the time of the above-mentioned resin (A) manufacture are mentioned.

  The weight average molecular weight in terms of polystyrene of the resin (X) is preferably from 3,000 to 100,000, more preferably from the point that the exposed portion is less likely to be reduced during development and the non-exposed portion is easily removed by development. Is 5,000 to 50,000.

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (X) is preferably 1.1 to 6 in terms of excellent developability when forming a pattern from the polymerizable resin composition. 0.0, more preferably 1.2 to 4.0. The molecular weight distribution can be measured by GPC (gel permeation chromatography).

The polymerizable compound (B) contained in the polymerizable resin composition of the present invention is a compound that can be polymerized, for example, by an active radical generated from the polymerization initiator (C), preferably a compound having an unsaturated bond. More preferably, it is a (meth) acrylic acid ester. Examples of the (meth) acrylic acid ester include a compound having one (meth) acryloyl group, a compound having two (meth) acryloyl groups, a compound having three or more (meth) acryloyl groups, and the like.
Specific examples of the compound having one (meth) acryloyl group include nonylphenyl carbitol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2- Hydroxyethyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone (meth) acrylate, ethoxylated nonylphenol (Meth) acrylate, propoxylated nonylphenol (meth) acrylate, N-vinylpyrrolidone and the like can be mentioned.

  Specific examples of the 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, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) Acrylate, 3-methyl-pentanediol di (meth) acrylate.

  Specific examples of the compound having three or more (meth) acryloyl groups include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxy Trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol Tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaeryth Tall hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, tripenta Reaction product of erythritol hepta (meth) acrylate and acid anhydride, caprolactone-modified trimethylolpropane tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meta) ) Acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) 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 tripentaerythritol hepta (meta ) Acrylate, caprolactone modified tripentaerythritol octa (meth) acrylate, reaction product of caprolactone modified pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of caprolactone modified dipentaerythritol penta (meth) acrylate and acid anhydride And a reaction product of caprolactone-modified tripentaerythritol hepta (meth) acrylate and acid anhydride. I can get lost.

  The polymerizable compound (B) is preferably a compound having three or more (meth) acryloyl groups. The polymerizable compounds may be used alone or in combination of two or more.

  The content of the polymerizable compound (B) is preferably 5 to 95% by mass, more preferably 20 to 80% by mass with respect to 100% by mass of the total amount of the resin (A) and the polymerizable compound (B). More preferably, it is 30-70 mass%. When the content of the polymerizable compound (B) is in the above range, there is a tendency to obtain a polymerizable resin composition having higher sensitivity to light having a wavelength of 400 nm or more, and from the polymerizable resin composition. There exists a tendency for the developability at the time of forming a pattern, the mechanical strength of the coating film obtained, smoothness, adhesiveness, solvent resistance, and reliability to become more favorable.

  The polymerization initiator (C) contained in the polymerizable resin composition of the present invention may be a compound that can initiate polymerization by the action of light or heat, such as a biimidazole compound, an alkylphenone compound, a triazine compound, Examples include acylphosphine oxide compounds and oxime compounds, and biimidazole compounds are preferred in that a polymerizable resin composition having higher sensitivity to light having a wavelength of 400 nm or more can be obtained.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4. , 4 ′, 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4, 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis ( 2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxy) Phenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), and the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Imidazole compounds (see, for example, JP-A-7-10913) and the like, preferably 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, or 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5 , 5′-tetraphenylbiimidazole.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl]- 2-methylpropan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (2-Methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butano 2- (3-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-propylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,3-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -Butanone, 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-chlorobe Dil) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-chloro Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-bromo Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methoxy) Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-methoxybenzyl) -2-dimethyl Amino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromo-4 -Methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one oligomer, etc. Is mentioned.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) ) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2) -Methylphenyl) Sulfonyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine

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

  Examples of the oxime compound include O-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, a compound represented by the formula (III), a compound represented by the formula (IV), and the like.

  Examples of the polymerization initiator further include benzoin compounds, benzophenone compounds, thioxanthone compounds, and other compounds.

  In addition to the polymerization initiator (C), a photopolymerization initiator or the like may be contained. Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, thioxanthone compounds, and other compounds. These may be used alone or in combination of two or more.

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

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

  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 other compounds include 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, and titanocene compounds.

  Further, a polymerization initiator having a group capable of causing chain transfer may be used. Examples of the polymerization initiator having a group capable of causing chain transfer include polymerization initiators described in JP-T-2002-544205.

The content of the polymerization initiator (C) in the polymerizable resin composition of the present invention is preferably 0.1 to 40 parts by mass with respect to 100 parts by mass of the total amount of the resin (A) and the polymerizable compound (B). More preferably, it is 1-30 mass parts.
When the polymerization initiator (C) is in the above range, there is a tendency to obtain a polymerizable resin composition having higher sensitivity to light having a wavelength of 400 nm or more, and the mechanical strength and smoothness of the obtained coating film. Tend to be better.

  The polymerization initiation assistant (C-1) contained in the polymerizable resin composition of the present invention is composed of a compound represented by the following formula (V-1) and a compound represented by the following formula (V-2). It is at least one kind selected.

（Ｖ）

(V)

[Formula (V-2) has at least one selected from the group consisting of X ¹ and ^{X 2,} X ¹ and ^{X 2} represents an aromatic ring.
R ¹ and R ^{2 in} Formula (V-1) and R ³ and R ⁴ in Formula (V-2) are each independently a saturated group having 1 to 12 carbon atoms that may have a substituent. An aryl group having 6 to 12 carbon atoms which may have a hydrocarbon group or a substituent. ]

Examples of the aromatic ring in X ¹ and X ² include benzene ring, methylbenzene ring, dimethylbenzene ring, ethylbenzene ring, propylbenzene ring, butylbenzene ring, pentylbenzene ring, hexylbenzene ring, cyclohexylbenzene ring, phenylbenzene ring, naphthalene. Ring, phenanthrene ring, chrysene ring, fluoranthene ring, benzo [a] pyrene ring, benzo [e] pyrene ring, perylene ring, and derivatives thereof.

  In the aromatic ring, at least one hydrogen atom contained in the aromatic ring may be substituted with a halogen atom or the like. Examples of the aromatic ring substituted with a halogen atom include a chlorobenzene ring, a dichlorobenzene ring, a bromobenzene ring, a dibromobenzene ring, a chlorophenylbenzene ring, a bromophenylbenzene ring, a chloronaphthalene ring, and a bromonaphthalene ring. .

Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms for R ¹ , R ² , R ³ , and R ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and 1-methyl-n. -Propyl group, 2-methyl-n-propyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, Examples include 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group and the like.
Examples of the substituent that the saturated hydrocarbon group having 1 to 12 carbon atoms may have include a substituted or unsubstituted hydroxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted sulfanyl group, and a halogen atom. Is mentioned.
Examples of the substituted or unsubstituted hydroxy group include a hydroxy group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, and a hexyloxy group.
Examples of the substituted or unsubstituted amino group include: an amino group; a monoalkylamino group substituted with an alkyl group having 1 to 6 carbon atoms such as a methylamino group, an ethylamino group, and a hexylamino group; a dimethylamino group, a diethylamino group, And a dialkylamino group substituted with an alkyl group having 1 to 6 carbon atoms such as a methylhexylamino group.
Examples of the substituted or unsubstituted sulfanyl group include a sulfanyl group; an alkylsulfanyl group having 1 to 6 carbon atoms such as a methylsulfanyl group, an ethylsulfanyl group, and a hexylsulfanyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
As a C1-C12 saturated hydrocarbon group substituted by the halogen atom, 1-chlorobutyl group, 2-chlorobutyl group, 3-chlorobutyl group, etc. are mentioned.

Examples of the aryl group having 6 to 12 carbon atoms in R ¹ , R ² , R ³ , and R ⁴ include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenyl group. Examples of the substituent that the aryl group having 6 to 12 carbon atoms may have include a halogen atom. Examples of the aryl group having 6 to 12 carbon atoms substituted by a halogen atom include chlorophenyl group, dichlorophenyl group, bromophenyl group, dibromophenyl group, chlorobromophenyl group, chlorobiphenyl group, dichlorobiphenyl group, bromophenyl group, dibromo Examples thereof include a phenyl group, a chloronaphthyl group, a dichloronaphthyl group, a bromonaphthyl group, and a dibromonaphthyl group.

The compound represented by the formula (V-2) preferably has X ¹ and X ^{2 in} that when the pattern is formed, the separation between the width of the mask to be used and the width of the obtained pattern becomes smaller. A compound.

Examples of the compound represented by the formula (V-1) include 1,4-bis (octanoyloxy) benzene, 1,4-bis (hexanoyloxy) benzene, and 1,4-bis (n-decanoyl). Oxy) benzene, 1,4-bis (benzoyloxy) benzene, 1,4-bis (naphthanoyloxy) benzene and the like. These may be used alone or in combination of two or more.
Examples of the compound represented by the formula (V-2) include 1,4-bis (octanoyloxy) naphthalene, 1,4-bis (hexanoyloxy) naphthalene, 1,4-bis (n-decanoyloxy). ) Naphthalene, 1,4-bis (benzoyloxy) naphthalene, 1,4-bis (naphthanoyloxy) naphthalene, 9,10-bis (acetyloxy) anthracene, 9,10-bis (propionyloxy) anthracene, 9, 10-bis (n-butyryloxy) anthracene, 9,10-bis (i-butyryloxy) anthracene, 9,10-bis (n-valeryloxy) anthracene, 9,10-bis (i-valeryloxy) anthracene, 9,10- Bis (n-hexanoyloxy) anthracene, 9,10-bis (n-heptanoyloxy) a Tracene, 9,10-bis (n-octanoyloxy) anthracene, 9,10-bis (2-ethylhexanoyloxy) anthracene, 9,10-bis (n-nonanoyloxy) anthracene, 9,10-bis (n -Decanoyloxy) anthracene, 9,10-bis (n-dodecanoyloxy) anthracene, 9,10-bis (benzoyloxy) anthracene, 9,10-bis (4-methylbenzoyloxy) anthracene, 9,10- And bis (2-naphthoyloxy) anthracene.
These may be used alone or in combination of two or more.

The content of the polymerization initiation assistant (C-1) is preferably 0.1 to 20 parts by mass, more preferably 100 parts by mass of the total amount of the resin (A) and the polymerizable compound (B). It is 0.5-15 mass parts, More preferably, it is 1-10 mass parts.
When the content of the polymerization initiation assistant (C-1) is in the above range, it has a higher sensitivity to light having a wavelength of 400 nm or more, and when the pattern is formed, the width of the mask used is obtained. There is a tendency to obtain a polymerizable resin composition having a smaller separation from the width of the pattern, a tendency to improve the transparency of the resulting coating film, and a tendency to further improve the productivity of the pattern to be formed.

Examples of the compound contained in the solvent (D) used in the polymerizable resin composition of the present invention include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, and 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, etc. Compound (compound containing -COO- in the molecule and not -O-);
Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether Ether compounds such as diethylene glycol dialkyl ethers (compounds containing —O— in the molecule and not containing —COO—);
Alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, and ethyl 3-ethoxypropionate Ester ether compounds such as alkoxy fatty acid esters such as methyl 3-methoxypropionate (compounds containing —COO— and —O— in the molecule);
Aromatic hydrocarbon compounds such as benzene, toluene, xylene, mesitylene;
Ketone compounds such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone;
Examples include alcohol compounds such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, methoxypropanol, methoxybutanol, ethoxybutanol, and glycerin.

The solvent (D) is preferably an organic solvent having a boiling point of 100 to 200 ° C., more preferably an ester ether compound, an alcohol compound, a ketone compound, or an ester compound in terms of easy application and easy drying. And more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutanol, methoxypropanol, methoxybutyl acetate, ethyl 3-ethoxypropionate, or methyl 3-methoxypropionate.
These solvents (D) may be used alone or in combination of two or more.

The content of the solvent (D) in the polymerizable resin composition of the present invention is preferably 60 to 90% by mass, more preferably 65 to 85% by mass with respect to 100% by mass of the polymerizable resin composition of the present invention. %.
When the content of the solvent (D) is in the above range, a spin coater, a slit & spin coater, a slit coater (sometimes called a die coater or a curtain flow coater), an ink jet, a roll coater, a dip coater, etc. When applied with a coating apparatus, the coating property tends to be better.

  Moreover, the polymerizable resin composition of the present invention may contain an amine compound, a carboxylic acid compound, and a thiol compound (T) to such an extent that the effects of the present invention are not impaired. It is preferable.

  Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4 2-dimethylhexyl dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4′-bis (diethylamino) ) Aromatic amine compounds such as benzophenone.

  Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N -Aromatic heteroacetic acids such as phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

  The thiol compound (T) is a compound having a sulfanyl group in the molecule. Especially, the compound which has a 2 or more sulfanyl group is preferable at the point which can obtain the polymeric resin composition which has a higher sensitivity with respect to the light of wavelength 400nm or more.

Examples of the thiol compound (T) include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylbenzoxazole, 2-sulfanylnicotinic acid, 2-sulfanylpyridine, 2 -Sulfanylpyridin-3-ol, 2-sulfanylpyridine-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-2-sulfanyl Pyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamino-6-sulfur Anilpyrimidine, 4,6-dihydroxy-2-sulfanylpyrimidine, 4,6-dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6-propyl Pyrimidine, 2-sulfanyl-4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol, 2-sulfanylimidazole 2-sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1,2,4-triazole, 3-amino-5-sulfanyl-1,2,4-triazole, 2-methyl- 4H-1,2,4-triazole-3-thio 4-methyl-4H-1,2,4-triazole-3-thiol, 3-sulfanyl 1H-1,2,4-triazole-3-thiol, 2-amino-5-sulfanyl-1,3 4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-disulfanyl-1,3,4-thiadiazole, (furan-2-yl) methanethiol, 2-sulfanyl-5 -Thiazolidone, 2-sulfanylthiazoline, 2-sulfanyl-4 (3H) -quinazolinone, 1-phenyl-1H-tetrazole-5-thiol, 2-quinolinethiol, 2-sulfanyl-5-methylbenzimidazole, 2-sulfanyl- 5-nitrobenzimidazole, 6-amino-2-sulfanylbenzothiazole, 5-chloro-2-sulfani Benzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 6-nitro-2-sulfanylbenzothiazole, 2-sulfanylnaphthimidazole, 2-sulfanylnaphthoxazole, 3-sulfanyl-1,2,4-triazole, 4-amino Sulfanyl in the molecule such as -6-sulfanylpyrazolo [2,4-d] pyridine, 2-amino-6-purinethiol, 6-sulfanylpurine, 4-sulfanyl-1H-pyrazolo [2,4-d] pyrimidine A monofunctional thiol compound having one group;
Hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropio , Trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, pentaerythritol tetrakis (3-mercapto Butyrate), 1,4-bis (3-mercaptobutyryloxy) butane, etc., polyfunctional having a plurality of sulfanyl groups in the molecule All compounds, and the like.

  The content of the thiol compound (T) is preferably 5 to 300 parts by mass and more preferably 10 to 200 parts by mass with respect to 100 parts by mass of the polymerization initiator (C). When the content of the polyfunctional thiol compound (T) is in the above range, a polymerizable resin composition having higher sensitivity to light having a wavelength of 400 nm or more can be obtained, and a pattern is formed from the polymerizable resin composition. There is a tendency for the developability to be better.

  The polymerizable resin composition of the present invention contains additives such as fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents, as necessary. May be.

  Examples of the filler include glass, silica, and alumina.

  Other polymer compounds include, for example, curable resins such as epoxy resins and maleimide resins (however, different from the resin (A)); polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate And thermoplastic resins such as polyester and polyurethane.

  Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-amino). Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Examples include trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

  Examples of the antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3). , 5-Di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2 , 4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, 3,9-bis [2- {3- (3-tert-butyl-4- Hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2′-methyle Bis (6-tert-butyl-4-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 4,4′-thiobis (2-tert-butyl-5-methylphenol) ), 2,2′-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′- Thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine -2,4,6 (1H, 3H, 5H) -trione, 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', ''-(Mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di -Tert-butyl-4-methylphenol and the like.

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

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

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

  The polymerizable resin composition of the present invention does not substantially contain colorants such as pigments and dyes. That is, in the curable resin composition of the present invention, the content of the colorant with respect to the entire composition is, for example, less than 1% by mass, preferably less than 0.5% by mass.

  Moreover, when the polymerizable 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 measurement wavelength of 400 to 700 nm using a spectrophotometer, the average transmittance is obtained. Is preferably 70% or more, and more preferably 80% or more.

  When the polymerizable resin composition of the present invention is used as a coating film, the average transmittance of the coating film is preferably 80% or more, more preferably 90% or more. This average transmittance is measured under the conditions of a measurement wavelength of 400 to 700 nm using a spectrophotometer for a coating film having a thickness of 3 μm after heat curing (for example, 100 to 250 ° C., 5 minutes to 3 hours). It is an average value when measured by. Thereby, the coating film excellent in transparency in the visible light region can be provided.

  The polymerizable resin composition of the present invention comprises a resin (A), a polymerizable compound (B), a polymerization initiator (C), the following polymerization initiation assistant (C-1) and a solvent (D), and as necessary. It can be produced by mixing other components with 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.

The polymerizable resin composition of the present invention can be formed by, for example, forming a coating film on a substrate such as a glass substrate or a film substrate, a substrate on which a color filter, a drive circuit, or the like is formed, or patterning it to a desired shape. A pattern can be formed. This coating film can be used as a part of components such as a display device and a lighting device.
For example, the pattern can be formed by the following method.

First, the polymerizable resin composition of the present invention is applied on a substrate. Next, by prebaking the applied polymerizable resin composition, volatile components such as a solvent are removed by prebaking or vacuum drying to obtain a smooth uncured coating film.
Examples of the coating apparatus used at the time of coating include a spin coater, a slit & spin coater, a slit coater, an ink jet, a roll coater, and a dip coater.
The thickness of the uncured coating film is preferably 1 to 6 μm.

Next, the uncured coating film is exposed by irradiating light such as ultraviolet rays generated from a mercury lamp or a light emitting diode through a mask for forming a target pattern.
The shape and size of the mask may be selected according to the application of the pattern.

  The polymerizable resin composition of the present invention has high sensitivity to light having a wavelength of 400 nm or more. Therefore, even in the case of irradiating light having a wavelength of 400 nm or more by using a filter that cuts a wavelength region of less than 400 nm or using a bandpass filter that extracts a wavelength region of 400 nm or more in an exposure machine used for exposure. A pattern with high sensitivity and a small separation from the width of the mask can be formed. At this time, if an apparatus such as a mask aligner or a stepper is used, the mask and the substrate can be accurately aligned.

  Subsequently, the uncured coating film after exposure is brought into contact with a developing solution and developed, and the non-exposed portion is dissolved, whereby a desired pattern shape can be obtained. Examples of the developing method include a liquid piling method, a dipping method, and a spray method. Further, the substrate may be tilted at an arbitrary angle during development.

  The developer is usually an aqueous solution containing an alkaline compound. The alkaline compound may be either an inorganic or organic alkaline compound. The developer may further contain a surfactant.

  The uncured coating film after development may be washed with water and further post-baked at 150 to 230 ° C. for 10 to 180 minutes as necessary.

  The pattern obtained from the polymerizable resin composition of the present invention through the above-described steps is matched with the film thickness of the photo spacer, patternable overcoat, liquid crystal alignment control protrusion, and coloring pattern used in the liquid crystal display device. Therefore, it is useful as a coating layer and an interlayer insulating film.

  In order to form a non-patterned coating film, the entire surface may be exposed without using a mask for forming a pattern, or the development process may be omitted when exposing an uncured coating film. The obtained coating film is transparent and useful as an overcoat or a touch panel.

  The display apparatus of this invention is an apparatus containing the said coating film. Examples of the display device include a liquid crystal display device and an organic EL display device.

  The illuminating device of this invention is an apparatus containing the said coating film. Examples of the illumination device include an organic EL illumination device. The said coating film is useful as a coating film which planarizes the level | step difference of a mesh electrode, for example.

  Although the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the terms of the claims, and includes the meaning equivalent to the description of the claims and all modifications within the scope.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

[Synthesis Example 1]
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, and 200 parts of 3-methoxy-1-butanol and 105 parts of 3-methoxybutyl acetate were added and stirred. While heating to 70 ° C. Next, 60 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) The compound is mixed at a molar ratio of 50:50.) 240 parts are dissolved in 140 parts of 3-methoxybutylacetate to prepare a solution, and the solution is added using a dropping funnel over 4 hours. It was dripped in the flask kept at 70 degreeC. On the other hand, a solution obtained by dissolving 30 parts of polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts of 3-methoxybutyl acetate was placed in a flask using another dropping funnel over 4 hours. It was dripped. After completion of dropping of the polymerization initiator solution, the solution was kept at 70 ° C. for 4 hours, and then cooled to room temperature to obtain a resin having a solid content of 32.6% and an acid value of 110 mg-KOH / g (in terms of solid content) ( A solution of Aa) was obtained. The obtained resin (Aa) had a weight average molecular weight Mw of 13,400 and a molecular weight distribution of 2.50.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin (Aa) were measured using the GPC method under the following conditions.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate; 1.0 mL / min detector; RI
The ratio of the weight average molecular weight and number average molecular weight obtained in the above-mentioned manner was defined as the molecular weight distribution (Mw / Mn).

Example 1 and Comparative Examples 1-5
Each component was mixed in the amounts shown in Table 1 to obtain a polymerizable resin composition. In addition, the blank in Table 1 means not adding.

In Table 1, the details of each component are as follows, and each value is a mass-based content. Moreover, the quantity of resin (Aa) is a mass part of solid content conversion.
Resin (Aa): Resin polymerizable compound obtained in Synthesis Example 1 (B): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (C): 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (B-CIM; manufactured by Hodogaya Chemical Co., Ltd .; biimidazole compound)
Polymerization initiation aid (C1): 9,10-bis (n-octanoyloxy) anthracene (Anthracure (registered trademark) UVS-581: manufactured by Kawasaki Kasei Kogyo Co., Ltd.)
Polymerization initiation aid (C2): 9,10-dibutoxyanthracene (Anthracure (registered trademark) UVS-1331: manufactured by Kawasaki Kasei Kogyo Co., Ltd.)
Polymerization initiation aid (C3): 4,4′-bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.)
Polymerization initiation aid (C4): 2,4-diethylthioxanthone (KAYACURE (registered trademark) DETX-S; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiation assistant (C5): 2-isopropylthioxanthone (manufactured by Tokyo Chemical Industry Co., Ltd.)
Thiol compound (T): pentaerythritol tetrakis (3-sulfanylpropionate) (PEMP; manufactured by SC Organic Chemical Co., Ltd.)
Solvent (D1): Propylene glycol monomethyl ether acetate solvent (D2): 1-methoxy-2-propanol solvent (D3): 3-methoxybutanol solvent (D4): 3-methoxybutyl acetate solvent (D) is a polymerizable resin The composition was mixed so that the solid content was the “solid content (%)” in Table 1. The value of solvent (D1), (D2), (D3) and (D4) represents the mass ratio in solvent (D).

<Average transmittance of composition>
Each of the obtained polymerizable resin compositions was measured at a wavelength of 400 to 700 nm using an ultraviolet-visible near-infrared spectrophotometer (V-650; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). The average transmittance (%) was measured. The results are shown in Table 1.

<Preparation of coating film>
A 2-inch square glass substrate (# 1737; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol and then dried. On this glass substrate, each of the polymerizable resin compositions obtained in Example 1 or Comparative Examples 1 to 5 was spin-coated so that the film thickness of the post-baked coating film was 3.0 μm, and then Pre-baking was performed at 100 ° C. for 3 minutes in a clean oven to obtain an uncured coating film. After standing to cool, the uncured coating film was exposed to an exposure amount of 200 mJ / cm ² (based on a wavelength of 405 nm) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation, light source; ultrahigh pressure mercury lamp). Irradiated with light. The film thickness of the uncured coating film obtained after exposure was measured. In addition, for irradiation to the uncured coating film, light obtained by passing the emitted light from the ultra-high pressure mercury lamp through an optical filter (LU0400; manufactured by Asahi Spectrometer Co., Ltd.), with a bright line having a wavelength of 400 nm or less cut. (Light including a 405 nm emission line (h line) and a 436 nm emission line (g line)) was used. In addition, a mask having a line pattern formed on the same plane was used as a photomask.
After light irradiation, the uncured coating film after exposure was immersed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 25 ° C. for 100 seconds, developed, and washed with water. . The film thickness of the obtained uncured coating film after development was measured. The obtained uncured coating film after development was post-baked at 230 ° C. for 20 minutes in an oven to obtain a coating film.
In addition, the film thickness measurement apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd.)) was used for the film thickness measurement.

<Average transmittance of coating film>
About the coating film obtained above, the average transmittance | permeability (%) in the measurement wavelength 400-700 nm was measured using the microspectrophotometer (OSP-SP200; product made by OLYMPUS). The results are shown in Table 1.

<Residual film ratio>
From the results of the film thickness (μm) of the uncured coating film after exposure measured above and the film thickness (μm) of the uncured coating film after development, the remaining film ratio was calculated according to the following formula.

Residual film ratio = film thickness of uncured coating film after development / film thickness of uncured coating film after exposure

The results are shown in Table 2. In addition, it has shown that the sensitivity with respect to light with a wavelength of 400 nm or more is so high that the value of a residual film rate is large.

<Pattern preparation>
A 2-inch square glass substrate (# 1737; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol and then dried. On this glass substrate, each of the polymerizable resin compositions obtained in Example 1 or Comparative Examples 1 to 5 was spin-coated so that the film thickness of the post-baked coating film was 1.0 μm, and then Pre-baking was performed at 100 ° C. for 3 minutes in a clean oven to obtain an uncured coating film. After cooling, the distance between the uncured coating film and the quartz glass photomask was set to 10 μm, and exposure was performed in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation, light source: ultrahigh pressure mercury lamp). Light was irradiated at an amount of 200 mJ / cm ² (wavelength 405 nm standard). In addition, for irradiation to the uncured coating film, light obtained by passing the emitted light from the ultra-high pressure mercury lamp through an optical filter (LU0400; manufactured by Asahi Spectrometer Co., Ltd.), with a bright line having a wavelength of 400 nm or less cut. (Light including a 405 nm emission line (h line) and a 436 nm emission line (g line)) was used. A quartz glass photomask having a width (mask width) shown in Table 3 and having a pattern formed on the same plane was used.

  After light irradiation, the uncured coating film after exposure was immersed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 25 ° C. for 100 seconds, developed, and washed with water. Then, the pattern was obtained by performing post-baking for 20 minutes at 230 degreeC in oven. The width (actual pattern width) of the obtained pattern was measured using a scanning electron microscope (S-4000; manufactured by Hitachi High-Technologies Corporation). The results are shown in Table 3. It shows that the closer the actual pattern width value is to the mask width value, the smaller the difference between the width of the mask to be used and the width of the pattern to be obtained.

  From the results of Example 1 shown in Table 2 and Table 3, the polymerizable resin composition of the present invention has higher sensitivity to light having a wavelength of 400 nm or more than Comparative Examples 1 to 5, and is a mask to be used. It can be seen that the difference between the width of the pattern and the width of the obtained pattern is small.

  Since the polymerizable resin composition of the present invention can easily form a pattern having a desired shape, has good sensitivity, and can form a pattern and a coating film having high transmittance, a display device or illumination This is useful for forming a structure constituting the apparatus.

Claims (6)

A polymerizable resin composition comprising the following resin (A), a polymerizable compound (B), a polymerization initiator (C), the following polymerization initiation assistant (C-1) and a solvent (D).
Resin (A): Resin polymerization initiation assistant (C-1) containing a structural unit derived from a compound having an alicyclic epoxy group or oxetanyl group and an unsaturated bond: represented by the following formula (V-1) And at least one selected from the group consisting of compounds represented by the following formula (V-2)

[Formula (V-2) has at least one selected from the group consisting of X ¹ and ^{X 2,} X ¹ and ^{X 2} represents an aromatic ring.
R ¹ and R ^{2 in} Formula (V-1) and R ³ and R ⁴ in Formula (V-2) are each independently a saturated group having 1 to 12 carbon atoms that may have a substituent. An aryl group having 6 to 12 carbon atoms which may have a hydrocarbon group or a substituent. ]   Furthermore, the polymeric resin composition of Claim 1 containing a thiol compound (T).   The polymerization property according to claim 1 or 2, wherein the polymerization initiator (C) contains at least one compound selected from the group consisting of a biimidazole compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and an oxime compound. Resin composition.   The coating film formed from the polymeric resin composition as described in any one of Claims 1-3.   The display apparatus containing the coating film of Claim 4.   The illuminating device containing the coating film of Claim 4.