KR20090050968A - Polymerizable resin composition - Google Patents

Abstract

Alkali-soluble resin (A), a polymeric compound (B), an initiator (C), an initiator adjuvant (D), and a solvent (E) are contained, and an initiator adjuvant (D) is a formula (I-1) and a formula (I-) Polymeric resin composition which is a compound containing the compound represented by at least 1 sort (s) chosen from the group which consists of 2).

[In Formula (I-1) and Formula (I-2), ring X ¹ , ring X ^2, and ring X ³ each independently represent an aromatic ring having 6 to 12 carbon atoms. Y ¹ to Y ⁴ each independently represent an oxygen atom or a sulfur atom. R ¹ to R ⁴ each independently represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.

The methylene group contained in the aromatic ring, the alkyl group and the aryl group may be substituted with an oxygen atom, -NH- or a sulfur atom, and the hydrogen atom contained in the aromatic ring, the alkyl group and the aryl group may be substituted with a halogen atom.]

Description

Polymerizable Resin Composition {POLYMERIZABLE RESIN COMPOSITION}

The present invention relates to a polymerizable resin composition.

It is proposed to form a spacer (photo spacer) by photolithography using a photosensitive resin between a color filter constituting a display device such as a liquid crystal display device or a touch panel and an array substrate. According to this method, a spacer can be formed in arbitrary places.

By the way, the light radiated | emitted from the mercury lamp used for the light source of photolithography has a high intensity spectrum normally about 436 nm, 408 nm vicinity, 365 nm vicinity, 315 nm vicinity, 313 nm vicinity, etc.

The exposure machine used in the actual photo-spacer formation process often uses a proximity exposure machine and a stepper, and the recent proximity exposure machine often cuts and uses short wavelength of less than 350 nm. In the stepper, light having a wavelength around 408 nm and around 365 nm is used.

Even when using an exposure machine that does not emit light having a short wavelength of less than 350 nm, a composition having sufficient curability, that is, a composition having sufficient sensitivity to light having a wavelength of around 436 nm, around 408 nm, and around 365 nm is proposed. It is. As such a composition, Patent Document 1 describes a composition containing 4,4'-bisdiethylaminobenzophenone. In addition, Patent Document 2 describes a composition containing anthracene.

Patent Document 1: Japanese Unexamined Patent Publication No. 2005-208360

Patent Document 2: Japanese Unexamined Patent Publication No. 2003-50459

In the conventional composition, although sufficient sensitivity is obtained for the light of the wavelength of around 436 nm, about 408 nm, and around 365 nm, the transmittance | permeability of the coating film or pattern obtained from this composition may not be fully obtained.

MEANS TO SOLVE THE PROBLEM As a result of examining the said subject, it turned out that the polymeric resin composition containing some kind of compound has sufficient sensitivity to the light of 350-450 nm range, and the transmittance | permeability of the coating film or pattern obtained from the composition is high enough. Figured out.

That is, this invention provides the following [1]-[8].

[One]. Alkali-soluble resin (A), a polymeric compound (B), an initiator (C), an initiator adjuvant (D), and a solvent (E) are contained, and an initiator adjuvant (D) is a formula (I-1) and a formula (I-) Polymeric resin composition which is a compound containing the compound represented by at least 1 sort (s) chosen from the group which consists of 2).

[In Formula (I-1) and Formula (I-2), ring X ¹ , ring X ^2, and ring X ³ each independently represent an aromatic ring having 6 to 12 carbon atoms. Y ¹ to Y ⁴ each independently represent an oxygen atom or a sulfur atom. R ¹ to R ⁴ each independently represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.

The methylene group contained in the aromatic ring, the alkyl group and the aryl group may be substituted with an oxygen atom, -NH- or a sulfur atom, and the hydrogen atom contained in the aromatic ring, the alkyl group and the aryl group may be substituted with a halogen atom.]

[2]. [1] to [1], wherein the initiator (C) is a compound containing at least one compound selected from the group consisting of a biimidazole compound, an acetophenone compound, a triazine compound, an acylphosphine oxide compound, and an oxime compound The polymerizable resin composition described.

[3]. Polymeric resin composition as described in [1] or [2] whose alkali-soluble resin (A) is resin which has at least 1 sort (s) of group chosen from the group which consists of an epoxy group and an oxetanyl group.

[4]. Polymeric resin composition in any one of [1]-[3] whose alkali-soluble resin (A) is resin which has a reactive double bond.

[5]. Polymeric resin composition in any one of [1]-[4] whose starting adjuvant (D) is a compound which further contains a polyfunctional thiol compound (T).

[6]. The coating film formed using the polymeric resin composition in any one of [1]-[5].

[7]. The pattern formed using the polymeric resin composition in any one of [1]-[5].

[8]. A display device comprising at least one selected from the group consisting of the coating film as described in [6] and the pattern as described in [7].

According to the polymeric resin composition of this invention, it can form the coating film or pattern which has sufficient sensitivity for the light of 350-450 nm range, and is high enough transmittance | permeability.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The polymerizable resin composition of the present invention contains an alkali-soluble resin (A), a polymerizable compound (B), an initiator (C), an initiation aid (D) and a solvent (E), and the initiation aid (D) is formula (D). It is a compound containing the compound represented by at least 1 sort (s) chosen from the group which consists of I-1) and Formula (I-2).

[In Formula (I-1) and Formula (I-2), ring X ¹ , ring X ^2, and ring X ³ each independently represent an aromatic ring having 6 to 12 carbon atoms. Y ¹ to Y ⁴ each independently represent an oxygen atom or a sulfur atom. R ¹ to R ⁴ each independently represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.

The methylene group contained in the aromatic ring, the alkyl group and the aryl group may be substituted with an oxygen atom, -NH- or a sulfur atom, and the hydrogen atom contained in the aromatic ring, the alkyl group and the aryl group may be substituted with a halogen atom.]

It is preferable that a starting adjuvant (D) is a compound containing the compound represented by Formula (I-2).

As alkali-soluble resin (A) used for the polymeric resin composition of this invention, alkali-soluble resin (A1) and alkali-soluble resin (A2) are illustrated. Alkali-soluble resin (A1) shows alkali solubility, and alkali-soluble resin (A2) shows alkali solubility and reactivity by the action of at least one of light and heat.

As alkali-soluble resin (A1), at least 1 sort (s) of compound (a) (Hereinafter, it may be called "(a)") chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and (a) The copolymer etc. which superpose | polymerize with the monomer (b) which can copolymerize with (it differs from (a)) (hereinafter may be called "(b)") are illustrated.

As (a), specifically, unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, a crotonic acid;

Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid;

Anhydrides of the above unsaturated dicarboxylic acids;

Unsaturated mono [(meth) acrylic acid of divalent or higher polyhydric carboxylic acid such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Iloxyalkyl] esters;

Unsaturated acrylate containing a hydroxyl group and a carboxyl group in the same molecule, such as (alpha)-(hydroxymethyl) acrylic acid, etc. are mentioned.

Among these, acrylic acid, methacrylic acid or maleic anhydride are preferably used in terms of copolymerization reactivity or alkali solubility. These are used individually or in combination.

As (b),

(Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate and tert-butyl (meth) acrylate;

Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (in the art, dicyclopentanyl as conventional name) (Meth) acrylic-acid cyclic alkyl esters, such as (meth) acrylate), dicyclopentanyloxyethyl (meth) acrylate, and isoboroyl (meth) acrylate;

Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5 2.1.0 ^2,6 ] decane-8-yl acrylate (common name in the art as dicyclopentanyl acrylate), dicyclo Acrylic acid cyclic alkyl esters such as pentaoxyethyl acrylate and isoboroyl acrylate;

(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;

Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate;

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

Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybi Cyclo [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-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2. 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5- Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-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-etherbicyclo [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-cyclohex Siloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (tert-butoxycarbonyl) bicyclo [ Bicyclo unsaturated compounds such as 2.2.1] hept-2-ene and 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl Dicarbonylimide derivatives such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among them, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferred in terms of copolymerization reactivity and alkali solubility.

These are used individually or in combination.

In the copolymer obtained by copolymerizing (a) and (b), the ratio of the structural component derived from each is a mole fraction, when the total mole number of the structural component which comprises said copolymer is 100 mol%. It is preferable to be in a range.

structural units derived from (a); 2-40 mol%

structural units derived from (b); 60 to 98 mol%

Moreover, it is more preferable if the ratio of the said structural component is the following ranges.

structural units derived from (a); 5 to 35 mol%

structural units derived from (b); 65 to 95 mol%

When said composition ratio exists in the range mentioned above, there exists a tendency for storage stability, developability, and solvent resistance to become favorable.

Alkali-soluble resin (A1) is, for example, described in the method described in the document "Experimental method of polymer synthesis" (Otsu Takayuki Seisen Co., Ltd., first chemical first edition March 1, 1972). It may be prepared with reference to the cited documents described.

Specifically, by injecting a predetermined amount, a polymerization initiator and a solvent of the units (a) and (b) constituting the copolymer into the reaction vessel and replacing oxygen with nitrogen, stirring, heating, and warming in the absence of oxygen A polymer is obtained. In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was obtained as a solid (powder) by methods, such as reprecipitation.

The polystyrene reduced weight average molecular weight of alkali-soluble resin (A1) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000. When the weight average molecular weight of resin (A1) which has alkali solubility exists in the said range, applicability | paintability tends to become favorable, and a film | membrane decrease does not generate | occur | produce well at the time of image development, and the missing property of a non-pixel part at the time of image development. This tends to be favorable and is preferable.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of alkali-soluble resin (A1) becomes like this. Preferably it is 1.1-6.0, More preferably, it is 1.2-4.0. When molecular weight distribution exists in the said range, since it exists in the tendency which is excellent in developability, it is preferable.

Content of alkali-soluble resin (A1) which can be used for the polymeric resin composition of this invention is a mass fraction with respect to solid content in a polymeric resin composition, Preferably it is 5-90 mass%, More preferably, it is 10-70 mass % to be. When content of alkali-soluble resin (A1) exists in the said range, solubility to a developing solution is enough, the development residue does not generate | occur | produce well on the board | substrate of a non-pixel part, and the film reduction of the pixel part of an exposure part at the time of image development It is hard to generate | occur | produce, and the omission property of a non-exposed part tends to be favorable, and it is preferable.

As alkali-soluble resin (A2) which shows alkali solubility and reactivity by the action of at least one of light and heat, (A21)-(A23) is illustrated.

Alkali-soluble resin (A21) has at least 1 sort (s) of group chosen from the group which consists of (a) and (b), an epoxy group, and an oxetanyl group, and also has compound (c) (hereinafter "(c) ) ").

The compound which has an epoxy group means the compound which has at least 1 sort (s) of group chosen from the group which consists of an aliphatic epoxy group and an alicyclic epoxy group, for example. The compound which has an oxetanyl group means the compound which has at least 1 sort (s) of group chosen from the group which consists of an aliphatic oxetanyl group and an alicyclic oxetanyl group, for example. The compound which has a reactive double bond means the compound which has an unsaturated bond.

Alkali-soluble resin (A22) is a copolymer of (a) and (b) which is a copolymer obtained by making a part of carboxyl group derived from (a) react with the epoxy group or oxetanyl group derived from (c).

Alkali-soluble resin (A23) is a copolymer of (a) and (c).

As a compound which has an epoxy group and has an aliphatic epoxy group among the compounds (c1) which have a reactive double bond, specifically, glycidyl (meth) acrylate, (beta) -methyl glycidyl (meth) acrylate, (beta)- Ethyl glycidyl (meth) acrylate, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, glycidyl vinyl ether, etc. are mentioned.

Among the compounds (c1) having an epoxy group and having a reactive double bond, examples of the compound having an alicyclic epoxy group include vinylcyclohexene monooxide 1,2-epoxy-4-vinylcyclohexane (for example, serotoside 2000; Cell Chemical Industry Co., Ltd.), 3, 4- epoxycyclohexyl methyl acrylate (for example, cycloma A400; Daicel Chemical Industry Co., Ltd. product), 3, 4- epoxycyclohexyl methyl methacrylate (Example For example, at least 1 sort (s) of compound chosen from the group which consists of a cyclochromic M100; the Daicel Chemical Industry Co., Ltd. product), the compound represented by Formula (II), and the compound represented by Formula (III) is mentioned.

[In Formula (II) and Formula (III), R and R 'respectively independently represent a hydrogen atom, a hydroxyl group, or a C1-C4 alkyl group.

X and X 'respectively independently represent a single bond or a C1-C6 alkylene group. The methylene group contained in this alkylene group may be substituted by the hetero atom.]

Specific examples of R and R 'include alkyl groups such as hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group;

Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxy-n-propyl group, 2-hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1-hydroxy -Isopropyl group, 2-hydroxy-isopropyl group, 1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-n And hydroxyl group-containing alkyl groups such as -butyl group. Preferably, a hydrogen atom, a methyl group, a hydroxymethyl group, 1-hydroxyethyl group, or 2-hydroxyethyl group is mentioned, More preferably, a hydrogen atom or a methyl group is mentioned.

X and X 'are single bonds, alkylene groups such as methylene group, ethylene group and propylene group; Hetero atom containing alkylene groups, such as an oxymethylene group, an oxyethylene group, an oxypropylene group, a thiomethylene group, a thioethylene group, a thiopropylene group, an amino methylene group, an aminoethylene group, an aminopropylene group, etc. are mentioned. Preferably, a single bond, a methylene group, an ethylene group, an oxymethylene group, or an oxyethylene group is mentioned, More preferably, a single bond or an oxyethylene group is mentioned.

As a compound represented by Formula (II), the compound etc. which are represented by Formula (II-1)-Formula (II-15) are mentioned, Preferably Formula (II-1), Formula (II-3), Formula ( II-5), formula (II-7), formula (II-9), formula (II-11)-formula (II-15), More preferably, formula (II-1), formula ( II-7), formula (II-9), and formula (II-15) are mentioned.

As a compound represented by Formula (III), the compound etc. which are represented by Formula (III-1)-Formula (III-15) are mentioned, Preferably Formula (III-1), Formula (III-3), Formula ( III-5), formula (III-7), formula (III-9), formula (III-11) to formula (III-15), and more preferably formula (III-1) and formula ( III-7), formula (III-9) and formula (III-15) are mentioned.

The at least 1 sort (s) of compound chosen from the group which consists of a compound represented by Formula (II) and a compound represented by Formula (III) may be used independently, respectively and may be mixed in arbitrary ratios. In the case of mixing, the mixing ratio is in a molar ratio, preferably [compound represented by formula (II)]: [compound represented by formula (III)], 5:95 to 95: 5, more preferably 10:90 90:10, More preferably, it is 20: 80-80: 20.

As a compound (c2) which has an oxetanyl group and also has a reactive double bond, it is 3-methyl-3- methacryloxy methyl oxetane, 3-methyl-3- acryloxy methyl oxetane, 3-ethyl-, for example. 3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxyethyl oxetane, 3-methyl-3-acryloxyether oxetane, 3-ethyl- 3-methacryloxyethyl oxetane, 3-ethyl-3-acryloxyethyl oxetane, etc. are mentioned.

These are used individually or in combination.

In alkali-soluble resin (A21), it is preferable that the ratio of the structural component guide | induced from each exists in the following ranges with a mole fraction with respect to the total mole number of the structural component which comprises alkali-soluble resin (A21).

structural units derived from (a); 2-40 mol%

structural units derived from (b); 1 to 65 mol%

structural units derived from (c); 2 to 95 mol%

 Moreover, it is more preferable if the ratio of the said structural component is the following ranges.

structural units derived from (a); 5 to 35 mol%

structural units derived from (b); 1 to 60 mol%

structural units derived from (c); 5 to 80 mol%

When said composition ratio exists in the range mentioned above, storage stability, developability, solvent resistance, heat resistance, and mechanical strength tend to become favorable.

The alkali-soluble resin resin (A21) is, for example, the method described in the document "Experimental Method for Polymer Synthesis" (Otsu Takayuki Seisen Co., Ltd., Chemical Copper, First Edition First Edition March 1, 1972) and the document. It may manufacture with reference to the cited document described in.

Specifically, oxygen is absent by injecting a predetermined amount, a polymerization initiator, and a solvent of a compound guiding units (a), (b) and (c) constituting the copolymer into a reaction vessel, and replacing oxygen with nitrogen. The polymer is obtained by stirring, heating, and keeping warm under the following. In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was obtained as a solid (powder) by methods, such as reprecipitation.

When preparing alkali-soluble resin resin (A22), a copolymer is manufactured by copolymerizing (a) and (b) first. It is preferable that the ratio of the structural component guide | induced from each exists in the following ranges with a mole fraction with respect to the total number of moles of the structural component which comprises said copolymer.

structural units derived from (a); 5-50 mol%

structural units derived from (b); 50 to 95 mol%

Moreover, it is more preferable if the ratio of the said structural component is the following ranges.

structural units derived from (a); 10 to 45 mol%

structural units derived from (b); 55 to 90 mol%

Next, in order to give reactivity by the action of light and heat, a part of the carboxylic acid and carboxylic anhydride of (a) derived from the copolymer obtained by copolymerizing (a) and (b) is (c) It reacts with the epoxy group or oxetanyl group derived from

The molar number of (c) is 5-80 mol% with respect to the mole number of (a), Preferably it is 10-75 mol%, More preferably, it is 15-70 mol%.

When a composition ratio exists in the said range, there exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and a sensitivity to become favorable.

Alkali-soluble resin resin (A22) can be manufactured through a two-step process. For example, the method described in the document "Experimental method of polymer synthesis" (Otsu Takayuki Seisakusho Co., Ltd. first edition first edition March 1, 1972) and Japanese Unexamined Patent Publication No. 2001-89533 It may be prepared by reference to the method.

Specifically, first, the process of the first step. A predetermined amount, a polymerization initiator, and a solvent of a compound inducing units (a) and (b) constituting a copolymer (i.e., alkali-soluble resin) obtained by copolymerizing (a) and (b) are injected into a reaction vessel, By replacing oxygen with nitrogen, alkali-soluble resin is obtained by stirring, heating, and keeping warm in the absence of oxygen. In addition, the obtained resin may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was obtained as solid (powder) by methods, such as reprecipitation. The polystyrene reduced weight average molecular weight of said resin becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000. When the weight average molecular weight of resin exists in the said range, applicability | paintability tends to become favorable, and film | membrane decrease does not occur easily at the time of image development, and the missing property of a non-pixel part at the time of image development tends to be favorable, and is preferable. Do.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the said resin becomes like this. Preferably it is 1.1-6.0, More preferably, it is 1.2-4.0. When molecular weight distribution exists in the said range, since there exists a tendency which is excellent in applicability | paintability and developability, it is preferable.

Next, the process of a 2nd step is said. Subsequently, the atmosphere in the flask is replaced with nitrogen from air, and for example, as a reaction catalyst of 5 to 80 mol% of the component (c), the carboxyl group and the epoxy group or the oxetanyl group, based on the number of moles of the component (a). As the mass basis, trisdimethylaminomethylphenol is 0.001% to 5% based on the total amount of the monomers (a) to (c), and hydroquinone is used as the mass amount based on the total amount of the monomers (a) to (c). The said resin and a structural component (c) can be made to react by putting 0.001-5% in a flask as a reference | standard, and continuing reaction for 1 to 10 hours at 60-130 degreeC. In addition, in the same manner as the polymerization conditions, the injection method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production facility, polymerization, and the like.

In alkali-soluble resin (A23), it is preferable that the ratio of the structural component guide | induced from each exists in the following ranges with a mole fraction with respect to the total mole number of the structural component which comprises alkali-soluble resin (A23).

structural units derived from (a); 5 to 95 mol%

structural units derived from (c); 5 to 95 mol%

Moreover, it is more preferable if the ratio of the said structural component is the following ranges.

structural units derived from (a); 10 to 90 mol%

structural units derived from (c); 10 to 90 mol%

When the said composition ratio exists in the range mentioned above, there exists a tendency for storage stability, developability, solvent resistance, heat resistance, and mechanical strength to become favorable.

The alkali-soluble resin resin (A23) is, for example, the method described in the document "Experimental method of polymer synthesis" (Otsu Takayuki Seisen Co., Ltd., Chemical Copper, First Edition First Printing March 1, 1972) and the document. It may manufacture with reference to the cited document described in.

Specifically, a predetermined amount, a polymerization initiator, and a solvent of the compound constituting the copolymer (a) and (c) constituting the copolymer are injected into the reaction vessel, and oxygen is substituted with nitrogen, thereby stirring and heating in the absence of oxygen. By keeping warm, a polymer is obtained. In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was obtained as a solid (powder) by methods, such as reprecipitation.

As a polymeric compound (B) contained in the polymeric resin composition of this invention, a monofunctional monomer, a bifunctional monomer, or the trifunctional or more than trifunctional polyfunctional monomer is mentioned.

As a specific example of a monofunctional monomer, 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.

Moreover, as a specific example of a bifunctional monomer, 1, 3- butanediol di (meth) acrylate, 1, 3- butanediol (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, and 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 Bis (acryloyloxyethyl) ether of A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentylglycoldi (meth) acrylate, ethoxylated neopentylglycoldi (meth) acrylate or 3- Methyl pentanediol di (meth) acrylate etc. are mentioned.

In addition, as a specific example of a trifunctional or more than trifunctional polyfunctional monomer, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate , Ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerytate Lithol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritolhepta (meth) acrylic Elate, reactant of tripentaerythritol octa (meth) acrylate, pentaerythritol tri (meth) acrylate and acid anhydride, dipenta Tritol penta (meth) acrylate and acid anhydride reactant, tripentaerythritol 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 (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylic Latex, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified tripentaerythritol tetra (meth) acrylate, caprolactone modified tripentaerythritol penta (meth) acrylate, caprolactone modified tripentaerythrate Lithol hexa (meth) acrylate, caprolactone modified tripentaerythritol hepta (meth) acrylate , Reactant of caprolactone-modified tripentaerythritol octa (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride, caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride The reactant or caprolactone modified tripentaerythritol hepta (meth) acrylate, an acid anhydride, etc. are mentioned.

In particular, a bifunctional or more than polyfunctional monomer is used preferably. These polymeric compounds (B) can be used individually or in combination of 2 or more types.

Content of a polymeric compound (B) is mass fraction with respect to the total amount of alkali-soluble resin (A) and a polymeric compound (B), Preferably it is 1-70 mass%, More preferably, it is 5-60 mass%. . When content of a polymeric compound (B) exists in the said range, there exists a tendency for the sensitivity, smoothness, reliability, and mechanical strength of a sensitivity, a coating film, and a pattern to become favorable, and it is preferable.

As an initiator (C) contained in the polymerizable resin composition of this invention, it is a compound which starts superposition | polymerization by the action of light or a heat, A biimidazole type compound, an acetophenone type compound, a triazine type compound, an acylphosphine oxide type compound Or an oxime type compound is preferable and a biimidazole type compound is especially preferable since it is excellent in sensitivity.

As said biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 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'-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 (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), 4,4' And imidazole compounds in which the phenyl group at the 5,5'-position is substituted with a carboalkoxy group (see, for example, JP-A-7-10913, etc.), and preferably 2,2 '. -Bis (2-chlorophenyl) -4,4 ', 5,5 '-Tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole.

As said acetophenone type compound, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy Ethoxy) phenyl] -2-methylpropane-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2- Methyl-propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3- Methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone , 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-propylbenzyl) -2-dimethylamino-1- (4-morpholi Nophenyl) -butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2, 3-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl ) -Butanone, 2- (2-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-chlorobenzyl) -2 -Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- ( 4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl ) -Butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methoxybenzyl) -2-dimethylamino-1 -(4-morpholinophenyl) -butanone, 2- (2-methyl-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2 -Me Methyl-4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromo-4-methoxybenzyl) -2-dimethylamino-1- Oligomers of (4-morpholinophenyl) -butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and the like.

As said triazine type compound, 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, etc. are mentioned.

2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc. are mentioned as said acylphosphine oxide type initiator.

Examples of the oxime compound include 0-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, a compound represented by formula (IV), a compound represented by formula (V), and the like.

The start adjuvant (D) contained in the polymeric resin composition of this invention is a compound containing the compound represented by at least 1 sort (s) chosen from the group which consists of a formula (I-1) and a formula (I-2).

[In Formula (I-1) and Formula (I-2), ring X ¹ , ring X ^2, and ring X ³ each independently represent an aromatic ring having 6 to 12 carbon atoms. Y ¹ to Y ⁴ each independently represent an oxygen atom or a sulfur atom. R ¹ to R ⁴ each independently represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.

The methylene group contained in the aromatic ring, the alkyl group and the aryl group may be substituted with an oxygen atom, -NH- or a sulfur atom, and the hydrogen atom contained in the aromatic ring, the aryl group and the aryl group may be substituted with a halogen atom. ]

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned.

Examples of the aromatic ring having 6 to 12 carbon atoms include benzene ring, methylbenzene ring, dimethylbenzene ring, ethylbenzene ring, propylbenzene ring, butylbenzene ring, pentylbenzene ring, hexylbenzene ring, cyclohexylbenzene ring, chlorobenzene ring and dichloro Benzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene ring, bromonaphthalene ring, phenanthrene ring, chrysene ring, fluorine Lanten ring, benzo [a] pyrene ring, benzo [e] pyrene ring, perylene ring, derivatives thereof and the like.

Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methyl-n-propyl group, 2-methyl-n-propyl group, tert-butyl group and n -Pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n- Propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group, 1-chloro-n-butyl group, 2-chloro-n-butyl group, 3-chloro-n-butyl group Can be mentioned.

Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, dibromophenyl group, chlorobromophenyl group, hydroxyphenyl group, alkoxyphenyl group, biphenyl group, chlorobiphenyl group, dichlorobiphenyl group and bromine A phenyl group, a dibromo phenyl group, a naphthyl group, a chloro naphthyl group, a dichloro naphthyl group, a bromonaphthyl group, a dibromonaphthyl group, a hydroxy naphthyl group, etc. are mentioned.

As a compound represented by at least 1 sort (s) chosen from the group which consists of a formula (I-1) and a formula (I-2),

Dialkoxynaphthalenes such as dimethoxynaphthalene, diethoxynaphthalene, dipropoxynaphthalene, diisopropoxynaphthalene and dibutoxynaphthalene

Dimethoxy anthracene, diethoxy anthracene, dipropoxy canthracene, diisopropoxy canthracene, dibutoxy anthracene, dipentaoxy anthracene, dihexaoxy anthracene, methoxyethoxy anthracene, methoxy propoxy canthracene, methoxy isopropoxy Dialkoxy such as anthracene, methoxybutoxy anthracene, ethoxy propoxycanthracene, ethoxy isopropoxythracene, ethoxy butoxy anthracene, propoxy isopropoxythracene, propoxy butoxy anthracene, isopropoxy butoxy anthracene Anthracene

Dialkoxy naphthacenes such as dimethoxynaphthacene, diethoxynaphthacene, dipropoxynaphthacene, diisopropoxynaphthacene and dibutoxynaphthacene

Etc., but is not limited thereto.

Content of an initiator (C) is a mass fraction with respect to the total amount of alkali-soluble resin (A) and a polymeric compound (B), Preferably it is 0.1-40 mass%, More preferably, it is 1-30 mass%.

Content of a starting adjuvant (D) is a mass fraction with respect to the total amount of alkali-soluble resin (A) and a polymeric compound (B), Preferably it is 0.01-20 mass%, More preferably, it is 0.1-10 mass%.

Content of the compound represented by at least 1 sort (s) chosen from the group which consists of a formula (I-1) and a formula (I-2) becomes like this. Preferably it is 50 to 100% with respect to content of a starting adjuvant (D), More preferably, Is 60 to 100%, more preferably 65 to 100%. When content of the compound represented by at least 1 sort (s) chosen from the group which consists of Formula (I-1) and Formula (I-2) exists in said range, when forming a coating film using the polymeric resin composition containing this, Transparency of a coating film becomes favorable and is preferable.

When the total amount of the initiator (C) is in the above range, the polymerizable resin composition becomes highly sensitive, and the strength of the coating film or pattern formed using the polymerizable resin composition and the surface of the coating film or pattern described above. Smoothness tends to be good and is preferable. In addition to the above, when the amount of the starting aid (D) is in the above range, the sensitivity of the obtained polymerizable resin composition is further increased, and the productivity of the pattern formed by using the polymerizable resin composition tends to be improved. desirable.

You may use an amine compound, the following carboxylic acid compound, and a polyfunctional thiol compound (T) to the extent which does not impair the effect of this invention. In particular, it is preferable to use a polyfunctional thiol compound (T).

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl and 4-dimethylaminobenzoic acid 2-ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively; Mihilers ketone) or 4,4'-bis (diethyl Aromatic amine compounds, such as amino) benzophenone, are mentioned.

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

The polyfunctional thiol compound (T) is a compound having two or more thiol groups in the molecule. Especially, the compound which has a 2 or more aliphatic thiol group is more preferable, since the sensitivity of the polymeric resin composition of this invention becomes high.

Specific examples of the polyfunctional thiol compound (T) include hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediolbisthiopropionate, butanediolbisthioglycolate, ethylene glycol bisthioglycolate, Trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylol propane tristyropropionate, trimethylol propane tristhioglycolate, pentaerythritol tetrakistyropropionate, pentaerythritol tetrakisthioglycolate And trishydroxyethyl tristyopiophytonate, pentaerythritol tetrakis (3-mercaptobutylate), 1,4-bis (3-mercaptobutyryloxy) butane and the like.

Content of a polyfunctional thiol compound (T) is mass fraction with respect to the total amount of alkali-soluble resin (A) and a polymeric compound (B), Preferably it is 0.5-20 mass%, More preferably, it is 1-15 mass%. to be. When content of a polyfunctional thiol compound (T) exists in said range, there exists a tendency for a sensitivity to become high and developability becomes favorable, and it is preferable.

As long as the effect of this invention is not impaired, a photoinitiator etc. can be used together further, As a photoinitiator, a benzoin type compound, a benzophenone type compound, a thioxanthone type compound, etc. are mentioned, for example.

More specifically, the following compounds are mentioned, These can be used individually or in combination of 2 or more types, respectively.

As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As said benzophenone type compound, benzophenone, the methyl o-benzoyl benzoate, 4-phenylbenzo phenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'- tetra (tert-butylperoxycarbonyl) benzophenone or 2,4,6-trimethylbenzophenone etc. are mentioned.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, or 1-chloro, for example 4-propoxy thioxanthone etc. are mentioned.

In addition, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphor quinone, methyl phenylglyoxylate, titanocene compound, etc. are illustrated as a photoinitiator.

Moreover, the photoinitiator described in Unexamined-Japanese-Patent No. 2002-544205 can be used as a photoinitiator which has group which can cause chain transfer.

As a photoinitiator which has group which can cause said chain transfer, the photoinitiator of following formula (5)-following formula (10) is mentioned, for example.

The solvent (E) used for the polymeric resin composition of this invention is specifically ethylene glycol monoalkyl ether, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. ;

Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and diethylene glycol ethyl methyl ether;

Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;

Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate and methoxy pentyl acetate;

Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene;

Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone and cyclopentanone;

Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, methoxybutanol, ethoxybutanol, and glycerin;

Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate;

Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.

Among the solvents described above, an organic solvent having a boiling point of 100 to 200 ° C. is preferably used in terms of coating properties and drying properties. Specific examples of the organic solvent having a boiling point of 100 to 200 ° C include alcohols such as alkylene glycol alkyl ether acetates, methoxybutanol and ethoxybutanol, ketones such as cyclohexanone, ethyl 3-ethoxypropionate and 3- Ester, such as methyl methoxy propionate, is mentioned, More preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxy butanol, methoxy butyl acetate, and 3-ethoxy propionate ethyl are mentioned. And 3-methoxypropionate methyl.

These solvents (E) can be used individually or in mixture of 2 or more types, respectively.

Content of the solvent (E) in the polymeric resin composition of this invention is a mass fraction with respect to polymeric resin composition, Preferably it is 60-90 mass%, More preferably, it is 65-85 mass%. If content of solvent (E) exists in the said range, it coats with coating apparatuses, such as a spin coater, a slit & spin coater, a slit coater (it may also be called a die coater and a curtain flow coater), an inkjet, a roll coater, and a dip coater. When it does, coating property has a favorable í * quality and is preferable.

In the polymerizable resin composition of the present invention, additives such as fillers, other polymer compounds, colorants, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, and chain transfer agents may be used in combination.

Specifically as a filler, glass, silica, alumina, etc. are illustrated.

Specific examples of other high molecular compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. Can be used.

As a coloring material, the compound classified as pigment in the color index (The Society of Dyers and Colorists published) is mentioned.

Specifically, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 Yellow pigments such as, 147, 148, 150, 153, 154, 166, 173, 194, and 214;

C.I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and the like orange pigments;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. ;

C.I. Blue pigments such as Pigment Blue 15, 15: 3, 15: 4, 15: 6 and 60;

C.I. Violet pigments such as pigment violet 1, 19, 23, 29, 32, 36 and 38;

C.I. Green pigments such as pigment green 7, 36;

C.I. Brown pigments such as pigment brown 23 and 25;

C.I. Black pigments, such as pigment black 1 and 7, etc. are mentioned.

As the pigment dispersant, commercially available surfactants can be used, and for example, surfactants such as silicone, fluorine, ester, cationic, anion, nonionic, and amphoteric and the like can be cited. It is used in combination. Examples of the above surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, and polyethyleneimines. Others, such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoi Chemical Co., Ltd.), F-Top (manufactured by Tokemu Products Co., Ltd.), Megapack (Dainippon Ink Chemical Co., Ltd.) ), Florade (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Supron (above, manufactured by Asahi Glass Co., Ltd.), Solsperth (manufactured by Geneca Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS), or PB821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.

Specific examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N. -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane or 3-mercapto Propyl trimethoxysilane, etc. are mentioned.

Specific examples of the antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate and 2- [1- (2-hydroxy- 3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenylacrylate, 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'-methylenebis (6 -tert-butyl-4-methylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert-butyl-5-methyl Phenol), 2,2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3'- thiodipropionate, dimyristyl 3,3'- thiodipropionate, Distearyl3,3'-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-part -4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 3,3 ', 3' ', 5,5', 5 '' -Hexa-tert-butyl-a, a ', a' '-(mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5-di -tert-butyl-4-hydroxyphenyl) propionate] or 2,6-di-tert-butyl-4-methylphenol and the like.

Specific examples of the ultraviolet absorber include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole and 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-dimethylphenyl) -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-benzotriazole- 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. are mentioned.

Specifically as a light stabilizer, a polymer consisting 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-dia Jadecane-1,10-diamine, decandioic acid, bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, 1,1-dimethylethylhydroperox Seed reaction, bis (1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] Butylmalonate, 2,4-bis [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 or methyl (1,2,2,6,6 -Pentamethyl-4-piperidinyl) sebacate, etc. are mentioned.

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

A polymeric resin composition can be apply | coated on the base material which formed the glass substrate, the film substrate, the color filter, or the drive circuit as follows, for example, can photocure and develop, and can form a coating film or a pattern. . First, this polymeric resin composition is apply | coated on the board | substrate (usually glass) or the layer which consists of solid content of the polymeric resin composition formed earlier, and prebaking from the apply | coated polymeric resin composition layer removes volatile components, such as a solvent, To obtain a smooth uncured coating. The thickness of the uncured coating film at this time is about 1-6 micrometers. The uncured coating film thus obtained is irradiated with ultraviolet rays generated from a mercury lamp or a light emitting diode via a mask for forming a target pattern.

In the pattern formation, the line width can be appropriately controlled according to the mask size.

In the recent exposure machine, the bandpass filter which cuts the light of less than 350 nm using the filter which cuts the said wavelength range, or extracts the light of the wavelength range of 436 nm, 408 nm, and 365 nm vicinity is the said wavelength range. It selectively extracts using and irradiates a parallel light beam uniformly to the whole exposure part. At this time, it is preferable to use a device such as a mask aligner or a stepper so that the correct alignment of the mask and the substrate is performed. In addition, the coating film after light irradiation is contacted with aqueous alkali solution, the non-exposed part is melted and developed, and the target coating film and pattern are obtained. The developing method may be any of a liquid mounting method, a dipping method or a spray method. In addition, you may incline a board | substrate at arbitrary angles at the time of image development.

The developing solution used for image development after patterning exposure is the aqueous solution containing an alkaline compound and surfactant normally.

The alkaline compound may be either an inorganic or organic alkaline compound.

Specific examples of the inorganic alkaline compounds include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, Sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate or ammonia and the like.

Moreover, as a specific example of an organic alkaline compound, tetramethylammonium hydroxide, 2-hydroxyethyl trimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, ethanolamine, etc. are mentioned. These inorganic and organic alkaline compounds can be used individually or in combination of 2 or more types, respectively. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

Moreover, any of nonionic surfactant, anionic surfactant, or cationic surfactant may be sufficient as surfactant in alkaline developing solution.

Specific examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkylaryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, and polyoxy Ethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, etc. are mentioned.

Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the cationic surfactants include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, and quaternary ammonium salts.

These surfactants may be used alone, or may be used in combination of two or more thereof.

The density | concentration of surfactant in alkaline developing solution becomes like this. Preferably it is the range of 0.01-10 mass%, More preferably, it is 0.05-8 mass%, More preferably, it is 0.1-5 mass%.

After image development, water washing is performed and the post-baking for 10 to 180 minutes can also be performed at 150-230 degreeC further as needed.

Using the polymerizable resin composition of this invention, a pattern can be formed on a board | substrate or a color filter substrate through each above process. This pattern is useful as a photo spacer and a patternable overcoat used for a liquid crystal display device. In the case of patterning exposure to an uncured coating film, when a photomask for forming a hole is used, holes can be formed, which is useful as an interlayer insulating film. At the time of exposure to the uncured coating film, a transparent film can be formed only by whole surface exposure and heat curing or heat curing without using a photomask, and this transparent film is useful as an overcoat and can also be used for a touch panel. have.

By attaching the coating film and pattern obtained in this way to display apparatuses, such as a liquid crystal display device, the display apparatus of the outstanding quality can be manufactured with high yield.

According to the present invention, it is possible to form a coating film or a pattern having a sufficient sensitivity for light having a wavelength of around 436 nm, around 408 nm, and around 365 nm at the time of exposure.

Example

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail based on an Example, it cannot be overemphasized that this invention is not limited by an Example. In the examples,% and parts indicating content to the amount of use are based on mass unless otherwise specified.

(Synthesis example of resin Aa)

Into a 1 L flask equipped with a reflux cooler, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, 200 parts of 3-methoxy-1-butanol and 105 parts of 3-methoxybutyl acetate were added and stirred. Heated to 70 ° C. Subsequently, 60 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1,0 ^2.6 ] decyl acrylate (compound represented by formula (II-1) and compound represented by formula (III-1) are molar ratios. 240 parts and 140 parts of 3-methoxybutyl acetates were dissolved, the solution was prepared, and the solution was dripped in the flask kept at 70 degreeC over 4 hours using the dropping funnel. On the other hand, the solution which melt | dissolved 30 parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 parts of 3-methoxybutyl acetate was dripped at the flask over 4 hours using another dropping funnel. I was. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, then cooled to room temperature, and then a solution of a copolymer (resin Aa) having a solid content of 32.6% and an acid value of 110 mg-KOH / g (solid content conversion). Got. The weight average molecular weight Mw of obtained resin Aa was 1.3 * 10 <^4> , and dispersion degree was 2.50.

(Synthesis example of resin Ab)

Into a 1 L flask equipped with a reflux cooler, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, 200 parts of 3-methoxy-1-butanol and 105 parts of 3-methoxybutyl acetate were added and stirred. Heated to 70 ° C. Subsequently, 55 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (II-1) and a compound represented by the formula (III-1)) in a molar ratio of 50: 50 phosphorus mixture) 175 parts and 70 parts of N-cyclohexyl maleimide were dissolved in 140 parts of 3-methoxybutyl acetate to prepare a solution, and the solution was kept at 70 ° C over 4 hours using a dropping pump. It was dripped in one flask.

On the other hand, the solution which melt | dissolved 30 parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 parts of 3-methoxybutyl acetates is dripped in the flask over 5 hours using another dropping pump. I was. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature, thereby obtaining a solution of a copolymer (resin Ab) having a solid content of 32.6% and an acid value of 34.3 mg-KOH / g. As for the weight average molecular weight (Mw) of obtained resin Ab, 1.4 * 10 <^4> and number average molecular weight (Mn) were 5.4 * 10 <^3> and dispersion degree was 2.5.

(Synthesis example of resin Ac)

Into a 1 L flask equipped with a reflux cooler, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, and 250 parts of propylene glycol monomethyl ether acetate was added and heated to 70 ° C while stirring. Subsequently, 52.6 parts of methacrylic acid, 105.2 parts of methyl methacrylate, 29.9 parts of benzyl methacrylate and 29.9 parts of N-benzylmaleimide were dissolved in propylene glycol monomethyl ether acetate to prepare a solution, and the solution was dissolved. It was dripped at the flask kept at 70 degreeC over 4 hours using the dropping pump.

On the other hand, the solution which melt | dissolved 30 parts of polymerization initiator 2,2'- azobis (2, 4- dimethylvaleronitrile) in 164 parts of propylene glycol monomethyl ether acetates was dripped in the flask over 5 hours using another dropping pump. I was. After dripping of the solution of a polymerization initiator was complete | finished, it hold | maintained at 70 degreeC for 4 hours, and cooled to room temperature after that.

Next, 37.4 parts of glycidyl methacrylate, 0.5 part of amine (1,8- diazabicyclo [5.4.0] undecene-7) taken as a catalyst, and 2,2'- as a polymerization inhibitor were added to this reaction liquid. 0.2 part of methylenebis (4-methyl-6-t-butylphenol) was added, and the mixture was kept at 100 ° C for 4 hours while bubbling air and nitrogen gas mixture adjusted to 5% oxygen concentration at a flow rate of 200 ml / min. It cooled, and obtained the solution of the copolymer (resin Ac) of 42.0% of solid content, and the acid value of 28.9 mg-KOH / g. The weight average molecular weight (Mw) of the obtained resin Ac was 8.2x10 <^3> , the number average molecular weight (Mn) was 4.7x10 <^3> , and dispersion degree was 1.8.

(Measurement of molecular weight)

About the measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of resin Aa-resin Ac, it implemented on the following conditions using GPC method.

Device ; K2479 (manufactured by Shimadzu Corporation)

column ; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0ml / min

Detector; RI

The ratio of the polystyrene reduced weight average molecular weight and number average molecular weight obtained above was made into dispersion degree (Mw / Mn).

(Example 1)

[Synthesis of Polymerizable Resin Composition 1]

153 parts of solution of Resin Aa (50 parts in terms of solid content), dipentaerythritol hexaacrylate (KAYARADDPHA; manufactured by Nippon Gunpowder Co., Ltd.) (B) 50 parts, 2,2'-bis (2-chlorophenyl) -4 , 4 ', 5,5'-tetraphenyl-1,2'-biimidazole (B-CIM; manufactured by Hodogaya Chemical Co., Ltd.) (C) 4 parts, 9,10-dibutoxyanthracene (DBA; Kawasaki Kasei Co., Ltd.) (D) 1 part, pentaerythritol tetrakistiopionate (PEMP; Sakai Chemical Industries, Ltd.) (T) 3 parts, 3-ethoxyethyl propionate (D) 88 5 parts of 3-methoxy-1-butanol (D) and 65 parts of 3-methoxybutyl acetate (D) were mixed to obtain a polymerizable resin composition 1.

[Production of Pattern 1]

A glass substrate (# 1737; manufactured by Corning Corporation) having a length of 2 inches was washed sequentially with a neutral detergent, water, and alcohol, and then dried. On this glass substrate, polymeric resin composition 1 is exposed by the exposure amount (405 nm) of 200mJ / cm <2>, spin-coating so that the film thickness after image development, water washing, and postbaking may be set to 3.0 micrometers, and it is next in a clean oven. It prebaked for 3 minutes at ° C. After cooling, the space | interval of the board | substrate which apply | coated this polymeric resin composition 1, and the quartz glass photomask was set to 10 micrometers, and air atmosphere was used using the exposure machine (TME-150RSK; Topcon Co., Ltd. light source, ultrahigh pressure mercury lamp). The light was irradiated with a light exposure amount (405 nm standard) of 200 mJ / cm 2. In addition, irradiation with the polymeric resin composition 1 at this time passed the light emitted from an ultrahigh pressure mercury lamp through an optical filter (LU0400; Asahi Spectrometer), and cut and used the light of 400 nm or less. Exposure was performed using the photomask whose one side has a square light-transmitting part of 10 micrometers, and the said square space | interval is 100 micrometers.

After light irradiation, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 100 seconds for development. After washing with water, post-baking was carried out at 220 ° C. for 20 minutes in an oven. Thus, pattern 1 was obtained.

(Units in numerical values in Table 1 are negative)

(Example 2)

Polymerizable resin composition 2 and pattern 2 were obtained like Example 1 so that it may become a composition shown in Table 1.

(Example 3)

The polymerizable resin composition 3 and the pattern 3 were obtained like Example 1 so that it might become the composition shown in Table 1.

(Comparative Example 1)

4,4'-bisdiethylaminobenzophenone (EAB-F) instead of the compound represented by at least 1 sort (s) chosen from the group which consists of Formula (I-1) and Formula (I-2) so that it may become a composition shown in Table 1. Polymerizable resin composition 4 and the pattern 4 were obtained like Example 1 except having used).

(Comparative Example 2-Comparative Example 9)

Except having used the compound described instead of the compound represented by at least 1 sort (s) chosen from the group which consists of Formula (I-1) and Formula (I-2) so that it may become a composition shown in Table 1, it carried out similarly to Example 1, Polymerizable resin composition 5-polymeric resin composition 12 and pattern 5-pattern 12 were obtained.

About the polymeric resin composition 1-polymeric resin composition 12 and the patterns 1-pattern 12, the following evaluation was performed and the result was shown in Table 2.

Solubility

The polymerizable composition was visually observed, and the case where there was no insoluble matter was defined as ○ and the case where there was an insoluble matter was ×.

<Pattern>

The pattern obtained by post-baking on exposure amount 100mJ / cm <2> and 220 degreeC on the conditions of 20 minutes was observed with a cross section using the scanning electron microscope (S-4100; the Hitachi Corporation make).

(Circle) and the case where pattern peeling generate | occur | produced (circle) and the case of (size of lower bottom surface <size of upper bottom surface) for the case of (size of lower bottom surface≥ size of upper bottom surface).

<Remnant Sensitivity>

The same operation as the evaluation of the pattern was carried out to form patterns of exposure amounts of 100 mJ / cm 2 and 200 mJ / cm 2. The pattern height after each post-baking was measured by the three-dimensional non-contact surface shape measuring system (Micromap MM527N-PS-M100; Ryka System Co., Ltd. make). Residual film sensitivity was computed by following formula (1).

Residual film sensitivity (%) = 100 × (height in exposure amount 100mJ / cm 2)

                   / (Height in exposure amount 200mJ / ㎠) (1)

The larger the numerical value of the residual film sensitivity (%), the smaller the exposure dose dependency of the pattern height and the better the process margin.

<Transmittance>

Using the polymeric resin composition, the cured film was produced so that the film thickness after post-baking might be set to 3.0 micrometers. In the middle of preparation of the cured film, the transmittance | permeability (%) in 400 nm is measured using the microscopic spectrophotometer (OSP-SP200; OLYMPUS company) about each step after prebaking, after exposure, and postbaking. It was.

Higher transmittance means less absorption. It was set as-when it was not able to measure because pattern peeling occurred.

From the results of Examples 1-3 shown in Table 2, when using the polymeric resin composition of this invention containing the starting adjuvant of a specific structure, it turns out that a pattern is favorable and the pattern and coating film which are excellent in the balance of a sensitivity and a transmittance | permeability are obtained. Can be. On the other hand, Comparative Example 1 had good sensitivity but low transmission, Comparative Example 9 had both low sensitivity and low transmittance, and Comparative Examples 2 to 8 had peeling of the pattern, indicating that both of the residual film sensitivity and the transmittance were high. Could not get

The polymeric resin composition of this invention can form the coating film and pattern which have a favorable pattern, and is excellent in the balance of a sensitivity and a transmittance | permeability, and match | match the film thickness of an overcoat, a photo spacer, an insulating film, the liquid crystal orientation control protrusion, and a coloring pattern. It can use suitably for formation of the film used for a display apparatus, such as a coating layer for these.

According to the polymeric resin composition of this invention, it can form the coating film or pattern which has sufficient sensitivity to light of the wavelength of 436 nm, 408 nm, and 365 nm vicinity at the time of exposure, and has a high transmittance | permeability.

Claims (8)

Alkali-soluble resin (A), a polymeric compound (B), an initiator (C), an initiator adjuvant (D), and a solvent (E) are contained, and an initiator adjuvant (D) is a formula (I-1) and a formula (I-) Polymeric resin composition which is a compound containing the compound represented by at least 1 sort (s) chosen from the group which consists of 2).

[In Formula (I-1) and Formula (I-2), ring X ¹ , ring X ^2, and ring X ³ each independently represent an aromatic ring having 6 to 12 carbon atoms. Y ¹ to Y ⁴ each independently represent an oxygen atom or a sulfur atom. R ¹ to R ⁴ each independently represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. The methylene group contained in the aromatic ring, the alkyl group and the aryl group may be substituted with an oxygen atom, -NH- or a sulfur atom, and the hydrogen atom contained in the aromatic ring, the alkyl group and the aryl group may be substituted with a halogen atom.] The method of claim 1, Polymeric resin whose initiator (C) is a compound containing at least 1 sort (s) of compound chosen from the group which consists of a biimidazole type compound, an acetophenone type compound, a triazine type compound, an acylphosphine oxide type compound, and an oxime type compound. Composition. The method according to claim 1 or 2, Polymeric resin composition whose alkali-soluble resin (A) is resin which has at least 1 sort (s) of group chosen from the group which consists of an epoxy group and an oxetanyl group. The method according to any one of claims 1 to 3, Polymeric resin composition whose alkali-soluble resin (A) is resin which has a reactive double bond. The method according to any one of claims 1 to 4, Polymeric resin composition whose starting aid (D) is a compound which further contains a polyfunctional thiol compound (T). The coating film formed using the polymeric resin composition of any one of Claims 1-5. The pattern formed using the polymeric resin composition of any one of Claims 1-5. A display device comprising at least one member selected from the group consisting of the coating film according to claim 6 and the pattern according to claim 7.