TWI559079B - Photosensitive resin composition and display device - Google Patents

Description

Photosensitive resin composition and display device

The present invention relates to a photosensitive resin composition and a display device.

In recent years, the liquid crystal display panel and the like have been increasing in size of the substrate. Generally, a transparent film or a pattern such as a coating layer is formed on the substrate surface, and the photosensitive resin composition is subjected to a spin coating method, a slit rotation method, or the like. Coating formation is carried out.

On the other hand, a method of forming a high-quality uniform coating film while liquefying the photosensitive resin composition solution from the viewpoint of improving the productivity and the correspondence with a large-sized screen has been reviewed.

From such a background, in order to form a good quality coating film, the choice of solvent type is reviewed. For example, as a solvent, a mixed solvent of propylene glycol monomethyl ether acetate, 3-ethoxyethyl propionate, 3-methoxy 1-butanol and 3-methoxybutyl acetate will be used. The photosensitive resin composition has been disclosed for use in the formation of a coating film (for example, Patent Document 1).

[Patent Document 1] JP-A-2008-181087, paragraph 91

However, when the photosensitive resin composition using the above-mentioned solvent is applied to the uneven substrate by a spin coating method by a representative coating method, it may be radiated on the coated surface along the uneven pattern. The case of ribs (hereinafter referred to as "stripes").

In other words, even if a solvent which has been proposed in the past is used, it is applied to a spin coating method, a slit rotation method, a squeeze coating method, or the like, and it is not necessary to obtain a high-quality coating film for all methods.

The present invention has an object of providing a photosensitive resin composition capable of forming a coating film in which the occurrence of streaks is suppressed and the entire coating film is uniform and high in quality.

That is, the present invention provides the following [1] to [11].

[1] A photosensitive resin composition comprising a resin (A), a polymerizable compound (B), a polymerization initiator (C), and a solvent (D), wherein the solvent (D) contains the formula (I) Show solvent.

R ¹ -O-(AO) _n -R ² (I)

(In the formula (I), R ¹ and R ² each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms, and A represents a linear or branched alkyl group having 1 to 3 carbon atoms. , n represents an integer of 2 or 3, and the plural A's may be the same or different.)

[2] The photosensitive resin composition according to [1], wherein the solvent (D) contains two or more types of solvents represented by the formula (I) which are different from each other.

[3] The photosensitive resin composition according to [1] or [2] wherein the solvent (D) contains diethylene glycol ethyl methyl ether.

[4] The photosensitive resin composition according to [3], wherein the solvent (D) contains diethylene glycol ethyl methyl ether in an amount of 10 to 90% by mass based on the total amount of the solvent.

[5] The photosensitive resin composition according to any one of [1] to [4] wherein the solvent (D) contains a group selected from the group consisting of diethylene glycol butyl methyl ether and triethylene glycol dimethyl ether. One of the solvents.

[6] The photosensitive resin composition according to [5], wherein the solvent (D) contains, in an amount of 10 to 50% by mass based on the total amount of the solvent, selected from the group consisting of diethylene glycol butyl methyl ether and triethylene glycol dimethyl group. At least one solvent in which the ether is grouped.

The photosensitive resin composition as described in any one of [1] to [6] wherein the solvent (D) contains a diethylene glycol ethyl methyl ether and diethylene glycol butyl methyl ether. And at least one solvent of the group consisting of triethylene glycol dimethyl ether.

[8] The photosensitive resin composition according to [7], wherein the solvent (D) is selected from the group consisting of diethylene glycol ethyl methyl ether in a total amount of 60% by mass or more and 100% by mass or less based on the total amount of the solvent. And at least one solvent of the group consisting of diethylene glycol butyl methyl ether and triethylene glycol dimethyl ether.

[9] A coating film which is formed by using the photosensitive resin composition according to any one of [1] to [8].

[10] A pattern formed by using the photosensitive resin composition according to any one of [1] to [8].

[11] A display device comprising at least one selected from the group consisting of the coating film according to [9] and the pattern described in [10].

According to the present invention, the generation of stripes can be suppressed, and the whole is uniform. And high quality coating.

Moreover, by using the photosensitive resin composition of the present invention, a high-quality display device or the like can be obtained.

The photosensitive resin composition of the present invention contains a resin (A), a polymerizable compound (B), a polymerization initiator (C), and a solvent (D). In the present specification, the compounds exemplified as the respective components are used singly or in combination, unless otherwise specified.

The resin (A) which is used in the present invention may, for example, be a resin (A1) having alkali solubility, or a resin (A2) having reactivity which is at least one of alkali solubility and light and heat.

The resin (A1) having an alkali solubility is at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter sometimes referred to as "(a)"), and A copolymer of the monomer (c) (hereinafter sometimes referred to as "(c)")) which is copolymerized with (a).

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; and 4-cyclohexene dicarboxylic acid. Unsaturated dicarboxylic acids such as methyl-5-prolinol-2,3-dicarboxylic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid , 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, etc. An acid; an anhydride of these unsaturated dicarboxylic acids; An unsaturated mono-((methyl) group of a polyvalent carboxylic acid having two or more valences such as succinic acid mono [2-(methyl) propylene oxiranyl] or benzoic acid mono [2-(methyl) propylene oxyethyl] a propylene oxyalkylene ester; for example, an unsaturated acrylate having a hydroxyl group and a carbonyl group in the same molecule of α-(hydroxymethyl)acrylic acid.

Among them, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferred from the viewpoint of copolymerization reactivity or alkali solubility.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- (meth)acrylic acid alkyl esters such as butyl (meth) acrylate; cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6} ] decane-8-yl (meth) acrylate (known in the art as a dicyclopentenyl (meth) acrylate as a conventional name), dicyclopentene oxyethyl (methyl) (meth)acrylic cyclic alkyl esters such as acrylate and isodecyl (meth) acrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] 癸Alkyl-8-yl acrylate (known in the art as a dicyclopentenyl acrylate as a conventional name), a cyclic alkyl acrylate such as dicyclopentyloxyethyl acrylate or isodecyl acrylate Classes; aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; aryl acrylates such as phenyl acrylate and phenyl methacrylate; Diethyl acid, a dicarboxylic acid diester such as diethyl fumarate or diethyl itaconate; a hydroxyalkyl ester such as 2-hydroxyethyl (meth) acrylate or 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-hydroxybicyclo[2.2 .1]hept-2-ene, 5-carbonylbicyclo[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-dicarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]heptane 2-ene, 5,6-bis(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-carbonyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-carbonyl-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2. 1]hept-2-ene, 5-carbonyl-6-methylbicyclo[2.2.1]hept-2-ene, 5-carbonyl-6-ethylbicyclo[2.2.1]hept-2-ene, 5, 6-Dicarbonylbicyclo[2.2.1]hept-2-ene anhydrate (humic anhydride), 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2 .1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene a bicyclic unsaturated compound such as 5,6-di(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenylmaleimide, N-cyclohexylmaleimide, N-Benzylmaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimine butyrate, N-Amber succinimide-6-maleimide caproate, N-amber succinimide-3-maleimide propionate, N-(9-acridinyl) malazone Dicarbonylimine derivatives such as imine; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile , methacrylonitrile, vinyl chloride, vinylidene chloride, propylene Amine, methacrylamide, vinyl acetate, 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, etc. It is preferable from the viewpoint of copolymerization reactivity and alkali solubility.

(a) and (c) may be used singly or in combination.

In the present specification, the (meth) acrylate means acrylate and/or methacrylate.

In the copolymer obtained by copolymerizing (a) and (c), the ratio of the constituent components derived from each of the constituents of the copolymer is a molar fraction when the total number of moles of the constituent components of the copolymer is 100 mol%. The following ranges are preferred.

The constituent unit derived from (a); 2~40mol%

The constituent unit derived from (c); 60~98mol%

Further, it is preferred that the ratio of the above constituent components is in the following range.

The constituent unit derived from (a); 5 to 35 mol%

Constituent unit derived from (c); 65~95mol%

When the composition ratio is in the above range, the storage stability, development properties, and solvent resistance tend to be good.

The resin (A1) having the above-mentioned alkali solubility can be referred to, for example, in the "Experimental Method for Polymer Synthesis" (published by Otsuka Ryokan, Ltd., the first edition of the Chemicals, the first edition of the first brush, issued on March 1, 1972). The method is produced by the method described in the literature.

Specifically, the quantitation, polymerization initiator, solvent, and the like of the units (a) and (c) constituting the copolymer are charged into a reaction vessel, and oxygen is substituted by nitrogen in the absence of oxygen. The method of stirring, heating, and heat preservation can be mentioned. Further, the polymerization initiator, the solvent and the like used therein are not particularly limited, and any of those generally used in the field can be used. For example, a polymerization initiator, a solvent, and the like described later can be used.

Further, the obtained copolymer may be directly used as a solution after the reaction, or may be a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. In particular, as the solvent in the polymerization, the solvent after the reaction can be used as it is by using the solvent (D) described later, and the production step can be simplified (the same applies to the resin (A2) hereinafter).

The polystyrene-equivalent weight average molecular weight of the alkali-soluble resin (A1) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000. When the weight average molecular weight of the alkali-soluble resin (A1) is in the above range, the coating property is good, and film formation is less likely to occur during development, and the non-pixel portion peeling property at the time of development is good, which is preferable.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the alkali-soluble resin (A1) is preferably from 1.1 to 6.0, more preferably from 1.2 to 4.0. When the molecular weight distribution is in the above range, the image forming property is excellent, which is preferable.

The content of the resin (A1) having an alkali solubility in the photosensitive resin composition of the present invention is preferably from 5 to 90% by mass based on the mass fraction of the solid content in the photosensitive resin composition. More preferably, it is 10 to 70% by mass. When the content of the alkali-soluble resin (A1) is in the above range, the solubility in the developing solution is sufficient, and it is difficult to cause development residue on the substrate of the non-pixel portion, and it is difficult to cause the pixel of the exposed portion at the time of development. Part of the film is reduced, and the non-exposed portion is good in peeling property.

The resin (A2) which has alkali solubility and reactivity by at least one of light and heat is a resin (A2-1): (a), (c), and carbon number 2-4. a compound of the cyclic ether structure (b) (hereinafter sometimes referred to as "(b)"), a resin (A2-2): (a), a copolymer of (c), and (b) The copolymer obtained by the reaction, the resin (A2-3): a copolymer of (a) and (b), and the like.

(b) is a compound having a cyclic ether structure having a carbon number of 2 to 4, and is a polymerizable compound having at least one structure selected from the group consisting of an epoxy group, an oxycyclobutane group, and a tetrahydrofuran group. (b) is a compound having a cyclic ether structure having 2 to 4 carbon atoms and having an ethylenic carbon-carbon unsaturated bond, having a cyclic ether structure having a carbon number of 2 to 4, and having an acrylonitrile group or a group Propylene The sulfhydryl compound is more preferred.

(b), for example, a monomer (b1) having an epoxy group (hereinafter sometimes referred to as "(b1)") or a monomer (b2) having an oxycyclobutane group (hereinafter sometimes referred to as "(b2)"), a monomer having a tetrahydrofuranyl group, and the like.

(b1) is, for example, a polymerizable compound having at least one structure selected from the group consisting of an aliphatic epoxy structure and an alicyclic epoxy structure. The monomer having the epoxy group is preferably a compound having at least one structure selected from the group consisting of an aliphatic epoxy structure and an alicyclic epoxy structure, and having an ethylenic carbon-carbon unsaturated bond. It is preferably one having at least one structure in which an aliphatic epoxy group and an alicyclic epoxy group are grouped, and a compound having an acryloyl group or a methacryl group.

The aliphatic epoxy structure is a structure in which a chain olefin is epoxidized.

In (b1), as a compound having an aliphatic epoxy structure and having an ethylenic carbon-carbon unsaturated bond, specific examples thereof include epoxypropyl (meth)acrylate and β-methylepoxypropyl group ( Methyl) acrylate, β-ethylepoxypropyl (meth) acrylate, propylene propyl vinyl ether, and a compound represented by the following formula described in JP-A-H07-248625.

(wherein R ¹¹ to R ^{13 are} each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m is an integer of 1 to 5).

Examples of the compound represented by the above formula include o-vinylbenzyloxypropyl ether, m-vinylbenzyloxypropyl ether, and p-vinylbenzyloxypropyl ether. α-Methyl-o-vinylbenzyloxypropyl ether, α-methyl-m-vinylbenzyloxypropyl ether, α-methyl-p-vinylbenzyl epoxy Propyl ether, 2,3-diepoxypropoxymethylstyrene, 2,4-dipropyleneoxypropylmethylstyrene, 2,5-diepoxypropoxymethylstyrene, 2,6- Dipropylene oxide methyl styrene, 2,3,4-trisoxypropoxymethyl styrene, 2,3,5-trisoxypropoxymethyl styrene, 2,3,6-tricyclic Oxypropoxymethylstyrene, 3,4,5-triglyoxypropoxymethylstyrene, 2,4,6-triglyoxypropoxymethylstyrene, and the like.

The alicyclic epoxy structure is a structure in which a cyclic olefin is epoxidized.

(b1) (b1), as a compound having an alicyclic epoxy structure and having an ethylenic carbon-carbon unsaturated bond, may be exemplified by vinylcyclohexene monooxide 1,2-epoxy 4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexyl methacrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3, 4 Epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industry Co., Ltd.) or at least one compound of the compound represented by the formula (I) and the compound represented by the formula (II).

In the formulae (I) and (II), R and R' each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted by a hydroxyl group.

X and X' each independently represent a single bond, a C _1~6 alkylene group, an oxy-C _1~6 alkylene group, a sulfur-C _1~6 alkylene group, an imine-C _1~6 alkylene group, C _1~6 alkyl-oxyl, C _1-6 alkyl-sulfide, or C _1-6 alkyl-imide. 〕

Specific examples of the alkyl group 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.

Examples of the hydroxyalkyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxy-n-propyl group, a 2-hydroxy-n-propyl group, and a 3-hydroxy-n-propyl group. , 1-hydroxy-isopropyl, 2-hydroxy-isopropyl, 1-hydroxy-n-butyl, 2-hydroxy-n-butyl, 3-hydroxy-n-butyl, 4-hydroxy-n- Butyl and the like.

The substituents R and R' 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 include a methyl group, an ethyl group, a propyl group and the like.

Examples of the oxyalkenyl group include an oxymethylene group, an oxyethylene group, and an oxypropylene group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propenoxy group and the like.

Examples of the sulfur alkyl group include a sulfur-extension methyl group, a sulfur-extension ethyl group, and a sulfur-extension propyl group.

Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group and the like.

Examples of the imine alkyl group include an imine methyl group, an imine extended ethyl group, and an imine extended propyl group.

The alkyleneimine group may, for example, be a methylimine group, an ethylenimine group or a propylenimine group.

The substituents X and X' are preferably a single bond, a methyl group, an ethyl group, an oxymethyl group or an oxyethylene group, and more preferably a single bond or an oxyethylene group.

The compound represented by the formula (I) may, for example, be a compound represented by the formula (I-1) to the formula (I-15). Preferably, the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9), the formula (I-11) to the formula (I) -15). More preferably, the formula (I-1), the formula (I-7), the formula (I-9), and the formula (I-15) can be given.

The compound represented by the formula (II) may, for example, be a compound represented by the formula (II-1) to the formula (II-15). Preferably, the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9), the formula (II-11) to the formula (II) -15). More preferably, the formula (II-1), the formula (II-7), the formula (II-9), and the formula (II-15) can be given.

At least one compound selected from the group consisting of the compound represented by the formula (I) and the compound represented by the formula (II) may be used alone. Also, these can be mixed at any ratio. When mixing, the mixing ratio is expressed by a molar ratio, preferably Formula (I): Formula (II) is 5:95 to 95:5, more preferably 10:90 to 90:10, and particularly preferably 20:80. ~80:20.

Examples of the compound having an oxycyclobutane group and having an unsaturated bond in (b2) of the copolymer (A2-1) and (A2-2) include, for example, 3-methyl-3-methylpropene. Oxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, 3-ethyl-3-methylpropoxymethyloxetane, 3-B 3-propenyloxymethyloxetane, 3-methyl-3-methylpropene Oxyethyl oxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropenyloxyethyloxetane, 3- Ethyl-3-propenyloxyethyloxetane and the like.

In the copolymer (A2-1), the ratio of the constituent components derived from each of the components is preferably in the following range with respect to the molar fraction of the total number of moles constituting the constituent components of the copolymer (A2-1).

The constituent unit derived from (a); 2~40mol%

The constituent unit derived from (c); 1 to 65 mol%

a constituent unit derived from (b1) or (b2); 2 to 95 mol 96

Further, it is preferred that the ratio of the above constituent components is in the following range.

The constituent unit derived from (a); 5 to 35 mol%

The constituent unit derived from (c); 1~60mol%

a constituent unit derived from (b1) or (b2); 5 to 80 mol%

When the composition ratio is in the above range, storage stability, developability, solvent resistance, heat resistance, and mechanical strength are good.

For the above-mentioned alkali-soluble resin (A2-1), for example, the "Experimental method for polymer synthesis" (Otsuya Ryokan, Ltd., the first edition of the Chemicals, the first edition, the first brush, issued on March 1, 1972) It is produced by the method described, the cited documents described in the literature, and the like.

Specifically, a predetermined amount of a polymerization initiator and a solvent which are derived from the compounds (a), (c), and (b1) or (b2) constituting the copolymer are contained in a reaction container. A method of stirring, heating, and holding in the absence of oxygen by substituting nitrogen for oxygen.

The resin (A2-2) can be produced, for example, by a two-stage step. this For the time being, please refer to the above-mentioned document "Experimental method for polymer synthesis" (the method described in the issue of the first issue of the first issue of the Chemicals of the Otsuka, the first issue of the shoji, March 1, 1972), JP-A-2001-89533 It is produced by the method described in the publication.

First, as a first step, a copolymer (that is, a resin having an alkali solubility) is obtained in the same manner as the method for producing the alkali-soluble resin (A1) described above.

At this time, in the same manner as described above, it can be used in various forms. Further, the weight average molecular weight and molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) in terms of polystyrene in the same manner as described above are preferred.

However, the ratio of the constituent components derived from each of (a) and (c) is preferably in the following range for the molar fraction of the total number of moles constituting the constituent components of the above-mentioned copolymer.

The constituent unit derived from (a); 5 to 50 mol%

The constituent unit derived from (c); 50 to 95 mol%

Further, the ratio of the above constituent components is preferably in the following range.

The constituent unit derived from (a); 10 to 45 mol%

The constituent unit derived from (c); 55~90mol%

As a second step, a part of the carboxylic acid and the carboxylic anhydride of (a) from the obtained copolymer is reacted with an epoxy group or an oxycyclobutane group derived from the above (b1) or (b2).

Specifically, the above is continued, and the environment inside the flask is replaced by nitrogen to air, and the number of moles of the constituent component (a) is 5 to 80 mol%. Component (b1) or (b2), as a reaction catalyst for a carbonyl group and an epoxy group or an oxycyclobutane group, for example, a total of dimethylaminomethylphenols for monomers (a) to (c) The amount is 0.001 to 5% by mass, and is used as a polymerization inhibitor. For example, hydroquinone is added to the total amount of monomers (a) to (c), and placed in a flask at 0.001 to 5% by mass, 60 to 130. The reaction was continued for 1 to 10 hours at °C. Thereby, the resin (A2-2) can be obtained. Further, similarly to the polymerization conditions, the charging method or the reaction temperature can be appropriately adjusted in consideration of the heat generation amount by the production equipment or the polymerization.

Further, the number of moles of (b1) or (b2) at this time is preferably from 10 to 75 mol%, preferably from 15 to 70 mol%, based on the number of moles of (a). By setting it as the range, the balance of storage stability, developing property, solvent resistance, heat resistance, mechanical strength, and sensitivity can be improved.

In the resin (A2-3), the ratio of the components derived from the respective components to the molar fraction of the total number of moles of the constituent components constituting the alkali-soluble resin (A2-3) is preferably in the following range.

The constituent unit derived from (a); 5 to 95 mol%

a constituent unit derived from (b1) or (b2); 5 to 95 mol%

Further, it is preferred that the ratio of the above constituent components is in the following range.

The constituent unit derived from (a); 10 to 90 mol%

a constituent unit derived from (b1) or (b2); 10 to 90 mol%

When the composition ratio is in the above range, storage stability, developability, solvent resistance, heat resistance, and mechanical strength can be improved.

Resin (A2-3), for example, can refer to the "Experimental Method of Polymer Synthesis" (Otsuno Ryokan, Ltd., Chemical Co., Ltd., 1st Edition, 1st Edition) It is manufactured by the method described in the "issued on March 1, 1972" and the cited documents described in the document.

Specifically, a predetermined amount, a polymerization initiator, and a solvent derived from a compound constituting the unit (a) and (b1) or (b2) constituting the copolymer are charged into a reaction vessel, and when oxygen is replaced by nitrogen The polymer can be obtained by stirring, heating and keeping warm in the absence of oxygen. Further, the obtained copolymer may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) take-out may be used by a method such as reprecipitation.

The polymerizable compound (B) contained in the photosensitive fat composition of the present invention is not particularly limited as long as it has polymerizability, and examples thereof include a monofunctional monomer, a bifunctional monomer, and a trifunctional or higher polyfunctional group. Monomers, etc.

Examples of the monofunctional monomer include nonylphenylcarbitol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-ethylhexylcarbitol ( Methyl) acrylate, 2-(2-ethoxyethoxy)ethyl (meth) acrylate, caprolactone (meth) acrylate, ethoxylated nonyl phenol (meth) acrylate (meth) acrylate such as propoxylated nonylphenol (meth) acrylate; styrene, α-, o-, m-, p-methyl styrene, p-methoxy styrene, p Styrene such as -tert butoxystyrene or chloromethylstyrene; diene such as butadiene, 2,3-dimethylbutadiene, isoprene; methyl (meth)acrylate; Ethyl methyl acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, (methyl) )acrylic acid Tert-butyl ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, stearate (meth)acrylate, (meth)acrylic acid Dicyclopentenyl ester, isodecyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclohexyl (meth)acrylate, (methyl) Adamantyl acrylate, allyl (meth) acrylate, propylene (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, decyl (meth) acrylate, ( Methyl)cyclopentyl acrylate, furyl (meth) acrylate, tetrahydrofuran (meth) acrylate, pyryl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate , (meth)acrylic acid toluene, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, (a) a (meth)acrylic acid alkyl ester such as perfluoro-i-propyl acrylate, triphenylmethyl (meth) acrylate, cumenyl (meth) acrylate or the like, or (cyclo) (meth) acrylate Aryl methacrylate; 2-hydroxy (meth) acrylate a hydroxyalkyl (meth) acrylate such as 2-hydroxypropyl (meth) acrylate; decyl (meth) acrylate, decyl phenyl (meth) acrylate, (meth) acrylonitrile, acrolein, a vinyl compound such as vinyl chloride, vinyl chloride, N-vinylpyrrolidone or vinyl acetate; an unsaturated dicarboxylic acid such as diethyl maleate, diethyl fumarate or diethyl itaconate. Diester; epoxypropyl (meth) acrylate, α-ethyl epoxypropyl (meth) acrylate, α-n-propyl epoxypropyl (meth) acrylate, α- N-butyl epoxypropyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxyheptyl (meth) acrylate, α-ethyl- An epoxy propyl compound such as 6,7-epoxyheptyl (meth) acrylate, allyl epoxidized propyl ether or vinyl epoxidized propyl ether.

Specific examples of the bifunctional monomer include 1,3-butylene glycol di(meth)acrylate, 1,3-butylene glycol (meth)acrylate, and 1,6-hexanediol II. (Meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(methyl) Acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bisphenol A bis(acryloxyethyl)ether, ethoxylated bisphenol A di(methyl) Acrylate, propoxylated neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, 3-methylpentanediol di(meth)acrylic acid Ester and the like.

Examples of the trifunctional or higher polyfunctional monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and gin(2-hydroxyethyl)trimeric isocyanate tris(methyl). Acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol (Meth) acrylate, dipentaerythritol hexa(meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol The opposite of (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri(meth) acrylate and anhydride Reactant, reactant of dipentaerythritol penta (meth) acrylate and anhydride, trimellititol hepta (meth) acrylate and anhydride caprolactone denatured trimethylolpropane tri(meth) acrylate, caprolactone denaturation Pentaerythritol tri(meth) acrylate, caprolactone denatured ginseng (2-hydroxyethyl) trimer isocyanate tri(meth) acrylate, caprolactone denatured pentaerythritol tetra (meth) acrylate, caprolactone denatured Pentaerythritol penta (meth) acrylate, caprolactone denatured dipentaerythritol hexa(meth) acrylate, caprolactone denatured tripentaerythritol tetra (meth) acrylate, caprolactone denatured tripentaerythritol penta (meth) acrylate , caprolactone denatured tripentaerythritol hexa(meth) acrylate, caprolactone denatured tripentaerythritol hepta (meth) acrylate, caprolactone denatured tripentaerythritol octa (meth) acrylate, caprolactone denatured pentaerythritol III ( A reaction of a methyl acrylate with an acid anhydride, a reaction of caprolactone denatured dipentaerythritol penta (meth) acrylate with an acid anhydride, a caprolactone denatured tripentaerythritol hepta (meth) acrylate, an acid anhydride, and the like. Among them, a monomer having two or more functional groups is preferably used.

The content of the polymerizable compound (B) is preferably from 1 to 70% by mass, and more preferably from 5 to 60% by mass, based on the total mass fraction of the resin (A) and the polymerizable compound (B). When the content of the polymerizable compound (B) is in the above range, the sensitivity, the smoothness, the reliability, and the mechanical strength of the coating film and the pattern are good, which is preferable.

The polymerization initiator (C) contained in the photosensitive resin composition of the present invention is not particularly limited as long as it is a compound which starts polymerization by the action of light or heat, and a known polymerization initiator can be used. .

As a polymerization initiator (C), for example, a bisimidazole compound, benzene The ethylketone compound, the triazine compound, the mercaptophosphine oxide compound, and the anthraquinone compound are preferred. Further, it is possible to use the photo-and/or thermal-cationic polymerization initiator described in JP-A-2008-181087 (for example, a ruthenium cation and an anion derived from Lewis acid). Among them, the biimidazole compound is preferred because it has excellent sensitivity.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, and 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (for example, JP-A-6-75372, JP-A-6-75373, etc.), 2, 2'-double ( 2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis Oxyphenyl)bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)bisimidazole, 2,2'-double (2-Chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)bisimidazole (for example, Japanese Patent Publication No. Sho 48-38403, JP-A-62-174204, etc.) The imidazole compound in which the phenyl group at the 4,4'5,5'-position is substituted with an alkoxycarbazine (for example, see JP-A-7-10913, etc.). Preferred examples are 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,3-dichlorophenyl). -4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole .

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2- Hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl) -propenyl)-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)-butanone, 2-(3-methylbenzene Methyl)-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-dimethylamine 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-chlorobenzene Methyl)-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-dimethyl Amino-1-(4-morpholinophenyl)-butanone, 2-(4-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butyl Ketone, 2-(2-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-methoxybenzyl) -2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(4-methoxybenzyl)-2-dimethylamino-1-(4- Morpholinophenyl)-butanone, 2-(2-methyl-4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone , 2-(2-methyl-4-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-bromo-4-methyl Oxybenzyl)) 2-Dimethylamino-1-(4-morpholinophenyl)-butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane- 1-ketone oligomers and the like.

Examples of the triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis (three). Chloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-three Pyrazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6- [2-(5-Methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl) ) vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl] -1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three And so on.

Examples of the mercaptophosphine oxide-based initiator include 2,4,6-trimethylphenylnonyldiphenylphosphine oxide.

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

Further, it is preferred to use the above polymerization initiator (C) and the polymerization initiation aid (C-1) at the same time. As a polymerization initiation aid (C-1), a formula The compound shown by (V).

In the formula (V), the dotted line indicated by X represents an aromatic ring having 6 to 12 carbon atoms which may be substituted by a halogen atom.

Y represents an oxygen atom or a sulfur atom.

R ¹ represents an alkyl group having 1 to 6 carbon atoms.

R ² represents an alkyl group having 1 to 12 carbon atoms which may be substituted by a halogen atom or an aryl group which may be substituted by a halogen atom. 〕

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

Examples of the aromatic ring having 6 to 12 carbon atoms include a benzene ring and a naphthalene ring.

Examples of the aromatic ring having 6 to 12 carbon atoms which may be substituted by a halogen atom include a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring, and a pentyl group. Benzene ring, hexylbenzene ring, cyclohexylbenzene ring, chlorobenzene ring, dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, Chlorophthalene ring, bromine ring, and the like.

Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methyl-n-propyl group, and a 2-methyl-n- group. Propyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl -n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, n-hexyl, cyclohexyl and the like.

As the alkyl group having 1 to 12 carbon atoms which may be substituted by a halogen atom, Methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methyl-n-propyl, 2-methyl-n-propyl, tert-butyl, n-pentyl , 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl Base-n-propyl, 2,2-dimethyl-n-propyl, n-hexyl, cyclohexyl, 1-chloro-n-butyl, 2-chloro-n-butyl, 3-chloro-n -butyl and the like.

Examples of the aryl group which may be substituted by a halogen atom include a phenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a dibromophenyl group, a chlorobromophenyl group, a biphenyl group, a chlorobiphenyl group, and a dichloro group. Biphenyl, bromophenyl, dibromophenyl, naphthyl, chloronaphthyl, dichloronaphthyl, bromonaphthyl, dibromonaphthyl and the like.

Further, in the present specification, all the chemical structural formulas differ depending on the carbon number, but are not particularly limited, and the above examples are applicable to the respective substituents. Also, it can be either a straight chain or a branch.

Specific examples of the compound represented by the formula (V) include 2-phenylhydrazinomethyl-3-methyl-naphtho[2,1-d]thiazoline and 2-phenylhydrazinomethyl-3-methyl -naphtho[1,2-d]thiazoline, 2-phenylhydrazinomethyl-3-methyl-naphtho[2,3-d]thiazoline, 2-(2-naphthoquinonemethyl)- 3-methylbenzothiazoline, 2-(1-naphthoquinonemethyl)-3-methylbenzothiazoline, 2-(2-naphthoquinonemethyl)-3-methyl-5-benzene Benzothiazoline, 2-(1-naphthoquinonemethyl)-3-methyl-5-phenylbenzothiazoline, 2-(2-naphthoquinonemethyl)-3-methyl-5 -fluorobenzothiazoline, 2-(1-naphthoquinonemethyl)-3-methyl-5-fluorobenzothiazoline, 2-(2-naphthoquinonemethyl)-3-methyl-5 -Chlorobenzothiazoline, 2-(1-naphthoquinonemethyl)-3-methyl-5-chlorobenzothiazoline, 2-(2-naphthoquinonemethyl)-3-methyl-5-bromobenzothiazoline, 2-(1-naphthoquinonemethyl)-3-methyl-5-bromobenzothiazoline, 2-(4-biphenylylmethyl)-3-methylbenzothiazoline, 2-(4-biphenylmethyl)-3-methyl-5-phenylbenzothiazoline, 2-( 2-naphthoquinonemethyl)-3-methyl-naphtho[2,1-d]thiazoline, 2-(2-naphthoquinonemethyl)-3-methyl-naphtho[1,2- d) thiazoline, 2-(4-biphenylmethyl)-3-methyl-naphtho[2,1-d]thiazoline, 2-(4-biphenylmethyl)-3-methyl -naphtho[1,2-d]thiazoline, 2-(p-fluorophenylhydrazinomethyl)-3-methyl-naphtho[2,1-d]thiazoline, 2-(p-fluorobenzene Mercaptomethyl)-3-methyl-naphtho[1,2-d]thiazoline, 2-phenylhydrazinomethyl-3-methyl-naphtho[2,1-d]oxazoline, 2 -phenylhydrazinomethyl-3-methyl-naphtho[1,2-d]oxazoline, 2-phenylhydrazinomethyl-3-methyl-naphtho[2,3-d]oxazoline , 2-(2-naphthoquinonemethyl)-3-methylbenzoxazoline, 2-(1-naphthoquinonemethyl)-3-methylbenzoxazoline, 2-(2- Naphthoquinonemethyl)-3-methyl-5-phenylbenzoxazoline, 2-(1-naphthoquinonemethyl)-3-methyl-5-phenylbenzoxazoline, 2 -(2-naphthoquinone 3-methyl-5-fluorobenzoxazoline, 2-(1-naphthoquinonemethyl)-3-methyl-5-fluorobenzoxazoline, 2-(2-naphthoquinone) Methyl)-3-methyl-5-chlorobenzoxazoline, 2-(1-naphthoquinonemethyl)-3-methyl-5-chlorobenzoxazoline, 2-(2-naphthoquinonemethyl)-3-methyl-5-bromobenzoxazole Porphyrin, 2-(1-naphthoquinonemethyl)-3-methyl-5-bromobenzoxazoline, 2-(4-biphenylmethyl)-3-methylbenzoxazoline, 2-(4-biphenylylmethyl)-3-methyl-5-phenylbenzoxazoline, 2-(2-naphthoquinonemethyl)-3-methyl-naphtho[2,1 -d]oxazoline, 2-(2-naphthoquinonemethyl)-3-methyl-naphtho[1,2-d]oxazoline, 2-(4-biphenylmethyl)-3 -methyl-naphtho[2,1-d]oxazoline, 2-(4-biphenylmethyl)-3-methyl-naphtho[1,2-d]oxazoline, 2-( p-Fluorobenzoylmethyl)-3-methyl-naphtho[2,1-d]oxazoline, 2-(p-fluorophenylhydrazinomethyl)-3-methyl-naphtho[1] , 2-d] oxazoline and the like.

Among them, 2-(2-naphthoquinonemethyl)-3-methylbenzothiazoline represented by the formula (V-1) and 2-benzoquinone group represented by the formula (V-2) are preferred. Methyl-3-methyl-naphtho[1,2-d]thiazoline and 2-(4-biphenylmethyl)-3-methyl-naphtho[1] represented by formula (V-3) , 2-d] thiazoline.

When these compounds are used, the obtained photosensitive resin composition is highly sensitive. Therefore, when the coating film or pattern is formed, the productivity of the coating film or pattern can be improved, which is preferable. The compound represented by the formula (V) is preferably sublimated by heat at the time of baking after coating, and is recolored by at least one of light and heat to improve transparency.

Further, as the polymerization initiation aid (C-1), at least one compound selected from the group consisting of the formula (VI) and the formula (VII) can be used.

Further, as the polymerization initiation aid (C-1), at least one compound selected from the group consisting of the formula (VI) and the formula (VII) can be used.

[In the formula (VI) and the formula (VII), the ring X ¹ and the ring X ² each independently represent an aromatic ring or a heterocyclic ring having 6 to 12 carbon atoms which may be substituted by a halogen atom. Y ¹ and Y ² represent an oxygen atom or a sulfur atom. R ¹ and R ² represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. These alkyl groups and aryl groups may be substituted by a halogen atom, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms.

Examples of the aromatic ring or heterocyclic ring which may be substituted by a halogen atom include a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring, and a pentylbenzene ring. Hexylbenzene ring, cyclohexylbenzene ring, chlorobenzene ring, dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene ring , bromine naphthalene ring, phenanthrene ring, ring ring, fluoranthene ring, benzo[a] anthracene ring, benzo[e]fluorene ring, anthracene ring and their derivatives.

Examples of the hydroxy-substituted alkyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group.

Examples of the hydroxy-substituted aryl group include a hydroxyphenyl group and a hydroxynaphthyl group.

Examples of the alkoxy-substituted alkyl group include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, a butoxymethyl group, an ethoxyethyl group, and an ethoxy group. Base, propoxy butyl and the like.

Examples of the alkoxy-substituted aryl group include a methoxyphenyl group and an ethoxynaphthyl group.

Specific examples of the compound represented by the formula (VI) and the formula (VII) include dioxane such as dimethoxynaphthalene, diethoxynaphthalene, dipropoxynaphthalene, diisopropoxynaphthalene or dibutoxynaphthalene. Oxynaphthalenes; dimethoxy hydrazine, diethoxy hydrazine, dipropoxy hydrazine, diisopropoxy hydrazine, dibutoxy oxime, dipentoxide, dihexamethylene oxime, methoxy ethoxy Base, methoxypropoxy oxime, methoxyisopropoxy Bismuth, methoxybutoxyxanium, ethoxypropoxy oxime, ethoxyisopropoxy oxime, ethoxybutoxy oxime, propoxyisopropoxy oxime, propoxy oxime, different a dialkoxy oxime such as propoxy oxybutoxide; dimethoxy butyl, diethoxy butyl, dipropoxy butyl, diisopropoxy butyl, dibutoxybutan, etc. Alkoxydin class; et al.

Further, as the polymerization initiator (C), a photopolymerization initiator can be used.

Examples of the photopolymerization initiator include a benzoin-based compound, a benzophenone-based compound, a thioxanthone-based compound, and an anthraquinone-based compound.

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-based compound include benzophenone, methyl o-phenylmercaptobenzoate, 4-phenylbenzophenone, and 4-phenylmercapto-4'-methyldiphenyl. Base sulfide, 3,3',4,4'-tetra (tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like.

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

Examples of the oxime-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl- 9,10-diethoxyanthracene, and the like.

Moreover, 10-butyl-2-chloroacridone, 2-ethylhydrazine, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound Used as a photopolymerization initiator.

Further, as a photopolymerization initiator having a group which causes a chain shift, a photopolymerization initiator described in JP-A-2002-544205 can be used.

Examples of the photopolymerization initiator having a group which causes the above-described linkage movement include photopolymerization initiators of the following formulas (1) to (6).

The photopolymerization initiator having a group which causes a chain shift can also be used as a component constituting the resin (A).

Further, it is preferred to use the above polymerization initiator and the polymerization initiation aid (C-2) at the same time.

Examples of the polymerization initiation aid (C-2) include an amine compound and a carboxylic acid compound.

The amine compound may, for example, be an aliphatic amine compound such as triethanolamine, methyldiethanolamine or triisopropanolamine, such as methyl 4-dimethylaminobenzoate or ethyl 4-dimethylaminobenzoate. , 4-dimethylamino benzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N,N-dimethyl-p- An aromatic amine compound of aniline, 4,4'-bis(dimethylamino)benzophenone (commonly known as: Michler's ketone), 4,4'-bis(diethylamino)benzophenone.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylbenzenesulfuric acid, methylethylbenzenesulfuric acid, dimethylphenylsulfuric acid, methoxyphenylthioacetic acid, and dimethoxy group. Aromatic heteroacetic acid such as phenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid class.

The content of the polymerization initiator (C) is preferably 0.1 to 40% by mass, and more preferably 1 to 30% by mass, based on the total mass of the resin (A) and the polymerizable compound (B). .

When the total amount of the polymerization initiator (C) is within this range, the photosensitive resin composition can be highly sensitive, and the strength of the coating film or pattern formed using the photosensitive resin composition, or the coating film or pattern can be used. The smoothness of the surface is good, so it is preferred.

The amount of polymerization initiation aid (C-1) and / or (C-2) used for the tree The total amount of the lipid (A) and the polymerizable compound (B) is preferably 0.01 to 50% by mass, and more preferably 0.1 to 40% by mass, based on the mass fraction.

When the amount of the polymerization initiation assistant (C-1) and/or (C-2) is in this range, the sensitivity of the obtained photosensitive resin composition can be further improved, and the pattern formed using the photosensitive resin composition can be used. The productivity of the substrate is improved, which is preferable.

In particular, when the compound represented by the formula (V) is used, the content of the polymerization initiation aid (C-1) is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass. The mass% is particularly preferably from 65 mass% to 100 mass%. When the content of the compound represented by the formula (V) is within this range, when the coating film is formed using the photosensitive resin composition containing the above, the transparency of the coating film is good, which is preferable.

Further, the photosensitive resin composition of the present invention may further contain a polyfunctional thiol compound (T). The polyfunctional thiol compound (T) is a compound having two or more sulfonyl groups in the molecule. In particular, when a compound having two or more sulfonyl groups bonded to carbon atoms of two or more aliphatic hydrocarbon groups is used, the sensitivity of the photosensitive resin composition of the present invention can be improved, which is preferable.

Specific examples of the polyfunctional thiol compound (T) include hexanedithiol, decanedithiol, 1,4-dimethylhydrothiobenzene, butanediol dithiopropionate, and butanediol. Dithioglycolate, ethylene glycol dithioglycolate, trimethylolpropane thioacetate, butanediol dithiopropionate, trimethylolpropane thiopropionate, trimethylol Propane thioglycolate, pentaerythritol, sulphur Propionate, pentaerythritol thioglycolate, hydroxyethyl thiopropionate, pentaerythritol bismuth (3-hydrothiobutyrate), 1,4-bis(3-hydrothiobutanyloxy) butyl Alkane, etc.

The content of the polyfunctional thiol compound (T) is preferably from 0.5 to 100% by mass, and more preferably from 1 to 90% by mass, based on the mass fraction of the polymerization initiator (C). In addition, the content of the polyfunctional thiol compound is preferably 0.1 to 20% by mass, more preferably 0.1 to 20% by mass, based on the total amount of the adhesive resin (A) and the photopolymerizable compound (C). It is 1 to 10% by mass. When the content of the polyfunctional thiol compound (T) is within this range, the sensitivity is improved and the developability is good, which is preferable.

The solvent (D) used in the photosensitive resin composition of the present invention can uniformly dissolve constituent components such as the resin (A), the polymerizable compound (B), and the polymerization initiator (C), and does not react with each component. The responder is better.

Further, the solvent (D) contains at least formula (I)

R ¹ -O-(AO) _n -R ² (I)

(In the formula (I), R ¹ and R ² each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms. A represents a linear or branched alkyl group having 1 to 3 carbon atoms. n represents an integer of 2 or 3. The plural A's may be the same or different.)

The solvent shown.

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methyl-n-propyl group, a 2-methyl-n-propyl group, and a tert-butyl group. The base or the like, as the alkylene group, may be a methyl group, an ethyl group, a propyl group or a methyl group.

Specific examples of the compound of the formula (I) include dimethyl glycol dimethyl ether, trimethyl glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and dipropylene glycol. Methyl ether, tripropylene glycol dimethyl ether, dimethyl glycol methyl ethyl ether, trimethyl glycol methyl ethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol methyl ethyl ether, Dipropylene glycol methyl ethyl ether, tripropylene glycol methyl ethyl ether, dimethyl glycol methyl propyl ether, trimethyl glycol methyl propyl ether, diethylene glycol methyl propyl ether, triethylene glycol Propyl ether, dipropylene glycol methyl propyl ether, tripropylene glycol methyl propyl ether, dimethyl glycol methyl butyl ether, trimethyl glycol methyl butyl ether, diethylene glycol methyl butyl ether, Triethylene glycol methyl butyl ether, dipropylene glycol methyl butyl ether, tripropylene glycol methyl butyl ether, dimethyl glycol diethyl ether, trimethyl glycol diethyl ether, diethylene glycol diethyl Ether, triethylene glycol diethyl ether, dipropylene glycol diethyl ether, tripropylene glycol diethyl ether, dimethyl glycol ethyl propyl ether, trimethyl glycol ethyl propyl ether, diethylene glycol ethyl Propyl ether, three Glycol ethyl propyl ether, dipropylene glycol ethyl propyl ether, tripropylene glycol ethyl propyl ether, dimethyl glycol ethyl butyl ether, trimethyl glycol ethyl butyl ether, diethylene glycol ethyl butyl Ethyl ether, triethylene glycol ethyl butyl ether, dipropylene glycol ethyl butyl ether, tripropylene glycol ethyl butyl ether, dimethyl glycol dipropyl ether, trimethyl glycol dipropyl ether, diethylene glycol Dipropyl ether, triethylene glycol dipropyl ether, Dipropylene glycol dipropyl ether, tripropylene glycol dipropyl ether, dimethyl glycol propyl butyl ether, trimethyl glycol propyl butyl ether, diethylene glycol propyl butyl ether, triethylene glycol propyl butyl Ethyl ether, dipropylene glycol propyl butyl ether, tripropylene glycol propyl butyl ether, dimethyl glycol dibutyl ether, trimethyl glycol dibutyl ether, diethylene glycol dibutyl ether, triethylene glycol Butyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dibutyl ether, and the like.

Among them, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl ether, and triethylene glycol dimethyl ether are preferred.

Further, it is preferred to use a solvent of the formula (I) in combination of two or more kinds. When it is used by combining these solvents, compatibility with each component of the photosensitive resin composition can be ensured, and it can be effectively applied to the uneven substrate by various coating methods and special spin coating methods. Prevent streaks from occurring.

The solvent of the formula (I) is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 90 to 100% by mass, based on the total amount of the solvent. When the content of the solvent of the formula (I) is within this range, it can be applied by spin coating, slit spin coating, slit coating (also referred to as mold coating, curtain blow coating), or injection molding. Various coating apparatuses such as coating, roll coating, and dip coating have good coatability.

In particular, when the solvent (D) contains diethylene glycol ethyl methyl ether, the total amount of the solvent is preferably from 10 to 100% by mass, and from 10 to 90% by mass, based on the diethylene glycol ethyl methyl ether. Preferably, it is preferably 30 to 90% by mass.

Further, the solvent (D) contains diethylene glycol butyl methyl ether and/or triethyl ethane In the case of the diol dimethyl ether, the total amount of the solvent is preferably from 0 to 50% by mass of diethylene glycol butyl methyl ether and/or triethylene glycol dimethyl ether, and preferably from 10 to 50% by mass. .

By being in this range, particularly in the spin coating method, generation of streaks can be effectively prevented.

The solvent (D) may preferably be composed of a solvent other than the above, and may contain other solvents.

Examples of the other solvent include alcohols such as monools and polyhydric alcohols, ethers exemplified below, aromatic hydrocarbons, ketones, and esters.

Examples of such an alcohol include methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, ethylene glycol, and ethylene glycol. Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, methyl lactate, ethyl lactate, methyl 2-methyl lactate, diacetone alcohol, 3 - methoxybutanol, glycerin, and the like. Among them, 3-methoxybutanol is also preferred.

The alcohol is preferably used in an amount of from 0 to 50% by mass, more preferably from 10 to 50% by mass, particularly preferably from 10 to 45% by mass, most preferably from 10 to 40% by mass, based on the total amount of the solvent (D).

When the alcohol is in this range, the solubility of the resin or the like can be sufficiently obtained, and the viscosity can be adjusted to achieve the uniformity of the obtained coating film. Further, when the photosensitive resin composition is applied by the extrusion coater, the nozzle tip can be prevented from drying, and the foreign matter can be prevented from being precipitated by the dried product, thereby ensuring prevention of vertical streaks due to foreign matter.

Further, examples of the solvent include ethylene glycol monomethyl ether and ethylene glycol. Monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monoalkyl ether of ethylene glycol monobutyl ether; methyl cellosolve acetate, ethyl cellosolve acetate, ethylene Ethylene glycol monoether acetate acetate such as alcohol monobutyl ether acetate or ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol single Alkanediol alkyl ether acetates such as propyl ether acetate, methoxybutyl acetate, methoxypentyl acetate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl Propylene glycol monoalkyl ethers such as propyl ether, propylene glycol monobutyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether propylene glycol propyl methyl ether, propylene glycol ethyl Propylene glycol alkyl ether propionate such as propylene glycol dialkyl ether propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate Butyl glycol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxy butyl alcohol, butoxybutyl alcohol; methoxy Butanediol monoalkyl ether acetates such as acetoxyacetate, ethoxybutyl acetate, propoxy butyl acetate, butoxybutyl acetate; methoxybutyl propionate Butane diol monoalkyl ether propionate such as ethoxybutyl propionate, propoxy butyl propionate or butoxybutyl propionate; benzene, toluene, xylene, mesitylene, etc. Aromatic hydrocarbons; methyl ethyl ketone, acetone, methyl pentanone, methyl isobutyl ketone, cyclohexyl Ketones such as ketones; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methyl Ethyl propionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, 3-hydroxypropionic acid Ester, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid Propyl ester, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate Ester, propyl propyl acetate, butyl propyl acetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, Propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, 2-butoxy Methyl propionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3-methoxypropionic acid Ester, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropionate Ester, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate Esters such as ester, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate; cyclic ethers such as tetrahydrofuran and pyran a cyclic ester such as γ-butyrolactone.

Among the above solvents, an organic solvent having a boiling point of from 100 ° C to 200 ° C is preferred from the viewpoint of coatability and dryness. Among them, alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers, 3-ethoxypropionate ethyl esters, 3-methyl Esters such as oxypropionic acid methyl, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, 3-ethoxypropionic acid The ester, 3-methoxypropionic acid methyl group is preferred.

The photosensitive resin composition of the present invention does not substantially contain a coloring agent such as a pigment or a dye. In the photosensitive resin composition of the present invention, when the content of the coloring agent of the entire composition is expressed by mass fraction, it is preferably less than 1% by mass, preferably less than 0.5% by mass.

The photosensitive resin composition of the present invention does not substantially contain the following colorants used in the field.

Compounds classified as Pigment in the publication of The Society of Dyers and Colourists, specifically CIPigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93 Yellow pigments such as 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; CIPigment Orange 13, 31, 36, 38 , 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CIPigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176 Red pigments such as 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; CIPigment blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments; CIPigment purple 1,19,23,29,32,36,38 and other purple pigments; CIPigment green 7,36, etc. Green pigment; CIPigment brown 23, 25 and other brown pigments; CIPigment black 1, 7 and other black pigments.

In the photosensitive resin composition of the present invention, various additives such as a filler, another polymer compound, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, a photosetter, and a chain shifting agent may be used in combination.

Examples of the filler include glass, cerium oxide, and aluminum oxide.

Examples of the other polymer compound include curable resin polyvinyl alcohol such as epoxy resin or maleimide resin, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, and polyester. , thermoplastic resins such as polyurethane, and the like.

The surfactant may be any of a surfactant such as an anthracene oxygen-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based or amphoteric surfactant. Specific examples thereof include polyethylene oxide alkyl ethers, polyethylene oxide alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, and tertiary amine depolymerization polymerizations. Commercially available surfactants can also be used in addition to urethanes and polyethyleneimines. For example, KP (Shin-Etsu Chemical Co., Ltd.) and Polyflow (Kyoei Chemical Co., Ltd.) (share) system, Eftop (Mitsubishi Material Electronic (share)), Megafac (DIC (share) system), Fluorad (Sumitomo 3M (share) system), Surflon (AGCSeimichemical (share) system), Solsperse (Zeneca (share) )), EFKA (manufactured by CIBA), AJISPERPB821 (manufactured by Ajinomoto Co., Ltd.).

Examples of the adhesion promoter include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginate (2-methoxyethoxy) decane, and N-(2-aminoethyl). 3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3 - glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3 - chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-hydrothiopropyltrimethoxydecane, and the like.

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-pentylphenyl acrylate, 6-[3-(3-tert-butyl) 4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo d,f][1,3,2]dioxaphosphorane ring Heptane, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoxy}-1,1-dimethylethyl]- 2,4,8,10-tetraoxaspiro[5.5]undecane, 2,2'-extended methyl bis(6-tert-butyl-4-methylphenol), 4,4'-butylene double (6-tert-butyl-3-methylphenol), 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2,2'-thiobis(6-tert-butyl Base 4-methylphenol), dilaurin 3,3'-thiodipropionate, myristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythritol (3-lauryl sulfur) Propionate), 1,3,5-gin(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H ,5H)-trione, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-three Tris-p-cresol, pentaerythritol oxime [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 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'-B) Hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxyl 4-butoxyphenyl)-6-(2,4-bis-butoxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-[1-octyloxycarbonyl) Oxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-(2H-benzotriazol-2-yl)-4,6-double (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, alkoxydiphenyl Ketone and so on.

Examples of the photosensitizer include a polymer obtained from succinic acid and (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethanol, and N,N',N". , N'''-肆 (4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)triazin-2-yl )-4,7-diazanonane-1,10-di Amine, sebacic acid, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidyl) ester, and 1,1-dimethylethylhydroperoxide 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)amine -6-(2-hydroxyethylamine)-1,3,5-triazine, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, Methyl (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate or the like.

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

The photosensitive resin composition of the present invention is applied to a substrate such as a substrate, for example, a substrate such as glass, metal or plastic, a color filter, various insulating films, a conductive film, or a driving circuit, as will be described later. It can be formed as a coating film. The coating film is preferably dried and hardened. Further, the obtained coating film is formed into a pattern in a desired shape, and can be used as a pattern. Further, these coating films and/or patterns are formed as a part of components such as a display device, and are used.

Further, the curable resin composition of the present invention is filled in a quartz container having an optical path length of 1 cm, and when the transmittance is measured under the conditions of a measurement wavelength of 400 to 700 nm using a spectrophotometer, the average transmittance is preferably 70%. More preferably, it is 75% or more. Thereby, in the field of visible light, a transparent pattern or a coating film can be formed.

First, the photosensitive resin composition of the present invention is applied onto a substrate.

As described above, the coating can be carried out using various coating apparatuses such as spin coating, slit spin coating, slit coating, injection coating, roll coating, and dip coating. Among them, coating by spin coating, in other words, coating by spin coating, spin coating, or the like is preferable from the viewpoints of solubility, prevention of drying, prevention of generation of foreign matter, and the like.

Next, it is preferred to remove volatile components such as a solvent by drying and/or prebaking. Thereby, a smooth unhardened coating film can be obtained.

The film thickness of the coating film at this time is not particularly limited, and may be appropriately adjusted depending on the material to be used, the use, and the like, and may be, for example, about 1 to 6 μm.

Further, when the desired pattern is to be formed on the obtained uncured coating film, the mask is irradiated with light such as ultraviolet rays generated by a mercury lamp or a light-emitting diode. The shape of the mask at this time is not particularly limited, and various shapes can be mentioned. Further, the line width and the like can be appropriately adjusted depending on the size of the mask or the like.

In recent exposure machines, light of less than 350 nm can be blocked by using a filter that blocks the wavelength range, or light in the vicinity of 436 nm, around 408 nm, and around 365 nm can be used to take out the bandpasses in these wavelength domains. The filter is selectively taken out, and the parallel light is uniformly irradiated on the entire exposure surface. At this time, in order to match the correct position of the mask and the substrate, a mask aligner, a stepper, or the like can be used.

Thereafter, a predetermined portion of the coating film in contact with the aqueous alkali solution, for example, a non-exposed portion is dissolved, and the desired pattern shape can be obtained by development.

As the developing method, any one of an overflow method, an impregnation method, a spray method, and the like can be used. The substrate can be tilted at any angle during development.

The developing solution used for development is generally an aqueous solution containing a basic compound and a surfactant.

The basic compound may be any of a micro inorganic or organic basic compound.

Specific examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium citrate, and cesium. Potassium acid, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, and the like.

Further, examples of the organic basic compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, and single ethyl Alkylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, and the like.

The concentration in the alkali developing solution of these inorganic and organic basic compounds is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass.

The surfactant may be any of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.

Examples of the nonionic surfactant include polyethylene oxide alkyl ether, polyethylene oxide aryl ether, polyethylene oxide alkyl aryl ether, other polyethylene oxide derivatives, and oxyethylene/oxygen. Propylene block copolymer, sorbitan fatty acid ester, polyepoxy sorbitan fatty acid ester, polyepoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyepoxy fatty acid ester, polycyclic ring Oxyethylene alkylamine and the like.

Examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl sulfate or sodium oleyl sulfate, and alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate. Dodecylbenzenesulfonic acid An alkyl aryl sulfonate such as sodium or sodium dodecyl naphthalene sulfonate.

Examples of the cationic surfactant include an amine salt such as stearylamine hydrochloride or lauryl trimethylammonium chloride or a fourth-order ammonium salt.

The concentration of the surfactant in the alkali developing solution is preferably in the range of 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, particularly preferably 0.1 to 5% by mass.

After the image is washed with water, further post-baking can be performed as necessary. The post-baking is preferably carried out, for example, at a temperature ranging from 150 to 230 ° C for 10 to 180 minutes.

The curable resin composition of the present invention is a coating film having a thickness of 3 μm after heat curing (for example, 150 to 250 ° C for 0.1 to 3 hours), and a transmittance is measured using a spectrophotometer at a measurement wavelength of 400 to 700 nm. The transmittance is preferably 90% or more, more preferably 95% or more. Thereby, a transparent pattern or a coating film can be formed in the visible light region.

The coating film or pattern thus obtained can be used, for example, as a photo spacer for a liquid crystal display device or an overcoat capable of forming a pattern. Further, in the case of patterning exposure of the uncured coating film, it is useful as an interlayer insulating film by using a mask for forming a hole. Further, in the case of exposure to an uncured coating film, a reticle is not used, and only a full exposure, heat curing or heat curing is performed, and a transparent film can be formed. The transparent film can be used as an overcoat. Moreover, it can also be used on a display device such as a touch panel. Thereby, a display device having a high-quality coating film or pattern can be produced at a high yield.

The photosensitive resin composition of the present invention is formed when various films and patterns are formed The material is, for example, suitable for forming a transparent film, particularly a transparent film constituting a part of a color filter, a pattern, a photo spacer, an overcoat, an insulating film, a liquid crystal alignment control protrusion, a microlens, a combined phase film Thick color pattern, coating layer, etc. Further, these coating films or patterns can be used as color filters, array substrates, and the like which are provided as a part of the components, and further include display devices such as color filters and/or array substrates, for example, liquid crystal display devices and organic ELs. Used by devices and the like.

Example

Hereinafter, the photosensitive resin composition of the present invention will be described in detail by way of examples, and the present invention is not limited by these examples. In the following examples and comparative examples, the content and the amount of the content and the amount are shown, and unless otherwise specified, the basis is based on the mass.

Synthesis Example 1

In a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer, 0.02 L/min of nitrogen was introduced to make a nitrogen atmosphere, and 140 parts of diethylene glycol ethyl methyl ether was placed, and the mixture was heated to 70 ° C while stirring. Next, 40 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ] mercapto acrylate (the compound represented by the formula (I-1) and the compound represented by the formula (II-1)) are prepared. a mixture of 50:50 in molar ratio.) 360 parts and a solution of 190 parts of diethylene glycol ethyl methyl ether. The solution was dropped using a pump, which took 4 hours and was kept at 70 ° C. Drip inside.

On the other hand, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in a solution of 240 parts of diethylene glycol ethyl methyl ether, and another drop was used. The pump was dropped into the flask for 5 hours. After the completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin Aa) having a solid content of 42.6% and an acid value of 60 mg-KOH/g. The obtained resin Aa had a weight average molecular weight (Mw) of 8,000 and a degree of dispersion of 1.91.

Synthesis Example 2

In a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer, 0.02 L/min of nitrogen was introduced to make a nitrogen atmosphere, and 305 parts of diethylene glycol ethyl methyl ether was placed, and the mixture was heated to 70 ° C while stirring. Next, 60 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.02.6]decyl acrylate (the compound represented by the formula (I-1) and the compound represented by the formula (II-1)) Mohr ratio, 50:50 mixture.) 240 parts dissolved in diethylene glycol ethyl methyl ether 140 parts to prepare a solution, the solution was used to drip the funnel, which took 4 hours, and was kept at 70 ° C flask Drip inside.

On the other hand, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts of diethylene glycol ethyl methyl ether, and other dropping funnels were used. It was added to the flask under a time of 4 hours. Aggregation initiation After the completion of the dropwise addition of the solution of the agent, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a solid polymer (resin Ab) having a solid content of 32.6% and an acid value of 110 mg-KOH/g (in terms of solid content). Solution. The obtained resin Ab had a weight average molecular weight Mw of 13,600 and a degree of dispersion of 2.49.

Synthesis Example 3

Into a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer, 0.02 L/min of nitrogen was introduced, and as a nitrogen atmosphere, 200 parts of 3-methoxy-1-butanol and 3-methoxybutyl acetate were placed. 105 parts were heated to 70 ° C while stirring. Next, 60 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.02.6]decyl acrylate (the compound represented by the formula (I-1) and the compound represented by the formula (II-1)) a molar ratio of 50:50 mixture.) 240 parts dissolved in 140 parts of 3-methoxybutyl acetate to prepare a solution, the solution was used to drip the funnel, took 4 hours, drip in 70 ° C Inside the flask.

On the other hand, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in a solution of 225 parts of 3-methoxybutyl acetate, and other drops were used. The funnel was dropped into the flask over a period of 4 hours. After the completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a copolymer of 32.6% solids and an acid value of 110 mg-KOH/g (in terms of solid content) (resin Ac )The solution. The obtained resin Ac had a weight average molecular weight Mw of 13,400 and a degree of dispersion of 2.50.

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

Device; K2479 (made by Shimadzu Corporation)

Pipe string; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ° C

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0mL/min

Detector; RI

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

Examples 1 to 10 and Comparative Example 1

The composition of Table 1 was mixed to obtain photosensitive resin compositions 1 to 11.

The components in Table 1 are as follows.

Polymerizable compound (B); dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator Ca; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole (B-CIM; Baotu Valley Chemistry ( Stock system)

Start-up auxiliary C2a; 9,10-dibutoxy oxime (DBA; Kawasaki Kasei Co., Ltd.)

Start-up aid C2b; pentaerythritol bismuth (3-sulfonyl propionate) (PEMP; SC organic chemistry (stock) system)

Starting additive C2c; 2-(2-naphthoquinonemethyl)-3-methylbenzothiazoline

Solvent Da; diethylene glycol ethyl methyl ether

Solvent Db; diethylene glycol butyl methyl ether

Solvent Dc; triethylene glycol dimethyl ether

Solvent Dd; propylene glycol monomethyl ether acetate

Solvent De; 3-ethoxyethyl propionate

Solvent Df; 3-methoxy 1-butanol

Solvent Dg; 3-methoxybutyl acetate

Solvent Dh; dipropylene glycol dimethyl ether

Additive 1; polyether modified polyoxyxide oil (SH8400 manufactured by Toray Dow Corning Co., Ltd.)

Additive 2; IRGANOX 3114 (manufactured by Ciba Japan Co., Ltd.)

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Each component shown in Table 2 was mixed at the ratio shown in Table 2, and the colored photosensitive resin composition 1 was obtained.

The 4 inch substrate was washed successively with a neutral detergent, water and alcohol, and dried. On the ruthenium substrate, the colored photosensitive resin composition 1 was subjected to roll coating after exposure, development, water washing, and post-baking at a exposure amount of 100 mJ/cm ² (365 nm) to a thickness of 3.0 μm. Next, in a clean oven, prebaking was carried out at 90 ° C for 3 minutes. After cooling, the distance between the substrate coated with the colored photosensitive resin composition 1 and the mask made of quartz glass was set to 100 μm, and an exposure machine (TME-150RSK; a light source manufactured by Topcon; an ultrahigh pressure mercury lamp) was used. Light irradiation was performed at an exposure amount of 100 mJ/cm ² (365 nm basis) in an atmospheric environment. Further, at this time, the irradiation of the colored photosensitive resin composition was carried out by passing the emitted light of the ultrahigh pressure mercury lamp through an optical filter (UV-35; manufactured by Asahi Techno GLASS Co., Ltd.). Further, as the photomask, a pattern (a light-transmissive portion having a square of 10 mm on one side and a square of 100 mm) was used as a mask on the same plane.

After the light irradiation, the coating film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 28° C. for development and image development, and after washing with water, the oven was subjected to a temperature of 220° C. After a minute of baking, a enamel substrate having a color pattern of a side length of 10 mm was formed.

The photosensitive resin composition of Examples 1 to 6 and Comparative Example 1 was cured by spin coating to a thickness of 2.0 μm on the tantalum substrate having a color pattern of 10 mm in length. Coating is carried out. Thereafter, the pressure reduction degree was reduced to 1.0 torr under reduced pressure using a vacuum dryer (manufactured by VCD Microtek Co., Ltd.). The coating was continued on a hot plate set at 95 ° C, and pre-baked for 2 minutes to form a coating film. After cooling, the surface of the film was irradiated with a Na lamp to visually confirm the surface of the coating film.

As a result, in Examples 1 to 6, almost no streaks were confirmed along the coloring pattern. The results are shown in Table 3.

Here, the streak is a radial spot from the step of the coloring pattern.

<Average transmittance of photosensitive resin composition>

For the photosensitive resin composition 1, an average transmittance (%) in the range of 400 to 700 nm was measured using an ultraviolet-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz vessel, optical path length; 1 cm). The results are shown in Table 3.

<Average transmittance of coating film>

At the time of light irradiation, the same operation as described above was carried out without using a photomask, and the film thickness after post-baking was 2.0 μm to prepare a coating film. The average transmittance (%) of the produced coating film at a wavelength of 400 to 700 nm was measured using a krypton microphotometer (OSP-SP200; manufactured by OLYMPUS). The results are shown in Table 3.

When the coating film is formed by using the photosensitive resin composition of the present invention, even when coating is formed on a relatively thick film, a high-quality coating film which does not cause streaks and which is uniform and smooth in the entire coating film can be formed.

Moreover, the coating drying time can be shortened, and the productivity can be improved. On the other hand, the tip end of the slit nozzle can be prevented from drying, and the generation of foreign matter due to drying, the incorporation of the coating film, and the vertical streaks can be prevented.

Further, the solubility of the resin and various components is good, and the storage stability can be improved.

When such a photosensitive resin composition is used to form a coating film or a pattern, when a display device is manufactured by using them, the yield can be improved.

Industrial availability

In the present invention, it is possible to form a coating film which suppresses generation of streaks and which is uniform and high in quality of the entire coating film.

Moreover, by using the photosensitive resin composition of the present invention, a high-quality display device or the like can be obtained.

Claims (9)

A photosensitive resin composition comprising a resin (A), a polymerizable compound (B), a polymerization initiator (C), and a solvent (D), and the resin (A) is a weight average in terms of polystyrene The resin having a molecular weight of 5,000 to 50,000, and the solvent (D) is a solvent represented by the formula (I) containing two or more types different from each other, and containing a diethylene glycol butyl methyl ether and a triethylene glycol dimethyl group. At least one solvent in which the ether is grouped; R ¹ -O-(AO) _n -R ² (I) (in the formula (I), R ¹ and R ² each independently represent a linear or branched carbon number of 1 The alkyl group of ~4, A represents a linear or branched alkyl group having 1 to 3 carbon atoms, n represents an integer of 2 or 3, and the plural A may be the same or different). The photosensitive resin composition of claim 1, wherein the solvent (D) contains diethylene glycol ethyl methyl ether. The photosensitive resin composition of claim 2, wherein the solvent (D) is a diethylene glycol ethyl methyl ether in an amount of 10 to 90% by mass based on the total amount of the solvent. The photosensitive resin composition of claim 1, wherein the solvent (D) is 10 to 50% by mass based on the total amount of the solvent selected from the group consisting of diethylene glycol butyl methyl ether and triethylene glycol dimethyl group. At least one solvent in which the ether is grouped. The photosensitive resin composition of claim 1 or 2, wherein the solvent (D) is selected from the group consisting of diethylene glycol ethyl methyl ether, And at least one solvent of the group consisting of diethylene glycol butyl methyl ether and triethylene glycol dimethyl ether. The photosensitive resin composition of the fifth aspect of the invention, wherein the solvent (D) is a diethylene glycol ethyl methyl ether selected from the group consisting of a total amount of the solvent of 60% by mass or more and 100% by mass or less. And at least one solvent of the group consisting of diethylene glycol butyl methyl ether and triethylene glycol dimethyl ether. A coating film characterized by using the photosensitive resin composition of the first aspect of the patent application. A pattern characterized by using a photosensitive resin composition as set forth in claim 1 of the patent application. A display device comprising at least one selected from the group consisting of a coating film according to claim 7 of the patent application and a pattern of claim 8 of the patent application.