KR20120022670A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE: A photo-sensitive resin composition, and patterns, a partition wall for ink jet, and a display device using the same are provided to maintain the superior contact angle of the patterns. CONSTITUTION: A photo-sensitive resin composition includes copolymer, polymer containing a structural unit derived from C4 to C6 perfluoroalkyl group containing unsaturated compound, a polymerizable compound, a polymerization initiator, and a solvent. The copolymer includes structural units. One structural unit derived from at least one selected from a group including unsaturated carboxylic acid and unsaturated carboxylic anhydride. Another structural unit is derived from unsaturated compound with a C2 to C4 cyclic ether structure.

Description

Photosensitive resin composition {PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a photosensitive resin composition.

In recent display apparatuses, a color filter, an ITO electrode of a liquid crystal display element, an organic EL display element, a circuit wiring board, etc. are produced by the inkjet method. Moreover, in the inkjet method, the partition formed using the photosensitive resin composition is used.

As such a photosensitive resin composition, it is C4-C? The photosensitive resin composition containing the polymer obtained by superposing | polymerizing the alpha-substituted acrylate which has a fluoroalkyl group of 6 is known (Japanese Patent Laid-Open No. 2008-287251).

However, in the photosensitive resin composition conventionally proposed, there existed a case where it cannot necessarily fully be satisfied about the heat resistance of the pattern obtained.

The present invention is the following [1]? [6] to provide.

[1] A photosensitive resin composition containing (A), (B), (C), (D) and (E).

(A) Structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and C2-C? Copolymer containing a structural unit derived from the unsaturated compound which has a cyclic ether structure of 4, but does not have a structural unit derived from the unsaturated compound which has a C4-6 perfluoroalkyl group.

(B) 4 carbon atoms? Polymers containing structural units derived from unsaturated compounds having a perfluoroalkyl group of 6

(C) polymerizable compound

(D) polymerization initiator

(E) solvent

[2] The photosensitive resin composition as described in [1] whose (B) is a copolymer containing the structural unit derived from at least 1 sort (s) further selected from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride.

[3] The photosensitive resin composition according to [1] or [2], wherein (C) is a polymerization initiator containing an oxime compound.

[4] [1] The pattern formed from the photosensitive resin composition in any one of [3].

[5] [1] The inkjet partition formed from the photosensitive resin composition in any one of [3].

[6] A display device comprising at least one member selected from the group consisting of a pattern as described in [4] and an inkjet partition as described in [5].

According to the photosensitive resin composition of this invention, the pattern excellent in heat resistance can be obtained.

FIG. 1: is sectional drawing which expands and shows typically a part of display apparatus 1 which is an example of the display apparatus of this invention.
FIG. 2 is a plan view schematically showing an enlarged part of the display device 1 which is an example of the display device of the present invention.
3 is a net taper shape when the pattern is used as a partition wall.

The photosensitive resin composition of this invention is a photosensitive resin composition containing (A), (B), (C), (D) and (E).

(A) Structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and C2-C? Copolymer containing a structural unit derived from the unsaturated compound which has a cyclic ether structure of 4, but does not have a structural unit derived from the unsaturated compound which has a C4-6 perfluoroalkyl group.

(Hereinafter may be called `` resin (A) '')

(B) 4 carbon atoms? A polymer containing a structural unit derived from an unsaturated compound having a perfluoroalkyl group of 6 (hereinafter referred to as "resin (B)")

(C) polymerizable compound

(D) polymerization initiator

(E) solvent

Moreover, the photosensitive resin composition of this invention differs from resin (A) and resin (B) (it may be called "resin (A1)" hereafter), a polymerization start adjuvant (D1), a polyfunctional thiol compound (T), and You may contain at least 1 sort (s) chosen from the group which consists of surfactant (F).

In addition, in this specification, the compound illustrated as each component can be used individually or in combination unless there is particular notice.

The photosensitive resin composition of this invention contains resin (A). As the resin (A),

Resin (A-1): At least 1 sort (a) (Hereinafter, it may be called "(a)") chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and carbon number 2? A copolymer obtained by polymerizing an unsaturated compound (b) having a cyclic ether structure of 4 (hereinafter sometimes referred to as "(b)"),

Resin (A-2): Monomer (c) copolymerizable with (a) and (b) (but does not have a C2-4 cyclic ether structure) (hereinafter may be referred to as "(c)") And copolymers formed by polymerizing (a) and (b). Provided that (a), (b) and (c) have 4 to 4 carbon atoms; It does not have a perfluoroalkyl group of 6.

As resin (A), resin (A-1) is preferable.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid and p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2- N, 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methyl ratio Bicyclo unsaturated compounds containing carboxyl groups, such as cyclo [2.2.1] hepto-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride Unsaturated dicarboxylic anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride (hymic acid anhydride);

Unsaturated mono [(meth) acryloyloxyalkyl of bivalent or more polyvalent carboxylic acids, such as monosuccinate mono [2- (meth) acryloyloxyethyl] and phthalate mono [2- (meth) acryloyloxyethyl] ] Esters;

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

Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in terms of copolymerization reactivity and alkali solubility.

In this specification, "(meth) acrylic acid" represents at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid. Notation, such as "(meth) acryloyl" and "(meth) acrylate", has the same meaning.

(b) has 2? It is an unsaturated compound which has a cyclic ether structure of 4 (for example, at least 1 sort (s) chosen from the group which consists of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring), Preferred are monomers having a cyclic ether structure of 4 and an ethylenically unsaturated double bond, and each having 2 to 4 carbon atoms. More preferred are monomers having a cyclic ether structure of 4 and a (meth) acryloyloxy group.

As (b), it is an unsaturated compound (b1) (henceforth "(b1)" hereafter) which has an oxiranyl group, and an unsaturated compound (b2) which has an oxetanyl group (hereinafter "(b2)"). The unsaturated compound (b3) (Hereinafter, it may be called "(b3)") which has a tetrahydrofuryl group, etc. are mentioned.

 As (b1), unsaturated compound (b1-1) (Hereinafter, it may be called "(b1-1)") which has a structure in which a linear or branched chain unsaturated aliphatic hydrocarbon group is epoxidized, unsaturated alicyclic type The unsaturated compound (b1-2) (Hereinafter, it may be called "(b1-2)") in which a hydrocarbon has the structure epoxidized is mentioned.

As (b1), the monomer which has an oxiranyl group and a (meth) acryloyloxy group is preferable, and the monomer which has the structure which epoxidized unsaturated alicyclic hydrocarbon and the (meth) acryloyloxy group is more preferable. If it is these monomers, the storage stability of the photosensitive resin composition is excellent.

Specific examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycy Dyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis ( Glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxy Methyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) Styrene, the compound of Unexamined-Japanese-Patent No. 7-248625, etc. are mentioned.

Examples of (b1-2) include vinylcyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane (eg, ceoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexyl Methyl acrylate (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.) ), A compound represented by formula (I), a compound represented by formula (II), and the like.

[In Formula (I) and Formula (II), R <^1> and R <^2> is a hydrogen atom or C1-C? The alkyl group of 4 is represented, and the hydrogen atom contained in this alkyl group may be substituted by the hydroxy group.

X ¹ and X ² represent a single bond, -R ^3- , * -R ³ -O-, * -R ³ -S-, * -R ³ -NH-.

R ³ has 1? The alkanediyl group of 6 is shown.

* Represents the number of bonds with O]

Carbon number 1? As an alkyl group of 4, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- butyl group etc. are mentioned specifically ,.

As an alkyl group substituted by the hydroxy group, a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy A hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. are mentioned.

As R <^1> and R <^2> , Preferably, a hydrogen atom, a methyl group, a hydroxymethyl group, 1-hydroxyethyl group, and 2-hydroxyethyl group are mentioned, More preferably, a hydrogen atom and a methyl group are mentioned.

Examples of the alkanediyl group include a methylene group, an ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane- 1, 6- diyl group etc. are mentioned.

Roneun X ¹ and X ^2, and preferably include a single bond, methylene group, ethylene group, * -CH ₂ -O- (* indicates the number of engagement with the O) group, * -CH ₂ CH ₂ -O- group and, more preferably, there may be mentioned a single bond, * -CH ₂ CH ₂ -O- group.

As a compound represented by Formula (I), it is a formula (I-1)? The compound etc. which are represented by any of formula (I-15) are mentioned. Preferably, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), and formula (I-11)? The compound represented by either of formula (I-15) is mentioned. More preferably, the compound represented by any of Formula (I-1), Formula (I-7), Formula (I-9), and Formula (I-15) is mentioned.

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

The compound represented by Formula (I) and the compound represented by Formula (II) can be used independently, respectively. Moreover, they can be mixed in arbitrary ratios. When mixing, the mixing ratio is in molar ratio, Preferably it is Formula (I): Formula (II), and it is 5:95? 95: 5, more preferably 10: 90? 90: 10, particularly preferably 20: 80? 80: 20.

As (b2), the monomer which has an oxetanyl group and a (meth) acryloyloxy group is preferable. Examples of (b2) include 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, and 3-methyl-3- ( Met) acryloyloxyethyl oxetane, 3-ethyl-3- (meth) acryloyloxyethyl oxetane, etc. are mentioned.

As (b3), the monomer which has a tetrahydrofuryl group and a (meth) acryloyloxy group is preferable.

Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (c), (meth) acrylic acid ester, N-substituted maleimide, unsaturated dicarboxylic acid diester, alicyclic unsaturated compound, styrene, another vinyl compound, etc. are mentioned.

As (meth) acrylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- butyl (meth) acrylate, etc. Alkyl esters of;

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) acrylate), dicyclopentanyloxyethyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (in this technical field, as a conventional name, " Cycloalkyl esters such as dicyclopentenyl (meth) acrylate '' and isobornyl (meth) acrylate;

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

Aryl and aralkyl ester, such as phenyl (meth) acrylate and benzyl (meth) acrylate, etc. are mentioned.

Examples of the unsaturated dicarboxylic acid diesters include diethyl maleate, diethyl fumarate, diethyl itaconate, and the like.

As N-substituted maleimide, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimidyl-3- maleimide benzoate, N-succinimidyl-4-malee Midbutylate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide and the like.

Examples of the alicyclic unsaturated compounds include bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene and 5-ethylbicyclo [2.2.1] hepto-2 -Ene, 5-hydroxybicyclo [2.2.1] hepto-2-ene, 5-hydroxymethylbicyclo [2.2.1] hepto-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hepto-2-ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6-dihydroxy Cibicyclo [2.2.1] hepto-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hepto-2-ene, 5,6-di (2'-hydroxyethyl) ratio Cyclo [2.2.1] hepto-2-ene, 5,6-dimethoxybicyclo [2.2.1] hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl-5- Methylbicyclo [2.2.1] hepto-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hepto -2- , 5-phenoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hepto-2-ene, 5,6-bis Bicyclo unsaturated compounds, such as (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene, etc. are mentioned.

As styrene, styrene, (alpha) -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy styrene, etc. are mentioned.

Other vinyl compounds include (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like. Can be mentioned.

As (c), styrene, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, bicyclo [2.2.1] hepto-2-ene, etc. are preferable at the point of copolymerization reactivity and alkali solubility. .

In resin (A-1), it is preferable that the ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total mole number of the structural unit which comprises resin (A-1).

structural unit derived from (a); 5? 60 mol% (more preferably 10-50 mol%)

structural unit derived from (b); 40? 95 mol% (more preferably 50-90 mol%)

If the ratio of the structural unit of resin (A-1) exists in said range, the storage stability of the photosensitive resin composition, the developability at the time of forming a pattern from the photosensitive resin composition, and the solvent resistance and heat resistance of the coating film and pattern obtained are And mechanical strength tends to be good.

As resin (A-1), resin (A-1) whose (b) is (b1) is preferable, and resin (A-1) whose (b) is (b1-2) is more preferable.

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

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are put in a reaction vessel, and, for example, by replacing with oxygen in the atmosphere by nitrogen, it is made into a deoxygen atmosphere and heated while stirring. And a method of keeping warm. In addition, the polymerization initiator, the solvent, etc. which are used here are not specifically limited, Any of the thing normally used in the said field | area can be used. For example, as a polymerization initiator, an azo compound (2,2'- azobisisobutyronitrile, 2,2'- azobis (2, 4- dimethylvaleronitrile), etc.) and an organic peroxide (benzoyl peroxide) Etc.) What is necessary is just to melt | dissolve each monomer as a solvent, The solvent etc. which are mentioned later as a solvent (E) of the photosensitive resin composition can be used. In order to adjust the molecular weight of resin obtained, you may add a chain transfer agent at the time of a polymerization reaction. Examples of the chain transfer agent include n-butanethiol, tert-butanethiol, n-dodecanethiol, 2-sulfanylethanol, thioglycolic acid, ethyl thioglycolate, 2-ethylhexyl thioglycolate, methoxybutyl thioglycolate, Thiols, such as 3-sulfanyl propionic acid and a sulfanyl group containing silicone (KF-2001: Shin-Etsu Chemical make); Halogenated alkyls, such as chloroform, carbon tetrachloride, and carbon tetrabromide, etc. are mentioned.

In addition, the obtained copolymer may use the solution after reaction as it is, the solution which concentrated or diluted may be used, and what was taken out as solid (powder) by methods, such as reprecipitation, may be used. In particular, the solution after reaction can be used as it is by using the same solvent as the solvent (E) mentioned later as a solvent at the time of this superposition | polymerization, and a manufacturing process can be simplified.

In resin (A-2), it is preferable that the ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total number of moles of all the structural units which comprise resin (A-2).

structural unit derived from (a); 2 ? 40 mol% (more preferably 5-35 mol%)

structural unit derived from (c); One ? 65 mol% (more preferably 1-60 mol%)

structural unit derived from (b); 2 ? 95 mol% (more preferably 5-80 mol%)

When the ratio of the structural unit of resin (A-2) exists in the said range, the storage stability of the photosensitive resin composition, the developability at the time of forming a pattern from the photosensitive resin composition, and the solvent resistance and heat resistance of the coating film and pattern obtained are obtained. And mechanical strength tends to be good.

As resin (A-2), resin (A-2) whose (b) is (b1) is preferable, and resin (A-2) whose (b) is (b1-2) is more preferable.

Resin (A-2) can be manufactured by the method similar to resin (A-1).

Preferably the weight average molecular weight of polystyrene conversion of resin (A) is 3,000? 100,000, more preferably 5,000? 50,000. When the weight average molecular weight of resin (A) exists in the said range, it exists in the tendency which is excellent in applicability | paintability, and it is hard to produce the film | membrane decrease of an exposed part at the time of image development, and it is easy to remove a non-exposed part by image development.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (A) is preferably 1.1? 6.0, more preferably 1.2? 4.0. When molecular weight distribution exists in the said range, it exists in the tendency which is excellent in developability.

The acid value of the resin (A) is 20? 150 mgKOH / g, preferably 40? 135 mgKOH / g, more preferably 50? 135 mgKOH / g. The acid value is a value measured by the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained by titration using an aqueous potassium hydroxide solution.

The content of the resin (A) is preferably 5? To the total amount of the resin (A), the resin (A1) and the polymerizable compound (C). 95 mass%, More preferably, it is 20? 80 mass%, Especially preferably, it is 40? 60 mass%. When content of resin (A) exists in said range, there exists a tendency for the developability of the photosensitive resin composition, the adhesiveness of the pattern obtained, solvent resistance, and a mechanical characteristic to become favorable.

The photosensitive resin composition of this invention contains resin (B). The resin (B) has 4 carbon atoms? It is a polymer containing the structural unit derived from the unsaturated compound (d) (henceforth "(d)" hereafter) which has 6 perfluoroalkyl groups.

As (d), the compound represented by a formula (d-0) is mentioned.

[In formula (d-0), R <^f> is a C4? 6 represents a perfluoroalkyl group.

R ^d represents a hydrogen atom, a halogen atom, a cyano group, a phenyl group, a benzyl group, or a C 1? The alkyl group of 21 may be represented and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom or a hydroxy group.

X ^d is a single bond, carbon number 1? 10 divalent aliphatic hydrocarbon groups, 3? 10 divalent alicyclic hydrocarbon groups or 6? Represents a divalent aromatic hydrocarbon group of 12, and -CH ₂ -contained in the aliphatic hydrocarbon group and the alicyclic hydrocarbon group is substituted with -O-, -CO-, -NR ^e- , -S- or -SO _2- May be]

R ^f has 4? It is a perfluoroalkyl group of 6, and a perfluoro butyl group and a perfluorohexyl group are preferable.

^{Carbon number} in R ^d ? Examples of the alkyl group of 21 include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. Linear alkyl groups;

Isopropyl group, isobutyl group, sec-butyl group, isopentyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethyl Butyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl , 1-propylbutyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group, 1-ethylhexyl group, 2 -Ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 2-propylpentyl group, 1-butylbutyl group, 1-butyl-2-methylbutyl group, 1-butyl-3-methylbutyl group, tert -Butyl group, 1,1-dimethylpropyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethyl-2- Methylpropyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 1,4-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl Tyl group, 2,4-dimethyl pentyl group, 3,3-dimethyl pen And the like group, a 3,4-dimethyl pentyl group, 1-ethyl-1-methylbutyl group, 2-ethyl-3-methyl-branched alkyl group such as a butyl group.

As R ^d , a hydrogen atom, a halogen atom and a methyl group are preferable.

^{Carbon number} at X ^d ? Examples of the 10 divalent aliphatic hydrocarbon group include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group and butane-1,3-diyl group Alkanediyl groups such as butane-1,2-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, and octane-1,8-diyl group Can be mentioned.

^{Carbon number} at X ^d ? Examples of the divalent alicyclic hydrocarbon group for 10 include a cyclopropanediyl group, a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group and a cyclodecanediyl group.

^{Carbon number} at X ^d ? As a bivalent aromatic hydrocarbon group of 12, a phenylene group, a naphthalenediyl group, etc. are mentioned.

X ^{d in} which -CH ₂ -is substituted with -O-, -CO-, -NR ^e- , -S- or -SO ₂ -is, for example, a formula (xd-1)? The group represented by a formula (xd-10), etc. are mentioned.

As X ^d , C 1? Alkanediyl group of 6 is preferable, and an ethylene group is more preferable.

As (d), the compound represented by a formula (d-1) is preferable.

[In formula (d-1), ^Rh is C4? 6 represents a perfluoroalkyl group.

R ^g Represents a hydrogen atom, a halogen atom or a methyl group]

As a compound represented by a formula (d-0), it is a compound (d-1)? Compound (d-94) etc. are mentioned. In the table, the formula number shown in the column X ^d represents the formula number of the group exemplified above. In addition, for example, the compound (d-1) is a compound represented by the following formula (d-1).

As resin (B), it is preferable that it is resin containing the structural unit derived from (d), and the structural unit derived from (a), and the structural unit derived from (d), and the structural unit derived from (a), It is more preferable that it is resin containing the structural unit derived from (b). Since resin (B) contains the structural unit derived from (a), since developability is excellent, there exists a tendency for the nonuniformity resulting from a residue and image development to be suppressed. When resin (B) contains the structural unit derived from (b), there exists a tendency which is excellent in solvent resistance. In addition, the resin (B) may include a structural unit derived from (c). The same thing as the above is mentioned as (a), (b) and (c).

When resin (B) is a copolymer of (a) and (d), it is preferable that ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total number of moles of the structural unit which comprises resin (B). Do.

structural unit derived from (a); 5? 40 mass% (more preferably 10-30 mass%)

structural unit derived from (d); 60? 95 mass% (more preferably 70-90 mass%)

When resin (B) is a copolymer of (a), (b) and (d), the ratio of the structural unit derived from each monomer is the following ranges with respect to the total number of moles of the structural unit which comprises resin (B). It is desirable to be at.

structural unit derived from (a); 5? 40 mass% (more preferably 10-30 mass%)

structural unit derived from (b); 5? 80 mass% (more preferably 10-70 mass%)

structural unit derived from (d); 10? 80 mass% (more preferably 20-70 mass%)

When resin (B) is a copolymer of (a), (b), (c) and (d), the ratio of the structural unit derived from each monomer is with respect to the total number of moles of the structural unit which comprises resin (B). It is preferable to exist in the following ranges.

structural unit derived from (a); 5? 40 mass% (more preferably 10-30 mass%)

structural unit derived from (b); 5? 70 mass% (more preferably 10-60 mass%)

structural unit derived from (c); 10? 50 mass% (more preferably 20-40 mass%)

structural unit derived from (d); 10? 80 mass% (more preferably 20-70 mass%)

When the ratio of each structural unit exists in the said range, it exists in the tendency which is excellent in liquid repellency and developability.

Preferably the weight average molecular weight of polystyrene conversion of resin (B) is 3,000? 20,000, more preferably 5,000? 15,000. When the weight average molecular weight of resin (A) exists in the said range, it exists in the tendency which is excellent in applicability | paintability, and it is hard to produce the film | membrane decrease of an exposed part at the time of image development, and it is easy to remove a non-exposed part by image development.

The acid value of the resin (B) is 20? 200 mgKOH / g, Preferably it is 40? 150 mgKOH / g.

The content of the resin (B) is preferably 0.001? To 100 parts by mass of the total amount of the resin (A), the resin (A1) and the polymerizable compound (C). 10 parts by mass, more preferably 0.01? 5 parts by mass. When content of resin (B) exists in the said range, there exists a tendency for the developability at the time of pattern formation and the pattern obtained to be excellent in liquid repellency.

The photosensitive resin composition of this invention may contain resin (A1). As the resin (A1),

Resin (A1-1): copolymer formed by polymerizing (a) and (c),

Resin (A1-2): Resin obtained by making (b) react with the copolymer formed by superposing | polymerizing (a) and (c),

Resin (A1-3): Resin obtained by making (a) react with the copolymer formed by superposing | polymerizing (b) and (c), etc. are mentioned.

In resin (A1-1), it is preferable that the ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total number of moles of all the structural units which comprise resin (A1-1).

structural unit derived from (a); 2 ? 40 mol% (more preferably 5-35 mol%)

structural unit derived from (c); 60? 98 mol% (more preferably 65-95 mol%)

If the ratio of the structural unit of resin (A1-1) exists in said range, the storage stability of the photosensitive resin composition, the developability at the time of forming a pattern from the photosensitive resin composition, and the solvent resistance of the coating film and pattern obtained are favorable. There is a tendency to lose.

Resin (A1-1) can be manufactured by the same method as resin (A-1).

Resin (A1-2) is resin obtained by making (b) react with the copolymer of (a) and (c).

Resin (A1-2) can be manufactured through a two-step process, for example. Also in this case, the method as described in the above-mentioned document "Experimental method of polymer synthesis" (Otsu Takayuki Chemical Co., Ltd., first chemical first edition March 1, 1972), Japanese Unexamined Patent Publication No. 2001-89533 It can manufacture with reference to the method etc. which were described in.

First, as a 1st step, it carries out similarly to the manufacturing method of resin (A-1) mentioned above, and obtains the copolymer of (a) and (c).

In this case, similarly to the above, the obtained copolymer may use the solution after reaction as it is, the concentrated or diluted solution may be used, and what was taken out as solid (powder) by methods, such as reprecipitation, may be used. Moreover, it is preferable to set it as the weight average molecular weight and molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of polystyrene conversion similar to the above.

However, it is preferable that the ratio of the structural unit derived from (a) and (c) exists in the following ranges with respect to the total mole number of all the structural units which comprise said copolymer.

structural unit derived from (a); 5? 50 mol% (more preferably 10-45 mol%)

structural unit derived from (c); 50? 95 mol% (more preferably 55-90 mol%)

Next, as a 2nd step, a part of carboxylic acid and carboxylic anhydride of (a) derived from the obtained copolymer is made to react with the cyclic ether of (b) mentioned above. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) or (b2) is preferably used for the resin (A1-2), and (b1-1) This is more preferable.

Specifically, following the above, the atmosphere in the flask is replaced with nitrogen by air, and the molar number of (a) is 5? 80 mol% (b) and the reaction catalyst (for example, tris (dimethylaminomethyl) phenol etc.) of a carboxy group and a cyclic ether are 0.001? With respect to the total amount of (a), (b) and (c). 5 mass% and a polymerization inhibitor (for example, hydroquinone, etc.) with respect to the total amount of (a), (b), and (c) 0.001? 5 mass% was put in a flask, and 60? At 130 ° C., 1? It is made to react for 10 hours and resin (A1-2) can be obtained. 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 this case, the number of moles of (b) is 10? To the number of moles of (a). It is preferable to set it as 75 mol%, More preferably, it is 15? 70 mol%. By setting it as this range, there exists a tendency for the balance of the storage stability of the photosensitive resin composition, the developability at the time of forming a pattern from the photosensitive resin composition, and the solvent resistance, heat resistance, mechanical strength, and the sensitivity of the coating film and pattern obtained to become favorable. .

Resin (A1-3) is obtained as a 1st step similarly to the manufacturing method of resin (A-1) mentioned above, and obtains the copolymer of (b) and (c).

In this case, similarly to the above, the obtained copolymer may use the solution after reaction as it is, the concentrated or diluted solution may be used, and what was taken out as solid (powder) by methods, such as reprecipitation, may be used.

It is preferable that the ratio of the structural unit derived from (b) and (c) exists in the following ranges with respect to the total mole number of all the structural units which comprise said copolymer.

structural unit derived from (b); 5? 95 mol% (more preferably 10-90 mol%)

structural unit derived from (c); 5? 95 mol% (more preferably 10-90 mol%)

Moreover, the carboxylic acid or carboxylic anhydride which (a) has in the cyclic ether derived from (b) in the copolymer of (b) and (c) similarly to the manufacturing method of resin (A1-2) It can be obtained by reacting. You may make carboxylic anhydride react with the hydroxyl group which arises by reaction of a cyclic ether, carboxylic acid, or carboxylic anhydride again.

The usage-amount of (a) made to react with said copolymer is 5? With respect to the number-of-moles of (b). It is preferable that it is 80 mol%. Since the reactivity of a cyclic ether is high and it is hard to remain unreacted (b), as (b), (b1) is preferable and (b1-1) is preferable.

Preferably the weight average molecular weight of polystyrene conversion of resin (A1) is 3,000? 100,000, more preferably 5,000? 50,000. When the weight average molecular weight of resin (A) exists in the said range, it exists in the tendency which is excellent in applicability | paintability, and it is hard to produce the film | membrane decrease of an exposed part at the time of image development, and it is easy to remove a non-exposed part by image development.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of resin (A1) becomes like this. 6.0, more preferably 1.2? 4.0. When molecular weight distribution exists in the said range, it exists in the tendency which is excellent in developability.

The acid value of the resin (A1) is 20? 150 mgKOH / g, preferably 40? 135 mgKOH / g, more preferably 50? 135 mgKOH / g.

The content of the resin (A1) is preferably 0? With respect to the total amount of the resin (A) and the resin (A1). 80 mass%, More preferably, it is 0? 50 mass%. When content of resin (A1) exists in the said range, a pattern can be formed with high sensitivity and it is excellent in developability.

The photosensitive resin composition of this invention contains a polymeric compound (C).

A polymerizable compound (C) is a compound which can superpose | polymerize with the active radical which generate | occur | produced from the polymerization initiator (D), For example, it is a compound etc. which have an ethylenically unsaturated bond, Preferably it is a (meth) acrylic acid ester compound.

As a polymeric compound (C) which has one ethylenically unsaturated bond, the thing similar to the compound illustrated as said (a), (b) and (c) is mentioned, Especially, (meth) acrylic acid ester is preferable. Do.

As a polymeric compound (C) which has two ethylenically unsaturated bonds, 1, 3- butanediol di (meth) acrylate, 1, 3- butanediol (meth) acrylate, 1, 6- hexanediol di (meth) acryl 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, bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (Meth) acrylate, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.

Examples of the polymerizable compound (C) having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxyethyl) isocyanurate tree. (Meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, propoxylated trimethylol propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylic Elate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol A reaction product of hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri (meth) acrylate and acid anhydride, Reactant of dipentaerythritol penta (meth) acrylate and acid anhydride, tripentaerythritolhepta (meth) acrylate and acid anhydride caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified pentaerythritol tree ( (Meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth ) Acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified tripentaerythritol tetra (meth) acrylate, caprolactone modified tripentaerythritol penta (meth) acrylate, caprolactone modified tree Pentaerythritol hexa (meth) acrylate, caprolactone modified tripentaerythritol hepta (meth ), A reaction product of caprolactone-modified tripentaerythritol octa (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride, and caprolactone-modified dipentaerythritol penta (meth) acrylate The reaction product of an acid anhydride, caprolactone modified tripentaerythritol hepta (meth) acrylate, an acid anhydride, etc. are mentioned. Especially, trifunctional or more than trifunctional photopolymerizable compound (C) is preferable and dipentaerythritol hexa (meth) acrylate is more preferable.

The content of the polymerizable compound (C) is preferably 5? To the total amount of the resin (A), the resin (A1) and the polymerizable compound (C). 95 mass%, More preferably, it is 20? 80 mass%. When content of a polymeric compound (C) exists in the said range, there exists a tendency for the sensitivity and the intensity | strength, smoothness, and reliability of the pattern obtained to become favorable.

The photosensitive resin composition of this invention contains a polymerization initiator (D). As a polymerization initiator (D), if it is a compound which can start superposition | polymerization by action of light or a heat | fever, it will not specifically limit, A well-known polymerization initiator can be used.

As a polymerization initiator (D), an alkylphenone compound, a biimidazole compound, a triazine compound, an acylphosphine oxide compound, and an oxime compound are mentioned, for example. Moreover, you may use the optical and / or thermal cationic polymerization initiator (for example, what consists of onium cation and an anion derived from Lewis acid) of Unexamined-Japanese-Patent No. 2008-181087. Especially, it is preferable that it is at least 1 sort (s) chosen from the group which consists of a biimidazole compound, an alkyl phenone compound, and an oxime ester compound, and it is especially preferable that it is an oxime ester compound. If it is a polymerization initiator containing these compounds, it exists in the tendency to become especially high sensitivity, and it is preferable.

As said alkylphenone compound, diethoxy acetophenone, 2-hydroxy-2-methyl-1- phenyl propane- 1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy Ethoxy) phenyl] -2-methylpropan-1-one, 2-hydroxy-1- ｛4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2- Methyl-propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-morpholino-1- (4-methylsulfanylphenyl) -2-methylpropan-1-one, 2-dimethylamino-2- Benzyl-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (2-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one, 2- Dimethylamino-2- (3-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholino Phenyl) butan-1-one, 2-dimethylamino-2- (2-ethylbenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (2-propylbenzyl ) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (2-butylbenzyl) -1- (4-morpholino Yl) butan-1-one, 2-dimethylamino-2- (2,3-dimethylbenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (2, 4-dimethylbenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (2-chlorobenzyl) -1- (4-morpholinophenyl) butan-1- On, 2-dimethylamino-2- (2-bromobenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (3-chlorobenzyl) -1- ( 4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-chlorobenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (3-bromobenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-bromobenzyl) -1- (4-morpholinophenyl) butane -1-one, 2-dimethylamino-2- (2-methoxybenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (3-methoxybenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-methoxybenzyl) -1- (4-morpholinophenyl) butan-1-one, 2- Dimethylamino-2- (2-methyl-4-methoxybenzyl)- 1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (2-methyl-4-bromobenzyl) -1- (4-morpholinophenyl) butan-1-one , 2-dimethylamino-2- (2-bromo-4-methoxybenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4 And oligomers of-(1-methylvinyl) phenyl] propan-1-one.

As said biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenylbiimidazole, 2,2'-bis (2,3-dichloro Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see, eg, 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-chloro Phenyl) -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 The imidazole compound (for example, Unexamined-Japanese-Patent No. 7-10913 etc.) etc. which the phenyl group of the 4 ', 5, and 5'-positions are substituted by the carboalkoxy group are mentioned. Preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.

As said triazine 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 and the like.

2,4,6-trimethylbenzoyldiphenylphosphine oxide etc. are mentioned as said acylphosphine oxide compound.

As said oxime ester compound, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-ethoxycarbonyloxy-1-phenylpropan-1-one- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclo Fentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine and the like. You may use commercial items, such as Irgacure (registered trademark) OXE-01, OXE-02 (above, Chiba Japan Corporation), and N-1919 (made by ADEKA Corporation).

Moreover, as a polymerization initiator (D), Benzoin type compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrene quinone, 2-ethylanthraquinone and camphor quinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. are mentioned. It is preferable to use these in combination with the polymerization start adjuvant (D1) mentioned later.

Moreover, you may use the photoinitiator described in Unexamined-Japanese-Patent No. 2002-544205 as a polymerization initiator which has group which can cause chain transfer.

As a polymerization initiator which has group which can cause said chain transfer, it is following formula (a)? The compound of (f) is mentioned.

The polymerization initiator which has group which can cause said chain transfer can be used also as a component (c) which comprises resin (A).

In the photosensitive resin composition of this invention, a polymerization start adjuvant (D1) can be used with the polymerization initiator (D) mentioned above. A polymerization start adjuvant (D1) is a compound or sensitizer used in combination with a polymerization initiator (D), and used in order to accelerate superposition | polymerization of the polymeric compound in which superposition | polymerization was started with a polymerization initiator. As a polymerization start adjuvant (D1), it is a following formula (III)? The compound represented by Formula (V), a thioxanthone compound, an amine compound, a carboxylic acid compound, etc. are mentioned.

[In the formula (III), the dotted line represented by W ¹ has 6 to 6 carbon atoms which may be substituted with a halogen atom. 12 aromatic rings.

Y ¹ represents -O- or -S-.

R ⁴ has 1? 6 monovalent saturated hydrocarbon group is shown.

R ⁵ may be substituted with a halogen atom. Carbon number 6? Which may be substituted with 12 monovalent saturated hydrocarbon group or halogen atom; 12 represents an aryl group]

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

6 carbon atoms? As an aromatic ring of 12, a benzene ring, a naphthalene ring, etc. are mentioned.

Carbon number which may be substituted by halogen atom; Examples of the 12 aromatic ring include a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring, a pentylbenzene ring, a hexylbenzene ring, a cyclohexylbenzene ring, and a chlorobenzene ring. , Dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene ring, bromonaphthalene ring and the like.

Carbon number 1? As the monovalent saturated hydrocarbon group of 6, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, 2-methylpropyl group, tert-butyl group, n- Pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, n-hexyl group, Cyclohexyl group etc. are mentioned.

Carbon number which may be substituted by halogen atom; As a monovalent saturated hydrocarbon group of 12, it is the said C1-C, for example. In addition to the monovalent saturated hydrocarbon group of 6, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, 1-chlorobutyl group, 2-chlorobutyl group, 3-chlorobutyl group, etc. are mentioned.

Carbon number which may be substituted by halogen atom; As the aryl group of 12, a phenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a dibromophenyl group, a chlorobromophenyl group, a biphenyl group, a chlorobiphenyl group, a dichlorobiphenyl group, a bromophenyl group, a dibromophenyl group, a naphthyl group And chloronaphthyl group, dichloronaphthyl group, bromonaphthyl group, dibromonaphthyl group and the like.

Specifically as a compound represented by Formula (III),

2- [2-oxo-2- (2-phenyl) ethylidene] -3-methylnaphtho [2,1-d] thiazoline, 2- [2-oxo-2- (2-phenyl) ethylidene] 3-methylnaphtho [1,2-d] thiazoline, 2- [2-oxo-2- (2-phenyl) ethylidene] -3-methylnaphtho [2,3-d] thiazoline, 2 -[2-oxo-2- (2-naphthyl) ethylidene] -3-methylbenzothiazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methylbenzothiazoline , 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-phenylbenzothiazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene]- 3-methyl-5-phenylbenzothiazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-fluorobenzothiazoline, 2- [2-oxo-2 -(1-naphthyl) ethylidene] -3-methyl-5-fluorobenzothiazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-chlorobenzo Thiazolin, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-chlorobenzothiazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene ] -3-methyl-5-bromobenzothiazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-bromobenzo Thiazolin, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methylbenzothiazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3- Methyl-5-phenylbenzothiazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methylnaphtho [2,1-d] thiazoline, 2- [2-oxo- 2- (2-naphthyl) ethylidene] -3-methylnaphtho [1,2-d] thiazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methylnaph To [2,1-d] thiazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methylnaphtho [1,2-d] thiazoline, 2- [2- Oxo-2- (4-fluorophenyl) ethylidene] -3-methylnaphtho [2,1-d] thiazoline, 2- [2-oxo-2- (4-fluorophenyl) ethylidene]- 3-methylnaphtho [1,2-d] thiazoline, 2- [2-oxo-2- (2-phenyl) ethylidene] -3-methylnaphtho [2,1-d] oxazoline, 2- [2-oxo-2- (2-phenyl) ethylidene] -3-methylnaphtho [1,2-d] oxazoline, 2- [2-oxo-2- (2-phenyl) ethylidene] -3 -Methylnaphtho [2,3-d] oxazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methylbenzooxazoline, 2- [2-oxo-2- ( 1-naphthyl) ethyl ] -3-methylbenzooxazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-phenylbenzooxazoline, 2- [2-oxo-2- (1 -Naphthyl) ethylidene] -3-methyl-5-phenylbenzooxazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-fluorobenzooxazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-fluorobenzooxazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene]- 3-methyl-5-chlorobenzooxazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-chlorobenzooxazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-bromobenzooxazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-bromobenzo Oxazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methylbenzooxazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3- Methyl-5-phenylbenzooxazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methylnaphtho [2,1-d] oxazoline, 2- [2-oxo- 2- (1-naphthyl) ethylidene] -3-methylnaphtho [1,2-d] oxazoline, 2- [2-jade -2- (4-phenylphenyl) ethylidene] -3-methylnaphtho [2,1-d] oxazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methyl Naphtho [1,2-d] oxazoline, 2- [2-oxo-2- (4-fluorophenyl) ethylidene] -3-methylnaphtho [2,1-d] oxazoline, 2- [ 2-oxo-2- (4-fluorophenyl) ethylidene] -3-methylnaphtho [1,2-d] oxazoline etc. are mentioned.

Of the formula (Ⅳ) and formula (Ⅴ), ring W ^2, W ³ and W ⁴ are independently a ring having 6 to each other? 12 aromatic rings or 2? The heterocyclic ring of 10 is shown, and the hydrogen atom contained in the aromatic ring and this heterocyclic ring may be substituted by the halogen atom. Y ² ? Y ⁵ independently of one another represents -O- or -S-. R ⁶ ? R ⁹ has 1? 12 monovalent saturated hydrocarbon groups or carbon atoms? The aryl group of 12 is represented, and the saturated hydrocarbon group and the hydrogen atom contained in this aryl group are a halogen atom, a hydroxyl group, or a C1-C? May be substituted with 6 alkoxy groups]

6 carbon atoms? As the aromatic ring of 12, the same aromatic ring as exemplified in the formula (III) may be mentioned, and the hydrogen atom contained in the aromatic ring may be optionally substituted with the halogen atom exemplified above.

Carbon number which may be substituted by halogen atom; As a heterocyclic ring of 10, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a pyran ring, etc. are mentioned.

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

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

Examples of the monovalent alkoxy group substituted saturated hydrocarbon group include methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, butoxymethyl group, ethoxyethyl group, ethoxypropyl group, propoxybutyl group and the like. .

As an alkoxy group substituted aryl group, a methoxyphenyl group, an ethoxy naphthyl group, etc. are mentioned.

As a compound represented by Formula (IV) and Formula (V), specifically,

Dialkoxy naphthalenes such as dimethoxynaphthalene, diethoxynaphthalene, dipropoxynaphthalene, diisopropoxynaphthalene and dibutoxynaphthalene;

9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, dipropoxycanthracene, diisopropoxycanthracene , Dibutoxy anthracene, dipentyloxy anthracene, dihexyloxy anthracene, methoxy ethoxy anthracene, methoxy propoxy thracene, methoxy isopropoxy canthracene, methoxy butoxy anthracene, ethoxy propoxy thracene, ethoxy isopro Dialkoxy anthracenes such as oxycanthracene, ethoxy butoxy anthracene, propoxy isopropoxy anthracene, propoxy butoxy anthracene and isopropoxy butoxy anthracene;

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

Etc. can be mentioned.

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

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

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, And aromatic heteroacetic acids such as chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxy acetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxy acetic acid.

As a combination of a polymerization initiator (D) and a polymerization start adjuvant (D1), an acetophenone compound, a thioxanthone compound, an acetophenone compound, and an aromatic amine compound are mentioned, Specifically, 2-morpholino-1- (4-methylsulfanylphenyl) -2-methylpropan-1-one with 2,4-diethyl thioxanthone, 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane-1 -One and 2,4-diethyl thioxanthone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one and 2,4-diethylthione Oxathonone, 2-morpholino-1- (4-methylsulfanylphenyl) -2-methylpropane-1-one, 2-isopropyl thioxanthone and 4-isopropyl thioxanthone, 2-morpholino -1- (4-methylsulfanylphenyl) -2-methylpropan-1-one with 4,4'-bis (diethylamino) benzophenone, 2-dimethylamino-2-benzyl-1- (4-mor Polynophenyl) butan-1-one and 4,4'-bis (diethylamino) benzophenone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) butane- One- And 4,4'-bis (diethylamino) benzophenone etc. are mentioned.

Especially, the combination of an acetophenone compound and a thioxanthone compound is preferable, and 2-morpholino-1- (4-methylsulfanylphenyl) -2-methylpropan-1-one and 2,4-diethyl thione More preferred are oxatone, 2-morpholino-1- (4-methylsulfanylphenyl) -2-methylpropan-1-one, 2-isopropyl thioxanthone and 4-isopropyl thioxanthone. If it is a combination of these, a pattern with high sensitivity and high visible light transmittance will be obtained.

The content of the polymerization initiator (D) is preferably 0.5? To 100 parts by mass of the total amount of the resin (A), the resin (A1) and the polymerizable compound (C). 30 parts by mass, more preferably 1? It is 20 mass parts, More preferably, it is 1? 10 parts by mass. If content of a polymerization initiator (D) exists in said range, a pattern can be obtained with high sensitivity.

The usage-amount of a polymerization start adjuvant (D1) becomes like this. Preferably it is 0.1? With respect to 100 mass parts of total amounts of resin (A), resin (A1), and a polymeric compound (C). 10 parts by mass, more preferably 0.3? 7 parts by mass. When the quantity of a polymerization start adjuvant (D1) exists in said range, a pattern can be obtained with high sensitivity, and the pattern obtained has favorable shape.

The photosensitive resin composition of this invention contains a solvent (E).

Examples of the solvent that can be used in the present invention include ester solvents (solvents containing -COO- in the molecule and not containing -O-) and ether solvents other than the ester solvents (-O- in the molecule). A solvent containing no -COO-, an ether ester solvent (a solvent containing -COO- and -O- in the molecule), a ketone solvent other than the ester solvent (-CO- in the molecule, and -COO Solvents that do not contain-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.

Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate Butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, and the like.

As an ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran , 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phentol, methyl an Or a brush.

As an ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, 3-methoxy propionate, ethyl 3-methoxy propionate, 3-ethoxy propionic acid Methyl, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2 -Methyl methyl propionate, 2-ethoxy-2-methyl ethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate , Di, and the like ethylene glycol monobutyl ether acetate.

As a ketone solvent, 4-hydroxy-4-methyl- 2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2- pentanone, Cyclopentanone, cyclohexanone, isophorone, etc. are mentioned.

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

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

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

You may use these solvents individually or in combination of 2 or more types.

The organic solvent whose boiling point in 1 atm is 120 degreeC or more and 180 degrees C or less is preferable among the said solvents from an applicability | paintability and a drying property. Especially, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-ethoxy propionate ethyl, diethylene glycol methyl ethyl ether, 3-methoxy butyl acetate, 3-methoxy- 1-butanol, etc. are preferable. If the solvent (E) is such a solvent, the nonuniformity at the time of application | coating can be suppressed and the flatness of a coating film can be made favorable.

The content of the solvent (E) in the photosensitive resin composition of the present invention is preferably 60? To the total amount of the photosensitive resin composition. 95 mass%, More preferably, it is 70? 90 mass%. In other words, the solid content of the photosensitive resin composition becomes like this. 40 mass%, More preferably, it is 10? 30 mass%. When content of a solvent (E) exists in the said range, there exists a tendency for the flatness of the film | membrane which applied the photosensitive resin composition to be high. Here, solid content means the quantity remove | excluding the solvent (E) from the photosensitive resin composition.

Moreover, the photosensitive resin composition of this invention may contain the polyfunctional thiol compound (T) further. A polyfunctional thiol compound (T) means the compound which has 2 or more sulfanyl group (-SH) in a molecule | numerator. In particular, when the compound which has a 2 or more sulfanyl group couple | bonded with the carbon atom derived from an aliphatic hydrocarbon group, there exists a tendency for the sensitivity of the photosensitive resin composition of this invention to become high.

Specific examples of the polyfunctional thiol compound (T) include hexanedithiol, decandithiol, 1,4-bis (methylsulfanyl) benzene, butanediolbis (3-sulfanylpropionate) and butanediolbis (3- Sulfanyl acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanylpropionate), trimethylolpropane tris (3-sulfanylprop Cypionate), trimethylol propane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), tris hydroxyethyl tris ( 3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), 1, 4-bis (3-sulfanyl butyloxy) butane, etc. are mentioned.

The content of the polyfunctional thiol compound (T) is preferably 0.1? To 100 parts by mass of the polymerization initiator (D). 10 parts by mass, more preferably 0.5? 7 parts by mass. When content of a polyfunctional thiol compound (T) exists in said range, since the sensitivity of the photosensitive resin composition becomes high and developability tends to become favorable, it is preferable.

The photosensitive resin composition of this invention may contain surfactant (F) (however different from resin (B)). As surfactant, silicone type surfactant, a fluorochemical surfactant, silicone type surfactant which has a fluorine atom, etc. are mentioned, for example.

As silicone type surfactant, surfactant which has a siloxane bond is mentioned.

Specifically, toray silicone DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, polyether modified silicone oil SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323 , KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momental, Performance, Japan, Japan Production).

As a fluorine type surfactant, surfactant which has a fluorocarbon chain | strand is mentioned.

Specifically, fluorinate (registered trademark) FC430, copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), megapak (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper R30 ( DIC Co., Ltd.), F-Top (registered trademark) EF301, copper EF303, copper EF351, copper EF352 (manufactured by Mitsubishi Material Electronics Chemical Co., Ltd.), Supron (registered trademark) S381, copper S382, copper SC101, copper SC105 (made by Asahi Glass Co., Ltd.), E5844 (made by Daikin Fine Chemical Research Institute), etc. are mentioned.

As silicone type surfactant which has a fluorine atom, surfactant which has a siloxane bond and a fluorocarbon chain | strand is mentioned. Specifically, Mega Park (registered trademark) R08, Copper BL20, Copper F475, Copper F477, Copper F443 (manufactured by DIC Corporation), and the like can be given. Preferably Megapak (registered trademark) F475 is mentioned.

Content of surfactant (F) is 0.001 mass% or more and 0.2 mass% or less with respect to the total amount of the photosensitive resin composition, Preferably it is 0.002 mass% or more and 0.1 mass% or less, More preferably, 0.01 mass% or more and 0.05 mass% It is as follows. By containing surfactant in this range, flatness of a coating film can be made favorable.

The photosensitive resin composition of this invention may contain various additives, such as a filler, another high molecular compound, an adhesion promoter, antioxidant, a ultraviolet absorber, a light stabilizer, a chain transfer agent, as needed.

The photosensitive resin composition of this invention does not contain coloring agents, such as a pigment and dye, substantially. That is, in the photosensitive resin composition of this invention, content of the coloring agent with respect to the whole composition is, for example, Preferably it is less than 1 mass%, More preferably, it is less than 0.5 mass%.

The photosensitive resin composition of this invention is filled into the quartz cell whose optical path length is 1 cm, and uses a spectrophotometer, and measures wavelength 400? The average transmittance when the transmittance is measured under the conditions of 700 nm is preferably 70% or more, and more preferably 80% or more.

When using the photosensitive resin composition of this invention as a coating film, the average transmittance of a coating film becomes like this. Preferably it is 90% or more, and it is more preferable to become 95% or more. This average transmittance | permeability is a coating film whose thickness after heat-hardening (for example, 100-250 degreeC, 5 minutes-3 hours of conditions) is 3 micrometers using a spectrophotometer, and measures wavelength 400? It is the average value when it measures on 700 nm conditions. Thereby, the coating film excellent in transparency in visible region can be provided.

The photosensitive resin composition of this invention is apply | coated on the board | substrates, such as glass, a metal, a plastic, or these board | substrates with which a color filter, various insulation or electrically conductive films, a drive circuit, etc. were formed, and patterned to a desired shape, Patterns can be formed. Moreover, you may form and use these coating films or patterns as a part of component parts, such as a display apparatus.

First, the photosensitive resin composition of this invention is apply | coated on a board | substrate.

Application | coating can be performed using various coating apparatuses, such as a spin coater, a slit & spin coater, a slit coater, an inkjet, a roll coater, and a dip coater.

 Next, it is preferable to dry or prebak, to remove volatile components, such as a solvent, and to dry. Thereby, a smooth uncured coating film can be obtained.

The film thickness of the coating film in this case is not specifically limited, It can adjust suitably according to the material to be used, a use, etc., for example, 1? It is about 6 micrometers.

Moreover, light, for example, a mercury lamp, the ultraviolet-ray generate | occur | produces from a light emitting diode, etc. are irradiated to the obtained uncured coating film through the photomask for forming a target pattern. The shape of the photomask at this time is not specifically limited, A shape and a size may be selected according to the use of a pattern.

In the recent exposure machine, the bandpass filter which cuts the light of less than 350 nm using the filter which cuts this wavelength range, or extracts the light of about 436 nm, 408 nm, and 365 nm vicinity in these wavelength ranges. It is possible to selectively take out using and irradiate almost parallel rays uniformly to the entire exposure surface. When apparatuses, such as a mask aligner and a stepper, are used, accurate position registration of a mask and a base material can be performed at this time.

The target pattern shape can be obtained by making the coating film after exposure contact a developing solution, melt | dissolving and developing a predetermined part, for example, a non-exposed part (namely, a non-pixel part).

The developing method may be any of a liquid mounting method, a dipping method, a spray method, and the like. In addition, you may tilt the base material at arbitrary angles at the time of image development.

As for the developing solution used for image development, the aqueous solution of a basic compound is preferable.

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

Specific examples of the inorganic basic compound 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, and carbonic acid. Potassium, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, etc. are mentioned.

As an organic basic compound, it is tetramethylammonium hydroxide, 2-hydroxyethyl trimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, for example. , Monoisopropylamine, diisopropylamine, ethanolamine and the like.

The concentration in the aqueous solution of these inorganic and organic basic compounds is preferably 0.01? 10 mass%, More preferably, it is 0.03? 5 mass%.

The developing solution may contain a surfactant.

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

As nonionic surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester , Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

Examples of the anionic surfactants 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, and dodecylbenzene sulfonic acid. Alkyl aryl sulfonates, such as sodium and sodium dodecyl naphthalene sulfonate, etc. are mentioned.

As cationic surfactant, amine salt, quaternary ammonium salt, etc., such as stearylamine hydrochloride and lauryl trimethylammonium chloride, etc. are mentioned, for example.

The concentration of the surfactant in the alkaline developer is preferably 0.01? 10 mass%, More preferably, it is 0.05? 8 mass%, More preferably, it is 0.1? 5 mass%.

A pattern can be obtained by performing water washing after image development. In addition, you may post-bake as needed. Post-baking, for example, 150? Temperature range of 240 ℃, 10? 180 minutes is preferred.

When exposing an uncured coating film, the coating film which does not have a pattern can be obtained by performing light irradiation to the whole surface, and / or omitting image development, without using the photomask in which the pattern was formed.

As an example of the display device of the present invention, an organic EL (electro luminescence) display device will be described below.

FIG. 1: is sectional drawing which expands and shows typically a part of display apparatus 1 which is an example of the display apparatus of this invention. FIG. 2 is a plan view schematically showing an enlarged part of the display device 1 which is an example of the display device of the present invention. The display device 1 mainly includes a support substrate 2, a partition 3 defining a partition set on the support substrate 2, and a partition formed by the partition 3. The organic electroluminescent element 4 is comprised. The partition 3 corresponds to the partition of the present invention.

The partition 3 is formed on the support substrate 2 in, for example, a lattice shape or a stripe shape. In addition, in FIG. 2, the display apparatus 1 in which the grid | lattice-shaped partition 3 was formed as one Embodiment is shown. Hatching was performed to the area | region in which the partition 3 was formed in the same figure.

On the support board | substrate 2, the some recessed part 5 prescribed | regulated by the partition 3 and the support board | substrate 2 is set. This recessed part 5 is corresponded to the division defined by the partition 3.

The partition 3 in the display device 1 is formed in a lattice shape. Therefore, when viewed from one side of the thickness direction Z of the support substrate 2 (henceforth "in planar view"), the some recessed part 5 is arrange | positioned in matrix form. In other words, the recesses 5 are formed in a row in the row direction X while being aligned in the column direction Y at a predetermined interval. The shape in plan view of each recessed part 5 is not specifically limited. For example, the concave portion 5 is formed in a shape such as a substantially rectangular shape, a substantially elliptical shape and a long shape in plan view. In the present embodiment, a substantially rectangular concave portion 5 is formed in plan view. In addition, in this specification, said row direction X and column direction Y mean the direction perpendicular | vertical to the thickness direction Z of a support substrate, and mean the direction perpendicular | vertical to each other.

In addition, when a stripe-shaped partition is formed as another embodiment, the partition is configured such that a plurality of partition members extending in the row direction X are arranged at predetermined intervals in the column direction Y, for example. In this embodiment, the stripe-shaped recess is defined by the stripe-shaped partition wall and the supporting substrate.

The partition wall is formed to become narrower as it is separated from the supporting substrate. For example, the cross-sectional shape when the partition wall extending in the column direction Y is cut into a plane perpendicular to the extension direction (column direction Y) is formed to be narrower as it is separated from the supporting substrate. In FIG. 1, a conformal trapezoidal partition is shown, and when the upper bottom is compared with the lower bottom of the support substrate side, the lower bottom is wider than the upper bottom. In addition, the cross section of the partition which is actually formed does not necessarily become trapezoidal shape, but may have a trapezoidal linear part and a rounded angle part.

It is preferable that the top surface of the partition 3 shows liquid repellency. In addition, a top surface means the plane which exists in the position which is most separated from the support substrate 2 among the surfaces of the partition 3. By the top surface of the partition 3 exhibiting liquid repellency, it is possible to prevent the ink supplied to the area surrounded by the partition 3 (the recessed portion 5) from flowing over the top surface of the partition 3 to the nearby area. .

The organic EL element 4 is formed in a section defined by the partition 3 (that is, the recess 5). When the lattice-shaped partition wall 3 in the display device 1 is formed, each organic EL element 4 is formed in each recessed part 5, respectively. In other words, the organic EL elements 4 are arranged in a matrix like the concave portions 5, and on the support substrate 2, the organic EL elements 4 are spaced a predetermined distance in the row direction X, and the column direction ( Y) is also formed to be aligned at a predetermined interval.

The shape of the partition 3 and its arrangement are appropriately set according to the specifications of the display device such as the number of pixels and the resolution, ease of manufacture, and the like. For example, the width | variety of the row direction X or the column direction Y of the partition 3 is 5 micrometers? It is about 50 micrometers, and the height of the partition 3 is 0.5 micrometer? 5 micrometers, and the space | interval between the partition walls 3 which adjoin in the row direction X or the column direction Y, ie, the width | variety of the row direction X or the column direction Y of the recessed part 5, is 10 micrometers. ? It is about 200 micrometers. Moreover, the width | varieties of the row direction X or the column direction Y of the 1st electrode 6 were 10 micrometers each, respectively. It is about 200 micrometers.

The partition 3 can be formed from the photosensitive resin composition of this invention by the formation method of the pattern mentioned above.

In addition, when a stripe-shaped partition is formed as another embodiment, the organic EL elements 4 are arranged at predetermined intervals in the row direction X at respective recesses extending in the row direction X, respectively.

Three types of organic EL elements 4 are formed in the display device 1. That is, (1) red organic EL element 4R for emitting red light, (2) green organic EL element 4G for emitting green light, and (3) blue organic EL element for emitting blue light ( 4B) is formed.

The organic EL element 4 is configured by stacking a first electrode, an organic EL layer, and a second electrode in this order from the support substrate side. In the present specification, one or a plurality of layers formed between the first electrode 6 and the second electrode 10 are called organic EL layers, respectively. The organic EL element 4 includes at least one light emitting layer as an organic EL layer. In addition, the organic EL element may further include an organic EL layer different from the light emitting layer in addition to the light emitting layer of one layer. For example, a hole injection layer, a hole transport layer, an electron block layer, an electron transport layer, an electron injection layer, etc. are formed between the 1st electrode 6 and the 2nd electrode 10 as an organic EL layer. In addition, a light emitting layer of two or more layers may be formed between the first electrode 6 and the second electrode 10.

The organic EL element 4 includes a first electrode 6 and a second electrode 10 as a pair of electrodes composed of an anode and a cathode. One electrode of the 1st electrode 6 and the 2nd electrode 10 is formed as an anode, and the other electrode is formed as a cathode. In the display device 1, a first electrode 6 functioning as an anode, a first organic EL layer 7 functioning as a hole injection layer, a second organic EL layer 9 functioning as a light emitting layer, and functioning as a cathode The 2nd electrode 10 is laminated | stacked on the support substrate 2 in this order, and is comprised.

The first electrode 6 is formed for each organic EL element 4. That is, the same number of first electrodes 6 as the organic EL elements 4 are formed on the support substrate 2. The first electrode 6 is formed corresponding to the arrangement of the organic EL elements 4, and is arranged in a matrix like the organic EL elements 4. In addition, the partition 3 is mainly formed in a grid | lattice form in the area | region except the 1st electrode 6, and is formed so that the peripheral part of the 1st electrode 6 may be covered (refer FIG. 1).

The first organic EL layer 7 corresponding to the hole injection layer is formed on the first electrode 6 in the recess 5, respectively. This 1st organic electroluminescent layer 7 is formed by changing the material or film thickness according to the kind of organic electroluminescent element as needed. Moreover, you may form all the 1st organic electroluminescent layers 7 with the same material and the same film thickness from a viewpoint of the ease of the formation process of the 1st organic electroluminescent layer 7.

The first organic EL layer 7 supplies the ink containing the material to be the first organic EL layer 7 to the region (concave portion 5) surrounded by the partition 3 by the inkjet method, and then dried. And the ink is solidified by heating and / or light irradiation.

The second organic EL layer 9 functioning as the light emitting layer is formed on the first organic EL layer 7 in the recess 5. As mentioned above, a light emitting layer is formed according to the kind of organic electroluminescent element. Therefore, the red light emitting layer 9R is formed in the recessed part 5 in which the red organic EL element 4R is formed, and the green light emitting layer 9G is formed in the recessed part 5 in which the green organic EL element 4G is formed. The blue light emitting layer 9B is formed in the recess 5 in which the blue organic EL element 4B is formed.

The 2nd electrode 10 is formed in the whole surface in the display area in which the organic electroluminescent element 4 is formed. That is, the 2nd electrode 10 is formed not only on the 2nd organic EL layer 9 but also on the partition 3, and is continuously formed over several organic electroluminescent element.

As described above, the organic EL display device can be manufactured by covering the plurality of organic EL elements 4 formed on the supporting substrate 2 with the sealing layer and the sealing substrate (not shown).

Since the pattern obtained from the photosensitive resin composition of this invention has high heat resistance and liquid repellency, it is used especially for manufacturing a color filter, the ITO electrode of a liquid crystal display element, an organic EL display element, a circuit wiring board, etc. by the inkjet method. It is useful as a partition. Further, for example, as a member for a touch panel, such as a photo spacer constituting a part of a color filter substrate and / or an array substrate, a patternable overcoat, an interlayer insulating film, a liquid crystal alignment control protrusion, a micro lens, a coating layer for film thickness adjustment, and the like. The coating film which is useful and does not have the pattern obtained as mentioned above is useful as an overcoat which comprises a part of a color filter substrate and / or an array substrate. Said color filter substrate and an array substrate are used suitably for a liquid crystal display device, an organic electroluminescence display, an electronic paper, etc.

Example

Hereinafter, an Example demonstrates this invention in more detail. "%" And "part" in an example are the mass% and a mass part, unless there is particular notice.

Synthesis Example 1

Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added thereto, and stirred. It heated to 70 degreeC. Next, molar ratio of 60 mass parts of methacrylic acid, 3, 4- epoxy cyclocyclo [5.2.1.0 ^2,6 ] decyl acrylate (a compound represented by Formula (I-1) and a compound represented by Formula (II-1)) To 50 parts by mass) and 240 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution was kept at 70 ° C. over 4 hours using a dropping funnel. It was dripped in the flask.

On the other hand, the solution which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 mass parts of 3-methoxybutyl acetates in the flask over 4 hours using another dropping funnel. It dripped. 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, followed by copolymerization of a solid content of 32.6 mass% and an acid value of 110 mg-KOH / g (solid content conversion) (resin Aa). A solution of was obtained. The weight average molecular weight Mw of obtained resin Aa was 1.3 * 10 <^4> , and molecular weight distribution was 2.50. Resin Aa is a copolymer having the following structural units.

Synthesis Example 2

Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, and 59 parts by mass of 3-methoxy-1-butanol and 81 parts by mass of 3-methoxybutyl acetate were added thereto while stirring. It heated to 70 degreeC.

Next, a molar ratio of 40 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1)) 360 mass parts of 50:50 mixture) was melt | dissolved in 80 mass parts of 3-methoxy-1-butanols, and 110 mass parts of 3-methoxybutyl acetates, and the solution was prepared. This solution was dripped in the flask kept at 70 degreeC over 4 hours using the dropping pump.

On the other hand, the solution which melt | dissolved 36 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 101 mass parts of 3-methoxy-1-butanol, and 139 mass parts of 3-methoxybutyl acetates, Another dropping pump was used to drop into the flask over 5 hours. 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, followed by copolymerization of a solid content of 42.5 mass% and an acid value of 56 mg-KOH / g (solid content conversion) (resin Ab). A solution of was obtained. The weight average molecular weight (Mw) of obtained resin Ab was 7.6 * 10 <^3> , and molecular weight distribution was 2.01. Resin Ab is a copolymer having the following structural units.

Synthesis Example 3

In a four-necked flask equipped with a reflux condenser, nitrogen inlet tube, thermometer, and stirring device, 30 parts of methacrylic acid, 30 parts of 2-hydroxyethyl methacrylate, 40 parts of isobornyl methacrylate, 2-sulfanyl 5.9 parts of ethanol and 163 parts of propylene glycol monomethyl ether acetate were added, and it heated at 70 degreeC, and stirred for 30 minutes under nitrogen stream. 1.3 parts of azobisisobutyronitrile were added to this, and it superposed | polymerized for 18 hours. Subsequently, 29.3 parts of 2-isocyanatoethyl acrylate (Carens AOI; manufactured by Showa Denko Co., Ltd.) were added, 50 ppm of hydroquinone monomethyl ether was added to the whole composition, and 45 ° C under nitrogen gas flow. By making it react for time, the solution of the copolymer (resin Ac) of 34 mass% of solid content was obtained. The weight average molecular weight (Mw) of obtained resin Ac was 4900. Resin Ac is a copolymer having the following structural units.

Synthesis Example 4

Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added thereto, and stirred. It heated to 70 degreeC. Next, a molar ratio of 55 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1)) , 50:50 mixture) 175 parts by mass and 70 parts by mass of N-cyclohexylmaleimide are dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution is 4 hours using a dropping pump. It dripped over the flask heated to 70 degreeC over. On the other hand, the solution which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 mass parts of 3-methoxybutyl acetates in the flask over 5 hours using another dropping pump. It dripped. 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, followed by copolymerization of a solid content of 32.6 mass% and an acid value of 105 mg-KOH / g (solid content conversion) A solution was obtained. As for the weight average molecular weight (Mw) of obtained resin Ad, 13,600 and number average molecular weight (Mn) were 5,400 and molecular weight distribution was 2.5. Resin Ad has the following structural units.

Synthesis Example 5

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 140 parts by mass of diethylene glycol ethylmethyl ether was added and heated to 70 ° C while stirring.

Subsequently, 40 mass parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a mixture of the compound represented by formula (I-1) and the compound represented by formula (II-1), molar ratio = 50:50) 340 parts by mass, dicyclopentenyl acrylate (a mixture of a compound represented by the following formula (x1) and a compound represented by the formula (x2), molar ratio = 50: 50) 20 parts by mass of diethylene glycol ethylmethyl ether 190 It melt | dissolved in the mass part and prepared the solution.

The obtained solution was dripped in the flask kept at 70 degreeC over 4 hours using the dropping pump.

On the other hand, the flask which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 240 mass parts of diethylene glycol ethylmethyl ethers, the flask over 5 hours using another dropping pump. It dripped in the inside.

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, and obtained the solution of the copolymer (resin Ae) of 41.8% of solid content. The weight average molecular weight (Mw) of obtained resin Ac was 9.6x10 <^3> , molecular weight distribution (Mw / Mn) was 2.02, and the acid value converted into solid content was 60 mg-KOH / g. Resin Ae has the following structural units.

Synthesis Example 6

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 140 parts by mass of diethylene glycol ethylmethyl ether was added and heated to 70 ° C while stirring.

Next, 40 parts by mass of methacrylic acid, a mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (a compound represented by formula (I-1) and a compound represented by formula (II-1), Molar ratio = 50: 50) 320 parts by mass and 40 parts by mass of dicyclopentanyl acrylate were dissolved in 190 parts by mass of diethylene glycol ethylmethyl ether to prepare a solution.

The obtained solution was dripped in the flask kept at 70 degreeC over 4 hours using the dropping pump.

On the other hand, the flask which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 240 mass parts of diethylene glycol ethylmethyl ethers, the flask over 5 hours using another dropping pump. It dripped in the inside.

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, and obtained the solution of the copolymer (resin Af) of 41.8% of solid content. The weight average molecular weight (Mw) of obtained resin Ad was 7.9x10 <^3> , molecular weight distribution (Mw / Mn) was 1.82, and the acid value converted into solid content was 60 mg-KOH / g. Resin Af has the following structural units.

(Synthesis Example 7)

78 parts of α-chloroacrylic acid 3,3,4,4,5,5,6,6,6-nonafluorohexyl, methacryl in a four-necked flask equipped with a reflux condenser, a nitrogen introduction tube, a thermometer, and a stirring device. 19.5 parts of acid, 19.5 parts of isobornyl methacrylate, 13 parts of glycidyl methacrylate, 12.7 parts of dodecanethiol, and 266 parts of propylene glycol monomethyl ether acetate were added, and heated at 70 ° C, followed by stirring under nitrogen stream for 30 minutes. did. 1 part of azobisisobutyronitrile was added to this, and it superposed | polymerized for 18 hours, and obtained the solution of the copolymer (resin Ba) of 33 mass% of solid content and acid value 68 mg-KOH / g (solid content conversion). The weight average molecular weight of obtained resin Ba was 7,500. Resin Ba is a copolymer having the following structural units.

Synthesis Example 8

Α-chloroacrylic acid 3,3,4,4,5,5,6,6,7,7,8,8,8-tree in 4-necked flask equipped with reflux cooling tube, nitrogen introduction tube, thermometer and stirring device 78 parts of decafluorooctyl, 19.5 parts of methacrylic acid, 19.5 parts of isobornyl methacrylate, 13 parts of glycidyl methacrylate, 12.7 parts of dodecanethiol, and 266 parts of propylene glycol monomethyl ether acetate were added thereto at 70 ° C. After heating, the mixture was stirred for 30 minutes under a nitrogen stream. 1 part of azobisisobutyronitrile was added to this, and it superposed | polymerized for 18 hours, and obtained the solution of the copolymer (resin Bb) of 33 mass% of solid content and acid value 65 mg-KOH / g (solid content conversion). The weight average molecular weight of obtained resin Bb was 6,800. Resin Bb is a copolymer having the following structural units. Resin Bb has the following structural units.

Synthesis Example 1? The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of resin obtained by 5 was performed on condition of the following using GPC method.

Device ; K2479 (manufactured by Shimadzu Corporation)

column ; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0 ml / min

Detector; RI

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

(Examples 1-4 and Comparative Example 1)

<Adjustment of the photosensitive resin composition>

The components of Table 3 were mixed, respectively, and the photosensitive resin composition 1? 5 was obtained.

Each component in Table 3 is as follows. The number of copies described in the column of Resin (A) and Resin (B) represents a mass part in terms of solid content.

Resin (A); Aa: Resin Aa obtained by the synthesis example 1

Resin (A); Ab: Resin Ab obtained in Synthesis Example 2

Resin (A); Ac: Resin Ac obtained in Synthesis Example 3

Resin (A); Ad: Resin Ad obtained by the synthesis example 4

Resin (A); Ae: Resin Ae obtained by the synthesis example 5

Resin (A); Af: Resin Af obtained by the synthesis example 6

Resin (B); Ba: Resin Ba obtained in Synthesis Example 7

Resin (B); Bb: Resin Bb obtained in Synthesis Example 8

Polymeric compound (C); Ca: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Gunpowder Co., Ltd.)

Polymeric compound (C); Cb: pentaerythritol tetraacrylate (A-TMMT; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

Polymerization initiator (D); Da: N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine (irgacure (registered trademark) OXE02; BASF Japan ( Manufacture)

Polymerization initiator (D); Db: 2-Hydroxy-1- ｛4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropane-1-one (irgacure (registered trademark) 127 BASF Japan Co., Ltd.)

Solvent (E); Ea; Propylene Glycol Monomethyl Ether Acetate

Solvent (E); Eb; Ethyl 3-ethoxypropionate

Solvent (E); Ec; 3-methoxy 1-butanol

Solvent (E); Ed; 3-methoxybutyl acetate

Solvent (E); Ee; Diethylene glycol methyl ethyl ether

The solvent (E) is mixed so that the solid content of the photosensitive resin composition becomes the "solid content (%)" of Table 3, and the solvent component (Ea) in the solvent (E)? The value of (Ee) shows the mass ratio in a solvent (E).

Other components; Za; Thermal crosslinker Cymel 300 (manufactured by Mitsui Cytec Co., Ltd.)

Other components; Zb; Tetrahydro phthalic anhydride (Licaxit TH; manufactured by Shin-Nihon Ewha Co., Ltd.)

<Average transmittance of the composition>

About the photosensitive resin composition obtained above, 400 degreeC was respectively used using the ultraviolet visible near-infrared spectrophotometer (V-650; Nihon spectroscopy) (quartz cell, optical path length; 1 cm), respectively. The average transmittance (%) in 700 nm was measured. The results are shown in Table 3.

<Production of coating film>

A glass substrate (Eagle XG; manufactured by Corning) having a width of 2 inches was washed sequentially with a neutral detergent, water, and alcohol, and then dried. On this glass substrate, the photosensitive resin composition 1? 4 were each spin-coated so that the film thickness after post-baking might be set to 3.0 micrometers, and it dried under reduced pressure until the pressure reduction degree became 66 kPa with a pressure reduction dryer (made by Microtech Co., Ltd.), and then, it heated at 80 degreeC with a hotplate at 2 degreeC. Prebaked for minutes and dried. After cooling, light of 50 mJ / cm <2> (365 nm standard) of exposure amount was irradiated in air | atmosphere using the exposure machine (TME-150RSK; Topcon Co., Ltd. light source, ultrahigh pressure mercury lamp). In addition, the irradiation to the photosensitive resin composition at this time used the ultrahigh pressure mercury lamp. After light irradiation, the said coating film was immersed and stirred for contacting the aqueous developing solution containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide for 60 second at 23 degreeC, and then heating at 230 degreeC in oven for 20 minutes ( Post-baking) to obtain a coating film.

About the photosensitive resin composition 5, the coating film was obtained by the same method as the above except changing exposure amount into 500 mJ / cm <2> (365 nm standard).

<Average transmittance of coating film>

About the obtained coating film, it used 400 micrometers using a microscopic spectrophotometer (OSP-SP200; OLYMPUS Corporation). The average transmittance (%) in 700 nm was measured. Higher transmittance means less absorption. The results are shown in Table 3.

<Contact angle>

The contact angle of the anisole was measured about the obtained coating film using the contact angle meter (DGD Fast / 60; GBX company make).

The higher the contact angle, the higher the liquid repellency. When the contact angle in a coating film is high, the contact angle is high also in the pattern formed using the same photosensitive resin composition. When a partition is formed with the photosensitive resin composition with a high contact angle, and ink is inlaid by the inkjet apparatus in the center surrounded by the partition, it is easy to splash ink. Therefore, when a color filter is produced by the inkjet method, mixing of the ink between adjacent pixel areas is unlikely to occur, for example.

<Solvent resistance evaluation>

The obtained coating film was immersed for 40 minutes in 40 degreeC N-methylpyrrolidone, and the film thickness and transmittance | permeability were measured. From the film thickness before and behind immersion, and the transmittance | permeability in 400 nm, the change rate was calculated | required according to the following Formula, respectively.

Film thickness change rate (%) = film thickness after immersion (micrometer) / film thickness before immersion (micrometer)

Permeability change rate (%) = transmittance after dipping (%) / transmittance before dipping (%)

Moreover, the adhesive test was done about the coating film after immersion. Sheaths were inserted into the coating film after immersion at intervals of 1 mm using a cutter and a super cutter guide (manufactured by Thai Oil Materials Co., Ltd.) to prepare 100 grids of 1 mm × 1 mm. Subsequently, a cello tape (registered trademark) 24 mm width (manufactured by Nichiban Co., Ltd.) was attached to the grid of the sheath of the coating film, and the cello tape was attached to the coating film by rubbing with an eraser from the cello tape. It grabbed at the tip and peeled at once, maintaining at right angles to a coating film surface. Then, the number of grid | lattices which remained on the board | substrate without peeling a coating film was visually counted. The larger the number of grids remaining on the substrate, the better the adhesion.

If the solvent resistance in a coating film is favorable, also solvent resistance will be favorable also in the pattern formed using the same photosensitive resin composition. The results are shown in Table 4.

<Heat resistance evaluation>

The obtained coating film was heated at 240 degreeC in clean oven for 1 hour, and the film thickness and transmittance | permeability were measured. The change rate was calculated | required from the film thickness before and behind heating, and the transmittance | permeability in 400 nm according to following Formula.

Film thickness change rate (%) = film thickness after heating (µm) / film thickness before heating (µm)

Permeability change rate (%) = transmittance after heating (%) / transmittance before heating (%)

If heat resistance in a coating film is favorable, heat resistance will also be favorable also in the pattern formed using the same photosensitive resin composition. The results are shown in Table 4.

<Pattern formation>

A glass substrate (Eagle XG; manufactured by Corning) having a width of 2 inches was washed sequentially with a neutral detergent, water, and alcohol, and then dried. On this glass substrate, the photosensitive resin composition 1? 4 and 6? 8 were each spin-coated so that the film thickness after post-baking might be set to 3.5 micrometers, and it dried under reduced pressure until the pressure reduction degree became 66 kPa with a pressure reduction dryer (made by Microtech Co., Ltd.), and then, it heated at 80 degreeC with a hotplate, Prebaked for minutes and dried. After cooling, the interval between the substrate coated with the photosensitive resin composition and the quartz glass photomask was 10 μm, and the exposure dose was measured under an atmospheric atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd., a light source; ultra-high pressure mercury lamp). Light of 50 mJ / cm 2 (365 nm standard) was irradiated. In addition, irradiation with respect to the photosensitive resin composition at this time was performed through the optical filter (UV-33; Asahi Spectrum Co., Ltd. make) the emission light from an ultrahigh pressure mercury lamp. As a photomask, a photomask in which a pattern (a square transmissive portion with one side was 13 µm and a square interval of 100 µm) (that is, a transmissive portion) was formed on the same plane was used.

After light irradiation, the coating film was immersed and stirred for 25 seconds at 25 ° C. for 100 seconds in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, followed by water washing and post-baking at 235 ° C. for 15 minutes in an oven. Was carried out to obtain a pattern.

About the photosensitive resin composition 5, the coating film was obtained by the same method as the above except changing exposure amount into 500 mJ / cm <2> (365 nm standard).

<Pattern shape observation>

The shape of the obtained pattern was observed using the scanning electron microscope (S-4000; the Hitachi, Ltd. make). When using a pattern as a partition, it is preferable that it is a forward taper (shape shown in FIG. 3).

From the result of the Example, it turns out from the photosensitive resin composition of this invention that the coating film and pattern excellent in heat resistance can be obtained, maintaining a high contact angle.

According to the photosensitive resin composition of this invention, the pattern excellent in heat resistance can be obtained.

1 indicator
2 support substrate
3 bulkhead
4 organic EL elements
5 recess
6 first electrode
7 first organic EL layer (hole injection layer)
9 2nd organic EL layer (light emitting layer)
10 second electrode

Claims (6)

The photosensitive resin composition containing (A), (B), (C), (D) and (E).
(A) Structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and C2-C? Copolymer containing a structural unit derived from the unsaturated compound which has a cyclic ether structure of 4, but does not have a structural unit derived from the unsaturated compound which has a C4-6 perfluoroalkyl group.
(B) 4 carbon atoms? Polymers containing structural units derived from unsaturated compounds having a perfluoroalkyl group of 6
(C) polymerizable compound
(D) polymerization initiator
(E) solvent The method of claim 1,
The photosensitive resin composition whose (B) is a copolymer containing the structural unit derived from at least 1 sort (s) further selected from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride. The method according to claim 1 or 2,
The photosensitive resin composition whose (C) is a polymerization initiator containing an oxime compound. The pattern formed from the photosensitive resin composition of Claim 1. The inkjet partition formed from the photosensitive resin composition of Claim 1. A display device comprising at least one member selected from the group consisting of the pattern according to claim 4 and the inkjet partition wall according to claim 5.

Images