JP2017032997A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition from which a pattern can be stably formed on glass.SOLUTION: A photosensitive resin composition comprises the following component (A), component (B), component (C), component (D) and component (E), in which the content of component (A) is 45 mass% or more and 80 mass% or less with respect to the total content of component (A) and component (C). The components are: (A) a copolymer containing a structural unit derived from at least one compound selected from the group consisting of an aromatic carboxylic acid having an ethylenically unsaturated bond and an aromatic carboxylic acid anhydride having an ethylenically unsaturated bond, and a structural unit derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms; (B) a polymer containing a structural unit having a perfluoroalkyl group having 4 to 6 carbon atoms; (C) a polymerizable compound; (D) a polymerization initiator; and (E) a silicon-containing compound containing two or more oxiranyl groups in one molecule.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a photosensitive resin composition.

In recent display devices and the like, a color filter, an ITO electrode of a liquid crystal display element, an organic electroluminescence (hereinafter referred to as “organic EL”) display element, a circuit wiring board, and the like are manufactured by an inkjet method. In the inkjet method, partition walls (patterns) formed on a substrate such as glass using a photosensitive resin composition are used. As a photosensitive resin composition, for example, a photosensitive resin composition containing a copolymer of vinyl benzoic acid and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate is known. (Patent Document 1).

Patent No. 5598621

However, it has been difficult to form a pattern stably on glass with the photosensitive resin composition.
Then, an object of this invention is to provide the photosensitive resin composition which can form a pattern stably on glass.

The present invention provides the following [1] to [5].
[1]
Including component (A), component (B), component (C), component (D), and component (E), the content of component (A) is the sum of component (A) and component (C) The photosensitive resin composition which is 45 to 80 mass% with respect to content.
(A) a structural unit derived from at least one compound selected from the group consisting of an aromatic carboxylic acid having an ethylenically unsaturated bond and an aromatic carboxylic acid anhydride having an ethylenically unsaturated bond; And a copolymer containing a structural unit derived from an unsaturated compound having a cyclic ether structure (hereinafter sometimes referred to as “resin (A)”).
(B) a polymer containing a structural unit having a perfluoroalkyl group having 4 to 6 carbon atoms (hereinafter sometimes referred to as “resin (B)”.
(C) Polymerizable compound (D) Polymerization initiator (E) Silicon-containing compound containing two or more oxiranyl groups per molecule [2]
The photosensitive resin composition according to [1], wherein the component (D) is a polymerization initiator containing at least one selected from the group consisting of a biimidazole compound, an alkylphenone compound, and an oxime ester compound.
[3]
The pattern formed with the photosensitive resin composition as described in [1] or [2].
[4]
An inkjet partition formed by the photosensitive resin composition according to [1] or [2].
[5]
A display device comprising at least one selected from the group consisting of the pattern according to [3] and the partition for inkjet according to [4].

  According to the photosensitive resin composition of the present invention, a pattern can be stably formed on glass. Furthermore, in a preferred embodiment of the present invention, a pattern with excellent wettability can be formed.

It 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. 1 is a plan view schematically showing an enlarged part of a display device 1 which is an example of a display device of the present invention.

  Hereinafter, the present invention will be described in detail.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention is a photosensitive resin composition comprising a component (A), a component (B), a component (C), a component (D), and a component (E). F) preferably contains a solvent (hereinafter referred to as “solvent (F)”). In the present specification, “solid content” means a component obtained by removing the solvent (F) from the photosensitive resin composition.
The photosensitive resin composition of the present invention comprises a resin other than the resin (A) and the resin (B) (hereinafter referred to as “resin (X)”), a polymerization initiation assistant (D1), a polyfunctional thiol compound ( It may contain at least one selected from the group consisting of T) and surfactant (G).
In addition, in this specification, unless otherwise indicated, the compound illustrated as each component can be used individually by 1 type or in combination of 2 or more types.

As the resin (A), for example,
Resin (A-1): At least one compound (a) selected from the group consisting of an aromatic carboxylic acid having an ethylenically unsaturated bond and an aromatic carboxylic acid anhydride having an ethylenically unsaturated bond (hereinafter referred to as “( a) "and a structural unit derived from an unsaturated compound (b) having a cyclic ether structure having 2 to 4 carbon atoms (hereinafter referred to as" (b) "); Resin (A-2): a monomer (c) that can be polymerized with (a) and (b) and does not have a cyclic ether structure having 2 to 4 carbon atoms (hereinafter, “ (C) "), and a polymer obtained by polymerizing (a) and (b).
However, none of (a), (b) and (c) has a perfluoroalkyl group having 4 to 6 carbon atoms.

  (A) is at least one compound selected from the group consisting of an aromatic carboxylic acid having an ethylenically unsaturated bond and an aromatic carboxylic acid anhydride having an ethylenically unsaturated bond, specifically, o- Aromatic carboxylic acids such as vinyl benzoic acid, m-vinyl benzoic acid, p-vinyl benzoic acid, 3-vinyl phthalic acid and 4-vinyl phthalic acid; aromatic carboxylic acids such as 3-vinyl phthalic anhydride and 4-vinyl phthalic anhydride An acid anhydride is mentioned.

(B) is a compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring). A monomer having an ether structure and an ethylenically unsaturated double bond is preferred, and a compound having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group is more preferred.
In this specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  Examples of (b) include a compound (b1) having an oxiranyl group (hereinafter referred to as “(b1)”), a compound (b2) having an oxetanyl group (hereinafter referred to as “(b2)”), And a compound (b3) having a tetrahydrofuryl group (hereinafter referred to as “(b3)”).

  Examples of (b1) include a compound (b1-1) having a structure in which an unsaturated aliphatic hydrocarbon group is epoxidized (hereinafter referred to as “(b1-1)”), unsaturated alicyclic carbonization. Compound (b1-2) (hereinafter referred to as “(b1-2)”) having a structure in which hydrogen is epoxidized is mentioned, and the storage stability of the photosensitive resin composition is excellent. A compound having a (meth) acryloyloxy group is preferable, and a compound having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized and a (meth) acryloyloxy group is more preferable.

  Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, and m-vinylbenzyl glycidyl ether. P-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl 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 (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6 -Tris (glycidyloxymethyl) styrene is mentioned. Other examples of (b1-1) include compounds described in JP-A-7-248625.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide (registered trademark) 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexyl. Methyl acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer (registered trademark) M100; manufactured by Daicel Chemical Industries, Ltd.) , Compounds represented by formula (I), and compounds represented by formula (II).

［式中、Ｒ¹及びＲ²は、それぞれ独立に、水素原子、又は、炭素原子数１〜４のアルキル基を表し、該アルキル基に含まれる水素原子はヒドロキシ基で置換されていてもよい。
Ｘ¹及びＸ²は、それぞれ独立に、単結合、＊−Ｒ³−、＊−Ｒ³−Ｏ−、＊−Ｒ³−Ｓ−、＊−Ｒ³−ＮＨ−を表す。
Ｒ³は、炭素原子数１〜６のアルカンジイル基を表す。
＊は、Ｏとの結合手を表す。］

[Wherein, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group. .
X ¹ and X ² each independently represent a single bond, * —R ³ —, * —R ³ —O—, * —R ³ —S—, * —R ³ —NH—.
R ³ represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Groups.

  Examples of the alkyl group substituted with a hydroxy group include a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxypropyl group, Examples thereof include a hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.

R ¹ and R ² are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

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

X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— (* represents a bond to O), or * —CH ₂ CH ₂ —O—. And more preferably a single bond or * —CH ₂ CH ₂ —O—.

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

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

  The compound represented by the formula (I) and the compound represented by the formula (II) may be used singly or in combination of two or more. When two or more compounds represented by the formula (I) and the compound represented by the formula (II) are used in combination, their content ratio [compound represented by the formula (I): represented by the formula (II) The compound] is on a molar basis, preferably 5:95 to 95: 5, more preferably 20:80 to 80:20.

  (B2) is preferably a compound having an oxetanyl group and a (meth) acryloyloxy group, more preferably 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- ( And (meth) acryloyloxymethyl oxetane, 3-methyl-3- (meth) acryloyloxyethyl oxetane, and 3-ethyl-3- (meth) acryloyloxyethyl oxetane.

  (B3) is preferably a compound having a tetrahydrofuryl group and a (meth) acryloyloxy group, more preferably tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.). ), Tetrahydrofurfuryl methacrylate.

  Examples of (c) include (meth) acrylic acid esters, N-substituted maleimides, unsaturated dicarboxylic acid diesters, alicyclic unsaturated compounds, unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, styrene, and other vinyls. Compounds.

Examples of (meth) acrylic acid esters include alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and tert-butyl (meth) acrylate. ;
Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (as a common name, “dicyclopentanyl (meth) Acrylate ”), dicyclopentanyloxyethyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (commonly referred to as“ dicyclopentenyl ( Meth) acrylate "), cycloalkyl esters such as isobornyl (meth) acrylate;
Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Examples include aryl and aralkyl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate.

  Examples of the N-substituted maleimide include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimide Examples include caproate, N-succinimidyl-3-maleimidopropionate, and N- (9-acridinyl) maleimide.

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

  Examples of the alicyclic unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2. .1] Hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′- Hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2 '-Hydroxyethyl) bicyclo [2.2.1] hept-2-e 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2 2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept- 2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2] 2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bi Black [2.2.1] hept-2-bicyclo unsaturated compounds such as ene.

Examples of the unsaturated carboxylic acid include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid Unsaturated dicarboxylic acids such as acids;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] bicyclounsaturated compounds containing a carboxy group such as hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ;
Examples thereof include unsaturated (meth) acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.

  Examples of the unsaturated carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic acid Unsaturated dicarboxylic acids such as anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride An acid anhydride is mentioned.

  Examples of styrene include styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, and p-methoxy styrene.

  Examples of other vinyl compounds include (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. .

  (C) is preferably styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, or bicyclo [2.2.1] hept because of good polymerization reactivity and alkali solubility. -2-ene.

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

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

  When the ratio of the constituent units of the resin (A-1) and the resin (A-2) is in the above range, the storage stability of the photosensitive resin composition, and development when forming a pattern from the photosensitive resin composition As well as solvent resistance, heat resistance and mechanical strength of the resulting coating film and pattern.

  As the resin (A-1), a resin (A-1) in which (b) is (b1) is preferable, and a resin (A-1) in which (b) is (b1-2) is more preferable.

  Resin (A) is, for example, a method described in the document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu, published by Chemical Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972), and It can manufacture with reference to the cited reference described in this literature.

  Specifically, a predetermined amount of (a) and (b) or (a), (b) and (c), a polymerization initiator, a solvent and the like are placed in a reaction vessel, and for example, nitrogen in the atmosphere is oxygenated. A method of heating and keeping warm while stirring in a deoxygenated atmosphere by substitution is exemplified. In addition, as a polymerization initiator, a solvent, etc. used here, what is normally used in the said field | area can be used, for example.

  Examples of the polymerization initiator include azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.), organic peroxides (benzoyl peroxide, etc.) Is mentioned.

  The solvent is not particularly limited as long as it dissolves each monomer, and a solvent described later can be used as the solvent (F) of the photosensitive resin composition.

In order to adjust the molecular weight of the resin obtained, a chain transfer agent may be added during the 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-sulfanylpropionic acid and sulfanyl group-containing silicone (KF-2001: manufactured by Shin-Etsu Chemical); halogenated alkyls such as chloroform, carbon tetrachloride, and carbon tetrabromide.

  As the obtained polymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, and a polymer taken out as a solid (powder) by a method such as reprecipitation is used. May be. When the same solvent as the solvent (F) described later is used as the solvent during the polymerization, the solution after the reaction can be used as it is, and the production process can be simplified.

  The weight average molecular weight in terms of polystyrene of the resin (A) is preferably 3,000 to 100, because the coatability is excellent, the film thickness of the exposed part is less likely to occur during development, and the non-exposed part is easily removed by development. 000, more preferably 5,000 to 50,000.

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (A) is preferably 1.1 to 6.0, and more preferably 1.2 to 4 because the developability is excellent. .0.

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

  Content of resin (A) is 45 mass% or more and 80 mass% or less with respect to the total content of resin (A) and polymeric compound (C), and was formed with the photosensitive resin composition. Since the wettability of the substrate surface patterned with the partition wall is improved, it is preferably 48% by mass to 75% by mass, and more preferably 50% by mass to 70% by mass.

  The structural unit having a C 4-6 perfluoroalkyl group contained in the resin (B) is, for example, an unsaturated compound (d) having a C 4-6 perfluoroalkyl group (hereinafter, “(d) It is a structural unit derived from.

  Examples of (d) include a compound represented by the formula (d-0).

［式中、
Ｒ^fは、炭素原子数４〜６のペルフルオロアルキル基を表す。
Ｒ^dは、水素原子、ハロゲン原子、シアノ基、フェニル基、ベンジル基又は炭素原子数１〜２１のアルキル基を表し、該アルキル基に含まれる水素原子は、ハロゲン原子又はヒドロキシ基で置換されていてもよい。
Ｘ^dは、単結合、炭素原子数１〜１０の２価の脂肪族炭化水素基、炭素原子数３〜１０の２価の脂環式炭化水素基、又は、炭素原子数６〜１２の２価の芳香族炭化水素基を表し、該脂肪族炭化水素基及び該脂環式炭化水素基に含まれる１つ以上の−ＣＨ₂−は、−Ｏ−、−ＣＯ−、−ＮＲ^e−、−Ｓ−又は−ＳＯ₂−で置き換わっていてもよい。］

[Where:
R ^f represents a perfluoroalkyl group having 4 to 6 carbon atoms.
R ^d represents a hydrogen atom, a halogen atom, a cyano group, a phenyl group, a benzyl group or an alkyl group having 1 to 21 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a halogen atom or a hydroxy group. May be.
X ^d is a single bond, a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, or 2 having 6 to 12 carbon atoms. And one or more —CH ₂ — contained in the aliphatic hydrocarbon group and the alicyclic hydrocarbon group are —O—, —CO—, —NR ^e —, It may be replaced by —S— or —SO ₂ —. ]

R ^f is preferably a perfluorobutyl group or a perfluorohexyl group.

Examples of the alkyl group having 1 to 21 carbon atoms represented by R ^d include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an n-heptyl group. Linear alkyl groups such as n-octyl group, n-nonyl group and n-decyl group;
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-ethylbutyl group, 1- Methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 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- -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 group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3,4-dimethylpentyl group, 1-ethyl-1-methylbutyl group, 2 -Branched alkyl groups such as ethyl-3-methylbutyl group.

R ^d is preferably a hydrogen atom, a halogen atom, or a methyl group.

Examples of the divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by X ^d include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, Butane-1,4-diyl group, butane-1,3-diyl group, butane-1,2-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7 -Alkanediyl groups such as a diyl group and an octane-1,8-diyl group.

Examples of the divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms represented by X ^d include a cyclopropanediyl group, a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group, A cyclodecandiyl group is mentioned.

Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms represented by X ^d include a phenylene group, a naphthalenediyl group, and a biphenyldiyl group (for example, a biphenyl-3,3′-diyl group). Can be mentioned.

One or more —CH ₂ — contained in the divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms and the divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms is —O—. Examples of X ^d replaced by —CO—, —NR ^e —, —S—, or —SO ₂ — include groups represented by formula (xd-1) to formula (xd-9).

X ^d is preferably an alkanediyl group having 1 to 6 carbon atoms, and more preferably an ethylene group.

  The compound represented by the formula (d-0) is preferably a compound represented by the formula (d-0 ′).

［式中、Ｒ^hは、炭素原子数４〜６のペルフルオロアルキル基を表す。Ｒ^gは、水素原子、ハロゲン原子又はメチル基を表す。］

[Wherein, R ^h represents a perfluoroalkyl group having 4 to 6 carbon atoms. R ^g represents a hydrogen atom, a halogen atom or a methyl group. ]

Examples of the compound represented by the formula (d-0) include compound (d-1) to compound (d-94). In the table, the formula numbers shown in the column ^Xd represent the formula numbers of the groups exemplified above.
For example, the compound (d-1) is a compound represented by the formula (d-1).

  The resin (B) is preferably a structural unit derived from (d), a structural unit derived from (a), an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (e) (where ( a resin comprising at least one structural unit selected from the group consisting of structural units derived from (different from a) (hereinafter referred to as “(e)”), and more preferably derived from (d). A structural unit derived from (e), more preferably a structural unit derived from (d), a structural unit derived from (e), and a structural unit derived from (b). It is resin containing.

  Examples of (e) include the compounds exemplified for the unsaturated carboxylic acid and unsaturated carboxylic acid anhydride in (c).

When the resin (B) contains the structural unit derived from (a) and / or (e), the developability is excellent, and thus unevenness resulting from the residue and development tends to be suppressed.
When resin (B) contains the structural unit derived from (b), there exists a tendency which is excellent in solvent resistance.
Resin (B) may contain other structural units. Examples of the monomer that leads to other structural units (hereinafter referred to as “(c ′)”) include, for example, unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides among the compounds shown in (c) above. The compound of this is mentioned.

When the resin (B) is a polymer of (a) and / or (e) and (d), the ratio of the structural units derived from each monomer is the structural unit constituting the resin (B). The total number of moles is preferably in the following range.
Structural units derived from (a) and / or (e); 5-40% by mass (more preferably 10-30% by mass)
Structural unit derived from (d); 60 to 95% by mass (more preferably 70 to 90% by mass)

When the resin (B) is a polymer of (a) and / or (e), (b), and (d), the ratio of structural units derived from each monomer constitutes the resin (B). The total number of moles of the structural units is preferably in the following range.
Structural units derived from (a) and / or (e); 5-40% by mass (more preferably 10-30% by mass)
Structural unit derived from (b); 5 to 80% by mass (more preferably 10 to 70% by mass)
Structural unit derived from (d); 10 to 80% by mass (more preferably 20 to 70% by mass)

When the resin (B) is a polymer of (a) and / or (e), (b), (c ′), and (d), the proportion of structural units derived from each monomer is The total number of moles of the structural units constituting (B) is preferably in the following range.
Structural units derived from (a) and / or (e); 5-40% by mass (more preferably 10-30% by mass)
Structural unit derived from (b); 5 to 70% by mass (more preferably 10 to 60% by mass)
Structural unit derived from (c ′); 10 to 50% by mass (more preferably 20 to 40% by mass)
Structural unit derived from (d); 10 to 80% by mass (more preferably 20 to 70% by mass)

  When the ratio of each structural unit is in the above range, the liquid repellency and developability are excellent.

  The weight average molecular weight in terms of polystyrene of the resin (B) is preferably 3,000 to 20,000 because it is excellent in coatability, is less likely to cause film loss in the exposed area during development, and more easily removed in the unexposed area by development. More preferably, it is 5,000 to 15,000.

  The acid value of the resin (B) is usually 20 to 200 mgKOH / g, preferably 40 to 150 mgKOH / g.

  The resin (B) content is excellent in developability during pattern formation, and the resulting pattern is excellent in liquid repellency, so the total of resin (A), resin (X) and polymerizable compound (C) Preferably it is 0.001-10 mass parts with respect to 100 mass parts of quantity, More preferably, it is 0.01-5 mass parts.

As the resin (X), for example,
Resin (X1-1): a polymer obtained by polymerizing (e) and (b),
Resin (X1-2): Polymer obtained by polymerizing (e), (b) and (c ′) Resin (X1-3): Polymer obtained by polymerizing (e) and (c ′) ,
Resin (X1-4): a resin obtained by reacting (b) with a polymer obtained by polymerizing (e) and (c ′),
Resin (X1-5): Resin obtained by making (a) and / or (e) react with the polymer formed by polymerizing (b) and (c ′).

In resin (X1-1), 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 structural units constituting the resin (X1-1).
Structural unit derived from (e); 5 to 60 mol% (more preferably 10 to 50 mol%)
Structural unit derived from (b); 40 to 95 mol% (more preferably 50 to 90 mol%)
When the ratio of the structural unit of the resin (X1-1) is in the above range, the storage stability of the photosensitive resin composition, the developability when forming a pattern from the photosensitive resin composition, and the coating obtained The solvent resistance of the film and pattern is improved.

In resin (X1-2), 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 structural units constituting the resin (X1-2).
Structural unit derived from (e); 2-45 mol% (more preferably 5-40 mol%)
Structural unit derived from (b); 2-95 mol% (more preferably 5-80 mol%)
Structural unit derived from (c ′); 1 to 65 mol% (more preferably 5 to 60 mol%)
When the ratio of the structural unit of the resin (X1-2) is in the above range, the storage stability of the photosensitive resin composition, the developability when forming a pattern from the photosensitive resin composition, and the coating obtained The solvent resistance of the film and pattern is improved.

In resin (X1-3), 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 all the structural units which comprise resin (X1-3).
Structural unit derived from (e); 2 to 40 mol% (more preferably 5 to 35 mol%)
Structural unit derived from (c ′); 60 to 98 mol% (more preferably 65 to 95 mol%)
When the ratio of the structural unit of the resin (X1-1) is in the above range, the storage stability of the photosensitive resin composition, the developability when forming a pattern from the photosensitive resin composition, and the coating obtained The solvent resistance of the film and pattern is improved.

  Resin (X1-4) can be manufactured through a two-step process, for example. In this case as well, the method described in the above-mentioned document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu Publishing Co., Ltd., Chemical Dojin Co., Ltd., First Edition, First Printing, published on March 1, 1972), It can be produced with reference to the method described in JP 89533.

As a first step, a polymer of (e) and (c ′) is obtained in the same manner as in the method for producing the resin (A-1) described above. In this case, in the same manner as described above, the obtained polymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powdered) by a method such as reprecipitation. You may use what was taken out as a body. Moreover, it is preferable to set it as the polystyrene conversion weight average molecular weight and molecular weight distribution similar to the above.
However, the ratio of the structural units derived from (e) and (c ′) is preferably in the following range with respect to the total number of moles of all structural units constituting the polymer.
Structural unit derived from (e): 5 to 50 mol% (more preferably 10 to 45 mol%)
Structural unit derived from (c ′); 50 to 95 mol% (more preferably 55 to 90 mol%)

As a second step, a part of the unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride derived from (e) derived from the obtained polymer is reacted with the cyclic ether of (b) described above. Since the cyclic ether has high reactivity and unreacted (b) hardly remains, (b1) or (b2) is preferred as (b) used in the resin (X1-2), and (b1-1) Is more preferable.
Specifically, following the above, the atmosphere in the flask is replaced from nitrogen to air, and the reaction catalyst of 5 to 80 mol% (b), carboxy group and cyclic ether with respect to the number of moles of (e). (For example, tris (dimethylaminomethyl) phenol), 0.001 to 5% by mass with respect to the total amount of (e), (b) and (c ′), and a polymerization inhibitor (for example, hydroquinone) Of 0.001 to 5% by mass in a flask with respect to the total amount of (a), (b) and (c), and reacted at 60 to 130 ° C. for 1 to 10 hours to give resin (X1 -4) can be obtained. In addition, like the polymerization conditions, the charging method and the reaction temperature can be adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.
In this case, the number of moles of (b) is the storage stability of the photosensitive resin composition, the developability when forming a pattern from the photosensitive resin composition, and the solvent resistance and heat resistance of the resulting coating film and pattern. Since the balance of property, mechanical strength, and sensitivity becomes good, it is preferably 10 to 75 mol%, more preferably 15 to 70 mol%, relative to the number of moles of (e).

Resin (X1-5) is a first step, and a polymer of (b) and (c ′) is obtained in the same manner as in the method for producing resin (A-1) described above.
In this case, in the same manner as described above, the obtained polymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powdered) by a method such as reprecipitation. You may use what was taken out as a body.
The ratio of the structural units derived from (b) and (c ′) is preferably in the following range with respect to the total number of moles of all structural units constituting the polymer.
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%)

Further, in the same manner as in the production method of the resin (X1-4), (a) and / or (e) is added to the cyclic ether derived from (b) in the polymer of (b) and (c ′). It can be obtained by reacting a carboxylic acid or carboxylic acid anhydride. Carboxylic anhydride may be further reacted with the hydroxy group generated by the reaction of cyclic ether with carboxylic acid or carboxylic anhydride.
The amount of (a) and / or (e) to be reacted with the polymer is preferably 5 to 80 mol% with respect to the number of moles of (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b), and (b1-1) is more preferable.

  The weight average molecular weight in terms of polystyrene of the resin (X) is preferably 3,000 to 100,000 because it is excellent in coatability, is less likely to cause film loss in the exposed area during development, and more easily removed in the unexposed area by development. More preferably, it is 5,000 to 50,000.

  Since the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (X) is excellent in developability, it is preferably 1.1 to 6.0, more preferably 1.2 to 4. .0.

  The acid value of resin (X) is usually 20 to 150 mgKOH / g, preferably 40 to 135 mgKOH / g, more preferably 50 to 135 mgKOH / g.

  When the resin (X) is contained, the content thereof is preferable with respect to the total amount of the resin (A) and the resin (X) because the pattern can be formed with high sensitivity and the developability is excellent. Is 1-80 mass%, More preferably, it is 1-50 mass%.

  The polymerizable compound (C) is, for example, a compound that can be polymerized by active radicals generated from the polymerization initiator (D), preferably a compound having an ethylenically unsaturated bond, and more preferably (meth). Acrylic ester.

  Examples of the polymerizable compound (C) having one ethylenically unsaturated bond include the same compounds as the compounds mentioned as the above (a), (b) and (c), preferably (meth) acrylic It is an acid ester.

  Examples of the polymerizable compound (C) having two ethylenically unsaturated bonds include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, and 1,6-hexanediol diester. (Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di Acrylate, bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentylglycol Di (meth) acrylate, 3-methyl pentanediol di (meth) acrylate.

  Examples of the polymerizable compound (C) having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth). ) Acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripe Taerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, Reaction product of tripentaerythritol hepta (meth) acrylate and acid anhydride, caprolactone-modified trimethylolpropane tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (Meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, capro Kuton-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol hepta (Meth) acrylate, caprolactone modified tripentaerythritol octa (meth) acrylate, reaction product of caprolactone modified pentaerythritol tri (meth) acrylate and acid anhydride, caprolactone modified dipentaerythritol penta (meth) acrylate and acid anhydride Reaction of reaction product, caprolactone-modified tripentaerythritol hepta (meth) acrylate with acid anhydride Preferred are polymerizable compounds (C) having three or more ethylenically unsaturated bonds, more preferably dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, penta Erythritol tri (meth) acrylate.

  Since the content of the polymerizable compound (C) improves the sensitivity, the strength of the pattern obtained, the smoothness, and the reliability, the total of the resin (A), the resin (X), and the polymerizable compound (C). Preferably it is 20-55 mass% with respect to quantity, More preferably, it is 30-45 mass%.

  The polymerization initiator (D) may be any compound that can initiate polymerization by the action of light or heat, and a known polymerization initiator can be used. Examples of the polymerization initiator (D) include alkylphenone, biimidazole, triazine, acylphosphine oxide, and O-acyloxime. As the polymerization initiator (D), a light and / or thermal cationic polymerization initiator (for example, a compound composed of an onium cation and an anion derived from a Lewis acid) described in JP-A-2008-18187 is used. May be. The polymerization initiator (D) is preferably at least one selected from the group consisting of a biimidazole compound, an alkylphenone compound, and an O-acyloxime compound, and more preferably because the photosensitive resin composition becomes highly sensitive. Is an alkylphenone compound.

  The O-acyl oxime compound is a compound having a partial structure represented by the formula (d1).

（式中、＊は結合手を表す。以下、同様である。）

(In the formula, * represents a bond. The same applies hereinafter.)

  Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane- 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-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) -Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9 Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (manufactured by BASF), N-1919 (manufactured by ADEKA) may be used as the O-acyloxime compound.

  The alkylphenone compound is, for example, a compound having a partial structure represented by the formula (d2) or the formula (d3), and a compound having a partial structure represented by the formula (d2) is preferable. In these partial structures, the benzene ring may have a substituent.

  Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4 -Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one Is mentioned. Commercially available products such as Irgacure (registered trademark) 369, 907, 379 (above, manufactured by BASF) may be used as the compound.

  Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2 -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxy Examples include acetophenone and benzyldimethyl ketal.

Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4,4. ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis (2-chlorophenyl) -4,4', 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,
2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5 ′ -Tetra (trialkoxyphenyl) biimidazole (for example, see JP-B-48-38403 and JP-A-62-174204), the phenyl group at the 4,4 ′, 5,5′-position is a carboalkoxy group Imidazole compounds substituted by the above (for example, JP-A-7-10
See 913. Preferably, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole.

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

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

In addition, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenyl Benzophenone compounds such as benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; Examples thereof include quinone compounds such as 10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate and titanocene compounds.

Examples of the polymerization initiator having a group capable of causing chain transfer include polymerization initiators described in JP-T-2002-544205.
The polymerization initiator having a group capable of causing chain transfer can also be used as the component (c) constituting the resin (A).

  The polymerization initiator (D) is preferably used in combination with the polymerization initiation assistant (D1). The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator.

  Examples of the polymerization initiation aid (D1) include thioxanthone, amine, and carboxylic acid. In addition, examples of the polymerization initiation assistant (D1) include compounds described in JP-A-2008-65319 and JP-A-2009-139932.

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

  Examples of the amine include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethyl 2-ethylhexyl aminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (common name; Michler's ketone), 4,4′-bis (diethylamino) benzophenone And aromatic amines such as

  Examples of the carboxylic acid include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, Aromatic heteroacetic acids such as N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid can be mentioned.

Examples of the combination of the polymerization initiator (D) and the polymerization initiator assistant (D1) include, for example, a combination of alkylphenone and thioxanthone, and a combination of alkylphenone and aromatic amine. 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2,4-diethylthioxanthone, 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane-1 -One and 2,4-diethylthioxanthone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one and 2,4-diethylthioxanthone, 2-morpholino-1 -(4-Methylsulfanylphenyl) -2-methylpropan-1-one and 2-isopropylthioxan And 4-isopropylthioxanthone, 2-morpholino-1- (4-methylsulfanylphenyl) -2-methylpropan-1-one and 4,4′-bis (diethylamino) benzophenone, 2-dimethylamino-2-benzyl- 1- (4-morpholinophenyl) butan-1-one and 4,4′-bis (diethylamino) benzophenone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) butane-1 -One and 4,4'-bis (diethylamino) benzophenone.
The combination is preferably alkylphenone and thioxanthone, more preferably 2-methyl-2-morpholino-1- (4-methylsulfanyl) because a pattern with high sensitivity and high visible light transmittance is obtained. Phenyl) propan-1-one and 2,4-diethylthioxanthone, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-isopropylthioxanthone and 4-isopropylthioxanthone.

  Since the content of the polymerization initiator (D) can obtain a pattern with high sensitivity, preferably the total amount of the resin (A), the resin (X) and the polymerizable compound (C) is 100 parts by mass. It is 0.5-30 mass parts, More preferably, it is 1-20 mass parts, More preferably, it is 1-10 mass parts.

  Since the content of the polymerization initiation assistant (D1) can obtain a pattern with high sensitivity and good shape, the total amount of the resin (A), the resin (X) and the polymerizable compound (C) is 100 parts by mass. On the other hand, it is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass.

Examples of the silicon-containing compound (E) containing two or more oxiranyl groups in one molecule include x-12-981s, x-12-984s, x-12-984 (ethanol solution of x-12-984s), KR -516, KR-517, x-41-1059A, x-41-1053, x-24-9590 (manufactured by Shin-Etsu Silicone Co., Ltd.).
Among silicon-containing compounds (E) containing two or more oxiranyl groups per molecule, one or more oxiranyl groups and one trialkoxysilyl group (for example, triethoxysilyl group or trimethoxysilyl group) per molecule A silicon-containing compound containing the above is preferable, and a silicon-containing compound which is an organic polymer containing two or more oxiranyl groups and one or more trialkoxysilyl groups in one molecule (for example, x-12-981s, x- 12-984s, x-12-984) are more preferable. The organic polymer is preferably an organic polymer having a main chain having an organic structure (organic chain). In addition, it is preferable that carbon number of the alkoxy group which a trialkoxy silyl group contains is 1-6, it is more preferable that it is 1-4, and it is further more preferable that it is 1 or 2.
The content of the silicon-containing compound (E) containing two or more oxiranyl groups per molecule is preferably 0.01 to 10 mass with respect to 100 mass parts of the total amount of the resin (A) and the polymerizable compound (C). Part, more preferably 0.05 to 7 parts by mass, still more preferably 0.05 to 3 parts by mass, and still more preferably 0.05 to 1 part by mass.

  Examples of the solvent (F) include ester solvents (solvents containing —COO— in the molecule and not containing —O—), ether solvents (solvents containing —O— in the molecule and not containing —COO—). , Ether ester solvents (solvents containing —COO— and —O— in the molecule), ketone solvents (solvents containing —CO— in the molecule and not containing —COO—), alcohol solvents, aromatic hydrocarbon solvents Amide solvent and dimethyl sulfoxide.

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

  Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol mono Ethyl 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, phenetole, methyl anisole.

  Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Ethyl ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methylpropionic acid Methyl, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate.

  Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, and cyclohexanone. And isophorone.

  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, and mesitylene.

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

  The solvent (F) is preferably an organic solvent having a boiling point of 120 ° C. or more and 180 ° C. or less, more preferably, because it can suppress unevenness during coating and improve the flatness of the coating film. Are propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol.

  The content of the solvent (F) is preferably 60 to 95% by mass, more preferably 70%, based on the total amount of the photosensitive resin composition, since the flatness of the film coated with the photosensitive resin composition is high. It is -90 mass%.

  The polyfunctional thiol compound (T) means a compound having two or more sulfanyl groups (—SH) in the molecule. When a compound having two or more sulfanyl groups bonded to a carbon atom derived from an aliphatic hydrocarbon group is used as the polyfunctional thiol compound (T), the sensitivity of the photosensitive resin composition is increased.

  Examples of the polyfunctional thiol compound (T) include hexanedithiol, decanedithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis (3-sulfanyl acetate). , Ethylene glycol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanylpropionate), trimethylolpropane tris (3-sulfanylpropionate), trimethylolpropane Tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxy Chirutorisu (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), 1,4-bis (3-sulfanyl-butyloxy) include butane.

  The content of the polyfunctional thiol compound (T) is preferably 0.1% with respect to 100 parts by mass of the polymerization initiator (D) because the sensitivity of the photosensitive resin composition is increased and the developability is improved. It is 1-10 mass parts, More preferably, it is 0.5-7 mass parts.

  The surfactant (G) is different from the resin (B), and examples thereof include a silicone surfactant, a fluorine surfactant, and a silicone surfactant having a fluorine atom.

  Examples of the silicone-based surfactant (non-fluorine-based) include surfactants having a siloxane bond. Specifically, Tole Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, 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, TSF4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) are mentioned.

  Examples of the fluorine-based surfactant (non-silicone-based) include surfactants having a fluorocarbon chain. Specifically, Fluorinert (registered trademark) FC430 and FC431 (Sumitomo 3M Co., Ltd.); Mega Fuck (registered trademark) F142D, F171, F172, F172, F173, F177, F183, R183 (manufactured by DIC Corporation); Ftop (registered trademark) EF301, EF303, EF351, EF352 (Mitsubishi) Material Electronics Chemical Co., Ltd.); Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.); E5844 (Daikin Fine Chemical Laboratory Co., Ltd.).

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, MegaFac® R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) may be mentioned, and MegaFace (registered trademark) F475 is preferable.

  The content of the surfactant (G) is usually 0.001% by mass to 0.2% by mass with respect to the total amount of the photosensitive resin composition, and the flatness of the coating film is improved. Preferably they are 0.002 mass% or more and 0.1 mass% or less, More preferably, they are 0.01 mass% or more and 0.05 mass% or less.

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

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

  The photosensitive resin composition of the present invention preferably has an average transmittance when filling a quartz cell having an optical path length of 1 cm and measuring the transmittance under a measurement wavelength of 400 to 700 nm using a spectrophotometer. Is 70% or more, more preferably 80% or more.

  When the photosensitive resin composition of the present invention is formed into a coating film, the average transmittance of the coating film is preferably 90% or more, more preferably 95% or more. This average transmittance is measured at a wavelength of 400 to 700 nm using a spectrophotometer on a coating film having a thickness of 3 μm after heat curing (for example, curing at 100 to 250 ° C. for 5 minutes to 3 hours). It is an average value when measured under these conditions.

  The photosensitive resin composition of the present invention is applied to a substrate made of, for example, glass, metal, plastic or the like; a color filter, an insulating film or conductive film, a drive circuit, or the like, and patterned into a desired shape. Thus, a pattern can be formed. Further, this pattern may be formed and used as a part of a component such as a display device.

[Coating film, pattern]
A coating film and a pattern can be formed using the photosensitive resin composition of the present invention. Here, an example of the method will be described.

First, the photosensitive resin composition of the present invention is applied on a substrate.
For coating, a coating apparatus such as a spin coater, a slit & spin coater, a slit coater, an ink jet, a roll coater, or a dip coater can be used.

Next, for example, the coated photosensitive resin composition is dried or pre-baked to remove volatile components such as a solvent and then dried to obtain a smooth uncured coating film.
What is necessary is just to adjust the thickness of an uncured coating film with the material to be used and a use, and it is 1-6 micrometers normally.

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

  In an exposure machine used for exposure, a bandpass filter that cuts out light of less than 350 nm using a filter that cuts this wavelength range, or extracts light in the vicinity of 436 nm, 408 nm, and 365 nm of these wavelength ranges. It is possible to selectively take out and irradiate substantially parallel rays uniformly on the entire exposed surface. If an apparatus such as a mask aligner or a stepper is used, accurate alignment between the mask and the substrate can be performed.

The exposed pattern is brought into contact with the developer to dissolve a predetermined portion, for example, a non-exposed portion (that is, a non-pixel portion), and development is performed, whereby a desired pattern shape can be obtained.
Examples of the developing method include a liquid piling method, a dipping method, and a spray method.
The substrate may be tilted at an arbitrary angle during development.

The developer used for development is preferably an aqueous solution of a basic compound.
The basic compound may be either an inorganic or organic basic compound.

  Examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate Sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia.

  Examples of organic basic compounds include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Can be mentioned.

  The concentration of the basic compound in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

The developer may contain a surfactant.
Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants.

  Nonionic surfactants include, for example, polyoxyethylene derivatives such as polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether; oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene Examples include sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.

  Examples of the anionic surfactant include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; sodium dodecylbenzenesulfonate and dodecylnaphthalenesulfone. And alkylaryl sulfonates such as sodium acid.

  Examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride or quaternary ammonium salts.

  The concentration of the surfactant in the developer is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and further preferably 0.1 to 5% by mass.

  After the development, the pattern can be obtained by washing the substrate with the coating film with water. You may post-bake as needed. Post bake is preferably performed at 150 to 240 ° C. for 10 to 180 minutes, for example.

  In addition, since the components contained in the photosensitive resin composition interact with each other by the exposure and development described above, the components are included as they are in the pattern (and inkjet partition walls) of the present invention. I don't mean.

  When exposing an uncured coating film, a photomask having a pattern is not used, but light irradiation is performed on the entire surface and / or development is omitted to obtain a coating film having no pattern. be able to.

[Display device]
An organic EL display device will be described below as an example of the display device of the present invention.

FIG. 1 is a cross-sectional view schematically showing an enlarged part of a display device 1 which is an example of the display device of the present invention.
FIG. 2 is an enlarged plan view schematically showing a 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, partition walls 3 that define preset sections on the support substrate 2, and a plurality of organic EL elements 4 that are provided in the sections defined by the partition walls 3. Consists of including. The partition 3 corresponds to the inkjet 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. Note that FIG. 2 shows a display device 1 provided with a grid-like partition wall 3 as an embodiment. In FIG. 2, the area where the partition walls 3 are provided is hatched.

  On the support substrate 2, a plurality of recesses 5 defined by the partition walls 3 and the support substrate 2 are set. The concave portion 5 corresponds to a section defined by the partition wall 3.

The partition walls 3 in the display device 1 are provided in a lattice shape. Therefore, when viewed from one side in the thickness direction Z of the support substrate 2 (hereinafter referred to as “in plan view”), the plurality of recesses 5 are arranged in a matrix. That is, the recesses 5 are provided with a predetermined interval in the row direction X and aligned in the column direction Y with a predetermined interval. The shape of each recess 5 in plan view is not limited. For example, the recess 5 is formed in a shape such as a substantially rectangular shape, a substantially oval shape, or an oval shape in plan view.
In this embodiment, the substantially rectangular recessed part 5 is provided by planar view. In the present specification, the row direction X and the column direction Y mean directions perpendicular to the thickness direction Z of the support substrate and perpendicular to each other.

  As another embodiment, when a stripe-shaped partition wall is provided, the partition wall is configured by, for example, a plurality of partition wall members extending in the row direction X being arranged at a predetermined interval in the column direction Y. Is done. In this embodiment, a stripe-shaped recess is defined by the stripe-shaped partition wall and the support substrate.

  The partition wall is formed so that the width becomes narrower as the distance from the support substrate increases. For example, when the partition wall extending in the column direction Y is cut along a plane perpendicular to the extending direction (column direction Y), the cross-sectional shape is formed so that the width becomes narrower as the distance from the support substrate increases. . In FIG. 1, an isosceles trapezoidal partition wall is shown. When the upper base is compared with the lower base on the support substrate side, the lower base is wider than the upper base. In addition, the cross section of the partition actually formed does not necessarily have a trapezoidal shape, and the straight part and corners of the trapezoidal shape may be rounded.

  It is preferable that the top surface of the partition wall 3 exhibits liquid repellency. The top surface means a flat surface that is located at a position farthest from the support substrate 2 in the surface of the partition wall 3. Since the top surface of the partition wall 3 exhibits liquid repellency, the ink supplied to the region (recessed portion 5) surrounded by the partition wall 3 is prevented from overflowing to the adjacent region through the top surface of the partition wall 3. Can do.

  The organic EL element 4 is provided in a section defined by the partition 3 (that is, the recess 5). When the grid-like partition 3 in the display device 1 is provided, each organic EL element 4 is provided in each recess 5. That is, the organic EL elements 4 are arranged in a matrix like the concave portions 5 and are arranged on the support substrate 2 with a predetermined interval in the row direction X and with a predetermined interval in the column direction Y. Is provided.

  The shape and arrangement of the partition walls 3 are set according to the specifications of the display device such as the number of pixels and resolution and the ease of manufacture. For example, the width in the row direction X or the column direction Y of the partition walls 3 is usually 5 μm to 50 μm. The height of the partition 3 is usually 0.5 μm to 5 μm. The interval between the partition walls 3 adjacent to each other in the row direction X or the column direction Y, that is, the width of the recess 5 in the row direction X or the column direction Y is usually 10 μm to 200 μm. The width of the first electrode 6 in the row direction X or the column direction Y is usually 10 μm to 200 μm, respectively.

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

  In addition, when stripe-like partition walls are provided as another embodiment, the organic EL elements 4 are arranged at predetermined intervals in the row direction X in the respective recesses extending in the row direction X.

  The display device 1 is provided with three types of organic EL elements 4. That is, (1) a red organic EL element 4R that emits red light, (2) a green organic EL element 4G that emits green light, and (3) a blue organic EL element 4B that emits blue light are provided. It is done.

  The organic EL element 4 is configured by laminating 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 provided between the first electrode 6 and the second electrode 10 are each referred to as an organic EL layer. The organic EL element 4 includes at least one light emitting layer as an organic EL layer. Note that the organic EL element may include an organic EL layer different from the light emitting layer, if necessary, in addition to the single light emitting layer. For example, a hole injection layer, a hole transport layer, an electron block layer, an electron transport layer, an electron injection layer, and the like are provided as an organic EL layer between the first electrode 6 and the second electrode 10. Further, two or more light emitting layers may be provided 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 including an anode and a cathode. One of the first electrode 6 and the second electrode 10 is provided as an anode, and the other electrode is provided as a cathode. In the display device 1, the first electrode 6 functioning as an anode, the first organic EL layer 7 functioning as a hole injection layer, the second organic EL layer 9 functioning as a light emitting layer, and the second functioning as a cathode. The electrode 10 is configured by being laminated on the support substrate 2 in this order.

  The first electrode 6 is provided for each organic EL element 4. That is, the same number of first electrodes 6 as the organic EL elements 4 are provided on the support substrate 2. The first electrodes 6 are provided corresponding to the arrangement of the organic EL elements 4 and are arranged in a matrix like the organic EL elements 4. In addition, although the partition 3 is formed in a lattice shape mainly in a region excluding the first electrode 6, it is further formed so as to cover the peripheral edge of the first electrode 6 (see FIG. 1).

The first organic EL layer 7 corresponding to the hole injection layer is provided on the first electrode 6 in the recess 5. The first organic EL layer 7 is provided with a different material or thickness depending on the type of the organic EL element, if necessary. Note that all the first organic EL layers 7 may be formed with the same material and the same thickness.
The first organic EL layer 7 supplies ink containing a material to be the first organic EL layer 7 to the region (recessed portion 5) surrounded by the partition walls 3 by an ink jet method, and then drying, heating, and / or light. It is formed by solidifying the ink by irradiation.

  The second organic EL layer 9 functioning as a light emitting layer is provided on the first organic EL layer 7 in the recess 5. As described above, the light emitting layer is provided according to the type of the organic EL element. Therefore, the red light emitting layer 9R is provided in the recess 5 where the red organic EL element 4R is provided, the green light emitting layer 9G is provided in the recess 5 where the green organic EL element 4G is provided, and the blue light emitting layer 9B is blue organic. It is provided in the recess 5 where the EL element 4B is provided.

  The second electrode 10 is formed on the entire surface in the display region where the organic EL element 4 is provided. That is, the second electrode 10 is formed not only on the second organic EL layer 9 but also on the partition 3 and is continuously formed across a plurality of organic EL elements.

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

  The pattern obtained from the photosensitive resin composition of the present invention is useful as a partition used for producing a color filter, an ITO electrode of a liquid crystal display element, an organic EL display element, a circuit wiring board, and the like by an inkjet method. Furthermore, for example, a photo spacer that forms part of the color filter substrate and / or the array substrate, a patternable overcoat, an interlayer insulating film, a liquid crystal alignment control protrusion, a microlens, and a coating for adjusting the thickness of the film It is useful as a member for a touch panel such as a layer. The coating film having no pattern is useful as an overcoat constituting a part of the color filter substrate and / or the array substrate. The color filter substrate and the array substrate are suitably used for a liquid crystal display device, an organic EL display device, electronic paper, and the like.

  Hereinafter, the present invention will be described in detail by way of examples. In Examples, “%” and “part” are mass% and mass part unless otherwise specified.

<Synthesis Example 1>
Into a flask equipped with a reflux condenser, dropping funnel and stirrer, a suitable amount of nitrogen was passed to replace the nitrogen atmosphere, and 166 parts of propylene glycol monomethyl ether acetate and 52 parts of methoxypropanol were added and heated to 85 ° C. while stirring. did. Subsequently, 233 parts of a mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8 and 9-yl acrylate, 77 parts of p-vinylbenzoic acid, 125 parts of propylene glycol monomethyl ether acetate A mixed solution of 115 parts of methoxypropanol was added dropwise over 4 hours. On the other hand, a mixed solution prepared by dissolving 32 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 210 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of dropping, the mixture was held at the same temperature for 3 hours, and then cooled to room temperature, and a polymer having a B-type viscosity (23 ° C.) of 46 mPa · s, a solid content of 33.7%, and a solution acid value of 83 mgKOH / g (resin Aa) A solution was obtained. The weight average molecular weight Mw in terms of polystyrene of the resin Aa was 7.7 × 10 ³ , and the molecular weight distribution was 1.90. Resin Aa has the following structural units.

<Synthesis Example 2>
In a four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer, α-chloroacrylic acid 3,3,4,4,5,5,6,6,6-nonafluorohexyl 78 Parts, 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, and heated to 70 ° C. for 30 minutes And stirred under a nitrogen stream. 1 part of azobisisobutyronitrile was added thereto and polymerized for 18 hours to obtain a polymer solution (resin Ba) having a solid content of 33% by mass and an acid value of 68 mgKOH / g (in terms of solid content). The weight average molecular weight Mw in terms of polystyrene of the resin Ba was 7.5 × 10 ³ , and the molecular weight distribution was 3.50. Resin Ba has the following structural units.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resins obtained in Synthesis Examples 1 and 2 were measured under the following conditions using a gel permeation chromatography (GPC) method.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min Detector; RI

<Examples 1-6, Comparative Examples 1-3>
(Preparation of photosensitive resin composition)
Each component was mixed as shown in Table 5 to prepare a photosensitive resin composition. In the table, “-” means not contained.

In Table 5, details of each component are as follows. The number of parts described in the column of resin (A) and resin (B) represents a mass part in terms of solid content.
Resin (A): Resin Aa
Resin (B): Resin Ba
Polymerizable compound (C): trimethylolpropane triacrylate (A-TMPT; manufactured by Shin-Nakamura Chemical Co., Ltd.)
Polymerization initiator (D): 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (Irgacure (registered trademark) 907; manufactured by BASF)
Polymerization initiation aid (D1): 4,4′-bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.)
Silicon-containing compound (E1): x-12-984s (manufactured by Shin-Etsu Silicone)
Silicon-containing compound (E2): 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303, manufactured by Shin-Etsu Silicone)
Silicon-containing compound (E3): 3-glycidoxypropylmethyldimethoxysilane (KBM-402, manufactured by Shin-Etsu Silicone)
Silicon-containing compound (E4): N-phenyl-3-aminopropyltrimethoxysilane (KBM-573, manufactured by Shin-Etsu Silicone)
Solvent (Fa): Propylene glycol monomethyl ether acetate Solvent (Fb): Ethyl 3-ethoxypropionate Solvent (Fc): 3-methoxy 1-butanol Solvent (Fd): 3-methoxybutyl acetate Solvent (F) is photosensitive The resin composition was mixed so that the solid content was the “solid content (%)” in Table 5, and the values of the solvents (Fa), (Fb), (Fc) and (Fd) were determined in the solvent (F). Represents the mass ratio.

(Average transmittance of the composition)
About the photosensitive resin composition obtained above, 400 to 700 nm using an ultraviolet visible near infrared spectrophotometer (V-650; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm), respectively. The average transmittance (%) was measured. The results are shown in Table 5.

(Preparation of coating film)
A 2-inch square glass substrate (Eagle XG; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol and dried. On this glass substrate, the photosensitive resin composition obtained above was spin-coated so that the thickness after post-baking was 3.0 μm, and the pressure was reduced with a vacuum dryer (manufactured by Microtech Co., Ltd.). After drying under reduced pressure until the temperature reached 66 kPa, it was prebaked at 80 ° C. for 2 minutes on a hot plate and dried. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Corporation, light source: ultrahigh pressure mercury lamp), irradiation was performed with light having an exposure amount of 50 mJ / cm ² (based on 365 nm) in an air atmosphere. In addition, the ultrahigh pressure mercury lamp was used for the light irradiation to the photosensitive resin composition at this time. After light irradiation, the coating film was swung in contact with an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23 ° C. for 60 seconds, and then contacted. A coating film was obtained by heating (post-baking) at 230 ° C. for 20 minutes in an oven.

(Average transmittance of coating film)
About the obtained coating film, the average transmittance | permeability (%) in 400-700 nm was measured using the microspectrophotometer (OSP-SP200; OLYMPUS company make). Higher transmittance means less absorption. The results are shown in Table 5.

(Contact angle)
About the obtained coating film, the contact angle of anisole was measured using the contact angle meter (DGD Fast / 60; GBX company make). A higher contact angle means higher liquid repellency. If the contact angle in a coating film is high, also in the pattern formed using the same photosensitive resin composition, a contact angle is high. When a partition is formed of a photosensitive resin composition having a high contact angle, and ink is printed by an ink jet apparatus inside the partition, the ink is easily repelled. Therefore, for example, when a color filter is manufactured by an inkjet method, ink color mixing between adjacent pixel regions hardly occurs. The results are shown in Table 7.

(Pattern formation)
A 2-inch square glass substrate (Eagle XG; manufactured by Corning) with ITO deposited on the surface was sequentially washed with a neutral detergent, water and 2-propanol and dried. On the glass substrate, the photosensitive resin composition was spin-coated so that the thickness after post-baking was 1.0 μm, and the degree of vacuum was 66 kPa with a vacuum dryer (manufactured by Microtech Co., Ltd.). After being dried under reduced pressure until it becomes, it was prebaked at 90 ° C. for 2 minutes on a hot plate and dried. After cooling, the distance between the substrate coated with the photosensitive resin composition and the quartz glass photomask is set to 100 μm, and the exposure apparatus (TME-150RSK; manufactured by Topcon Corporation, light source: ultrahigh pressure mercury lamp) is used to form the atmosphere. Under an atmosphere, light having an exposure amount of 200 mJ / cm ² (based on 365 nm) was irradiated.
As a photomask, a pattern (a shape in which the shape of the light-shielding portion is 300 μm in the long axis direction and 100 μm in the short axis direction and a shape in which four corners are cut into circles (long circle)) is formed on the same plane. Was used. After light irradiation, the coating film was applied at 23 ° C. to a developer prepared by diluting an aqueous tetramethylammonium hydroxide solution (manufactured by Tokuyama Co., Ltd., Toxo SD25) with pure water to a concentration of 2.38%. The film was immersed for 60 seconds for development, washed with water, and post-baked in an oven at 230 ° C. for 20 minutes to obtain a pattern.

(Wettability)
Solvents for evaluating the wettability of the partition walls include N, N-dimethylacetamide (Wako Pure Chemical Industries, 99.5% or more) and 1,3-dimethyl-2-imidazolidinone (Tokyo Chemical Industry Co., Ltd.). Two types were selected (99.0% or more). Since the two selected solvents have low viscosity, cyclohexanol (manufactured by Wako Pure Chemical Industries, Ltd., 98.0% or more) is used as a viscosity adjusting material so that the liquid can be filled into the partition walls by an inkjet device. Added and used as a mixed solvent. Since it was difficult for the solvent alone to observe the spread of spread after drying with a microscope, rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd., purity 95% or more) was used as the solute.
As the solution, three types of solutions shown in Table 6 were prepared. In the table, “-” means not contained.

  Using an inkjet device (Lilex120L manufactured by ULVAC, Inc.) in the partition walls, 200 μL of solutions 1 to 3 were filled in each partition wall into 1000 partition walls, and after drying, the solute spread to the partition wall end. 30 observations were performed using (OLIMPUS, MX61L, lens: LCPFLN20xLCD). In all of the solutions 1 to 3, when all 30 sites were spread and spread, “A” was described as being good wettability, and “B” was indicated as being poor in wettability. The results are shown in Table 7.

(Development adhesion, storage stability)
The photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were prepared immediately after preparation and those stored at 23 ° C., humidity 50%, and light-shielded for 1 month after preparation.
A 2-inch square glass substrate (Eagle XG; manufactured by Corning) was sequentially washed with a neutral detergent, water, and alcohol, and each of the two types of photosensitive resin compositions on the glass substrate was post-baked. Spin coat to a thickness of 1.0 μm, dry under reduced pressure with a vacuum dryer (Microtech Co., Ltd.) until the degree of vacuum is 66 kPa, then pre-bake at 90 ° C. for 2 minutes on a hot plate. And dried. After cooling, the distance between the substrate coated with the photosensitive resin composition and the quartz glass photomask is set to 100 μm, and the exposure apparatus (TME-150RSK, manufactured by Topcon Corporation, light source: ultrahigh pressure mercury lamp) Under an atmosphere, light having an exposure amount of 200 mJ / cm ² (based on 365 nm) was irradiated. As a photomask, a pattern (a shape in which the shape of the light-shielding portion is 300 μm in the long axis direction and 100 μm in the short axis direction and a shape in which four corners are cut into circles (long circle)) is formed on the same plane. Was used.
After light irradiation, the coating film was applied at 23 ° C. to a developer prepared by diluting a tetramethylammonium hydroxide aqueous solution (manufactured by Tokuyama Co., Ltd., Toxo SD25) with pure water to a concentration of 2.38%. The film was immersed and developed for 60 seconds while shaking, and the remaining pattern was observed after washing. When all the patterns remain, the pattern survivability is indicated as “A”, and when the whole or a part of the pattern is peeled off or a defect is generated, the pattern survivability is regarded as poor. B ”. The results are shown in Table 7.

  According to Table 7, the photosensitive resin composition of the present invention can stably form a pattern on glass, and obtain a pattern with excellent wettability while maintaining a good contact angle. It is recognized that

DESCRIPTION OF SYMBOLS 1 Display apparatus 2 Support substrate 3 Partition 4 Organic EL element 5 Recessed part 6 1st electrode 7 1st organic EL layer (hole injection layer)
9 Second organic EL layer (light emitting layer)
10 Second electrode

Claims (5)

Including component (A), component (B), component (C), component (D), and component (E), the content of component (A) is the sum of component (A) and component (C) The photosensitive resin composition which is 45 to 80 mass% with respect to content.
(A) a structural unit derived from at least one compound selected from the group consisting of an aromatic carboxylic acid having an ethylenically unsaturated bond and an aromatic carboxylic acid anhydride having an ethylenically unsaturated bond; A copolymer comprising a structural unit derived from an unsaturated compound having a cyclic ether structure of 4 (B) a polymer comprising a structural unit having a perfluoroalkyl group having 4 to 6 carbon atoms (C) a polymerizable compound (D ) Polymerization initiator (E) Silicon-containing compound containing two or more oxiranyl groups in one molecule   The photosensitive resin composition of Claim 1 whose component (D) is a polymerization initiator containing at least 1 sort (s) chosen from the group which consists of a biimidazole compound, an alkylphenone compound, and an oxime ester compound.   The pattern formed with the photosensitive resin composition of Claim 1 or 2.   The partition for inkjet formed with the photosensitive resin composition of Claim 1 or 2.   A display device comprising at least one selected from the group consisting of the pattern according to claim 3 and the partition for inkjet according to claim 4.

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