JP6776708B2 - Photosensitive resin composition - Google Patents

Description

The present invention relates to a photosensitive resin composition.

In recent display devices and the like, color filters, ITO electrodes of liquid crystal display elements, organic electroluminescence (hereinafter referred to as "organic EL") display elements, circuit wiring substrates and the like are manufactured by an inkjet method. In the inkjet method, a partition wall (pattern) formed on a substrate such as glass using a photosensitive resin composition is used. As the photosensitive resin composition, for example, a photosensitive resin composition containing a copolymer of vinylbenzoic 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 stably form a pattern on the glass with the photosensitive resin composition.
Therefore, an object of the present invention is to provide a photosensitive resin composition capable of stably forming a pattern on glass.

The present invention provides the following [1] to [5].
[1]
It contains the component (A), the component (B), the component (C), the component (D), and the component (E), and the content of the component (A) is the sum of the component (A) and the component (C). A photosensitive resin composition having a content of 45% by mass or more and 80% by mass or less with respect to the 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 2 to 2 carbon atoms. Copolymer containing a structural unit derived from an unsaturated compound having a cyclic ether structure of 4 (hereinafter, may be referred to as "resin (A)").
(B) A polymer containing a structural unit having a perfluoroalkyl group having 4 to 6 carbon atoms (hereinafter, may be referred to as "resin (B)". "
(C) Polymerizable compound (D) Polymerization initiator (E) Silicon-containing compound containing two or more oxylanyl groups in one 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]
A pattern formed by the photosensitive resin composition according to [1] or [2].
[4]
A partition wall for an inkjet formed by the photosensitive resin composition according to [1] or [2].
[5]
A display device including at least one selected from the group consisting of the pattern described in [3] and the partition wall for an inkjet described in [4].

According to the photosensitive resin composition of the present invention, a stable pattern can be formed on the glass. Further, in a preferred embodiment of the present invention, a pattern having excellent wettability can be formed.

It is sectional drawing which shows the part of the display device 1 which is an example of the display device of this invention in an enlarged manner schematically. It is a top view which shows a part of the display device 1 which is an example of the display device of this invention by enlarging.

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 containing a component (A), a component (B), a component (C), a component (D), and a component (E), but further components ( It is preferable that F) contains a solvent (hereinafter, referred to as "solvent (F)"). In addition, in this specification, "solid content" means the component which removed the solvent (F) from the photosensitive resin composition.
The photosensitive resin composition of the present invention includes a resin (A) and a resin other than the resin (B) (hereinafter referred to as "resin (X)"), a polymerization initiator (D1), and a polyfunctional thiol compound (hereinafter referred to as "resin (X)"). It may contain at least one selected from the group consisting of T) and the surfactant (G).
In addition, in this specification, the compound exemplified as each component may be used alone or in combination of 2 or more unless otherwise specified.

As the resin (A), for example,
Resin (A-1): At least one compound (a) selected from the group consisting of aromatic carboxylic acids having ethylenically unsaturated bonds and aromatic carboxylic acid anhydrides having ethylenically unsaturated bonds (hereinafter, "(. A structural unit derived from "a)") and an unsaturated compound (b) having a cyclic ether structure having 2 to 4 carbon atoms (hereinafter referred to as "(b)"). Compound (A-2): A monomer (c) capable of polymerizing with (a) and (b) and having no cyclic ether structure having 2 to 4 carbon atoms (hereinafter, " A polymer obtained by polymerizing (c) ", (a), and (b) can be mentioned.
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, and specifically, o-. Aromatic carboxylic acids such as vinyl benzoic acid, m-vinyl benzoic acid, p-vinyl benzoic acid, 3-vinylphthalic acid, 4-vinylphthalic acid; aromatic carboxylic acids such as 3-vinylphthalic anhydride and 4-vinylphthalic anhydride Acid anhydrides can be mentioned.

Reference numeral (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 oxylane ring, an oxetane ring and a tetrahydrofuran ring), and has a cyclic ether structure having 2 to 4 carbon atoms. A monomer having an ether structure and an ethylenically unsaturated double bond is preferable, and a compound having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group is more preferable.
As used herein, the term "(meth) acrylic acid" refers to 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 having an oxylanyl group (b1) (hereinafter referred to as “(b1)”), a compound having an oxetanyl group (b2) (hereinafter referred to as “(b2)”), and the like. Examples thereof include a compound (b3) having a tetrahydrofuryl group (hereinafter, referred to as “(b3)”).

Examples of (b1) include a compound (b1-1) having an epoxidized unsaturated aliphatic hydrocarbon group (hereinafter referred to as “(b1-1)”), and an unsaturated alicyclic hydrocarbon. A compound (b1-2) having an epoxidized structure of hydrogen (hereinafter referred to as “(b1-2)”) can be mentioned, and since the photosensitive resin composition is excellent in storage stability, it can be combined with an oxylanyl group (hereinafter referred to as “(b1-2)”). A compound having a meta) acryloyloxy group is preferable, and a compound having an unsaturated alicyclic hydrocarbon epoxidized structure 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 can be mentioned. 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, celloxide (registered trademark) 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylbenzene. Methyl acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer (registered trademark) M100; manufactured by Daicel Chemical Industry Co., Ltd.) , The compound represented by the formula (I), and the compound represented by the 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。］

[In the formula, 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 independently represent a single bond, * -R ^3- , * -R ^3- O-, * -R ^3- S-, and * -R ^3- NH-, respectively.
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. The group is mentioned.

Examples of the alkyl group substituted with the hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and 1-. Examples thereof include hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 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, hexane-1,6-Diyl group.

X ¹ and X ² are preferably single bonds, methylene groups, ethylene groups, * -CH _2- O- (* represents a bond with O), or * -CH ₂ CH _2- O-. Yes, 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 formulas (I-1) to (I-15), and the compounds represented by the formulas (I-1) and (I-15) are preferable. 3), formula (I-5), formula (I-7), formula (I-9) or a compound represented by formulas (I-11) to (I-15), more preferably of the formula. It is a compound represented by (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 formulas (II-1) to (II-15), preferably formulas (II-1) and (II-). 3), a compound represented by the formula (II-5), the formula (II-7), the formula (II-9) or the formulas (II-11) to (II-15), more preferably the formula. It is a compound represented by (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 alone 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 ratios [compound represented by the formula (I): represented by the formula (II)). Compound] is on a molar basis, preferably 5:95 to 95: 5, and more preferably 20:80 to 80:20.

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

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

Examples of (c) include (meth) acrylic acid ester, N-substituted maleimide, unsaturated dicarboxylic acid diester, alicyclic unsaturated compound, unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, styrene, and other vinyl. Examples include compounds.

Examples of the (meth) acrylic acid ester 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 ] decane-8-yl (meth) acrylate (commonly known as "dicyclopentanyl (meth)" Also referred to as "acrylate"), dicyclopentanyloxyethyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate (commonly known as "dicyclopentenyl (meth)". Cycloalkyl esters such as "meth) acrylate") and isobornyl (meth) acrylate;
Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Aryl and aralkyl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate can be mentioned.

Examples of the N-substituted maleimide include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, and N-succinimidyl-6-maleimide. Caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide can be mentioned.

Examples of unsaturated dicarboxylic acid diesters include diethyl maleate, diethyl fumarate, and diethyl itaconic acid.

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-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2. 1] Hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-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- Examples thereof include bicyclounsaturated compounds such as 2-ene and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene.

Examples of unsaturated carboxylic acids 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-cyclohexendicarboxylic 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 A bicyclounsaturated compound containing a carboxy group such as [2.2.1] hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of divalent or higher valent carboxylic acids such as monosuccinate [2- (meth) acryloyloxyethyl] and mono [2- (meth) acryloyloxyethyl] phthalates. ;
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 acid anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic acid. Unsaturated dicarboxylic acids such as anhydrides, 1,2,3,6-tetrahydrophthalic anhydrides, dimethyltetrahydrophthalic anhydrides, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydrides, etc. Acid anhydrides can be mentioned.

Examples of styrene include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene.

Other vinyl compounds include, for example, (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, vinyl acetate, 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene. ..

As (c), styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, or bicyclo [2.2.1] hept is preferable because it has good polymerization reactivity and alkali solubility. -2-En.

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 same as that of the structural unit derived from (a). It is preferable that the total number of moles of the constituent units derived from b) is in the following range.
Constituent unit derived from (a); 5-60 mol% (more preferably 10-50 mol%)
Constituent unit derived from (b); 40-95 mol% (more preferably 50-90 mol%)

In the resin (A-2), the content of the structural unit derived from (c) is based on the total number of moles (100 mol parts) 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 part or less, and more preferably more than 0 mol part and 280 mol part or less.

When the ratio of the constituent units of the resin (A-1) and the resin (A-2) is within the above range, the storage stability of the photosensitive resin composition and the development when forming a pattern from the photosensitive resin composition The properties and the solvent resistance, heat resistance and mechanical strength of the obtained coating film and pattern tend to be good.

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

The resin (A) is, for example, the method described in the document "Experimental Method for Polymer Synthesis" (written by Takayuki Otsu, Kagaku-Dojin Co., Ltd., 1st edition, 1st print, published on March 1, 1972). It can be manufactured with reference to the cited documents described in the document.

Specifically, predetermined amounts 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, oxygen in the atmosphere is added by nitrogen. An example is a method of heating and keeping warm while stirring to create a deoxidized atmosphere by substituting. As the polymerization initiator, solvent and the like used here, for example, those usually used in the art can be used.

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

The solvent may be any one that dissolves each monomer, and a solvent described later can be used as the solvent (F) of the photosensitive resin composition.

A chain transfer agent may be added during the polymerization reaction in order to adjust the molecular weight of the obtained resin.
Examples of the chain transfer agent include n-butanethiol, tert-butanethiol, n-dodecanethiol, 2-sulfanylethanol, thioglycolic acid, ethyl thioglycolate, 2-ethylhexyl thioglycolate, and methoxybutyl thioglycolate. Thiols such as 3-sulfanyl propionic acid and sulfanyl group-containing silicone (KF-2001: manufactured by Shin-Etsu Chemical Co., Ltd.); alkyl halides such as chloroform, carbon tetrachloride and carbon tetrabromide can be mentioned.

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

The polystyrene-equivalent weight average molecular weight of the resin (A) is preferably 3,000 to 100, because it has excellent coatability, is less likely to cause film loss in the exposed portion during development, and is easily removed by development in the non-exposed portion. It is 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, more preferably 1.2 to 4 because of its excellent developability. It is 0.0.

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 required to neutralize 1 g of the resin, and can be determined by titrating with an aqueous potassium hydroxide solution.

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

The structural unit having a perfluoroalkyl group having 4 to 6 carbon atoms contained in the resin (B) is, for example, an unsaturated compound (d) having a perfluoroalkyl group having 4 to 6 carbon atoms (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。］

[During the ceremony,
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. You may.
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. Representing a valent aromatic hydrocarbon group, the aliphatic hydrocarbon group and one or more −CH ₂ − contained in the alicyclic hydrocarbon group are −O−, −CO−, −NR ^e− ,. -S- or -SO ₂ - may be replaced by. ]

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. , N-octyl group, n-nonyl group, n-decyl group and other 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-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-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 group, 2,4-dimethylpentyl group, 3, Examples thereof include branched alkyl groups such as 3-dimethylpentyl group, 3,4-dimethylpentyl group, 1-ethyl-1-methylbutyl group and 2-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, and 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 Examples thereof include an alkandiyl group 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, and a cycloheptanediyl group. Cyclodecandyl groups can be 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 a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms is −O−. ^{, -CO -, - NR e -} , - S- or -SO ₂ - as the X ^d been replaced by, for example, groups represented by the formula (xd-1) ~ 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。］

[In the formula, 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 compounds (d-1) to (d-94). In the table, the formula number shown in the ^Xd column represents the formula number of the group exemplified above.
For example, 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), and an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (e) (provided that (however, A resin containing at least one constituent unit selected from the group consisting of constituent units derived from) (different from a) (hereinafter referred to as "(e)"), more preferably derived from (d). A resin containing a constituent unit derived from (e) and a constituent unit derived from (e), more preferably a constituent unit derived from (d), a constituent unit derived from (e), and a constituent unit derived from (b). It is a resin containing.

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

Since the resin (B) contains the structural units derived from (a) and / or (e), the developability is excellent, so that the residue and unevenness due to development tend to be suppressed.
Since the resin (B) contains a structural unit derived from (b), the solvent resistance tends to be excellent.
The resin (B) may contain other structural units. Examples of the monomer (hereinafter referred to as “(c')”) for deriving other structural units include unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides among the compounds shown in (c) above. Compounds include.

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). It is preferably in the following range with respect to the total number of moles.
Constituent 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 the structural units derived from each monomer constitutes the resin (B). It is preferably in the following range with respect to the total number of moles of the constituent units.
Constituent 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 ratio of the structural units derived from each monomer is the resin. It is preferably in the following range with respect to the total number of moles of the structural units constituting (B).
Constituent 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)
Constituent 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 within the above range, the liquid repellency and developability are excellent.

The polystyrene-equivalent weight average molecular weight of the resin (B) is excellent in coatability, the film of the exposed portion is less likely to be thinned during development, and the non-exposed portion is easily removed by development, so that it is preferably 3,000 to 20,000. It is more preferably 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 content of the resin (B) is excellent in developability at the time of pattern formation, and the obtained pattern is excellent in liquid repellency. Therefore, the total of the resin (A), the resin (X) and the polymerizable compound (C) The amount is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass.

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): Examples thereof include a resin obtained by reacting (a) and / or (e) with a polymer obtained by polymerizing (b) and (c').

In the resin (X1-1), the ratio of the structural units derived from each monomer is preferably in the following range with respect to the total number of moles of all the structural units constituting the resin (X1-1).
Constituent unit derived from (e); 5-60 mol% (more preferably 10-50 mol%)
Constituent unit derived from (b); 40-95 mol% (more preferably 50-90 mol%)
When the ratio of the constituent units of the resin (X1-1) is within the above range, the storage stability of the photosensitive resin composition, the developability when forming a pattern from the photosensitive resin composition, and the obtained coating are obtained. The solvent resistance of the film and pattern is improved.

In the resin (X1-2), the ratio of the structural units derived from each monomer is preferably in the following range with respect to the total number of moles of all the structural units constituting the resin (X1-2).
Constituent unit derived from (e); 2 to 45 mol% (more preferably 5 to 40 mol%)
Constituent unit derived from (b); 2 to 95 mol% (more preferably 5 to 80 mol%)
Constituent unit derived from (c'); 1-65 mol% (more preferably 5-60 mol%)
When the ratio of the constituent units of the resin (X1-2) is within the above range, the storage stability of the photosensitive resin composition, the developability when forming a pattern from the photosensitive resin composition, and the obtained coating are obtained. The solvent resistance of the film and pattern is improved.

In the resin (X1-3), the ratio of the structural units derived from each monomer is preferably in the following range with respect to the total number of moles of all the structural units constituting the resin (X1-3).
Constituent unit derived from (e); 2-40 mol% (more preferably 5-35 mol%)
Constituent unit derived from (c'); 60-98 mol% (more preferably 65-95 mol%)
When the ratio of the constituent units of the resin (X1-1) is within the above range, the storage stability of the photosensitive resin composition, the developability when forming a pattern from the photosensitive resin composition, and the obtained coating are obtained. The solvent resistance of the film and pattern is improved.

The resin (X1-4) can be produced, for example, through a two-step process. In this case as well, the method described in the above-mentioned document "Experimental Method for Polymer Synthesis" (written by Takayuki Otsu, Kagaku-Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972), JP-A-2001 It can be produced with reference to the method described in Japanese Patent Application Laid-Open No. 89533.

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

As a second step, a part of the unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride of (e) derived from the obtained polymer is reacted with the cyclic ether of (b) described above. Since the reactivity of the cyclic ether is high and the unreacted (b) is unlikely to remain, (b1) or (b2) is preferable as the (b) used for the resin (X1-2), and (b1-1). Is more preferable.
Specifically, following the above, the atmosphere in the flask is replaced with air from nitrogen, and the reaction catalyst of (b) the carboxy group and the cyclic ether in an amount of 5 to 80 mol% with respect to the number of moles of (e). (For example, tris (dimethylaminomethyl) phenol) is 0.001 to 5% by mass based on the total amount of (e), (b) and (c'), and a polymerization inhibitor (for example, hydroquinone). To the total amount of (a), (b) and (c), 0.001 to 5% by mass was placed in a flask and reacted at 60 to 130 ° C. for 1 to 10 hours to obtain a resin (X1). -4) can be obtained. As with the polymerization conditions, the charging method and the reaction temperature can be adjusted in consideration of the production equipment, the calorific value due to 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 obtained coating film and pattern. Since the balance between properties, mechanical strength and sensitivity is good, it is preferably 10 to 75 mol%, more preferably 15 to 70 mol% with respect to the number of moles of (e).

As the first step, the resin (X1-5) obtains a polymer of (b) and (c') in the same manner as in the above-mentioned method for producing the resin (A-1).
In this case, similarly to the above, the obtained polymer may be a solution after the reaction as it is, a concentrated or diluted solution may be used, or a solid (powder) by a method such as reprecipitation. You may use the one 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 the structural units constituting the polymer.
Constituent unit derived from (b); 5 to 95 mol% (more preferably 10 to 90 mol%)
Constituent unit derived from (c'); 5 to 95 mol% (more preferably 10 to 90 mol%)

Further, in the same manner as in the method for producing the resin (X1-4), the cyclic ether derived from (b) in the polymer of (b) and (c') contains (a) and / or (e). It can be obtained by reacting the carboxylic acid or carboxylic acid anhydride having. The hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or the carboxylic acid anhydride may be further reacted with the carboxylic acid 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 the unreacted (b) is unlikely to remain, (b1) is preferable as (b), and (b1-1) is more preferable.

The polystyrene-equivalent weight average molecular weight of the resin (X) is excellent in coatability, the film of the exposed portion is less likely to be thinned during development, and the non-exposed portion is easily removed by development. It is more preferably 5,000 to 50,000.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (X) is preferably 1.1 to 6.0, more preferably 1.2 to 4 because it is excellent in developability. It is 0.0.

The acid value of the resin (X) is usually 20 to 150 mgKOH / g, preferably 40 to 135 mgKOH / g, and 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 to 80% by mass, more preferably 1 to 50% by mass.

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

Examples of the polymerizable compound (C) having one ethylenically unsaturated bond include the same compounds as those listed in (a), (b) and (c) above, and 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 di. (Meta) 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, bisphenol A bis (acryloyloxyethyl) ether, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, 3-methylpentane Dioldi (meth) acrylate can be mentioned.

Examples of the polymerizable compound (C) having three or more ethylenically unsaturated bonds include trimethritol propanthritol (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxyethyl) isocyanuratetri (meth). ) Pentaerythritol ethoxylated trimethylolpropanetri (meth) acrylate, propoxythritol trimethylolpropanetri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Tryentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri ( Reaction of meta) acrylate and acid anhydride, reaction of dipentaerythritol penta (meth) acrylate and acid anhydride, reaction of tripentaerythritol hepta (meth) acrylate and acid anhydride, caprolactone-modified trimethylol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol Pentaerythritol. (Meta) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone Modified tripentaerythritol hepta (meth) acrylate, caprolactone-modified tripentaerythritol octa (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride reaction product, caprolactone-modified dipentaerythritol penta (meth) acrylate Reaction with acid anhydride, caprolactone-modified tripentaerythritol hepta (meth) acrylate and acid anhydride Examples thereof include a polymerizable compound (C) having three or more ethylenically unsaturated bonds, and more preferably dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, and penta. It is an erythritol tri (meth) acrylate.

The content of the polymerizable compound (C) is the sum of the resin (A), the resin (X) and the polymerizable compound (C) because the sensitivity, the strength of the obtained pattern, the smoothness, and the reliability are improved. It is preferably 20 to 55% by mass, more preferably 30 to 45% by mass, based on the amount.

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 described in JP-A-2008-18187 (for example, a compound composed of an onium cation and an anion derived from Lewis acid) is used. You may. 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 because the photosensitive resin composition becomes highly sensitive, and more preferably. Is an alkylphenone compound.

The O-acyloxime 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-acyloxym compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-. 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4) −Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-Il] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropane-1 −On-2-imine can be mentioned. As the O-acyloxime compound, commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) and the like may be used.

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 and 2-dimethylamino-1- (4). -Morholinophenyl) -2-benzyl butane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one Can be mentioned. As the compound, commercially available products such as Irgacure (registered trademark) 369, 907, 379 (all manufactured by BASF) may be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2). -Hydroxyethoxy) phenyl] Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, α, α-diethoxy Examples thereof include acetophenone and benzyl dimethyl 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, JP-A-6-75373), 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-Tetraphenyl biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,
2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5' -Tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204), the phenyl group at the 4,4', 5,5'-position is a carboalkoxy group. The imidazole compound substituted with (eg, Japanese Patent Application Laid-Open No. 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 and 2,4-bis (trichloromethyl) -6- (4-methoxy). Naftyl) -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- (fran-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 Be done.

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-benzoyl benzoate and 4-phenyl. Benzophenone compounds such as benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9, Kinone-based compounds such as 10-phenanthrene quinone, 2-ethylanthraquinone, and camphorquinone; examples thereof include 10-butyl-2-chloroacrydone, benzyl, methyl phenylglycoxylate, and titanosen compounds.

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

The polymerization initiator (D) is preferably used in combination with the polymerization initiator (D1). The polymerization initiator (D1) is a compound or a sensitizer used to promote the polymerization of a polymerizable compound whose polymerization has been initiated by the polymerization initiator.

Examples of the polymerization initiator (D1) include thioxanthone, amine, and carboxylic acid. In addition, examples of the polymerization initiator (D1) include the compounds described in JP-A-2008-65319 and JP-A-2009-139923.

Examples of the 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 and 4-dimethyl. 2-Ethylhexyl aminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone Aromatic amines such as.

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

Examples of the combination of the polymerization initiator (D) and the polymerization initiator (D1) include a combination of alkylphenyl and thioxanthone, and a combination of alkylphenyl and aromatic amine. Specifically, for example, 2-Methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2,4-diethylthioxanthone, 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane-1 -On and 2,4-diethylthioxanthone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) butane-1-one and 2,4-diethylthioxanthone, 2-morpholino-1 -(4-Methylsulfanylphenyl) -2-methylpropan-1-one, 2-isopropylthioxanthone 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) butane-1-one and 4,4'-bis (diethylamino) benzophenone, 2-dimethylamino Included are -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 can be obtained. Phenyl) propane-1-one and 2,4-diethylthioxanthone, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propane-1-one, 2-isopropylthioxanthone and 4-isopropylthioxanthone.

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

Since the content of the polymerization initiator (D1) is highly sensitive and a pattern having a good shape can be obtained, 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, and more preferably 0.3 to 7 parts by mass.

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

Examples of the solvent (F) include an ester solvent (a solvent containing -COO- in the molecule and not containing -O-) and an ether solvent (a solvent containing -O- in the molecule and not containing -COO-). , Ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent, aromatic hydrocarbon solvent , Amid solvent, dimethyl sulfoxide and the like.

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

Examples of the ether solvent 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, and 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 Examples thereof include methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyletol and 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 Examples thereof include glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, and cyclohexanone. , 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 higher and 180 ° C. or lower at 1 atm because it can suppress unevenness during coating and improve the flatness of the coating film, and more preferably. Is 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, because the film coated with the photosensitive resin composition has high flatness. ~ 90% by mass.

The polyfunctional thiol compound (T) means a compound having two or more sulfanil 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, decandithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanyl propionate), and butanediol bis (3-sulfanyl acetate). , Ethylene glycol bis (3-sulfanyl acetate), trimethylolpropanthris (3-sulfanyl acetate), butanediol bis (3-sulfanyl propionate), trimethylolpropanthris (3-sulfanyl propionate), trimethylolpropane Tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyethyltris (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl) Butane), 1,4-bis (3-sulfanylbutyloxy) butane can be mentioned.

The content of the polyfunctional thiol compound (T) increases the sensitivity of the photosensitive resin composition and improves the developability. Therefore, the content of the polyfunctional thiol compound (T) is preferably 0. It is 1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass.

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

Examples of the silicone-based surfactant (non-fluorine-based) include surfactants having a siloxane bond, and specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, etc. 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, Examples thereof include TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan LLC).

Examples of the fluorine-based surfactant (non-silicone-based) include surfactants having a fluorocarbon chain, and specifically, Fluorinert (registered trademark) FC430 and FC431 (manufactured by Sumitomo 3M Co., Ltd.); Mega Fuck (registered trademark) F142D, F171, F172, F173, F177, F183, R30 (manufactured by DIC Co., Ltd.); Ftop (registered trademark) EF301, EF303, EF351, EF352 (Mitsubishi) Materials Denshi Kasei Co., Ltd.); Surfron (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.); E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain, and specifically, Megafvck (registered trademark) R08, BL20, F475, F477, and others. The same F443 (manufactured by DIC Co., Ltd.) can be mentioned, preferably Megafuck (registered trademark) F475.

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

The photosensitive resin composition of the present invention contains additives such as a filler, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, and chain transfer agents, if necessary. You may.

The photosensitive resin composition of the present invention does not substantially contain a colorant such as a pigment or a dye. 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 it is filled in a quartz cell having an optical path length of 1 cm and the transmittance is measured under the condition of 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 by using a spectrophotometer to measure 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) at a measurement wavelength of 400 to 700 nm. It is an average value when measured under the conditions of.

The photosensitive resin composition of the present invention is applied onto, for example, a substrate such as glass, metal, plastic, etc .; The 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 by 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 onto a substrate.
For coating, a coating device such as a spin coater, a slit & spin coater, a slit coater, an inkjet, a roll coater, or a dip coater can be used.

Then, for example, the applied photosensitive resin composition is dried or prebaked to remove volatile components such as a solvent and dried to obtain a smooth uncured coating film.
The thickness of the uncured coating film may be adjusted depending on the material used and the application, and is usually 1 to 6 μm.

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

In the exposure machine used for exposure, light less than 350 nm is cut by using a filter that cuts this wavelength range, and light near 436 nm, 408 nm, and 365 nm is taken out by a bandpass filter that extracts these wavelength ranges. It can be selectively taken out by using and uniformly irradiating the entire exposed surface with substantially parallel light rays. If a device such as a mask aligner or a stepper is used, accurate alignment between the mask and the base material can be performed.

A desired pattern shape can be obtained by bringing the exposed coating film into contact with a developing solution to dissolve a predetermined portion, for example, a non-exposed portion (that is, a non-pixel portion) and developing the coating film.
Examples of the developing method include a liquid filling method, a dipping method, and a spraying method.
The base material 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, and potassium silicate. , Sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia.

Examples of the organic basic compound 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.

Examples of the nonionic surfactant include polyoxyethylene derivatives such as polyoxyethylene alkyl ether, polyoxyethylene aryl ether, and polyoxyethylene alkyl aryl ether; oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, and polyoxyethylene. Examples thereof 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 dodecylnaphthalene sulfone. Examples thereof include 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 developing solution 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 development, a pattern can be obtained by washing the substrate with the coating film with water. Post-baking may be performed if necessary. Post-baking is preferably carried out, for example, at 150 to 240 ° C. for 10 to 180 minutes.

Since the components contained in the photosensitive resin composition interact with each other by the above-mentioned exposure and development, the pattern (and the partition wall for an inkjet) of the present invention contains the components as they are. Not at all.

When the uncured coating film is exposed, a coating film having no pattern is obtained by irradiating the entire surface with light without using a photomask on which a pattern is formed and / or omitting development. be able to.

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

FIG. 1 is an enlarged sectional view schematically showing a 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 comprises a support substrate 2, a partition wall 3 that defines a partition set in advance on the support substrate 2, and a plurality of organic EL elements 4 provided in the partition defined by the partition wall 3. Consists of including. The partition wall 3 corresponds to the partition wall for an inkjet of the present invention.

The partition wall 3 is formed on the support substrate 2 in a grid pattern or a stripe pattern, for example. 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 wall 3 is provided is hatched.

A plurality of recesses 5 defined by the partition wall 3 and the support substrate 2 are set on the support substrate 2. The recess 5 corresponds to a section defined by the partition wall 3.

The partition walls 3 in the display device 1 are provided in a grid pattern. Therefore, when viewed from one side of the thickness direction Z of the support substrate 2 (hereinafter, referred to as "in a plan view"), a plurality of recesses 5 are arranged in a matrix. That is, the recesses 5 are provided so as to be arranged at a predetermined interval in the row direction X and also at a predetermined interval in the column direction Y. The shape of each recess 5 in a plan view is not limited. For example, the recess 5 is formed in a substantially rectangular shape, a substantially elliptical shape, an oval shape, or the like in a plan view.
In the present embodiment, the recess 5 having a substantially rectangular shape in a plan view is provided. In the present specification, the row direction X and the column direction Y mean a direction perpendicular to the thickness direction Z of the support substrate and a direction perpendicular to each other.

In addition, as another embodiment, when a striped partition wall is provided, the partition wall is configured such that, for example, a plurality of partition wall members extending in the row direction X are arranged at predetermined intervals in the column direction Y. Will be done. In this embodiment, the striped bulkhead and the support substrate define a striped recess.

The partition wall is formed so that the width becomes narrower as the distance from the support substrate increases. For example, the cross-sectional shape of a partition wall extending in the row direction Y when cut in a plane perpendicular to the extending direction (row direction Y) is formed so that the width becomes narrower as the distance from the support substrate increases. .. FIG. 1 shows an isosceles trapezoidal partition wall, and when the upper base and the lower base on the support substrate side are compared, the lower base is wider than the upper base. The cross section of the partition wall actually formed does not necessarily have a trapezoidal shape, and the straight portion and the corner 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 plane existing at the position farthest from the support substrate 2 on the surface of the partition wall 3. Since the top surface of the partition wall 3 exhibits liquid repellency, it is possible to prevent the ink supplied to the region (recess 5) surrounded by the partition wall 3 from overflowing to the adjacent region along the top surface of the partition wall 3. Can be done.

The organic EL element 4 is provided in a compartment (that is, a recess 5) defined by the partition wall 3. When the grid-like partition wall 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 each recess 5, and are arranged on the support substrate 2 with a predetermined interval in the row direction X and a predetermined interval in the column direction Y. It is provided.

The shape of the partition wall 3 and its arrangement are set according to the specifications of the display device such as the number of pixels and the resolution and the ease of manufacturing. For example, the width of the partition wall 3 in the row direction X or the column direction Y is usually 5 μm to 50 μm. The height of the partition wall 3 is usually 0.5 μm to 5 μm. The distance 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 wall 3 can be formed by the same method as the above-mentioned pattern forming method using the photosensitive resin composition of the present invention.

When a striped partition wall is provided as another embodiment, the organic EL element 4 is arranged in each recess extending in the row direction X at a predetermined interval 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. Be done.

The organic EL element 4 is configured by laminating the first electrode, the organic EL layer, and the second electrode in this order from the support substrate side. In the present specification, one or more layers provided between the first electrode 6 and the second electrode 10 are referred to as organic EL layers, respectively. The organic EL element 4 includes at least one light emitting layer as the organic EL layer. In addition to the one light emitting layer, the organic EL element may include an organic EL layer different from the light emitting layer, if necessary. 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 between the first electrode 6 and the second electrode 10 as an organic EL layer. 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 that functions as an anode, the first organic EL layer 7 that functions as a hole injection layer, the second organic EL layer 9 that functions as a light emitting layer, and the second that functions as a cathode. The electrodes 10 are 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 element 4 are provided on the support substrate 2. The first electrode 6 is provided corresponding to the arrangement of the organic EL element 4, and is arranged in a matrix like the organic EL element 4. The partition wall 3 is mainly formed in a grid pattern in a region other than the first electrode 6, but 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 for each type of organic EL element, if necessary. In addition, 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 a region (recessed portion 5) surrounded by a partition wall 3 by an inkjet method, and then dries, heats, and / or lights. It is formed by irradiating and solidifying the ink.

The second organic EL layer 9 that functions 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 in which the red organic EL element 4R is provided, the green light emitting layer 9G is provided in the recess 5 in which 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 wall 3, and is continuously formed over a plurality of organic EL elements.

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

The pattern obtained from the photosensitive resin composition of the present invention is useful as a partition wall used for manufacturing a color filter, an ITO electrode of a liquid crystal display element, an organic EL display element, a circuit wiring substrate, or the like by an inkjet method. Further, for example, a photo spacer forming a part of a color filter substrate and / or an array substrate, a patternable overcoat, an interlayer insulating film, a protrusion for controlling liquid crystal orientation, 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. A coating film having no pattern is useful as an overcoat forming a part of a color filter substrate and / or an 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 the examples, "%" and "part" are mass% and parts by mass unless otherwise specified.

<Synthesis example 1>
An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace it with a nitrogen atmosphere, and 166 parts of propylene glycol monomethyl ether acetate and 52 parts of methoxypropanol were added and heated to 85 ° C. with stirring. did. Then, 233 parts of a mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8 and 9-yl acrylate, 77 parts of p-vinylbenzoic acid, 125 parts of propylene glycol monomethyl ether acetate. , And 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 the dropping, the polymer (resin Aa) 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 was kept at the same temperature for 3 hours and then cooled to room temperature. A solution was obtained. The weight average molecular weight Mw in terms of polystyrene of the resin Aa is 7.7 × 10 ^3, the molecular weight distribution of 1.90. The resin Aa has the following structural units.

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

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

<Examples 1 to 6 and Comparative Examples 1 to 3>
(Preparation of photosensitive resin composition)
As shown in Table 5, each component was mixed to prepare a photosensitive resin composition. In addition, "-" in the table means that it does not contain.

In Table 5, the details of each component are as follows. The number of copies described in the columns of resin (A) and resin (B) represents parts by mass 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 Industry Co., Ltd.)
Polymerization initiator (D): 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (Irgacure (registered trademark) 907; manufactured by BASF)
Polymerization Initiator (D1): 4,4'-bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Industry Co., Ltd.)
Silicon-containing compound (E1): x-12-984s (manufactured by Shinetsu Silicone Co., Ltd.)
Silicon-containing compound (E2): 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303, manufactured by Shinetsu Silicone Co., Ltd.)
Silicon-containing compound (E3): 3-glycidoxypropylmethyldimethoxysilane (KBM-402, manufactured by Shinetsu Silicone Co., Ltd.)
Silicon-containing compound (E4): N-phenyl-3-aminopropyltrimethoxysilane (KBM-573, manufactured by Shinetsu Silicone Co., Ltd.)
Solvent (Fa): Propylene glycol monomethyl ether acetate Solvent (Fb): Ethyl 3-ethoxypropionate Solvent (Fc): 3-methoxy1-butanol Solvent (Fd): 3-methoxybutyl acetate Solvent (F) is photosensitive The resin composition is mixed so that the solid content is "solid content (%)" in Table 5, and the values of the solvent (Fa), (Fb), (Fc) and (Fd) are set in the solvent (F). Represents the mass ratio of.

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

(Preparation of coating film)
A 2-inch square glass substrate (Eagle XG; manufactured by Corning Inc.) was washed successively with a neutral detergent, water and alcohol, and dried. Each of the photosensitive resin compositions obtained above was spin-coated on this glass substrate 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 degree reached 66 kPa, it was prebaked and dried at 80 ° C. for 2 minutes on a hot plate. After cooling, an exposure machine (TME-150RSK; manufactured by Topcon Corporation, light source; ultra-high pressure mercury lamp) was used to irradiate light with an exposure amount of 50 mJ / cm ² (365 nm standard) under an atmospheric atmosphere. An ultra-high pressure mercury lamp was used to irradiate the photosensitive resin composition with light at this time. After light irradiation, the coating film is immersed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 60 seconds while being shaken and brought into contact with the coating film. A coating film was obtained by heating (post-baking) at 230 ° C. for 20 minutes in an oven.

(Average transmittance of coating film)
The average transmittance (%) at 400 to 700 nm was measured with respect to the obtained coating film using a microspectroscopy device (OSP-SP200; manufactured by OLYMPUS). Higher transmittance means less absorption. The results are shown in Table 5.

(Contact angle)
With respect to the obtained coating film, the contact angle of anisole was measured using a contact angle meter (DGD Fast / 60; manufactured by GBX). The higher the contact angle, the higher the liquid repellency. If the contact angle in the coating film is high, the contact angle is also high in the pattern formed by using the same photosensitive resin composition. When a partition wall is formed of a photosensitive resin composition having a high contact angle and ink is printed by an inkjet device in the partition wall surrounded by the partition wall, the ink is easily repelled. Therefore, for example, when a color filter is produced by an inkjet method, color mixing of ink between adjacent pixel regions is unlikely to occur. The results are shown in Table 7.

(Pattern formation)
A 2-inch square glass substrate (Eagle XG; manufactured by Corning Inc.) on which ITO was vapor-deposited on the surface was sequentially washed with a neutral detergent, water and 2-propanol, and dried. Each of the above photosensitive resin compositions was spin-coated on this glass substrate so that the thickness after post-baking was 1.0 μm, and the degree of decompression was 66 kPa with a vacuum dryer (manufactured by Microtech Co., Ltd.). After drying under reduced pressure until it became dry, it was prebaked on a hot plate at 90 ° C. for 2 minutes and dried. After cooling, the distance between the substrate coated with this photosensitive resin composition and the quartz glass photomask is set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd., light source; ultra-high pressure mercury lamp) is used to create an atmosphere. Under an atmosphere, light with an exposure of 200 mJ / cm ² (365 nm standard) was irradiated.
As the 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 the four corners are cut into circles (oval circle)) is formed on the same plane. Was used. After light irradiation, the coating film was added to a developing solution prepared by diluting a tetramethylammonium hydroxide aqueous solution (Tokuso SD25 manufactured by Tokuyama Co., Ltd.) with pure water so as to have a concentration of 2.38% at 23 ° C. It was immersed and developed while shaking for 60 seconds, washed with water, and post-baked at 230 ° C. for 20 minutes in an oven to obtain a pattern.

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

Using an inkjet device (Litlex 120L manufactured by ULVAC) in the partition wall, 200 pL of the solution 1 to 3 is filled in each partition wall at 1000 sites, and a microscope is used to check whether the solute spreads to the end of the partition wall after drying. (MX61L manufactured by OLIMPUS, lens: LCPFLN20xLCD) was used to observe 30 points. In all of the solutions 1 to 3, when all 30 points were spread and spread, the wettability was described as "A", and the other areas were described as "B" because the wettability was poor. 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 blending and those stored at 23 ° C., humidity 50%, and shaded for 1 month after blending.
A 2-inch square glass substrate (Eagle XG; manufactured by Corning Inc.) is washed sequentially with a neutral detergent, water and alcohol, and the above two types of photosensitive resin compositions are placed on the glass substrate after post-baking. Spin-coated to a thickness of 1.0 μm, dried under reduced pressure with a vacuum dryer (manufactured by Microtech Co., Ltd.) until the degree of reduced pressure reaches 66 kPa, and then prebaked at 90 ° C. for 2 minutes on a hot plate. And dried. After cooling, the distance between the substrate coated with this photosensitive resin composition and the quartz glass photomask is set to 100 μm, and an exposure machine (TME-150RSK, manufactured by Topcon Co., Ltd., light source: ultra-high pressure mercury lamp) is used to create an atmosphere. Under an atmosphere, light with an exposure of 200 mJ / cm ² (365 nm standard) was irradiated. As the 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 the four corners are cut into circles (oval circle)) is formed on the same plane. Was used.
After light irradiation, the coating film was added to a developing solution prepared by diluting a tetramethylammonium hydroxide aqueous solution (Tokuso SD25 manufactured by Tokuyama Co., Ltd.) with pure water so as to have a concentration of 2.38%. It was immersed and developed while shaking for 60 seconds, and the remaining condition of the pattern was observed after washing with water. If all the patterns remain, it is indicated as "A" because the pattern persistence is good, and if all or part of the pattern is peeled off or missing, the pattern persistence is considered to be poor. Notated as "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 can obtain a pattern having excellent wettability while maintaining a good contact angle. Is recognized as possible.

1 Display device 2 Support substrate 3 Partition wall 4 Organic EL element 5 Recess 6 First electrode 7 First organic EL layer (hole injection layer)
9 Second organic EL layer (light emitting layer)
10 Second electrode

Claims (5)

It contains the component (A), the component (B), the component (C), the component (D), and the component (E), and the content of the component (A) is the sum of the component (A) and the component (C). A photosensitive resin composition having a content of 45% by mass or more and 80% by mass or less with respect to the 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 2 to 2 carbon atoms. Copolymer containing a structural unit derived from an unsaturated compound having a cyclic ether structure of 4 (B) Polymer containing a structural unit having a perfluoroalkyl group having 4 to 6 carbon atoms (C) Polymerizable compound (D) ) Polymerization initiator (E) A silicon-containing compound containing two or more oxylanyl groups and one or more trialkoxysilyl groups in one molecule. The photosensitive resin composition according to claim 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. A pattern formed by the photosensitive resin composition according to claim 1 or 2. A partition wall for an inkjet formed by the photosensitive resin composition according to claim 1 or 2. A display device including at least one selected from the group consisting of the pattern according to claim 3 and the partition wall for an inkjet according to claim 4.

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