TWI704416B - Photosensitive resin composition, pattern, partition wall for inkjet, and display device - Google Patents

Abstract

The subject of the present invention is to provide a photosensitive resin composition capable of stably forming patterns on glass.

The solution of the present invention is a photosensitive resin composition containing component (A), component (B), component (C), component (D), and, component (E), component (A) content system The total content with respect to the component (A) and the component (C) is 45% by mass or more and 80% by mass or less.

(A) A structural unit derived from a compound 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 anhydride having an ethylenically unsaturated bond, and Copolymer of unsaturated compounds with cyclic ether structure with 2 to 4 carbon atoms

(B) Polymers containing structural units having perfluoroalkyl groups with 4-6 carbon atoms

(C) Polymeric compound

(D) Polymerization initiator

(E) A silicon-containing compound containing two or more oxiranyl groups in one molecule.

Description

Photosensitive resin composition, pattern, partition wall for inkjet, and display device

The present invention relates to a photosensitive resin composition.

In recent years, display devices, etc., are made by inkjet methods such as color filters, ITO electrodes of liquid crystal display elements, organic electroluminescence (hereinafter referred to as "organic EL") display elements, and circuit wiring substrates. In the inkjet method, partitions (patterns) formed on a substrate such as glass using a photosensitive resin composition are used. As the photosensitive resin composition, for example, a photosensitive resin composition containing a copolymer of vinyl benzoic acid and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ] decyl acrylate is known (Patent Document 1).

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 5596621

However, the aforementioned photosensitive resin composition is difficult to stabilize in Patterns are formed on the glass.

Therefore, the purpose of the present invention is to provide a photosensitive resin composition capable of stably forming patterns on glass.

The present invention provides the following [1]~[5].

[1]

A photosensitive resin composition containing component (A), component (B), component (C), component (D), and component (E). The content of component (A) is relative to component (A) The total content with component (C) is 45% by mass to 80% by mass,

(A) A structural unit derived from a compound 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 anhydride having an ethylenically unsaturated bond, and Copolymer of structural unit of unsaturated compound of cyclic ether structure with 2 to 4 carbon atoms (hereinafter sometimes referred to as "resin (A)")

(B) A polymer containing a structural unit having a perfluoroalkyl group with 4 to 6 carbon atoms (hereinafter sometimes referred to as "resin (B)")

(C) Polymeric compound

(D) Polymerization initiator

(E) A silicon-containing compound containing two or more oxiranyl groups in one molecule.

[2]

The photosensitive resin composition of [1], wherein the component (D) is a polymerization initiator containing at least one selected from the group consisting of biimidazole compounds, Alkylphenone compounds, and oxime ester compounds Agent.

[3]

A pattern formed by the photosensitive resin composition as [1] or [2].

[4]

A partition wall for inkjet is formed by the photosensitive resin composition as [1] or [2].

[5]

A display device includes at least one selected from the group consisting of a pattern such as [3] and a partition wall for inkjet such as [4].

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

1‧‧‧Display device

2‧‧‧Support substrate

3‧‧‧Next door

4‧‧‧Organic EL element

5‧‧‧Concave

6‧‧‧The first electrode

7‧‧‧The first organic EL layer (hole injection layer)

9‧‧‧The second organic EL layer (light emitting layer)

10‧‧‧Second electrode

[FIG. 1] A cross-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] A plan view schematically showing a part of the display device 1 which is an example of the display device of the present invention.

Hereinafter, the present invention will be described in detail.

[Photosensitive resin composition]

Although the photosensitive resin composition of the present invention is a photosensitive resin composition containing component (A), component (B), component (C), component (D), and component (E), it preferably further contains As a solvent for component (F) (hereinafter referred to as "solvent (F)"). In this specification, the term "solid content" means a component obtained by removing the solvent (F) from the photosensitive resin composition.

In addition, the photosensitive resin composition of the present invention may include a resin selected from the group consisting of resin (A) and resin (B) (hereinafter referred to as "resin (X)"), polymerization initiation auxiliary (D1), and polyfunctional sulfur At least one of the group consisting of alcohol compound (T) and surfactant (G).

In addition, in this specification, the compound exemplified as each component can be used individually by 1 type or in combination of 2 or more types, unless it specifically limits.

As the resin (A), for example,

Resin (A-1): A compound (a) containing at least one compound derived from the group consisting of aromatic carboxylic acids having ethylenically unsaturated bonds and aromatic carboxylic acid anhydrides having ethylenically unsaturated bonds ( Hereinafter referred to as "(a)"), the polymerization of the structural unit derived from the unsaturated compound (b) (hereinafter referred to as "(b)") having a cyclic ether structure with 2 to 4 carbon atoms Things,

Resin (A-2): A monomer (c) that can polymerize with (a) and (b) and does not have a cyclic ether structure with 2 to 4 carbon atoms (hereinafter referred to as "(c)"), A polymer with (a) and (b).

However, (a), (b) and (c) do not have a perfluoroalkyl group with 4-6 carbon atoms.

(a) At least one compound selected from the group consisting of an aromatic carboxylic acid having an ethylenically unsaturated bond and an aromatic carboxylic anhydride having an ethylenically unsaturated bond, specifically, o-ethylene Aromatic carboxylic acids such as methyl benzoic acid, m-vinyl benzoic acid, p-vinyl benzoic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid; 3-vinyl phthalic anhydride, 4 -Aromatic carboxylic anhydrides such as vinyl phthalic anhydride.

(b) It is a compound having a cyclic ether structure with 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an ethylene oxide ring, an Oxetane ring and a tetrahydrofuran ring). It is preferably a monomer having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated double bond, and more preferably a monomer having a cyclic ether structure with 2 to 4 carbon atoms and a (meth)acryloxy group Compound.

In this specification, the term "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

As (b), for example, a compound having an oxirane group (b1) (hereinafter referred to as "(b1)"), a compound having an oxirane group (b2) (hereinafter referred to as "(b2)") , Compound (b3) having a tetrahydrofuran group (hereinafter referred to as "(b3)").

As (b1), for example, a compound (b1-1) (hereinafter referred to as "(b1-1)") having a structure of epoxylated unsaturated aliphatic hydrocarbon group, The compound (b1-2) (hereinafter referred to as "(b1-2)") having the structure of epoxy-based unsaturated alicyclic hydrocarbon, since the photosensitive resin composition has excellent storage stability, it is preferable to have The compound of an oxirane group and a (meth)acryloxy group is more preferably a compound having a structure of an epoxylated unsaturated alicyclic hydrocarbon and a (meth)acryloxy group.

Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, and β-ethylglycidyl (meth)acrylate , Glycidyl vinyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl Benzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxy) Methyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene Methyl)styrene, 2,3,4-gins(glycidoxymethyl)styrene, 2,3,5-gins(glycidoxymethyl)styrene, 2,3,6 -Ginseng (glycidoxymethyl) styrene, 3,4,5-gins (glycidoxymethyl) styrene, 2,4,6-gins (glycidoxymethyl) benzene Vinyl. As (b1-1), other compounds described in JP 7-248625 A can be cited.

Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE (registered trademark) 2000; Daicel Chemical Industry Co., Ltd.) ), 3,4-epoxycyclohexyl methacrylate (e.g. CYCLOMER (registered trademark) A400: manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexyl methacrylate (e.g. CYCLOMER (registered trademark) M100; Daicel Chemical Industry Co., Ltd.), The compound represented by formula (I) and the compound represented by formula (II).

[式中，R¹及R²分別獨立表示氫原子、或、碳原子數1~4之烷基，該烷基所包含之氫原子可被羥基取代。X¹及X²分別獨立表示單鍵、*-R³-、*-R³-O-、*-R³-S-、*-R³-NH-。R³係表示碳原子數1~6之烷二基(Alkanediyl)。*係表示與O的鍵結手]。

[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 by a hydroxyl group. X ¹ and X ² each independently represent a single bond, *-R ³ -, *-R ³ -O-, *-R ³ -S-, and *-R ³ -NH-. R ³ represents an alkanediyl group (Alkanediyl) having 1 to 6 carbon atoms. *Denotes the bond with O].

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

Examples of the alkyl group substituted by hydroxy include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1 -Methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl.

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 represented by R ³ include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and pentane. -1,5-diyl, hexane-1,6-diyl.

X ¹ and X ^{2 are} preferably a single bond, a methylene group, an ethylene group, *-CH ₂ -O- (* means a bonding hand with O), or, *-CH ₂ CH ₂ -O-, More preferably, it is a single bond, or, *-CH ₂ CH ₂ -O-.

As the compound represented by the formula (I), for example, compounds represented by the formula (I-1) to the formula (I-15) can be cited, and the formula (I-1), the formula (I-3), and the formula (I- 5) Compounds represented by formula (I-7), formula (I-9) or formula (I-11)~formula (I-15), more preferably formula (I-1), formula (I-7) , The compound represented by formula (I-9) or formula (I-15).

As the compound represented by the formula (II), for example, compounds represented by the formula (II-1) to the formula (II-15) can be cited, and the formula (II-1), the formula (II-3), and the formula (II- 5), formula (II-7), formula (II-9) or formula (II-11) ~ formula (II-15) The compound is more preferably a compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15).

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

As (b2), a compound having a propylene oxide group and a (meth)acryloxy group is preferred, and 3-methyl-3-(meth)acryloxymethyl propylene oxide is more preferred. -Ethyl-3-(meth)acryloxymethyl propylene oxide, 3-methyl-3-(meth)acryloxyethyl propylene oxide, 3-ethyl-3-(formaldehyde) Base) propylene oxide oxyethyl propylene oxide.

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

As (c), for example, (meth)acrylate, N-substituted maleimide, unsaturated dicarboxylic acid diester, alicyclic unsaturated compound, unsaturated carboxylic acid, unsaturated carboxylic anhydride, benzene Ethylene and other vinyl compounds.

Examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and sec-butyl (meth)acrylate , Tert-butyl (meth)acrylate and other alkyl esters; cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane -8-yl (meth)acrylate (as a common name, also known as "Pentanyl (meth)acrylate"), dicyclopentanyloxyethyl (meth)acrylate , Tricyclic [5.2.1.0 ^2,6 ] decene-8-yl (meth)acrylate (as a common name, also known as "dicyclopentenyl (meth)acrylate"), isobornyl ( Cycloalkyl esters such as meth)acrylate; Hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Phenyl (meth)acrylate, benzyl Aryl and aralkyl esters such as (meth)acrylate.

Examples of N-substituted maleimines include N-phenyl Maleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N -Succinimidyl-4-maleiminobutyrate, N-succinimidyl-6-maleiminohexanoate, N-succinimidyl-3-maleimino Imine propionate, N-(9-acridinyl) maleimide.

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

As the alicyclic unsaturated compound, for example, bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]heptane -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-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2. 1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5- Hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[ 2.2.1]Hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexoxycarbonylbicyclo[2.2.1]hept-2-ene, 5 -Phenoxycarbonyl bicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyl) (Oxycarbonyl) bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds.

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-cyclohexene dicarboxylic acid, etc. Saturated dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept -2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6 -Methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other carboxyl-containing bicyclic unsaturated compounds; succinic acid mono[2- (Meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl] and other unsaturated mono[(meth)acrylic acid Oxyalkyl] ester; α-(hydroxymethyl)acrylic acid and other unsaturated (meth)acrylates containing hydroxyl and carboxyl groups in the same molecule.

Examples of unsaturated carboxylic acid anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrobenzene Dicarboxylic acid anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. Saturated dicarboxylic anhydride.

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

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

As (c), since polymerization reactivity and alkali solubility are good, Therefore, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, or, bicyclo[2.2.1]hept-2-ene are preferred. .

In resin (A-1) and resin (A-2), the content of the constituent unit derived from (a) and the content of the constituent unit derived from (b) are preferably relative to the constituent unit derived from (a) The total number of moles with the constituent unit derived from (b) is in the following range.

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

The 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 preferably relative to the total number of moles (100 moles) of the structural unit derived from (a) and the structural unit derived from (b) Part) is more than 0 mol part and 300 mol part or less, 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 in the above-mentioned range, there are the storage stability of the photosensitive resin composition, the developability when the pattern is formed from the photosensitive resin composition, and The solvent resistance, heat resistance, and mechanical strength of the resulting coating film and pattern tend to become better.

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) can be, for example, the method described in the document "Experimental Method of Polymer Synthesis" (Otsu Takayuki Publishing House (Stock) Chemical Doujin 1st Edition, Issue 1 March 1, 1972), and the document The cited documents are made as references.

Specifically, it is exemplified that predetermined amounts of (a) and (b) or (a) and (b) and (c), polymerization initiator, solvent, etc. are placed in the reaction vessel, for example, by By replacing the oxygen in the atmosphere with nitrogen, it becomes a method of heating and keeping warm while stirring in a deoxidizing environment. Furthermore, the polymerization initiator, solvent, etc. used here can be used, for example, by those generally used in this field.

As the polymerization initiator, for example, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), organic peroxides Products (benzyl peroxide, etc.).

As the solvent, what is necessary is to dissolve each monomer, and as the solvent (F) of the photosensitive resin composition, the solvent described later can be used.

In order to adjust the molecular weight of the resulting resin, a chain transfer agent can be added during the polymerization reaction.

As the chain transfer agent, for example, n-butane mercaptan, tert-butane mercaptan, n-dodecyl mercaptan, 2-hydrothioethanol, ethanethiol acid, ethyl ethanethiolate, ethane Thiols such as 2-ethylhexyl thiol acid, methoxybutyl ethanethiolate, 3-hydrothiopropionic acid, silicon oxide containing hydrogen sulfide groups (KF-2001: manufactured by Shin-Etsu Chemical); chloroform , Carbon tetrachloride, carbon tetrabromide and other halogenated alkyl groups.

The resulting polymer can be used directly as a solution after the reaction, or a concentrated or diluted solution, and can be used as a solid (powder) taken out by methods such as reprecipitation. In this polymerization, when the same solvent is used as the solvent (F) described later as the solvent, the solution after the reaction can be used as it is, and the production steps can be simplified.

The weight average molecular weight in terms of polystyrene of the resin (A) is excellent in coatability, and it is difficult to cause film damage in the exposed part during development, and the non-exposed part is easy to be removed by development, so it is preferably 3,000 to 100,000, more preferably 5,000~50,000.

Since the molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (A) is excellent in developability, it is preferably 1.1 to 6.0, more preferably 1.2 to 4.0.

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 by using 1 g of resin as the amount (mg) of potassium hydroxide necessary for neutralization, and can be obtained by titration using an aqueous potassium hydroxide solution.

The content of the resin (A) relative to the total content of the resin (A) and the polymerizable compound (C) is usually 45% by mass or more and 80% by mass or less. This is because the partition pattern formed by the photosensitive resin composition The wettability of the substrate surface is good, so it is preferably from 48% by mass to 75% by mass, and more preferably from 50% by mass to 70% by mass.

The structural unit having a perfluoroalkyl group with 4 to 6 carbon atoms contained in the resin (B) is, for example, an unsaturated compound (d) derived from a perfluoroalkyl group with 4 to 6 carbon atoms (hereinafter referred to as "(D)") constitute the unit.

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

[式中，R^f係表示碳原子數4~6之全氟烷基。

[In the formula, 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 may be substituted by a halogen atom or a hydroxyl group.

X ^d represents a single bond, a divalent aliphatic hydrocarbon group with 1 to 10 carbon atoms, a divalent alicyclic hydrocarbon group with 3 to 10 carbon atoms, or a divalent aromatic hydrocarbon group with 6 to 12 carbon atoms. The aliphatic hydrocarbon group and one or more -CH ₂ -contained in the alicyclic hydrocarbon group may be substituted with, -O-, -CO-, -NR ^e -, -S- or -SO ₂ -].

R ^{f is} preferably perfluorobutyl or perfluorohexyl.

Examples of the alkyl group having 1 to 21 carbon atoms represented by R ^d include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n- Linear alkyl groups such as octyl, n-nonyl, n-decyl, etc.; isopropyl, isobutyl, sec-butyl, isopentyl, 1-methylpentyl, 2-methylpentyl , 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methyl Hexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 1-propylbutyl, 1-methylheptyl, 2-methylheptyl , 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethyl Hexyl, 2-propylpentyl, 1-butylbutyl, 1-butyl-2-methylbutyl, 1-butyl-3-methylbutyl, tert-butyl, 1,1- Dimethylpropyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1-ethyl -2-methylpropyl, 1,1-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 2, 2-Dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3,4-dimethylpentyl, 1- Branched chain alkyl groups such as ethyl-1-methylbutyl and 2-ethyl-3-methylbutyl.

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 methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, and butane- 1,4-diyl, butane-1,3-diyl, butane-1,2-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane- 1,7-diyl, octane-1,8-diyl and other alkanediyl groups.

Examples of the divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms represented by X ^d include cyclopropane diyl, cyclobutane diyl, cyclopentane diyl, cyclohexane diyl, and cycloheptane diyl. , Cyclodecane diyl.

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

One or more -CH ₂ -contained in a divalent aliphatic hydrocarbon group with 1 to 10 carbon atoms and a divalent alicyclic hydrocarbon group with 3 to 10 carbon atoms are -O-, -CO-,- X ^d substituted by NR ^e -, -S- or -SO ₂ -can be, for example, groups represented by formula (xd-1) to formula (xd-9).

X ^{d is} preferably an alkanediyl group having 1 to 6 carbon atoms, more preferably an ethylidene group.

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

[式中，R^h係表示碳原子數4~6之全氟烷基；R^g係表示氫原子、鹵素原子或甲基]。

[In the formula, R ^h represents a perfluoroalkyl group having 4-6 carbon atoms; R ^g represents a hydrogen atom, a halogen atom or a methyl group].

Examples of the compound represented by the formula (d-0) include compound (d-1) to compound (d-94). In the table, the formula number shown in the X ^d column represents the formula number of the base exemplified above.

For example, compound (d-1) is a compound represented by formula (d-1).

The resin (B) preferably contains a structural unit derived from (d), a structural unit derived from (a), and is selected from unsaturated carboxylic acid and/or unsaturated carboxylic anhydride (e) (except with ( a) Different) (hereinafter referred to as "(e)") the resin of at least one of the constituent units in the group consisting of the constituent units, more preferably the constituent unit derived from (d) and the resin derived from (e) The resin of the constituent unit of, is more preferably a resin containing the constituent unit derived from (d), the constituent unit derived from (e), and the constituent unit derived from (b).

As (e), the unsaturated carboxylic acid and unsaturated carboxylic acid in (c) can be mentioned Anhydride exemplified compound.

Since the resin (B) contains the structural unit derived from (a) and/or (e), since it is excellent in developability, it has a tendency to suppress unevenness derived from residue or development.

Resin (B) has a tendency to be excellent in solvent resistance by containing the constituent unit derived from (b).

The resin (B) may contain other structural units. As monomers directed to other structural units (hereinafter referred to as "(c')"), for example, among the compounds shown in (c) above, compounds other than unsaturated carboxylic acids and unsaturated carboxylic anhydrides can be cited.

When the resin (B) is a polymer of (a) and/or (e) and (d), it is preferable that the ratio of the constituent units derived from each monomer to the total of the constituent units of the resin (B) The number of moles is in the following range.

Component units derived from (a) and/or (e); 5-40% by mass (more preferably 10-30% by mass)

The constituent unit derived from (d); 60~95% by mass (more preferably 70~90% by mass)

When the resin (B) is a polymer of (a) and/or (e) and (b) and (d), it is preferable that the ratio of the constituent unit derived from each monomer to the constituent resin (B) is The total number of moles of the constituent units is in the following range.

Component units derived from (a) and/or (e); 5-40% by mass (more preferably 10-30% by mass)

The constituent unit derived from (b); 5~80% by mass (more preferably 10~70% by mass)

The constituent unit derived from (d); 10~80% by mass (more preferably 20~70% by mass)

When the resin (B) is a polymer of (a) and/or (e) and (b) and (c,) and (d), it is preferable that the ratio of the constituent unit derived from each monomer to The total number of moles of the constituent units of the constituent resin (B) is in the following range.

Component units derived from (a) and/or (e); 5-40% by mass (more preferably 10-30% by mass)

The constituent unit derived from (b); 5~70% by mass (more preferably 10~60% by mass)

The constituent unit derived from (c’); 10-50% by mass (more preferably 20-40% by mass)

The constituent unit derived from (d); 10~80% by mass (more preferably 20~70% by mass)

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

The weight average molecular weight in terms of polystyrene of the resin (B) is excellent in coating properties, and it is difficult to cause film damage in the exposed part during development, and the non-exposed part is easily removed by development, so it is preferably 3,000 to 20,000, more preferably 5,000~15,000.

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 during pattern formation and the resulting pattern is excellent in liquid repellency, so it is 100 mass relative to the total amount of resin (A), resin (X) and polymerizable compound (C) Parts, preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass.

As the resin (X), for example,

Resin (X1-1): a polymer formed by polymerizing (e) and (b),

Resin (X1-2): a polymer formed by polymerizing (e), (b) and (c’)

Resin (X1-3): a polymer formed by polymerizing (e) and (c’),

Resin (X1-4): Resin obtained by reacting (b) the polymer formed by polymerizing (e) and (c'),

Resin (X1-5): A resin obtained by reacting (a) and/or (e) with the polymer formed by polymerizing (b) and (c').

In the resin (X1-1), the ratio of the constituent units derived from each monomer is preferably in the following range with respect to the total number of moles of all constituent units of the constituent resin (X1-1).

The constituent unit derived from (e); 5-60 mol% (more preferably 10-50 mol%)

The 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 in the above range, the storage stability of the photosensitive resin composition, the developability when a pattern is formed from the photosensitive resin composition, and the resulting coating film and pattern The solvent resistance becomes better.

In the resin (X1-2), it is preferable that the ratio of the constituent units derived from each monomer is in the following range with respect to the total number of moles of all constituent units of the constituent resin (X1-2).

The constituent unit derived from (e); 2~45 mol% (more preferably 5~40 mol%)

The constituent unit derived from (b); 2~95 mol% (more preferably 5~80 mol%)

The 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 in the above range, the storage stability of the photosensitive resin composition, the developability when a pattern is formed from the photosensitive resin composition, and the resulting coating film and pattern The solvent resistance becomes better.

In the resin (X1-3), the ratio of the constituent units derived from each monomer is preferably in the following range with respect to the total number of moles of all constituent units of the constituent resin (X1-3).

The constituent unit derived from (e); 2~40 mol% (more preferably 5~35 mol%)

The 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 in the above range, the storage stability of the photosensitive resin composition, the developability when a pattern is formed from the photosensitive resin composition, and the resulting coating film and pattern The solvent resistance becomes better.

The resin (X1-4) can be produced through a two-stage process, for example. In this case, the method described in the above-mentioned document "Experimental Method of Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd. Chemical Doujin 1st Edition, First Edition, Issued on March 1, 1972), Japan Special Publication 2001 The method described in Bulletin -89533 is used as a reference to manufacture.

As the first stage, the same method as the above-mentioned resin (A-1) production method is performed to obtain the polymers of (e) and (c'). In this case, similar to the above, the resulting polymer can be directly used as a solution after the reaction, a concentrated or diluted solution can be used, and a solid (powder) taken out by a method such as reprecipitation can be used. In addition, the weight average molecular weight and molecular weight distribution in terms of polystyrene are the same as those described above.

However, the ratio of the constituent units derived from (e) and (c') is preferably in the following range with respect to the total number of moles of all constituent units constituting the aforementioned polymer.

The constituent unit derived from (e); 5~50 mol% (more preferably 10~45 mol%)

The constituent unit derived from (c’); 50~95 mol% (more preferably 55~90 mol%)

As the second stage, a part of the unsaturated carboxylic acid and/or unsaturated carboxylic anhydride derived from (e) of the obtained polymer is reacted with the cyclic ether of (b) mentioned above. Since the reactivity of the cyclic ether is high, and the unreacted (b) is hard to remain, the (b) used as the resin (X1-2) is preferably (b1) or (b2), more preferably (b1- 1).

Specifically, following the above, the environment in the flask can be replaced from nitrogen to air, and (b) relative to the number of moles of (e) is 5 to 80 mole%, and the reaction of the carboxyl group and the cyclic ether can be contacted. The medium (e.g. ginseng (dimethylaminomethyl) phenol) is 0.001 to 5% by mass relative to the total amount of (e), (b) and (c'), and the polymerization inhibitor (e.g., hydroquinone, etc.) The total amount of (a), (b), and (c) is 0.001 to 5% by mass, which is put into a flask, and reacted at 60 to 130° C. for 1 to 10 hours to obtain resin (X1-4). Still, as with the polymerization conditions, it is possible to adjust the placement method and reaction temperature in consideration of manufacturing equipment or heat generation due to polymerization.

In this case, the molar number of (b) is due to the storage stability of the photosensitive resin composition, the developability when the pattern is formed from the photosensitive resin composition, and the solvent resistance and heat resistance of the resulting coating film and pattern. The balance of performance, mechanical strength, and sensitivity becomes better, and relative to the number of moles of (e), it is preferably 10 to 75 mole%, more preferably 15 to 70 mole%.

The resin (X1-5) as the first stage is carried out in the same manner as the above-mentioned resin (A-1) manufacturing method to obtain the polymers of (b) and (c').

In this case, similar to the above, the resulting polymer can be directly used as a solution after the reaction, a concentrated or diluted solution can be used, and a solid (powder) taken out by a method such as reprecipitation can be used.

The ratio of the constituent units derived from (b) and (c') is preferably in the following range with respect to the total number of moles of all constituent units constituting the aforementioned polymer.

The constituent unit derived from (b); 5~95 mol% (more preferably 10~90 mol%)

The constituent unit derived from (c’); 5~95 mol% (more preferably 10~90 mol%)

Furthermore, in the same manner as the production method of resin (X1-4), it is possible to make (a) and/or (e) a cyclic ether derived from (b) in the polymer of (b) and (c') ) It is obtained by reacting the carboxylic acid or carboxylic anhydride possessed. The hydroxyl group generated by the reaction of the cyclic ether with the carboxylic acid or the carboxylic anhydride can further react the carboxylic anhydride.

The amount of (a) and/or (e) used to react the aforementioned polymer is preferably 5 to 80 mol% relative to the number of mols of (b). Since the reactivity of the cyclic ether is high and the unreacted (b) hardly remains, (b) is preferably (b1), and more preferably (b1-1).

The weight average molecular weight in terms of polystyrene of the resin (X) is excellent in coatability, and it is difficult to cause film damage in the exposed part during development, and the non-exposed part is easily removed by development, so it is preferably 3,000 to 100,000, more preferably 5,000~50,000.

Since the molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (X) is excellent in developability, it is preferably 1.1 to 6.0, more preferably 1.2 to 4.0.

The acid value of 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 resin (X) is contained, its content can form patterns with high sensitivity, and because of its excellent developability, it is preferably 1 to 80% by mass relative to the total amount of resin (A) and resin (X), and more preferably It is 1-50% by mass.

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

As the polymerizable compound (C) having one ethylenically unsaturated bond, for example, the same compounds as those exemplified as the aforementioned (a), (b) and (c) can be cited, preferably (meth)acrylate .

As the polymerizable compound (C) having two ethylenically unsaturated bonds, for example, 1,3-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylate, 1 ,6-Hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, three Ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bis(acryloxyethyl) ether of bisphenol A, ethoxylated Bisphenol A di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, 3-methylpentanediol Di(meth)acrylate.

As the polymerizable compound (C) having three ethylenically unsaturated bonds, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ginseng (2-hydroxyethyl) Isocyanurate tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tetra( Meth) acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate Meth) acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, the reactant of pentaerythritol tri(meth)acrylate and acid anhydride, dipentaerythritol penta(meth)acrylate and The reactant of acid anhydride, tripentatetratetraethylene The reactant of alcohol seven (meth)acrylate and acid anhydride, caprolactone modified trimethylolpropane tri(meth)acrylate, caprolactone modified pentaerythritol tri(meth)acrylate, caprolactone modified Quality ginseng (2-hydroxyethyl) isocyanurate tri(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol penta(meth)acrylate , Caprolactone modified dipentaerythritol hexa(meth)acrylate, caprolactone modified tripentaerythritol tetra(meth)acrylate, caprolactone modified tripentaerythritol penta(meth)acrylate, caprolactone modified Quality tripentaerythritol hexa (meth) acrylate, caprolactone modified tripentaerythritol seven (meth) acrylate, caprolactone modified tripentaerythritol octa (meth) acrylate, caprolactone modified pentaerythritol three (meth) The reaction product of acrylate and acid anhydride, the reaction product of caprolactone-modified dipentaerythritol penta(meth)acrylate and acid anhydride, the reaction product of caprolactone-modified tripentaerythritol hepta(meth)acrylate and acid anhydride, Preferably, it is a polymerizable compound (C) having three or more ethylenically unsaturated bonds, more preferably dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate基)acrylate.

The content of the polymerizable compound (C) has good sensitivity, strength, smoothness, and reliability of the resulting pattern, so it is relative to the total amount of resin (A), resin (X), and polymerizable compound (C). It is preferably 20 to 55% by mass, more preferably 30 to 45% by mass.

As the polymerization initiator (D), if it is a compound that can start polymerization by the action of light or heat, a known polymerization initiator can be used. Examples of the polymerization initiator (D) include alkylphenones, biimidazoles, triazines, phosphine oxides, and O-oximes. As a polymerization initiator (D), it can be The light and/or thermal cationic polymerization initiator described in JP 2008-181087 A (for example, a compound composed of an onium cation and an anion derived from Lewis acid) is used. Since the polymerization initiator (D) is highly sensitive to the photosensitive resin composition, it is preferably at least one selected from the group consisting of biimidazole compounds, alkylphenone compounds, and O-oxime compounds, and more preferably For alkyl phenone compounds.

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

(式中，*係表示鍵結手，以下相同)。

(In the formula, * refers to the bonding hands, the following is the same).

Examples of O- oxime compounds include N-benzyloxy-1-(4-phenylhydrothiophenyl)butan-1-one-2-imine, N-benzyloxy -1-(4-phenylhydrosulfanylphenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylhydrosulfanylphenyl)-3 -Cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole-3- Yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxide Cyclopentylmethoxy) benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-( 2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl-6- (2-Methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. As O-acetoxime compound, Irgacure can be used (Registered trademark) Commercial products such as OXE01, OXE02 (the above are made by BASF), and N-1919 (made by ADEKA).

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

As a compound having a partial structure represented by the formula (d2), for example, 2-methyl-2-morpholinyl-1-(4-methylhydrothiophenyl)propan-1-one, 2-dimethyl Amino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl ]-1-[4-(4-Morpholinyl)phenyl]butan-1-one. As the aforementioned compound, commercially available products such as Irgacure (registered trademark) 369, 907, 379 (the above are made by BASF Corporation) can be used.

As the compound having a partial structure represented by the formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-( 2-hydroxyethoxy)phenyl)propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one The oligomer, α,α-diethoxy acetophenone, benzyl dimethyl ketal.

As the biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro Phenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Laid-Open No. 6-75372 Bulletin, Japanese Patent Laid-Open No. 6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2 -Chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5' -Tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (e.g. Refer to Japanese Patent Publication No. 48-38403 and Japanese Patent Application Publication No. 62-174204), 4,4',5,5'-position phenyl group substituted by carbonyl alkoxy (Carboalkoxy) imidazole compounds (for example, refer to Japanese Patent Laid-Open No. 7-10913), preferably 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis( 2, 3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5, 5'-Tetraphenylbiimidazole.

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) Yl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl (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)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2- Yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl ]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5- Triazine.

As the phosphine oxide compound, for example, 2,4,6-trimethylbenzyldiphenylphosphine oxide is mentioned.

In addition, as the polymerization initiator (D), for example, benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.; benzophenone, o-benzylbenzene Formic acid Methyl ester, 4-phenylbenzophenone, 4-benzyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl) Benzophenone compounds such as benzophenone and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10 -Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound.

As the polymerization initiator having a group capable of causing chain transfer, for example, the polymerization initiator described in JP 2002-544205 A can be cited.

A polymerization initiator having a group capable of causing chain transfer can also be used as the component (c) constituting the resin (A).

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

Examples of the polymerization initiation auxiliary (D1) include Thioxanthone, amine, and carboxylic acid. Other examples of the polymerization initiation adjuvant (D1) include compounds described in Japanese Patent Application Publication No. 2008-65319 and Japanese Patent Application Publication No. 2009-139932.

As the thioxanthone, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro -4-Propoxythioxanthone.

Examples of amines include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-Dimethylaminobenzoic acid Isoamyl ester, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl-p-toluidine, 4,4'-bis( Dimethylamino)benzophenone (common name; Michler's ketone), 4,4'-bis(diethylamino)benzophenone and other aromatic amines.

As the carboxylic acid, for example, phenyl thio acetic acid, methyl phenyl thio acetic acid, ethyl phenyl thio acetic acid, methyl ethyl phenyl thio acetic acid, dimethyl phenyl thio acetic acid Glycilic acid, methoxyphenyl hydrosulfanyl acetic acid, dimethoxyphenyl hydrosulfanyl acetic acid, chlorophenyl hydrosulfan acetic acid, dichlorophenyl sulfanyl acetic acid, N-phenylglycine, benzene Aromatic heteroacetic acid such as oxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

As the combination of the polymerization initiator (D) and the polymerization initiation auxiliary (D1), for example, a combination of an alkyl phenone and thioxanthone, a combination of an alkyl phenone and an aromatic amine, specifically, for example, Examples include 2-methyl-2-morpholinyl-1-(4-methylhydrothiophenyl)propane-1-one, 2,4-diethylthioxanthone, 2-dimethylamino -2-benzyl-1-(4-morpholinylphenyl)butan-1-one and 2,4-diethylthioxanthone, 2-dimethylamino-2-(4-methyl Benzyl)-1-(4-morpholinylphenyl)butan-1-one and 2,4-diethylthioxanthone, 2-morpholinyl-1-(4-methylsulfanylbenzene) Yl)-2-methylpropane-1-one and 2-isopropylthioxanthone and 4-isopropylthioxanthone, 2-morpholin-1-(4-methylsulfanylphenyl) -2-Methylpropane-1-one and 4,4'-bis(diethylamino)benzophenone, 2-dimethylamino-2-benzyl-1-(4-morpholinyl) Phenyl) butane-1-one and 4,4'-bis(diethylamino)benzophenone, 2-dimethylamino-2-(4-methylbenzyl)-1-( 4-morpholinylphenyl)butan-1-one and 4,4'-bis(diethylamino)benzophenone.

Due to the high sensitivity and high visible light transmittance pattern, the aforementioned group The combination is preferably alkylphenone and thioxanthone, more preferably 2-methyl-2-morpholinyl-1-(4-methylsulfanylphenyl)propan-1-one and 2,4- Diethylthioxanthone, 2-methyl-2-morpholin-1-(4-methylsulfanylphenyl)propan-1-one, 2-isopropylthioxanthone and 4-isopropyl Thioxanthone.

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

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

As the silicon-containing compound (E) containing two or more oxirane groups in one molecule, for example, x-12-981s, x-12-984s, x-12-984(x-12-984s ethanol solution ), KR-516, KR-517, x-41-1059A, x-41-1053, x-24-9590 (the above are made by Shin-Etsu Silicon Oxygen Co., Ltd.).

Among the silicon-containing compounds (E) containing two or more oxirane groups in one molecule, preferably containing two or more oxirane groups and one or more trialkoxysilyl groups (such as triethyl The silicon-containing compound of oxysilyl group and trimethoxysilyl group) is more preferably an organic polymer containing two or more oxirane groups and one or more trialkoxysilyl groups in one molecule, that is, a silicon-containing compound ( For example, x-12-981s, x-12-984s, x-12-984). The organic polymer is preferably an organic polymer whose main chain is an organic structure (organic chain). Still, trioxane The carbon number of the alkoxy group contained in the oxysilyl group is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 or 2.

The content of the silicon-containing compound (E) containing two or more oxirane groups per molecule is preferably 0.01-10 parts by mass relative 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 still more preferably 0.05 to 1 parts by mass.

As the solvent (F), for example, ester solvents (solvents containing -COO- in the molecule but not containing -O-), ether solvents (solvents containing -O- in the molecule but not containing -COO-), ethers Ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, Dimethyl sulfoxide.

Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoacetate Amyl ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, cyclohexane Alcohol acetate, γ-butyrolactone.

As the ether solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, Tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, two Ethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole (Anisole), phenylethyl ether, methyl anisole.

As the ether ester solvent, for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, 2-methoxypropyl propionate, 2-ethoxy methyl propionate, 2-ethoxy ethyl propionate, 2-methoxy-2-methyl propionate, 2- Ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether ethyl Acid ester.

As the ketone solvent, for example, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone, isophorone.

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

Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and trimethylbenzene.

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

The solvent (F) suppresses unevenness during coating and can improve the flatness of the coating film. Therefore, the boiling point at 1 atm is preferably 120°C or higher. Organic solvents below 180°C, more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetic acid Esters, 3-methoxy-1-butanol.

Since the content of the solvent (F) is high in flatness of the film coated with the photosensitive resin composition, it is preferably 60 to 95% by mass, and more preferably 70 to 90% by mass relative to the total amount of the photosensitive resin composition.

The polyfunctional thiol compound (T) means a compound having two or more sulfhydryl groups (-SH) in the molecule. As the polyfunctional thiol compound (T), when a compound having two or more sulfhydryl groups bonded to a carbon atom derived from an aliphatic hydrocarbon group is used, the sensitivity of the photosensitive resin composition is improved.

As the polyfunctional thiol compound (T), for example, hexanedithiol, decanedithiol, 1,4-bis(methylhydrothio)benzene, butanediol bis(3-hydrothiopropyl) Acid ester), butanediol bis(3-hydrothioacetate), ethylene glycol bis(3-hydrothioacetate), trimethylolpropane (3-hydrothioacetate) , Butanediol bis (3-hydrothio propionate), trimethylol propane ginseng (3-hydrothio propionate), trimethylol propane ginseng (3-hydrothio acetate), Pentaerythritol 4 (3-hydrothio propionate), pentaerythritol 4 (3-hydrothioacetate), ginseng hydroxyethyl ginseng (3-hydrothiopropionate), pentaerythritol 4 (3-hydrothio propionate) Butyrate), 1,4-bis(3-hydrothiobutyloxy)butane.

The content of the polyfunctional thiol compound (T) increases the sensitivity of the photosensitive resin composition and improves the developability, so it is preferably 0.1-10 parts by mass relative to 100 parts by mass of the polymerization initiator (D), and more Preferably it is 0.5-7 mass parts.

Surfactant (G) is different from resin (B), for example Silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants with fluorine atoms.

Examples of silicone-based surfactants (non-fluorine-based) include surfactants having siloxane bonds, specifically, Toray Silicone DC3PA, the same as SH7PA, the same as DC11PA, the same as SH21PA, the same as SH28PA, and the same as SH29PA , Same as SH30PA, polyether modified silicone oil SH8400 (trade name: Toray Dow Corning Co., Ltd.); KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (made by Momentive Performance Materials Japan contract company).

As the fluorine-based surfactant (non-silicone-based), for example, a surfactant having a fluorocarbon chain, specifically, Fluorinert (registered trademark) FC430, the same FC431 (manufactured by Sumitomo 3M Co., Ltd.); Megafac (Registered trademark) F142D, same as F171, same as F172, same as F173, same as F177, same as F183, same as R30 (DIC (share) system); Eftop (registered trademark) EF301, same as EF303, same as EF351, same as EF352 (Mitsubishi Materials Electronics Chemical (stock) system); Surflon (registered trademark) S381, the same as S382, the same as SC101, and the same as SC105 (Asahi Glass (stock) system); E5844 ((share) Daikin Fine Chemical Research Institute).

As the silicone-based surfactant having fluorine atoms, for example, surfactants having silicone bonds and fluorocarbon chains can be cited. Specifically, Megafac (registered trademark) R08, the same as BL20, the same as F475, and the same as F477 can be cited , Same as F443 (DIC (share) system), preferably Megafac (registrar Mark) F475.

The content of the surfactant (G) is usually 0.001% by mass to 0.2% by mass relative to the total amount of the photosensitive resin composition. Since the flatness of the coating film becomes better, it is preferably 0.002% by mass to 0.1% by mass. , More preferably 0.01% by mass or more and 0.05% by mass or less.

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

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

The photosensitive resin composition of the present invention is filled in a quartz cell with an optical path length of 1 cm. The average transmittance is preferably 70% or more when the transmittance is measured using a spectrophotometer at a wavelength of 400 to 700 nm, and more preferably Above 80%.

When the photosensitive resin composition of the present invention is used as 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 when a coating film with a thickness of 3μm after heat curing (for example, curing at 100-250°C, 5 minutes to 3 hours) is measured with a spectrophotometer at a measurement wavelength of 400-700nm average value.

For example, the photosensitive resin composition of the present invention can be coated on a substrate of glass, metal, plastic, etc.; on the aforementioned substrate for forming a color filter, an insulating film or a conductive film, a driving circuit, etc., patterning into a desired shape Shape, forming a pattern. Furthermore, this pattern can be formed and used as a part of constituent parts of a display device or the like.

[Coating, pattern]

The photosensitive resin composition of the present invention can be used to form coating films and patterns. Here, an example of this method is described.

First, the photosensitive resin composition of the present invention is coated on a substrate.

Coating devices such as spin coater, slit & spin coater, slit coater, inkjet, roll coater, dip coater, etc. can be used for coating.

Secondly, for example, by drying or pre-baking the coated photosensitive resin composition, volatile components such as solvents are removed and dried to obtain a smooth uncured coating film.

The thickness of the uncured coating film can be adjusted by the material used and the purpose, and it is usually 1~6μm.

Secondly, the uncured coating film passes through the mask used to form the target pattern and irradiates light (for example, ultraviolet light generated from a mercury lamp or a light-emitting diode) for exposure.

The shape and size of the mask can be selected according to the purpose of the pattern.

In the exposure machine used for exposure, the light below 350nm can be cut with a filter that cuts this wavelength region, or a band pass filter that takes out these wavelength regions can be used to selectively extract around 436nm, around 408nm, and 365nm The nearby light irradiates slightly parallel light uniformly on the entire exposure surface. If you use mask aligner, stepper, etc. It can be accurately positioned between the mask and the substrate.

The exposed coating film can be brought into contact with a developer to dissolve and develop a predetermined portion, such as a non-exposed portion (ie, a non-pixel portion), to obtain a desired pattern shape.

Examples of the development method include a bath method, a dipping method, and a spray method.

Still, the substrate can be inclined at any angle during development.

The developer used in the development is preferably an aqueous solution of an alkaline compound.

The basic compound may be any of inorganic and organic basic compounds.

Examples of inorganic alkaline compounds 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 bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonia.

As organic basic compounds, for example, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, two Ethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine.

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

The developer may contain a surfactant.

Examples of surfactants include nonionic surfactants, anionic surfactants, and cationic surfactants.

Examples of nonionic surfactants include polyoxy Polyoxyethylene derivatives of ethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, etc.; oxyethylene/oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid Esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines.

Examples of anionic surfactants include higher alcohol sulfates such as sodium lauryl sulfate and sodium oleyl sulfate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; dodecyl benzene Alkyl aryl sulfonates such as sodium sulfonate and sodium dodecyl naphthalene sulfonate.

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

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

After development, the pattern can be obtained by washing the coated substrate with water. It can be post-baked if necessary. The post-baking is preferably carried out at 150-240°C for 10 to 180 minutes, for example.

In addition, the components contained in the photosensitive resin composition interact with each other by the above-mentioned exposure and development, and therefore, in the pattern (and the partition for inkjet) of the present invention, the components are not contained in a direct state.

When exposing the uncured coating film, a pattern-forming mask is not used, and a coating film without a pattern can be obtained by irradiating the entire surface with light and/or omitting development.

[Display device]

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

FIG. 1 is a cross-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 a plan view schematically showing a part of the display device 1 which is an example of the display device of the present invention.

The display device 1 mainly includes a support substrate 2, a partition wall 3 defining a predetermined compartment on the support substrate 2, and a plurality of organic EL elements 4 provided in the partition defined by the partition wall 3. The partition 3 corresponds to the partition for inkjet of the present invention.

The partition wall 3 is formed on the support substrate 2 and is formed in a lattice shape or a stripe shape, for example. Furthermore, in FIG. 2, as an embodiment, a display device 1 provided with a grid-shaped partition 3 is shown. In FIG. 2, hatching is implemented in the area where the partition 3 is provided.

A plurality of recesses 5 defined by the partition wall 3 and the supporting substrate 2 are provided on the supporting substrate 2. The recess 5 is equivalent to a compartment defined by the partition wall 3.

The partition 3 of the display device 1 is arranged in a grid shape. Therefore, as seen from one side in the thickness direction Z of the support substrate 2 (hereinafter referred to as "plan view"), the plurality of recesses 5 are arranged in a matrix. That is, the recesses 5 are arranged in a row with a predetermined interval in the row direction X, and at the same time in the column direction Y, and arranged in a row at a predetermined interval. The shape of each recess 5 in plan view is not limited. For example, the recess 5 is formed in a substantially rectangular shape, a substantially elliptical shape, Oval shape and other shapes.

In this embodiment, a substantially rectangular recess 5 is provided in plan view. In this specification, the above-mentioned row direction X and column direction Y mean directions perpendicular to the thickness direction Z of the support substrate and directions perpendicular to each other.

As another embodiment, when stripe-shaped partition walls are provided, the partition walls are configured such that a plurality of partition wall members extending in the row direction X are arranged at predetermined intervals in the column direction Y. In this embodiment, the stripe-shaped recesses are defined by the stripe-shaped partition walls and the supporting substrate.

The partition wall is formed by partitioning from the support substrate so that the width becomes narrow. For example, the cross-sectional shape when the partition wall extending in the column direction Y is cut in a plane perpendicular to the extending direction (column direction Y) is formed by partitioning from the supporting substrate to narrow the width. In Fig. 1, the partition wall in the shape of an isosceles trapezoid has been shown. When comparing the upper base and the lower base on the supporting substrate side, the lower base is wider than the upper base. However, the cross-section of the partition actually formed is not necessarily trapezoidal, and sometimes the straight portions and corners of the trapezoid are rounded.

Preferably, the top surface of the partition wall 3 exhibits liquid repellency. In addition, the term “top surface” refers to a plane that exists at the most spaced position from the support substrate 2 among the surfaces 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 from the area (recess 5) surrounded by the partition wall 3 from flowing over the top surface of the partition wall 3 to the adjacent area.

The organic EL element 4 is arranged in a compartment defined by the partition wall 3 (ie, the recess 5). In the case of the grid-shaped partition 3 provided in the display device 1, each organic EL element 4 is analyzed and installed in each recess 5. That is, there is The organic EL elements 4 are arranged in a matrix like the recesses 5, and the supporting substrate 2 is arranged in a row with a predetermined interval in the row direction X, and at the same time in the column direction Y at a predetermined interval.

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

The partition 3 can be formed by the same method as the pattern forming method described above using the photosensitive resin composition of the present invention.

As another embodiment, when stripe-shaped partition walls are provided, the recesses of the organic EL element 4 extending in the row direction X are arranged at predetermined intervals in the row direction X.

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

The organic EL element 4 is formed by laminating the first electrode, the organic EL layer, and the second electrode in this order from the support substrate side. In this specification, one or more layers provided between the first electrode 6 and the second electrode 10 are respectively referred to as an organic EL layer. The organic EL element 4 includes at least one light-emitting layer as an organic EL layer. Still, in addition to the first layer of organic EL elements In addition to the optical layer, if necessary, an organic EL layer different from the light-emitting layer may be provided. For example, between the first electrode 6 and the second electrode 10, a hole injection layer, a hole transport layer, an electron barrier layer, an electron transport layer, an electron injection layer, etc. are provided as an organic EL layer. In addition, two or more light-emitting layers may be provided between the first electrode 6 and the second electrode 10.

The organic EL element 4 is a counter electrode composed of an anode and a cathode, and includes a first electrode 6 and a second electrode 10. 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 functions as an anode, the first organic EL layer 7 functions as a hole injection layer, the second organic EL layer 9 functions as a light-emitting layer, and it functions as a cathode The second electrode 10 is laminated on the supporting substrate 2 in this order.

The first electrode 6 is provided on each organic EL element 4. That is, the same number of first electrodes 6 as the organic EL elements 4 are provided on the support substrate 2. The first electrodes 6 are provided corresponding to the arrangement of the organic EL elements 4 and are arranged in a matrix like the organic EL elements 4. Although the partition wall 3 is mainly formed in a lattice shape in the area except for the first electrode 6, it is further formed to cover the periphery of the first electrode 6 (see FIG. 1).

The first organic EL layer 7 corresponding to the hole injection layer is respectively provided on the first electrode 6 in the recess 5. If necessary, the first organic EL layer 7 may be provided with various materials or thicknesses for each type of organic EL device. Still, all the first organic EL layers 7 may be formed of the same material and the same thickness.

The first organic EL layer 7 is supplied by the inkjet method in the area (recessed portion 5) surrounded by the ink partition 3 containing the material of the first organic EL layer 7, followed by drying, heating and/or light Irradiation cures the ink to form.

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 mentioned above, the light-emitting layer is provided according to the type of organic EL device. Therefore, the red light emitting layer 9R is provided in the recess 5 provided by the red organic EL element 4R, the green light emitting layer 9G is provided in the recess 5 provided by the green organic EL element 4G, and the blue light emitting layer 9B is provided in the blue organic EL element. The recess 5 provided by the element 4B.

The second electrode 10 is formed over the entire display area 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 formed continuously by a plurality of organic EL elements.

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

The pattern obtained from the photosensitive resin composition of the present invention is useful as a partition wall used in the production of color filters, ITO electrodes of liquid crystal display elements, organic EL display elements, and circuit wiring substrates by the inkjet method. Furthermore, for example, it is used as a gap material (Photospacer), patternable overcoat, interlayer insulating film, protrusions for liquid crystal alignment control, microlens, for adjusting a part of the color filter substrate and/or array substrate. The coating layer of the entire film thickness is useful as a member for touch panels. The coating film without a pattern is useful as an external coating constituting a part of the color filter substrate and/or the array substrate. The color filter substrate and the array substrate are suitable for use in liquid crystal display devices, organic EL display devices, electronic paper, etc.

[Example]

Hereinafter, the present invention will be described in detail with examples. In the examples, "%" and "parts" refer to mass% and mass parts unless otherwise specified.

<Synthesis Example 1>

In a flask equipped with a reflux cooler, a dropping funnel and a stirrer, a proper amount of circulating nitrogen is substituted into a nitrogen environment, 166 parts of propylene glycol monomethyl ether acetate and 52 parts of methoxypropanol are added, and heated to 85°C while stirring . Next, 233 parts of a mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8 and 9-yl acrylate, 77 parts of p-vinyl benzoic acid, and propylene glycol monomethyl ether acetic acid The mixed solution of 125 parts of ester and 115 parts of methoxypropanol was dropped in 4 hours. On the other hand, a mixed solution in which 32 parts of 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 210 parts of propylene glycol monomethyl ether acetate was dropped over 5 hours. After the dripping is over, keep it at the same temperature for 3 hours and then cool to room temperature to obtain a type B viscosity (23℃) of 46mPa. s. A polymer (resin Aa) solution with a solid content of 33.7% and an acid value of 83mgKOH/g. The weight average molecular weight Mw of the resin Aa in terms of polystyrene was 7.7×10 ³ , and the molecular weight distribution was 1.90. Resin Aa has the following structural units.

<Synthesis Example 2>

Add 78 parts of α-chloroacrylic acid 3,3,4,4,5,5,6,6,6-nonafluorohexyl into a four-necked flask equipped with reflux cooling tube, nitrogen introduction tube, thermometer and stirring device, methyl 19.5 parts of acrylic acid, 19.5 parts of isobornyl methacrylate, 13 parts of glycidyl methacrylate, 12.7 parts of dodecyl mercaptan, and 266 parts of propylene glycol monomethyl ether acetate, after heating to 70°C , 30 minutes, stirring under nitrogen flow. 1 part of azobisisobutyronitrile was added here, and polymerization was performed 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 (in terms of solid content). The weight average molecular weight Mw of the resin Ba in terms of polystyrene is 7.5×10 ³ , and the molecular weight distribution is 3.50. The resin Ba has the following structural units.

The weight average molecule of the resin obtained in Synthesis Examples 1 and 2 The measurement of the amount (Mw) and the number average molecular weight (Mn) was performed using the gel permeation chromatography (GPC) method under the following conditions.

Device; K2479 ((share) manufactured by Shimadzu Corporation)

String; SHIMADZU Shim-pack GPC-80M

Column temperature; 40℃

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0mL/min

Detector; RI

<Examples 1 to 6, Comparative Examples 1 to 3> (Preparation of photosensitive resin composition)

The components were mixed as shown in Table 5 to prepare a photosensitive resin composition. Still, the "-" in the table means not contained.

In Table 5, the contents of each component are as follows. The parts described in the columns of resin (A) and resin (B) represent 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 Shinnakamura Chemical Industry Co., Ltd.)

Polymerization initiator (D): 2-methyl-2-morpholinyl-1-(4-methylsulfanylphenyl)propan-1-one (Irgacure (registered trademark) 907; manufactured by BASF Corporation)

Polymerization initiation auxiliary (D1): 4,4'-bis(diethylamino)benzophenone (EAB-F; manufactured by Hodogaya Chemical Industry Co., Ltd.)

Silicon-containing compound (E1): x-12-984s (manufactured by Shin-Etsu Silicon Oxygen)

Silicon-containing compound (E2): 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (KBM-303, manufactured by Shin-Etsu Silicon Oxygen)

Silicon-containing compound (E3): 3-glycidoxypropylmethyldimethoxysilane (KBM-402, manufactured by Shin-Etsu Silicone Corporation)

Silicon-containing compound (E4): N-phenyl-3-aminopropyltrimethoxysilane (KBM-573, manufactured by Shin-Etsu Silicon Oxygen)

Solvent (Fa): propylene glycol monomethyl ether acetate

Solvent (Fb): ethyl 3-ethoxypropionate

Solvent (Fc): 3-methoxy 1-butanol

Solvent (Fd): 3-methoxybutyl acetate

The solid content of the solvent (F)-based photosensitive resin composition is mixed so as to become the "solid content (%)" in Table 5. The values of solvents (Fa), (Fb), (Fc) and (Fd) are shown in The mass ratio in the solvent (F).

(Average transmittance of composition)

For the photosensitive resin composition obtained above, UV Visible and near infrared spectrophotometer (V-650; manufactured by JASCO Corporation) (quartz cell, optical path length; 1cm), and measure the average transmittance (%) at 400~700nm. The results are shown in Table 5.

(Production of coating film)

A 2-inch square glass substrate (EAGLE XG; manufactured by Corning Incorporated) was washed with a neutral lotion, water, and alcohol in this order, and dried. On this glass substrate, the photosensitive resin composition obtained above was spin-coated so that the thickness after the post-baking became 3.0 μm, and then a vacuum dryer (manufactured by Microtech Co., Ltd.) was used to reduce the pressure to After drying under reduced pressure to 66 kPa, it was pre-baked and dried on a hot plate at 80°C for 2 minutes. After cooling, an exposure machine (TME-150RSK; made by Topcon Co., Ltd., light source; ultra-high pressure mercury lamp) was used to irradiate light with an exposure amount of 50mJ/cm ² (365nm standard) in an atmospheric environment. At this time, an ultra-high pressure mercury lamp was used for the light irradiation of the photosensitive resin composition. After light irradiation, in an aqueous developer containing 0.12% of non-ionic surfactant and 0.04% of potassium hydroxide, the coating film is immersed at 23°C for 60 seconds while shaking to make contact. Next, it is carried out in an oven at 230°C Heating for 20 minutes (post-baking) gave a coating film.

(Average transmittance of coating film)

For the obtained coating film, a microscopy photometer (OSP-SP200; manufactured by OLYMPUS) was used to measure the average transmittance (%) at 400~700nm. Increased transmittance means less absorption. The results are shown in Table 5.

(Contact angle)

For the obtained coating film, the contact angle of anisole (Anisole) was measured using a contact angle meter (DGD Fast/60; manufactured by GBX Corporation). The higher the contact angle, the higher the liquid repellency. If the contact angle of the coating film is high, the contact angle of the pattern formed by using the same photosensitive resin composition will be high. The partition wall is formed of a photosensitive resin composition with a relatively high contact angle, and the ink is easily repelled when the ink is transferred by the inkjet device surrounded by the partition wall. Therefore, for example, when a color filter is produced by an inkjet method, it is difficult to produce ink mixing between adjacent pixel regions. The results are shown in Table 7.

(Pattern formation)

A 2 inch square glass substrate (EAGLE XG; manufactured by Corning Corporation) on which ITO was deposited on the surface was washed with a neutral lotion, water, and 2-propanol in this order and dried. On this glass substrate, spin-coated the above-mentioned photosensitive resin composition so that the thickness after baking becomes 1.0μm, and then use a vacuum dryer (manufactured by Microtech) to reduce the pressure to 66kPa After drying under reduced pressure, it was pre-baked at 90°C for 2 minutes on a hot plate to dry it. After cooling, the distance between the substrate coated with the photosensitive resin composition and the quartz glass mask was set to 100 μm, and the exposure machine (TME-150RSK; made by Topcon Co., Ltd., light source; ultra-high pressure mercury lamp) was used to irradiate Under the atmospheric environment, the light exposure is 200mJ/cm ² (365nm standard). Furthermore, as the mask, a pattern (the shape of the light-shielding part is a rectangle with 300 μm in the long axis direction and 100 μm in the short axis direction with four sides cut into circles (long circles)) that is formed on the same plane. After the light is irradiated, a tetramethylammonium hydroxide aqueous solution (made by Tokuyama Co., Ltd., TOKUSO SD25) is diluted with pure water to prepare a developer solution at a concentration of 2.38%, and the coating film is swayed at 23°C. Development was performed by immersion for 60 seconds, and after washing with water, post-baking was performed in an oven at 230°C for 20 minutes to obtain a pattern.

(Wettability)

Among the solvents for evaluating the wettability of the next wall, N,N-dimethylacetamide (manufactured by Wako Pure Chemical Industries, Ltd., 99.5% or more), and 1,3-dimethyl-2-imidazolinone were selected 2 types (manufactured by Tokyo Chemical Industry Co., Ltd., 99.0% or more). The selected two solvents have low viscosity, so the inkjet device makes it possible to fill the solution of the partition wall. As a viscosity adjustment material, cyclohexanol (Wako Pure Chemical Industries, Ltd., 98.0% or more) is added. , Used as a mixed solvent. For the solvent monomer, it is difficult to observe the coating spread after drying under a microscope, so Rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd., purity 95% or more) is used as the solute.

As solutions, three solutions shown in Table 6 were prepared. Still, the "-" in the table means not contained.

In the next wall, an inkjet device (manufactured by ULVAC, Litlex120L), fill each partition with solution 1~3 for every 200pL at 1000 points, and use a microscope (Olimpus, MX61L, lens: LCPFLN20xLCD) for 30 points to determine whether the solute diffuses to the end of the partition after drying. The observation. When all solutions 1 to 3 and 30 spots spread, the wettability is good, so it is marked as "A", and other wettability is marked as "B". The results are shown in Table 7.

(Development adhesion, storage stability)

With regard to the photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3, those prepared to be blended immediately and those that were stored at 23° C., humidity 50%, and shading for 1 month after blending.

Wash a 2 inch square glass substrate (EAGLE XG; manufactured by Corning Corporation) with a neutral lotion, water and alcohol in order. On this glass substrate, the above two photosensitive resin compositions will be baked separately Spin coating so that the thickness becomes 1.0μm, and then use a vacuum dryer (manufactured by Microtech Co., Ltd.) to make it dry under reduced pressure until the pressure reaches 66kPa, and then pre-baked on a hot plate at 90°C for 2 minutes Let it dry. After cooling, the distance between the substrate coated with the photosensitive resin composition and the quartz glass mask was set to 100 μm, and the exposure machine (TME-150RSK; made by Topcon Co., Ltd., light source; ultra-high pressure mercury lamp) was used to irradiate Under the atmospheric environment, the light exposure is 200mJ/cm ² (365nm standard). Furthermore, as the mask, a pattern (the shape of the light-shielding part is a rectangle with 300 μm in the long axis direction and 100 μm in the short axis direction with four sides cut into circles (long circles)) that is formed on the same plane.

After the light is irradiated, the tetramethylammonium hydroxide aqueous solution (Tokuso SD25, manufactured by Tokuyama Co., Ltd.) is diluted with pure water to prepare a developer solution so that the concentration becomes 2.38%, and the coating film is shaken at 23°C Perform development while immersing for 60 seconds. After washing, observe the residual status of the pattern after washing. When all the patterns remain, the pattern survivability is good, so it is marked as "A". When all or part of the pattern is peeled off or missing, the pattern survivability is not good, so it is marked as "B". The results are shown in Table 7.

According to Table 7, it is considered that the photosensitive resin composition of the present invention can stably form a pattern on glass, and can obtain a pattern that maintains a good contact angle and is excellent in wettability.

Claims (5)

A photosensitive resin composition containing component (A), component (B), component (C), component (D), and component (E). The content of component (A) is relative to component (A) The total content with component (C) is 45% by mass or more and 80% by mass or less, (A) contains aromatic carboxylic acids derived from ethylenically unsaturated bonds and aromatic carboxylic anhydrides having ethylenically unsaturated bonds The copolymer (B) consisting of a structural unit of at least one compound in the constituted group and a structural unit derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms (B) includes a copolymer having 4 to 4 carbon atoms. The polymer (C) polymerizable compound (D) polymerization initiator (E) which is the constituent unit of 6 perfluoroalkyl group contains a silicon-containing compound containing two or more oxiranyl groups in one molecule. The photosensitive resin composition of claim 1, wherein the component (D) is a polymerization initiator containing at least one selected from the group consisting of biimidazole compounds, Alkylphenone compounds and oxime ester compounds Agent. A pattern formed by the photosensitive resin composition of claim 1 or 2. A partition wall for inkjet, which is formed by the photosensitive resin composition of claim 1 or 2. A display device, which contains a pattern selected from claim 3 And at least one of the group consisting of the partition wall for inkjet as in claim 4.

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