KR102008050B1 - Photosensitive resin composition - Google Patents

Abstract

(A), (B), (C) and (D), and
The photosensitive resin composition whose content of (A) is 45 mass% or more and 80 mass% or less with respect to the sum total content of (A) and (C).
(A) A structural unit derived from the aromatic carboxylic acid which has an ethylenically unsaturated bond, and the structural unit derived from the unsaturated compound which has a C2-C4 cyclic ether structure, and contains perfluoro of 4 to 6 carbon atoms Polymers without structural units with alkyl groups
(B) A polymer containing a structural unit having a perfluoroalkyl group having 4 to 6 carbon atoms
(C) polymerizable compound
(D) polymerization initiator

Description

Photosensitive resin composition {PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a photosensitive resin composition.

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

As such a photosensitive resin composition, the photosensitive resin composition containing the copolymer of methacrylic acid and 3, 4- epoxy cyclocyclo [5.2.1.0 ^2.6 ] decyl acrylate as a resin is known (patent document 1), for example.

Japanese Laid-Open Patent Publication 2012-73603

When the ink containing the organic functional material is applied to the partition formed on the substrate and the recess defined by the substrate, the wettability of the substrate surface is high so that the recess substrate surface is completely covered with ink. It is preferable that the wettability of the upper surface of the partition wall is high (high liquid repellency) in order to prevent the ink from leaking outside the target area. However, the wettability of the partition substrate formed by the photosensitive resin composition proposed conventionally and the board | substrate formed by the board | substrate may not be satisfied.

This invention provides the following [1]-[6].

[1] containing (A), (B), (C) and (D),

The photosensitive resin composition whose content of (A) is 45 mass% or more and 80 mass% or less with respect to the sum total content of (A) and (C).

(A) A structural unit derived from the aromatic carboxylic acid which has an ethylenically unsaturated bond, and the structural unit derived from the unsaturated compound which has a C2-C4 cyclic ether structure, and contains perfluoro of 4 to 6 carbon atoms Polymers without structural units with alkyl groups

(B) A polymer containing a structural unit having a perfluoroalkyl group having 4 to 6 carbon atoms

(C) polymerizable compound

(D) polymerization initiator

[2] The photosensitive resin composition as described in [1] whose (D) is a polymerization initiator containing at least 1 sort (s) chosen from the group which consists of a biimidazole compound, an alkylphenone compound, and an O-acyl oxime compound.

[3] A pattern formed of the photosensitive resin composition according to [1] or [2].

[4] A partition for ink jet formed by the photosensitive resin composition according to [1] or [2].

[5] A display device comprising the pattern of [3].

[6] A display device comprising the inkjet partition described in [4].

According to the photosensitive resin composition of this invention, the pattern excellent in wettability, ie, the wettability of the surface of the recessed part board | substrate formed by a partition and a board | substrate, is high, and the pattern of the liquid repellency of the upper surface of a partition can be obtained.

1 is a cross-sectional view schematically illustrating an enlarged portion of the display device 1.
FIG. 2 is a plan view schematically illustrating an enlarged part of the display device 1 according to the embodiment of the present invention.

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

(A) A structural unit derived from the aromatic carboxylic acid which has an ethylenically unsaturated bond, and the structural unit derived from the unsaturated compound which has a C2-C4 cyclic ether structure, and contains perfluoro of 4 to 6 carbon atoms Polymer which does not have structural unit which has alkyl group (Hereinafter, it may be called "resin (A).")

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

(C) polymerizable compound

(D) polymerization initiator

Moreover, it is preferable that the photosensitive resin composition of this invention contains a solvent (E).

The photosensitive resin composition of this invention is resin (A may be called "resin (A1)" hereafter) other than resin (A) and resin (B), a polymerization start adjuvant (D1), a polyfunctional thiol compound (T), and an interface You may contain at least 1 sort (s) chosen from the group which consists of an activator (F).

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

As resin (A) contained in the photosensitive resin composition of this invention,

Resin (A-1): The structural unit derived from the aromatic carboxylic acid (a) (Hereinafter, it may be called "(a)") which has an ethylenically unsaturated bond, and a C2-C4 cyclic ether structure. A polymer containing a structural unit derived from an unsaturated compound having (b) (hereinafter may be referred to as "(b)"),

Resin (A-2): Monomer (c) which can superpose | polymerize with (a) and (b) and does not have a C2-C4 cyclic ether structure (henceforth "(c)" may be called) And polymers formed by polymerizing (a) and (b). However, (a), (b) and (c) do not all have a C4-C6 perfluoroalkyl group.

(a) is at least 1 sort (s) of monomer chosen from the group which consists of aromatic carboxylic acid which has an ethylenically unsaturated bond, and aromatic carboxylic anhydride which has ethylenically unsaturated bond, Specifically, o-vinyl benzoic acid and m- Aromatic carboxylic acids such as vinyl benzoic acid, p-vinyl benzoic acid, 3-vinyl phthalic acid and 4-vinyl phthalic acid; aromatic carboxylic acid anhydrides such as 3-vinyl phthalic anhydride and 4-vinyl phthalic anhydride.

(b) is a monomer which has a C2-C4 cyclic ether structure (for example, at least 1 sort (s) chosen from the group which consists of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring), The monomer which has a cyclic ether structure and ethylenically unsaturated double bond is preferable, and the monomer which has a C2-C4 cyclic ether structure and a (meth) acryloyloxy group is more preferable.

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

As (b), for example, the monomer (b1) which has an oxylanyl group (hereinafter may be called "(b1)"), and the monomer (b2) which has an oxetanyl group (henceforth "(b2)" The monomer (b3) (Hereinafter, it may be called "(b3)") which has a tetrahydrofuryl group, etc. are mentioned.

As (b1), the monomer (b1-1) (Hereinafter, it may be called "(b1-1)") which has a structure in which the unsaturated aliphatic hydrocarbon group was epoxidized, and the monomer which has a structure in which the unsaturated alicyclic hydrocarbon was epoxidized ( b1-2) (Hereinafter, it may be called "(b1-2).").

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

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

Examples of (b1-2) include vinylcyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane (for example, Ceroxide® 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4 -Epoxycyclohexylmethyl acrylate (for example, Cychroma (R) A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, cycloma (registered) Trademark) M100; manufactured by Daicel Chemical Industries, Ltd.), a compound represented by formula (I), a compound represented by formula (II), and the like.

[In Formula (I) and Formula (II), R <^1> and R <^2> respectively independently represents a hydrogen atom or a C1-C4 alkyl group, and the hydrogen atom contained in this alkyl group may be substituted by the hydroxy group. .

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

R <^3> represents a C1-C6 alkanediyl group.

* Represents a bond with O.]

As a C1-C4 alkyl group represented by R <^1> and R <^2> , a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- butyl group, etc. are mentioned.

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

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

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

X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group,

* -CH ₂ -O- (* represents a bond with O) group, * -CH ₂ CH ₂ -O- group, More preferably, a single bond and a * -CH ₂ CH ₂ -O- group Can be mentioned.

As a compound represented by Formula (I), the compound etc. which are represented by Formula (I-1)-Formula (I-15) are mentioned. Especially, Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9) or Formula (I-11) to Formula (I-15) ) Is preferable, and the compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15) is more preferable.

As a compound represented by Formula (II), the compound etc. which are represented by Formula (II-1)-Formula (II-15) are mentioned. Especially, Formula (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II-9), or Formula (II-11) to Formula (II-15) ) Is preferable, and the compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) is more preferable.

The compound represented by Formula (I) and the compound represented by Formula (II) may be used independently, respectively, or may use 2 or more types together. When using the compound represented by Formula (I) and the compound represented by Formula (II) together, these content ratios [The compound represented by Formula (I): The compound represented by Formula (II)] are mole-based, Preferably it is 5 : 95-95: 5, More preferably, it is 20: 80-80: 20.

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

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

As (b3), tetrahydrofurfuryl acrylate (For example, biscoat V # 150, Osaka Organic Chemical Industry Co., Ltd. product), tetrahydrofurfuryl methacrylate, etc. are mentioned specifically ,.

As (c), (meth) acrylic acid ester, N-substituted maleimide, unsaturated dicarboxylic acid diester, alicyclic unsaturated compound, unsaturated carboxylic acid, unsaturated carboxylic anhydride, styrene, others Vinyl compounds; and the like.

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

Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane 8-yl (meth) acrylate (in this technical field, dicyclopentanyl ( (Meth) acrylate.), Dicyclopentanyloxyethyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (in the technical field, "Dish" Cyclopentenyl (meth) acrylate "), and cycloalkyl esters such as isobornyl (meth) acrylate;

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

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

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

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

Examples of the alicyclic unsaturated compounds include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene and 5-ethylbicyclo [2.2.1] hept-2- N, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl bicyclo [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- dihydroxy ratio Cyclo [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-methyl Bicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonyl bicyclo [2.2.1] hept- 2-ene, 5-cyclohexyloxycarbonyl bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonyl bicyclo [2.2.1] hept-2-ene, 5, 6-bis (tert- Bicyclo unsaturated compounds, such as butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, and 5, 6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Etc. can be mentioned.

Examples of the 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 Unsaturated dicarboxylic acids such as 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 Bicyclo unsaturated compounds containing carboxyl groups, such as [2.2.1] hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

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

Unsaturated (meth) acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as (alpha)-(hydroxymethyl) acrylic acid, etc. are mentioned.

Examples of the unsaturated carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2, And unsaturated dicarboxylic anhydrides such as 3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride.

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

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

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

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

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

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

When the ratio of the structural unit of resin (A-1) exists in said range, the storage stability of the photosensitive resin composition, the developability at the time of forming a pattern from the photosensitive resin composition, and the solvent resistance of the coating film and pattern obtained, There exists a tendency for heat resistance and mechanical strength to become favorable.

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

The resin (A-1) is described in, for example, the method described in the document "Experimental Method of Polymer Synthesis" (Osaka Yuki Publishing Co., Ltd., Chemical Co., Ltd., First Edition First Edition March 1, 1972) and the document. It can manufacture with reference to the cited document.

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

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

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

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

Structural unit derived from (c); 1-65 mol% (more preferably 1-60 mol%)

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

When the ratio of the structural unit of resin (A-2) exists in said range, the storage stability of the photosensitive resin composition, the developability at the time of forming a pattern from the photosensitive resin composition, and the solvent resistance of the coating film and pattern obtained, There exists a tendency for heat resistance and mechanical strength to become favorable.

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

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

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

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of resin (A) becomes like this. Preferably it is 1.1-6.0, More preferably, it is 1.2-4.0. When molecular weight distribution exists in the said preferable range, it exists in the tendency which is excellent in developability.

The acid value of resin (A) is 20-150 mgKOH / g normally, Preferably it is 40-135 mgKOH / g, More preferably, it is 50-135 mgKOH / g. 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 obtained by titration using an aqueous potassium hydroxide solution.

Content of resin (A) is 45 mass% or more and 80 mass% or less with respect to the total content of resin (A) and a polymeric compound (C), Preferably they are 48 mass% or more and 75 mass% or less, More preferably, Is 50 mass% or more and 70 mass% or less.

When content of resin (A) exceeds 80 mass% with respect to the total content of resin (A) and a polymeric compound (C), when developing the coating film formed from the photosensitive resin composition, there exists a tendency for developing time to become long.

When content of resin (A) exists in the said preferable range, the wettability of the base surface patterned by the partition formed with the photosensitive resin composition becomes favorable.

The photosensitive resin composition of this invention contains resin (B). Resin (B) is a polymer containing the structural unit derived from the unsaturated compound (d) (Hereinafter, it may be called "(d)") which has a C4-C6 perfluoroalkyl group.

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

R <^f> represents a C4-C6 perfluoroalkyl group in a formula (d-0).

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 with a halogen atom or a hydroxy group.

X ^d represents a single bond, a divalent aliphatic hydrocarbon group of 1 to 10 carbon atoms, a divalent alicyclic hydrocarbon group of 3 to 10 carbon atoms, or a divalent aromatic hydrocarbon group of 6 to 12 carbon atoms, the aliphatic hydrocarbon group and the alicyclic hydrocarbon thereof -CH ₂ -contained in the group may be substituted with -O-, -CO-, -NR ^e- , -S- or -SO _2- .]

R ^f is a C 4 to C 6 perfluoroalkyl group, and a perfluorobutyl group and a perfluorohexyl group are preferable.

As a C1-C21 alkyl group in R <^d> , a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-no Linear alkyl groups such as a silyl group and n-decyl group;

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

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

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

As a C3-C10 bivalent alicyclic hydrocarbon group in X <^d> , a cyclopropanediyl group, a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptandiyl group, a cyclodecanediyl group, etc. are mentioned. Can be.

As a C6-C12 bivalent aromatic hydrocarbon group in X <^d> , a phenylene group, a naphthalenediyl group, etc. are mentioned.

-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 Examples of X ^d substituted with-include groups represented by formulas (xd-1) to (xd-10).

As X <^d> , a C1-C6 alkanediyl group is preferable and an ethylene group is more preferable.

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

R <^h> represents a C4-C6 perfluoroalkyl group in [formula (d-0 ').

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

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

As resin (B), the structural unit derived from (d), the structural unit derived from said (a), and unsaturated carboxylic acid and / or unsaturated carboxylic anhydride (e) (however, (a) It is preferable that it is resin containing at least 1 sort (s) chosen from the group which consists of a structural unit derived from (it may be called "(e)" hereafter), and the structural unit derived from (d), and (e) It is more preferable that it is resin containing the structural unit derived from, and it is still more preferable that it is resin containing the structural unit derived from (d), the structural unit derived from (e), and the structural unit derived from (b). Do. Since resin (B) contains the structural unit derived from (a) and / or (e), since developability is excellent, there exists a tendency for the nonuniformity resulting from a residue and image development to be suppressed. When resin (B) contains the structural unit derived from (b), there exists a tendency which is excellent in solvent resistance. In addition, the resin (B) may contain other structural units. As a monomer (Hereinafter, it may be called "(c ')") which guide | induces another structural unit, For example, monomers other than unsaturated carboxylic acid and unsaturated carboxylic anhydride among those shown by said (c). Can be mentioned.

When resin (B) is a polymer of (a) and / or (e) and (d), the ratio of the structural unit derived from each monomer is the following with respect to the total number of moles of the structural unit which comprises resin (B). It is preferable to exist in the range of.

Structural unit derived from (a) and / or (e); 5-40 mass% (more preferably 10-30 mass%)

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

In the case where the resin (B) is a polymer of (a) and / or (e), (b) and (d), the total moles of the structural units constituting the resin (B) in the ratio of the structural units derived from each monomer It is preferable to exist in the following ranges with respect to.

Structural unit derived from (a) and / or (e); 5-40 mass% (more preferably 10-30 mass%)

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

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

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

Structural unit derived from (a) and / or (e); 5-40 mass% (more preferably 10-30 mass%)

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

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

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

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

The weight average molecular weight of polystyrene conversion of resin (B) becomes like this. Preferably it is 3,000-20,000, More preferably, it is 5,000-15,000. When the weight average molecular weight of resin (B) exists in the said preferable range, it exists in the tendency which was excellent in applicability | paintability, and it is hard to produce the film | membrane reduction of an exposure part at the time of image development, and a non-exposure part is easy to remove by image development.

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

Content of resin (B) is 0.001-10 mass parts, More preferably, it is 0.01-5 mass parts with respect to 100 mass parts of total amounts of resin (A), resin (A1), and a polymeric compound (C). . When content of resin (B) exists in said preferable range, it is excellent in developability at the time of pattern formation, and the pattern obtained tends to be excellent in liquid repellency.

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

Resin (A1-1): A polymer obtained by superposing | polymerizing (e) and (b),

Resin (A1-2): A polymer obtained by polymerizing (e) and (b) and (c ')

Resin (A1-3): A polymer obtained by superposing | polymerizing (e) and (c '),

Resin (A1-4): Resin obtained by making (b) react with the polymer formed by superposing | polymerizing (e) and (c '),

Resin (A1-5): The resin etc. which are obtained by making (a) and / or (e) react with the polymer which superposes | polymerizes (b) and (c ') are mentioned.

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

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

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

When the ratio of the structural unit of resin (A1-1) exists in said range, the storage stability of the photosensitive resin composition, the developability at the time of forming a pattern from the photosensitive resin composition, and the solvent resistance of the coating film and pattern obtained are It tends to be good.

In resin (A1-2), it is preferable that the ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total number of moles of all the structural units which comprise resin (A1-2).

Structural unit derived from (e); 2-45 mol% (more preferably 5-40 mol%)

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

Structural unit derived from (c '); 1-65 mol% (more preferably 5-60 mol%)

When the ratio of the structural unit of resin (A1-2) exists in said range, the storage stability of the photosensitive resin composition, the developability at the time of forming a pattern from the photosensitive resin composition, and the solvent resistance of the coating film and pattern obtained are It tends to be good.

In resin (A1-3), it is preferable that the ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total mole number of all the structural units which comprise resin (A1-3).

Structural unit derived from (e); 2-40 mol% (more preferably 5-35 mol%)

Structural unit derived from (c '); 60-98 mol% (More preferably, 65-95 mol%)

When the ratio of the structural unit of resin (A1-1) exists in said range, the storage stability of the photosensitive resin composition, the developability at the time of forming a pattern from the photosensitive resin composition, and the solvent resistance of the coating film and pattern obtained are It tends to be good.

Resin (A1-4) is resin obtained by making (b) react with the polymer of (e) and (c ').

Resin (A1-4) can be manufactured through a two-step process, for example. Also in this case, the method as described in the above-mentioned document "Experimental method of polymer synthesis" (Otsu Takayuki Publishing Co., Ltd. first edition first edition March 1, 1972). It can manufacture with reference to the method etc. which were described in.

First, as a 1st step, the polymer of (e) and (c ') is obtained similarly to the manufacturing method of resin (A-1) mentioned above.

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

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

Structural unit derived from (e); 5-50 mol% (more preferably 10-45 mol%)

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

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

Specifically, subsequent to the above, the atmosphere in the flask is replaced with nitrogen by air, and the reaction catalyst of 5 to 80 mol% of (b), a carboxyl group and a cyclic ether (for example, to the number of moles of (e)) 0.001-5 mass% with respect to the total amount of (e), (b), and (c '), and a polymerization inhibitor (for example, hydroquinone etc.) to (a), ( 0.001-5 mass% is put in a flask with respect to the total amount of b) and (c), it is made to react at 60-130 degreeC for 1 to 10 hours, and resin (A1-4) can be obtained. In addition, similarly to the polymerization conditions, the injection method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production equipment, the polymerization and the like.

In this case, the number of moles of (b) is preferably 10 to 75 mol%, more preferably 15 to 70 mol% with respect to the number of moles of (e). By setting it as said preferable range, the storage stability of the photosensitive resin composition, the developability at the time of forming a pattern from the photosensitive resin composition, and the balance of the solvent resistance, heat resistance, mechanical strength, and the sensitivity of the coating film and pattern obtained become favorable. There is this.

Resin (A1-5) is a 1st step and obtains the polymer of (b) and (c ') similarly to the manufacturing method of resin (A-1) mentioned above.

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

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

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

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

Moreover, the carboxyl which (a) and / or (e) has in the cyclic ether derived from (b) in the polymer of (b) and (c ') similarly to the manufacturing method of resin (A1-4). It can obtain by making acid or carboxylic anhydride react. You may make carboxylic anhydride further react with the hydroxyl group which arises by reaction of a cyclic ether, carboxylic acid, or carboxylic anhydride.

It is preferable that the usage-amount of (a) and / or (e) made to react with said polymer is 5-80 mol% with respect to the number-of-moles of (b). (B1) is preferable and (b1-1) is preferable as (b) from the point that reactivity of a cyclic ether is high and unreacted (b) is hard to remain.

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

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of resin (A1) becomes like this. Preferably it is 1.1-6.0, More preferably, it is 1.2-4.0. When molecular weight distribution exists in the said preferable range, it exists in the tendency which is excellent in developability.

The acid value of resin (A1) is 20-150 mgKOH / g, Preferably it is 40-135 mgKOH / g, More preferably, it is 50-135 mgKOH / g.

When it contains resin (A1), the content is preferably 1 to 80 mass%, more preferably 1 to 50 mass%, based on the total amount of the resin (A) and the resin (A1). When content of resin (A1) exists in the said preferable range, a pattern can be formed with high sensitivity and it is excellent in developability.

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

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

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

Examples of the polymerizable compound (C) having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxyethyl) isocyanurate tree. (Meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, propoxylated trimethylol propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylic Elate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol Hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri (meth) acrylate and reactants of acid anhydride , Reactant of dipentaerythritol penta (meth) acrylate and acid anhydride, reactant of tripentaerythritolhepta (meth) acrylate and acid anhydride, caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified penta Erythritol tri (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerytate Ritol penta (meth) 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 tripentaerythr Hepta (meth) acrylate, caprolactone modified tripentaerythritol octa (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate and reactants of acid anhydride, caprolactone modified dipentaerythritol penta (meth) The reactant of an acrylate and an acid anhydride, the reactant of a caprolactone modified tripentaerythritol hepta (meth) acrylate, and an acid anhydride, etc. are mentioned. Especially, the polymeric compound (C) which has three or more ethylenically unsaturated bonds is preferable, and dipentaerythritol hexa (meth) acrylate, trimethylol propane tri (meth) acrylate, and pentaerythritol tri (meth) Acrylate is more preferable.

Content of polymeric compound (C) is 20-55 mass% with respect to the total amount of resin (A), resin (A1), and a polymeric compound (C), Preferably it is 30-45 mass%. When content of a polymeric compound (C) exists in the said range, there exists a tendency for the sensitivity and the intensity | strength, smoothness, and reliability of the pattern obtained to become favorable.

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

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

The O-acyl oxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * represents a bonding hand.

As said O-acyl oxime compound, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanyl, for example) Phenyl) octan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- ｛2-methyl-4- ( 3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl # -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbox Bazol-3-yl] -3-cyclopentylpropane-1-one-2-imine, and the like. You may use commercially available products, such as Irgacure (trademark) OXE01, OXE02 (above BASF Corporation), and N-1919 (ADEKA Corporation).

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

As a compound which has a partial structure represented by a formula (d2), for example, 2-methyl-2- morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] Butan-1-one etc. are mentioned. You may use commercial items, such as Irgacure (trademark) 369, 907, 379 (above, BASF Corporation make).

As a compound which has a partial structure represented by Formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- ( Oligomer of 2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one and α, α-diethoxyacetophenone, benzyl dimethyl ketal and the like.

In terms of sensitivity, as the alkylphenone compound, a compound having a partial structure represented by formula (d2) is preferable.

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, etc.), 2,2'- Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxy Phenyl) 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, eg, JP-A-48-38403, JP-A-62-174204, etc.), The imidazole compound (For example, refer Unexamined-Japanese-Patent No. 7-10913 etc.) in which the phenyl group of a 4,4 ', 5,5'-position is substituted by the carboalkoxy group. Preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- ( 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloro Rhomethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2 , 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl)- 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc. are mentioned as said acylphosphine oxide compound.

Moreover, as a polymerization initiator (D), Benzoin type compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; Benzophenone, methyl o-benzoyl benzoate, 4-phenyl Benzo such as benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone Phenone compounds; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound and the like. Can be mentioned. It is preferable to use these in combination with the polymerization start adjuvant (D1) mentioned later.

As a polymerization initiator which has a group which can cause chain transfer, you may use the polymerization initiator of Unexamined-Japanese-Patent No. 2002-544205.

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

In the photosensitive resin composition of this invention, a polymerization start adjuvant (D1) can be used with the polymerization initiator (D) mentioned above. A polymerization start adjuvant (D1) is a compound or sensitizer used in combination with a polymerization initiator (D), and used in order to accelerate superposition | polymerization of the polymeric compound in which superposition | polymerization was started with a polymerization initiator. As a polymerization start adjuvant (D1), a thioxanthone compound, an amine compound, a carboxylic acid compound, the compound of Unexamined-Japanese-Patent No. 2008-65319, 2009-139932, etc. are mentioned.

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

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

As the carboxylic acid compound, phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chloro And aromatic heteroacetic acids such as phenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

As a combination of a polymerization initiator (D) and a polymerization start adjuvant (D1), an alkyl phenone compound, a thioxanthone compound, an alkyl phenone compound, and an aromatic amine compound are mentioned, Specifically, 2-methyl-2- morpholino -1- (4-methylsulfanylphenyl) propane-1-one with 2,4-diethyl thioxanthone, 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane-1- On and 2,4-diethyl thioxanthone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one and 2,4-diethylthioke Santone, 2-morpholino-1- (4-methylsulfanylphenyl) -2-methylpropan-1-one, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2-morpholino- 1- (4-methylsulfanylphenyl) -2-methylpropan-1-one with 4,4'-bis (diethylamino) benzophenone, 2-dimethylamino-2-benzyl-1- (4-morpholi Nophenyl) butan-1-one and 4,4'-bis (diethylamino) benzophenone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) butane-1 -On And 4,4'-bis (diethylamino) benzophenone.

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

As for content of a polymerization initiator (D), with respect to 100 mass parts of total amounts of resin (A), resin (A1), and a polymeric compound (C), Preferably it is 0.5-30 mass parts, More preferably, it is 1-20 mass parts It is 1-10 mass parts more preferably. If content of a polymerization initiator (D) exists in said preferable range, a pattern can be obtained with high sensitivity.

The amount of the polymerization start aid (D1) used is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass relative to 100 parts by mass of the total amount of the resin (A), the resin (A1) and the polymerizable compound (C). It is wealth. When the quantity of a polymerization start adjuvant (D1) exists in said preferable range, a pattern can be obtained with high sensitivity, and the pattern obtained has favorable shape.

The photosensitive resin composition of this invention may contain the solvent (E).

Examples of the solvent that can be used in the present invention include, for example, an ester solvent (a solvent containing -COO- in a molecule and no -O-), an ether solvent (-O- in a molecule, and -COO). Solvent without-), ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and no -COO-), alcohol It can be used, selecting from a solvent, an aromatic hydrocarbon solvent, an amide solvent, and dimethyl sulfoxide.

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

As the ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phentol, methyl anisole Etc. can be mentioned.

As the ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate and methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2- Methyl methyl propionate, 2-ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate Bit, di, and the like ethylene glycol monobutyl ether acetate.

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

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

As an aromatic hydrocarbon solvent, benzene, toluene, xylene, mesitylene, etc. are mentioned.

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

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

Among the solvents described above, organic solvents having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm are preferable from the viewpoint of applicability and dryness. Especially, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-ethoxy propionate ethyl, diethylene glycol methyl ethyl ether, 3-methoxy butyl acetate, 3-methoxy- 1-butanol, etc. are preferable. If the solvent (E) is such a preferable solvent, the nonuniformity at the time of application | coating can be suppressed and the flatness of a coating film can be made favorable.

Content of the solvent (E) in the photosensitive resin composition of this invention is 60-95 mass% with respect to the total amount of the photosensitive resin composition, Preferably it is 70-90 mass%.

In other words, solid content of the photosensitive resin composition becomes like this. Preferably it is 5-40 mass%, More preferably, it is 10-30 mass%. When content of a solvent (E) exists in said preferable range, there exists a tendency for the flatness of the film | membrane which applied the photosensitive resin composition to be high. Here, solid content means the quantity which removed the solvent (E) from the photosensitive resin composition.

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

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

Content of a polyfunctional thiol compound (T) becomes like this. Preferably it is 0.1-10 mass parts, More preferably, it is 0.5-7 mass parts with respect to 100 mass parts of polymerization initiators (D). When content of a polyfunctional thiol compound (T) exists in said preferable range, since the sensitivity of the photosensitive resin composition becomes high and developability tends to become favorable, it is preferable.

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

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

Specifically, Toray silicone DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, polyether modified silicone oil SH8400 (brand name: Toray Dow Corning Co., Ltd. product), KP321, KP322 , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 ), And the like.

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

Specifically, fluorine nut (registered trademark) FC430, copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), mega pack (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper R30 ( DIC Co., Ltd.), F-Top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Material Electronic Chemicals Co., Ltd.) (Asahi Glass Co., Ltd. product), E5844 (made by Daikin Fine Chemical Research Institute), etc. are mentioned.

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

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

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

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane , 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3 -Chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltri Methoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane , 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, and the like.

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

In the photosensitive resin composition of this invention, when the optical path length is filled into the quartz cell of 1 cm, and the transmittance | permeability was measured on the conditions of 400-700 nm of measurement wavelengths using the spectrophotometer, the average transmittance is preferably 70% or more, More preferably, it is 80% or more.

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

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

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

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

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

The film thickness of the coating film in this case is not specifically limited, According to the material to be used, a use, etc. can be adjusted suitably, For example, it is about 1-6 micrometers.

Further, light, for example, mercury lamp, ultraviolet light generated from a light emitting diode, or the like is irradiated to the obtained uncured coating film through a photomask for forming a target pattern. The shape of the photomask at this time is not specifically limited, A shape and a size may be selected according to the use of a pattern.

In a recent exposure machine, a band pass filter that cuts light of less than 350 nm using a filter that cuts this wavelength range, or extracts light around 436 nm, 408 nm, and 365 nm, has a wavelength range. It can take out selectively, and irradiates a substantially parallel light beam uniformly to the whole exposure surface. When apparatuses, such as a mask aligner and a stepper, are used, the mask and a base material can be correctly aligned at this time.

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

The developing method may be any of a liquid mounting method, a dipping method and a spray method. In addition, during development, the substrate may be tilted at any angle.

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

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

Specific examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, Sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like.

As an organic basic compound, For example, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine and the like.

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

The developing solution may contain a surfactant.

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

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

Examples of the anionic surfactants include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and sodium dodecylbenzene sulfonate. And alkyl aryl sulfonates such as sodium dodecyl naphthalene sulfonate.

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

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

After image development, a pattern can be obtained by performing water washing. In addition, you may post-bake as needed. The postbaking is preferably, for example, a temperature range of 150 to 240 ° C for 10 to 180 minutes.

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

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

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

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

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

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

Moreover, when a stripe-shaped partition is formed as another embodiment, a partition is comprised so that a some partition wall member extended in the row direction X may be arrange | positioned at predetermined intervals in the column direction Y, for example. In this embodiment, the stripe-shaped recess is defined by the stripe-shaped partition wall and the supporting substrate.

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

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

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

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

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

Moreover, when stripe-shaped partitions are formed as another embodiment, the organic EL elements 4 are arranged at predetermined intervals in the row direction X, respectively, in the recesses extending in the row direction X. FIG.

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

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

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

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

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

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

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

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

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

Since the pattern obtained from the photosensitive resin composition of this invention has high wettability of the recessed part substrate surface formed by a partition and a board | substrate, and high liquid repellency of the upper surface of a partition, especially the ITO of a color filter and a liquid crystal display element by the inkjet method. It is useful as a partition used for producing an electrode, an organic EL display element, a circuit wiring board, and the like. Further, for example, a photo spacer constituting a part of a color filter substrate and / or an array substrate, a patternable overcoat, an interlayer insulating film, a projection for controlling liquid crystal alignment, a microlens, a coating layer for adjusting the film thickness, and the like, for a touch panel The coating film which is useful as a member and does not have a pattern obtained as mentioned above is useful as an overcoat which comprises a part of a color filter substrate and / or an array substrate. Said color filter substrate and an array substrate are used suitably for a liquid crystal display device, an organic electroluminescence display, an electronic paper, etc.

Example

Hereinafter, an Example demonstrates this invention in more detail. "%" And "part" in an example are the mass% and a mass part, unless it mentions specially.

Synthesis Example 1

A proper amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace 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 while stirring. 233 parts of a mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8 or / and 9-ylacrylate, 77 parts of p-vinylbenzoic acid, 125 parts of propylene glycol monomethyl ether acetate, methoxy 115 parts of mixed solutions of propanol were dripped over 4 hours. On the other hand, the mixed solution which melt | dissolved 32 parts of 2, 2- azobis (2, 4- dimethylvaleronitrile) in 210 parts of propylene glycol monomethyl ether acetates was dripped over 5 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 3 hours, and then cooled to room temperature to obtain a polymer (resin Aa) solution having a B viscosity (23 ° C) of 46 mPas, a solid content of 33.7%, and a solution acid value of 83 mgKOH / g. The weight average molecular weight Mw of obtained resin Aa was 7.7x10 <^3> , and molecular weight distribution was 1.90.

Resin Aa has the following structural units.

Synthesis Example 2

Into a flask equipped with a reflux cooler, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added thereto, followed by stirring. It heated to degreeC. Subsequently, 60 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1), in molar ratio, 50: mixed at 50.) A flask prepared by dissolving 240 parts by mass and 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and keeping the dissolved solution at 70 ° C. over 4 hours using a dropping funnel. Dropped in.

On the other hand, the solution which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 mass parts of 3-methoxybutyl acetates in the flask over 4 hours using another dropping funnel. Dropped. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature. Got it. The weight average molecular weight Mw of obtained resin A1a was 1.3 * 10 <^4> , and molecular weight distribution was 2.50. Resin A1a has the following structural units.

Synthesis Example 3

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

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of resin obtained by the synthesis example was performed on condition of the following using GPC method.

Equipment; K2479 (manufactured by Shimadzu Corporation)

Column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ° C.

Solvent; THF (Tetrahydrofuran)

Flow rate; 1.0 ml / min

Detector; RI

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

(Examples 1-4 and Comparative Examples 1-3)

<Adjustment of the photosensitive resin composition>

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

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

Resin (A); Aa: Resin Aa obtained in Synthesis Example 1

Resin (A1); A1a: Resin A1a obtained in Synthesis Example 2

Resin (B); Ba: Resin Ba obtained in Synthesis Example 3

Polymerizable compound (C); Ca: trimethylolpropane triacrylate (A-TMPT; manufactured by Shin-Nakamura Chemical Co., Ltd.)

Polymeric compound (C); Cb: dipentaerythritol hexaacrylate (KAYARAD® DPHA; manufactured by Nippon Kayaku Co., Ltd.)

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

Polymerization initiator (D); Db: ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) (irgacure (Registered trademark) OXE02; manufactured by BASF Corporation)

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

Solvent (E); Ea; propylene glycol monomethyl ether acetate

Solvent (E); Eb; ethyl 3-ethoxypropionate

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

Solvent (E); Ed; 3-methoxybutyl acetate

The solvent (E) is mixed so that the solid content of the photosensitive resin composition becomes "solid content (%)" in Table 3, and the values of the solvent components (Ea) to (Ed) in the solvent (E) are in the solvent (E). The mass ratio is shown.

<Average transmittance of the composition>

About the photosensitive resin composition obtained above, 400-700 nm in ultraviolet-visible near-infrared spectrophotometer (V-650; Nippon Spectroscopy Co., Ltd. product) (quartz cell, optical path length; 1 cm), respectively Average transmittance | permeability (%) was measured. The results are shown in Table 3.

<Production of coating film>

The glass substrate (Eagle XG; Corning Corporation make) of 2 inches of length was wash | cleaned sequentially with neutral detergent, water, and alcohol, and it dried. On this glass substrate, the photosensitive resin composition obtained above is spin-coated so that the film thickness after postbaking may be set to 3.0 micrometers, respectively, and pressure-reduced until a pressure reduction degree becomes 66 kPa with a pressure reduction dryer (made by Microtech Co., Ltd.). After drying, it prebaked at 80 degreeC for 2 minutes with a hotplate, and it dried. After cooling, the light of the exposure amount 50mJ / cm <2> (365 nm standard) was irradiated in air | atmosphere using the exposure machine (TME-150RSK; Topcon Co., Ltd. product, light source; ultrahigh pressure mercury lamp). In addition, the irradiation with respect to the photosensitive resin composition at this time used the ultrahigh pressure mercury lamp. After light irradiation, the said coating film was immersed and stirred for 60 second at 23 degreeC and the aqueous developing solution containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide, and then heated in 230 degreeC for 20 minutes in oven ( Post-baking) to obtain a coating film.

<Average transmittance of coating film>

About the obtained coating film, the average transmittance | permeability (%) in 400-700 nm was measured using the microscopic spectrophotometer (OSP-SP200; the product made by OLYMPUS). Higher transmittance means less absorption. The results are shown in Table 3.

<Contact angle>

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

The higher the contact angle, the higher the liquid repellency. When the contact angle in a coating film is high, the contact angle is high also in the pattern formed using the same photosensitive resin composition. When a partition is formed with the photosensitive resin composition with a high contact angle, and ink is greeted by the inkjet apparatus inside the enclosure, the ink tends to turn. Therefore, when a color filter is produced by the inkjet method, for example, mixing of ink between neighboring pixel areas is unlikely to occur. The results are shown in Table 5.

<Pattern formation>

The glass substrate of 2 inches in length and width (Igland XG; Corning) which ITO was deposited on the surface was sequentially washed with neutral detergent, water, and 2-propanol, and dried. On this glass substrate, the said photosensitive resin composition was spin-coated so that the film thickness after post-baking might be set to 1.0 micrometer, respectively, and it dried under reduced pressure until the pressure reduction degree became 66 kPa by the pressure reduction dryer (made by Microtech Co., Ltd.). Thereafter, the plate was dried by prebaking at 90 ° C. for 2 minutes.

After cooling, the interval between the substrate coated with the photosensitive resin composition and the quartz glass photomask was 100 μm, and the exposure dose was measured under an atmospheric atmosphere using an exposure machine (TME-150RSK; Topcon Co., Ltd. light source; ultrahigh pressure mercury lamp). Light of 200 mJ / cm 2 (365 nm standard) was irradiated. In addition, as a photomask, what was formed on the same plane as the pattern (shape (circle circle) which cut | disconnected the four corner | round | yen circular form from the rectangle whose shape of a light shielding part is 300 micrometers of a major axis direction, and 100 micrometers of a uniaxial direction) in circular shape) was used.

After the light irradiation, the coating film was added to a developer prepared by diluting an aqueous tetramethylammonium hydroxide solution (manufactured by Tokuyama Co., Ltd., Tokuso SD25) with pure water so that the concentration was 2.38% for 60 seconds. It immersed and developed while shaking, and after washing with water, it post-baked for 20 minutes at 230 degreeC in the oven, and obtained the pattern.

<Wetability>

[Solution Preparation for Wetability Evaluation]

As a solvent for evaluating the wettability of a partition, N, N-dimethylacetamide (made by Wako Pure Chemical, 99.5% or more), 1, 3- dimethyl- 2-imidazolidinone (made by Tokyo Chemical Industry Co., Ltd., 99.0%) Two kinds of above were selected. Since the selected two kinds of solvents have a low viscosity, cyclohexanol (manufactured by Wako Pure Chemical Industries, Ltd., 98.0% or more) is added as a viscosity adjusting material so that the liquid can be filled into the partition wall by the inkjet device, and the mixed solvent Used as.

Moreover, since it is difficult to observe the application | coating diffusion after drying with a microscope as a solvent, rhodamine B (made by Tokyo Chemical Industry Co., Ltd., purity 95% or more) was used as a solute.

The solution produced three types of Table 4 below.

[Wetability Evaluation]

Using an inkjet device (Litlex120L manufactured by ULVAC) in the partition wall, the solution described above was filled into 1000 partition walls at 200 pL in each partition wall, and a microscope (OLIMPUS Corporation) was used to determine whether the solute diffused to the partition wall end after drying. 30 locations were observed using Manufacture MX61L and lens LCPFLN20xLCD). In all the solutions shown in Table 4, when all 30 places were apply | coated and spread | diffused, it was set as (circle) and said that it was good, and other than that was made into x. The results are shown in Table 5.

From the results of the examples, it can be seen from the photosensitive resin composition of the present invention that a coating film and a pattern excellent in wettability can be obtained while maintaining a contact angle at which color mixing of ink does not occur.

According to the photosensitive resin composition of this invention, the pattern excellent in wettability, ie, the wettability of the surface of the recessed part board | substrate formed by a partition and a board | substrate, is high, and the pattern of the liquid repellency of the upper surface of a partition can be obtained.

1: display device
2: support substrate
3: bulkhead
4: organic EL device
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 (6)

(A), (B), (C) and (D), and
The photosensitive resin composition whose content of (A) is 45 mass% or more and 80 mass% or less with respect to the sum total content of (A) and (C).
(A) A structural unit derived from the aromatic carboxylic acid which has an ethylenically unsaturated bond, and the structural unit derived from the unsaturated compound which has a C2-C4 cyclic ether structure, and contains perfluoro of 4 to 6 carbon atoms Polymers without structural units with alkyl groups
(B) A polymer containing a structural unit having a perfluoroalkyl group having 4 to 6 carbon atoms
(C) polymerizable compound
(D) polymerization initiator The method of claim 1,
(D) Photosensitive resin composition which is a polymerization initiator containing at least 1 sort (s) chosen from the group which consists of a biimidazole compound, an alkylphenone compound, and an O-acyl oxime compound. The pattern formed by the photosensitive resin composition of Claim 1 or 2. The inkjet partition formed by the photosensitive resin composition of Claim 1 or 2. A display device comprising the pattern of claim 3. The display device containing the inkjet partition of Claim 4.

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