KR101511476B1 - Photosensitive resin composition - Google Patents

Abstract

The present invention relates to a photosensitive resin composition. A thin film including the photosensitive resin composition is formed on a substrate in which an electrode is formed. After an opening is formed on the thin film through a photolithography method so that the surface of the electrode is exposed, a value of polarity components of surface free energy of the electrode is more than or equal to 15 mN/m.

Description

[0001] PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a photosensitive resin composition, a partition wall, a substrate, a display, and a substrate evaluation method.

In recent display devices and the like, a color filter, an ITO electrode of a liquid crystal display element, an organic EL display element, a circuit wiring board and the like are produced by a coating method such as an ink-jet method. In the method of forming an element using such a coating method, a partition wall formed by using a photosensitive resin composition is used.

For example, after forming a thin film containing the photosensitive resin composition on a substrate on which an electrode is formed, an opening is formed in the thin film by photolithography so that the surface of the electrode is exposed, A predetermined thin film is formed on the electrode by dropping ink containing a thin film material into the opening of the partition and heating and drying the same.

As such a photosensitive resin composition, there is known a photosensitive resin composition comprising a polymer obtained by, for example, polymerizing an? -Substituted acrylate having a fluoroalkyl group having 4 to 6 carbon atoms (Patent Document 1).

Japanese Patent Application Laid-Open No. 2007-73603

As described above, the photosensitive resin composition is once removed from the electrode surface during patterning after being temporarily formed on the electrode, but the wettability of the electrode surface to the ink varies depending on the type of the photosensitive resin composition. Therefore, depending on the type of the photosensitive resin composition, the ink supplied on the electrode may not spread on the electrode. In the photosensitive resin composition proposed in the related art, the spreading property of the ink on the electrode in the opening There is a case that the above-mentioned problem can not be sufficiently satisfied. Accordingly, an object of the present invention is to provide a photosensitive resin composition having good spreadability of an entire surface inside a partition wall opening of an ink applied on an electrode obtained after pattern formation.

The present invention provides the following [1] to [12].

[1] A photosensitive resin composition,

Forming a thin film containing the photosensitive resin composition on a substrate on which an electrode is formed and then forming an opening in the thin film by photolithography so that the surface of the electrode is exposed so that the value of the polarity component of the surface free energy of the electrode Is not less than 15 mN / m.

[2] The photosensitive resin composition according to [1], wherein the photosensitive resin composition comprises (A), (B) and (C)

(A) a resin having a structural unit containing a group represented by the following formula [i].

(Wherein R 1, R 2, R 3, R 4 and R 5 are each independently -OH, -SH, -COOH, -CHO, a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, -COR 7, , -OCOR7 or -OR7, and at least one of R1, R2, R3, R4 and R5 is -OH, -SH, -COOH or -CHO, R7 is an alkyl group having 1 to 8 carbon atoms, an alkyl group having 2 to 5 carbon atoms An alkoxyalkyl group, an aryl group or a benzyl group)

(B) a polymerizable compound

(C) Polymerization initiator

[3] The photosensitive resin composition according to [2], wherein the structural unit is represented by the following formula [ii].

(In the formula [ii], R1, R2, R3, R4 and R5 have the same meanings as described above, and R6 represents a hydrogen atom, a methyl group or an ethyl group)

[4] The photosensitive resin composition according to [2] or [3], wherein the polymerization initiator is a photopolymerization initiator and the polymerizable compound is polymerized by radical polymerization.

[5] The photosensitive resin composition according to any one of [2] to [4], wherein at least one of R 1, R 2, R 3, R 4 and R 5 is -COOH or -OH and the others are hydrogen atoms.

[6] The photosensitive resin composition according to any one of [1] to [5], further comprising a liquid repellent agent.

[7] The photosensitive resin composition according to [6], wherein the liquid repellent agent is a polymer comprising a structural unit derived from an unsaturated compound having a perfluoroalkyl group having 4 to 6 carbon atoms.

[8] The photosensitive resin composition according to any one of [1] to [7], wherein the electrode is a transparent electrode.

[9] A barrier rib formed by the photosensitive resin composition according to any one of [1] to [8].

[10] A substrate comprising the partition wall and the electrode according to [9].

[11] A display device comprising a substrate according to [10].

[12] forming a thin film containing a photosensitive resin composition on a substrate on which an electrode is formed,

An opening is formed in the thin film by photolithography so that the surface of the electrode is exposed,

And evaluating the wettability of the electrode based on the value of the polar component of the surface free energy of the electrode.

According to the photosensitive resin composition of the present invention, after the formation of the pattern, a substrate having a partition wall having excellent spreadability of the entire surface inside the partition wall opening of the ink coated on the electrode can be obtained.

1 is a cross-sectional view schematically showing a part of the display device 1 in an enlarged manner.
2 is a plan view schematically showing a part of the display device 1 of the embodiment of the present invention in an enlarged manner.

The photosensitive resin composition of the present invention is characterized in that a thin film containing the photosensitive resin composition is formed on a substrate on which an electrode is formed and then an opening is formed in the thin film by photolithography so that the surface of the electrode is exposed, And the value of the polar component of the surface free energy is 15 mN / m or more.

When such a photosensitive resin composition is used to form a barrier rib on a substrate on which an electrode is formed, if ink containing a thin film material to be formed on the electrode is applied on the electrode, the ink spreads on the electrode without splashing on the electrode , And solidified by drying or the like, a flat thin film can be formed on the entire surface in the opening of the partition wall.

The value of the polar component of the surface free energy of the electrode after formation of the opening is preferably 15 mN / m or more, more preferably 15.5 mN / m or more.

From the viewpoint of the wettability, the value of the polarity component of the surface free energy of the electrode after formation of the opening is not particularly limited, but is usually 50 mN / m or less, and furthermore 40 mN / m or less.

The resin in the photosensitive resin composition of the present invention is not particularly limited as far as the value of the polar component of the surface free energy of the electrode after opening formation is 15 mN / m or more. For example, acrylic resin, polyimide resin, Resins, and epoxy resins, among which acrylic resins and epoxy resins are preferred.

The photosensitive resin composition preferably includes the following (A), (B) and (C).

(A) a resin having a structural unit containing a group represented by the following formula [i]

(B) a polymerizable compound

(C) Polymerization initiator

The resin (A) is a resin having a structural unit containing a group represented by the above formula [i], and the structural unit is derived from a monomer (a) (hereinafter also referred to as "(a)").

(a) is preferably a monomer having an ethylenically unsaturated double bond and a group represented by the formula [i].

The structural unit containing a group represented by the formula [i] is preferably a structural unit represented by the following formula [ii]. That is, the structural unit derived from (a) is preferably a structural unit represented by the following formula (ii).

Wherein R 1, R 2, R 3, R 4 and R 5 each independently represent -OH, -SH, -COOH, -CHO, a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, And at least one of R 1, R 2, R 3, R 4 and R 5 is -OH, -SH, -COOH or -CHO. R7 represents an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 5 carbon atoms, an aryl group, or a benzyl group. R6 represents a hydrogen atom, a methyl group or an ethyl group.

At least one of R 1, R 2, R 3, R 4 and R 5 is -COOH or -OH from the viewpoint of wettability on the electrode surface, and R 1, R 2, R 3, It is preferably a hydrogen atom.

R 1, R 2, R 3, R 4 and R 5 in the formulas [i] and [ii] are each independently an alkyl group having 1 to 8 carbon atoms alkoxy group, -COOR7, -OCOR7, -COR7, -CN , -NHR7, -NR7R8, -NO 2, -CONH 2, may be -CONHR7, -SOR7, or -SO ₂ R7. Provided that R7 has the same meaning as described above. R 8 represents, independently of R 7, an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 5 carbon atoms, an aryl group, or a benzyl group.

As the halogen atom, Cl, Br or I can be mentioned, and Cl or Br is preferable.

Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, ethyl group, n-propyl group, isopropoxy group, n-butyl group, t-butyl group, n-pentyl group, n- An octyl group, and a methyl group or an ethyl group is preferable.

Examples of the alkoxyalkyl group having 2 to 5 carbon atoms include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, a propylmethyl group and a propylethyl group. Ethyl group is preferable.

Examples of the aryl group include a phenyl group and a naphthyl group. However, it is not limited thereto and may have a substituent.

(a) may be at least one selected from the group consisting of o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2- mercaptostyrene, 3- mercaptostyrene, 4- mercaptostyrene, 2- But are not limited to, 4-vinylpyridine, 4-vinylpyridine, 4-vinylpyridine, 4-vinylpyrrolidone, Vinylbenzoic acid, p-vinylbenzoic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3-vinylphthalic anhydride, 4-vinylphthalic acid, Vinyl monoethyl ester, 5-vinyl isophthalic acid monoethyl ester, 4-vinyl salicylic acid, 5-vinyl monoethyl ester, 5-vinyl isophthalic acid monomethyl ester, Vinyl salicylic acid, 5-vinyl salicylaldehyde, 5-vinyl acetylsalicylic acid, ethyl 4-vinylbenzenesulfonate, 4-vinyl resorcinol, Vinyl resorcinol monomethoxy methyl ether, 4-vinyl resorcinol bismethoxy methyl ether, 4-vinyl resorcinol monomethoxy ethyl ether, 4-vinyl resorcinol bismethoxy ethyl ether, 4-vinyl benzo Vinylbenzenesulfonic acid, m-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-vinylbenzoic acid, m- Vinyl benzoic acid, and p-vinyl benzoic acid. Further, (a) is not limited to the above example.

The photosensitive resin composition of the present invention may further contain a resin other than the resin (A) (hereinafter sometimes referred to as "resin (A1)"), a solvent (D), a polymerization initiator (E) A surfactant (G), and an adhesion-promoting agent (H).

In the present specification, the compounds exemplified as respective components can be used alone or in combination, unless otherwise specified.

The resin (A) may further contain a structural unit derived from a monomer (x) other than the monomer (a) (hereinafter sometimes referred to as "(x)").

(x) is not particularly limited as long as it is a monomer other than (a) and does not have a perfluoroalkyl group having 4 to 6 carbon atoms. For example, a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms , "(B)"), at least one monomer (e) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter also referred to as "(e)" ) And the other monomer (c) (hereinafter occasionally referred to as "(c)"). Of these, (b) or (c) is preferable.

(b) is a monomer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one kind selected from the group consisting of oxirane ring, oxetane ring and tetrahydrofuran ring), preferably 2 to 4 carbon atoms Of a cyclic ether structure and an ethylenically unsaturated double bond, more preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

(b2) having an oxiranyl group (hereinafter sometimes referred to as "(b1)"), an oxetanyl group-containing monomer (b2) , And a monomer (b3) having a tetrahydrofuryl group (hereinafter sometimes referred to as "(b3)").

(b1-1) having a structure in which a straight-chain or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)"), an unsaturated alicyclic hydrocarbon having an epoxy (B1-2) (hereinafter sometimes referred to as " (b1-2) ").

(b1) is preferably a monomer having an oxiranyl group and a (meth) acryloyloxy group, more preferably a monomer having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized and a (meth) acryloyloxy group. If these monomers are used, the storage stability of the photosensitive resin composition is excellent.

(meth) acrylate,? -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o (meth) acrylate, -Vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl-m-vinylbenzyl glycidyl (Glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, Styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) ) Styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6- , And JP-A-7-248625.

(b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Sucoxide 2000, manufactured by Daicel Chemical Industries, Ltd.), 3,4- (For example, Cyclomer A400 manufactured by Dai-ichi Kogaku Kogyo K.K.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100 manufactured by Dai-ichi Kogaku Kogyo KK A compound represented by the formula (I) and a compound represented by the formula (II).

In the formula (I) and formula (II), R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, hydrogen atoms contained in the alkyl group may be substituted with a hydroxy group, X ¹ And X ² independently represent a single bond, -R ³ -, -R ³ -O-, -R ³ -S-, or -R ³ -NH-, and R ³ represents a C 1-6 Represents an alkandiyl group, and * represents a bond with O)

Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group.

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

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

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane- A 6-diyl group and the like.

X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- (* represents a bond with O), * -CH ₂ CH ₂ -O- group , More preferably a single bond, * -CH ₂ CH ₂ -O- group.

Examples of the compound represented by the formula (I) include a compound represented by any one of the formulas (I-1) to (I-15). Among them, the compound represented by the formula (I-1), the compound represented by the formula (I-3), the compound represented by the formula (I-5), the compound represented by the formula (I- ) Is more preferably a compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15).

Examples of the compound represented by the formula (II) include compounds represented by any one of the formulas (II-1) to (II-15). Among them, the compound represented by the formula (II-1), the formula (II-3), the formula (II-5), the formula (II- ) Is more 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 alone or in combination of two or more. When the compound represented by formula (I) and the compound represented by formula (II) are used in combination, the content ratio thereof (compound represented by formula (I): compound represented by formula (II) Preferably from 5:95 to 95: 5, more preferably from 20:80 to 80:20.

(b2) is preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, 3-methyl-3- ) Acryloyloxyethyloxetane, 3-ethyl-3- (meth) acryloyloxyethyloxetane, and the like.

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

Specific examples of the compound (b3) include tetrahydrofurfuryl acrylate (for example, Viscot V # 150, manufactured by Osaka Kikin Kagaku Kogyo Co., Ltd.) and tetrahydrofurfuryl methacrylate.

(e) include unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides.

Examples of the unsaturated carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, maleic acid, citraconic acid, mesaconic acid, itaconic acid, 1,4-cyclohexene dicarboxylic acid, methyl-5-norbornene- Dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept- Mono [2- (meth) acryloyloxyethyl], and? - (hydroxymethyl) acrylic acid.

Examples of the unsaturated carboxylic acid anhydrides include unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, and 5,6-dicarboxybicyclo [2.2.1] hept-2- .

(meth) acrylic acid esters, N-substituted maleimide unsaturated dicarboxylic acid diesters, alicyclic unsaturated compounds, styrenes, and other vinyl compounds. Among them, (meth) acrylates and styrenes are preferable.

Examples of the (meth) acrylic esters include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec- Esters;

Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in the technical field, dicyclopentanil (Meth) acrylate), dicyclopentanyloxyethyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate Cyclopentenyl (meth) acrylate "), and isobornyl (meth) acrylate;

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

Phenyl (meth) acrylate, and benzyl (meth) acrylate; and aralkyl esters.

Among the (meth) acrylate esters, alkyl esters are preferred.

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

Examples of the N-substituted maleimides include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl- , N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimidepropionate, N- (9-acridinyl) maleimide 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, 5-ethylbicyclo [2.2.1] hept- , 5-hydroxycyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept- 2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept- Ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2- Hydroxycyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbis 2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept- - ene, 5-phenoxycar 2,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbamoyl) Nonyl) bicyclo [2.2.1] hept-2-ene and the like.

Examples of the styrene include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene and the like. Among them, styrene is preferable.

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

The resin (A) may be a resin containing only a structural unit derived from (a), but a resin containing a structural unit derived from (a) and a structural unit derived from (x) is preferable.

When the resin (A) is a resin containing a structural unit derived from (a) and a structural unit derived from (x), it depends on the acidity of the structural unit used in (a) Is preferably within the following range with respect to the total number of moles of the structural units constituting the resin (A).

a structural unit derived from (a); 5 to 70 mol% (more preferably 10 to 60 mol%),

(x); 30 to 95 mol% (more preferably 40 to 90 mol%),

When the ratio of the structural unit of the resin (A) is within the above range, the storage stability of the photosensitive resin composition, developability in forming a pattern from the photosensitive resin composition, and solvent resistance, heat resistance and mechanical strength of the obtained coating film and pattern are satisfactory There is a tendency to disappear.

In particular, when any one of R1 to R5 is -COOH, it is preferable that the ratio of the structural unit derived from each monomer is within the following range with respect to the total number of moles of the structural units constituting the resin (A).

a structural unit derived from (a); 5 to 50 mol%

(x); 50 to 95 mol%

The resin (A) can be obtained by a method described in, for example, "Experimental Method of Polymer Synthesis" (Takatsuki Otsu Kogaku Co., Ltd., 1st Ed., 1st Ed., March 1, 1972, And references cited in the literature.

Specifically, a predetermined amount of (a) and, if necessary, (x), a polymerization initiator and a solvent are placed in a reaction vessel and oxygen in the atmosphere is replaced by nitrogen, for example, A method of heating and keeping warm is exemplified. The polymerization initiator and solvent used herein are not particularly limited, and any of those commonly used in the field can be used. Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), organic peroxides (such as benzoyl peroxide) As the solvent, any one that dissolves each monomer may be used. As the solvent (D) of the photosensitive resin composition, a solvent described later or the like may be used. In order to adjust the molecular weight of the resulting resin, a chain transfer agent may be added during the polymerization reaction. Examples of the chain transfer agent include n-butanethiol, tert-butanethiol, n-dodecanethiol, 2-sulfanylethanol, thioglycolic acid, ethyl thioglycolate, 2-ethylhexyl thioglycolate, methoxybutyl thioglycolate, 3- Sulfanylpropionic acid, and a sulfany group-containing silicone (KF-2001; manufactured by Shinetsu Chemical Co., Ltd.); And halogenated alkyls such as chloroform, carbon tetrachloride and carbon tetrabromide.

In particular, when (a) has a phenolic hydroxyl group, a monomer in which the phenolic hydroxyl group of (a) has been protected with a protective group in advance may be used at the time of polymerization. Examples of the protecting group include a tertiary alkyl group such as a tert-butyl group; And an acyl group such as an acetyl group.

After polymerization using such a monomer protected with a protecting group, the resin (A) can be obtained by deprotecting the protecting group.

The obtained polymer may be a solution after the reaction as it is, or a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by re-precipitation or the like. In particular, by using the same solvent as the solvent (D) described later as a solvent in the polymerization, the solution after the reaction can be used as it is, and the production process can be simplified.

The weight average molecular weight of the resin (A) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the resin (A) is within the above range, the coating property tends to be excellent, the film thickness of the exposed portion is hardly reduced at the time of development, and the unexposed portion is liable to be removed by development.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin (A) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. When the molecular weight distribution is in the above-mentioned range, the developability tends to be excellent.

The acid value of the resin (A) is usually 20 to 200 mg KOH / g, preferably 40 to 180 mg KOH / g, and more preferably 50 to 180 mg KOH / g. By using a resin having an acid value in this range, the value of the polarity component of the surface free energy of the electrode after formation of the opening can be set to 15 mN / m or more. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin and can be determined by titration using an aqueous solution of potassium hydroxide.

The content of the resin (A) is preferably from 5 to 95% by mass, more preferably from 20 to 80% by mass, and particularly preferably from 5 to 95% by mass, relative to the total amount of the resin (A), the resin (A1) and the polymerizable compound By mass to 45% by mass to 80% by mass. When the content of the resin (A) is in the above range, the developability of the photosensitive resin composition, the adhesiveness of the resulting pattern, the solvent resistance, and the mechanical properties tend to be good.

The photosensitive resin composition of the present invention may contain a liquid repellent agent (F). The liquid repellent agent (F) is a resin that exhibits liquid repellency. The material used is not particularly limited as long as the surface of the structure after pattern formation is higher in lyophobicity than the structure itself. However, . The resin that exhibits liquid repellency to be used includes, for example, a structural unit having a perfluoroalkyl group having 1 to 8 carbon atoms (which may have an etheric oxygen atom between carbon atoms), preferably a structural unit having 4 to 8 carbon atoms (D) (hereinafter occasionally referred to as " (d) ") having a perfluoroalkyl group having 1 to 6 carbon atoms.

(d) may be a compound represented by the formula (d-0).

Wherein R ^f represents a perfluoroalkyl group having 4 to 6 carbon atoms and 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, X ^d represents a single bond, a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a divalent alicyclic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom or a hydroxy group. And the -CH ₂ - included in the aliphatic hydrocarbon group and the alicyclic hydrocarbon group is substituted with -O-, -CO-, -NR ^e -, -S- or -SO ₂ - Maybe]

R ^f is a perfluoroalkyl group having 4 to 6 carbon atoms, preferably a perfluorobutyl group and a perfluorohexyl group.

Examples of the alkyl group having 1 to 21 carbon atoms in R ^d include methyl, ethyl, n-propyl, n-butyl, n-pentyl, a straight chain alkyl group such as n-decyl group;

A methylpentyl group, a 4-methylpentyl group, a 1-ethylbutyl group, a 2-ethylpentyl group, an isobutyl group, an isobutyl group, an isopentyl group, Propylphenyl group, 3-ethylpentyl group, 3-methylpentyl group, 3-methylpentyl group, 3-methylpentyl group, 3-methylpentyl group, Methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group, 1-ethylhexyl group, 2-methylheptyl group, Ethylhexyl group, 2-propylpentyl group, 1-butylbutyl group, 1-butyl-2-methylbutyl group, 1-butyl- Dimethylbutyl group, 1, 2-dimethylbutyl group, 1, 3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethyl- Methylpropyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 1,4-dimethylpentyl group, 2,2-dimethylpentyl group, T-butyl, 2,4-dimethylpentyl, 3,3-dimethyl Group, and the like can be mentioned 3,4-dimethyl-pentyl group, 1-ethyl-1-methylbutyl group, 2-ethyl-3-methyl branched alkyl groups 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 in X ^d include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, Diyl group, a butane-1,2-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane- And an alkanediyl group such as a diary.

Examples of the divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms in X ^d include a cyclopropanediyl group, a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group, and a cyclodecanediyl group .

Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms in X ^d include a phenylene group and a naphthalenediyl group.

Examples of X ^d substituted with -CH ₂ - by -O-, -CO-, -NR ^e -, -S- or -SO ₂ - include, for example, groups represented by formulas (xd-1) to And the like.

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

(d) is preferably a compound represented by the following formula (yd-1).

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

Examples of the compound represented by the formula (d-0) include compounds (d-1) to (d-94). In the table, the formula number in the column X ^d represents the formula number of the group exemplified above. Further, for example, the compound (d-1) is a compound represented by the following formula (d-1).

The resin (F) is preferably a copolymer containing a structural unit derived from (d) and a structural unit derived from (e), and the structural unit derived from (d) and the structural unit derived from (e) and a structural unit derived from the structural unit (b). Since the resin (F) contains a structural unit derived from (e), the development is excellent and unevenness resulting from residual or phenomenon tends to be suppressed. It is preferable that the resin (F) contains a structural unit derived from (b) because it tends to have excellent solvent resistance. The resin (F) may also contain a structural unit derived from (c). (e), (b) and (c) are the same as described above.

When the resin (F) is a copolymer of (e) and (d), it is preferable that the ratio of the structural unit derived from each monomer is within the following range with respect to the total number of moles of the structural units constituting the resin (F).

(e); 5 to 50% by mass (more preferably 10 to 40% by mass)

(d); 50 to 95% by mass (more preferably 70 to 90% by mass)

When the resin (F) is a copolymer of (e), (b) and (d), the proportion of the structural units derived from each monomer is in the following range with respect to the total number of moles of the structural units constituting the resin (F) .

(e); 5 to 40% by mass (more preferably 10 to 30% by mass)

(b); 5 to 80% by mass (more preferably 10 to 70% by mass)

(d); 10 to 80% by mass (more preferably 20 to 70% by mass)

When the resin (F) is a copolymer of (e), (b), (c) and (d), the ratio of the structural unit derived from each monomer is preferably Is preferable.

(e); 5 to 40% by mass (more preferably 10 to 30% by mass)

(b); 5 to 70% by mass (more preferably 10 to 60% by mass)

(c); 10 to 50% by mass (more preferably 20 to 40% by mass)

(d); 10 to 80% by mass (more preferably 20 to 70% by mass)

When the proportion of each structural unit is in the above range, the liquid repellency and developability tend to be excellent.

The weight average molecular weight of the resin (F) in terms of polystyrene is preferably 3,000 to 20,000, more preferably 5,000 to 15,000. When the weight average molecular weight of the resin (F) is within the above-mentioned range, the coating property tends to be excellent, the film of the exposed portion is hardly reduced during development, and the unexposed portion is liable to be removed by development.

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

The content of the resin (F) is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass based on 100 parts by mass of the total amount of the resin (A), the resin (A1) and the polymerizable compound (B). When the content of the resin (F) is within the above range, the developability at the time of pattern formation is excellent, and the resulting pattern tends to have excellent lyophobicity.

The resin (A1) is not particularly limited as long as it is a resin other than the resin (A) and the resin (F). As the resin (A1)

Resin (A1-1): a copolymer obtained by polymerizing (e) and (b)

Resin (A1-2): a copolymer obtained by polymerizing (e), (b) and (c)

Resin (A1-3): a copolymer obtained by polymerizing (e) and (c)

Resin (A1-4): A resin obtained by reacting (b) a copolymer obtained by polymerizing (e) and (c)

Resin (A1-5): A resin obtained by reacting (e) a copolymer obtained by polymerizing (b) and (c).

Among them, the resin (A1-1) and the resin (A1-2) are preferable.

In the resin (A1-1), it is preferable that the ratio of the structural unit derived from each monomer is within the following range with respect to the total number of moles of the total structural units constituting the resin (A1-1).

(e); 5 to 60 mol% (more preferably 10 to 50 mol%)

(b); 40 to 95% by mole (more preferably 50 to 90% by mole)

When the proportion of the structural unit of the resin (A1-1) is within the above range, the storage stability of the photosensitive resin composition, the developability in forming a pattern from the photosensitive resin composition, and the solvent resistance of the obtained coating film and pattern tend to be good have.

In the resin (A1-2), it is preferable that the ratio of the structural unit derived from each monomer is within the following range with respect to the total number of moles of the total structural units constituting the resin (A1-2).

(e); 2 to 45 mol% (more preferably 5 to 40 mol%),

(b); 2 to 95 mol% (more preferably 5 to 80 mol%),

(c); 1 to 65 mol% (more preferably 5 to 60 mol%),

When the ratio of the structural unit of the resin (A1-2) is within the above range, the storage stability of the photosensitive resin composition, developability in forming a pattern from the photosensitive resin composition, and solvent resistance of the obtained coating film and pattern tend to be good have.

In the resin (A1-3), it is preferable that the ratio of the structural unit derived from each monomer is in the following range with respect to the total number of moles of the total structural units constituting the resin (A1-3).

(e); 2 to 40 mol% (more preferably 5 to 35 mol%),

(c); 60 to 98% by mole (more preferably 65 to 95% by mole)

When the proportion of the structural unit of the resin (A1-3) is within the above range, the storage stability of the photosensitive resin composition, developability in forming a pattern from the photosensitive resin composition, and solvent resistance of the resulting coating film and pattern tend to be good have.

Resins (A1-1) to (A1-3) can be produced by the same method as Resin (A).

Resin (A1-4) is a resin obtained by reacting the copolymer (e) and (c) with (b).

The resin (A1-4) can be produced, for example, by a two-step process. Also in this case, the method described in the above-mentioned "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Co., Ltd., 1st Ed., First edition, March 1, 1972) 89533, and the like.

First, as a first step, a copolymer of (e) and (c) is obtained in the same manner as in the above-mentioned production method of the resin (A).

In this case, in the same manner as described above, the solution obtained after the reaction may be used as it is, or a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by a method such as re-precipitation. The weight average molecular weight and the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) in terms of polystyrene similar to those described above are preferable.

However, it is preferable that the proportion of the structural units derived from (e) and (c) is in the following range with respect to the total number of moles of the total structural units constituting the copolymer.

(e); 5 to 50 mol% (more preferably 10 to 45 mol%),

(c); 50 to 95% by mole (more preferably 55 to 90% by mole)

Subsequently, as a second step, a part of the carboxylic acid or carboxylic acid anhydride (e) derived from the obtained copolymer is reacted with the cyclic ether of the above-mentioned (b). (B1) or (b2) is preferably used as the resin (A1-4), and (b1-1) is preferably used as the resin (A1-4) because the reactivity of the cyclic ether is high and unreacted More preferable.

Specifically, the atmosphere in the flask was replaced with air in the flask, and 580 mol% of (b) of the reaction catalyst of a carboxyl group and a cyclic ether (for example, tris (E), (b) and (c) in an amount of 0.001 to 5 mass% based on the total amount of (e), (b) and (c), and a polymerization inhibitor (such as hydroquinone) (c), and the mixture is allowed to react at 60 to 130 캜 for 1 to 10 hours to obtain a resin (A1-4). In addition, as in the case of the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production facilities and the amount of heat generated by polymerization.

In this case, the number of moles of (b) is preferably 10 to 75 mol%, and more preferably 15 to 70 mol% based on the number of moles of (e). This range tends to improve the storage stability of the photosensitive resin composition, developability in forming a pattern from the photosensitive resin composition, and balance of solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained coating film and pattern.

As the first step of the resin (A1-5), a copolymer of (b) and (c) is obtained in the same manner as in the above-mentioned production method of the resin (A).

In this case, in the same manner as described above, the solution obtained after the reaction may be used as it is, or a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by a method such as re-precipitation.

the ratio of the structural units derived from (b) and (c) to the total number of moles of the total structural units constituting the copolymer is in the following range.

(b); 5 to 95 mol% (more preferably 10 to 90 mol%)

(c); 5 to 95 mol% (more preferably 10 to 90 mol%)

In the same manner as in the production of the resin (A1-4), the carboxylic acid or carboxylic acid anhydride of (e) in the cyclic ether derived from (b) in the copolymer of (b) . The carboxylic acid anhydride may also be reacted with the hydroxyl group generated by the reaction of the cyclic ether with the carboxylic acid or the carboxylic acid anhydride.

The amount of (e) to be reacted with the copolymer is preferably 5 to 80 mol% based on the number of moles of (b). (B) is preferably (b1), and (b1-1) is preferable in that the reactivity of the cyclic ether is high and unreacted (b) is hard to remain.

The weight average molecular weight of the resin (A1) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the resin (A1) is within the above range, the coating property tends to be excellent, and the film thickness of the exposed portion is hardly reduced at the time of development, and the unexposed portion is liable to be removed as development.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin (A1) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. When the molecular weight distribution is in the above-mentioned range, the developability tends to be excellent.

The acid value of the resin (A1) is usually from 20 to 200 mgKOH / g, preferably from 40 to 180 mgKOH / g, and more preferably from 50 to 180 mgKOH / g.

When the resin (A1) is contained, its content is preferably 1 to 80% by mass, more preferably 1 to 50% by mass, based on the total amount of the resin (A) and the resin (A1). When the content of the resin (A1) is in the above range, the pattern can be formed with high sensitivity, and the developing property is excellent.

When the resin (A1) is contained, its content is preferably 1 to 80% by mass, more preferably 1 to 50% by mass, based on the total amount of the resin (A) and the resin (A1). When the content of the resin (A1) is in the above range, the pattern can be formed with high sensitivity, and the developing property is excellent.

The photosensitive resin composition of the present invention preferably contains a polymerizable compound (B).

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

Examples of the polymerizable compound (B) having one ethylenically unsaturated bond include the same ones as the compounds exemplified above as (a), (b) and (c), and among them, (meth) acrylate esters are preferable.

Examples of the polymerizable compound (B) having two ethylenically unsaturated bonds include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,6-hexanediol di (meth) , Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di 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, and the like.

Examples of the polymerizable compound (B) having three or more ethylenic unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, propoxylated trimethylol propane tri , Tripentaerythritol 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 acid anhydride A reaction product of dipentaerythritol penta (meth) acrylate and an acid anhydride, a reaction product of tripentaerythritol hepta (meth) acrylate and an acid anhydride, caprolactone-modified trimethylolpropane tri (meth) acrylate, Caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified pentaerythritol tetra (Meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta ) Acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified (Meth) acrylate, caprolactone-modified tripentaerythritol octa (meth) acrylate, a reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate and an acid anhydride, caprolactone-modified dipenta A reaction product of an erythritol penta (meth) acrylate and an acid anhydride, and a reaction product of caprolactone-modified tripentaerythritol (meth) acrylate and an acid anhydride. Among them, a polymerizable compound (B) having three or more ethylenic unsaturated bonds is preferable, and dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) Acrylate is more preferable.

The content of the polymerizable compound (B) is preferably 5 to 95% by mass, more preferably 20 to 80% by mass, based on the total amount of the resin (A), the resin (A1) and the polymerizable compound (B).

When the content of the polymerizable compound (B) is in the above range, the sensitivity and the strength, smoothness and reliability of the obtained pattern tend to be improved.

The photosensitive resin composition of the present invention comprises a polymerization initiator (C). The polymerization initiator (C) is not particularly limited as long as it is a compound capable of initiating polymerization by the action of light or heat, and a known polymerization initiator can be used.

Examples of the polymerization initiator (C) include oxime compounds, alkylphenone compounds, imidazole compounds, triazine compounds and acylphosphine oxide compounds. Further, the light and / or thermal cationic polymerization initiator described in Japanese Patent Laid-Open No. 2008-181087 (for example, one comprising an onium cation and an anion derived from a Lewis acid) may also be used. Among them, at least one selected from the group consisting of a nonimidazole compound, an alkylphenone compound and an oxime compound is preferable, and an alkylphenone compound is particularly preferable. A polymerization initiator containing these compounds is particularly preferable because it tends to be highly sensitive.

The oxime compound is a compound having a partial structure represented by the formula (d1). Herein, * denotes a combined hand.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- - ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] (3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan- 1-imine, N- acetoxy- 1- [ -9-ethyl-6- (2-methylbenzoyl) -9H-carbazole < / RTI > -3-yl] -3-cyclopentylpropan-1-one-2-imine. Commercially available products such as Irgacure OXE01 and OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may also be used.

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

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- (4-morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) Butane-1-one and the like. IRGACURE 369, 907, 379 (manufactured by BASF Co., Ltd.), and the like.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy- 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy- ,?,? -diethoxyacetophenone, and benzyl dimethyl ketal.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d2).

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- 4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-B-6-75372 and JP-A-6-75373) Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis Tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra -Chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (for example, Japanese Patent Publication (Kokai) No. 48-38403, (See, for example, Japanese Unexamined Patent Application Publication No. 7-10913, etc.) in which the phenyl group at the 4,4 ', 5,5'-position is substituted by a carboalkoxy group ) And the like. Preferable examples include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- 4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- Methyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- 2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4,6-trichloromethyl- Bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- - [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

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

Examples of the polymerization initiator (C) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- butylperoxycarbonyl) benzophenone Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, camphorquinone, etc .; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These may be added with a polymerization initiator (E) described later.

As a polymerization initiator having a group capable of chain transfer, a polymerization initiator described in JP-A-2002-544205 may also be used.

The polymerization initiator having a group capable of causing chain transfer can also be used as the monomer (c) which is a structural unit which can be contained in the resin (A).

In the photosensitive resin composition of the present invention, the polymerization initiator (E) may be used together with the polymerization initiator (C) described above. The polymerization initiator (E) is used in combination with the polymerization initiator (C) and is a compound or a sensitizer used for promoting the polymerization of the polymerizable compound initiated by the polymerization initiator. Examples of the polymerization initiator (E) include thioxanthone compounds, amine compounds, carboxylic acid compounds, compounds described in JP-A-2008-65319 and JP-A-2009-139932, and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- ≪ / RTI > propoxycyclohexanone, and the like.

Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; aliphatic amine compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, Ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'- And aromatic amine compounds such as phenanone.

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

Examples of the combination of the polymerization initiator (C) and the polymerization initiator (E) include an acetophenone compound, a thioxanthone compound, an acetophenone compound and an aromatic amine compound. Specific examples thereof include 2-morpholino- Methylphenylphenyl) -2-methylpropan-1-one with 2,4-diethylthioxanthone, 2-dimethylamino-2-benzyl- 1- (4-morpholinophenyl) butan- Diethyl thioxanthone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan- Methylphenyl-2-methylpropan-1-one, 2-isopropylthioxanthone and 4-isopropylthioxanthone, 2-morpholino-1- (4-methylsulfanylphenyl) -2-methylpropan-1-one and 4,4'-bis (diethylamino) benzophenone, 2-dimethylamino- ) Butane-1-one with 4,4'-bis (diethylamino) benzophenone, 2-dimethylamino-2- (4- And the like can be mentioned 4,4'-bis (diethylamino) benzophenone.

Among them, a combination of an acetophenone compound and a thioxanthone compound is preferable, and a combination of 2-morpholino-1- (4-methylsulfanylphenyl) -2-methylpropan- Oxanthone, 2-morpholino-1- (4-methylsulfanylphenyl) -2-methylpropan-1-one and 2-isopropylthioxanthone and 4-isopropylthioxanthone are more preferable. If these are combined, a pattern with high sensitivity and high visible light transmittance can be obtained.

The content of the polymerization initiator (C) is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the total amount of the resin (A), the resin (A1) and the polymerizable compound (B) More preferably 1 to 10 parts by mass. When the content of the polymerization initiator (C) is in the above range, a pattern with high sensitivity can be obtained.

The amount of the polymerization initiator (E) to be used is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass based on 100 parts by mass of the total amount of the resin (A), the resin (A1) and the polymerizable compound (B) Wealth. When the amount of the polymerization initiator (E) is in the above range, a pattern can be obtained with high sensitivity, and the obtained pattern has a good shape.

The photosensitive resin composition of the present invention may contain a solvent (D).

Examples of the solvent which can be used in the present invention include ester solvents (solvents containing -COO- in the molecule and not including -O-), ether solvents (including -O- in the molecule and -COO- (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not including -COO-), alcohol solvent, An aromatic hydrocarbon solvent, an amide solvent, dimethylsulfoxide, and the like.

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

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1 , 4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, .

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Methoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Methyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, propyleneglycol monomethyl ether acetate, 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.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4- Cyclohexanone, isophorone, and the like.

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

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

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

These solvents may be used alone or in combination of two or more.

Among the above-mentioned solvents, an organic solvent having a boiling point of 120 占 폚 or more and 180 占 폚 or less at 1 atm is preferable from the viewpoint of coatability and drying property. Among them, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol and the like are preferable. When the solvent (D) is one of these solvents, it is possible to suppress non-uniformity during coating and improve the flatness of the coating film.

The content of the solvent (D) in the photosensitive resin composition of the present invention is preferably 60 to 95% by mass, more preferably 70 to 90% by mass, based on the total amount of the photosensitive resin composition.

In other words, the solid content of the photosensitive resin composition is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass. When the content of the solvent (D) is in the above range, the flatness of the film coated with the photosensitive resin composition tends to be high. Here, the solid content means the amount excluding the solvent (D) from the photosensitive resin composition.

Further, the photosensitive resin composition of the present invention may further contain a polyfunctional thiol compound (T). The polyfunctional thiol compound (T) refers to a compound having two or more sulfanyl groups (-SH) in the molecule. In particular, when a compound having two or more sulfanyl groups bonded to carbon atoms derived from an aliphatic hydrocarbon group is used, the sensitivity of the photosensitive resin composition of the present invention tends to be high.

Specific examples of the polyfunctional thiol compound (T) include hexane dithiol, decanediol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanyl propionate), trimethylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyethyl tris (3 -Sulfanylpropionate), pentaerythritoltetrakis (3-sulfanylbutyrate), and 1,4-bis (3-sulfanylbutyloxy) butane.

The content of the polyfunctional thiol compound (T) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass based on 100 parts by mass of the polymerization initiator (C). When the content of the polyfunctional thiol compound (T) is within the above range, the sensitivity of the photosensitive resin composition is high and the developing property tends to be good.

The photosensitive resin composition of the present invention may contain a surfactant (G) (however, it is different from the resin (F)). As the surfactant, for example, a silicone surfactant, a fluorinated surfactant, and a silicon surfactant having a fluorine atom can be given.

As the silicone surfactant, a surfactant having a siloxane bond can be mentioned.

Concretely, TORAY silicone DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, polyether-modified silicone oil SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323 , KP324, KP340, KP341 (manufactured by Shinetsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials Japan Manufactured by KODO CHEMICAL CO., LTD.).

As the fluorochemical surfactant, a surfactant having a fluorocarbon chain can be mentioned.

Concretely, the following materials are used: Fluorinert (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Megafax (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper R30 (Trade name) manufactured by Mitsubishi Material Denshi Kasei Co., Ltd.), SUPPLON (registered trademark) S381, S382, SC101, and SC101 (manufactured by DIC Corporation), EFTAX (registered trademark) EF301, EF303, EF351 and EF352 SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Co., Ltd.).

Examples of the silicone surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specifically, Megafax (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation) and the like can be mentioned. Preferable is Megafax (registered trademark) F475.

The content of the surfactant (G) is 0.001 to 0.2% by mass, preferably 0.002 to 0.1% by mass, more preferably 0.01 to 0.05% by mass, based on the total amount of the photosensitive resin composition to be. When the surfactant is contained in this range, the flatness of the coating film can be improved.

The photosensitive resin composition of the present invention may contain various additives such as a filler, another polymer compound, an adhesion promoting agent (H), an antioxidant, an ultraviolet absorber, a light stabilizer, and a chain transfer agent.

The adhesion promoting agent (H) is not particularly limited so long as it does not precipitate a solid material upon reaction with the photosensitive resin composition at the time of addition or at room temperature, and examples thereof include silane coupling agents, KBM-803, KBE-9007 (manufactured by Shin-Etsu Chemical Co., Ltd.) or Z-6040, Z-6043, KBM- Z-6011, Z-6020, Z-6094, Z-6062, Z-6094, Z-6030, Z-6519, Z-6300 and Z-6883 (manufactured by Dow Corning Toray Co., Ltd.) .

The photosensitive resin composition of the present invention contains substantially no coloring agent such as pigment and dye. That is, in the photosensitive resin composition of the present invention, the content of the colorant in the entire composition is preferably, for example, less than 1% by mass, more preferably less than 0.5% by mass.

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

When the photosensitive resin composition of the present invention is used as a coating film, the average transmittance of the coating film is preferably 90% or more, more preferably 95% or more. The average transmittance is measured by using a spectrophotometer under the condition of a wavelength of 400 to 700 nm and a thickness of 3 占 퐉 after heat curing (for example, curing at 100 to 250 占 폚 for 5 minutes to 3 hours) It is the average value in one case. As a result, it is possible to provide a coating film excellent in transparency in a visible light region.

The photosensitive resin composition of the present invention is applied onto a substrate such as glass, metal, plastic or the like, or a substrate on which a color filter, various insulating or conductive films, a driving circuit, etc. are formed and patterned into a desired shape, . Further, this pattern may be formed and used as a part of a component such as a display device.

First, the photosensitive resin composition of the present invention is coated on a substrate, and patterning is performed by the photolithography method described below.

The application of the photosensitive resin composition can be carried out by using various applicators such as a spin coater, a slit & spin coater, a slit coater, an ink jet, a roll coater and a dip coater.

Subsequently, drying or pre-baking is preferably performed by removing volatile components such as a solvent and drying. Thereby, a smooth uncured coating film can be obtained.

The thickness of the coating film in this case is not particularly limited and can be appropriately adjusted depending on the material to be used and the application, and is, for example, about 1 to 6 mu m.

The obtained uncured coating film is irradiated with light, for example, a mercury lamp or ultraviolet rays generated from the light emitting diode through a photomask for forming a desired pattern. The shape of the photomask at this time is not particularly limited, and the shape and size may be selected depending on the use of the pattern.

In recent exposures, light having a wavelength of less than 350 nm is cut using a filter that cuts the wavelength region, or light having wavelengths around 436 nm, around 408 nm, and around 365 nm is cut by a band-pass filter band pass filter, so that the entire exposure surface can be uniformly irradiated with a substantially parallel light beam. When a device such as a mask aligner or a stepper is used, precise alignment between the mask and the substrate can be performed at this time.

A desired pattern shape can be obtained by bringing a coated film after exposure into contact with a developer to dissolve and develop a predetermined portion, for example, an unexposed portion (i.e., a non-pixel portion).

The developing method may be any of a puddle method, a dipping method, and a spraying method. It is also possible to tilt the substrate at an arbitrary angle at the time of development.

The developing solution used for development is preferably an aqueous solution of a basic compound.

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

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

The organic basic compound includes, for example, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Propylamine, diisopropylamine, ethanolamine, and the like.

The concentration of these inorganic and organic basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass.

The developing solution may contain a surfactant.

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

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

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

The concentration of the surfactant in the alkali 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 development, washing with water is carried out to obtain a pattern. In addition, post-baking may be performed if necessary. The post-baking is preferably performed at a temperature in the range of, for example, 150 to 240 캜 for 10 to 180 minutes.

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

In the present embodiment, a thin film containing the photosensitive resin composition is formed on the substrate on which the electrode is formed as described above, and then the opening is formed in the thin film by the photolithography method so that the surface of the electrode is exposed.

Then, based on the value of the polar component of the surface free energy of the electrode, the wettability of the electrode is evaluated, and thereby the evaluation of the substrate can be performed.

When the value of the polarity component of the surface free energy of the electrode is, for example, 15 mN / m or more, it is determined that the substrate is a substrate applicable to a display device or the like as a partition wall- Or less, it can be determined that the substrate can not be applied to a display device or the like as a barrier-wall-attached substrate.

Further, based on the evaluation result, the photosensitive resin composition for forming the barrier rib can also be evaluated.

That is, a thin film containing the photosensitive resin composition is formed on the substrate on which the electrode is formed as described above, and then an opening is formed in the thin film by the photolithography method so that the surface of the electrode is exposed, The wettability of the electrode can be evaluated based on the value of the polarity component of the surface free energy of the photosensitive resin composition, whereby the photosensitive resin composition can be evaluated.

If the value of the polarity component of the surface free energy of the electrode is, for example, 15 mN / m or more, it is determined that the photosensitive resin composition is applicable as the photosensitive resin composition for forming the barrier rib. On the other hand, Is 15 mN / m or less, it can be judged to be a photosensitive resin composition which can not be applied as a photosensitive resin composition for forming barrier ribs.

The value of the polarity component of the surface energy of the electrode can be calculated, for example, by measuring a contact angle of a predetermined solution on the electrode surface and using a predetermined calculation formula based on the measured value.

In this embodiment, for example, the polarity component value of the surface energy of the electrode can be calculated using the Owensand-Wendt method. In the Owens and Went law, the following formula applies.

γl (1 + cosθ) = 2 (γsd · γld) 1/2 +2 (γsp · γlp) 1/2

Γd is the surface free energy of the liquid, γld is the dispersive force component of the surface free energy of the liquid, γlp is the polar component of the surface free energy of the liquid, γsd is the dispersive force component of the surface energy of the solid, The polar component of energy, and? Represents the contact angle, respectively)

Here, since the unknowns are two (? Sd,? Sp), if two types of liquids in which the dispersed component and the polarity component are known are used, these? Sd and? Sp can be calculated.

From the above equation, the following equation is derived and the slope is (? Sp) ^1/2 and the slice is (? Sd) ^1/2 from the first-order regression equation of the following formula.

? 1 (1 + cos?) / 2 (? ld) ^1/2 VS (? lp /? ld) ^1/2

If two types of liquids in which the dispersed component and the polar component are known are used, it is possible to calculate the polar component of the surface free energy of the electrode. For example, when the polar component is present in three or more kinds of solvents (for example, (For example, three points) in the substrate surface may be measured, and the average may be used to evaluate the contact angle.

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

1 is a cross-sectional view schematically showing an enlarged portion of a part of a display device 1 which is an example of a display device of the present invention. 2 is a plan view schematically showing an enlarged part of a part of the display device 1 which is an example of the display device of the present invention. The display apparatus 1 mainly includes a support substrate 2 and partition walls 3 partitioning the partition defined in advance on the support substrate 2 and a plurality of partition walls 3 partitioned by the partition walls 3, Of the organic EL device 4 of the present invention.

As the support substrate 2, for example, a glass substrate, a substrate including a resin, a substrate including a metal, a substrate including a semiconductor, and the like are used.

The barrier ribs 3 are formed on the support substrate 2, for example, in a lattice shape or a stripe shape. 2 shows a display device 1 in which lattice-shaped partition walls 3 are provided as an embodiment. In the same figure, hatched areas are provided in areas where the partitions 3 are provided.

A plurality of concave portions 5 (hereinafter also referred to as an opening portion 5) defined by the partition 3 and the supporting substrate 2 are set on the supporting substrate 2. And this opening 5 corresponds to a section where the partition 3 is partitioned.

The partition 3 in the display device 1 is provided in a lattice shape. Therefore, a plurality of openings 5 are arranged in a matrix shape on one side of the support substrate 2 in the thickness direction Z (hereinafter sometimes referred to as " viewed in a plan view "). That is, the openings 5 are arranged at a predetermined interval in the row direction (X) and at a predetermined interval in the column direction (Y). The shape seen from the plane of each opening 5 is not particularly limited. For example, the openings 5 are formed in a shape such as a substantially rectangular shape, a substantially elliptical shape, and a saw-toothed shape when viewed from the top. In this embodiment, an opening 5 having a substantially rectangular shape in plan view is provided. In this specification, the row direction (X) and the column direction (Y) are directions perpendicular to the thickness direction (Z) of the support substrate and also perpendicular to each other.

In another embodiment, when stripe-shaped barrier ribs are formed, the barrier ribs are formed by, for example, arranging a plurality of barrier rib members extending in the row direction X at a predetermined interval in the column direction (Y). In this embodiment, stripe-shaped depressions are defined by the stripe-shaped partition walls and the support substrate.

The barrier ribs are formed so as to have a narrow width as they are separated from the support 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 extending direction (column direction Y) is formed to be narrower as it is spaced from the support substrate . In Fig. 1, a partition wall having an isosceles trapezoidal shape is shown. When the upper floor and the floor below the supporting substrate side are compared, the lower floor side is wider than the upper floor. In addition, the cross-section of the partition wall actually formed does not always have a trapezoidal shape, but a straight portion and a corner of a trapezoidal shape may be rounded.

The barrier ribs can be formed by photolithography as described above. In the present embodiment, a thin film containing the photosensitive resin composition is formed on a substrate on which a first electrode of an organic EL element described later is formed, and then an opening is formed in the thin film by photolithography so that the surface of the electrode is exposed Thereby forming a barrier rib.

It is preferable that the partition wall 3 exhibits lyophobicity on its top face (top face). The term "top surface" means a plane existing at a position that is the farthest from the surface of the partition 3 from the support substrate 2. Examples of the method for forming the partition wall 3 exhibiting lyophobicity on the top surface include a method using the photosensitive resin composition containing the above-described liquid repellent agent (F), or a method of lyophilizing the surface of the partition wall after formation of the partition wall. For example, by performing plasma treatment on the partition 3 in an atmosphere containing fluoride, the surface of the partition 3 can be provided with lyophobicity. The fluoride in this treatment is in a gaseous state, and as the fluoride, CF ₄ , CHF ₃ , CH ₂ F ₂ , C ₃ F ₈ , C ₄ F ₆ , C ₄ F ₈ and the like can be used. By performing such a plasma treatment, fluorine atoms bond to the surface of the partition wall 3, and lyophobicity is imparted to the partition wall 3.

It is possible to prevent the ink supplied to the region surrounded by the partition 3 (the opening 5) from overflowing to the adjacent region along the top surface of the partition 3 because the top surface of the partition 3 shows lyophobicity.

The organic EL element 4 is provided in a partition (that is, the opening 5) partitioned by the partition 3.

When the lattice-shaped partition walls 3 in the display device 1 are provided, the organic EL elements 4 are provided in the openings 5, respectively. That is, the organic EL elements 4 are arranged in a matrix in the same manner as the respective openings 5, and are arranged on the support substrate 2 in the column direction Y with a predetermined gap in the row direction X And are arranged with a predetermined interval therebetween.

The shape and arrangement of the barrier ribs 3 are appropriately set according to the specifications of the display device such as the number of pixels and the resolution, ease of manufacture, and the like. For example, the width of the partition wall 3 in the row direction X or the column direction Y is about 5 to 50 mu m, the height of the partition wall 3 is about 0.5 to 5 mu m, Or the width of the row direction X or the column direction Y of the opening portion 5, that is, the interval between the partition walls 3 adjacent to the column direction Y is about 10 μm to 200 μm. The widths of the first electrodes 6 in the row direction X or the column direction Y are about 10 to 200 mu m, respectively.

The partition wall 3 can be formed from the photosensitive resin composition of the present invention by the above-described pattern formation method.

In another embodiment, when the stripe-shaped barrier ribs are provided, the organic EL elements 4 are arranged at predetermined intervals in the row direction X in the respective openings extended in the row direction X.

Three kinds of organic EL elements 4 are provided in the display device 1. [ (2) a green organic EL element 4G that emits green light; and (3) a blue organic EL element 4B that emits blue light. The red organic EL element 4R emits red light, Respectively.

The organic EL element 4 is constituted by stacking a first electrode, an organic EL layer, and a second electrode in this order from the support substrate side. In the present specification, one or more layers provided between the first electrode 6 and the second electrode 10 are referred to as organic EL layers, respectively. The organic EL element 4 has at least one luminescent layer as an organic EL layer. Further, the organic EL element may further include an organic EL layer different from the light emitting layer in addition to the one light emitting layer. For example, a hole injecting layer, a hole transporting layer, an electron blocking layer, an electron transporting layer, and an electron injecting layer are provided as an organic EL layer between the first electrode 6 and the second electrode 10. In addition, two or more light emitting layers may be provided between the first electrode 6 and the second electrode 10.

The organic EL element 4 is a pair of electrodes including a positive electrode and a negative electrode and includes a first electrode 6 and a second electrode 10. One of the first electrode 6 and the second electrode 10 is provided as an anode and the other electrode is provided as a cathode. The display device 1 of the present embodiment includes a first electrode 6 functioning as an anode, a first organic EL layer 7 serving as a hole injection layer, a second organic EL layer 9 serving as a light emitting layer, And a second electrode 10 functioning as a cathode are laminated on the support substrate 2 in this order.

For the first electrode 6, a transparent electrode is generally used. The transparent electrode is not particularly limited, and examples of the transparent electrode include indium tin oxide (ITO), zinc dope indium oxide (IZO), fluorine doped tin oxide (FTO), antimony doped tin oxide (ATO) Doped zinc oxide (AZO), and gallium doped zinc oxide (GZO), and tin-doped indium oxide (ITO) and zinc-doped indium oxide (IZO) are preferable.

The first electrode 6 is provided for each organic EL element 4. That is, the same number of the first electrodes 6 as the organic EL element 4 is provided on the supporting substrate 2. [ The first electrodes 6 are provided corresponding to the arrangement of the organic EL elements 4 and arranged in a matrix like the organic EL elements 4. [ The barrier ribs 3 are formed in a lattice shape in a region except for the first electrode 6, but are also formed so as to cover the periphery of the first electrode 6 (see Fig. 1).

The layers (the first organic EL layers 7 corresponding to the hole injection layers) provided in contact with the first electrodes 6 are provided on the first electrodes 6 in the openings 5, respectively. The first organic EL layer 7 is provided with a different material or film thickness for each type of organic EL element, if necessary. Further, from the viewpoint of the simplicity of the step of forming the first organic EL layer 7, all the first organic EL layers 7 can be formed with the same material and the same film thickness.

The first organic EL layer 7 is formed by supplying an ink containing a material to be the first organic EL layer 7 to an area (opening 5) surrounded by the partition 3 and drying it, heating it and / And light irradiation is performed to solidify the ink. The method of supplying the ink is not particularly limited, but printing methods such as an ink jet method and an aerosol jet method can be mentioned.

The solvent or the dispersion medium of the ink used for forming the layer (the first organic EL layer 7) provided in contact with the first electrode 6 may be formed by dissolving and / or dispersing the material serving as the first organic EL layer 7 There is no particular limitation, but in order to dissolve and / or disperse the material of the first organic EL layer 7 well, a polar solvent may be included.

The polar solvent is not particularly limited and may be, for example, an alcohol, a ketone, a glycol ester, a glycol ether, N, N-dimethylformamide, N, N-dimethylacetamide, Pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide and N-cyclohexyl-2-pyrrolidinone. Further, in the present specification, the polar solvent means that the value of sp (solubility parameter) of the solvent is 10 or more.

As described above, when the ink used for forming the layer (the first organic EL layer 7) provided in contact with the first electrode 6 contains a polar solvent in particular, when the ink is supplied to the opening of the partition wall, When the value of the polarity component of the surface free energy of the electrode after formation of the opening is 15 mN / m or more, as described above, it is difficult to spread the first electrode 6 on the first electrode 6, (First organic EL layer 7) provided in contact with the first electrode 6 can be formed because the ink supplied on the electrode 6 spreads uniformly over the entire surface in the opening of the partition wall .

Examples of the solvent or dispersion medium other than the polar solvent included in the ink used for forming the layer (the first organic EL layer 7) provided in contact with the first electrode 6 include cyclohexylbenzene, anisole, xylene, Is used.

A second organic EL layer 9 serving as a light emitting layer is provided on the first organic EL layer 7 in the opening portion 5. As described above, the light emitting layer is provided according to the type of the organic EL element. The red light emitting layer 9R is provided in the opening 5 where the red organic EL device 4R is installed and the green light emitting layer 9G is provided in the opening 5 where the green organic EL device 4G is installed And the blue light emitting layer 9B is provided in the opening 5 where the blue organic EL device 4B is installed.

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

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

Since the pattern obtained from the photosensitive resin composition of the present invention has high wettability, it is particularly useful as a partition wall used for manufacturing a color filter, an ITO electrode of a liquid crystal display element, an organic EL display element, a circuit wiring board, etc. by an inkjet method . Further, it is also possible to use, for example, a color filter substrate and / or a photo-spacer constituting a part of an array substrate, a patternable overcoat, an interlayer insulating film, a projection for controlling liquid crystal alignment, a microlens, And a coating film having no pattern obtained as described above is useful as an overcoat constituting a part of a color filter substrate and / or an array substrate. The color filter substrate and the array substrate described above are suitably used for a liquid crystal display, an organic EL display, an electronic paper, and the like.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. In the examples, "% " and " part " are by mass% and mass part, unless otherwise specified.

[Synthesis Example 1]

A flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with a nitrogen stream in a nitrogen atmosphere, and 166 parts of propylene glycol monomethyl ether acetate and 52 parts of methoxypropanol were placed and heated to 85 DEG C with stirring. 233 parts of a mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8 and / or 9-yl acrylate, 77 parts of p-vinylbenzoic acid, 125 parts of propylene glycol monomethyl ether acetate, And 115 parts of isopropanol was added dropwise to the flask over 4 hours.

On the other hand, a mixed solution obtained by dissolving 32 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 210 parts of propylene glycol monomethyl ether acetate was dropped into the flask over 5 hours. After completion of the dropwise addition, the mixture was maintained at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer (resin A1a) having a B-type viscosity (23 캜) of 46 mPas, a solid content of 33.7% and a solution acid value of 83 mg-KOH / g. The obtained resin (A1a) had a weight average molecular weight (Mw) of 7.7 × 10 ³ and a molecular weight distribution of 1.90. The resin (A1a) has the following structural units.

(Synthesis Example 2)

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was appropriately flown into a nitrogen atmosphere, 140 parts of diethylene glycol ethyl methyl ether was added, and the mixture was heated to 70 캜 with stirring. Subsequently, 40 parts of methacrylic acid; And 360 parts of a mixture of a monomer (I-1) and a monomer (II-1) (monomer (I-1): monomer (II-1) in a mixture = 50: 50) were dissolved in 190 parts of diethylene glycol ethyl methyl ether And the solution was dropped into the flask over a period of 4 hours using a dropping funnel.

On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 240 parts of diethylene glycol ethyl methyl ether was added dropwise to the flask . After completion of the dropwise addition of the polymerization initiator solution, the solution was kept at 70 캜 for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin A1b) having a solid content of 42.3%. The resin (A1b) thus obtained had a weight average molecular weight (Mw) of 8.0 × 10 ³ , a molecular weight distribution (Mw / Mn) of 1.91 and an acid value of 60 mg-KOH / g. The resin (A1b) has the following structural unit.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in Synthesis Examples 1 and 2 were measured by the GPC method under the following conditions.

Device; K2479 (Shimazu Seisakusho Co., Ltd.)

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Flow rate; 1.0 mL / min

Detector; RI

The ratio (Mw / Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained as described above was defined as a molecular weight distribution.

(Examples 1 to 3 and Comparative Examples 1 to 6)

≪ Adjustment of photosensitive resin compositions 1 to 8 >

With respect to Examples 1 to 5 and Comparative Example 1, the components in Table 3 were each mixed with a solvent (G) so that the solid content (%) was as shown in Table 3 to obtain a photosensitive resin composition.

For Comparative Example 2, Zeocoat CP1010 (manufactured by Nippon Zeon Co., Ltd.) was used.

For Comparative Example 3, SU-83000 (manufactured by Nippon Kayaku Co., Ltd.) diluted with propylene glycol monomethyl ether acetate in the same volume as the material was used. Hereinafter, the photosensitive resin compositions of Examples 1 to 5 are referred to as photosensitive resin compositions 1 to 5 and the photosensitive resin compositions of Comparative Examples 1 to 3 as photosensitive resin compositions 6 to 8.

The components in Table 3 are as follows. The number of parts in the column of resin indicates the mass part in terms of solid content.

Resin (A); Aa: Copolymer of p-hydroxystyrene and butyl acrylate [copolymerization ratio 50:50, weight average molecular weight; 12600] (Marukarinker (registered trademark) CBA; manufactured by Maruzen Sekiyu Kagaku Co., Ltd.)

Resin (A); Ab: copolymer of p-hydroxystyrene and styrene [copolymerization ratio is 50:50, weight average molecular weight; 4000] (Marukarinker (registered trademark) CST; manufactured by Maruzen Sekiyu Kagaku Co., Ltd.)

Resin (A1); A1a: Resin A1a obtained in Synthesis Example 1

Resin (A1); A1b: Resin A1b obtained in Synthesis Example 2

Resin (A1); A1c: Resin A1c obtained in Synthesis Example 3

Polymerizable compound (B); B: Trimethylolpropane triacrylate (A-TMPT; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

A polymerization initiator (C); Propane-1-one (Irgacure (registered trademark) 907, manufactured by BASF)

Polymerization initiator (E); 4,4'-bis (diethylamino) benzophenone (EAB-F, manufactured by Hodogaya Chemical Industry Co., Ltd.)

The solvent (G) is obtained by mixing the following solvent components (Ga) to (Gd) by 25 mass%, respectively.

Solvent (G); 25 mass% of Ga; Propylene glycol monomethyl ether acetate

Solvent (G); 25 mass% of Gb; Ethyl 3-ethoxypropionate

Solvent (G); 25 mass% of Gc; 3-Methoxy-1-butanol

Solvent (G); 25 mass% of Gd; 3-methoxybutylacetate

The components in Table 3 were each mixed in a solvent (G) so that the solid content of the photosensitive resin composition was the " solid content (%) "

[Substrate cleaning]

The surface was cleaned with a brush for 30 seconds while flowing pure water through a glass substrate (Eagle XG manufactured by Corning Incorporated) having a size of 370 mm x 470 mm x 0.5 mm in a cleaning device (Shibaura Seisakusho Co., Ltd.) Further, the film was further cleaned by a pure shower for 60 seconds, and air drying was performed.

[Production of substrate with transparent conductive film]

An ITO target (90% In ₂ O ₃ -10% SnO ₂ , manufactured by Tosoh Corporation) was coated on the cleaned substrate using a sputtering apparatus (ULVAC Inline Sputtering System, type SDP-570VT) And after heating to 300 DEG C in a heating chamber, a transparent conductive film ITO was formed to a thickness of 50 nm in a sputter chamber at a power of 1.05 kW, an argon gas pressure of 0.6 Pa, and a deposition time of 115 seconds. Further, the substrate after film formation was annealed in air at 230 캜 for 30 minutes to obtain a glass substrate with ITO.

[Fabrication of substrate with barrier ribs]

(Fabrication of barrier-board-attached substrate of Example 1)

A UV-O3 cleaning apparatus (PL3-200-15, manufactured by Hitachi High-Technologies Corporation) was used for the substrate with the above-prepared transparent conductive film, and an integrated light quantity of 400 mJ / cm ² , Subjected to hydrophilic treatment, cleaned with pure water, and air-dried. 30 g of the photosensitive resin composition 1 having been subjected to the adjustment was dropped on the substrate, and the resultant was rotated at 900 rpm for 7 seconds by a spin coater to form a thin film containing the photosensitive resin composition 1. Thereafter, the resultant was dried under reduced pressure to 66 Pa in a vacuum drying apparatus (TR28340CPD-CLT, manufactured by Tokyo Oka Kogyo Kabushiki Kaisha), and contacted with a hot plate at 110 캜 for 110 seconds and prebaked. Subsequently, exposure was performed using an exposure apparatus (LE4000A, manufactured by Hitachi High-Technologies Corporation). An exposure dose of 200 mJ / cm ² , and a gap of 100 m. In the photomask, a pattern (a shape in which the shape of the light-shielding portion was cut from a rectangle having a length of 300 mu m in the major axis direction and a 100 mu m in the minor axis direction and an arc shape with four corners thereof) was formed on the same plane. Thereafter, a developer prepared by diluting an aqueous solution of tetramethylammonium hydroxide (TOKUSO SD25, manufactured by Tokuyama Corporation) with pure water to a concentration of 2.38% was used, and the coating film was applied to a shower developing machine (manufactured by Sepha Technologies, After washing with water and air drying, post-baking was carried out in an oven (HSC-4 made by Aspect Co., Ltd.) at 230 캜 for 20 minutes to obtain a pattern.

(Fabrication of barrier-coated substrates of Examples 2 to 5 and Comparative Example 1)

A substrate with barrier ribs of Examples 2 to 5 and Comparative Example 1 was prepared in the same manner as in Example 1 except that the photosensitive resin compositions 2 to 6 were used in place of the photosensitive resin composition 1.

(Fabrication of a substrate with a partition wall in Comparative Example 2)

A photosensitive resin composition 7 was used in place of the photosensitive resin composition 1, and a pattern (shape of an opening was formed by cutting a circular arc of a rectangular shape with a length of 300 mu m in the major axis direction and a 100 mu m in the minor axis direction into an arc shape A substrate with a barrier rib of Comparative Example 2 was fabricated in the same manner as in Example 1 except that the photomask formed on the same plane was used to perform exposure and post-baking was performed at 230 캜 for 60 minutes.

(Fabrication of substrate with barrier rib in Comparative Example 3)

Comparative Example 3 was prepared in the same manner as in Example 1 except that the photosensitive resin composition 8 was used in place of the photosensitive resin composition 1, and propylene glycol monomethyl ether acetate was used as a developing solution to immerse the substrate in water while rocking at 23 DEG C for 80 seconds, Were prepared.

[Preparation of solution for wettability evaluation]

As the solvent for evaluating the wettability of the partition walls, N, N-dimethylacetamide (manufactured by Wako Pure Chemical Industries, Ltd., not less than 99.5%), 1,3-dimethyl-2-imidazolidinone (manufactured by Tokyo Kasei Kogyo Kabushiki Kaisha) , 99.0% or more) were selected. Since the two selected solvents are low in viscosity, cyclohexanol (98.0% or more, manufactured by Wako Pure Chemical Industries, Ltd.) is used as the viscosity adjusting material so that the liquid can be filled into the partition walls by the ink jet apparatus, Was used as a solvent.

In addition, since it is difficult to observe the spreading property of the solvent after drying by a microscope, Rhodamine B (manufactured by Tokyo Kasei Kogyo Co., Ltd., purity of 95% or more) was used as the solute.

Three solutions 1, 2 and 3 shown in Table 4 were prepared.

[Evaluation of wettability]

Using the ink jet apparatus (Litlex 120L manufactured by ULVAC Co.), the above solutions 1, 2 and 3 were packed in the respective partitions with 200 pL into 1000 partitions in the partitions, and after the drying, the solute spread to the partitions of the partitions 30 observations were made using a microscope (MX61L manufactured by OLIMPUS, lens LCPFLN20xLCD), and when all 30 locations were observed, wettability was good.

In the presently used barrier ribs, since the evaluation is carried out in the state in which there is no lyophobicity, leakage from the barrier ribs occurs when the solution is filled, but the spreadability is evaluated by the liquid remaining in the barrier ribs.

[Polarity evaluation]

(Contact angle measurement)

(Purity: 99.5% or more), formamide (manufactured by Sigma Aldrich Co., purity: 99.5% or more), diiodomethane (manufactured by Sigma Aldrich), or the like, using pure water, glycerol , Purity: 99%) were used, and three points in the substrate surface were measured, and the evaluation was carried out by averaging.

(Polarity calculation)

For the polarity calculation, the above-mentioned Owens and Went method was applied. In this embodiment, the contact angle is measured using the four kinds of solvents, and based on the values, the polarity calculation software disclosed in the following URL is used to calculate the surface free energy of the electrode based on the Owens & And the value of the polarity component was calculated.

<URL: http://www007.upp.so-net.ne.jp/y-kondo/surface.htm>

The results of Examples and Comparative Examples are shown in Table 5. In Table 5, the goodness is indicated by &quot; &quot; and the failure is indicated by &quot; X &quot;.

From the results of the above examples, it can be seen that, when the photosensitive resin composition of the present invention is used, the surface of the ITO after formation of the pattern on which the electrode surface is exposed has a high polar component of surface free energy and a good wettability on the surface of ITO .

According to the photosensitive resin composition of the present invention, a pattern having excellent wettability on the electrode surface can be obtained.

1 display device
2 supporting substrate
3 barrier
4 organic EL device
5 recess (opening)
6 First electrode
7 First organic EL layer (hole injection layer)
9 Second organic EL layer (light emitting layer)
10 Second electrode

Claims (15)

A photosensitive resin composition comprising the following (A), (B) and (C)
Forming a thin film containing the photosensitive resin composition on a substrate on which an electrode is formed and then forming an opening in the thin film by photolithography so that the surface of the electrode is exposed so that the value of the polarity component of the surface free energy of the electrode Is not less than 15 mN / m.
(A) a resin having a structural unit containing a group represented by the following formula [i]

(Wherein R 1, R 2, R 3, R 4 and R 5 are each independently -OH, -SH, -COOH, -CHO, a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, -COR 7, , -OCOR7 or -OR7, and at least one of R1, R2, R3, R4 and R5 is -OH, -SH, -COOH or -CHO, R7 is an alkyl group having 1 to 8 carbon atoms, an alkyl group having 2 to 5 carbon atoms An alkoxyalkyl group, an aryl group or a benzyl group)
(B) a polymerizable compound
(C) Polymerization initiator The photosensitive resin composition according to claim 1, wherein the structural unit is represented by the following formula (ii).

(In the formula [ii], R1, R2, R3, R4 and R5 have the same meanings as described above, and R6 represents a hydrogen atom, a methyl group or an ethyl group) The photosensitive resin composition according to claim 1, wherein the polymerization initiator is a photopolymerization initiator and the polymerizable compound is polymerized by radical polymerization. The photosensitive resin composition according to claim 2, wherein the polymerization initiator is a photopolymerization initiator and the polymerizable compound is polymerized by radical polymerization. The photosensitive resin composition according to claim 1, wherein at least one of R 1, R 2, R 3, R 4, and R 5 is -COOH or -OH and the remainder is a hydrogen atom. 3. The photosensitive resin composition according to claim 2, wherein at least one of R1, R2, R3, R4, and R5 is -COOH or -OH, and the remainder is a hydrogen atom. 4. The photosensitive resin composition according to claim 3, wherein at least one of R1, R2, R3, R4, and R5 is -COOH or -OH, and the remainder is a hydrogen atom. 5. The photosensitive resin composition according to claim 4, wherein at least one of R1, R2, R3, R4, and R5 is -COOH or -OH, and the remainder is a hydrogen atom. The photosensitive resin composition according to any one of claims 1 to 8, further comprising a liquid repellent agent. The photosensitive resin composition according to claim 9, wherein the liquid repellent agent is a polymer comprising a structural unit derived from an unsaturated compound having a perfluoroalkyl group having 4 to 6 carbon atoms. The photosensitive resin composition according to any one of claims 1 to 8, wherein the electrode is a transparent electrode. A barrier rib formed by the photosensitive resin composition according to any one of claims 1 to 8. A substrate comprising the barrier rib and the electrode according to claim 12. A display device comprising the substrate according to claim 13. A thin film containing a photosensitive resin composition is formed on a substrate on which an electrode is formed,
An opening is formed in the thin film by photolithography so that the surface of the electrode is exposed,
And evaluating the wettability of the electrode based on the value of the polar component of the surface free energy of the electrode.

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