TWI662362B - Photosensitive resin composition - Google Patents

Abstract

The present invention is a photosensitive resin composition. The photosensitive resin composition forms a film made of a photosensitive resin composition on a substrate on which an electrode has been formed, and secondly, the electrode is formed on the film by a photolithography method. The value of the polar component of the free energy on the surface of the electrode after the surface is exposed to form an opening is 15 mN / m or more.

Description

Photosensitive resin composition

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

In recent years, color filters, ITO electrodes of liquid crystal display elements, organic EL display elements, circuit wiring boards, and the like have been produced by coating methods such as the inkjet method. In the method for forming a device using such a coating method, a partition wall formed using a photosensitive resin composition is used.

For example, after forming a thin film made of the photosensitive resin composition on a substrate on which an electrode has been formed, an opening is formed in the thin film by photolithography so that the surface of the electrode is exposed. A partition wall having an opening is provided on the electrode, and then an ink containing a thin film material is dropped into the opening of the partition wall, and a predetermined thin film is formed on the electrode by heating and drying.

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

Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Publication No. 2012-73603

As described above, once the photosensitive resin composition is formed on the electrode, it is removed from the electrode when it is patterned, but the applicability of the photosensitive resin composition to the electrode surface is based on the photosensitive resin composition. The kind varies. Therefore, depending on the type of the photosensitive resin composition, the ink applied to the electrode may not be spread on the electrode, and in the previously proposed photosensitive resin composition, the coating on the electrode in the opening of the partition wall is concerned. The spreadability of the ink may not always be satisfied. Therefore, an object of the present invention is to provide a photosensitive resin composition having good spreadability on the entire surface inside the opening of the partition wall by applying ink applied on the electrode obtained after pattern formation.

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

[1] A photosensitive resin composition, wherein the photosensitive resin composition forms a thin film made of the photosensitive resin composition on a substrate on which an electrode has been formed, and secondly, the electrode is formed on the film by a photolithography method. The value of the polar component of the free energy on the surface of the electrode after the surface is exposed to form an opening is 15 mN / m or more.

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

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

(In formula [i], R1, R2, R3, R4, and R5 each independently represent -OH, -SH, -COOH, -CHO, a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, -COR7,- COOR7, -OCOR7, or -OR7, and at least one of R1, R2, R, R4, and R5 is -OH, -SH, -COOH, or -CHO. R7 represents an alkyl group having 1 to 8 carbon atoms, and 2 ~ 5 alkoxyalkyl, aryl or benzyl.)

(B) 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 formula [ii], R1, R2, R3, R4, and R5 represent the same meanings as 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 the aforementioned R1, R2, R3, R4, and R5 is -COOH or -OH, and the other is a hydrogen atom.

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

[7] The photosensitive resin composition according to [6], wherein the liquid-repellent agent includes a polymer including 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 partition wall formed by the photosensitive resin composition according to any one of [1] to [8].

[10] A substrate comprising a partition wall and an electrode as in [9].

[11] A display device including the substrate according to [10].

[12] A substrate evaluation method, in which a thin film made of a photosensitive resin composition is formed on a substrate on which an electrode has been formed, and an opening is formed on the thin film by exposing the surface of the electrode by photolithography. The coating property of the electrode was evaluated 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, the ink applied on the electrode after pattern formation can be obtained on the entire surface inside the opening of the partition wall. Coating a substrate with a partition wall with excellent spreadability.

1‧‧‧ display device

2‧‧‧ support substrate

3‧‧‧ next door

4‧‧‧Organic EL Element

4R‧‧‧Red Organic EL Element

4G‧‧‧Green Organic EL Element

4B‧‧‧Blue Organic EL Element

5‧‧‧ Recess (opening)

6‧‧‧The first electrode

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

9‧‧‧ 2nd organic EL layer (light emitting layer)

10‧‧‧ 2nd electrode

FIG. 1 is a cross-sectional view schematically showing an enlarged part of the display device 1.

FIG. 2 is a plan view schematically showing a part of a display device 1 according to an embodiment of the present invention.

The photosensitive resin composition of the present invention relates to a photosensitive A flexible resin composition is formed by forming a thin film made of a photosensitive resin composition on a substrate on which an electrode has been formed, and then forming the opening by opening the surface of the electrode on the film by photolithography to expose the surface of the electrode. The value of the polar component of the surface free energy is 15 mN / m or more.

A preferred form of the photosensitive resin composition of the present invention is

The above-mentioned photosensitive resin composition was supplied onto a substrate on which an electrode was formed, and the substrate was rotated at 900 rpm for 7 seconds to form a thin film composed of the above-mentioned photosensitive resin composition. The substrate on which the above-mentioned film was formed was dried under reduced pressure at 66 Pa. Then, pre-baking was performed at 110 ° C for 110 seconds, and secondly, so that the surface of the electrode was exposed, the pre-baking film was exposed at 200 mJ / cm ² , and 2.38% by mass of hydroxide was used. The methyl ammonium aqueous solution was developed at 23 ° C. for 80 seconds. After washing with water, post-baking was performed, and the surface of the electrode exposed at the opening of the film was free by photolithography to form an opening in the film. The photosensitive resin composition having a value of a polar component of energy of 15 mN / m or more.

One aspect of the aforementioned electrode-formed substrate is a glass substrate with ITO, which is equipped with an ITO target in a sputtering device, heated to 300 ° C in a heating chamber, and then powered with 1.05kW, argon in the sputtering chamber. The air pressure was 0.6 Pa and the film formation time was 115 seconds. The transparent conductive film ITO was formed on the substrate to a thickness of 50 nm, and the substrate after the film formation was further annealed at 230 ° C. for 30 minutes in the air.

Using this photosensitive resin composition, an electrode is formed When the partition wall is formed on the substrate, when the ink containing the thin film material to be formed on the electrode is applied to the electrode, the ink is not repelled on the electrode and is spread on the electrode. Therefore, the electrode is dried by drying. When curing is performed, a flat film can be formed on the entire surface of the opening in the partition wall.

Electrode after opening, that is, thin film after opening The value of the polar component of the surface free energy of the electrode exposed at the opening is preferably 15 mN / m or more, and more preferably 15.5 mN / m or more.

From a coating point of view, the electrode after opening is formed The upper limit value of the polar component of the free energy of the surface of the electrode exposed from the opening of the thin film after the opening is not necessarily set, but it is usually 50 mN / m or less and 40 mN / m or less.

As the resin in the photosensitive resin composition of the present invention, The value of the polar component of the surface free energy of the electrode after the opening, that is, the surface of the electrode exposed at the opening of the thin film after the opening is not particularly limited, can be exemplified by the commonly used acrylic acid. Resins, polyimide resins, cycloolefin resins, epoxy resins, etc. Among these, acrylic resins and epoxy resins are also preferred.

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

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

(B) Polymerizable compound

(C) Polymerization initiator

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

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

The structural unit including the base 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].

In the formulae [i] and [ii], R1, R2, R3, R4, and R5 each independently represent -OH, -SH, -COOH, -CHO, a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms. , -COR7, -COOR7, -OCOR7, or -OR7, and at least one of R1, R2, R3, R4, and R5 is -OH, -SH, -COOH, or -CHO. R7 represents an alkyl group having 1 to 8 carbons, an alkoxyalkyl group having 2 to 5 carbons, an aryl group, or a benzyl group. R6 represents a hydrogen atom, a methyl group or an ethyl group.

From the viewpoint of coating properties on the electrode surface, At least one of R1, R2, R3, R4, and R5 is -COOH or -OH, and R1, R2, R3, R4, and R5 which are different from -COOH or -OH are preferably hydrogen atoms.

Moreover, only when at least one of R1, R2, R3, R4, and R5 in formulas [i] and [ii] is -OH, -SH, -COOH, or -CHO, can each independently have a carbon number of 1 to 8 the alkoxy group, -COOR7, -OCOR7, -COR7, -CN , -NHR7, -NR7R8, -NO 2, -CONH 2, -CONHR7, -SOR7 , or, -SO ₂ R7. However, R7 represents the same meaning as above. R8 and R7 each independently represent 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.

Examples of the halogen atom include Cl, Br, or I, and Cl Or Br is preferred.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl and ethyl Group, n-propyl, iso-propoxy, n-butyl, t-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, octyl, methyl, or ethyl Better.

Examples of the alkoxyalkyl group having 2 to 5 carbon atoms include methoxy Methylmethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propylmethyl, propylethyl, methoxymethyl Preferably, methoxyethyl.

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

Examples of (a) include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-mercaptostyrene, 3-mercaptostyrene, 4-mercaptostyrene, and 2-vinylaniline. , 3-vinylaniline, 4-vinylaniline, 3-dimethylaminostyrene, 3-diethylaminostyrene, 3-monomethylaminostyrene, 3-monoethylamine Styrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2-bromostyrene, 3-bromostyrene, 4-bromostyrene, o-vinyl benzoic acid, m-vinyl Benzoic acid, p-vinyl benzoic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3-vinyl phthalic acid monomethyl ester, 3 -Vinylphthalic acid monoethyl ester, 5-vinyl isophthalic acid, 5-vinyl isophthalic acid monomethyl ester, 5-vinyl isophthalic acid monoethyl ester, 4-vinylsalicylic acid, 5 -Vinylsalicylic acid, 5-vinylsalicaldehyde, 5-vinylacetamisalic acid, 4-vinylbenzenesulfonic acid ethyl 4-vinylresorcinol, 4-vinylresorcinol mono Methoxymethyl ether, 4-vinylresorcinol bismethoxymethyl ether, 4-vinylresorcinol Mono-methoxyethyl ether, resorcinol bis 4-vinyl-methoxyethyl ether, 4-vinyl-benzonitrile, 4-vinyl-benzenepropanoic acid, methyl 4-vinyl-phenylpropionic acid And the like, preferably o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-vinyl benzoic acid, m-vinyl benzoic acid, and p-vinyl benzoic acid. Moreover, (a) is not subject to the above examples.

In addition, the photosensitive resin composition of the present invention may include It is selected from resins other than resin (A) (hereinafter also referred to as "resin (A1)"), solvent (D), polymerization initiation aid (E), liquid repellent (F), and surfactant ( G) At least one of the groups of the adhesion promoter (H).

Moreover, in this specification, the chemical examples exemplified as each component Compounds, unless otherwise specifically defined, can be used alone or in combination with users.

The resin (A) may further contain a monomer (x) derived from (a) other than (a) There are also structural units called "(x)" below.

(x) is only for monomers other than (a) and does not have a carbon number of 4 to 6 The perfluoroalkyl group is not particularly limited, and examples thereof include a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms (hereinafter also referred to as "(b)"), At least one monomer (e) grouped by free unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter also referred to as "(e)"), other monomer (c) (hereinafter also referred to as "( c) ", among which (b) or (c) is also preferred.

(b) is a cyclic ether structure having 2 to 4 carbon atoms (for example, selected from At least one of the monomers grouped by an ethylene oxide ring, a propylene oxide ring, and a tetrahydrofuran ring) is preferably a monomer having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated double bond, A monomer having a cyclic ether structure with 2 to 4 carbon atoms and a (meth) acryloxy group is more preferred.

Examples of (b) include a monomer having an ethylene oxide group. (B1) (hereinafter also referred to as "(b1)"), monomer having propylene oxide (b2) (hereinafter also referred to as "(b2)"), monomer having tetrahydrofuranyl (B3) (hereinafter sometimes referred to as "(b3)"), etc.

Examples of (b1) include those having a linear or branched chain shape. Monomer (b1-1) (hereinafter also referred to as "(b1-1)") having an unsaturated alicyclic hydrocarbon structure, and monomer (b1) having an alicyclic structure of unsaturated alicyclic hydrocarbons -2) (hereinafter also referred to as "(b1-2)").

(b1) is based on having ethylene oxide and (meth) acryloxy Monomers are preferred, and monomers having a structure in which unsaturated alicyclic hydrocarbons are epoxidized and (meth) acrylic fluorenyloxy groups are more preferred. When these monomers are used, the storage stability of the photosensitive resin composition is excellent.

Specific examples of (b1-1) include glycidyl (methyl) Acrylates, β-Methyl Glycidyl (meth) acrylate, β-Ethyl Glycidyl (meth) acrylate, Glycidyl Ether, O-Vinyl Benzyl Glycidyl Ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m -Vinyl benzyl glycidyl ether, α-methyl-p-vinyl benzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (Glycidoxymethyl) styrene, 2,5-bis (glycidoxymethyl) styrene, 2,6-bis (glycidoxymethyl) styrene, 2,3, 4-gins (glycidoxymethyl) styrene, 2,3,5-gins (glycidyloxymethyl) styrene, 2,3,6-gins (glycidyloxymethyl) Styrene, 3,4,5-gins (glycidoxymethyl) styrene, 2,4,6-gins (glycidyloxymethyl) styrene, Japanese Patent Laid-Open No. 7-248625 Documented compounds, etc.

Examples of (b1-2) include monocycloethylene cyclohexene, 1,2-epoxy-4-vinylcyclohexane (for example, Ceroxide 2000; manufactured by Dell Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer A400; Dell Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; Dell Chemical Industry Co., Ltd.), a compound represented by Formula (I), Formula (II) ).

[In the formula (I) and the formula (II), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group. X ¹ and X ² each independently represent a single bond ^{lines, -R 3 -, * - R} 3 -O -, * - R 3 -S-, or * -R ³ -NH-. R ³ represents an alkanediyl group having 1 to 6 carbon atoms. * Indicates a bond with O. ]

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

Examples of the alkyl group which may be substituted by a hydroxyl group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1- Hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

Examples of R ¹ and R ² include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include methylene, vinyl, and propyl- 1,2-diyl, propan-1,3-diyl, butan-1,4-diyl, pent-1,5-diyl, hex-1,6-diyl, etc.

X ¹ and X ² may preferably include such as a single bond, methylene, _{ethylene, * - CH 2 -O - (} * indicates the bond of the O) group, * - CH ₂ CH ₂ -O- group More preferred examples include single bonds and * -CH ₂ CH ₂ -O- groups.

Examples of the compound represented by the formula (I) include formulae (I-1) to A compound represented by any one of the formula (I-15), and the like. Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), or formula (I-11) to formula (I- The compound represented by 15) is preferred, and the compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15) is more preferred.

Examples of the compound represented by the formula (II) include compounds represented by any one of the formulae (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), or formula (II-11) to formula (II- The compound represented by 15) is preferred, and the compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) is more preferred.

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of two or more kinds. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, these content ratios [compound represented by the formula (I): compound represented by the formula (II)] are on a Mohr basis, It is preferably 5:95 to 95: 5, and more preferably 20:80 to 80:20.

(b2) A monomer having a propylene oxide group and a (meth) acryloxy group is preferred. Examples of (b2) include 3-methyl-3- (meth) acryloxymethyl propylene oxide and 3-ethyl-3- (meth) acryloxymethyl epoxy. Propane, 3-methyl-3- (meth) propenyloxyethyl propylene oxide, 3-ethyl-3- (meth) propenyloxyethyl propylene oxide, and the like.

The (b3) is preferably a monomer having a tetrahydrofuranyl group and a (meth) acrylfluorenyl group.

Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

Examples of (e) include unsaturated carboxylic acids and unsaturated carboxylic anhydrides.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, maleic acid, citraconic acid, mesaconic acid, itaconic acid, 1, 4-cyclohexene dicarboxylic acid, and methyl-5. -Norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy- 5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] Hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, succinic acid mono [2- (meth) acryloxyethyl], α- (hydroxymethyl ) Acrylic and so on.

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

Examples of (c) include (meth) acrylates, N-substituted maleimide-based unsaturated dicarboxylic acid diesters, alicyclic unsaturated compounds, styrenes, and other vinyl groups. Compounds etc. Among them, (meth) acrylates and styrenes are also preferable.

Examples of (meth) acrylates include meth (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and sec-butyl (meth) Alkyl esters of acrylate, tert-butyl (meth) acrylate, etc .; cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclic [5.2.1.0 ^{2, 6} ] decane-8-yl (meth) acrylate (commonly used in this technical field is called dicyclopentylfluorenyl (meth) acrylate), dicyclopentamyloxyethyl (methyl Acrylate), tricyclic [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate (in this technical field, its common name is "dicyclopentenyl (methyl) Cycloalkyl esters such as "acrylate"), isofluorenyl (meth) acrylate, etc .; hydroxyalkyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Esters; aryl (aryl) esters such as phenyl (meth) acrylate, benzyl (meth) acrylate, and the like.

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

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

Examples of the N-substituted maleimide include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-succinimide Amino-3-maleimide imino benzoate, N-succinimide imino-4-maleimide butyrate, N-succinimide imino-6-maleimide Acid esters, N-succinimidylimido-3-maleimidoiminopropionate, N- (9-acridyl) maleimidoimine, and the like.

Examples of the alicyclic unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2.1] Hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyl (Ethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5 , 6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (2'-hydroxyethyl Group) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] heptane- 2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl- 5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] heptane -2-ene, 5-phenoxycarbonyl bicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5, 6-Bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and other bicyclic unsaturated compounds.

Examples of the styrenes include styrene and α-methylbenzene Ethylene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and the like. Among them, styrene is also preferred.

Examples of other vinyl compounds include (meth) propylene Nitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butane Olefin and so on.

The resin (A) may be constituted only by the structural unit derived from (a) The resin is preferably a resin composed of a structural unit derived from (a) and a structural unit derived from (x).

The resin (A) is derived from the structural unit derived from (a) and derived from (x) In the case of resin composed of structural units, it is based on the structural unit used in (a). The acidity of the site differs, but the ratio of the structural unit derived from each monomer is preferably within the following range with respect to the total number of moles of the structural unit lipid constituting the resin (A).

Structural units derived from (a); 5 ~ 70 mole% (preferably 10 ~ 60 mole%)

Structural unit derived from (x); 30 ~ 95 mole% (preferably 40 ~ 90 mole%)

When the ratio of the structural unit of the resin (A) is within the above-mentioned range, the storage stability of the photosensitive resin composition, the developability when a pattern is formed from the photosensitive resin composition, and the obtained coating film and drawing The solvent resistance, heat resistance, and mechanical strength of the type tend to be good.

In particular, when any one of the aforementioned R1 to R5 is -COOH, the ratio of the structural units derived from each monomer to the total mole number of the structural units constituting the resin (A) is preferably within the following range. .

Tectonic units derived from (a); 5 ~ 50 mole%

Constructed from (x); 50 ~ 95 mole%

For the resin (A), refer to, for example, a method described in a document "Experimental Method of Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd., Chemical First Press, 1st Edition, March 1, 1972) and the document The references are manufactured.

Specifically, for example, if a predetermined amount of (a) and (x), a polymerization initiator, and a solvent used in a reaction vessel are put in a reaction vessel, for example, deoxidation may be performed by replacing nitrogen in the atmosphere with nitrogen. Environment, the method of stirring and heating at the same time. In addition, the polymerization initiator, solvent, and the like used here are not particularly limited, and any one generally used by users in this field can be used. For example, as a polymerization initiator, such as azo compounds include (2,2 '- azobisisobutyronitrile, 2,2' - azobis (2,4-dimethylvaleronitrile) and the like), or The organic peroxide (such as benzamidine oxide) may be any solvent as long as it can dissolve each monomer, and the solvent (D) of the photosensitive resin composition can be a solvent described later. In order to adjust the molecular weight of the obtained 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-sulfofluorenylethanol, thioglycolic acid, ethyl thioglycolate, and thioglycolic acid. Thiols such as 2-ethylhexyl ester, methoxybutyl thioglycolate, 3-sulfopropylpropanoic acid, polysiloxane containing sulfofluorenyl group (KF-2001: manufactured by Shin-Etsu Chemical Co., Ltd.); chloroform; Halogenated alkyls such as carbon chloride and carbon tetrabromide.

In particular, (a) in the case of having a phenolic hydroxyl group, In the meantime, a monomer in which the phenolic hydroxyl group of (a) is previously protected with a protecting group may be used. Examples of the protecting group include tertiary alkyl groups such as tert-butyl, and fluorenyl groups such as ethylfluorenyl.

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

Moreover, the obtained polymer can be used directly after the reaction. As the solution, a concentrated or diluted solution can also be used, or it can be taken out as a solid (powder) by a method such as reprecipitation. In particular, during the polymerization, by using the same solvent as the solvent (D) described later as the solvent, the solution after the reaction can be directly used, and the manufacturing steps can be simplified.

Polystyrene equivalent weight average molecular weight of resin (A) It is preferably 3,000 to 100,000, and more preferably 5,000 to 50,000. If the weight average molecular weight of the resin (A) is within the aforementioned range, it tends to be excellent in coatability, and it is difficult to reduce the number of films in the exposed portion during development, and the non-exposed portion is easily 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 within the above range, there is a tendency that the developability is excellent.

The acid value of the resin (A) is usually 20 to 200 mgKOH / g, preferably 40 to 180 mgKOH / g, and more preferably 50 to 180 mgKOH / g. By using a resin having an acid value in this range, the value of the polar component of the free energy on the surface of the electrode after the opening is formed can be made 15 mN / m or more. Here, the acid value refers to a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin, and it can be obtained by titration with an aqueous potassium hydroxide solution.

Relative to the total amount of the resin (A), the resin (A1), and the polymerizable compound (C), the content of the resin (A) is preferably 5 to 95% by mass, more preferably 20 to 80% by mass, and particularly preferably 45 ~ 80% by mass. When the content of the resin (A) is within the above range, the developability of the photosensitive resin composition, the pattern adhesion obtained, the solvent resistance, and the mechanical properties tend to be good.

The photosensitive resin composition of the present invention may further include a liquid repellent agent (F). The liquid-repellent agent (F) is a resin that exhibits liquid-repellency. The surface of the structure after the pattern is formed is not particularly limited if the liquid-repellency is higher than the structure monomer. The contact angle of anisole on the surface of the structure is preferably 30 ° or more. Examples of the resin used to exhibit liquid repellency include, for example, a perfluoroalkyl group having 1 to 8 carbon atoms The structural unit having an etheric oxygen atom) is preferably a structural unit containing a monomer (d) derived from a perfluoroalkyl group having 4 to 6 carbon atoms (hereinafter also referred to as "(d)"). Of polymers.

Examples of (d) include compounds represented by formula (d-0).

[In the formula (d-0), R ^f represents a perfluoroalkyl group having 4 to 6 carbon atoms. R ^d represents a hydrogen atom, a halogen atom, a cyano group, a phenyl group, a benzyl group, or an alkyl group having 1 to 21 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom or a hydroxyl group. X ^d represents a single bond, a bivalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a bivalent alicyclic hydrocarbon group having 3 to 10 carbon atoms or a bivalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and the aliphatic hydrocarbon group And -CH ₂ -contained in the alicyclic hydrocarbon group may be substituted with -O-, -CO-, -NR ^e- , -S-, or -SO _2- . ]

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

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

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

^Examples of the divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms in X ^d include methylene, vinyl, propane-1,3-diyl, ethylene-1,2-diyl, and butane-1. , 4-diyl, butan-1,3-diyl, butan-1,2-diyl, pent-1,5-diyl, hex-1,6-diyl, more -1,7-diyl , Octyl-1,8-diyl, and the like.

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

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

Examples of X ^d in which -CH ₂ -is replaced by -O-, -CO-, -NR ^e- , -S-, or -SO ₂ -include, for example, formulas (xd-1) to (xd-10) The base indicated.

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

(d) The compound represented by the following formula (yd-1) is preferable.

[In the formula (yd-1), R ^h represents a perfluoroalkyl group having 4 to 6 carbon atoms. R ^g represents a hydrogen atom, a halogen atom, or a methyl group. ]

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

Resin (F) consists of structural units derived from (d) and The copolymer of the structural unit described in (e) is preferable, and the resin including the structural unit derived from (d) and the structural unit derived from (e) and the structural unit derived from (b) is preferable. Since the resin (F) contains a structural unit derived from (e), since it has excellent developability, there is a tendency that unevenness due to residue or development is suppressed. The resin (F) is preferred because it contains a structural unit derived from (b) and has a tendency to have excellent solvent resistance. The resin (F) may include a structural unit derived from (c). Examples of (e), (b), and (c) include the same as described above.

When the resin (F) is a copolymer of (e) and (d), the ratio of the structural units derived from each monomer to the total mole number of the structural units constituting the resin (F) is in the following range: good.

Structural unit derived from (e); 5-50% by mass (preferably 10-40% by mass)

Structural unit derived from (d); 50 ~ 95 mass% (preferably 70 ~ 90 mass%)

When the resin (F) is a copolymer of (e), (b), and (d), the ratio of the structural unit derived from each monomer to the total molar number of the structural unit constituting the resin (F) is in The following range is preferable.

Structural unit derived from (e); 5 ~ 40 mass% (preferably 10 ~ 30 mass%)

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

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

When the resin (F) is a copolymer of (e), (b), (c), and (d), the total mole number of the structural unit constituting the resin (F) is derived from the structural unit of each monomer. The ratio is preferably within the following range.

Structural unit derived from (e); 5 ~ 40 mass% (preferably 10 ~ 30 mass%)

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

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

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

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

The polystyrene equivalent weight average molecular weight of the resin (F) is preferably 3,000 to 20,000, and more preferably 5,000 to 15,000. When the weight average molecular weight of the resin (F) is within the aforementioned range, there is a tendency that the coating property is excellent, and a film of an exposed portion is unlikely to be reduced during development, and the non-exposed portion is easily removed by development.

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

The content of the resin (F) is preferably 0.001 to 10 parts by mass, and 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). If the content of the resin (F) is within the aforementioned range, there is a tendency that the developability is excellent when the pattern is formed, and the obtained pattern is excellent in the liquid repellency.

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

Resin (A1-1): a copolymer obtained by polymerizing (e) and (b), resin (A1-2): a copolymer obtained by polymerizing (e) with (b) and (c), resin ( A1-3): copolymers (e) and (c) polymerized resins (A1-4): copolymers (e) and (c) polymerized and (b) reversed Resin and resin (A1-5) obtained as a result: A copolymer obtained by polymerizing (b) and (c) and then reacting with (e).

Among them, resin (A1-1) and resin (A1-2) are also preferred.

In the resin (A1-1), the ratio of the structural unit derived from each monomer to the total mole number of all structural units constituting the resin (A1-1) is preferably within the following range.

Structural unit derived from (e); 5 ~ 60 mole% (preferably 10 ~ 50 mole%)

Derived from the structural unit of (b); 40 ~ 95 mole% (preferably 50 ~ 90 mole%)

If the ratio of the structural unit of the resin (A1-1) is within the above-mentioned range, the storage stability of the photosensitive resin composition, the developability when forming a pattern from the photosensitive resin composition, and the obtained coating film and The pattern tends to have good solvent resistance.

In the resin (A1-2), the ratio of the structural unit derived from each monomer to the total mole number of all structural units constituting the resin (A1-2) is preferably within the following range.

Structural unit derived from (e); 2 ~ 45 mole% (preferably 5 ~ 40 mole%)

Structural unit derived from (b); 2 ~ 95 mole% (preferably 5 ~ 80 mole%)

Structural unit derived from (c); 1 ~ 65 mole% (preferably 5 ~ 60 mole%)

If the ratio of the structural unit of the resin (A1-2) is within the above range, the storage stability of the photosensitive resin composition, the developability when the pattern is formed from the photosensitive resin composition, and the obtained coating film and The pattern tends to have good solvent resistance.

In the resin (A1-3), the ratio of the structural units derived from each monomer to the total mole number of all the structural units constituting the resin (A1-3) is preferably within the following range.

Structural unit derived from (e); 2 ~ 40 mole% (preferably 5 ~ 35 mole%)

Derived from the structural unit of (c); 60 ~ 98 mole% (preferably 65 ~ 95 mole%)

If the ratio of the structural unit of the resin (A1-3) is within the above range, the storage stability of the photosensitive resin composition, the developability when a pattern is formed from the photosensitive resin composition, and the obtained coating film and The pattern tends to have good solvent resistance.

The resins (A1-1) to (A1-3) can be produced by the same method as the resin (A).

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

The resin (A1-4) can be produced, for example, through a two-step process. In this case, you can refer to the method described in the above-mentioned document "Experimental Methods for Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd., First Edition, Chemical Dolls, First Edition, March 1, 1972), Japanese Patent Laid-Open 2001 Manufactured by the method described in Japanese Patent No. -89533.

First, as the first stage, the same procedure as in the above-mentioned resin (A) production method was carried out to obtain a copolymer of (e) and (c).

In this case, as described above, the copolymer obtained can be used directly after the reaction, or it can be used as a concentrated or diluted solution, or it can be taken out as a solid (powder) by reprecipitation or the like. A polystyrene-equivalent weight average molecular weight and molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] are preferably prepared.

However, the ratio of the structural units derived from (e) and (c) to the total mole number of the total structural units constituting the aforementioned copolymer is preferably within the following range.

Structural unit derived from (e); 5 ~ 50 mole% (preferably 10 ~ 45 mole%)

Structural unit derived from (c); 50 ~ 95 mole% (preferably 55 ~ 90 mole%)

Next, as a second stage, a part of the carboxylic acid or carboxylic anhydride derived from (e) of the obtained copolymer is reacted with the cyclic ether of (b). Since the cyclic ether is highly reactive and the unreacted (b) is difficult to remain, the (b) used in the resin (A1-4) is preferably (b1) or (b2), and (b1-1) is used as Better.

Specifically, following the above, the environment in the flask was replaced from nitrogen to air, and the number of moles with respect to (e) was 580 mol% of (b), with respect to (e), (b), and (c). The total amount of) is 0.001 to 5% by mass of the reaction catalyst of the carboxyl group and the cyclic ether (for example, (dimethylaminomethyl) phenol, etc.), and relative to (e), (b), and (c) Polymerization inhibitor in a total amount of 0.001 to 5% by mass (For example, hydroquinone, etc.) is put in a flask, and it is made to react at 60-130 degreeC for 1-10 hours, and resin (A1-4) is obtained. In addition, in the same manner as the polymerization conditions, the addition method or the reaction temperature may be appropriately adjusted in consideration of the production equipment or the amount of heat generated by the polymerization.

In this case, the molar number of (b) is preferably 10 to 75 mol%, and more preferably 15 to 70 mol% relative to the molar number of (e). With this range, there are storage stability of the photosensitive resin composition, image development property when the pattern is formed from the photosensitive resin composition, and solvent resistance, heat resistance, and mechanical properties of the obtained coating film and pattern The balance of intensity and sensitivity tends to be good.

The resin (A1-5) was used as the first stage, and was performed in the same manner as the method for producing the resin (A) described above to obtain a copolymer of (b) and (c).

In this case, as described above, the copolymer obtained can be used directly after the reaction, or it can be used as a concentrated or diluted solution, or it can be taken out as a solid (powder) by reprecipitation or the like.

The ratio of the structural units derived from (b) and (c) to the total mole number of all the structural units constituting the aforementioned copolymer is preferably within the following range.

Structural units derived from (b); 5 ~ 95 mole% (preferably 10 ~ 90 mole%)

Structural unit derived from (c); 5 ~ 95 mole% (preferably 10 ~ 90 mole%)

In addition, it can be carried out in the same manner as the production method of the resin (A1-4), and the cyclic ether derived from (b) in the copolymer of (b) and (c) can be made into (e) Some carboxylic acids or carboxylic anhydrides are obtained by reaction. The hydroxy group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride may be reacted with a carboxylic acid anhydride.

The amount of (e) used in the reaction with the aforementioned copolymer is relatively In terms of the mole number of (b), 5 to 80 mole% is preferred. Since the cyclic ether is reactive and unreacted (b) is difficult to remain, (b) is preferably (b1), and (b1-1) is more preferred.

Polystyrene equivalent weight average molecular weight of resin (A1) It is preferably 3,000 ~ 100,000, more preferably 5,000 ~ 50,000. If the weight average molecular weight of the resin (A1) is within the aforementioned range, it tends to be excellent in coatability, and it is unlikely to cause a decrease in the film of the exposed portion during development, and the non-exposed portion is easily removed by 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 within the above range, there is a tendency that the developability is excellent.

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

When the resin (A1) is contained, its content is preferably 1 to 80% by mass and more preferably 1 to 50% by mass relative to the total amount of the resin (A) and the resin (A1). When the content of the resin (A1) is within the aforementioned range, a pattern can be formed with high sensitivity and excellent developability.

When the resin (A1) is contained, its content is preferably 1 to 80% by mass and more preferably 1 to 50% by mass relative to the total amount of the resin (A) and the resin (A1). When the content of the resin (A1) is within the aforementioned range, a pattern can be formed with high sensitivity and excellent developability.

The photosensitive resin composition of the present invention contains polymerizability Compound (B) is preferred.

The polymerizable compound (B) can be obtained from the polymerization initiator (C). The compound which polymerizes the generated active radical, for example, a compound having an ethylenically unsaturated bond, etc., is preferably a (meth) acrylate compound.

As a polymerizable compound with one ethylenically unsaturated bond Examples of the substance (B) include the same compounds as the compounds (a), (b), and (c) described above, and among them, (meth) acrylates are also preferable.

As a polymerizable compound with 2 ethylenically unsaturated bonds Examples of the substance (B) include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, and 1,6-hexanediol di (meth) Acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, bis (acryloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propylene Oxidized neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, and the like.

Polymerizability as having 3 or more ethylenically unsaturated bonds Examples of the compound (B) include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and ginseng (2-hydroxyethyl) isotricyanate tri (methyl). Acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (5) (Meth) acrylate, di Pentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, three Pentaerythritol octa (meth) acrylate, reactant of pentaerythritol tri (meth) acrylate and anhydride, reactant of dipentaerythritol penta (meth) acrylate and anhydride, tripentaerythritol hepta (meth) acrylate and anhydride Reactant, caprolactone-denatured trimethylolpropane tri (meth) acrylate, caprolactone-denatured pentaerythritol tri (meth) acrylate, caprolactone-denatured ginseng (2-hydroxyethyl) isocyanuric acid Ester tri (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, Caprolactone modified tripentaerythritol tetra (meth) acrylate, caprolactone modified tripentaerythritol penta (meth) acrylate, caprolactone modified tripentaerythritol hexa (meth) acrylate, caprolactone modified tripentaerythritol seven ( Methacrylate , Caprolactone-modified pentaerythritol octa (meth) acrylate, Caprolactone-modified pentaerythritol tri (meth) acrylate and anhydride reaction, Caprolactone-modified dipentaerythritol penta (meth) acrylate and anhydride reaction Products, caprolactone denatured tripentaerythritol hepta (meth) acrylate and reactant of acid anhydride, etc.

Among them, the polymerizable compound (B) having three or more ethylenically unsaturated bonds is also preferable, and dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tri ( Methacrylate is preferred.

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

If the content of the polymerizable compound (B) is within the aforementioned range, The sensitivity, smoothness, and reliability of the obtained or acquired pattern tend to be good.

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

Examples of the polymerization initiator (C) include an oxime compound Compounds, alkylphenone compounds, biimidazole compounds, triazine compounds and fluorenylphosphine oxide compounds. In addition, a light and / or thermal cationic polymerization initiator described in Japanese Patent Application Laid-Open No. 2008-181087 (for example, an onium cation and a Lewis acid-derived anion) may be used. Among these, at least one selected from the group consisting of a biimidazole compound, an alkyl phenone compound, and an oxime compound is preferable, and an alkyl phenone compound is particularly preferable. If it is a polymerization initiator containing these compounds, it tends to have a high sensitivity especially, so it is preferable.

The oxime compound is a compound having a partial structure represented by formula (d1). In the following, * represents a bond.

Examples of the O-fluorenyl oxime compound include N-benzyloxy-1- (4-phenylsulfonylphenyl) but-1-one-2-imine, and N-benzylhydrazone. Oxy-1- (4-phenylsulfonylphenyl) oct-1-one-2-imine, N-benzylfluorenyloxy-1- (4-phenylsulfonylphenyl) -3- Cyclopentylpropan-1-one-2-imine, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzylfluorenyl) -9H-carbazol-3-yl] Ethane-1-imine, N-ethoxyl-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxane Pentenylmethyloxy) benzylfluorenyl} -9H-carbazol-3-yl] ethane-1-imine, N-ethoxyl-1- [9-ethyl-6- (2- Methylbenzylfluorenyl) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-imine, N-benzylfluorenyloxy-1- [9-ethyl-6- (2-methyl Benzylfluorenyl) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercially available products such as Irgacure OXE01, OXE02 (above, manufactured by BASF), and N-1919 (made by ADEKA) can also be used.

The alkyl phenone compound has a moiety represented by formula (d2) A compound having a partial structure or a partial structure represented by formula (d3). In these partial structures, the benzene ring may be polymerized with a substituent.

As a compound having a partial structure represented by formula (d2), Examples include 2-methyl-2-morpholinyl-1- (4-methylsulfonylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholine Phenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholine Group) phenyl] butan-1-one and the like. Commercial products such as Irgacure 369, 907, and 379 (above, manufactured by BASF) can also be used.

As a compound having a partial structure represented by formula (d3), Examples include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl -1--1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenyl Phenyl) propan-1-one oligomers, α, α-diethoxyacetophenone, benzyldimethylketal and the like.

From the viewpoint of sensitivity, alkyl phenone compounds are A partially structured compound represented by (d2) is preferred.

Examples of the biimidazole compound include 2,2'-bis (2- (Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenyl Bisimidazole (for example, refer to Japanese Patent Application Laid-Open No. 6-75372, Japanese Patent Application Laid-Open No. 6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5' -Tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (alkoxyphenyl) biimidazole, 2,2'-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetrakis (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5 '-Tetrakis (trialkoxyphenyl) biimidazole (for example, refer to Japanese Patent Application Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, etc.), benzene at 4,4'5,5'-position An imidazole compound in which the group is substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Application Laid-Open No. 7-10913). Preferred examples include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichloro (Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl Biimidazole.

Examples of the triazine compound include 2,4-bis (trichloro (Methyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1 , 3,5-triazine, 2,4-bis (trichloromethyl) -6-piperidyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4 -Methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethyl Alkenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-triazine and the like.

Examples of the fluorenylphosphine oxide compound include 2,4,6-trimethylbenzylfluorenyldiphenylphosphine 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, o- Benzylidene benzoate methyl, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butyl Peroxycarbonyl) benzophenone compounds such as benzophenone, 2,4,6-trimethylbenzophenone; quinones such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone Compounds; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds, and the like. These systems may be added with a polymerization initiation aid (E) described later.

Moreover, as a polymerization initiator which can cause a chain transfer, the polymerization initiator described in Japanese Patent Application Publication No. 2002-544205 can also be used.

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

In the photosensitive resin composition of the present invention, a polymerization initiator (E) can be used together with the polymerization initiator (C). The polymerization initiator (E) is used in combination with the polymerization initiator (C), and promotes the An initiator or a sensitizer used for the polymerization of a polymerizable compound that starts polymerization. Examples of the polymerization initiation aid (E) include thioxanthone compounds, amine compounds, carboxylic acid compounds, compounds described in JP-A-2008-65319 and JP-A-2009-139932.

Examples of the thioxanthone compound include 2-isopropyl Thioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

Examples of the amine compound include triethanolamine and methyldiamine. Aliphatic amine compounds such as ethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate , 2-dimethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethyl-p-toluidine, 4,4'-bis (dimethyl Amino) benzophenone (commonly known as miguelone), 4,4'-bis (diethylamino) benzophenone-like aromatic amine compounds.

Examples of the carboxylic acid compound include phenylsulfonylethyl Acid, methylphenylsulfonylacetic acid, ethylphenylsulfonylacetic acid, methylethylphenylsulfonylacetic acid, dimethylphenylsulfonylacetic acid, methoxyphenylsulfonylacetic acid , Dimethoxyphenylsulfonylacetic acid, chlorophenylsulfonylacetic acid, dichlorophenylsulfonylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthalene Aromatic heteroacetic acids such as glycine, naphthyloxyacetic acid, etc.

As a group of the polymerization initiator (C) and the polymerization initiator (E) Examples include acetophenone compounds and thioxanthone compounds, acetophenone compounds and aromatic amine compounds, and specific examples include 2-morpholinyl-1- (4-methyl Sulfosulfanylphenyl) -2-methylpropan-1-one with 2,4-diethylthioxanthone, 2-dimethylamino-2-benzyl-1- (4-morpholinyl Phenyl) butan-1-one with 2,4-diethylthioxanthone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinylphenyl) Butan-1-one and 2,4-diethylthioxanthone, 2-morpholinyl-1- (4-methylsulfonylphenyl) -2-methylpropan-1-one and 2-iso Propylthioxanthone with 4-isopropylthioxanthone, 2-morpholinyl-1- (4-methylsulfonylphenyl) -2-methylpropan-1-one with 4,4'- Bis (diethylamino) benzophenone, 2-dimethylamino-2-benzyl-1- (4-morpholinylphenyl) butan-1-one, and 4,4'-bis ( Diethylamino) benzophenone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinylphenyl) butan-1-one and 4,4 '-Bis (diethylamino) benzophenone and the like.

Among them, acetophenone compounds and thioxanthone compounds are also used. A preferred combination is 2-morpholinyl-1- (4-methylsulfonylphenyl) -2-methylpropan-1-one with 2,4-diethylthienone, 2-morpholine Preferable are methyl-1- (4-methylsulfonylphenyl) -2-methylpropan-1-one and 2-isopropylthioxanthone and 4-isopropylthioxanthone. With such a combination, a pattern with high visible light transmittance can be obtained under high sensitivity.

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

Relative to resin (A), resin (A1) and polymerizable compound (B) The total amount is 100 parts by mass, and the amount of the polymerization initiation aid (E) used is preferably 0.1 to 20 parts by mass, and more preferably 0.3 to 15 parts by mass. Polymerization initiation aid If the amount of the agent (E) is within the aforementioned range, a pattern can be obtained with high sensitivity, and the obtained pattern shape is good.

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

As a solvent that can be used in the present invention, for example, it can be obtained from Ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether ester solvents (containing -COO- in the molecule) Solvents with -O-), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents, aromatic hydrocarbon solvents, amidine solvents, dimethylarsine, etc. are selected for use.

Examples of the ester solvent include methyl lactate and ethyl lactate. Ester, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, Ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, cyclohexanol acetate, γ-butyrolactone, etc. .

Examples of the ether solvent include ethylene glycol monomethyl ether and ethyl ether. Glycol monoethyl ether, glycol monopropyl ether, glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, Tetrahydropiperan, 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, phenyl ether, methylbenzene Methyl ether and so on.

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

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

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

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

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

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

Among the solvents mentioned above, from the viewpoint of coating properties and drying properties, Organic solvents having a boiling point of 120 ° C. to 180 ° C. at 1 atm are preferred. 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 preferred. When the solvent (D) is such a solvent, unevenness in coating can be suppressed and the flatness of the coating film can be improved.

The content of the solvent (D) in the photosensitive resin composition of the present invention The amount is preferably 60 to 95% by mass, and more preferably 70 to 90% by mass relative to the total amount of the photosensitive resin composition. 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 within the above range, the flatness of the film coated with the photosensitive resin composition tends to be high. Here, the solid content refers to the amount after removing the solvent (D) from the photosensitive resin composition.

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

Specific examples of the polyfunctional thiol compound (T) include Hexanedithiol, decanedithiol, 1,4-bis (methylsulfonyl) benzene, butanediol bis (3-sulfonylpropionate), butanediol bis (3-sulfonylethyl) Acid esters), ethylene glycol bis (3-sulfonylacetate), trimethylolpropane ginseng (3-sulfonylacetate), butanediol bis (3-sulfonylpropionate) , Trimethylolpropane ginseng (3-sulfonylpropionate), trimethylolpropane ginseng (3-sulfonylacetate), pentaerythritol Alcohol (3-sulfofluorenyl propionate), Pentaerythritol (3-sulfofluorenyl acetate), Phenylhydroxyethyl ginseng (3-sulfofluorenyl propionate), Pentaerythritol (3-sulfofluorenyl propionate) Butyrate), 1,4-bis (3-sulfomethylbutoxy) butane, and the like.

Polyfunctional sulfur with respect to 100 parts by mass of the polymerization initiator (C) The content of the alcohol compound (T) is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 7 parts by mass. If the content of the polyfunctional thiol compound (T) is within the above range, the sensitivity of the photosensitive resin composition tends to be high and the developability tends to be good.

The photosensitive resin composition of the present invention may also contain interfacial activity. Sex agent (G) (however, it is different from resin (F)). Examples of the surfactant include a polysiloxane-based surfactant, a fluorine-based surfactant, and a polysiloxane-based surfactant having a fluorine atom.

Examples of the polysiloxane-based surfactant include a surfactant having a siloxane bond.

Specific examples include Toray Polysilicone DC3PA, the same SH7PA, the same DC11PA, the same SH21PA, the same SH28PA, the same SH29PA, the same SH30PA, and the polyether modified polysiloxane oil SH8400 (trade name: Toray Dow Corning (Stock)) ), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (made by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials Japan Corporation)制) and so on.

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain.

Specific examples include Fluorinert (registered trademark) FC430, same as FC431 (Sumitomo 3M (shares)), Megafac (registered trademark) F142D, same F171, same F172, same F173, same F177, same F183, and R30 (DIC (Share) system, Eftop (registered trademark) EF301, same EF303, same EF351, same EF352 (Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, same S382, same SC101, same SC105 (Asahi Glass ( Share) system), E5844 ((share) Daikin Fine Chemical Research Institute) and so on.

As a polysiloxane-based surfactant having a fluorine atom, Examples include surfactants having a siloxane bond and a fluorocarbon chain. Specific examples include Megafac (registered trademark) R08, the same BL20, the same F475, the same F477, and the F443 (DIC (shares) system). Preferable examples include Megafac (registered trademark) F475.

Interfacial activity relative to the total amount of photosensitive resin composition The content of the agent (G) is 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less, and more preferably 0.01% by mass or more and 0.05% by mass or less. By containing a surfactant in this range, the flatness of a coating film can be made favorable.

The photosensitive resin composition of the present invention may be packaged as necessary. Various additives including fillers, other polymer compounds, adhesion promoter (H), antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents, etc.

As long as the above adhesion improving agent (H) is added, or There is no particular limitation on the solid matter that does not precipitate out due to the reaction with the photosensitive resin composition during storage at room temperature, and examples thereof include a silane coupling agent. Examples include KBM-303, KBE-402, KBM-403, KBM-503, KBM-573, KBM-803, KBE-9007 (made by Shin-Etsu Chemical Industry Co., Ltd.), or Z-6040, Z- 6043, Z-6011, Z-6020, Z-6094, Z-6062, Z-6094, Z-6030, Z-6519, Z-6300, Z-6883 (made by Toray Dow Corning Co., Ltd.), etc.

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

When the photosensitive resin composition of the present invention is filled in a long optical path 1cm quartz trough, and the average transmittance when measuring the transmittance using a spectrophotometer under the conditions of a measurement wavelength of 400 to 700nm is preferably 70% or more, 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, and more preferably 95% or more. This average transmittance is a coating film with a thickness of 3 μm after using a spectrophotometer and then measuring a wavelength of 400 to 700 nm to measure heat curing (for example, curing at 100 to 250 ° C for 5 minutes to 3 hours). Time average. Thereby, a coating film excellent in transparency in the visible light field can be provided.

The photosensitive resin composition of the present invention can be applied in examples. For example, a substrate made of glass, metal, plastic, or the like, or coated on a substrate formed with color filters, various insulating or conductive films, driving circuits, etc., is patterned into a desired shape to form a pattern. Also, this pattern can be formed as It is used as a part of a component of a display device or the like.

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

The coating of the photosensitive resin composition can be performed using various coating devices such as a spin coater, slit & spin coater, slit coater, inkjet, roll coater, dip coater, and the like. .

Secondly, it is preferable to perform drying or pre-baking to remove volatile components such as solvents and the like for drying. Thereby, a smooth, unhardened coating film can be obtained.

The film thickness of the coating film at this time is not particularly limited, and can be appropriately adjusted according to the materials, applications, and the like to be used, for example, about 1 to 6 μm.

Furthermore, the obtained uncured coating film is irradiated with light through a photomask for forming a desired pattern, for example, ultraviolet rays generated from a mercury lamp and a light emitting diode are irradiated. At this time, the shape of the photomask is not particularly limited, and the shape or size may be selected according to the purpose of the pattern.

In recent years, the exposure function can be used to cut off light below 350 nm using a filter that cuts off this wavelength range. For light near 436 nm, 408 nm, and 365 nm, a band-pass filter that takes out these wavelength ranges can be used to selectively extract light. In addition, the entire exposure surface is uniformly irradiated with slightly parallel light. If a device such as a mask aligner, stepper is used, the correct position of the mask and the substrate can be corrected at this time.

After the exposed coating film is brought into contact with the developing solution, a predetermined portion, such as a non-exposed portion (ie, a non-pixel portion) is dissolved and developed to obtain the intended pattern shape.

The developing method may be any of a liquid holding method, a dipping method, and a spray method. In addition, the substrate may be inclined at an arbitrary angle during 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, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, and sodium silicate. , Potassium silicate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonia, etc.

Examples of the organic basic compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, and monoethylamine. , Diethylamine, triethylamine, monoisopropylamine, 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 further include a surfactant.

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

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene derivatives, and polyoxyethylene / polyoxylates. Propylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, poly Oxyethylene sorbitol fatty acid esters, glycerol fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, and the like.

Examples of the anionic surfactant include: Higher alcohol sulfates like sodium lauryl sulfate or sodium oleyl alcohol sulfate, alkyl sulfates like sodium lauryl sulfate or ammonium lauryl sulfate, sodium dodecylbenzenesulfonate or twelve Alkyl aryl sulfonates such as sodium naphthalene sulfonate.

Examples of the cationic surfactant include hard Lipidylamine hydrochloride or lauryltrimethylammonium-like amine inflammation or fourth-order ammonium salt.

The concentration of the surfactant in the alkali imaging solution is based on The range of 0.01 to 10% by mass is preferred, 0.05 to 8% by mass is preferred, and 0.1 to 5% by mass is more preferred.

After development, the pattern can be obtained by washing with water. And also Post-bake if necessary. The post-baking is preferably performed at a temperature range of 150 to 240 ° C for 10 to 180 minutes.

Do not use patterned light when exposing unhardened coatings The cover can obtain a coating film having no pattern by omitting light irradiation and / or development on the entire surface.

In this embodiment, on the substrate on which the electrodes have been formed, such as A thin film made of the photosensitive resin composition is formed as described above. Secondly, an opening is formed in the thin film by the photolithography method so that the surface of the electrode is exposed.

Second, according to the polarity of the surface free energy of the aforementioned electrode The value of the component evaluates the coatability of the electrode, thereby enabling evaluation of the substrate.

If the value of the polar component of the surface free energy of the electrode is, for example, Above 15mN / m, the substrate with the partition wall is judged to be suitable for substrates of display devices, etc. On the other hand, if the value of the polar component of the surface free energy of the electrode is below 15mN / m, the substrate with the partition wall is used It was determined that it could not be applied to a substrate of a display device or the like.

And based on this evaluation result, the photosensitive resin composition for forming a partition can also be evaluated.

That is, on the substrate on which the electrode has been formed, a thin film made of the photosensitive resin composition is formed as described above, and then the surface of the electrode is exposed so that the thin film is formed on the thin film by the photolithography method described above. The opening is formed, and the coating property of the electrode is evaluated based on the value of the polar component of the free energy of the surface of the electrode, whereby the evaluation of the photosensitive resin composition can be performed.

A preferred form of the substrate evaluation method of the present invention is a substrate evaluation method, which comprises: supplying a photosensitive resin composition to a substrate on which an electrode has been formed; and rotating the substrate at 900 rpm for 7 seconds to form the photosensitive material. A step of forming a thin film of a resin composition, a step of drying the substrate on which the thin film has been formed under reduced pressure at 66 Pa, and a step of pre-baking at 110 ° C for 110 seconds. Expose the pre-baked film at 200 mJ / cm ² , use a 2.38% by weight tetramethylammonium hydroxide aqueous solution, develop at 23 ° C. for 80 seconds, and perform post-baking photolithography after washing with water. The step of forming an opening in the thin film and the step of evaluating the coatability of the electrode are based on the value of the polar component of the surface free energy of the electrode exposed on the opening of the thin film.

If the value of the polar 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 can be used as a photosensitive resin composition for forming a photosensitive resin composition for a partition wall. On the other hand, the polar component of the free energy of the electrode surface If the value is 15 mN / m or less, it is determined that it cannot be used as a photosensitive resin composition for forming a photosensitive resin composition for partition walls.

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

In this embodiment, for example, the value of the polar component of the surface energy of the electrode can be calculated using the Owensand Wendt method. The Owensand Wendt method applies the following formula.

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

(In the formula, γl represents the surface free energy of the liquid, γld represents the surface free energy dispersion force component, γlp represents the liquid surface free energy polarity component, γsd represents the solid surface energy dispersion force component, and γsp represents the solid The polar component of surface free energy, θ represents the contact angle.)

Here, there are two unknowns (γsd, γsp). If the known two types of liquids are used as the dispersed component and the polar component, these γsd and γsp can be calculated.

From the above formula, the following formula can be derived. From the linear regression formula of the following formula, the slope is (γsp) ^1/2 and the intercept is (γsd) ^1/2 .

γl (1 + cosθ) / 2 (γld) ^1/2 VS (γlp / γld) ^1/2

In addition, if the known two types of liquids are used as the dispersing component and the polar component, the polar component of the free energy on the surface of the electrode can be calculated. For example, when the three or more types of solvents (such as four types) are used as the polar components, It can also be evaluated by measuring the contact angles of a plurality of points (for example, 3 points) on the substrate surface, and calculating the average.

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

FIG. 1 is a cross-sectional view schematically showing a part of the display device 1 as an example of a display device of the present invention. FIG. 2 is a plan view schematically showing a part of the display device 1 as an example of the display device of the present invention. The display device 1 mainly includes a support substrate 2, a partition wall 3 that divides a predetermined area on the support substrate 2, and a plurality of organic EL elements 4 that are disposed in the area divided by the partition wall 3.

The support substrate 2 is, for example, a glass substrate, a substrate made of resin, a substrate made of metal, or a substrate made of semiconductor.

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

The support substrate 2 is provided with a partition wall 3 and a support base. The plurality of recesses 5 defined in the plate 2 (hereinafter may be referred to as openings 5). This opening 5 corresponds to a region divided by the partition wall 3.

The partition walls 3 in the display device 1 are arranged in a grid shape. because Here, when viewed from one of the thickness directions Z of the support substrate 2 (hereinafter also referred to as “in a plan view”), the plurality of openings 5 are arranged in a matrix shape. That is, the openings 5 are arranged at predetermined intervals in the row direction X, and at the same time, the openings 5 are arranged at regular intervals in the column direction Y. The shape of each opening 5 in a plan view is not particularly limited. For example, the opening portion 5 is formed into a shape such as a substantially rectangular shape, a substantially elliptical shape, and an elliptical shape in a plan view. In this embodiment, a substantially rectangular opening 5 is provided in a plan view. Moreover, in the present specification, the above-mentioned row direction X and column direction Y mean directions perpendicular to the thickness direction Z of the supporting substrate, and mutually perpendicular directions.

Furthermore, as another embodiment, a strip-shaped partition is provided. In the case of a wall, the partition wall is configured by, for example, arranging a plurality of partition wall members extending in the row direction X at predetermined intervals in the column direction Y. In this form, a strip-shaped recess is defined by a strip-shaped partition wall and a support substrate.

The partition system is formed so that the width changes as it moves away from the support substrate. narrow. For example, when a partition wall extending in the column direction Y is cut on a plane perpendicular to the extending direction (the column direction Y), the cross-sectional shape is formed so that the width becomes narrower as it moves away from the support substrate. The partition wall of the isosceles trapezoid shape is shown in FIG. 1. When the upper bottom is compared with the lower bottom on the supporting substrate side, the width of the lower bottom is wider than the upper bottom. Moreover, the cross section of the partition wall actually formed does not have to be trapezoidal, and the linear portions and corners of the trapezoidal shape may be rounded.

The partition wall can be formed by the photolithography method as described above. In this embodiment, a thin film made of the photosensitive resin composition is formed on a substrate on which a first electrode of an organic EL element described later is formed. Next, the surface of the electrode is exposed by a photolithography method. An opening is formed in the film, and a partition wall is formed.

The partition wall 3 preferably exhibits liquid repellency on its top surface. Furthermore, the top surface refers to a plane existing on the surface of the partition wall 3 at a position farthest from the support substrate 2. Examples of the method for forming the partition wall 3 having a liquid-repellent property on the top surface include a method using a photosensitive resin composition containing the liquid-repellent agent (F) described above, or a liquid-repellent treatment on the surface of the partition wall after formation. method. For example, by performing a plasma treatment on the partition wall 3 in an environment containing a fluoride, the surface of the partition wall 3 can be provided with liquid repellency. The fluoride in this treatment is gaseous. 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 are bonded to the surface of the partition wall 3, and the liquid repellency is imparted to the partition wall 3.

The top surface of the partition 3 can prevent liquid supply by exhibiting liquid repellency. The ink applied to the area (opening 5) surrounded by the partition wall 3 overflows to the adjacent area through the top surface of the partition wall 3.

The organic EL element 4 is arranged in the area divided by the partition wall 3. Area (ie, opening 5). When a grid-like partition wall 3 is provided in the display device 1, each organic EL element 4 is provided in each opening 5. That is, the organic EL elements 4 are arranged in a matrix like the openings 5, and are arranged on the support substrate 2 at predetermined intervals in the row direction X and at the same time in the column direction Y. Spaced and neatly arranged.

The shape and configuration of the next wall 3 are based on the prime number and resolution It is appropriate to set the specifications of the display device such as the degree or ease of manufacture. For example, the width in the row direction X or the column direction Y of the partition wall 3 is about 5 μm to 50 μm, the height of the partition wall 3 is about 0.5 μm to 5 μm, and the interval between the partition walls 3 in the adjacent row direction X or column direction Y is the opening 5 The width in the row direction X or the column direction Y is about 10 μm to 200 μm. The width of the first electrode 6 in the row direction X or the column direction Y is about 10 μm to 200 μm, respectively.

The partition 3 can be formed from The photosensitive resin composition of the invention.

Moreover, as another embodiment, it is next to a stripe At this time, the organic EL elements 4 are arranged at predetermined intervals in the row direction X in each of the openings extending in the row direction X.

The display device 1 is provided with three types of organic EL elements 4. That is, the red organic EL element 4R that emits red light, the green organic EL element 4G that emits green light, and the blue organic EL element 4B that emits blue light.

The organic EL element 4 is based on the first circuit from the supporting substrate side. The electrode, the organic EL layer, and the second electrode are laminated in order. In this specification, one or a plurality of layers provided between the first electrode 6 and the second electrode 10 are referred to as an organic EL layer, respectively. The organic EL element 4 includes at least one light emitting layer as an organic EL layer. In addition, in addition to a light-emitting layer, an organic EL element may have an organic EL layer different from the light-emitting layer if necessary. For example, the first electrode 6 and the second electrode Between 10, a hole injection layer, a hole transport layer, an electron barrier layer, an electron transport layer, and an electron injection layer are provided as an organic EL layer. In addition, two or more light emitting layers may be provided between the first electrode 6 and the second electrode 10.

The organic EL element 4 is composed of an anode and a cathode. One pair of electrodes includes a first electrode 6 and a second electrode 10. One of the first electrode 6 and the second electrode 10 is provided as an anode, and the other electrode is provided as a cathode. In the display device 1 of this embodiment, the first electrode 6 functions as an anode, the first organic EL layer 7 functions as a hole injection layer, the second organic EL layer 9 functions as a light emitting layer, and the first organic EL layer functions as a cathode. The order of the two electrodes 10 is formed by laminating on the support substrate 2.

The first electrode 6 is generally a transparent electrode. as long as The transparent electrode is not limited in type. Examples include tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), fluorine-doped tin oxide (FTO), and antimony-doped tin oxide (ATO). , Titanium oxide transparent electrode, aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), but tin-doped indium oxide (ITO) and zinc-doped indium oxide (IZO) are preferred.

The first electrode 6 is provided in each organic EL element 4. That is, the same number of first electrodes 6 as the organic EL element 4 are provided on the support substrate 2. The first electrode 6 is provided corresponding to the arrangement of the organic EL element 4, and is arranged in a matrix like the organic EL element 4. Moreover, the partition wall 3 is formed in a grid shape mainly in a region where the first electrode 6 is removed, and is formed so as to surround the outer edge portion of the first electrode 6 (see FIG. 1).

A layer provided adjacent to the first electrode 6 (equivalent to a hole injection) The layered first organic EL layer 7) is provided on the first electrode 6 in each of the openings 5. The first organic EL layer 7 may be provided with different materials or film thicknesses according to the type of each organic EL element as necessary. In addition, from the viewpoint of the simplicity of the formation steps of the first organic EL layer 7, the entire first organic EL layer 7 may be formed of the same material and the same film thickness.

The first organic EL layer 7 will contain the first organic EL layer 7 The ink of the material of the layer 7 is supplied to the area (opening 5) surrounded by the partition wall 3, and is formed by curing the ink by drying, heating, and / or light irradiation. The method of applying ink is not particularly limited, and examples thereof include printing methods such as an inkjet method and an air-jet method.

A layer provided adjacent to the first electrode 6 (first organic EL The ink coating solvent or dispersion medium used in the formation of layer 7) is not particularly limited as long as it is a liquid that can dissolve and / or disperse the material of the first organic EL layer 7. 1 The material of the organic EL layer 7 is well dissolved and / or dispersed, and a polar solvent may be contained.

As the above polar solvent, a general one can be used, which is not Those that are particularly limited include, for example, alcohols, ketones, glycol esters, glycol ethers, N, N-dimethylformamide, N, N-dimethylacetamide, N -Methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and dimethylsulfinium, N-cyclohexyl-2-pyrrolidone and the like. Moreover, in this specification, a polar solvent means the solvent whose sp (Solubility Parameter) value is 10 or more.

Therefore, the layer provided adjacent to the first electrode 6 (the first When the ink used for the formation of the organic EL layer 7) includes a polar solvent, when the ink is supplied to the opening of the partition wall, the first electrode 6 Being bounced off makes it difficult to uniformly spread the coating on the entire surface of the opening. However, as described above, if the value of the polar component of the surface free energy of the electrode after the opening is 15 mN / m or more, The ink applied to the first electrode 6 is evenly spread on the entire surface of the opening in the partition wall, so that a flat layer (the first organic EL layer 7) adjacent to the first electrode 6 can be formed. .

The solvent or dispersing medium other than the polar solvent contained in the ink used for forming the layer (the first organic EL layer 7) provided adjacent to the first electrode 6 can be used such as cyclohexylbenzene, anisole, stubble, Toluene, etc.

The second organic EL layer 9 functioning as a light emitting layer is located at the opening. 5 is provided on the first organic EL layer 7. As described above, the light emitting layer is provided in accordance with the type of the organic EL element. Therefore, the red light emitting layer 9R is provided in the opening 5 provided with the red organic EL element 4R, the green light emitting layer 9G is provided in the opening 5 provided with the green organic EL element 4G, and the blue light emitting layer 9B is provided in An opening 5 is provided in the blue organic EL element 4B.

The second electrode 10 is entirely formed on the organic EL device. On the display area of element 4. That is, the second electrode 10 is formed not only on the second organic EL layer 9 but also on the partition wall 3, and is formed continuously across a plurality of organic EL elements.

As described above, by using a sealing layer and a closed substrate A plurality of organic EL elements 4 (not shown) formed on the support substrate 2 can produce an organic EL display device.

The pattern obtained from the photosensitive resin composition of the present invention is Since it has high coating properties, it is particularly useful as a barrier for color filters, liquid crystal display element ITO electrodes, organic EL display elements, circuit wiring boards, etc. produced by the inkjet method. In addition, for example, it can be used as a photospacer constituting a part of a color filter substrate and / or an array substrate, a patternable protective film, an interlayer insulating film, a protrusion for controlling liquid crystal alignment, a microlens, The coating layer for adjusting the film thickness and the like, and the components for the touch panel do not have the pattern coating film obtained as described above, which can be useful as a protective film constituting a part of the color filter substrate and / or the array substrate. The color filter substrate and the array substrate are suitable for use in a liquid crystal display device, an organic EL display device, an electronic paper, and the like.

Examples

Hereinafter, the present invention will be described in more detail based on examples. In the example, "%" and "part" are mass% and mass parts unless otherwise noted.

[Synthesis example 1]

Allow nitrogen to flow into a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to replace it with a nitrogen atmosphere. Add 166 parts of propylene glycol monomethyl ether acetate and 52 parts of methoxypropanol, and stir while heating to 85 ℃. Next, 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-vinyl benzoic acid, and propylene glycol were added over 4 hours. A mixed solution of 125 parts of monomethyl ether acetate and 115 parts of methoxypropanol was dropped into the flask.

On the other hand, a mixed solution in which 32 parts of 2,2-azobis (2,4-dimethylvaleronitrile) was dissolved in 210 parts of propylene glycol monomethyl ether acetate was dropped into the flask over 5 hours. After the dropwise addition, the mixture was kept 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 ° C) of 46 mPas, a solid content of 33.7%, and a solution acid value of 83 mg-KOH / g. Solution. 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)

Nitrogen was appropriately flowed into a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to replace the nitrogen atmosphere. 140 parts of diethylene glycol ethyl methyl ether was added and stirred, and simultaneously heated to 70 ° C. Next, 40 parts of methacrylic acid was prepared; and a mixture of the monomer (I-1) and the monomer (II-1) {the monomer (I-1) in the mixture: the mole of the monomer (II-1) Ratio = 50: 50} 360 parts of a solution prepared by dissolving 190 parts of diethylene glycol ethyl methyl ether, and this solution was dropped into a flask over a period of 4 hours using a dropping funnel.

On the other hand, using another dropping pump, 30 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in diethylene glycol ethyl methyl ether over 5 hours. 240 parts of the solution was dropped into the flask. After the dripping of the polymerization initiator solution was completed, it was held at 70 ° C 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 obtained resin A1b 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 units.

(Synthesis example 3)

176 parts of t-butoxystyrene and 5.8 parts of azobisbutyronitrile were placed in a flask equipped with a cooling tube, a stirrer and a thermometer, and 250 parts of propylene glycol monomethyl ether was added to dissolve the polymer, and polymerized at 75 ° C. 4 hours. 50 parts of a 5% sulfuric acid aqueous solution was mixed with the obtained polyt-butoxystyrene solution, and a hydrolysis reaction was performed at 100 ° C for 3 hours. After washing the reaction product three times with 1,000 parts of deionized water, 500 parts of propylene glycol monomethyl ether acetate was added for solvent Instead, an alkali-soluble resin (polyhydroxystyrene, resin Ac) having a weight average molecular weight (Mw) of 24,000 was obtained.

(Synthesis example 4)

In a flask equipped with a cooling tube, a stirrer, and a thermometer, 145 parts of propylene glycol monomethyl ether acetate was stirred while nitrogen substitution was performed, and the temperature was raised to 120 ° C. To this, 20 parts of styrene, 57 parts of glycidyl methacrylate, and 82 parts of a monoacrylate ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise and continued at 140 ° C. Stir for 2 hours. Next, the reaction vessel was replaced with air, and 27 parts of acrylic acid was added, 0.7 parts of dimethylaminomethylphenol and 0.12 parts of hydroquinone were added, and the reaction was continued at 120 ° C. for 6 hours. Thereafter, 52 parts of tetrahydroanthylphthalic acid (THPA) and 0.7 part of triethylamine were added, and reacted at 120 ° C for 3.5 hours to obtain a weight average molecular weight (Mw) of about 7,000 and a solid acid value of 84 mg-KOH. / g of alkali-soluble resin (resin Ad).

(Synthesis example 5)

In a flask equipped with a cooling tube, a stirrer and a thermometer, 400 parts of epoxy resin (manufactured by Nippon Kayaku Co., Ltd .: XD-1000) was added to 361 parts of propylene glycol monomethyl ether, and dissolved at 90 ° C for 3 hours. Next, 142 parts of methacrylic acid, 0.27 parts of methoquinone, and 10.8 parts of dimethylbenzylamine were added, and the reaction was carried out at 90 ° C for 15 hours. Thereafter, 201 parts of tetrahydroanhydrophthalic acid was added, and after reacting at 90 ° C for 4 hours, 382 parts of propylene glycol monomethyl ether was added to obtain a weight average molecular weight (Mw) represented by the following formula: 2,000, alkali-soluble resin (resin Ae) with a solid acid value of 103 mg-KOH / g.

(In the formula, n represents an integer. Me represents a methyl group.)

(Synthesis example 6)

In a flask equipped with a cooling tube, a stirrer and a thermometer, 450 parts of propylene glycol monomethyl ether, 50 parts of p-vinyl benzoic acid, 12 parts of N-phenylmaleimide, and 2-hydroxyethyl methacrylic acid were placed. 20 parts of the ester and 18 parts of 2-ethylhexyl methacrylate were heated to 92 ° C while injecting nitrogen gas. Next, a solution prepared by dissolving 6 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) in 50 parts of propylene glycol monomethyl ether acetate was added and kept at the same temperature for 3 hours to make Its polymerization. Thereafter, a solution prepared by dissolving 3 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) in 26.7 parts of propylene glycol monomethyl ether acetate was added to raise the temperature of the reaction solution to At 100 ° C, the solution was polymerized by maintaining the temperature at this temperature for 1 hour to obtain a solution of the binder resin (resin Af) (solid content concentration = 16% by mass). The resin Af had a weight average molecular weight (Mw) of 9,850 and a solid acid value of 184 mg-KOH / g.

(Synthesis example 7)

Installed with reflux cooling pipe, nitrogen introduction pipe, thermometer and stirring device In a four-necked flask, 78 parts of α-chloroacrylic acid 3,3,4,4,5,5,6,6,6-nonafluorohexyl, 19.5 parts of methacrylic acid, 19.5 parts of isofluorenyl methacrylate, 13 parts of glycidyl methacrylate, 12.7 parts of dodecanethiol, and 266 parts of propylene glycol monomethyl ether acetate were heated to 70 ° C. and stirred under a nitrogen stream for 30 minutes. To this was added 1 part of azobisisobutyronitrile and polymerized for 18 hours to obtain a polymer (resin Fa) having a weight average molecular weight (Mw) of 7,500, a solid content of 33% by mass, and a solid content of an acid value of 68 mg-KOH / g. Its solution. The resin Fa has the following structural units.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resins obtained in Synthesis Examples 1 to 7 were measured using the GPC method under the following conditions.

Installation; K2479 ((share) Shimadzu Corporation)

Column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0mL / min

Detector; RI

The ratio of the weight-average molecular weight and the number-average molecular weight (Mw / Mn) obtained in terms of polystyrene conversion obtained above was used as the molecular weight distribution.

(Examples 1 to 5, Comparative Examples 1 to 3, and Reference Examples 1 to 4) <Adjustment of photosensitive resin composition 1 to 8>

In Examples 1 to 5, Comparative Examples 1 and Reference Examples 1 to 4, the components in Table 3 were mixed with a solvent (D) to be described later so that the solid content (%) became the ratio described in Table 3, and further sensitivity was obtained. Resin composition.

In Comparative Example 2, Zeocoat CP1010 (manufactured by Jayne Co., Ltd.) was used.

In Comparative Example 3, SU-83000 (manufactured by Nippon Kayaku Co., Ltd.) was diluted in propylene glycol monomethyl ether acetate having the same capacity as the material. Hereinafter, the photosensitive resin compositions of Examples 1 to 5 will be described as photosensitive resin compositions 1 to 5, and the photosensitive resin compositions of Comparative Examples 1 to 3 will be described as photosensitive resin compositions 6 to 8, respectively. The photosensitive resin compositions of Reference Examples 1 to 4 are described as photosensitive resin compositions 9 to 12, respectively.

Each component in Table 3 is shown below. The number of parts described in the column of resin represents parts by mass in terms of solid content.

Resin (A); Copolymer of Aa: p-hydroxystyrene and butyl acrylate [copolymerization ratio of 50:50, weight average molecular weight; 12600] (MARUKA LYNCUR (registered trademark) CBA; Maruzan Petrochemical Co., Ltd.) )

Resin (A); Ab: copolymer of p-hydroxystyrene and styrene [copolymerization ratio of 50:50, weight average molecular weight; 4000] (MARUKA LYNCUR (registered trademark) CST; Maruzan Petrochemical Co., Ltd.)

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

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

Resin (A); Ac: Resin Ac obtained in Synthesis Example 3

Resin (A); Ad; Resin Ad obtained in Synthesis Example 4

Resin (A); Ae; resin Ae obtained in Synthesis Example 5

Resin (A); Af; resin Af obtained in Synthesis Example 6

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

Polymerizable compound (B); Bb: Dipentaerythritol polyacrylate (A-9550; manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

Polymerizable compound (B); Bc: Denacol Acrylate DA-314 (manufactured by Nagase Chemtex)

Polymerizable compound (B); Bd: Ogsol EA-200 (manufactured by Osaka Gas Chemical Co., Ltd.)

Polymerization initiator (C); Ca; 2-methyl-2-morpholinyl-1- (4-methylsulfonylphenyl) propan-1-one (Irgacure (registered trademark) 907; manufactured by BASF Corporation )

Polymerization initiator (C); Cb; 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) but-1-one (Irgacure (registered trademark) 309; manufactured by BASF Corporation )

Polymerization initiator (C); Cc; 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-methyl (4-ethoxycarbonylphenyl) -1,2' -Bimidazole (manufactured by Hodogaya Chemical Industry Co., Ltd.)

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

Liquid repellent (F); Fa; Resin Fa obtained in Synthesis Example 7

Liquid repellent (F); Fb; Megafac (registered trademark) RS72 (manufactured by DIC)

Surfactant (G); Ga; polyether denatured polysiloxane surfactant "BYK330" (manufactured by Vic Chemical)

Surfactant (G); Gb; Fluorine surfactant Megafac (registered trademark) "F-554" (manufactured by DIC)

Adhesion enhancer (H); γ-glycidoxypropyltrimethoxysilane

Colored dispersion liquid (I); by a bead mill, 13 parts by mass of CI Pigment Red 254 / CI Pigment Red 177 / CI Pigment Yellow 150 = 50/35/15 (mass ratio) mixture, dispersant BYK-LPN21116 ( Amine value = 73, acid value = 0, manufactured by Bic-Chemy) 10 parts by mass of the solution (nonvolatile content = 40% by mass), and 77 parts by mass of propylene glycol monomethyl ether acetate as a solvent were mixed and dispersed for 12 hours By

The solvent (D) is a mixture of the following solvent components (Da) to (Dd) at a ratio shown in Table 4.

Solvent (D); Da; propylene glycol monomethyl ether acetate

Solvent (D); Db; ethyl 3-ethoxypropionate

Solvent (D); Dc; propylene glycol monomethyl ether

Solvent (D); Dd; 3-methoxybutyl acetate

The solid content of the photosensitive resin composition refers to those in which the components in Table 3 are separately mixed with the solvent (D) so as to be the "solid content (%)" in Table 3.

[Substrate cleaning]

Using a cleaning device (manufactured by Shibaura Co., Ltd.), the pure water was flowed to a glass substrate (Eagle XG manufactured by Corning Corporation) of 370 mm × 470 mm × 0.5 mm, and the surface was cleaned using a brush at the same time for 30 seconds. The pure water shower was additionally washed for 60 seconds, and then dried in the air.

[Make substrate with transparent conductive film]

An ITO target (manufactured by Tosoh Corporation; 90% In ₂ O _3- ) 10% SnO ₂ ), after heating in a heating chamber to 300 ° C., in a sputtering chamber, the transparent conductive film ITO was formed to a thickness of 50 nm under an electric power of 1.05 kW, an argon pressure of 0.6 Pa, and a film formation time of 115 seconds. Then, the film-formed substrate was annealed at 230 ° C. for 30 minutes in the air to obtain a glass substrate with ITO.

[Make a substrate with a wall] (Fabrication of a Substrate with a Partition Wall in Example 1)

For the substrate with a transparent conductive film produced as described above, a UV-O ₃ cleaning device (manufactured by Hitachi High-Technologies Corporation; PL3-200-15) was used to perform a hydrophilization treatment at a cumulative light amount of 400 mJ / cm ² and washed with pure water. Clean and dry in air. To this substrate, 30 g of the adjusted photosensitive resin composition 1 was dropped, and the film was formed by coating the photosensitive resin composition 1 with a spin coater at 900 rpm for 7 seconds. Thereafter, it was dried under reduced pressure at 66 Pa in a vacuum drying apparatus (manufactured by Tokyo Chemical Industry Co., Ltd .; TR28340CPD-CLT), and pre-baked by contacting it on a hot plate at 110 ° C. for 110 seconds. Next, exposure was performed using an exposure device (manufactured by Hitachi High-Tech; LE4000A). The exposure amount was set to 200 mJ / cm ² , and the Gap was set to 100 μm. The photomask is a shape in which a pattern is formed on the same plane (the shape of the light-shielding portion is a rectangle (long circle) of 300 μm in the long axis direction and 100 μm in the short axis direction, and its four corners are cut out in an arc shape). Thereafter, a developing solution prepared by diluting an aqueous tetramethylammonium hydroxide solution (tokuso SD25, manufactured by Tokuyama Co., Ltd.) with pure water to a concentration of 2.38% was used to rinse the developing machine (Sefatec Corporation). The coating film was developed at 23 ° C for 80 seconds, washed with water and air-dried, and then baked in an oven (ESPEC: HSC-4) at 230 ° C for 20 minutes to obtain a pattern. .

(Production of substrates with partition walls in Examples 2 to 5 and Comparative Example 1)

Except that the photosensitive resin composition 2 was replaced with the photosensitive resin composition 2 to 6, the same procedures as in Example 1 were carried out to prepare substrates with partition walls in Examples 2 to 5 and Comparative Example 1.

(Production of the substrate with a partition wall of Comparative Example 2)

Instead of the photosensitive resin composition 1, the photosensitive resin composition 7 is used instead, and a pattern formed on the same plane is used (the shape of the opening is a rectangle of 300 μm from the major axis direction and 100 μm from the minor axis direction. A photomask with a shape (oblong) formed by cutting off its four corners was exposed and subjected to post-baking at 230 ° C for 60 minutes. The rest was implemented in the same manner as in Example 1 to make a partition with a partition wall of Comparative Example 2. Substrate.

(Production of a substrate with a partition wall in Comparative Example 3)

Except for using photosensitive resin composition 8 instead of photosensitive resin composition 1, and using propylene glycol monomethyl ether acetate as the developing liquid system, shaking at 23 ° C for 80 seconds and simultaneously dipping for development, etc. It carried out similarly to Example 1, and produced the board | substrate with a partition wall of Comparative Example 3.

Except that instead of the photosensitive resin composition 1, the photosensitive resin compositions 9 to 12 were used, and the rest were implemented in the same manner as in Example 1 to prepare the substrates with partition walls of Reference Examples 1 to 4.

[Preparation of solution for coating property evaluation]

Select 2 types of N, N-dimethylacetamide (made by Wako Pure Chemical Industries, Ltd., 99.5% or more), 1,3-dimethyl-2-imidazolinone (made by Tokyo Chemical Industry Co., Ltd., 99.0% or more) As a solvent for evaluating the coating property of the partition wall. Due to the low viscosity of the two types of solvents selected, in order to allow the inkjet device to be filled with liquid in the next wall, cyclohexanol (manufactured by Wako Pure Chemical Industries, Ltd., 98.0% or more) was used as the viscosity adjustment material. As a mixed solvent.

When only the solvent itself is used, it is difficult to observe the spreadability of the coating after drying under a microscope. Therefore, Rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd., purity 95% or higher) was used as the solute.

Three types of solutions 1, 2, 3 are prepared as shown in Table 5 below.

[Check method of opening]

When observing the patterned substrate using a microscope (MX61L manufactured by OLIMPUS, lens LMPFLN10xBD), the organic film that can be confirmed under the microscope at the aforementioned magnification is regarded as a partition wall, and the partition wall is stored on the substrate and the magnification is The organic film cannot be observed under a microscope, and the part where the electrode is exposed is regarded as an opening.

[Coatability evaluation]

In the partition wall, an inkjet device (Litlex 120L manufactured by ULVAC) was used to fill the above solutions 1, 200, and 200 pL in each partition wall and 1000 partition walls. After drying, use a microscope (MX61L manufactured by OLIMPUS, Lens LCPFLN20xLCD) to observe whether the solute spreads to the end of the next wall, and observe 30 places, When the coating was spread at all 30 places, the coating property was considered good.

The next wall used this time is in a state of no liquid repellency As the evaluator is implemented next, when the solution is filled, leakage may occur from the partition wall. Therefore, the remaining liquid in the partition wall is used to evaluate the spreadability of the coating.

[Polarity evaluation] (Contact angle measurement)

Use the exposed part of ITO in the substrate after the next wall is made. Use pure water, glycerol (made by Sigma-Aldrich, purity 99.5% or more), formamidine (made by Sigma-Aldrich, purity 99.5% or more), two Four types of solvents of methyl iodide (made by Sigma-Aldrich Co., Ltd., purity: 99%) were measured at three points in the plane of the substrate, averaged, and evaluated.

(Polarity calculation)

The polarity calculation is based on the Owensand Wendt method described above. In this embodiment, the contact angle is measured using the above-mentioned four types of solvents, and based on this value, the polarity calculation software disclosed by the following URL is used to calculate the value of the polar component of the surface free energy of the electrode according to the Owensand Wendt method.

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

The results of Examples, Comparative Examples and Reference Examples are shown in Table 6. In Table 6, "○" indicates good, and "×" indicates bad.

From the results of the above examples, it can be found that if the photosensitive resin composition of the present invention is used, the surface of the ITO after the pattern exposed on the electrode surface is formed, the value of the polar component that can obtain the surface free energy is high, and ITO Pattern with excellent surface coating.

Industrial availability

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

Claims (11)

A photosensitive resin composition is formed by using the photosensitive resin composition to form a thin film made of the photosensitive resin composition on a substrate on which an electrode has been formed, and then using a photolithography method to make the electrode thin on the film. The value of the polar component of the free energy on the surface of the electrode after the surface is exposed to form an opening is 15 mN / m or more; wherein the photosensitive resin composition includes the following (A), (B), and (C); (A) has Resin containing a structural unit represented by the following formula [i] and a structure in which an unsaturated alicyclic hydrocarbon is subjected to epoxidation (In formula [i], R1, R2, R3, R4, and R5 each independently represent -OH, -SH, -COOH, -CHO, hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms, -COR7, -COOR7, -OCOR7, or -OR7, at least one of R1, R2, R3, R4, and R5 is -OH, -SH, -COOH, or -CHO; R7 represents an alkyl group having 1 to 8 carbon atoms, and 2 ~ (Alkoxyalkyl, aryl or benzyl) of 5) (B) Polymerizable compound (C) Polymerization initiator. The photosensitive resin composition according to claim 1, wherein the aforementioned structural unit is represented by the following formula [ii], (In the formula [ii], R1, R2, R3, R4, and R5 represent the same meaning as described above, and R6 represents a hydrogen atom, a methyl group, or an ethyl group). The photosensitive resin composition according to claim 1 or 2, wherein the (C) polymerization initiator is a photopolymerization initiator, and the polymerizable compound is polymerized by radical polymerization. The photosensitive resin composition according to claim 1 or 2, wherein at least one of the aforementioned R1, R2, R3, R4, and R5 is -COOH or -OH, and the other is a hydrogen atom. The photosensitive resin composition according to claim 1 or 2, further comprising a liquid repellent. The photosensitive resin composition according to claim 5, wherein the liquid-repellent agent is a polymer including a structural unit derived from an unsaturated compound having a perfluoroalkyl group having 4 to 6 carbon atoms. A partition wall formed by the photosensitive resin composition according to any one of claims 1 to 6. A substrate is provided with a partition wall and an electrode as in claim 7. The substrate according to claim 8, wherein the aforementioned electrode is a transparent electrode. A display device includes a substrate as claimed in claim 9. A substrate evaluation method comprising forming a thin film made of a photosensitive resin composition according to any one of claims 1 to 6 on a substrate on which an electrode has been formed, and using a photolithography method to make the electrode on the thin film. An opening was formed on the exposed surface of the electrode, and the coating property of the electrode was evaluated based on the value of the polar component of the surface free energy of the electrode.