TW201546543A - Photosensitive resin composition - Google Patents

Abstract

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

Description

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 a display device or the like in recent years, an ITO electrode, an organic EL display element, a circuit wiring board, or the like of a color filter, a liquid crystal display element, or the like is produced by a coating method such as an inkjet method. In the method of forming an element by such a coating method, a partition wall formed using a photosensitive resin composition is used.

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

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 technical literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2012-73603

As described above, once the photosensitive resin composition is formed on the electrode, it is removed from the electrode at the time of patterning, but the coating property to the surface of the electrode is based on the photosensitive resin composition. It varies depending on the type. Therefore, depending on the kind of the photosensitive resin composition, the ink applied to the electrode is not coated on the electrode, and in the photosensitive resin composition previously proposed, the coating on the inner electrode of the partition opening is applied. There is also a case where the spreadability of the ink is not necessarily satisfied. Accordingly, an object of the present invention is to provide a photosensitive resin composition which is excellent in coating spreadability of the ink applied to the electrode obtained after the pattern formation is formed on the entire inner surface of the partition opening.

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

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

[2] The photosensitive resin composition of [1], wherein the photosensitive resin composition contains the following (A), (B), and (C).

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

(In the 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 a carbon number of 2~ 5 alkoxyalkyl, aryl or benzyl.)

(B) Polymeric compound

(C) polymerization initiator

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

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

[4] The photosensitive resin composition of [2] or [3], wherein the aforementioned The polymerization initiator is a photopolymerization initiator, and the above 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 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] which further comprises a liquid repellent.

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

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

[9] A partition wall formed of the photosensitive resin composition according to any one of [1] to [8].

[10] A substrate comprising the partition wall of [9] and an electrode.

[11] A display device comprising the substrate of [10].

[12] A substrate evaluation method in which a film composed of a photosensitive resin composition is formed on a substrate on which an electrode is formed, and an opening is formed by exposing a surface of the electrode to the film by photolithography. The coatability 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 to the electrode after the pattern formation can be obtained on the entire inner surface of the partition opening A substrate with a partition wall excellent in spreadability is applied.

1‧‧‧ display device

2‧‧‧Support substrate

3‧‧‧ next door

4‧‧‧Organic EL components

4R‧‧‧Red Organic EL Components

4G‧‧‧Green Organic EL Components

4B‧‧‧Blue organic EL components

5‧‧‧ recess (opening)

6‧‧‧1st electrode

7‧‧‧1st organic EL layer (hole injection layer)

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

10‧‧‧2nd electrode

1 is a cross-sectional view schematically showing a portion 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 resin composition comprising a film composed of a photosensitive resin composition on a substrate on which an electrode has been formed, and a second electrode formed by exposing the surface of the electrode on the film by photolithography The value of the polar component of the surface free energy is 15 mN/m or more.

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

The photosensitive resin composition was supplied onto the substrate on which the electrode was formed, and the substrate was rotated at 900 rpm for 7 seconds to form a film composed of the photosensitive resin composition, and the substrate on which the film was formed was dried under reduced pressure at 66 Pa. Then, prebaking was performed at 110 ° C for 110 seconds, and secondly, the pre-baked film was exposed at 200 mJ/cm ² to expose the surface of the electrode, and 2.38 mass% of hydroxide was used. The methylammonium aqueous solution was imaged at 23 ° C for 80 seconds, and after water washing, post-baking was performed, and the surface of the electrode exposed at the opening of the film was freely formed by photolithography on the film. A photosensitive resin composition having a polar component of energy of 15 mN/m or more.

One aspect of the substrate on which the electrode has been formed is an ITO-attached glass substrate which is provided with an ITO target in a sputtering apparatus, and is heated to 300 ° C in a heating chamber, and has a power of 1.05 kW and argon in the sputtering chamber. The transparent conductive film ITO was formed into a film of 50 nm on the substrate at a gas pressure of 0.6 Pa and a film formation time of 115 seconds, and the substrate after the film formation was further annealed at 230 ° C for 30 minutes in the atmosphere.

Using such a photosensitive resin composition, an electrode has been formed When the partition wall is formed on the substrate, when the ink containing the film material to be formed on the electrode is applied to the electrode, since the ink is applied to the electrode without being repelled on the electrode, it is dried by drying. When the curing is carried out, a flat film can be formed on the entire surface in the opening of the partition wall.

An electrode after the opening is formed, that is, a film after the opening is formed 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, more preferably 15.5 mN/m or more.

From the viewpoint of coating properties, the electrode after the opening is formed, that is, The value of the polar component of the surface free energy of the electrode exposed to the opening of the film after the opening is not particularly limited, but 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 electrode having the opening, that is, the value of the polar component of the surface free energy of the electrode exposed to the opening of the film after the opening is not particularly limited as long as it is 15 mN/m or more, and for example, acrylic acid generally used is exemplified. Resins, polyimine 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) a resin having a structural unit containing a group represented by the following formula [i]

(B) Polymeric compound

(C) polymerization initiator

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

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

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

In the above formulae [i] and [ii], R1, R2, R3, R4 and R5 each independently represent -OH, -SH, -COOH, -CHO, a hydrogen atom, a halogen atom, and an alkyl group having 1 to 3 carbon atoms. And -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, an alkoxyalkyl group having 2 to 5 carbon atoms, an aryl group or a benzyl group. R6 represents a hydrogen atom, a methyl group or an ethyl group.

And, from the viewpoint of coatability on the surface of the electrode, the aforementioned At least one of R1, R2, R3, R4 and R5 is -COOH or -OH, and a R1, R2, R3, R4, and R5-based hydrogen atom which is different from -COOH or -OH is preferred.

Further, only in the formula [i], [ii], when at least one of R1, R2, R3, R4 and R5 is -OH, -SH, -COOH or -CHO, each of them can independently be 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, the R7 series represents the same meaning as described 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 better.

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

Examples of the alkoxyalkyl group having 2 to 5 carbon atoms include methoxy Methyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propylmethyl, propylethyl, methoxymethyl Methoxyethyl is preferred.

As the aryl group, a phenyl group or a naphthyl group can be exemplified. However, it is not limited to this 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-vinylbenzoic acid, m-vinyl Benzoic acid, p-vinylbenzoic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3-vinyl decanoic acid monomethyl ester, 3 -vinyl phthalate monoethyl ester, 5-vinyl isophthalic acid, 5-vinylisodecanoic acid monomethyl ester, 5-vinylisodecanoic acid monoethyl ester, 4-vinyl lauric acid, 5 -vinyl lauric acid, 5-vinyl sulphonaldehyde, 5-vinyl acetyl sulphate, 4-vinyl benzene sulfonate ethyl 4-vinyl resorcinol, 4-vinyl resorcinol Methoxymethyl ether, 4-vinyl resorcinol bismethoxymethyl ether, 4-vinylisophthalic acid Mono-methoxyethyl ether, resorcinol bis 4-vinyl-methoxyethyl ether, 4-vinyl-benzonitrile, 4-vinyl-benzenepropanoic acid, methyl 4-vinyl-phenylpropionic acid The base or the like is preferably o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid. Moreover, (a) is not subject to the above examples.

Further, the photosensitive resin composition of the present invention may also contain Resin other than the resin (A) (hereinafter also referred to as "resin (A1)"), solvent (D), polymerization initiator (E), liquid repellent (F), surfactant ( G), at least one of the groups of the adhesion enhancer (H).

In addition, in this specification, as an example of each component The compounds, unless specifically defined otherwise, can be used alone or in combination with a user.

The resin (A) may further comprise a monomer (x) derived from (a) (in terms of There are also structural units called "(x)").

(x) only monomers other than (a) and have no carbon number 4~6 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 referred to as "(b)"), and selection. At least one monomer (e) (hereinafter also referred to as "(e)") and other monomers (c) in which a group of free unsaturated carboxylic acids and unsaturated carboxylic anhydrides are grouped (hereinafter also referred to as "( In the case of c)", (b) or (c) is preferred among these.

(b) is a cyclic ether structure having a carbon number of 2 to 4 (for example, selected from The monomer of at least one of the group consisting of an oxirane ring, a propylene oxide ring and a tetrahydrofuran ring is preferably a monomer having a cyclic ether structure of 2 to 4 carbon atoms and an ethylenically unsaturated double bond. More preferably, it is a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloxy group.

As (b), for example, a single sheet having an oxirane group The body (b1) (hereinafter also referred to as "(b1)"), the propylene oxide group-containing monomer (b2) (hereinafter also referred to as "(b2)"), and the tetrahydrofuranyl group Body (b3) (hereinafter also referred to as "(b3)").

As (b1), it may be, for example, a linear or branched chain. A monomer (b1-1) having an epoxidized structure of an unsaturated aliphatic hydrocarbon (hereinafter also referred to as "(b1-1)"), and a monomer having an epoxidized structure of an unsaturated alicyclic hydrocarbon (b1) -2) (The following is also called "(b1-2)").

(b1) having an oxiranyl group and a (meth) acryloxy group The monomer is preferably a monomer having a structure in which an unsaturated alicyclic hydrocarbon is subjected to an epoxidation and a (meth)acryloxy group. When it is such a monomer, the photosensitive resin composition is excellent in storage stability.

Specific examples of (b1-1) include a glycidyl group (methyl group). Acrylate, β-methylepoxypropyl (meth) acrylate, β-ethyl epoxypropyl (meth) acrylate, epoxypropyl vinyl ether, o-vinyl benzyl epoxide Ether, m-vinylbenzyl epoxypropyl ether, p-vinylbenzyl epoxypropyl ether, α-methyl-o-vinylbenzyl epoxypropyl ether, α-methyl-m -vinylbenzylepoxypropyl ether, α-methyl-p-vinylbenzylepoxypropyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-double (glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3, 4-gin (glycidoxymethyl)styrene, 2,3,5-glycol (glycidoxymethyl)styrene, 2,3,6-glycol (glycidoxymethyl) Styrene, 3,4,5-glycol (glycidoxymethyl)styrene, 2,4,6-glycol (glycidoxymethyl)styrene, Japanese Patent Laid-Open No. Hei 7-248625 The compound or the like described.

(b1-2), for example, monooxyethylene cyclohexene, 1,2-epoxy-4-vinylcyclohexane (for example, Ceroxide 2000; manufactured by Dale Chemicals Co., Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer A400; Dell Chemical Industry Co., Ltd., 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Dell Chemical Industry Co., Ltd.), a compound represented by the formula (I), and a formula (II) ) the compound represented by the like.

In the formulae (I) and (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 with 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 the bond with O. ]

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

The alkyl group which may be substituted by a hydroxyl group may, for example, be a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, or a 1- Hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

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

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

X ¹ and X ^{2 are} preferably a single bond, a methylene group, a vinyl group, a *-CH ₂ -O- (* represents a bond with O) group, and a *-CH ₂ CH ₂ -O- group. More preferably, it is a single bond, *-CH ₂ CH ₂ -O- group.

The compound represented by the formula (I) is exemplified by the formula (I-1)~ A compound represented by any one of the formula (I-15) and the like. Wherein, the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9) or the formula (I-11) to the formula (I- 15) The compound represented by the formula (I-1), the formula (I-7), the formula (I-9) or the formula (I-15) is preferred.

The compound represented by the formula (II) may, for example, be a compound represented by any one of the formulae (II-1) to (II-15). Wherein, also by formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11)~ formula (II- 15) The compound represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15) is 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. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the content ratio [the compound represented by the formula (I): the compound represented by the formula (II)] is on the molar basis. It is preferably 5:95 to 95:5, preferably 20:80 to 80:20.

(b2) is preferably a monomer having an oxypropylene group and a (meth)acryloxy group. As (b2), for example, 3-methyl-3-(meth)acryloxymethyl propylene oxide, 3-ethyl-3-(methyl) propylene methoxymethyl epoxy Propane, 3-methyl-3-(methyl)propenyloxyethyl propylene oxide, 3-ethyl-3-(methyl) propylene methoxyethyl propylene oxide, and the like.

(b3) is preferably a monomer having a tetrahydrofuranyl group and a (meth)acryloxy 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 the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, maleic acid, citraconic acid, mesaconic acid, itaconic acid, 1, 4-cyclohexene dicarboxylic acid, and methyl-5. -nordecene-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-(methyl)propenyloxyethyl], α-(hydroxymethyl) ) Acrylic, etc.

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

Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and sec-butyl (methyl). Alkyl esters of acrylate, tert-butyl (meth) acrylate, etc.; cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6} ] decane-8-yl (meth) acrylate (common name in the art is called dicyclopentanyl (meth) acrylate), dicyclopentanyloxyethyl (A) Acrylate, tricyclo [5.2.1.0 ^2,6 ]nonene-8-yl (meth) acrylate (in the technical field, the conventional name is called "dicyclopentenyl (methyl)) a cycloalkyl ester such as acrylate") or an isodecyl (meth) acrylate; a hydroxyalkyl group such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate An ester; an aryl group such as a phenyl (meth) acrylate or a benzyl (meth) acrylate; and an aralkyl ester.

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

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

Examples of the N-substituted maleimide group include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-amber. Amino-3-maleimide benzoate, N-succinimide-4-maleimine butyrate, N-succinimide-6-maleimine An acid ester, N-succinimide-3-maleimide propionate, N-(9-acridinyl)maleimide or 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-ethyl bicyclol. [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-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl Bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]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]g 2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5, a bicyclic unsaturated compound such as 6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene.

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.

As other vinyl compounds, for example, (meth) propylene Nitrile, vinyl chloride, dichloroethylene, (meth) acrylamide, vinyl acetate, 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butane Alkene and the like.

The resin (A) may be composed only of structural units derived from (a) Resin, but it is preferably a resin composed of a structural unit derived from (a) and a structural unit derived from (x).

In the resin (A) is derived from the structural unit derived from (a) and derived from (x) The resin composed of the structural unit is based on the construction sheet used in (a) The acidity of the bit differs, but the ratio of the structural units derived from the respective monomers is preferably in the following range with respect to the total number of moles of the structural unit of the constituent resin (A).

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

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

When the ratio of the structural unit of the resin (A) is within the above range, the storage stability of the photosensitive resin composition, the development property when the photosensitive resin composition forms a pattern, and the obtained coating film and pattern are obtained. The solvent resistance, heat resistance and mechanical strength of the type tend to be good.

In particular, when any one of R1 to R5 is -COOH, the ratio of the structural units derived from the respective monomers is preferably in the following range with respect to the total number of moles of the structural unit constituting the resin (A). .

From (a) structural unit; 5~50 m%

Structural unit derived from (x); 50~95 mol%

The resin (A) can be referred to, for example, the method described in the document "Polymer Synthesis Experiment Method" (Otsuka Ryokan, Ltd., 1st Edition, 1st Edition, 1st issue, March 1, 1972). The cited documents are manufactured.

Specifically, it is exemplified that a predetermined amount of (a), a polymerization initiator, a solvent, and the like, which are used as necessary, are placed in a reaction vessel, for example, by using nitrogen instead of the atmosphere to form deoxidation. Environment, mixing and heating and keeping warm. Further, the polymerization initiator, the solvent and the like used herein are not particularly limited, and any one of ordinary users in the 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, and the solvent (D) of the photosensitive resin composition may be a solvent or the like described later. In order to adjust the molecular weight of the obtained resin, a chain transfer agent may also be added during the polymerization reaction. Examples of the chain transfer agent include n-butanethiol, tert-butanethiol, n-dodecylmercaptan, 2-sulfonylethanol, thioglycolic acid, ethyl thioglycolate, and thioglycolic acid. 2-ethylhexyl ester, methoxybutyl thioglycolate, 3-sulfonyl propionic acid, sulfonyl group-containing polyoxyl (KF-2001: manufactured by Shin-Etsu Chemical Co., Ltd.), thiol, chloroform, tetra A halogenated alkyl group such as carbon chloride or carbon tetrabromide.

In particular, (a) in the case of having a phenolic hydroxyl group, in polymerization Further, a monomer which previously protected the phenolic hydroxyl group (a) with a protecting group may also be used. The protective group may, for example, be a tertiary alkyl group such as tert-butyl or a fluorenyl group such as an ethenyl group.

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

Moreover, the obtained polymer system can be directly used after the reaction. As the solution, a concentrated or diluted solution may be used, or a solid (powder) may be taken out by a method such as reprecipitation. In particular, in the case of the polymerization, the solvent after the reaction can be used as the solvent by using the same solvent as the solvent (D) described later, and the production step can be simplified.

Polystyrene-converted weight average molecular weight of resin (A) It is preferably 3,000 to 100,000, preferably 5,000 to 50,000. When the weight average molecular weight of the resin (A) is within the above range, the coating property tends to be excellent, and the film of the exposed portion is less likely to be formed 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 from 1.1 to 6.0, preferably from 1.2 to 4.0. When the molecular weight distribution is within the above range, the development property tends to be excellent.

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

The content of the resin (A) is preferably from 5 to 95% by mass, preferably from 20 to 80% by mass, based on the total of the resin (A), the resin (A1) and the polymerizable compound (C). 45~80% by mass. When the content of the resin (A) is within the above range, the development of the photosensitive resin composition tends to be good, and the obtained pattern adhesion, solvent resistance, and mechanical properties tend to be good.

The photosensitive resin composition of the present invention may further contain a liquid repellent (F). The liquid-repellent agent (F) is a resin which exhibits liquid repellency, and the surface of the structure after the pattern formation is higher than the structure monomer, and the substance to be used is not particularly limited, but It is preferred that the contact angle of the anisole on the surface of the structure is 30 or more. The resin used for exhibiting liquid repellency may, for example, be a perfluoroalkyl group having a carbon number of 1 to 8 (may also be present between 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)"). The polymer.

(d) is a compound 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 by a halogen atom or a hydroxyl group. X ^d represents a single bond, an aliphatic hydrocarbon group having a carbon number of 1 to 10, an alicyclic hydrocarbon group having a carbon number of 3 to 10, or an aromatic hydrocarbon group having a carbon number of 6 to 12, which is an aliphatic hydrocarbon group. And -CH ₂ - contained in the alicyclic hydrocarbon group may be substituted by -O-, -CO-, -NR ^e -, -S- or -SO ₂ -. ]

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

Examples of the alkyl group having 1 to 21 carbon atoms in R ^d include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n- a linear alkyl group such as octyl, n-fluorenyl or n-fluorenyl; 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-B 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- A branched chain alkyl group such as ethyl-3-methylbutyl group.

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

The divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms in X ^d may, for example, be a methylene group, a vinyl group, a propane-1,3-diyl group, a ethane-1,2-diyl group or a butyl group-1. ,4-diyl, butyl-1,3-diyl, butyl-1,2-diyl, pent-1,5-diyl, hex-1,6-diyl, more-1,7-diyl An alkanediyl group such as octane-1,8-diyl.

Examples of the alicyclic hydrocarbon group having a carbon number of 3 to 10 in X ^d include a cyclopropyldiyl group, a cyclobutyldiyl group, a cyclopentadienyl group, a cyclohexanediyl group, a cycloheptanediyl group, and a ring.癸二基基等.

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

X ^d substituted by -CH ₂ - by -O-, -CO-, -NR ^e -, -S- or -SO ₂ - may, for example, be a formula (xd-1) to (xd-10) The base represented.

X ^d is preferably a C 2 to 6 alkanediyl group, and a vinyl group is preferred.

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

[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. ]

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

Resin (F) is comprised of structural units derived from (d) and derived from The copolymer of the structural unit of (e) is preferred, and it is preferred to include a structural unit derived from (d) and a structural unit derived from (e) and a structural unit derived from (b). Since the resin (F) contains a structural unit derived from (e), it is excellent in developability, and thus the unevenness due to residue or development tends to be suppressed. The resin (F) is preferred because it contains a structural unit derived from (b) and has excellent solvent resistance. Further, the resin (F) may also contain a structural unit derived from (c). Examples of (e), (b), and (c) are the same as described above.

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

The structural unit derived from (e); 5 to 50% by mass (preferably 10 to 40% by mass)

The structural unit derived from (d); 50 to 95% by mass (preferably 70 to 90% by mass)

When the resin (F) is a copolymer of (e), (b), and (d), the ratio of the structural unit derived from each monomer is based on the total number of moles of the structural unit constituting the resin (F). The following range is preferred.

The structural unit derived from (e); 5 to 40% by mass (preferably 10 to 30% by mass)

The structural unit derived from (b); 5 to 80% by mass (preferably 10 to 70% by mass)

The structural unit derived from (d); 10 to 80% by mass (preferably 20 to 70% by mass)

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

The structural unit derived from (e); 5 to 40% by mass (preferably 10 to 30% by mass)

The structural unit derived from (b); 5 to 70% by mass (preferably 10 to 60% by mass)

The structural unit derived from (c); 10 to 50% by mass (preferably 20 to 40% by mass)

The structural unit derived from (d); 10 to 80% by mass (preferably 20 to 70% by mass)

When the ratio of each structural unit is in the above range, the liquid repellency and the development property tend to be excellent.

The polystyrene-equivalent weight average molecular weight of the resin (F) is preferably 3,000 to 20,000, preferably 5,000 to 15,000. When the weight average molecular weight of the resin (F) is in the above range, the coating property tends to be excellent, and the film of the exposed portion is less likely to be formed 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, preferably 40 to 150 mgKOH/g.

The content of the resin (F) is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the total of the resin (A), the resin (A1) and the polymerizable compound (B). When the content of the resin (F) is within the above range, the image forming property is excellent at the time of pattern formation, and the pattern obtained is preferred in 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). As the resin (A1), for example,

Resin (A1-1): a copolymer obtained by polymerizing (e) and (b), and a resin (A1-2): a copolymer obtained by polymerizing (e) and (b) and (c), and a resin ( A1-3): a copolymer obtained by polymerizing (e) and (c), a resin (A1-4): a copolymer obtained by polymerizing (e) and (c) and (b) A resin or a resin (A1-5) which is obtained: a resin obtained by polymerizing (b) and (c) and a resin obtained by reacting (e).

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

In the resin (A1-1), the ratio of the structural units derived from the respective monomers is preferably in the following range with respect to the total number of moles of the total structural unit constituting the resin (A1-1).

The structural unit derived from (e); 5 to 60 mol% (preferably 10 to 50 mol%)

The structural unit derived from (b); 40 to 95 mol% (preferably 50 to 90 mol%)

When the ratio of the structural unit of the resin (A1-1) is within the above range, the storage stability of the photosensitive resin composition, the development property when the photosensitive resin composition forms a pattern, and the obtained coating film and The solvent resistance of the pattern tends to be good.

In the resin (A1-2), the ratio of the structural units derived from the respective monomers is preferably in the following range with respect to the total number of moles of the total structural unit constituting the resin (A1-2).

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

The structural unit derived from (b); 2 to 95 mol% (preferably 5 to 80 mol%)

The structural unit derived from (c); 1 to 65 mol% (preferably 5 to 60 mol%)

When the ratio of the structural unit of the resin (A1-2) is within the above range, the storage stability of the photosensitive resin composition, the development property when the photosensitive resin composition forms a pattern, and the obtained coating film and The solvent resistance of the pattern tends to be good.

In the resin (A1-3), the ratio of the structural units derived from the respective monomers is preferably in the following range with respect to the total number of moles of the total structural unit constituting the resin (A1-3).

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

Structural unit derived from (c); 60 to 98 mol% (preferably 65 to 95 mol%)

When 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 development property when the photosensitive resin composition forms a pattern, and the obtained coating film and The solvent resistance of the pattern tends to be good.

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, via a two-stage process. In this case, please refer to the above-mentioned document "Experimental method for polymer synthesis" (the method described in the issue of the first issue of the first issue of the Otsuka Ryokan, Ltd.). The method described in the publication No. -89533 is manufactured.

First, as the first stage, the copolymer of (e) and (c) was obtained in the same manner as in the production method of the above resin (A).

In this case, as in the above, the copolymer obtained may be used as it is, or may be used as a solid (powder) by reprecipitation or the like. Further, it is preferable to form a weight average molecular weight and a molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] in terms of polystyrene as described above.

However, the ratio of the structural units derived from (e) and (c) is preferably in the following range with respect to the total number of moles constituting the total structural unit of the copolymer.

The structural unit derived from (e); 5 to 50 mol% (preferably 10 to 45 mol%)

The structural unit derived from (c); 50 to 95% by mole (preferably 55 to 90% by 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 the above (b). Since the reactivity of the cyclic ether is high and the unreacted (b) is not easily retained, the (b) used in the resin (A1-4) is preferably (b1) or (b2), and (b1-1) is Preferably.

Specifically, in the above, the environment inside the flask was replaced with nitrogen from air, and the number of moles relative to (e) was 580 mol% (b), relative to (e), (b), and (c). a total of 0.001 to 5% by mass of a reaction catalyst for a carboxyl group and a cyclic ether (for example, dimethylaminomethyl phenol), and relative to (e), (b), and (c) a polymerization inhibitor of 0.001 to 5% by mass (for example, hydroquinone or the like) is placed in a flask and allowed to react at 60 to 130 ° C for 1 to 10 hours to obtain a resin (A1-4). Further, similarly to the polymerization conditions, the addition method or the reaction temperature may be appropriately adjusted in consideration of the production equipment or the calorific value due to the polymerization.

Further, in this case, the number of moles of (b) is preferably from 10 to 75 mol%, preferably from 15 to 70 mol%, based on the number of moles of (e). In this range, the storage stability of the photosensitive resin composition, the development performance when the photosensitive resin composition forms a pattern, and the solvent resistance, heat resistance, and mechanical properties of the obtained coating film and pattern are obtained. The balance of strength and sensitivity becomes a good tendency.

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

In this case, as in the above, the copolymer obtained may be used as it is, or may be used as a solid (powder) by reprecipitation or the like.

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

The structural unit derived from (b); 5 to 95 mol% (preferably 10 to 90 mol%)

The structural unit derived from (c); 5 to 95 mol% (preferably 10 to 90 mol%)

Further, in the same manner as the method for producing the resin (A1-4), the cyclic ether derived from (b) and (e) in the copolymer of (b) and (c) can be used. It is obtained by reacting a carboxylic acid or a carboxylic acid anhydride. The hydroxyl group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride can also be reacted with a carboxylic acid anhydride.

The amount of (e) used in the reaction with the aforementioned copolymer is relative In the case of the number of moles of (b), it is preferably from 5 to 80 mol%. Since (b) is less likely to remain due to the reactivity of the cyclic ether and unreacted, (b) is preferably (b1), and (b1-1) is preferred.

Polystyrene-equivalent weight average molecular weight of resin (A1) It is preferably 3,000 to 100,000, preferably 5,000 to 50,000. When the weight average molecular weight of the resin (A1) is within the above range, the coating property tends to be excellent, and the film of the exposed portion is less likely to be formed 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 from 1.1 to 6.0, preferably from 1.2 to 4.0. When the molecular weight distribution is within the above range, the development property tends to be excellent.

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

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

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

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 is polymerized by the generation of the active radical, for example, a compound having an ethylenically unsaturated bond, etc., is preferably a (meth) acrylate compound.

As a polymerizable compound having one ethylenically unsaturated bond The compound (B) is the same as the compounds exemplified as the above (a), (b) and (c), and among them, (meth) acrylates are preferred.

As a polymerizable compound having two ethylenically unsaturated bonds The substance (B) may, for example, be 1,3-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylate or 1,6-hexanediol di(methyl). 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, bisphenol A bis(acryloyloxyethyl)ether, ethoxylated bisphenol A di(meth)acrylate, C Oxylated neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, 3-methylpentanediol di(meth)acrylate, and the like.

As a polymerizable property having three or more ethylenically unsaturated bonds The compound (B) may, for example, be trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate or gin(2-hydroxyethyl)isocyanate tri(methyl). Acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol five ( Methyl) acrylate, two Pentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, three a reaction of pentaerythritol octa (meth) acrylate, pentaerythritol tri(meth) acrylate with an acid anhydride, a reaction of dipentaerythritol penta (meth) acrylate with an acid anhydride, tripentaerythritol hepta (meth) acrylate and an acid 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 denatured pentaerythritol tetra(meth)acrylate, caprolactone denatured dipentaerythritol penta (meth) acrylate, caprolactone denatured dipentaerythritol hexa(meth) acrylate, Caprolactone denatured tripentaerythritol tetrakis(meth)acrylate, caprolactone denatured tripentaerythritol penta (meth) acrylate, caprolactone denatured tripentaerythritol hexa(meth) acrylate, caprolactone denatured tripentaerythritol VII ( Methacrylate , caprolactone denatured tripentaerythritol octa (meth) acrylate, caprolactone denatured pentaerythritol tri(meth) acrylate and anhydride reaction, caprolactone denatured dipentaerythritol penta (meth) acrylate and anhydride reaction And caprolactone denatured the reaction product of tripentaerythritol hepta (meth) acrylate with an acid anhydride.

Among them, a polymerizable compound (B) having three or more ethylenically unsaturated bonds is preferred, and dipentaerythritol hexa(meth) acrylate, trimethylolpropane tri(meth) acrylate, pentaerythritol tri ( Methyl) acrylate 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). Preferably, it is preferably 20 to 80% by mass.

If the content of the polymerizable compound (B) is within the aforementioned range, In addition, there is a tendency that the intensity, smoothness, and reliability of the sensitivity or the acquired pattern become good.

The photosensitive resin composition of the present invention contains a polymerization initiator (C). The polymerization initiator (C) can be a compound which can be polymerized by the action of light or heat, that is, a known polymerization initiator can be used without particular limitation.

As the polymerization initiator (C), for example, hydrazine compound A compound, an alkylphenone compound, a biimidazole compound, a triazine compound, and a mercaptophosphine oxide compound. Further, a photo-and/or thermal cationic polymerization initiator (for example, a ruthenium cation and an anion derived from a Lewis acid) described in JP-A-2008-181087 can also be used. Among them, at least one selected from the group consisting of a biimidazole compound, an alkylphenone compound, and an anthracene compound is preferred, and an alkylphenone compound is particularly preferred. In the case of a polymerization initiator containing these compounds, it is particularly preferred to have a high sensitivity.

The above hydrazine compound is a compound having a partial structure represented by the formula (d1). Below, * represents the bond.

The O-indenyl hydrazine compound may, for example, be N-benzyloxy-1-(4-phenylsulfonylphenyl)butan-1-one-2-imine or N-benzyl hydrazine. Oxy-1-(4-phenylsulfonylphenyl)oct-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfonylphenyl)-3- Cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-indazol-3-yl] Ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxe) Pentenylmethyloxy)benzylhydrazinyl}-9H-indazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2- Methylbenzylbenzyl)-9H-indazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzyloxy-1-[9-ethyl-6-(2-A Benzymidyl)-9H-indazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (above, manufactured by BASF Corporation) and N-1919 (made by Adeka Co., Ltd.) can also be used.

The aforementioned alkyl phenone compound has a moiety represented by the formula (d2) A sub-structure or a partially constructed compound represented by formula (d3). In these partial structures, the benzene ring may also have a substituent.

As a compound having a partial structure represented by the formula (d2), For example, 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) Phenyl) butan-1-one and the like. Commercial products such as Irgacure 369, 907, and 379 (above, manufactured by BASF Corporation) can also be used.

As a compound having a partial structure represented by the formula (d3), For example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl 1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenyl) Oligomeric phenyl)propan-1-one, α,α-diethoxyacetophenone, benzyldimethylketal, and the like.

From the viewpoint of sensitivity, alkyl benzophenone compounds are of the formula The compound of the partial structure represented by (d2) is preferred.

The biimidazole compound may, for example, be 2,2'-bis(2- Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenyl The benzyl imidazole (for example, refer to JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5' -tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-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 Publication No. Sho 48-38403, JP-A-62-174204, etc.), benzene at 4,4'5,5'-position The imidazole compound in which the group is substituted with an alkoxycarbonyl group (for example, refer to JP-A-7-10913, etc.) and the like. Preferred examples are 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-piperidin-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) 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.

The above-mentioned mercaptophosphine oxide compound may, for example, be 2,4,6-trimethylbenzylidenediphenylphosphine oxide.

Further, 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 benzoic acid methyl, 4-phenylbenzophenone, 4-benzylindolyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butyl a benzophenone compound such as peroxycarbonyl)benzophenone or 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethylhydrazine, camphorquinone, etc. a compound; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, a titanocene compound, and the like. These may also be added with a polymerization starting aid (E) described later.

Further, as a polymerization initiator which can cause a chain transfer, a polymerization initiator described in JP-A-2002-544205 can also be used.

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

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

As the thioxanthone compound, for example, 2-isopropyl group is mentioned Thioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

Examples of the amine compound include triethanolamine and methyl group. An aliphatic amine compound such as ethanolamine or triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate , 2-dimethylamino benzoic acid 2-ethylhexyl ester, benzoic acid 2-dimethylaminoethyl ester, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethyl Amino) benzophenone (commonly known as: migal ketone), 4,4'-bis(diethylamino)benzophenone-like aromatic amine compound.

Phenylsulfonyl B Acid, methylphenylsulfonyl acetic acid, ethyl phenylsulfonyl acetic acid, methyl ethyl phenylsulfonyl acetic acid, dimethylphenylsulfonyl acetic acid, methoxyphenylsulfonyl acetic acid Dimethoxyphenylsulfonyl acetic acid, chlorophenylsulfonyl acetic acid, dichlorophenylsulfonyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthalene Aromatic heteroacetic acid such as glucosamine or naphthyloxyacetic acid.

As a group of a polymerization initiator (C) and a polymerization initiator (E) The compound may, for example, be an acetophenone compound and a thioxanthone compound, an acetophenone compound or an aromatic amine compound, and specifically, for example, 2-morpholinyl-1-(4-methyl) Sulfosylphenyl)-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 Propyl thioxanthone with 4-isopropylthioxanthone, 2-morpholinyl-1-(4-methylsulfonylphenyl)-2-methylpropan-1-one and 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. Preferably, the combination is 2-morpholinyl-1-(4-methylsulfonylphenyl)-2-methylpropan-1-one with 2,4-diethylthiazinone, 2-morpholine Preferably, -1-(4-methylsulfonylphenyl)-2-methylpropan-1-one and 2-isopropylthioxanthone and 4-isopropylthioxanthone are preferred. If this combination is used, a pattern of high visible light transmittance can be obtained with high sensitivity.

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

Relative to the resin (A), the resin (A1), and the polymerizable compound (B) The total amount of the polymerization initiator (E) to be used is preferably 0.1 to 20 parts by mass, preferably 0.3 to 15 parts by mass. Aggregation start aid When the amount of the agent (E) is within the above range, the pattern can be obtained with high sensitivity, and the shape of the pattern obtained is good.

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

As a solvent which can be used in the present invention, for example, Ester solvent (solvent containing -COO- in the molecule but not containing -O-), ether solvent (solvent containing -O- in the molecule but not containing -COO-), ether ester solvent (containing -COO- in the molecule) It is selected and used among a ketone solvent (a solvent containing -CO- in the molecule but not containing -COO-), an alcohol solvent, an aromatic hydrocarbon solvent, a guanamine solvent, dimethyl hydrazine, and the like.

Examples of the ester solvent include methyl lactate and lactate B. 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 acetate, ethyl acetate, cyclohexanol acetate, γ-butyrolactone, etc. .

Examples of the ether solvent include ethylene glycol monomethyl ether and B. Glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, Tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, Diethylene glycol dibutyl ether, anisole, phenethyl ether, methylbenzene Methyl ether and the like.

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-methylpropanoate, 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 Ester, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.

As the ketone solvent, for example, 4-hydroxy-4-methyl-2-pentyl Ketone, 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 glycerin.

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

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

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

Among the above solvents, from the viewpoints of coatability and dryness, It is preferred to use an organic solvent having a boiling point of from 120 ° C to 180 ° C at 1 atm. Among them, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-ethoxypropionic acid ethyl, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol or the like is preferred. When the solvent (D) is used as a solvent, it is possible to suppress unevenness in coating and to improve the flatness of the coating film.

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 based on the total amount of the photosensitive resin composition. In other words, the solid content of the photosensitive resin composition is preferably from 5 to 40% by mass, preferably from 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 fraction refers to the amount after removing the solvent (D) from the photosensitive resin composition.

Further, 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 sulfonyl groups (-SH) in the molecule. In particular, when a compound in which two or more sulfonyl groups are 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 be high.

Specific examples of the polyfunctional thiol compound (T) include Hexanedithiol, decanedithiol, 1,4-bis(methylsulfonyl)benzene, butanediol bis(3-sulfonylpropionate), butanediol bis(3-sulfonyl) Acid ester), ethylene glycol bis(3-sulfonyl acetate), trimethylolpropane ginseng (3-sulfonyl acetate), butanediol bis(3-sulfonyl propionate) , trimethylolpropane ginseng (3-sulfonylpropionate), trimethylolpropane ginseng (3-sulfonyl acetate), pentaerythritol Alcohol (3-sulfonylpropionate), pentaerythritol bismuth (3-sulfonyl acetate), hydroxyethyl ginseng (3-sulfonylpropionate), pentaerythritol bismuth (3-sulfonyl fluorenyl) Butyrate), 1,4-bis(3-sulfonylbutoxy)butane, and the like.

Multifunctional sulfur relative 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, preferably 0.5 to 7 parts by mass. When the content of the polyfunctional thiol compound (T) is in the above range, the sensitivity of the photosensitive resin composition tends to be high, and the developability tends to be good, which is preferable.

The photosensitive resin composition of the present invention may also contain an interface activity Agent (G) (however, it is different from resin (F)). The surfactant is, for example, a polyfluorene-based surfactant, a fluorine-based surfactant, a polyfluorene-based surfactant having a fluorine atom, or the like.

The polyoxo-based surfactant may, for example, be a surfactant having a decane bond.

Specifically, for example, Toray Polyoxygen DC3PA, the same SH7PA, the same DC11PA, the same SH21PA, the same SH28PA, the same SH29PA, the same SH30PA, the polyether modified polyoxyxene oil SH8400 (trade name: Toray Dow Corning (stock) system ), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials Japan System) and so on.

The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain.

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

As a polyfluorene-based surfactant having a fluorine atom, A surfactant such as a siloxane chain and a fluorocarbon chain is exemplified. Specific examples thereof include Megafac (registered trademark) R08, BL30, F475, F477, and F443 (DIC). Preferably, Megafac (registered trademark) F475 is mentioned.

Interface 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 including a surfactant in this range, the flatness of the coating film can be improved.

The photosensitive resin composition of the present invention may also be packaged as necessary Various additives such as a filler, other polymer compound, adhesion enhancer (H), antioxidant, ultraviolet absorber, light stabilizer, chain transfer agent, and the like.

The above-mentioned adhesion enhancer (H) is as long as it is added, or In the storage under normal temperature, the solid matter is not precipitated by the reaction with the photosensitive resin composition, and is not particularly limited, and examples thereof include a decane coupling agent. For example, KBM-303, KBE-402, KBM-403, KBM-503, KBM-573, KBM-803, KBE-9007 (manufactured by Shin-Etsu Chemical 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 (manufactured by Toray Dow Corning Co., Ltd.), and the like.

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

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

When the photosensitive resin composition of the present invention is formed into a coating film, The average transmittance of the coating film is preferably 90% or more, and more preferably 95% or more. The average transmittance is measured by using a spectrophotometer and measuring a wavelength of 400 to 700 nm, and measuring a coating having a thickness of 3 μm after heat hardening (for example, hardening at 100 to 250 ° C for 5 minutes to 3 hours). The average of the time. Thereby, a coating film excellent in transparency in the visible light region can be provided.

The photosensitive resin composition of the present invention can be coated in an example For example, on a substrate such as glass, metal, or plastic, or on a substrate on which a color filter, various insulating or conductive films, a driving circuit, or the like is formed, the pattern is formed into a desired shape to form a pattern. Also, this pattern can be formed It is used for a part of a component such as a display device.

First, the photosensitive resin composition of the present invention is applied onto a substrate and patterned by photolithography as described below.

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

Next, drying is preferably carried out by drying or prebaking to remove volatile components such as a solvent. Thereby, the unhardened coating film can be obtained and smoothed.

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

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

In recent years, the exposure function is used to cut off light of less than 350 nm using a filter that is cut off in this wavelength region. For light near 436 nm, near 408 nm, and near 365 nm, a band pass filter that takes out these wavelength regions is selectively used. In addition, the entire exposed surface is uniformly illuminated with slightly parallel rays. If a device such as a reticle aligner or a stepper is used, the correct position of the reticle and the substrate can be corrected.

When the coating film after the exposure is brought into contact with the developing liquid, the predetermined portion, for example, the non-exposed portion (that is, the non-pixel portion) is dissolved, and development is performed, whereby the intended pattern shape can be obtained.

The development method may be any of a liquid-filling method, a dipping method, a spray method, and the like. Moreover, the substrate can be tilted 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 either an inorganic or an organic basic compound.

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 citrate. , potassium citrate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, and the like.

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

The aforementioned developing solution may also contain a surfactant.

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

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, and polyoxyethylene/polyoxygen. Propylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, poly Oxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, and the like.

As an anionic surfactant, for example, a higher alcoholic sulfate salt like sodium cinnamate or sodium oleyl sulfate, sodium alkyl lauryl sulfate or ammonium lauryl sulfate, sodium dodecylbenzene sulfonate or twelve Alkyl aryl sulfonates such as sodium naphthalene sulfonate.

As a cationic surfactant, for example, hard Lipidylamine hydrochloride or a lauryl trimethylammonium chloride or a fourth ammonium salt or the like.

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

After development, the pattern can be obtained by washing with water. And also Post-baking can be done as necessary. The post-baking system is preferably carried out, for example, at a temperature ranging from 150 to 240 ° C for 10 to 180 minutes.

When the unhardened film is exposed, the light that has formed the pattern is not used. 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 electrode has been formed, The film composed of the photosensitive resin composition is formed as described above, and then, the surface of the electrode is exposed, and an opening is formed in the film by the photolithography method described above.

Secondly, according to the polarity of the free energy of the surface of the aforementioned electrode The value of the component was used to evaluate the coatability of the electrode, whereby the evaluation of the substrate was carried out.

The value of the polar component of the surface free energy of the electrode, for example When the value is 15 mN/m or more, it is determined that the substrate as the partition wall can be applied to a substrate such as a display device, and when the value of the polar component of the surface free energy of the electrode is 15 mN/m or less, the substrate is a partition wall. It is determined that it is not applicable to a substrate such as a display device.

Further, based on the evaluation results, the photosensitive resin composition for forming the partition walls can also be evaluated.

That is, a film composed of the photosensitive resin composition is formed on the substrate on which the electrode has been formed, and the surface of the electrode is exposed first, and the photolithography method is used to form the film on the film. The opening is formed, and the coating property of the electrode is evaluated based on the value of the polar component of the surface free energy of the electrode, whereby the evaluation of the photosensitive resin composition can be performed.

A preferred embodiment of the substrate evaluation method of the present invention is a substrate evaluation method comprising: supplying a photosensitive resin composition onto a substrate on which an electrode has been formed, and rotating the substrate at 900 rpm for 7 seconds to form the photosensitive property a step of forming a film composed of a resin composition, and drying the substrate on which the film is formed at a pressure of 66 Pa, and then prebaking at 110 ° C for 110 seconds, whereby the surface of the electrode can be exposed. The pre-baked film was exposed at 200 mJ/cm ² , using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, and developed at 23 ° C for 80 seconds, and then subjected to post-baking photolithography after washing with water. Further, the step of forming an opening in the film and the step of evaluating the coatability of the electrode based on the value of the polar component of the surface free energy of the electrode exposed on the opening of the film.

When 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 as the photosensitive resin composition for forming the partition wall can be applied, and the polar component of the free energy of the surface of the electrode is conversely applied. When the value is 15 mN/m or less, it is determined that the photosensitive resin composition which is a photosensitive resin composition for partition walls is not applicable.

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

In the present 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 to the following formula.

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

(where γl represents the surface free energy of the liquid, γld represents the dispersive component of the surface free energy of the liquid, γlp represents the polar component of the surface free energy of the liquid, γsd represents the dispersive component of the surface energy of the solid, and γsp represents the solid component The polar component of the surface free energy, θ represents the contact angle.)

Here, since there are two unknowns (γsd, γsp), the γsd and γsp can be calculated by using the known two types of liquids as the dispersion component and the polar component.

From the above formula, the following formula can be derived. From the one-time regression equation 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, when the liquid component of the surface is freely used, the polar component of the surface free energy of the electrode can be calculated by using the known two kinds of liquids. For example, when the polar component is a solvent of three or more types of solvents (for example, four types). The average can also be evaluated by measuring the contact angle of a plurality of points (for example, three points) in the plane of the substrate.

An example of an organic EL (electroluminescence) display device as a display device of the present invention will be described below.

1 is a cross-sectional view schematically showing a part of a display device 1 which is 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 which is an example of the display device of the present invention. The display device 1 mainly includes a support substrate 2, a partition wall 3 that partitions a predetermined area on the support substrate 2, and a plurality of organic EL elements 4 that are provided in a region partitioned by the partition walls 3.

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

The partition 3 is formed, for example, in a lattice shape or a strip shape on the support substrate 2. Further, in FIG. 2, a display device 1 provided with a lattice-shaped partition wall 3 is shown as one embodiment. In the same figure, hatching is applied to the field in which the partition wall 3 is provided.

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

The partition walls 3 in the display device 1 are arranged in a lattice shape. because This is observed from one of the thickness directions Z of the support substrate 2 (hereinafter, also referred to as "in the case of a plan view"), and the plurality of openings 5 are arranged in a matrix. That is, the openings 5 are provided so as to be spaced apart from each other by a predetermined interval in the row direction X, and are also aligned in the column direction Y at predetermined intervals. The shape of each opening 5 in plan view is not particularly limited. For example, the opening 5 is formed in a shape of a substantially rectangular shape, a slightly elliptical shape, an elliptical shape or the like in plan view. In the present embodiment, the opening portion 5 having a substantially rectangular shape is provided in plan view. Further, in the present specification, the above-described row direction X and column direction Y mean a direction perpendicular to the thickness direction Z of the support substrate and perpendicular to each other.

Still, as another embodiment, a strip-shaped partition is provided. In the case of the wall, the partition wall is formed by, for example, a plurality of partition 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 the strip-shaped partition wall and the support substrate.

The partition wall is formed to vary in width as it goes away from the support substrate narrow. For example, when the partition wall extending in the column direction Y is cut on a plane perpendicular to the extending direction (column direction Y), the cross-sectional shape is formed so as to be narrower in width as it goes away from the support substrate. The partition wall of the isosceles trapezoidal shape is shown in Fig. 1. When the upper bottom is compared with the bottom of the support substrate side, the width of the lower base is wider than that of the upper base. Further, the cross section of the partition wall actually formed does not necessarily have to be trapezoidal, and the straight portion and the corner of the trapezoidal shape may have a circular shape.

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

The partition 3 is preferably such that liquid repellency is exhibited on the top surface thereof. Further, the top surface refers to a plane existing on the surface of the partition wall 3 at the position farthest from the support substrate 2. The method of forming the partition 3 for exhibiting liquid repellency on the top surface may be, for example, a method of using a photosensitive resin composition containing the liquid-repellent agent (F), or a liquid-repellent treatment of the surface after formation of the partition wall. method. For example, by subjecting the partition 3 to a plasma treatment in an environment containing a fluoride, liquid repellency can be imparted to the surface of the partition 3. The fluoride in the present treatment is in the form of a gas, and as the fluoride, for example, CF ₄ , CHF ₃ , CH ₂ F ₂ , C ₃ F ₈ , C ₄ F ₆ , C ₄ F ₈ or the like can be used. By performing such plasma treatment, fluorine atoms are bonded to the surface of the partition wall 3, and the partition wall 3 is imparted with liquid repellency.

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

The organic EL element 4 is disposed by the partition wall 3 On the area (ie, the opening 5). When the lattice-shaped partition walls 3 are provided in the display device 1, the respective organic EL elements 4 are provided in the respective opening portions 5. In other words, the organic EL elements 4 are arranged in a matrix shape in the same manner as the respective opening portions 5, and are arranged on the support substrate 2 at a predetermined interval in the row direction X, and are also spaced apart in the column direction Y. Arranged at intervals.

The shape of the partition 3 and its configuration are based on the prime number and resolution The specifications of the display device such as the degree, the ease of manufacture, and the like are appropriately set. For example, the width of the row 3 in the row direction X or the column direction Y 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 the column direction Y, that is, the opening portion 5 The width of the row direction X or the column direction Y is about 10 μm to 200 μm. Further, the width of the first electrode 6 in the row direction X or the column direction Y is about 10 μm to 200 μm.

The partition 3 can be formed by the above-mentioned pattern forming method. The photosensitive resin composition of the invention is formed.

Still, as another embodiment, next to the strip In the opening portions extending in the row direction X of the organic EL element 4, they are arranged at predetermined intervals in the row direction X.

Three types of organic EL elements are disposed in the display device 1. 4. In other words, the red organic EL element 4R that emits (1) red light, the green organic EL element 4G that emits green light (2), and the blue organic EL element 4B that emits blue light are (3).

The organic EL element 4 is in accordance with the first electric power from the support substrate side. The electrode, the organic EL layer, and the second electrode are laminated to each other. In the present 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 is provided with at least one light-emitting layer as an organic EL layer. Further, in addition to the light-emitting layer of one layer, the organic EL element may have an organic EL layer different from the light-emitting layer as 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, an electron injection layer, and the like are provided as an organic EL layer. Further, two or more light-emitting layers may be provided between the first electrode 6 and the second electrode 10.

In the organic EL element 4, it is composed of an anode and a cathode. One of the counter electrodes includes the first electrode 6 and the 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 the present embodiment, the first electrode 6 acting as an anode, the first organic EL layer 7 acting as a hole injection layer, the second organic EL layer 9 acting as a light-emitting layer, and the cathode The order of the 2 electrodes 10 is formed by lamination on the support substrate 2.

The first electrode 6 is generally a transparent electrode. as long as The type of the transparent electrode is not limited, and examples thereof include tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), fluorine-doped tin oxide (FTO), and antimony-doped tin oxide (ATO). A titanium oxide transparent electrode, aluminum-doped zinc oxide (AZO), or gallium-doped zinc oxide (GZO), preferably tin-doped indium oxide (ITO) or zinc-doped indium oxide (IZO).

The first electrode 6 is provided in each of the organic EL elements 4. The same number of the first electrodes 6 as the organic EL elements 4 are provided on the support substrate 2. The first electrodes 6 are provided corresponding to the arrangement of the organic EL elements 4, and are arranged in a matrix shape in the same manner as the organic EL elements 4. Further, the partition wall 3 is formed in a lattice shape mainly in the field in which 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 adjacent to the first electrode 6 (corresponding to a hole injection) The first organic EL layer 7) to be layered is provided on the first electrode 6 in the opening 5, respectively. The first organic EL layer 7 may be provided with different materials or film thicknesses depending on the type of each of the organic EL elements. Further, from the viewpoint of the ease of the formation step of the first organic EL layer 7, all of the first organic EL layers 7 may be formed of the same material and the same film thickness.

The first organic EL layer 7 will be included as the first organic EL The ink applied to the material of the layer 7 is supplied to the region surrounded by the partition wall 3 (the opening portion 5), and is dried, heated, and/or irradiated with light to be formed by curing the ink. The method of supplying the ink to be applied is not particularly limited, and examples thereof include a printing method such as an inkjet method or a gas-soluble jet method.

The layer provided adjacent to the first electrode 6 (the first organic EL The solvent or dispersion medium for ink application used for the formation of the layer 7) is not particularly limited as long as it can dissolve and/or disperse the liquid as the material of the first organic EL layer 7, but in order to The material of the organic EL layer 7 is well dissolved and/or dispersed, and there is a case where a polar solvent is contained.

As the above polar solvent, a general one can be used, which is not The type is particularly limited, and examples thereof include alcohols, ketones, glycol esters, glycol ethers, N,N-dimethylformamide, N,N-dimethylacetamide, and N. - methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl hydrazine, N-cyclohexyl-2-pyrrolidone, and the like. Further, in the present specification, the polar solvent means a solvent having a sp (Solubility Parameter) value of 10 or more.

Therefore, the layer provided adjacent to the first electrode 6 (the first one has The ink to be applied to the formation of the EL layer 7) is applied to the first electrode 6 when the ink is supplied to the opening of the partition wall in the case where the polar solvent is particularly contained. When it is bounced off, it is easy to produce a situation in which it is difficult to uniformly coat the entire surface in 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 uniformly coated and spread on the entire surface in the opening of the partition wall, so that a layer which is flat adjacent to the first electrode 6 can be formed (the first organic EL layer 7). .

A solvent or a dispersion medium other than the polar solvent contained in the ink to be applied to the layer (the first organic EL layer 7) provided adjacent to the first electrode 6 may be used, for example, cyclohexylbenzene, anisole, anthracene, or the like. Toluene, etc.

The second organic EL layer 9 functioning as a light-emitting layer is in 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 portion 5 in which the red organic EL element 4R is provided, and the green light-emitting layer 9G is provided in the opening portion 5 in which the green organic EL element 4G is provided, and the blue light-emitting layer 9B is disposed in The opening 5 of the blue organic EL element 4B is provided.

The second electrode 10 is integrally formed in the organic EL The display area of component 4 is on. In other words, 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 An organic EL display device (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 composed of In particular, it is useful as a partition wall used for producing a color filter, an ITO electrode of a liquid crystal display element, an organic EL display element, a circuit wiring board, or the like by an inkjet method. Further, for example, it may be useful as a photo spacer for constituting a part of the color filter substrate and/or the array substrate, a protective film capable of patterning, an interlayer insulating film, a protrusion for liquid crystal alignment control, a microlens, The coating layer for adjusting the film thickness or the like, the member for the touch panel, and the coating film having the pattern obtained as described above can be used 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 suitably used for a liquid crystal display device, an organic EL display device, electronic paper, or the like.

Example

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

[Synthesis Example 1]

A suitable amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 166 parts of propylene glycol monomethyl ether acetate and 52 parts of methoxypropanol were added and stirred, and simultaneously heated to 85. °C. 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-vinylbenzoic acid, and propylene glycol were added in 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 of 32 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 210 parts of propylene glycol monomethyl ether acetate was dropped into the flask over 5 hours. After the completion of the dropwise addition, the mixture was kept at the same temperature for 3 hours, and then cooled to room temperature to obtain a copolymer 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 (resin A1a). 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 unit.

(Synthesis Example 2)

A suitable amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace the nitrogen atmosphere, and 140 parts of diethylene glycol ethyl methyl ether was added and stirred, and simultaneously heated to 70 °C. Next, 40 parts of methacrylic acid are prepared; and a mixture of the monomer (I-1) and the monomer (II-1) {monomer (I-1) in the mixture: the molar of the monomer (II-1) Ratio = 50: 50} 360 parts of a solution obtained by dissolving 190 parts of diethylene glycol ethyl methyl ether, and the solution was dropped into the flask over 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 in 5 hours. A solution of 240 parts was dropped into the flask. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept 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 unit.

(Synthesis Example 3)

In a flask equipped with a cooling tube, a stirrer, and a thermometer, 176 parts of t-butoxystyrene and 5.8 parts of azobisbutyronitrile were placed, and 250 parts of propylene glycol monomethyl ether was added thereto to be dissolved, and polymerization was carried out at 75 ° C. 4 hours. 50 parts of a 5% aqueous sulfuric acid solution was mixed with the obtained poly-t-butoxystyrene solution, and the hydrolysis reaction was carried out at 100 ° C for 3 hours. After washing the reaction product three times with 1000 parts of deionized water, 500 parts of propylene glycol monomethyl ether acetate was added to carry out a solvent. Instead of this, 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, nitrogen substitution was carried out while stirring 145 parts of propylene glycol monomethyl ether acetate, and the temperature was raised to 120 °C. In this case, 20 parts of styrene, 57 parts of epoxy 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 inside of the reaction vessel was replaced with air, and after adding 27 parts of acrylic acid, 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 tetrahydroanhydrous decanoic acid (THPA) and 0.7 parts of triethylamine were added, and the mixture was reacted at 120 ° C for 3.5 hours to obtain a weight average molecular weight (Mw) of about 7,000 and a solid content of acid value of 84 mg-KOH. /g alkali soluble resin (resin Ad).

(Synthesis Example 5)

In a flask equipped with a cooling tube, a stirrer, and a thermometer, 400 parts of an epoxy resin (manufactured by Nippon Kasei 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 mixture was reacted at 90 ° C for 15 hours. Thereafter, 201 parts of tetrahydroanhydrous ruthenic 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, an alkali-soluble resin (resin Ae) having a solid content of 103 mg-KOH/g.

(wherein, n represents an integer. Me represents a methyl group.)

(Synthesis Example 6)

For flasks equipped with cooling tubes, mixers and thermometers, 450 parts of propylene glycol monomethyl ether, 50 parts of p-vinylbenzoic acid, 12 parts of N-phenylmaleimide, 2-hydroxyethyl methacrylic acid were placed. 20 parts of ester and 18 parts of 2-ethylhexyl methacrylate were injected with nitrogen and simultaneously heated to 92 °C. Next, a solution obtained 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. It is polymerized. Thereafter, a solution obtained 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 A solution of the binder resin (resin Af) (solid content concentration = 16% by mass) was obtained by heating at 100 ° C for 1 hour while maintaining the temperature. The weight average molecular weight (Mw) of the resin Af was 9,850, and the solid acid value was 184 mg-KOH/g.

(Synthesis Example 7)

Equipped with a reflux cooling tube, a nitrogen inlet tube, a thermometer and a stirring device In a four-necked flask, 78 parts of α-chloroacrylic acid 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, 19.5 parts of methacrylic acid, and 19.5 parts of isodecyl methacrylate were placed. 13 parts of glycidyl methacrylate, 12.7 parts of dodecyl mercaptan, and 266 parts of propylene glycol monomethyl ether acetate were heated to 70 ° C, and then stirred under a nitrogen stream for 30 minutes. To this, 1 part of azobisisobutyronitrile was added 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 68 mg-KOH/g. Solution. The resin Fa has the following structural unit.

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 by the GPC method under the following conditions.

Device; K2479 (made by Shimadzu Corporation)

Pipe string; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ° C

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0mL/min

Detector; RI

The ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained above was defined as a 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 each of Examples 1 to 5, Comparative Example 1, and Reference Examples 1 to 4, the components of Table 3 were mixed with a solvent (D) to be described later so that the solid content (%) thereof became the ratio described in Table 3, and the photosensitivity was further obtained. Resin composition.

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

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

The components in Table 3 are as follows. The parts stated in the column of the resin represent parts by mass in terms of solid content.

Resin (A); Aa: copolymer of p-hydroxystyrene and butyl acrylate [copolymerization ratio: 50:50, weight average molecular weight; 12,600] (MARUKA LYNCUR (registered trademark) CBA; Maruzen 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; Maruzen 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 Co., Ltd.)

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

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

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)butan-1-one (Irgacure (registered trademark) 309; manufactured by BASF Corporation )

Polymerization initiator (C); Cc; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-fluorene (4-ethoxycarbonylphenyl)-1,2' -Biimidazole (Baotu Valley 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 Wa obtained in Synthesis Example 7

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

Surfactant (G); Ga; polyether-denatured polyoxo-based surfactant "BYK330" (manufactured by Vic Chemical Co., Ltd.)

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

Tightness enhancer (H); γ-glycidoxypropyltrimethoxydecane

Coloring Dispersion (I); 13 parts by mass of a mixture of CI Pigment Red 254/CI Pigment Red 177/CI Pigment Yellow 150=50/35/15 (mass ratio) by a bead mill, dispersant BYK-LPN21116 ( 10 parts by mass of the solution (amine price = 73, acid value = 0, manufactured by Bic-Chemy Co., Ltd.) (nonvolatile content = 40% by mass), 77 parts by mass of propylene glycol monomethyl ether acetate as a solvent, 12 hours of mixing, ‧ dispersion By

The solvent (D) was mixed with the following solvent components (Da) to (Dd) in the proportions shown in Table 4.

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

Solvent (D); Db; 3-ethoxypropionic acid ethyl

Solvent (D); Dc; propylene glycol monomethyl ether

Solvent (D); Dd; 3-methoxybutyl acetate

The solid content of the photosensitive resin composition was obtained by mixing the components of Table 3 with the solvent (D) so as to have the "solid content (%)" of Table 3.

[Substrate cleaning]

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

[Production of substrate with transparent conductive film]

An ITO target (made by Tosoh Corporation; 90% In ₂ O ₃ -) was attached to the sputtering apparatus (input type sputtering apparatus manufactured by ULVAC Co., Ltd., type SDP-570VT) by using the substrate to be cleaned as described above. 10% SnO ₂ ), after heating to 300 ° C in a heating chamber, the transparent conductive film ITO was formed into a film of 50 nm in a sputtering chamber at a power of 1.05 kW, an argon gas pressure of 0.6 Pa, and a film formation time of 115 seconds. Then, the substrate after the film formation was annealed at 230 ° C for 30 minutes in the air to obtain a glass substrate with ITO.

[Production of substrate with partition] (Production of the substrate with the partition wall of Example 1)

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

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

The substrates of the partition walls of Examples 2 to 5 and Comparative Example 1 were produced in the same manner as in Example 1 except that the photosensitive resin compositions 2 to 6 were used instead of the photosensitive resin composition 1.

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

In place of the photosensitive resin composition 1, the photosensitive resin composition 7 was used instead, and the pattern was formed on the same plane (the shape of the opening was a rectangle of 300 μm in the long axis direction and 100 μm in the short axis direction, and an arc The photomask of the shape of the four corners (long circle) was subjected to exposure, and after baking at 230 ° C for 60 minutes, the other steps were carried out in the same manner as in Example 1 to form a partition wall of Comparative Example 2. Substrate.

(Production of the substrate of the partition wall of Comparative Example 3)

The photosensitive resin composition 8 was used instead of the photosensitive resin composition 1, and propylene glycol monomethyl ether acetate was used as the developing liquid, and the mixture was shaken at 23 ° C for 80 seconds while being immersed for development. The substrate of the partition wall of Comparative Example 3 was produced in the same manner as in Example 1.

The substrate of the partition walls of Reference Examples 1 to 4 was produced in the same manner as in Example 1 except that the photosensitive resin compositions 9 to 12 were used instead of the photosensitive resin composition 1.

[Production of solution for coating evaluation]

Two types of N,N-dimethylacetamide (manufactured by Wako Pure Chemical Co., Ltd., 99.5% or more) and 1,3-dimethyl-2-imidazolidinone (manufactured by Tokyo Chemical Industry Co., Ltd., 99.0% or more) It is a solvent used for the evaluation of the coating property of a partition. In order to enable the ink jet device to fill the partition wall with a low viscosity, the solvent of the selected two types of solvents is used as a viscosity adjusting material by using cyclohexanol (manufactured by Wako Pure Chemical Industries, Ltd., 98.0% or more). As a mixed solvent.

Further, when only the solvent itself was used, it was difficult to observe the coating spreadability after drying under a microscope, and Rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd., purity: 95% or more) was used as the solute.

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

[Method of Confirmation of Opening]

When a patterned substrate is observed using a microscope (MX61L manufactured by OLIMPUS Co., Ltd., lens LMPFLN10xBD), the organic film which is confirmed to exist under the microscope of the above magnification is regarded as a partition wall, and a partition wall is present on the substrate at the aforementioned magnification. The organic film could not be observed under the microscope, and the portion exposing the electrode was regarded as an opening.

[Coating property evaluation]

In the partition, an inkjet device (Litlex 120L manufactured by ULVAC Co., Ltd.) was used, and each of the above-mentioned solutions 1, 2, and 3 was filled in 200 μL in each partition wall, and was filled in a partition wall of 1,000. After drying, a microscope (MX61L, manufactured by OLIMPUS) was used. Lens LCPFLN20xLCD) observes whether or not the solute is unfolded to the end of the partition wall, and performs observation at 30 points, If the coating is spread at 30 points, the coating property is considered to be good.

The next door of this use is in a state of no liquid repellency Since the evaluator was carried out as described below, there was a case where the solution was leaked from the partition wall. Therefore, the evaluation of the coating spreadability was carried out using the residual liquid in the partition wall.

[Polarity evaluation] (contact angle measurement)

Pure water, glycerol (manufactured by Sigma-Aldrich, purity: 99.5% or more), formamide (manufactured by Sigma-Aldrich, purity: 99.5% or more), and two were used in the portion where the ITO was exposed in the substrate after the production of the partition wall. Four kinds of solvents of methyl iodide (manufactured by Sigma-Aldrich Co., Ltd., purity: 99%) were subjected to three-point measurement in the in-plane of the substrate, and the average was calculated and evaluated.

(polarity calculation)

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

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

The results of the examples, comparative examples and reference examples are shown in Table 6. In Table 6, "○" indicates good, and "X" indicates poor.

From the results of the above examples, it was found that when the photosensitive resin composition of the present invention is used, the surface of the ITO after the pattern formed on the surface of the electrode is formed, and the value of the polar component of the surface free energy is high, and ITO is obtained. A pattern with excellent surface coating properties.

Industrial availability

According to the photosensitive resin composition of the present invention, it is possible to obtain a pattern excellent in coatability on the surface of the electrode.

Claims (12)

A photosensitive resin composition which forms a film composed of the photosensitive resin composition on a substrate on which an electrode is formed by using a photosensitive resin composition, and secondly, the electrode is formed on the film by photolithography The value of the polar component of the surface free energy of the electrode after the opening is formed by the surface is 15 mN/m or more. The photosensitive resin composition of claim 1, wherein the photosensitive resin composition comprises the following (A), (B), and (C); (A) has a structure including a group represented by the following formula [i] Unit of resin (In the 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, 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 a carbon number of 2~ (5) alkoxyalkyl group, aryl group or benzyl group (B) polymerizable compound (C) polymerization initiator. The photosensitive resin composition of claim 2, wherein the structural unit is represented by the following formula [ii], (In the formula [ii], R1, R2, R3, R4 and R5 represent the same meanings as defined above, and R6 represents a hydrogen atom, a methyl group or an ethyl group). The photosensitive resin composition of claim 2 or claim 3, wherein the polymerization initiator is a photopolymerization initiator, and the polymerizable compound is polymerized by radical polymerization. The photosensitive resin composition according to any one of claims 2 to 4, wherein at least one of R1, R2, R3, R4, and R5 is -COOH or -OH, and the other is a hydrogen atom. The photosensitive resin composition according to any one of claims 1 to 5, further comprising a liquid repellent. The photosensitive resin composition of claim 6, wherein the liquid repellent is a polymer comprising a structural unit derived from an unsaturated compound having a perfluoroalkyl group having 4 to 6 carbon atoms. The photosensitive resin composition according to any one of claims 1 to 7, wherein the electrode is a transparent electrode. A partition wall formed by the photosensitive resin composition according to any one of claims 1 to 8. A substrate comprising a partition wall and an electrode as claimed in claim 9. A display device having a substrate as claimed in claim 10. A substrate evaluation method for forming a film composed of a photosensitive resin composition on a substrate on which an electrode is formed, and forming an opening by exposing a surface of the electrode on the film by photolithography, according to the electrode The value of the polar component of the surface free energy was used to evaluate the coating properties of the electrode.