KR20140007799A - Photosensitive resin composition, patterned structure, display device, and partition wall - Google Patents

Abstract

This invention provides the negative photosensitive resin composition which is excellent in liquid repellency, heat resistance, and solvent resistance, and does not leave a photosensitive resin composition as a residue in the site | parts other than a pattern formation part, and can form a pattern. The photosensitive resin composition of this invention is a negative photosensitive resin composition containing alkali-soluble resin (A), a fluorine-type liquid repellent agent (B), a crosslinking agent (C), and an acid generator (D), and a fluorine-based liquid repellent agent (B) is carbon It is an addition polymer containing the structural unit derived from the unsaturated compound which has a fluoroalkyl group of 4-6 atoms, and the addition rate of a fluorine-type liquid repellent (B) is 0.01 to 1.0 weight% with respect to the total solid in a composition.

Description

PHOTOSENSITIVE RESIN COMPOSITION, PATTERNED STRUCTURE, DISPLAY DEVICE, AND PARTITION WALL}

The present invention relates to a photosensitive resin composition, a pattern structure, a display device, and a partition wall.

As a method of manufacturing a display device and the like in recent years, a color filter constituting a part of the device or the like, an ITO electrode of a liquid crystal display device, an organic electroluminescent device (hereinafter also referred to as an "organic EL device"), a circuit wiring board, etc. The manufacturing method by coating type processes, such as a method, is reported. In application | coating type processes, such as the inkjet method, the partition formed using the photosensitive resin composition is used.

For example, in the display device using an organic EL element, three types of organic EL elements are provided on the support substrate. That is, (1) a red organic EL element that emits red light, (2) a green organic EL element that emits green light, and (3) a blue organic EL element that emits blue light are provided on a supporting substrate. have. A partition wall defining a pixel pattern is usually provided on the support substrate, and the three kinds of organic EL elements are arranged in alignment with the partitions formed by the partition walls (that is, regions surrounded by the partition walls).

Each organic EL element is formed by sequentially stacking the first electrode 2, the organic EL layer 4, and the second electrode 7 in the region 5 surrounded by the partition wall 3 (see FIG. 1).

With reference to FIG. 2, the formation method of the organic EL layer 4 is demonstrated. First, the first electrode 2 and the partition 3 are formed on the support substrate 1. Next, the ink 6 containing the material used as the organic EL layer 4 and a solvent is supplied to the area | region 5 enclosed by the partition 3 (FIG. 2A). The supplied ink 6 is accommodated in the region 5 surrounded by the partition 3 (FIG. 2B), and the organic EL layer 4 is formed by evaporation of the solvent of the ink 6 in the region 5. (FIG. 2C). As an application | coating type process which supplies such the ink 6, the inkjet method, the nozzle coating method, etc. are proposed.

The partition 3 which defines a pixel pattern is pattern-formed by photolithography using the photosensitive resin composition here. The partition 3 used in the coating type process needs to reliably receive and hold the ink 6 supplied in the region 5 enclosed by the partition, and has so-called liquid repellency so that an unintended point does not get wet. Is required.

As a photosensitive resin composition for forming the member which shows the said liquid repellency, the photosensitive resin composition containing the polymer obtained by superposing | polymerizing the alpha-position substituted acrylate which has a fluoroalkyl group of 4 to 6 carbon atoms is known, for example. (Patent Document 1).

Japanese Patent Laid-Open No. 2008-287251

However, when the pattern structure like the said partition is formed using the photosensitive resin composition conventionally proposed, since the partition which has appropriate liquid repellency is formed, the ink supplied in the area | region enclosed by the partition will be accommodated and retained, but the pattern obtained The heat resistance of the structure was low, there was a problem in stability. In addition, in the case where the partition wall is formed on the support substrate to form the organic EL element, the residue of the photosensitive resin composition may remain at portions other than the portion where the pattern is formed, and the ink for forming the organic EL layer by this residue In some cases, when the coating film is formed, the film thickness may be sufficiently uniform and a flat coating film may not be formed.

Therefore, the objective of this invention is providing the negative photosensitive resin composition which is excellent in liquid repellency and heat resistance, and does not remain as a residue in the site | part other than a pattern formation part, and can form a pattern.

The present invention provides the following photosensitive resin composition, pattern structure, display device, and partition wall.

[1] A negative photosensitive resin composition containing an alkali-soluble resin (A), a fluorine-based liquid repellent (B), a crosslinking agent (C), and an acid generator (D),

The fluorine-based liquid-repellent agent (B) is an addition polymer containing a structural unit derived from an unsaturated compound having a fluoroalkyl group having 4 to 6 carbon atoms, and the addition ratio of the fluorine-based liquid-repellent agent (B) is 0.01 to total solids in the composition. Photosensitive resin composition which is 1.0 weight%.

[2] The photosensitive resin composition according to the above [1], further comprising a solvent (E).

[3] The photosensitive resin composition according to the above [1] or [2], wherein the alkali-soluble resin (A) contains a phenol resin.

[4] The photosensitive composition according to any one of [1] to [3], wherein the alkali-soluble resin (A) contains a novolak resin.

[5] The structural unit derived from at least one of the above-mentioned [1] to [4], wherein the fluorine-based liquid repellent (B) is selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. The photosensitive resin composition which is an addition polymer.

[6] The photosensitive resin according to any one of [1] to [5], wherein the fluorine-based liquid repellent (B) is an addition polymer containing a structural unit derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms. Composition.

[7] A pattern structure formed using the photosensitive resin composition according to any one of [1] to [6].

[8] A display device comprising the pattern structure according to the above [7].

[9] An inkjet partition wall, comprising the pattern structure according to the above [7].

This invention is excellent in liquid repellency and heat resistance, and can provide the negative photosensitive resin composition by which pattern formation is possible in the site | parts other than a pattern formation part, without leaving a photosensitive resin composition as a residue.

1 is a cross-sectional view of an organic EL element in a display device.
FIG. 2A is a diagram for explaining a method of forming an organic EL layer. FIG.
2B is a diagram for explaining a method of forming an organic EL layer.
2C is a diagram for explaining a method of forming an organic EL layer.
FIG. 3A is a diagram for explaining a method of forming a partition.
3B is a view for explaining a method of forming a partition wall.
FIG. 3C is a diagram for explaining a method of forming a partition.
FIG. 3D is a diagram for explaining a method of forming a partition wall. FIG.
4A is a diagram for explaining a method of forming a partition wall.
4B is a diagram for explaining a method of forming a partition wall.
4C is a diagram for explaining a method of forming a partition wall.
4D is a diagram for explaining a method of forming a partition wall.

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

(A) an alkali-soluble resin

(B) fluorine-based liquid repellent

(C) crosslinking agent

(D) acid generator

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

The fluorine-based liquid repellent agent (B) included in the photosensitive resin composition of the present invention is an unsaturated compound having a fluoroalkyl group having 4 to 6 carbon atoms (for example, an unsaturated compound having a fluoroalkyl group and a carbon-carbon double bond). It is an addition polymer containing the structural unit derived, and its addition ratio is 0.01-1.0 weight% with respect to the total solid in the photosensitive resin composition.

The fluorine-based liquid repellent agent (B) is a polymer containing a structural unit derived from an unsaturated compound (d) having a perfluoroalkyl group having 4 to 6 carbon atoms (hereinafter also referred to as "unsaturated compound (d)"). to be.

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

[In formula (d-0), R ^f represents a fluoroalkyl group having 4 to 6 carbon atoms.

R ^d represents a hydrogen atom, a halogen atom, a cyano group, a phenyl group, a benzyl group or an alkyl group having 1 to 21 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom or a hydroxy group.

X ^d represents a single bond, a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and the aliphatic hydrocarbon described above. Group and at least one -CH ₂ -contained in the alicyclic hydrocarbon group is -O-, -CO-, -COO-, -C ₆ H _4- (phenylene group), -NR ^e- , -S- or- May be substituted with SO _2- .]

R ^f is preferably a perfluoroalkyl group having 4 to 6 carbon atoms. As an example, a perfluoro butyl group and a perfluorohexyl group are mentioned, A perfluoro butyl group is preferable.

Examples of halogen atoms in R ^d include F, Cl, Br, and I.

Examples of the alkyl group having 1 to 21 carbon atoms in R ^d include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group and n-jade Linear alkyl groups such as a methyl group, n-nonyl group and n-decyl group;

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

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

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

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

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

R ^e is an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

-CH ₂ -in the aliphatic hydrocarbon group and the alicyclic hydrocarbon group is -O-, -CO-, -COO-, -C ₆ H _4- (phenylene group), -NR ^e- , -S- or -SO Examples of X ^d substituted with ₂ − include groups represented by formulas (xd-1) to (xd-10).

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

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

<Table 1-1>

<Table 1-2>

<Table 2-1>

<Table 2-2>

The fluorine-based liquid repellent (B) is preferably a resin containing a structural unit derived from an unsaturated compound (d) and a structural unit derived from an unsaturated compound (a) described later, and a structural unit derived from an unsaturated compound (d). And it is more preferable that it is resin containing the structural unit derived from an unsaturated compound (a), and the structural unit derived from the unsaturated compound (b) mentioned later. Since a fluorine-type liquid repellent agent (B) contains the structural unit derived from an unsaturated compound (a), since developability is excellent, there exists a tendency for the nonuniformity resulting from a residue and image development to be suppressed. It exists in the tendency for solvent resistance to be excellent because a fluorine-type liquid repellent agent (B) contains the structural unit derived from an unsaturated compound (b). In addition, a fluorine-type liquid repellent agent (B) may also contain the structural unit derived from the unsaturated compound (c) mentioned later.

When the fluorine-based liquid-repellent agent (B) is a copolymer of an unsaturated compound (a) and an unsaturated compound (d), the ratio of the structural unit derived from each monomer is with respect to the sum total of the structural units which comprise a fluorine-based liquid-repellent agent (B), It is preferable to exist in the following ranges.

Structural units derived from an unsaturated compound (a); 5 to 40% by weight (more preferably 10 to 30% by weight)

Structural units derived from unsaturated compounds (d); 60 to 95 weight percent (more preferably 70 to 90 weight percent)

When the fluorine-based liquid repellent agent (B) is a copolymer of an unsaturated compound (a), an unsaturated compound (b) and an unsaturated compound (d), the ratio of the structural unit derived from each monomer makes the structure which comprises a fluorine-based liquid repellent agent (B). It is preferable to exist in the following ranges with respect to the total number-of-moles of a unit.

Structural units derived from an unsaturated compound (a); 5 to 40% by weight (more preferably 10 to 30% by weight)

Structural units derived from unsaturated compounds (b); 5 to 80 wt% (more preferably 10 to 70 wt%)

Structural units derived from unsaturated compounds (d); 10 to 80 wt% (more preferably 20 to 70 wt%)

When the fluorine-based liquid repellent agent (B) is a copolymer of an unsaturated compound (a), an unsaturated compound (b), an unsaturated compound (c) and an unsaturated compound (d), the proportion of the structural unit derived from each monomer is a fluorine-based liquid repellent agent ( It is preferable to exist in the following ranges with respect to the total number of moles of the structural unit which comprises B).

Structural units derived from an unsaturated compound (a); 5 to 40% by weight (more preferably 10 to 30% by weight)

Structural units derived from unsaturated compounds (b); 5 to 80 wt% (more preferably 10 to 70 wt%)

Structural units derived from unsaturated compounds (c); 10 to 50% by weight (more preferably 20 to 40% by weight)

Structural units derived from unsaturated compounds (d); 10 to 80 wt% (more preferably 20 to 70 wt%)

When the ratio of each structural unit is in the above-mentioned range, there exists a tendency which is excellent in liquid repellency and developability.

The weight average molecular weight of polystyrene conversion of a fluorine-type liquid repellent (B) becomes like this. Preferably it is 3,000-20,000, More preferably, it is 5,000-15,000. When the weight average molecular weight of the fluorine-based liquid repellent agent (B) is in the above range, the coating property tends to be excellent, and the film reduction of the exposed portion hardly occurs during development, and the non-exposed portion is more likely to be removed by development.

The acid value of the fluorine-based liquid repellent (B) is 20 to 200 mgKOH / g, preferably 40 to 150 mgKOH / g.

When content of the fluorine-type liquid repellent agent (B) in the photosensitive resin composition makes the total weight of alkali-soluble resin (A) and a crosslinking agent (C) 100 weight part, Preferably it is 0.001-10 mass parts, More preferably, it is 0.01-1. 5 parts by mass. When content of a fluorine-type liquid repellent agent (B) exists in the said range, there exists a tendency which is excellent in developability at the time of pattern formation, and excellent in the liquid repellency of the obtained pattern (upper surface).

The unsaturated compound (a) is an unsaturated compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. As an unsaturated compound (a), For example, unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, a crotonic acid, o-vinyl benzoic acid, m-vinyl benzoic acid, p-vinyl benzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2- N, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methyl ratio Bicyclo unsaturated compounds containing carboxyl groups such as cyclo [2.2.1] hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride Unsaturated dicarboxylic anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);

Unsaturated mono [(meth) acryloyloxyalkyl of a divalent or higher polyhydric carboxylic acid such as monosuccinic acid [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] 〕ester;

and unsaturated acrylates containing a hydroxy group and a carboxyl group in the same molecule as?-(hydroxymethyl) acrylic acid.

Among them, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in terms of copolymerization reactivity and alkali solubility.

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

Unsaturated compound (b) is unsaturated having a cyclic ether having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring (oxolan ring)) It is a compound, and the monomer which has a C2-C4 cyclic ether and ethylenically unsaturated double bond is preferable, and the monomer which has a C2-C4 cyclic ether and a (meth) acryloyloxy group is more preferable.

Examples of the unsaturated compound (b) include an unsaturated compound (b1) having an oxiranyl group (hereinafter also referred to as "unsaturated compound (b1)") and an unsaturated compound (b2) having an oxetanyl group (hereinafter referred to as "unsaturated compound (b2) "Unsaturated compound (b3)" (hereinafter also referred to as "unsaturated compound (b3)") having a tetrahydrofuryl group is mentioned.

Examples of the unsaturated compound (b1) include an unsaturated compound (b1-1) having a structure in which an alkene is epoxidized (hereinafter also referred to as an "unsaturated compound (b1-1)") and an unsaturated compound having a structure in which a cycloalkene is epoxidized (b1) -2) (hereinafter also referred to as "unsaturated compound (b1-2)").

As an unsaturated compound (b1), the monomer which has an oxiranyl group and a (meth) acryloyloxy group is preferable, and the monomer which has the structure which epoxidized cycloalkene and a (meth) acryloyloxy group is more preferable. When these monomers are used, the storage stability of the photosensitive resin composition is excellent.

As an unsaturated compound (b1-1), glycidyl (meth) acrylate, (beta) -methylglycidyl (meth) acrylate, (beta) -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, for example , o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glyc Cydyl ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (Glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyl Oxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl ) Styrene, the compound described in Unexamined-Japanese-Patent No. 7-248625, etc. are mentioned. have.

Examples of the unsaturated compound (b1-2) include vinylcyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, cyclomer-A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, cyclomer- M100; Daicel Chemical Industries, Ltd.), the compound represented by Formula (I), the compound represented by Formula (II), etc. are mentioned.

In formulas (I) and (II), R ¹ and R ² independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be substituted with a hydroxy group.

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

R ³ represents an alkanediyl group having 1 to 6 carbon atoms.

* Represents a bond with O.

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

Examples of the alkyl group having 1 to 4 carbon atoms substituted with a hydroxy group include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3 -Hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxy A oxybutyl group etc. are mentioned.

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

As the alkanediyl group represented by R ³ , for example, methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1 , 5-diyl group, hexane-1,6-diyl group and the like.

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

As a compound represented by Formula (I), the compound etc. which are represented by Formula (I-1)-Formula (I-15) are mentioned, for example. Preferably, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), formula (I-11) to formula (I-15) ). More preferably, Formula (I-1), Formula (I-7), Formula (I-9), and Formula (I-15) are mentioned.

As a compound represented by Formula (II), the compound etc. which are represented by Formula (II-1)-Formula (II-15) are mentioned, for example. Preferably, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), formula (II-11) to formula (II-15) ).

More preferably, Formula (II-1), Formula (II-7), Formula (II-9), and Formula (II-15) are mentioned.

The compound represented by the formula (I) and the compound represented by the formula (II) may each be used alone. In addition, these can also be mixed and used in arbitrary ratios. When mixing the compound represented by the formula (I) and the compound represented by the formula (II), they are in a molar ratio of formula (I): formula (II), preferably 5:95 to 95: 5, more preferably Is mixed from 10:90 to 90:10, particularly preferably from 20:80 to 80:20.

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

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

Examples of the unsaturated compound (b3) include tetrahydrofurfuryl acrylate (for example, biscoat V # 150, manufactured by Osaka Yuki Chemical Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like. have.

As an unsaturated compound (c), (meth) acrylic acid ester, N-substituted maleimide, unsaturated dicarboxylic acid diester, alicyclic unsaturated compound, styrene, another vinyl compound etc. are mentioned, for example. .

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

Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (in the art, dicyclopentanyl as conventional name) Cycloalkyl esters such as (meth) acrylate), dicyclopentanyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate;

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

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

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

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

As alicyclic unsaturated compounds, it is bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethyl bicyclo [2.2.1], for example. Hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl ) Bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6- Dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2'-hydroxy Ethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2 -Ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl -5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2. 1] hept-2-ene, 5-phenoxy Carbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxy Bicyclo unsaturated compounds, such as a cycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. are mentioned.

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

Examples of other vinyl compounds include (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3 Butadiene etc. are mentioned.

As the unsaturated compound (c), for example, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are copolymerizable and alkali soluble. It is preferable in terms of.

<Alkali-soluble resin (A)>

The photosensitive resin composition of this invention contains alkali-soluble resin (A). As alkali-soluble resin (A), coating film property is favorable and what is necessary is just to be compatible with another component.

Content of alkali-soluble resin (A) when the sum total of alkali-soluble resin (A), crosslinking agent (C), and acid generator (D) in the photosensitive resin composition of this invention is 100 weight% becomes like this. 60 to 98% by weight. When content of alkali-soluble resin (A) exists in the said range, there exists a tendency for the developability of the photosensitive resin composition, the adhesiveness of the pattern obtained, solvent resistance, and a mechanical characteristic to become favorable.

On the structure of an organic EL device, it is necessary to pattern-form a photosensitive resin composition, for example on a transparent electrode (ITO (tin doped indium oxide) and IZO (zinc doped indium oxide: abbreviation IZO)).

Since a transparent electrode and the photosensitive resin composition have favorable adhesiveness, even if alkali-soluble resin is used, the residue of the photosensitive resin composition in parts other than a pattern structure, for example, the periphery of the opening part of a pattern structure after forming a pattern structure, will remain. It may be left.

When ink containing an organic EL material is applied into the opening of the pattern structure by the inkjet method or the like, the ink is dewetted by the resin residue remaining on the periphery of the opening. When this "dewetting" is slight, unevenness may arise in the film thickness, such as a light emitting layer. For example, the film thickness of a light emitting layer may become thinner than the peripheral part compared with the center part of an opening part. For this reason, the electric resistance of the peripheral part of a light emitting layer becomes low compared with the center part, and when a voltage is applied to a light emitting layer, an electric current flows intensively in a peripheral part, and the center part becomes dark compared with a peripheral part. Thus, when a nonuniformity arises in a film thickness, the light emission nonuniformity considered to be due to a film thickness difference may arise. In particular, when "Dewetting" is remarkable, no light emitting layer or the like is formed at the periphery of the opening, and when an electrode is formed on the light emitting layer as it is, current leakage occurs between a pair of electrodes, and a current is generated in the light emitting layer formed in the pixel. Does not flow, and the phenomenon that it does not emit light may occur.

As a result of earnest examination by the present inventors, in order to solve the said subject, it discovered that it is preferable to use vinylphenol resin (henceforth "polyvinyl phenol") or novolak resin as alkali-soluble resin (A). In particular, by using polyvinylphenol and novolak resin together, adhesion between the pattern structure on which the photosensitive resin composition is formed and the substrate (or the electrode) is secured, and there is substantially no residue in the region except the pattern structure (the residue Difficult to leave), the heat resistance temperature was found to be significantly improved.

As polyvinyl phenol, the homopolymer of vinyl phenol, the copolymer of vinyl phenol, and the monomer copolymerizable with this is mentioned.

Polyvinyl phenol is used alone or in combination of two or more vinyl phenols such as 4-vinyl phenol, 3-vinyl phenol, 2-vinyl phenol, 2-methyl-4-vinyl phenol, 2,6-dimethyl-4-vinyl phenol And can be obtained by radical polymerization using a polymerization initiator such as azobisisobutyronitrile or benzoyl peroxide.

Vinyl phenols and polyvinyl phenols are described in detail in Maruzen Sekiyu Kagaku Co., Ltd., "Basic Phenol Basics and Applications" (published by Education Publication Center). As a monomer copolymerizable with vinylphenol, isopropenyl phenol, acrylic acid, methacrylic acid, styrene, maleic anhydride, maleic acid imide, vinyl acetate, etc. are mentioned, for example. Among these, the homopolymer of vinylphenol is preferable and the homopolymer of p-vinylphenol is especially preferable.

The average molecular weight of polyvinyl phenol is the weight average molecular weight (Mw) of monodisperse polystyrene conversion measured by gel permeation chromatography (GPC), and is usually 3,000 to 20,000, preferably 4,000 to 15,000, more preferably 5,000 to 10,000. When the weight average molecular weight of polyvinyl phenol is too small, since molecular weight does not fully increase even if the crosslinking reaction of an exposure area | region arises, it becomes easy to melt | dissolve in an alkaline developing solution and the effect of improving heat resistance falls. When the weight average molecular weight of polyvinyl phenol is too large, the difference of solubility with respect to the alkaline developing solution of an exposure area and an unexposed area | region becomes small, and it becomes difficult to obtain a favorable resist pattern.

As a novolak resin, what is widely used in the technical field of a resist can be used. The novolak resin can be obtained by, for example, reacting phenols with aldehydes or ketones in the presence of an acidic catalyst (for example, oxalic acid).

As phenols, a phenol, o-cresol, m-cresol, p-cresol, 2, 3- dimethyl phenol, 2, 5- dimethyl phenol, 3, 4- dimethyl phenol, 3, 5- dimethyl phenol, 2 , 4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butyl Phenol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 4-tert-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3- Propylphenol, 4-propylphenol, 2-isopropylphenol, 2-methoxy-5-methylphenol, 2-tert-butyl-5-methylphenol, thymol, isothymol and the like. These may be used alone or in combination of two or more.

Examples of the aldehydes include formaldehyde, formalin, paraformaldehyde, trioxane, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, and the like. m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn Benzaldehyde, terephthalaldehyde and the like. Acetone, methyl ethyl ketone, diethyl ketone, diphenyl ketone, etc. are mentioned as ketones. These may be used alone or in combination of two or more.

Among the above-mentioned, the novolak resin which used metacresol and paracresol together and condensed these and formaldehyde, formalin, or paraformaldehyde is especially preferable from a viewpoint of the sensitivity controllability of a resist. The input weight ratio (methcresol: paracresol) of methacresol and paracresol is 80: 20-20: 80 normally, Preferably it is 70: 30-50: 50. It is also preferable to use 3,5-dimethylphenol (ie, 3,5-xylenol). In this case, the input weight ratio (cresols: 3,5-xyllenol) of cresols (total amount of metacresol and paracresol) and 3,5-xylenol is usually 50:50 to 80:20, preferably Preferably from 60:40 to 70:30. The average molecular weight of the novolak resin is a weight average molecular weight in terms of monodisperse polystyrene measured by GPC, and is usually 1,000 to 10,000, preferably 2,000 to 7,000, more preferably 2,500 to 6,000. When the weight average molecular weight of novolak resin is too small, even if the crosslinking reaction of an exposure part generate | occur | produces, a molecular weight increase effect is small and it becomes easy to melt | dissolve in an alkaline developing solution.

If the weight average molecular weight of the novolak resin is too large, the difference in solubility in the alkaline developer of the exposed portion and the unexposed portion is small, and it is difficult to obtain a good resist pattern. The weight average molecular weight of polyvinyl phenol and a novolak resin can be controlled to a desired range by adjusting synthetic | combination conditions. In addition, for example, (1) a method of pulverizing the resin obtained by synthesis and solid-liquid extraction with an organic solvent having a suitable solubility, and (2) the resin obtained by synthesis is dissolved in a good solvent, The weight average molecular weight can be controlled by the method of dropwise addition or dropping of the poor solvent, solid-liquid or liquid-liquid extraction, or the like.

The measurement of the weight average molecular weight by GPC is performed on condition of the following using SC8020 (made by TOSO Corporation) as a GPC measuring apparatus.

Column: each one combination of TSKGEL G3000HXL and G200HXL1000 manufactured by TOSO,

Temperature: 38 ℃,

Solvent: tetrahydrofuran,

Flow rate: 1.0 ml / min,

Sample: 0.1 ml injection of a sample with a concentration of 0.05 to 0.6% by weight.

The use ratio of polyvinylphenol and novolak resin is a weight ratio of polyvinylphenol: novolak resin, and is usually 30:70 to 95: 5, preferably 35:65 to 95: 5, more preferably 40:60 to It is in the range of 90:10.

As the proportion of the polyvinylphenol increases, the heat resistance of the resist pattern becomes better, but the peeling off of the substrate becomes easier. When the ratio of novolak resin becomes large, the problem of peeling of the resist pattern from a board | substrate will be solved, but heat resistance will fall. Therefore, the balance of heat resistance and peeling resistance becomes favorable because the ratio of both exists in the said range.

&Lt; Acid Generator (D) >

As an acid generator (D), the compound which generate | occur | produces an acid by actinic light, and the compound which generate | occur | produce an acid by heat are illustrated.

The compound which generates an acid by actinic light is not particularly limited as long as it is a substance that generates brested acid or a Lewis acid when exposed by activating radiation, and there are no onium salts, halogenated organic compounds, quinonediazide compounds, α, Known ones such as α'-bis (sulfonyl) diazomethane compounds, α-carbonyl-α'-sulfonyldiazomethane compounds, sulfone compounds, organic acid ester compounds, organic acid amide compounds, and organic acid imide compounds Can be. Among these, aromatic sulfonic acid esters, aromatic iodonium salts, aromatic sulfonium salts, aromatic compounds having a halogenated alkyl residue, and the like are preferable. It is preferable to select these acid generators (D) from the viewpoint of spectral sensitivity according to the wavelength of the light source which exposes a pattern.

Examples of the onium salts include iodonium salts such as diazonium salts, ammonium salts and diphenyl iodonium triplates, sulfonium salts such as triphenylsulfonium triplates, phosphonium salts, arsonium salts, and oxonium salts. Can be mentioned.

As a halogenated organic compound, a halogen containing oxadiazole type compound, a halogen containing triazine type compound, a halogen containing acetophenone type compound, a halogen containing benzophenone type compound, a halogen containing sulfoxide type compound, a halogen containing sulfone type compound, a halogen Containing thiazole compounds, halogen-containing oxazole compounds, halogen-containing triazole compounds, halogen-containing 2-pyrone compounds, other halogen-containing heterocyclic compounds, halogen-containing aliphatic hydrocarbon compounds, halogen-containing aromatic hydrocarbon compounds, sulfenyl halide compounds, and the like. Can be mentioned.

Specific examples of the halogenated organic compound include tris (2,3-dibromopropyl) phosphate, tris (2,3-dibromo-3-chloropropyl) phosphate, tetrabromochlorobutane, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloroγmethyl) -S-triazine, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromocyclo Dodecene, hexabromobiphenyl, allyltribromophenyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, bis (chloroethyl) ether of tetrachlorobisphenol A, bis (bromoethyl) of tetrabromobisphenol A Ether, bis (2,3-dichloropropyl) ether of bisphenol A, bis (2,3-dibromopropyl) ether of bisphenol A, bis (2,3-dichloropropyl) ether of tetrachlorobisphenol A, tetrabro Bis (2,3-dibromopropyl) ether of mobisphenol A, tetrachlorobisphenol S, Tetrabromobisphenol S, bis (chloroethyl) ether of tetrachlorobisphenol S, bis (bromoethyl) ether of tetrabromobisphenol S, bis (2,3-dichloropropyl) ether of bisphenol S, bis of bisphenol S (2,3-dibromopropyl) ether, tris (2,3-dibromopropyl) isocyanurate, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, Halogen flame retardants such as 2,2-bis (4- (2-hydroxyethoxy) -3,5-dibromophenyl) propane; Dichlorodiphenyltrichloroethane, pentachlorophenol, 2,4,6-trichlorophenyl, 4-nitrophenylether, 2,4-dichlorophenyl, 3'-methoxy-4'-nitrophenylether, 2,4 -Dichlorophenoxyacetic acid, 4,5,6,7-tetrachlorophthalide, 1,1-bis (4-chlorophenyl) ethanol, 1,1-bis (4-chlorophenyl) -2,2,2 Organic chloro-based pesticides such as -trichloroethanol, 2,4,4 ', 5-tetrachlorodiphenyl sulfide, and 2,4,4', 5-tetrachlorodiphenyl sulfone.

Specific examples of the quinone diazide compound include 1,2-benzoquinone diazide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-4-sulfonic acid ester and 1,2-naphthoquinone diazide-5- Sulfonic acid esters of quinonediazide derivatives such as sulfonic acid esters, 2,1-naphthoquinonediazide-4-sulfonic acid esters, and 2,1-benzoquinonediazide-5-sulfonic acid esters; 1,2-benzoquinone-2-diazide-4-sulfonic acid chloride, 1,2-naphthoquinone-2-diazide-4-sulfonic acid chloride, 1,2-naphthoquinone-2-diazide-5- Sulfonic acid chlorides of quinonediazide derivatives such as sulfonic acid chloride, 1,2-naphthoquinone-1-diazide-6-sulfonic acid chloride and 1,2-benzoquinone-1-diazide-5-sulfonic acid chloride have.

Specific examples of the α, α′-bis (sulfonyl) diazomethane-based compound include α, α having an unsubstituted, symmetrically or asymmetrically substituted alkyl group, alkenyl group, aralkyl group, aromatic group or heterocyclic group '-Bis (sulfonyl) diazomethane and the like.

Specific examples of the α-carbonyl-α′-sulfonyldiazomethane-based compound include α- having an unsubstituted, symmetrically or asymmetrically substituted alkyl group, alkenyl group, aralkyl group, aromatic group, or heterocyclic group Carbonyl- (alpha) '-sulfonyl diazomethane etc. are mentioned.

As a specific example of a sulfone compound, the sulfone compound, disulfone compound, etc. which have an unsubstituted, symmetrically or asymmetrically substituted alkyl group, an alkenyl group, an aralkyl group, an aromatic group, or a heterocyclic group are mentioned.

Specific examples of the organic acid esters include carboxylic acid esters, sulfonic acid esters, and phosphoric acid esters. Examples of the organic acid amides include carboxylic acid amides, sulfonic acid amides, and phosphoric acid amides. Acid imide, sulfonate imide, phosphide imide and the like.

In addition, as an acid generator (D), cyclohexyl methyl (2-oxocyclohexyl) sulfonium trifluoromethane sulfonate, dicyclohexyl (2-oxocyclohexyl) sulfonium trifluoro methane sulfonate, 2- Oxocyclohexyl (2-norbornyl) sulfoniumtrifluoromethanesulfonate, 2-cyclohexylsulfonylcyclohexanone, dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium Trifluoromethanesulfonate, diphenyliodonium trifluoromethanesulfonate, N-hydroxysuccinimidetrifluoromethanesulfonate, phenyl paratoluenesulfonate, and the like.

The acid generator (D) is usually used in an amount of 0.1 to 10 parts by weight, preferably 0.3 to 8 parts by weight, and more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (A). If the ratio of the acid generator (D) is too small or excessive, the shape of the resist pattern may be deteriorated.

<Crosslinking System (C)>

A crosslinking agent (C) is a compound (subduction substance) which can bridge | crosslink alkali-soluble resin in presence of the acid generate | occur | produced by irradiation of actinic light (exposure). As such a crosslinking agent, well-known acid crosslinking compounds, such as an alkoxy methylation urea resin, the alkoxy methylation melamine resin, the alkoxy methylation uron resin, the alkoxy methylation glycoluril resin, and the alkoxy methylation amino resin, are mentioned, for example. In addition, alkyl ether melamine resin, benzoguanamine resin, alkyl ether benzoguanamine resin, urea resin, alkyl ether urea resin, urethane-formaldehyde resin, resol type phenol formaldehyde resin, alkyl ether resol type phenol form Aldehyde resin, an epoxy resin, etc. are mentioned.

Among these, an alkoxy methylated amino resin is preferable, and specific examples thereof include methoxymethylated amino resin, ethoxymethylated amino resin, n-propoxymethylated amino resin, n-butoxymethylated amino resin and the like. Among these, methoxymethylated amino resins such as hexamethoxymethylmelamine are particularly preferable in view of good resolution. As a commercial item of the alkoxy methylated amino resin, for example, PL-1170, PL-1174, UFR65, CYMEL300, CYMEL303 (above, Mitsui Cytec Co., Ltd.), BX-4000, Nikalak MW-30, MX290 (above, Sanwa Chemical) Company) etc. are mentioned.

These crosslinking agents can be used individually or in combination of 2 types or more, respectively. The crosslinking agent (C) is usually used in an amount of 0.5 to 60 parts by weight, preferably 1 to 50 parts by weight, and more preferably 2 to 40 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (A). If the amount of the crosslinking agent is too small, it is difficult for the crosslinking reaction to proceed sufficiently, so that the residual film ratio of the resist pattern after development using the alkaline developer is lowered, or deformation such as swelling or meandering of the resist pattern is likely to occur. When the usage-amount of a crosslinking agent is too much, there exists a possibility that a resolution may fall.

The photosensitive resin composition of this invention can contain a solvent (E).

Examples of the solvent that can be used in the present invention include ester solvents (solvents containing -COO-), ether solvents other than ester solvents (solvents containing -O-), ether ester solvents (-COO- and -O- Solvent), ketone solvents other than ester solvents (solvents containing -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.

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

As an ether solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, Tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phentol And methyl anisole.

As an ether ester solvent, For example, methyl methoxy acetate, methoxy acetate, methoxy butyl acetate, methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-methoxy propionate, 3-methoxy propionate, 3- Methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy Methyl oxy-2-methyl propionate, 2-ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate , Propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether Acetate, di, and the like ethylene glycol monobutyl ether acetate.

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

As an alcohol solvent, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, etc. are mentioned, for example.

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

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

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

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

Content of the solvent (E) in the photosensitive resin composition becomes like this. Preferably it is 60 to 95 weight%, More preferably, it is 70 to 90 weight% with respect to the total amount of the component contained in the photosensitive resin composition. In other words, solid content of the photosensitive resin composition becomes like this. Preferably it is 5-40 weight%, More preferably, it is 10-30 weight%. When content of a solvent exists in the said range, there exists a tendency for the flatness of the film | membrane formed by apply | coating the photosensitive resin composition to be high. Solid content means the component remove | excluding the solvent from the photosensitive resin composition here.

The compound which absorbs actinic light (henceforth "light absorber (H)") can also be added to the photosensitive resin composition of this invention as needed.

When the photosensitive resin composition contains a compound that absorbs the actinic light, the light absorbs the light that proceeds in the depth direction of the resist film during exposure, so that the resist pattern can be obtained from the forward taper phase or the reverse taper shape or the overhang phase. have. The shape of the resist pattern is also affected by the reflection of light exposed by a substrate or an ITO film formed on the substrate. Therefore, the light absorbing agent (H) is required also for the reflection prevention of exposure light. In particular, the photosensitive resin composition using a combination of an acid generator (D) and a crosslinking agent (C) is a crosslinking chemically amplified resist, and an acid generated by irradiation of light diffuses in the resist film and crosslinks to a region where light does not reach. Since a reaction is caused, the shape of a resist pattern can be controlled by providing the light absorbing agent (H) which absorbs actinic light.

As a light absorber (H), the compound which has an absorption region in the wavelength range can be selected according to the wavelength of an exposure light source. However, in the case where the light absorbent (H) is a compound having low solubility in an alkaline developer, since the light absorber (H) is likely to remain on the substrate after development, an acidic residue such as a phenolic hydroxyl group, a carboxyl group or a sulfonyl group is provided. And the compound which raised the solubility to alkaline developing solution is preferable. In addition, for the purpose of solving the problem of residue generation, it is preferable to select a compound having a higher absorbance so that sufficient absorbance can be obtained with a small amount of addition. When the formed resist pattern is exposed to high temperatures in a post-exposure baking (PEB) or sputtering process, the light absorbent (H) may sublimate and contaminate the device. Therefore, the light absorbent (H) is a compound having low sublimability. Is preferably.

As a light absorber (H) used by this invention, what is called an azo dye is preferable. Examples of the azo dye include azobenzene derivatives, azonaphthalene derivatives, azobenzene or azonaphthalene substituents of arylpyrrolidone, and heterocyclic arylazo compounds such as pyrazolone, benzpyrazolone, pyrazole, imidazole, and thiazole. Etc. can be mentioned.

These aryl azo compounds can appropriately select the length of the conjugated system, the kind of substituents, etc. in order to set the absorption wavelength to a desired region. For example, an arylazo compound having a short wavelength absorption region is substituted with an electron withdrawing group such as a sulfonic acid (metal salt) group, a sulfonic acid ester group, a sulfonic group, a carboxyl group, a cyano group, a (substituted) aryl or an alkylcarbonyl group or a halogen. can do. Further, an aryl azo in which the absorption wavelength is set to a long wavelength region by substitution according to electron donating groups such as amino, hydroxy, alkoxy or aryloxy groups substituted with (substituted) alkyl, (substituted) aryl or polyoxyalkylene. You may make it a compound. As a substituent, there exist groups which reduce the solubility to an alkaline developing solution like an amino group, and a group which raises the solubility to an alkaline developing solution like a carboxyl group and a hydroxyl group, so that the sensitivity of the photosensitive resin composition of this invention may become a practical level. It is preferable to select the kind of substituent appropriately.

In the case of an azo dye, by selecting the structure of a compound and the kind of substituent, various compounds which absorb an actinic light in the wide wavelength range of 200-500 nm can be used. The selection of the length and the substituent of such a conjugated system is also suitable for compounds other than azo dyes. As a compound mainly corresponding to the light source of a 300-400 nm wavelength range, the styrene derivative obtained by condensing a (substituted) benzaldehyde and the compound which has an active methylene group is mentioned. Examples of the benzaldehyde substituent include an alkylamino group substituted with a hydroxy group, an alkoxy group or a halogen atom, a polyoxyalkyleneamino group, a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, an alkylcarbonyl group or an arylcarbonyl group.

As a compound which has an active methylene group, 1, 3- diketones, such as acetonitrile, (alpha)-cyanoacetic acid ester, (alpha) -cyano ketones, malonic acid ester, acetoacetic acid ester, etc. are mentioned, for example.

As the light absorbing agent (H), natural compounds such as methine dyes obtained by condensation of arylpyrazolone and arylaldehyde, arylbenzotriazoles, azomethine dyes obtained as condensates of amines and aldehydes, curcumin, xanthone, and the like Can also be used. The developing characteristic can be adjusted using the compound which absorbs exposure light, changes solubility to alkaline developing solution, or crosslinks reaction, such as quinone diazide sulfonic-acid esterified product of the dye which has an arylhydroxy group, and a bisazide compound.

As the light absorbing agent (H), for example, cyano vinyl styrene-based compound, 1-cyano-2- (4-dialkylaminophenyl) ethylene, p- (halogen substituted phenylazo) -dialkylaminobenzene 1-alkoxy-4- (4'-N, N-dialkylaminophenylazo) benzenes, dialkylamino compounds, 1,2-dicyanoethylene, 9-cyanoanthracene, 9-anthrylmethylenemalo Nonnitrile, N-ethyl-3-carbazolyl methylenemalononitrile, 2- (3,3-dicyano-2-propenylidene) -3-methyl-1,3-thiazoline and the like can be used.

Among the commercially available dyes, those useful as light absorbers (H) include, for example, oil yellow # 101, oil yellow # 103, oil yellow # 117, oil pink # 312, oil green BG, oil blue BOS, oil blue # 603 , Oil black BY, oil black BS, oil black T-505 (above Orient Chemical Co., Ltd. make), crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170B), malachite green (CI42000), methylene blue (CI52015), etc. are mentioned.

Examples of the 1-cyano-2- (4-dialkylaminophenyl) ethylenes include 1-carboxy-1-cyano-2- (4-di-n-hexylaminophenyl) ethylene and 1-carboxy. Carboxyl group in 1 position, such as -1-cyano-2- (4-di-n-butylaminophenyl) ethylene and 1-carboxy-1-cyano-2- (4-di-n-heptylaminophenyl) ethylene 1-cyano-2- (4-dialkylaminophenyl) ethylene which has the following is mentioned.

These 1-cyano-2- (4-dialkylaminophenyl) ethylenes, oil yellow # 101, oil yellow # 103, oil yellow # 107, etc. are excellent in the formation of the resist pattern profile of an inverted tape form. Particularly preferred. In addition, an inverse taper shape means the shape which becomes wider as the cross-sectional shape of the pattern structure formed by pattern-forming the photosensitive resin composition is separated from a board | substrate. In the case of forming a resist pattern having an inverted taper shape or an overhanging cross section, the amount of the light absorbing agent (H) can be appropriately determined depending on the film thickness of the photosensitive resin composition, the kind of the light absorbing agent (H), and the like. In the case of thick, light may be relatively difficult to transmit, and in the case of thin, relatively large amount is used. The light absorbing agent (H) is usually used in an amount of 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, and particularly preferably 1 to 8 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. In the case of forming a resist pattern having a forward tapered cross section, the amount of the light absorbing agent (H) is smaller than that in the case of forming an inverse taper or overhang resist pattern, and the amount of the light absorbing agent (H) is small, with respect to 100 parts by weight of the alkali-soluble resin (A), Unused (0) to less than 0.1 parts by weight is used.

The photosensitive resin composition of this invention may contain surfactant (F). As surfactant (F), silicone type surfactant, a fluorine type surfactant, silicone type surfactant which has a fluorine atom, etc. are mentioned, for example. However, surfactant (F) has a compound of a structure different from a fluorine-type liquid repellent (B) as a main component.

Examples of the silicone-based surfactants include surfactants having siloxane bonds. For example, Toray Silicone DC3PA, Copper SH7PA, Copper DC11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Polyether-modified silicone oil SH8400 Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials Japan Kogyo Co., Ltd.), etc. are mentioned.

As a fluorine type surfactant, surfactant which has a fluorocarbon chain | strand is mentioned, For example, Fluoronate (trademark) FC430, Copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapack (trademark) F142D , F171, F172, F173, F177, F183, R30 (manufactured by DIC Corporation), FTOP® EF301, EF303, EF351, EF352 (Mitsubishi Material Denshi Kasei Co., Ltd.) Manufacture), Suplon (trademark) S381, S382, SSC101, SSC105 (made by Asahi Glass Co., Ltd.), E5844 (made by Daikin Fine Chemical Co., Ltd.), etc. are mentioned.

As silicone type surfactant which has a fluorine atom, surfactant which has a siloxane bond and a fluorocarbon chain | strand is mentioned, For example, Megapack (R) R08, copper BL20, copper F475, copper F477, copper F443 (DIC) Co., Ltd.) etc. are mentioned. Preferably Megapack (trademark) F475 is mentioned.

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

In the photosensitive resin composition of this invention, various additives, such as a filler, another high molecular compound, an adhesion promoter, antioxidant, a ultraviolet absorber, a light stabilizer, a chain transfer agent, can also be used together as needed.

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

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

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

The photosensitive resin composition of this invention is apply | coated on these board | substrates which formed the base material, for example, substrates, such as glass, a metal, a plastic, color filters, various insulation or conductive films, a drive circuit, etc., as mentioned later, for example. And can be formed as a coating film. It is preferable that the coating film dried and hardened | cured. Moreover, the obtained coating film can also be patterned to a desired shape, and can also be used as a pattern structure. Moreover, these coating films or pattern structures can also be formed and used as a part of component parts, such as a display apparatus.

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

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

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

In this case, the film thickness of a coating film is not specifically limited, It can adjust suitably according to the material, a use, etc. to be used, for example, about 1-6 micrometers.

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

In recent exposure machines, light below 350 nm is blocked using a filter that blocks this wavelength range, or light around 436 nm, 408 nm and 365 nm is used by using a band pass filter for extracting these wavelength ranges. By taking out selectively, a substantially parallel light beam can be irradiated uniformly to the whole exposure surface. By using a device such as a mask aligner or a stepper, accurate position alignment between the mask and the substrate can be performed at this time.

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

The developing method may be any of a puddle method, a dipping method, a spray method, and the like. The substrate may also be tilted at any angle during development.

As for the developing solution used for image development, the aqueous solution of a basic compound is preferable. The basic compound may be any of inorganic and organic basic compounds.

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

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

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

The developer may contain a surfactant.

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

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

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

Examples of the cationic surfactants include amine salts and quaternary ammonium salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride.

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

After development, the patterned structure can be obtained by patterning with water washing. In addition, post-baking can be performed as needed. It is preferable to perform post-baking for 10 to 180 minutes in the temperature range of 150-240 degreeC, for example.

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

Thus, the pattern structure obtained from the photosensitive resin composition of this invention has high heat resistance and liquid repellency, and since there are no residues (or very few) other than the formation part of a pattern, especially in a coating type process, such as an inkjet method, a color filter and a liquid crystal It is useful as a partition used for producing the ITO electrode of an display element, an organic electroluminescent display element, a circuit wiring board, etc. In particular, the photosensitive resin composition of this invention is used suitably as a partition for manufacturing an organic electroluminescent element from the said characteristic.

The partition formation process which forms the partition provided in order to form an organic electroluminescent element on a support substrate using the said photosensitive resin composition is demonstrated with reference to FIG. Moreover, although the taper shape of the partition shown in FIG. 3 is an illustration, it does not necessarily need to be an illustrated shape, What is necessary is just a structure which can form an organic electroluminescent layer in the coating film of uniform and flat film thickness.

First, the support substrate 1 in which the 1st electrode 2 was formed is prepared (FIG. 3A). Next, the photosensitive resin composition 11 is formed into a film on the support substrate 1 by a coating process, and prebaking is performed (FIG. 3B). Then, light is selectively irradiated only to the site | part which should form a partition through the mask 10 with respect to the photosensitive resin composition formed into a film (FIG. 3C). In addition, the partition wall 3 is formed by developing and performing post-baking (FIG. 3D).

In addition, the partition 3 is not limited to a single structure, For example, you may further form the partition 3a on the partition 3 shown in FIG. 3 (refer FIG. 4A-4D). These overlapping partitions 3 and 3a can also be formed using the same photosensitive resin composition, and can also be formed using a different photosensitive resin composition. Moreover, although the taper shape of the partition shown in FIGS. 4A-4D is an illustration, it does not necessarily need to be an illustrated shape, What is necessary is just a structure which can form an organic EL layer in the coating film of uniform and flat film thickness.

Accordingly, the stacked partition walls may have the same or different shapes.

Thus, when forming a partition by overlapping, for example, the support substrate obtained by FIG. 3D WHEREIN: Furthermore, the photosensitive resin composition is apply-coated and prebaked (FIG. 4B), and it exposes (FIG. 4C), and develops. And the partition 3a is formed by performing post-baking (FIG. 4D).

Next, the structure of the organic electroluminescent element used as an organic electroluminescence display is demonstrated.

<Configuration of Organic EL Element>

The organic EL element has at least one light emitting layer as the organic EL layer, but may have, for example, a hole injection layer, a hole transport layer, an electron block layer, a hole block layer, an electron transport layer, an electron injection layer, or the like as the organic EL layer. have.

An example of the layer structure which an organic EL element can take is shown below.

a) anode / light emitting layer / cathode

b) anode / hole injection layer / light emitting layer / cathode

c) anode / hole injection layer / light emitting layer / electron injection layer / cathode

d) anode / hole injection layer / light emitting layer / electron transport layer / cathode

e) anode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode

f) anode / hole transport layer / light emitting layer / cathode

g) anode / hole transport layer / light emitting layer / electron injection layer / cathode

h) anode / hole transport layer / light emitting layer / electron transport layer / cathode

i) Anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

j) Anode / hole injection layer / hole transport layer / light emitting layer / cathode

k) anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode

l) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode

m) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

n) anode / light emitting layer / electron injection layer / cathode

o) anode / light emitting layer / electron transport layer / cathode

p) anode / light emitting layer / electron transport layer / electron injection layer / cathode

(Here, the symbol "/" indicates that each layer having the symbol "/" is laminated adjacently. The same applies hereinafter)

In addition, a first electrode serving as an anode may be disposed near the supporting substrate with respect to the second electrode, and a first electrode serving as a cathode may be disposed near the supporting substrate with respect to the second electrode.

<Support substrate>

What does not change chemically in the process of manufacturing organic electroluminescent element is preferably used for a support substrate, For example, glass, a plastic, a polymer film, a silicon plate, what laminated | stacked these, etc. are used.

<Anode>

In the case of the organic EL element of the structure which the light radiate | emitted from a light emitting layer is radiate | emitted externally through an anode, the electrode which shows light transmittance is used for an anode. As an electrode which shows light transmittance, thin films, such as a metal oxide, a metal sulfide, and a metal, can be used, The thing with high electrical conductivity and light transmittance is used preferably. Specifically, a thin film containing indium oxide, zinc oxide, tin oxide, ITO, indium zinc oxide (IZO), gold, platinum, silver, and copper is used as the anode, and among these, ITO, Thin films containing IZO or tin oxide are preferably used. As a manufacturing method of an anode, a vacuum vapor deposition method, sputtering method, an ion plating method, a plating method, etc. are mentioned. Moreover, organic transparent conductive films, such as polyaniline or its derivative (s), polythiophene or its derivative (s), can also be used as said anode.

<Cathode>

As the material of the cathode, a material having a small work function, easy injection of electrons into the light emitting layer, and high electrical conductivity is preferable. In addition, as an organic EL element having a configuration in which light is taken out from the anode side, a material having a high reflectance with respect to visible light is preferable as the material of the cathode in order to reflect light emitted from the light emitting layer from the cathode to the anode side. As the negative electrode, for example, alkali metals, alkaline earth metals, transition metals and Group 13 metals of the periodic table can be used. Examples of the material of the cathode include lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium and ytterbium. Metals such as; Two or more alloys of the above metals; An alloy of at least one of the above metals and at least one of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin; Or a graphite or graphite interlayer compound or the like is used. Examples of the alloy include a magnesium-silver alloy, a magnesium-indium alloy, a magnesium-aluminum alloy, an indium-silver alloy, a lithium-aluminum alloy, a lithium-magnesium alloy, a lithium-indium alloy, a calcium-aluminum alloy, and the like. As the cathode, a transparent conductive electrode containing a conductive metal oxide, a conductive organic substance, or the like can be used. Specifically, examples of the conductive metal oxide include indium oxide, zinc oxide, tin oxide, ITO and IZO, and conductive organic materials include polyaniline or derivatives thereof, polythiophenes or derivatives thereof, and the like. The cathode may also be composed of a laminate in which two or more layers are laminated. Moreover, an electron injection layer can also be used as a cathode.

As a manufacturing method of a cathode, a vacuum vapor deposition method, an ion plating method, etc. are mentioned, for example.

The film thickness of the positive electrode or the negative electrode is appropriately set in consideration of the required characteristics, the simplicity of the film forming process, and the like, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm. The electrode corresponding to the second electrode in the anode and the cathode may be formed so that the film thickness becomes thicker than the distance in the thickness direction of the support substrate between the interface between the second electrode and the organic EL layer and the top surface of the partition wall. have.

<Hole injection layer>

Examples of the hole injection material constituting the hole injection layer include oxides such as vanadium oxide, molybdenum oxide, ruthenium oxide, and aluminum oxide, phenylamine compounds, starburst amine compounds, phthalocyanine compounds, amorphous carbons, and polyaniline. And polythiophene derivatives.

As a film-forming method of a hole injection layer, film-forming from the solution containing a hole injection material is mentioned, for example. For example, the hole injection layer can be formed by apply | coating into a film-forming solution containing a hole injection material by a predetermined | prescribed coating method, and solidifying it further.

The film thickness of the hole injection layer is appropriately set in consideration of the required properties and the simplicity of the process, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm. To 200 nm.

&Lt; Hole transport layer &

Examples of the hole transport material constituting the hole transport layer include polyvinylcarbazole or derivatives thereof, polysilane or derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, pyrazoline derivatives, arylamine derivatives and stilbene derivatives. , Triphenyldiamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, polyarylamines or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylenevinylene) or derivatives thereof, or poly (2,5- Thienylenevinylene) or derivatives thereof, and the like.

The film thickness of the hole transporting layer is set in consideration of required properties, simplicity of the film forming process, and the like, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

<Light Emitting Layer>

The light emitting layer is usually formed of an organic material that mainly emits fluorescence and / or phosphorescence, or a dopant supporting the organic material. The dopant is added, for example, to improve the luminous efficiency or to change the emission wavelength. The organic material constituting the light emitting layer may be a low molecular compound or a high molecular compound, and in the case of forming the light emitting layer by a coating process, the light emitting layer preferably contains a high molecular compound. The number average molecular weight of polystyrene conversion of the high molecular compound which comprises a light emitting layer is about 10 <^3> -10 <^8> , for example. As a light emitting material which comprises a light emitting layer, the following pigment | dye type material, a metal complex system material, a polymer type material, and a dopant material are mentioned, for example.

(Pigment material)

Examples of the dye-based material include a cyclopentamine derivative, a tetraphenylbutadiene derivative compound, a triphenylamine derivative, an oxadiazole derivative, a pyrazoloquinoline derivative, a distyrylbenzene derivative, a distyryl arylene derivative, a pyrrole derivative and a thi Ophen ring compounds, pyridine ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, oxadiazole dimers, pyrazoline dimers, quinacridone derivatives, coumarin derivatives and the like.

(Metal complex system material)

Examples of the metal complex system material include rare earth metals such as Tb, Eu, and Dy, or Al, Zn, Be, Ir, and Pt in the central metal, and include oxadiazole, thiadiazole, phenylpyridine, and phenylbenzo. The metal complex which has imidazole, a quinoline structure, etc. in a ligand is mentioned, For example, the metal complex which has light emission from triplet excited states, such as an iridium complex and a platinum complex, an aluminum quinolinol complex, a benzoquinolinol beryllium The complex, a benzoxazolyl zinc complex, a benzothiazole zinc complex, an azomethyl zinc complex, a porphyrin zinc complex, a phenanthroline europium complex, etc. are mentioned.

(High molecular weight material)

Examples of the polymer-based material include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, and the dye system. And a polymerized material or a metal complex light emitting material.

The thickness of the light emitting layer is usually about 2 nm to 200 nm.

<Electron transport layer>

As the electron transporting material constituting the electron transporting layer, known materials can be used. For example, oxadiazole derivatives, anthraquinomethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinones or the like Derivatives, tetracyanoanthracinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, Polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof, and the like.

The film thickness of the electron transporting layer is appropriately set in consideration of required characteristics, simplicity of the film forming process, and the like, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm. To 200 nm.

<Electron injection layer>

As the material constituting the electron injection layer, an optimal material is appropriately selected according to the type of the light emitting layer, for example, an alloy containing at least one of alkali metal, alkaline earth metal, alkali metal and alkaline earth metal, alkali metal or Oxides, halides, carbonates, mixtures of these substances, and the like of alkaline earth metals. Examples of alkali metals, oxides, halides and carbonates of alkali metals include lithium, sodium, potassium, rubidium, cesium, lithium oxide, lithium fluoride, sodium oxide, sodium fluoride, potassium oxide, potassium fluoride, rubidium oxide, rubidium fluoride, Cesium oxide, cesium fluoride, lithium carbonate and the like. Examples of the oxides, halides, and carbonates of alkaline earth metals and alkaline earth metals include magnesium, calcium, barium, strontium, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, barium oxide, barium fluoride, strontium oxide, strontium fluoride, and carbonate. Magnesium etc. are mentioned. The electron injection layer may be composed of a laminate in which two or more layers are laminated, and examples thereof include LiF / Ca and the like.

As a film thickness of an electron injection layer, about 1 nm-about 1 micrometer are preferable.

Each organic EL layer described above can be formed by, for example, a coating method such as a nozzle printing method, an inkjet printing method, an iron plate printing method, an intaglio printing method, a vacuum deposition method, a sputtering method, or a CVD method.

In addition, in the application | coating type | mold process, the ink containing the material and solvent which become each organic EL layer is apply | coated and formed into a film, and a solvent is evaporated and it solidifies and an organic EL layer is formed, but the solvent of the ink used at that time For example, chlorine solvents such as chloroform, methylene chloride and dichloroethane, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone and methyl ethyl ketone, ethyl acetate and acetic acid Ester solvents, such as butyl and an ethyl cellosolve acetate, water, etc. are used.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples. "%" And "part" in an example are the weight% and a weight part, unless it mentions specially.

(Synthesis Example 1)

30 parts of methacrylic acid, 30 parts of 2-hydroxyethyl methacrylate, 40 parts of isobornyl methacrylate, 2-sulfanylethanol in a four-necked flask equipped with a reflux cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device. 5.9 parts and 163 parts of propylene glycol monomethyl ether acetate were added, and it heated at 70 degreeC, and stirred for 30 minutes under nitrogen stream. 1.3 parts of azobisisobutyronitrile were added to this, and it superposed | polymerized for 18 hours. Thereafter, 29.3 parts of 2-isocyanatoethyl acrylate (Karens AOI; manufactured by Showa Denko Co., Ltd.) were added, 50 ppm of hydroquinone monomethyl ether was added to the entire composition, and the reaction was carried out at 45 ° C. for 1 hour under a nitrogen stream. This obtained the solution of the copolymer (alkali-soluble resin Ab) of 34 weight% of solid content. The weight average molecular weight (Mw) of obtained alkali-soluble resin Ab was 4900.

(Synthesis Example 2)

78 parts of α-chloroacrylic acid 3,3,4,4,5,5,6,6,6-nanofluorohexyl, methacryl in a four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirring device. 19.5 parts of acid, 19.5 parts of isobornyl methacrylate, 13 parts of glycidyl methacrylate, 12.7 parts of dodecanethiol, and 266 parts of propylene glycol monomethyl ether acetate were added thereto, and heated to 70 ° C, followed by 30 minutes under nitrogen stream. Stirred. 1 part of azobisisobutyronitrile was added to this, and it superposed | polymerized for 18 hours and obtained the solution of the copolymer (fluorine-type liquid repellent agent Ba) of 33 weight% of solid content, and acid value 68 mg-KOH / g (solid content conversion). The weight average molecular weight of obtained resin Ba was 7,500.

The fluorine-based liquid repellent agent Ba has the following structural units.

(Synthesis Example 3)

Α-chloromethacrylic acid 3,3,4,4,5,5,6,6,7,7,8,8,8 in a four-necked flask equipped with reflux cooling tube, nitrogen introduction tube, thermometer and stirring device Add 78 parts of tridecafluorooctyl, 19.5 parts of methacrylic acid, 19.5 parts of isobornyl methacrylate, 13 parts of glycidyl methacrylate, 12.7 parts of dodecanethiol, and 266 parts of propylene glycol monomethyl ether acetate. After heating to 占 폚, the mixture was stirred under nitrogen stream for 30 minutes. 1 part of azobisisobutyronitrile was added to this, and it superposed | polymerized for 18 hours and obtained the solution of the copolymer (fluorine-type liquid repellent Bb) of 33 weight% of solid content and acid value 65 mg-KOH / g (solid content conversion). The weight average molecular weight of obtained resin Bb was 6,800.

Fluorine-based liquid repellent Bb has the following structural units.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of resin obtained by the synthesis examples 1, 2 and 3 was performed on condition of the following using GPC method.

Device; K2479 (manufactured by Shimadzu Corporation)

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Flow rate; 1.0 mL / min

Detector; RI

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

(Synthesis Example 4)

Novolak resin (weight average molecular weight 4,000) obtained by dehydrating condensation of formaldehyde with 90 weight part of poly p-vinylphenol (weight average molecular weight 6,000), and m-cresol / p-cresol at the input ratio of 70/30 (weight ratio) 10 Alkali-soluble resin Aa containing a weight part was obtained.

Furthermore, the novolak resin (weight average molecular weight 4,000) obtained by dehydrating condensation of formaldehyde with 60 weight part of poly p-vinylphenol (weight average molecular weight 6,000), and m-cresol / p-cresol at the input ratio of 70/30 (weight ratio). Alkali-soluble resin Aa 'containing 40 weight part was obtained.

<Production of Photosensitive Resin>

Each component was mixed with solvent Ea (propylene glycol monomethyl ether acetate) so that solid content might be 18.0%, and the negative photosensitive resin compositions 1, 2, and 3 of Table 3 below were obtained.

In Table 3, the numerical value of each component in an Example shows the weight% (composition ratio) of each component when the solid content (A + C + D) is 100 weight part in the photosensitive resin composition. The numerical value of each component in a comparative example shows the weight% (composition ratio) of each component when the solid content (A + B + C + G) is 100 weight part in the photosensitive resin composition.

Each component used by the Example and the comparative example is as follows.

Ca: melamine type resin crosslinking agent (made by Mitsui Scitex, Cymel 303)

Cb: melamine-based resin crosslinking agent (manufactured by Mitsui Scitex, Cymel 300)

Ha; Light absorber (dye) ORIGAGA Co., Ltd. make: oil yellow

Ga: tetrahydro phthalic anhydride (Licaside TH: Shin-Nihon Rika Co., Ltd. product)

Gb: 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropane-1-one (photopolymerization initiator Irgacure 127; BASF Japan Co., Ltd.

Gc: pentaerythritol tetraacrylate (polymerizable compound A-TMMT; Shin-Nakamura Chemical Co., Ltd. make)

<Transmittance of Composition>

For the photosensitive resin composition obtained above, the average transmittance at 400 to 700 nm, respectively, using an ultraviolet visible near infrared spectrophotometer (V-650; manufactured by Nihon Bunk Co., Ltd.) (quartz cell, optical path length; 1 cm). (%) Was measured. The results are shown in Table 4 below.

<Production of coating>

A glass substrate (Eagle XG; manufactured by Corning) having a side of 2 inches was washed sequentially with a neutral detergent, water, and alcohol, and then dried. On this glass substrate, the photosensitive resin compositions 1, 2, and 3 obtained above are spin-coated so that the film thickness after post-baking may be set to 3.0 micrometers, respectively, and a pressure reduction degree will be 66 kPa by a vacuum dryer (microtech). It was dried under reduced pressure until it was then dried by prebaking at 80 ° C. for 2 minutes with a hot plate. After cooling, light of an exposure dose of 50 mJ / cm 2 (365 nm standard) was irradiated under an atmospheric atmosphere using an exposure machine (TME-150 RSK; manufactured by Topcon Corporation, a light source; ultra-high pressure mercury lamp). In addition, the irradiation to the photosensitive resin composition at this time used the ultrahigh pressure mercury lamp. After light irradiation, the photosensitive resin compositions 1 and 2 bridge | crosslinked the exposure part by baking by a hot plate at 110 degreeC for 60 second. Thereafter, the coating film was immersed and stirred for 60 seconds at 23 ° C. for 60 seconds in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, and then heated (post-baked) at 230 ° C. for 20 minutes in an oven. A coating film was obtained.

About the photosensitive resin composition 3, the coating amount was obtained by the method similar to the above except the exposure amount was replaced with 500 mJ / cm <2> (365 nm reference | standard), and baking after light irradiation was not performed.

<Average transmittance of coating film>

About the obtained coating film, the average transmittance | permeability (%) in 400-700 nm was measured using the microscopic spectrophotometer (OSP-SP200; Olympus company). Higher transmittance means less absorption.

<Contact angle>

About the obtained coating film, the contact angle with the anisole was measured using the contact angle meter (DGD Fast / 60; GBX Corporation make). The measurement results are shown in Table 5 below.

Higher contact angle means higher liquid repellency. When the contact angle in a coating film is high, the contact angle is high also in the pattern formed using the same photosensitive resin composition. When a partition is formed with the photosensitive resin composition with a high contact angle, and ink is apply | coated in the center surrounded by the said partition, ink is easy to dewet. For this reason, when a color filter is produced by the inkjet method, mixing of the ink between adjoining pixel areas hardly occurs, for example.

&Lt; Evaluation of heat resistance &

The obtained coating film was heated at 240 degreeC in clean oven for 1 hour, and the film thickness and transmittance | permeability were measured. From the film thickness before and after heating, and the transmittance | permeability in 400 nm, change rate was calculated | required respectively by the following formula.

Film thickness change rate (%) = film thickness after heating (μm) / film thickness before heating (μm) × 100

Transmittance change rate (%) = transmittance after heating (%) / transmittance before heating (%) x 100

If heat resistance in a coating film is favorable, heat resistance will be favorable also in the pattern formed using the same photosensitive resin composition. The results are shown in Table 6 below.

&Lt; Pattern formation >

A glass substrate (Eagle XG; manufactured by Corning) having a side of 2 inches was washed sequentially with a neutral detergent, water, and alcohol, and then dried. On this glass substrate, the photosensitive resin compositions 1 and 2 were spin-coated so that the film thickness after post-baking might be set to 3.5 micrometers, respectively, and it dried under reduced pressure until the pressure reduction degree became 66 kPa with a pressure reduction dryer (Microtech Co., Ltd. product). Thereafter, the plate was dried by prebaking at 80 ° C. for 2 minutes. After cooling, the space | interval of the board | substrate which apply | coated this photosensitive resin composition 1, 2, 3, and the quartz glass photomask was set to 10 micrometers, and the exposure machine (TME-150 RSK; Topcon Co., Ltd. light source, ultrahigh pressure mercury lamp) Light was irradiated with an exposure dose of 50 mJ / cm 2 (365 nm standard) in an air atmosphere. In addition, irradiation to the photosensitive resin composition at this time was performed through the optical beam (UV-33; Asahi Bunko Co., Ltd. make) the light emitted from an ultrahigh pressure mercury lamp. As a photomask, a photomask in which a pattern (a plurality of square transmissive portions of 13 μm in one side were formed and the interval of the square was 100 μm) (that is, a transmissive portion) was formed on the same plane was used.

After light irradiation, the photosensitive resin compositions 1 and 2 bridge | crosslinked the exposure part by baking by a hot plate at 110 degreeC for 60 second. Thereafter, the coating film was immersed and shaken in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C for 100 seconds for development. After washing with water, post-baking was carried out at 235 ° C for 15 minutes in an oven. It carried out and obtained the pattern.

About the photosensitive resin composition 3, the coating amount was obtained by the method similar to the above except the exposure amount was replaced with 500 mJ / cm <2> (365 nm reference | standard), and baking after light irradiation was not performed.

<Determination of "Presence" of Residues Other Than Pattern Part>

Pure water and anisole were filled with an inkjet device (Litrex142P manufactured by ULVAC) in an area surrounded by a partition including the pattern structure formed above. It was observed under a microscope whether dewetting did not occur at the boundary between the partition wall and the area surrounded by the partition wall. Dewetting did not generate | occur | produce in the partitions obtained from the photosensitive resin compositions 1 and 2 which are Examples, and dewetting occurred in the partition obtained from the photosensitive resin composition 3 which is a comparative example.

From the results of the examples, it can be seen that by using the negative photosensitive resin composition of the present invention, a pattern having no residue (very little) other than the coating film and the pattern portion excellent in heat resistance can be formed.

1: support substrate
2: first electrode
3: partition wall
3a: bulkhead
4: organic EL layer
5: area enclosed by the bulkhead
6: ink
7: Second electrode
10: mask
11: photosensitive resin composition

Claims (9)

It is a negative photosensitive resin composition containing alkali-soluble resin (A), a fluorine-type liquid repellent agent (B), a crosslinking agent (C), and an acid generator (D),
The fluorine-based liquid-repellent agent (B) is an addition polymer containing a structural unit derived from an unsaturated compound having a fluoroalkyl group having 4 to 6 carbon atoms, and the addition ratio of the fluorine-based liquid-repellent agent (B) is 0.01 to total solids in the composition. Photosensitive resin composition which is 1.0 weight%. The photosensitive resin composition of Claim 1 which further contains a solvent (E). The photosensitive resin composition of Claim 1 in which alkali-soluble resin (A) contains a phenol resin. The photosensitive resin composition of Claim 1 in which alkali-soluble resin (A) contains a novolak resin. The photosensitive resin composition of Claim 1 whose fluorine-type liquid repellent agent (B) is an addition polymer containing the structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride. The photosensitive resin composition of Claim 1 whose fluorine-type liquid repellent agent (B) is an addition polymer containing the structural unit derived from the unsaturated compound which has a C2-C4 cyclic ether structure. The pattern structure formed using the photosensitive resin composition of Claim 1. A display device comprising the pattern structure according to claim 7. An inkjet partition wall comprising the pattern structure according to claim 7.

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