TW202248299A - Photosensitive resin composition, cured object, layered product, display device, and method for producing display device - Google Patents

Abstract

A purpose of the present invention is to obtain a photosensitive resin composition capable of giving banks which have few defects and in which the open portions have excellent wettability by inks and the bank top surfaces have excellent liquid repellency after a UV ozone treatment. This photosensitive resin composition comprises a polysiloxane (A), an alkali-soluble resin (B), and a photosensitizer (C), wherein the polysiloxane (A) has a specific repeating-unit structure.

Description

Photosensitive resin composition, cured product, laminate, display device, and manufacturing method of display device

The present invention relates to a photosensitive resin composition, a cured product, a laminate, a display device, and a method for manufacturing the display device.

In display devices with thin displays such as smartphones, tablet PCs, and televisions, many products in which functional layers are formed by printing methods represented by inkjet methods have been developed. For example, in the case of an organic electroluminescence (hereinafter referred to as "organic EL") display device, it is known that after forming a barrier rib pattern on a substrate, an inkjet method is used to drop a luminescent material and a hole transport material in the opening between the barrier ribs. A method of forming an organic EL display device having a functional layer by using a functional material solution such as an electron transport material.

Generally speaking, an organic EL display device has a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate. voltage to emit light. Among them, a photosensitive resin composition capable of patterning by ultraviolet irradiation is generally used as a material for a planarization layer and a material for an insulating layer. Among them, the photosensitive resin composition using polyimide resin or polybenzoxazole resin can provide a highly durable organic EL display due to its high heat resistance and less gas components generated from the cured product. It is suitably used in terms of the device (Patent Document 1).

When the functional layer is formed by the inkjet method, it is necessary to impart liquid repellency to the upper surface of the partition wall for the purpose of preventing color mixing of the ink injected into the adjacent opening. Also, in order to prevent white spots on the display device, the openings between the partitions must have good wettability to ink.

In order to achieve this, a method of expressing liquid repellency by performing a fluorination treatment by plasma irradiation on a layer above a barrier rib pattern on a substrate has been examined (Patent Document 2).

In addition, a method of forming a partition wall using a photosensitive resin composition containing an alkali-soluble resin and a liquid-repellent compound has also been examined. For example, a resist composition containing a fluorine-based acrylic polymer (Patent Document 3) and a photosensitive resin composition containing a polysiloxane having a fluorinated alkyl group (Patent Document 4) have been examined. [Prior Art Literature] [Patent Document]

Patent Document 1: Japanese Patent Laid-Open No. 2002-91343 Patent Document 2: Japanese Patent Laid-Open No. 2002-207114 Patent Document 3: Japanese Patent Laid-Open No. 2012-220855 Patent Document 4: International Publication No. 2019/159000

(Problem to be solved by the invention)

Since the upper surface of the partition wall formed by the technology of Patent Document 1 is not liquid-repellent, there is a problem that the functional material solution dripped by the inkjet method crosses the partition wall and mixes into nearby pixels, resulting in poor light emission.

In the technique of Patent Document 2, the liquid-repellent component also adheres to the openings between the partitions due to the fluorination treatment, and there is a problem of insufficient ink wettability at the openings.

The techniques of Patent Document 3 and Patent Document 4 have sufficient liquid repellency, and can be used as a photosensitive resin composition for pattern formation. However, the UV ozone resistance of the fluorine-based acrylic polymer of Patent Document 3 deteriorates, and the liquid repellency of the upper surface of the partition wall after UV ozone treatment is insufficient. In addition, heat resistance deteriorates, and there is a problem of ink wettability due to contamination of the opening during aging.

The polysiloxane having a fluorine atom in Patent Document 4 is superior in heat resistance, but has insufficient alkali solubility, and thus has a problem of ink wettability due to residues in openings after development. In addition, there is a problem that fluorinated alkyl groups emit light and aggregate to cause defects in cured products.

Therefore, the object of the present invention is to obtain a photosensitive resin composition, which can produce a partition wall with few defects, ink wettability of the opening, and excellent liquid repellency of the partition wall upper surface after UV ozone treatment. (technical means to solve the problem)

In order to solve the above-mentioned problems, the present invention has the following constitutions.

That is, the photosensitive resin composition of the present invention contains polysiloxane (A), alkali-soluble resin (B) and photosensitizer (C); among them, The polysiloxane (A) has the repeating unit structure of (i), (ii) and (iii); (i) repeating unit structure shown in formula (1) and/or repeating unit structure shown in formula (2); (ii) repeating unit structure shown in formula (3) and/or repeating unit structure shown in formula (4); (iii) repeating unit structure shown in formula (5) and/or repeating unit structure shown in formula (6);

[chemical 1]

R ^f is a fluorinated alkyl group with 7 to 21 fluorine and 5 to 12 carbons, R ¹ is a hydrogen atom, an alkyl group with 1 to 6 carbons, an acyl group with 1 to 6 carbons, or an alkyl group with 6 to 15 carbons Aryl; R2 is an aryl group with ⁶ ~15 carbons, ^R3 is a single bond or an alkylene group with 1~ ⁴ carbons, Y is 1 or 2; R4 is an acidic group with 2~20 carbons Organic group; ✽ means covalent bond. (compared to the effect of previous technology)

According to the photosensitive resin composition of the present invention, a partition wall having few defects, excellent ink wettability at the opening, and excellent liquid repellency on the top surface of the partition wall after UV ozone treatment can be obtained.

Embodiments of the present invention will be described in detail.

The photosensitive resin composition of the present invention contains polysiloxane (A), alkali-soluble resin (B) and photosensitizer (C), and the polysiloxane (A) has (i), (ii) and The repeating unit structure of (iii). (i) repeating unit structure shown in formula (1) and/or repeating unit structure shown in formula (2); (ii) repeating unit structure shown in formula (3) and/or repeating unit structure shown in formula (4); (iii) repeating unit structure shown in formula (5) and/or repeating unit structure shown in formula (6);

[Chem 2]

R ^f is a fluorinated alkyl group with a fluorine number of 7-21 and a carbon number of 5-12, and R ¹ is a hydrogen atom, an alkyl group with a carbon number of 1-6, an acyl group with a carbon number of 1-6, or an Aryl; R2 is an aryl group with ⁶ ~15 carbons, ^R3 is a single bond or an alkylene group with 1~ ⁴ carbons, Y is 1 or 2; R4 is an acidic group with 2~20 carbons Organic group; ✽ means covalent bond.

In the photosensitive resin composition of the present invention, the total content of polysiloxane (A), alkali-soluble resin (B) and photosensitive agent (C) is preferably 50% by mass in 100% by mass of the photosensitive resin composition % or more, more preferably 70 mass % or more. The upper limit is not particularly limited, and is 100% by mass. Moreover, when the photosensitive resin composition contains the organic solvent (D) mentioned later, the said total content means the total content in 100 mass % of photosensitive resin compositions excluding the organic solvent (D).

＜Polysiloxane (A)＞ Polysiloxane (A) has the repeating unit structure of (i), (ii) and (iii). (i) repeating unit structure shown in formula (1) and/or repeating unit structure shown in formula (2); (ii) repeating unit structure shown in formula (3) and/or repeating unit structure shown in formula (4); (iii) repeating unit structure shown in formula (5) and/or repeating unit structure shown in formula (6); When the photosensitive resin composition contains polysiloxane (A), high liquid repellency can be imparted to the upper surface of the cured product. Furthermore, since the main chain polysiloxane has excellent UV ozone resistance, it can impart high liquid repellency to the upper surface of the cured product after UV ozone treatment. In addition, since the polysiloxane in the main chain has excellent heat resistance, it will not be decomposed during the curing step, preventing liquid-repellent components from scattering toward the opening, and can improve the wettability of the functional ink coated on the opening.

[Chem 3]

R ^f is a fluorinated alkyl group with a fluorine number of 7-21 and a carbon number of 5-12, and R ¹ is a hydrogen atom, an alkyl group with a carbon number of 1-6, an acyl group with a carbon number of 1-6, or an Aryl; R2 is an aryl group with ⁶ ~15 carbons, ^R3 is a single bond or an alkylene group with 1~ ⁴ carbons, Y is 1 or 2; R4 is an acidic group with 2~20 carbons Organic group; ✽ means covalent bond.

Polysiloxane (A) has (i) a repeating unit structure represented by formula (1) and/or a repeating unit structure represented by formula (2). R ^f in the repeating unit structure represented by formula (1) and/or in the repeating unit structure represented by formula (2) is a fluorinated alkyl group having 7 to 21 fluorine and 5 to 12 carbon atoms. More preferably, it is a fluorinated alkyl group with 9-13 fluorine and 6-8 carbon atoms. By being a fluorinated alkyl group with a fluorine number of 7 or more and a carbon number of 5 or more, good liquid repellency can be exhibited on the upper surface of the cured product. Moreover, good compatibility with the alkali-soluble resin mentioned later can be acquired by being a fluorinated alkyl group with 21 or less fluorine and 12 or more carbon atoms. Furthermore, in order to reduce the environmental load, it is preferably a fluorinated alkyl group having 13 or less fluorine and 8 or less carbon atoms.

Specific examples of the fluorinated alkyl group represented by ^Rf include heptafluoropentyl, nonafluorohexyl, tridecafluorooctyl, heptadecafluorodecyl, 5,5,6,6,7,7, 7-heptafluoro-4,4-bis(trifluoromethyl)heptyl, etc. From the viewpoint of liquid repellency and environmental load, nonafluorohexyl and tridecafluorooctyl groups having 9 to 13 fluorine and 6 to 8 carbon atoms are preferred.

In 100 mol% of the total repeating unit structure of polysiloxane (A), preferably the total of the repeating unit structure shown in formula (1) and the repeating unit structure shown in formula (2) contains 5-30 mole %. More preferably, it is 10-25 mol%. By containing the repeating unit structure represented by the formula (1) and/or the repeating unit structure represented by the formula (2) at 5 mole % or more, good liquid repellency can be exhibited. Also, by containing 30 mol% or less, aggregation of fluorinated alkyl groups can be reduced.

Polysiloxane (A) has (ii) a repeating unit structure represented by formula (3) and/or a repeating unit structure represented by formula (4). Since the repeating unit structure shown in formula (3) and/or the repeating unit structure shown in formula (4) has an aryl group, the aggregation of the ^fluorinated alkyl group represented by R is suppressed by the steric hindrance of the aryl group, and it can be obtained Hardened product with few defects.

In the repeating unit structure shown in formula (3) and/or in the repeating unit structure shown in formula (4), R ² is an aryl group with 6 to 15 carbon atoms. In the present invention, from the viewpoint of the effect of inhibiting aggregation of the fluorinated alkyl group represented by ^Rf , it is preferable that at least one of R2 is a structure represented by ^formula (26) or formula (27).

[chemical 4]

R ¹⁶ is hydroxyl, alkyl with 1 to 5 carbons, alkoxy with 1 to 5 carbons, halogenated alkyl with 1 to 5 carbons, hydroxyalkyl with 1 to 5 carbons, or 1 to 5 carbons Halogenated hydroxyalkyl; b is an integer from 0 to 3; ✽ represents a covalent bond.

Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group and the like. Specific examples of the alkoxy group having 1 to 5 carbon atoms include methoxy, ethoxy and the like. Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, trichloromethyl, pentachloroethyl, heptachloropropyl and the like. Specific examples of the hydroxyalkyl group having 1 to 5 carbon atoms include hydroxymethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group and the like. Examples of the halogenated hydroxyalkyl group having 1 to 5 carbon atoms include the following structures.

[chemical 5]

In formula (27), the bonding position of R ¹⁶ can be any of the two rings of the naphthalene ring.

b is an integer from 0 to 3. From the viewpoint of polymerizability, b is preferably 0-2, more preferably 0-1.

Specific examples of formula (26) include phenyl, 3-methylphenyl, 4-methylphenyl, 3-ethylphenyl, 4-ethylphenyl, 3-tert-butylphenyl Base, 4-tert-butylphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 3-trifluoromethylphenyl, 4- Trifluoromethylphenyl, 3-hydroxymethylphenyl, 4-hydroxymethylphenyl, and the structure represented by formula (7), etc.

[chemical 6]

Here, ✽ represents a covalent bond directly bonded to R ³ . When R ³ is a single bond, it represents a covalent bond directly bonded to a silicon atom. a represents an integer from 1 to 3. From the viewpoint of polymerizability, a is preferably 1 to 2, and a is more preferably 1. Specific examples of the structure represented by formula (7) include the following structures.

[chemical 7]

Specific examples of formula (27) include 1-naphthyl, 2-naphthyl, 4-methyl-1-naphthyl, 4-hydroxy-1-naphthyl, 4-hydroxymethyl-1-naphthalene Base etc.

In the present invention, from the viewpoint of the aggregation inhibitory effect and polymerizability control of the fluorinated alkyl group represented by ^Rf , at least one of R2 is more preferably 1-naphthyl, ² -naphthyl, or the formula The structure shown in (7).

Y in the repeating unit structure represented by formula (4) is more preferably 1 from the viewpoint of polymerizability control.

In the repeating unit structure shown in formula (3) and/or in the repeating unit structure shown in formula (4), R ³ is a single bond or an alkylene group with 1 to 4 carbon atoms. Specific examples of the alkylene group having 1 to 4 carbon atoms include methylene, ethylene, n-propyl, isopropyl, n-butyl, and t-butylene.

In 100 mol% of the total repeating unit structure of polysiloxane (A), preferably the total of the repeating unit structure shown in formula (3) and the repeating unit structure shown in formula (4) contains 20 to 70 moles %. More preferably, it is 30~60 mole%. When the total of the repeating unit structure represented by the formula (3) and the repeating unit structure represented by the formula (4) is contained at least 20 mol %, a good aggregation inhibitory effect of the fluorinated alkyl group can be obtained. Also, from the viewpoint of polymerizability control, it is preferably 70 mol% or less.

Polysiloxane (A) has (iii) the repeating unit structure represented by formula (5) and/or the repeating unit structure represented by formula (6). The repeating unit structure shown in formula (5) and/or the repeating unit structure shown in formula (6) has an organic group with 2 to 20 carbon atoms containing an acidic group, so the solubility of the alkali developer is improved, and a good The wettability of the opening. In addition, aggregation of the above-mentioned fluorinated alkyl groups is suppressed, and a cured product with few defects can be obtained.

In the present invention, the organic group with 2 to 20 carbon atoms containing an acidic group is preferably an organic group with 2 to 20 carbon atoms containing at least one acidic group selected from the group consisting of carboxyl, carboxylic anhydride, hydroxyl and sulfonic acid groups. base, more preferably the structure shown in formula (8) or formula (9).

[chemical 8]

R ¹⁵ is a single bond or an alkylene group having 1 to 10 carbon atoms. ✽ denotes a covalent bond.

From the viewpoint of the wettability of the opening, R ⁴ more preferably has a carboxyl group. That is, in the photosensitive resin composition of the present invention, R ⁴ is preferably an organic group with 2 to 20 carbon atoms containing a carboxyl group. Furthermore, a dicarboxylic group obtained by hydrolyzing a carboxylic acid anhydride group is more preferable. Specific examples of organic groups with 2 to 20 carbon atoms containing acidic groups include 2-hydroxyethyl, 3-hydroxypropyl, bis(2-hydroxyethyl)-3-aminopropyl, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, and the following structure (α), structure (β). As the structure having a carboxyl group, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, structure (α) and structure (β) are preferable, and structure (α) and structure (β) are more preferable.

[chemical 9]

Here, ✽ represents a covalent bond directly bonded to a silicon atom.

In 100 mol% of the total repeating unit structure of polysiloxane (A), preferably the total of the repeating unit structure shown in formula (5) and the repeating unit structure shown in formula (6) contains 1 to 40 moles %. More preferably, it is 5-30 mol%. When the total of the repeating unit structure represented by the formula (5) and the repeating unit structure represented by the formula (6) is more than 1 mole %, good ink wettability and compatibility at the opening can be obtained. Moreover, good liquid repellency can be obtained by containing 40 mol% or less.

Polysiloxane (A) preferably further has the repeating unit structure of (vii). (vii) Repeating unit structure shown in formula (25)

[chemical 10]

✽ denotes a covalent bond.

By having the repeating unit structure of (vii), the degree of polymerization of the polysiloxane (A) increases, and the polysiloxane (A) is not easily decomposed during the curing step, preventing the liquid-repellent component from flying toward the opening, and further Improve the wettability of functional ink applied to the opening.

In polysiloxane (A), it is preferably 30-300 moles of the repeating unit structure of (vii) above, more preferably 101-200 moles, relative to 100 moles of the repeating unit structure of (iii) above. ears. The acidic group contained in the repeating unit structure of (iii) can increase the degree of polymerization of the repeating unit structure of (vii) because it acts as an acid catalyst. In polysiloxane (A), the heat resistance of polysiloxane (A) can be improved by containing 30 mole parts or more of the repeating unit structure of (vii) relative to 100 mole parts of the repeating unit structure of (iii). Improvement, the polysiloxane (A) is not easy to decompose during the aging step, prevents the liquid-repellent component from flying toward the opening, and can further improve the wettability of the functional ink coated on the opening. In addition, polysiloxane (A) contains 300 mole parts or less of the repeating unit structure of (vii) with respect to 100 mole parts of the repeating unit structure of (iii), and is compatible with the alkali-soluble resin (B) described later. Compatibility between them is easy to improve.

The polysiloxane (A) may also have (iv) a repeating unit structure represented by formula (10) and/or a repeating unit structure represented by formula (11).

[chemical 11]

R ¹ is a hydrogen atom, an alkyl group with 1 to 6 carbons, an acyl group with 1 to 6 carbons, or an aryl group with ⁶ to ^{15 carbons} , and ^{R 5} represents the Any of different organic groups with 1 to 10 carbon atoms.

R ⁵ is not particularly limited as long as it is an organic group having 1 to 10 carbons different from any of R ^f , R ² -R ³ -, and R ⁴ . Specific examples of R include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclohexyl and other hydrocarbon groups; ³ -aminopropyl , N-(2-aminoethyl)-3-aminopropyl, N-β-(aminoethyl)-γ-aminopropyl and other amino-containing groups; β-cyanoethyl, etc. The base of the cyano group; glycidoxymethyl, α-glycidoxyethyl, α-glycidoxypropyl, β-glycidoxypropyl, γ-glycidoxy Propyl, α-glycidoxybutyl, β-glycidoxybutyl, γ-glycidoxybutyl, σ-glycidoxybutyl, (3,4-epoxy 3-(3,4-epoxycyclohexyl)methyl, 3-(3,4-epoxycyclohexyl)propyl, 4-(3,4-epoxycyclohexyl)butyl and other epoxy-containing groups; 3-chloropropane 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl and other fluorine-containing groups; γ-acryloylpropyl, γ-methyl α, β-unsaturated ester group containing α, β-unsaturated ester group such as acryl propyl group; vinyl group containing vinyl group such as vinyl group and styryl group; etc.

In formulas (1), (3), (5) and (10), R is ^a hydrogen atom, an alkyl group with 1 to 6 carbons, an acyl group with 1 to 6 carbons, or an aryl group with 6 to 15 carbons . From the viewpoint of polymerizability control, R is preferably a hydrogen atom or an alkyl group with ¹ to 6 carbons; specific examples of the alkyl group with 1 to 6 carbons include methyl, ethyl, n-propyl, etc. Base, isopropyl, n-butyl, isobutyl, tertiary butyl, etc. Among them, a hydrogen atom, a methyl group, and an ethyl group are more preferable from the viewpoint of polymerizability control.

In the photosensitive resin composition of the present invention, the content of polysiloxane (A) is preferably not less than 0.1 parts by mass and not more than 10 parts by mass relative to 100 parts by mass of the alkali-soluble resin (B) described later. More preferably, it is 0.2 mass part or more and 5 mass parts or less. Favorable liquid repellency can be obtained when content of polysiloxane (A) is 0.1 mass part or more. Moreover, aggregation of the said fluorinated alkyl group can be suppressed by being 10 mass parts or less.

Polysiloxane (A) can be prepared, for example, by making an alkoxysilane represented by the following formulas (12), (13) and (14), and if necessary, the following formulas (15) and (28), in a solvent Obtained by hydrolysis and polycondensation. The polysiloxane (A) is preferably the polysiloxane thus obtained.

[chemical 12]

R ^f is a fluorinated alkyl group with a fluorine number of 7-21 and a carbon number of 5-12, and R ¹ is a hydrogen atom, an alkyl group with a carbon number of 1-6, an acyl group with a carbon number of 1-6, or an Aryl. R ² is an aryl group with 6-15 carbons, R ³ is a single bond or an alkylene group with 1-4 carbons, and Z is 1 or 2. R ⁴ is an organic group with 2 to 20 carbon atoms containing an acidic group. R ⁵ is an organic group with 1 to 10 carbon atoms.

The hydrolysis reaction is in a solvent, after adding an acid catalyst and water to the alkoxysilanes shown in formulas (12), (13) and (14), and formulas (15) and (28) if necessary, in the room The temperature is ~110°C and the reaction is carried out for 1~180 minutes. By carrying out the hydrolysis reaction under such conditions, a rapid reaction can be suppressed. The reaction temperature is more preferably 40-105°C.

In addition, after the silanol compound is obtained by the hydrolysis reaction, it is preferable to heat the reaction liquid above 50° C. and below the boiling point of the solvent for 1 to 100 hours to carry out the condensation reaction. Also, in order to increase the degree of polymerization of the siloxane compound obtained by the condensation reaction, an acid or alkali catalyst may be added, or reheating may be performed.

Various conditions in the hydrolysis reaction can be appropriately set in consideration of the scale of the reaction, the size and shape of the reaction vessel, and the like. For example, by setting acid concentration, reaction temperature, reaction time, etc., polysiloxane with a target degree of polymerization can be obtained.

As the water used in the hydrolysis reaction, ion-exchanged water is preferable. The amount of water can be selected arbitrarily, and it is preferably used in the range of 1.0-4.0 moles relative to 1 mole of the alkoxysilane compound.

Examples of the solvent used in the hydrolysis reaction include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, and 3-hydroxy-3-methyl-2-butanone , 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxy 1-butanol, 3-methyl-3-methoxy-1-butanol, ethylene glycol, propylene glycol, benzyl alcohol, 2-methyl benzyl alcohol, 3-methyl benzyl alcohol, 4-methyl benzyl alcohol Benzyl alcohol, 4-isopropylbenzyl alcohol, 1-phenylethanol, 2-phenyl-2-propanol, 2-ethylbenzyl alcohol, 3-ethylbenzyl alcohol, 4-ethylbenzyl alcohol, etc. solvent; diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, 1,2-dimethoxyethane, 1 , 2-diethoxyethane, dipropylene glycol dimethyl ether and other ether solvents; γ-butyrolactone, δ-valerolactone, propylene carbonate, ethyl acetate, n-propyl acetate, isopropyl acetate , n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1-butyl acetic acid Ester-based solvents such as esters, ethyl acetylacetate, cyclohexanol acetate, etc.; N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyliso Butyramide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylpropylene urea and other amide-based solvents; toluene, xylene and other aromatic hydrocarbons, etc.

As the acid catalyst used for the hydrolysis reaction, acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acid or its anhydride, ion exchange resin, etc. are mentioned. A particularly preferred system uses an acidic aqueous solution of formic acid, acetic acid or phosphoric acid.

The content of the acid catalyst is preferably at least 0.05 parts by mass, more preferably at least 0.1 parts by mass, based on 100 parts by mass of the total alkoxysilane compounds used in the hydrolysis reaction. Also, the content of the acid catalyst is preferably at most 10 parts by mass, more preferably at most 5 parts by mass. Here, the total amount of alkoxysilane compounds includes all of the alkoxysilane compounds, their hydrolyzates, and their condensates, and the same applies hereinafter. By setting the amount of the acid catalyst to 0.05 parts by mass or more, hydrolysis proceeds smoothly, and by setting the amount of the acid catalyst to 10 parts by mass or less, the hydrolysis reaction can be easily controlled.

Also, from the viewpoint of storage stability of the composition, it is preferable that the polysiloxane solution after hydrolysis and partial condensation does not contain the above-mentioned catalyst, and the catalyst can be removed if necessary. The removal method is not particularly limited, but water washing and/or ion exchange resin treatment are preferred from the viewpoint of ease of operation and removability. Washing with water refers to a method of diluting a polysiloxane solution with an appropriate hydrophobic solvent, washing with water several times, and concentrating the obtained organic layer with an evaporator or the like. The so-called ion exchange resin treatment refers to the method of contacting the polysiloxane solution with an appropriate ion exchange resin.

(A) The weight average molecular weight (Mw) of the polysiloxane is not particularly limited, but it is preferably 500 or more, more preferably 1,500 or more in terms of polystyrene as measured by gel permeation chromatography (GPC). Moreover, it is preferably 20,000 or less, more preferably 10,000 or less.

＜Alkali-soluble resin (B)＞ The photosensitive resin composition of the present invention contains an alkali-soluble resin (B).

The alkali-soluble resin in the present invention refers to a resin whose dissolution rate defined below is 50 nm/min or more. More specifically, it means that the solution of γ-butyrolactone dissolved in resin is coated on a silicon wafer, and pre-baked at 120°C for 4 minutes to form a pre-baked film with a thickness of 10 μm ± 0.5 μm, and the above-mentioned pre-baked film Resin having a dissolution rate of 50nm/min or more obtained from the amount of thickness reduction when rinsing with pure water after immersion in 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution at 23±1°C for 1 minute .

The alkali-soluble resin (B) preferably has an alkali-soluble group in the structural unit of the resin and/or its main chain terminal in order to impart alkali solubility. The alkali-soluble group refers to a functional group that increases the solubility in alkaline solution by interacting or reacting with alkali. As a preferable alkali-soluble group, a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a thiol group etc. are mentioned, for example.

As long as the alkali-soluble resin (B) has a structure having the above-mentioned alkali-soluble group, the main chain skeleton of the polymer constituting the resin and the type of side chain are not limited. Examples thereof include polyimide resins, polybenzoxazole resins, polyamideimide resins, acrylic resins, novolak resins, polyhydroxystyrene resins, phenol resins, and polysiloxane resins. Not limited to these.

The alkali-soluble resin (B) preferably has a trifluoromethyl group. The trifluoromethyl group can reduce the water absorption of the cured product of the photosensitive resin composition and improve the durability of the display device. Also, since the trifluoromethyl group does not impart liquid repellency, it is possible to form a cured product with a lyophilic surface by "half-exposure" described later.

In the photosensitive resin composition of the present invention, the alkali-soluble resin (B) preferably contains a precursor selected from polyimide, polybenzoxazole, polyamideimide, any one of these, and One or more of the group consisting of copolymers of the same. These alkali-soluble resins may be contained alone, or may contain a plurality of alkali-soluble resins in combination. These alkali-soluble resins have high heat resistance, so if they are used in display devices, there will be less outgassing at high temperatures above 200°C after heat treatment, which can improve the durability of display devices.

Polyimide can be obtained, for example, by reacting tetracarboxylic acid or tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, and the like with diamine, diisocyanate compound, trimethylsilylated diamine, and the like. The polyimide system has tetracarboxylic acid residues and diamine residues. In addition, polyimide can be obtained, for example, by subjecting polyamic acid, which is one of polyimide precursors obtained by reacting tetracarboxylic dianhydride and diamine, to dehydration and ring-closure by heat treatment. During this heat treatment, a solvent such as m-xylene or the like that azeotropes with water may be added. Alternatively, a dehydration condensation agent such as carboxylic anhydride or dicyclohexylcarbodiimide or a base such as triethylamine can be added as a ring-closing catalyst, and it can be obtained by dehydrating and ring-closing by chemical heat treatment. In addition, it can also be obtained by adding a weakly acidic carboxylic acid compound and performing dehydration and ring closure at a low temperature below 100°C.

Polybenzoxazole can be obtained, for example, by reacting a bisaminophenol compound with a dicarboxylic acid, a dicarboxylic acid chloride, a dicarboxylic acid active ester, or the like. The polybenzoxazole series has dicarboxylic acid residues and bisaminophenol residues. In addition, polybenzoxazole can be obtained, for example, by dehydrating and ring-closing polyhydroxyamide, which is one of the precursors of polybenzoxazole obtained by reacting a bisaminophenol compound with a dicarboxylic acid, by heat treatment. get. Or it can be obtained by adding phosphoric anhydride, alkali, carbodiimide compound, etc., and performing dehydration and ring closure by chemical treatment.

As a polyimide precursor, polyamic acid, polyamic acid ester, polyamic acid amide, polyisoimide etc. are mentioned, for example. For example, polyamic acid can be obtained by reacting tetracarboxylic acid or tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, etc., with diamine or diisocyanate compound, or trimethylsilylated diamine. Polyimide can be obtained by subjecting the polyamic acid obtained by the above method to dehydration and ring closure by heating or chemical treatment with acid or alkali.

As a polybenzoxazole precursor, polyhydroxyamide etc. are mentioned, for example. For example, polyhydroxyamide can be obtained by reacting bisaminophenol, dicarboxylic acid or dicarboxylic acid chloride, dicarboxylic acid active ester, and the like. Polybenzoxazole, for example, can be obtained by dehydrating and ring-closing the polyhydroxyamide obtained by the above-mentioned method by heating or chemical treatment with phosphoric anhydride, alkali, carbodiimide compound, and the like.

The polyamideimide precursor can be obtained, for example, by reacting tricarboxylic acid, corresponding tricarboxylic anhydride, tricarboxylic anhydride halide, etc., with diamine or diisocyanate. Polyamidoimide can be obtained, for example, by dehydrating and ring-closing the precursor obtained by the above-mentioned method through heating or chemical treatment with acid or alkali.

As a copolymer of polyimide, polybenzoxazole, polyamideimide, any of these precursors, it can be block copolymerization, random copolymerization, alternating copolymerization, graft copolymerization Any one of aggregates or a combination of these. For example, a block copolymer can be obtained by reacting tetracarboxylic acid, corresponding tetracarboxylic dianhydride, tetracarboxylic diester dichloride, etc. with polyhydroxyamide. Furthermore, dehydration and ring closure can also be carried out by heating or chemical treatment such as acid or alkali.

In the photosensitive resin composition of the present invention, polyimide, polybenzoxazole, polyamidoimide, any of these precursors and their copolymers are preferably based on the carboxylic acid component and/or the residue of the diamine component has the structure shown in formula (16). Since the structure represented by the formula (16) has excellent compatibility with the above polysiloxane (A), aggregation of the polysiloxane (A) can be suppressed and a cured product with few defects can be obtained. Furthermore, the trifluoromethyl group contained in the structure represented by formula (16) can reduce the water absorption of the hardened photosensitive resin composition and improve the durability of the display device. In addition, since the trifluoromethyl group does not impart liquid repellency, it is possible to form a cured product with a lyophilic surface by "half-exposure" described later.

[chemical 13]

✽ denotes a covalent bond.

Among the photosensitive resin compositions of the present invention, polyimide, polybenzoxazole, poly Amidimide, any of these precursors, and copolymers thereof have a structure represented by formula (16) in the residue of the carboxylic acid component and the residue of the diamine component.

The alkali-soluble resin (B) preferably has a structural unit represented by any one of formulas (17) to (20), more preferably has a structural unit represented by formula (20). Two or more resins having such structural units may be contained, and two or more structural units may be copolymerized. The resin of the alkali-soluble resin (B) preferably contains 3-1000 structural units represented by any one of the formulas (17)-(20) in the molecule, more preferably contains 20-200 units.

[chemical 14]

In formulas (17)~(20), R ⁶ and R ⁹ are tetravalent organic groups, R ⁷ , R ⁸ and R ¹¹ are divalent organic groups, R ¹⁰ is trivalent organic groups, R ¹² is 2~6 valent organic groups An organic group, R ¹³ is a 2-12 valent organic group. R ¹⁴ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. p is an integer of 0~2, and q is an integer of 0~10. n is an integer of 0~2.

Preferably, R ⁶ to R ¹³ all have aromatic rings and/or aliphatic rings.

Partial structures including R ⁶ , R ⁸ , R ¹⁰ , R ¹² (COOR ¹⁴ ) _n (OH) _p in formulas (17) to (20) can be obtained, for example, by using the corresponding carboxylic acid components. That is, for example, it can be obtained by using R ⁶ as a tetracarboxylic acid, R ⁸ as a dicarboxylic acid, R ¹⁰ as a tricarboxylic acid, and R ¹² as a di-, tri-, or tetracarboxylic acid. Examples of carboxylic acid components used to obtain R ⁶ , R ⁸ , R ¹⁰ , R ¹² (COOR ¹⁴ ) _n (OH) _p , as examples of dicarboxylic acids include terephthalic acid, isophthalic acid, diphenyl Ether dicarboxylic acid, bis(carboxyphenyl) hexafluoropropane, biphenyl dicarboxylic acid, diphenyl ketone dicarboxylic acid, triphenyl dicarboxylic acid, etc.; as an example of tricarboxylic acid, for example, 1 , 2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, etc.; as examples of tetracarboxylic acids, for example, 1,2,4 ,5-Benzenetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3' -Biphenyl tetracarboxylic acid, 3,3',4,4'-diphenyl ketone tetracarboxylic acid, 2,2',3,3'-diphenyl ketone tetracarboxylic acid, 2,2-bis( 3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4- Dicarboxyphenyl) phenylene, bis(3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalene tetracarboxylic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 2,3, Aromatic tetracarboxylic acids such as 5,6-pyridine tetracarboxylic acid, 3,4,9,10-perylene tetracarboxylic acid, or butane tetracarboxylic acid, 1,2,3,4-cyclopentane tetracarboxylic acid and other aliphatic tetracarboxylic acids. Among them, in formula (18), one or two carboxyl groups of tricarboxylic acid and tetracarboxylic acid correspond to COOR ¹⁴ groups. These acid components can be used as they are, or as acid anhydrides, active esters, and the like. Moreover, these acid components of 2 or more types can also be used in combination.

In the photosensitive resin composition of the present invention, the alkali-soluble resin (B) is as described above, and preferably has the structure shown in formula (16) in the residue of the carboxylic acid component, so as the carboxylic acid component, preferably bis (carboxyphenyl)hexafluoropropane, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane.

Partial structures including R ⁷ , R ⁹ , R ¹¹ , and R ¹³ (OH) _q in formulas (17) to (20) can be obtained, for example, by using the corresponding diamine components. Examples of diamine components used to obtain R ⁷ , R ⁹ , R ¹¹ , and R ¹³ (OH) _q include bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amine Base-4-hydroxyphenyl) phenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4 -Hydroxyphenyl) ether, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl)diamine and other hydroxyl-containing diamines, 3-sulfonic acid-4,4 Diamines containing sulfonic acids such as '-diaminodiphenyl ether, diamines containing thiol groups such as dimercaptophenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'- Diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4 '-Diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4-bis(4-aminophenoxy base) benzene, petroleum ether, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalene diamine, 2,6-naphthalene diamine, bis(4-aminophenoxyphenyl) phenylene, bis(3 -aminophenoxyphenyl)pyridine, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4- Aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3, 3'-Dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl Base-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl) -Aromatic diamines such as 4,4'-diaminobiphenyl, or some of the hydrogen atoms of these aromatic rings are replaced by alkyl groups with 1 to 10 carbons, trifluoromethyl groups, halogen atoms, etc. alicyclic diamines such as cyclohexyldiamine and methylenebiscyclohexylamine, and siloxane-based diamines such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane. These diamines can be used as they are, or can be used as corresponding diisocyanate compounds and trimethylsilylated diamines. Moreover, these 2 or more types of diamine components can also be used in combination. For applications requiring heat resistance, it is preferable to use aromatic diamines at least 50 mol% of all diamines.

In the photosensitive resin composition of the present invention, the alkali-soluble resin (B) is as described above, and preferably has the structure shown in formula (16) in the residue of the carboxylic acid component, so as the diamine component, it is preferably bis (3-Amino-4-hydroxyphenyl)hexafluoropropane.

Also, in the photosensitive resin composition of the present invention, from the viewpoint of adhesion between the substrate and the substrate, the alkali-soluble resin (B) preferably has 1,3-bis(3-aminopropyl) in the diamine component. base) siloxane-based diamines such as tetramethyldisiloxane.

R ⁶ to R ¹³ in formulas (17) to (20) may contain phenolic hydroxyl groups, sulfonic acid groups, thiol groups, etc. in their skeletons. By using a resin with moderate phenolic hydroxyl groups, sulfonic acid groups or thiol groups, it becomes a positive-type photosensitive resin composition with moderate alkali solubility.

Also, in order to improve the storage stability of the photosensitive resin composition, the resin of the alkali-soluble resin (B) is preferably prepared by a well-known monoamine, acid anhydride, monocarboxylic acid, monoacid chlorine compound, and monoactive ester at the end of the main chain. Compounds and other terminal terminators for termination. The introduction ratio of the monoamine used as the terminal terminator is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, based on the total amine components. Also, the introduction ratio of the monoamine is preferably 60 mol% or less, particularly preferably 50 mol% or less, based on the total amine components. The introduction ratio of acid anhydride, monocarboxylic acid, monoacid chlorine compound or monoactive ester compound used as a terminal terminator is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, based on the diamine component. In addition, the above introduction ratio is preferably not more than 100 mol %, particularly preferably not more than 90 mol %, based on the diamine component. A plurality of different terminal groups can also be introduced by reacting a plurality of terminal terminators.

In the resin having the structural unit represented by any one of the formulas (17) to (19), the repeating number of the structural unit is preferably 3 or more and 200 or less. Also, in the resin having the structural unit represented by the formula (20), the repeating number of the structural unit is preferably 10 or more and 1000 or less. If it falls within this range, a thick film can be formed easily.

The alkali-soluble resin (B) may be composed only of the structural unit represented by any one of formulas (17) to (20), or may be a copolymer or a mixture with other structural units. In this case, the structural unit represented by any one of the formulas (17) to (20) preferably contains 10% by mass or more of the entire resin, more preferably 30% by mass or more. The type and amount of the structural unit used for copolymerization or mixing can be selected within the range not to impair the mechanical properties of the film obtained by the final heat treatment.

＜Sensitizer (C)＞ The photosensitive resin composition of the present invention contains a photosensitive agent (C). The photosensitizer (C) may be a negative type that is hardened by light, or a positive type that is soluble by light. As a photosensitizer (C), it is preferable to contain a polymerizable unsaturated compound and a photoinitiator (C-1), or a quinone diazide compound (C-2), etc. By containing the quinonediazide compound (C-2), since a positive-type photosensitive resin composition can be obtained, a step-shaped cured product can be formed by one photolithography by "half-exposure" described later, so it is preferable . Therefore, in the photosensitive resin composition of this invention, it is preferable that a photosensitive agent (C) contains a quinone diazide compound (C-2). Hereinafter, "polymerizable unsaturated compound and photopolymerization initiator (C-1)" may be abbreviated as "(C-1)" in some cases.

Examples of polymerizable unsaturated compounds in (C-1) include unsaturated double bond functional groups such as vinyl, allyl, acryl, and methacryl, and/or unsaturated compounds such as propynyl. Compounds with triple bond functional groups, etc. Among them, a conjugated vinyl group, acryl group, and methacryl group are preferable in terms of polymerizability. In addition, the number of the functional groups contained is preferably 1 to 4 in one molecule from the viewpoint of stability, and may not be the same groups. Also, the polymerizable unsaturated compound is preferably one with a molecular weight of 30 to 800. If the molecular weight is in the range of 30-800, the compatibility with polymers and reactive diluents is good. Specific examples of polymerizable unsaturated compounds include 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate ester, isomethacrylate, isomethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate ester, methylenebisacrylamide, N,N-dimethylacrylamide, N-methylolacrylamide, 2,2,6,6-tetramethylpiperidinyl methacrylate, 2 ,2,6,6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl-2,2,6 ,6-tetramethylpiperidinyl acrylate, ethylene oxide modified bisphenol A diacrylate, ethylene oxide modified bisphenol A dimethacrylate, N-vinylpyrrolidone, N- Vinyl caprolactam, etc. These can be used individually or in combination of 2 or more types.

In the present invention, the content of the polymerizable unsaturated compound in (C-1) is not particularly limited, but it is preferably 5 parts by mass from the viewpoint of improving alkali solubility with respect to 100 parts by mass of the alkali-soluble resin (B). From the viewpoint of favorable pattern formation, it is preferably not more than 50 parts by mass.

、異丙基9-氧硫

、2-甲基-1-[4-(甲硫基)苯基]-2-

啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁酮-1等，但並不限定於此等。The photopolymerization initiator in (C-1) mainly generates free radicals by irradiating light in the ultraviolet to visible region, thereby initiating polymerization. From the viewpoint of usability of a general-purpose light source and the viewpoint of rapid hardening, a photopolymerization initiator selected from acetophenone derivatives, benzophenone derivatives, benzoin ether derivatives, and ketone derivatives is preferable. agent. Examples of preferred photopolymerization initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy- 2-phenylacetophenone, 1-hydroxy-cyclohexyl phenyl ketone, isobutyl benzoin ether, benzoin methyl ether, 9-oxosulfur

, Isopropyl 9-oxosulfur

, 2-methyl-1-[4-(methylthio)phenyl]-2-

Linyl propan-1-one, 2-benzyl-2-dimethylamino-1-(4-

Linylphenyl)-butanone-1, etc., but not limited thereto.

In this invention, although content of the photoinitiator in (C-1) is not specifically limited, Preferably it is 1 mass part or more and 10 mass parts or less with respect to 100 mass parts of alkali-soluble resins (B). If it falls within this range, it becomes easy to ensure the interaction with resin required for formation of a favorable pattern, and the transmittance for obtaining appropriate sensitivity.

As the quinone diazide compound (C-2), for example, a sulfonic acid in which quinone diazide is bonded to a polyhydroxy compound with an ester bond, and a diazide bonded to a polyamine compound with a sulfonamide bond. A sulfonic acid of quinone azide, a sulfonic acid of quinone diazide bonded to a polyhydroxypolyamine compound through an ester bond and/or a sulfonamide bond, and the like. All the functional groups of these polyhydroxy compounds, polyamine compounds, and polyhydroxypolyamine compounds may not be substituted by quinone diazide, but it is preferable that 40 mol% or more of all the functional groups are substituted by diazide on average. substituted by quinone azide. In the present invention, the molar % of functional groups substituted by quinone diazide is referred to as the quinone diazide substitution rate. By using such a quinone diazide compound, a positive-type photosensitive resin composition that is sensitive to i-rays (wavelength 365nm), h-rays (wavelength 405nm), and g-rays (wavelength 436nm) of mercury lamps belonging to general ultraviolet rays can be obtained. thing.

The polyhydroxy compound used here has 2 or more, preferably 3 or more phenolic hydroxyl groups in a molecule|numerator. The polyhydroxy compound can be for example Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC , DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR- PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (the above are trade names, Asahi Organic Material Industry ( stock)), 2,6-dimethoxymethyl-4-tertiary butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetyloxymethyl-p- Cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), novolac Resin etc., but not limited to these.

Polyamine-based compounds can be exemplified by 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4 ,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, etc., but not limited thereto.

Also, examples of the polyhydroxypolyamine-based compound include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-dihydroxybenzidine, and the like, but are not limited thereto.

In addition, as the sulfonic acid of quinone diazide, for example, 1,2-naphthoquinone-4-sulfonic acid diazide, 1,2-naphthoquinone-5-sulfonic acid diazide, etc., but not limited wait here.

In the present invention, as the quinonediazide compound (C-2), it is preferable to use a quinonediazide sulfonic acid bonded to a polyhydroxy compound. By using this quinone diazide compound, it is possible to be sensitive to i-rays (wavelength 365nm), h-rays (wavelength 405nm), and g-rays (wavelength 436nm) of mercury lamps belonging to general ultraviolet rays, and high sensitivity and higher resolution.

As a more preferable quinone diazide compound (C-2), the compound represented by formula (21) or formula (22) can be mentioned, for example.

[chemical 15]

In formula (21) and formula (22), Q independently represents a hydrogen atom, a group represented by structural formula (23) or a group represented by structural formula (24).

[chemical 16]

Q in the formula (21) and the formula (22) preferably independently represents a hydrogen atom or a group represented by the structural formula (23) from the viewpoint of sensitivity.

The quinonediazide substitution rate can be obtained as follows: in the case of polyhydroxy compounds, it is set as "(the number of moles of quinonediazide sulfonate groups)/(the number of moles of hydroxyl groups before esterification of the polyhydroxy compound) )×100”; in the case of polyamine-based compounds, it is set as “(the number of moles of quinone diazide sulfonamide groups)/(the number of moles of amino groups before amidation of polyamine-based compounds)× 100"; in the case of polyhydroxypolyamine-based compounds, it is set as "{(the number of moles of quinonediazide sulfonate group)+(the number of moles of quinonediazide sulfonamide group)}/{ (the number of moles of hydroxyl groups of the polyhydroxypolyamine-based compound before esterification)+(the number of moles of amino groups of the polyhydroxypolyamine-based compound before amidation)}×100”.

In the present invention, two or more kinds of quinone diazide compounds can be used. At this time, as the quinone diazide substitution rate, the value obtained by multiplying the quinone diazide substitution rate for each quinone diazide compound by the ratio to the total quinone diazide compound as follows , and can be obtained by summing them up. Σ((Quinone diazide substitution rate of a certain quinone diazide compound)×(Ratio of a certain quinone diazide compound to the total quinone diazide compound)) In addition, the quinonediazide substitution rate of the quinonediazide compound in the photosensitive resin composition is obtained by separating the resin component of the photosensitive resin composition by reprecipitation, etc., and then by column fractionation. It contains ingredients and can be determined by NMR or IR for chemical structure identification.

啉、吡啶、二環己基胺等有機鹼的存在下，與聚羥基化合物進行反應而獲得。The production method of the quinone diazide compound is not particularly limited, by making the quinone diazide sulfonic acid halide (preferably the quinone diazide sulfonic acid chloride) in acetone, dioxane, In a solvent such as tetrahydrofuran, in an inorganic base such as sodium carbonate, sodium bicarbonate, sodium hydroxide or potassium hydroxide, or trimethylamine, triethylamine, tripropylamine, diisopropylamine, tributylamine , pyrrolidine, piperidine, piperidine,

In the presence of organic bases such as line, pyridine, and dicyclohexylamine, it is obtained by reacting with polyhydroxy compounds.

In the present invention, the content of the quinone diazide compound (C-2) is not particularly limited, and the content of the quinone diazide compound (C-2) is preferably the content relative to 100 parts by mass of the alkali-soluble resin (B) It is 10 mass parts or more, More preferably, it is 20 mass parts or more. Moreover, it is preferably at most 50 parts by mass, more preferably at most 40 parts by mass. By setting the content of the quinone diazide compound in this range, photosensitivity can be obtained without hindering liquid repellency.

When the photosensitive resin composition of the present invention contains a quinone diazide compound (C-2) in the photosensitive agent (C), the alkali-soluble resin (B) preferably contains a phenol resin and/or polyhydroxybenzene Vinyl. Moreover, these 2 or more types of phenol resins and/or polyhydroxystyrene resins can also be used in combination. By containing the quinonediazide compound (C-2) and the phenolic resin and/or the polyhydroxystyrene resin, the amount of film reduction in the developing step can be reduced, so it is easy to make polysiloxane (A) remain in the developing process After the surface of the film, better liquid repellency can be obtained.

Phenolic resins include novolac phenol resins and cresol phenol resins, which can be obtained by polycondensing various phenolic compounds alone or a mixture of them using aldehyde compounds such as formaldehyde according to known methods.

Examples of the phenolic compound constituting the novolac phenol resin or cresol phenol resin include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-Dimethylphenol, 2,6-Dimethylphenol, 3,4-Dimethylphenol, 3,5-Dimethylphenol, 2,3,4-Trimethylphenol, 2,3 ,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylene bisphenol, methylene bis-p-cresol, resorcinol, ortho Hydroquinone, 2-methylresorcinol, 4-methylresorcinol, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methyl Oxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α- Naphthol, β-naphthol, etc.; these may be used alone or as a mixture of plurals. In addition, as the aldehyde compound, in addition to formaldehyde, for example, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, etc. can be used alone or as a mixture of plural.

As the polyhydroxystyrene resin, a homopolymer of vinylphenol or a copolymer with styrene can also be used.

The preferred weight-average molecular weight of the phenolic resin and polyhydroxystyrene resin is 2,000-20,000, preferably 3,000-10,000 in terms of polystyrene conversion of GPC (gel permeation chromatography). Within this range, a high-concentration and low-viscosity resin composition can be obtained.

When the photosensitive resin composition of the present invention contains the quinone diazide compound (C-2) in the photosensitive agent (C), from the viewpoint of liquid repellency, 100% by mass of the alkali-soluble resin (B) %, preferably 20% by mass or more of phenol resin and/or polyhydroxystyrene resin, more preferably 30% by mass or more. Moreover, from the viewpoint of outgassing, it is preferably at most 50% by mass, more preferably at most 40% by mass.

＜Organic solvent (D)＞ The photosensitive resin composition of the present invention preferably contains an organic solvent (D). Examples of the organic solvent (D) include ethers, acetates, esters, ketones, aromatic hydrocarbons, amides, alcohols and the like.

More specifically, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol mono Methyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-propyl ether Butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether Ethers such as base ether, diethylene glycol diethyl ether or tetrahydrofuran; butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether Acetate (hereinafter referred to as "PGMEA"), 3-methoxybutyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol Monoethyl ether acetate, diethylene glycol monobutyl ether acetate, cyclohexanol acetate, propylene glycol diacetate, propylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate , 3-methoxy-3-methyl-1-butyl acetate, 1,4-butanediol diacetate, 1,3-butanediol diacetate or 1,6-hexanediol Acetate esters such as alcohol diacetate, Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone or 3-heptanone, Alkyl lactate such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate , 2-Hydroxy-2-methyl propionate ethyl ester, 3-methoxy propionate methyl ester, 3-methoxy propionate ethyl ester, 3-ethoxy propionate methyl ester, 3-ethoxypropionate ethyl acetate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxy Butyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate , isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, acetyl acetate Other esters such as ethyl ester or ethyl 2-oxobutyrate, aromatic hydrocarbons such as toluene or xylene, N-methylpyrrolidone, N,N-dimethylformamide or N,N-di Amides such as methylacetamide, or butanol, isobutanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy Alcohols such as butanol or diacetone alcohol, etc.

The amount of the above-mentioned organic solvent (D) is changed depending on the required thickness or the coating method adopted, so there is no special limitation, relative to the solid content of the photosensitive resin composition (other components except the organic solvent (D)) 100 parts by mass, preferably 100 to 2000 parts by mass, particularly preferably 150 to 900 parts by mass.

＜Other ingredients＞ The photosensitive resin composition of the present invention may further contain a thermal crosslinking agent. The so-called thermal crosslinking agent refers to a compound having at least two thermally reactive functional groups headed by hydroxymethyl group, alkoxymethyl group, epoxy group, and oxetanyl group in the molecule. The thermal crosslinking agent crosslinks the alkali-soluble resin (B) or other components to improve the durability of the hardened product.

Various known compounds may be included as the compound having at least two alkoxymethyl groups or methylol groups. Preferable examples of such compounds include, for example, HMOM-TPPHBA, HMOM-TPHAP (the above are trade names, produced by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270 , NIKALAC MX-279, NIKALAC MW-100LM, and NIKALAC MX-750LM (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.), which can be obtained from the above companies, respectively.

Various known compounds can be contained as the compound having at least two epoxy groups or oxetanyl groups. Preferable examples of such compounds, those having an epoxy group can for example be VG3101L (trade name, manufactured by Printec (stock)), TEPIC (registered trademark) S, TEPIC G, TEPIC P (the above are trade names, manufactured by Nissan Chemical Industry ( Co., Ltd.), EPICLON N660, EPICLON N695, HP7200 (the above are brand names, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), DENACOL EX-321L (trade name, manufactured by Nagase ChemteX Co., Ltd.), NC6000, EPPN502H, NC3000 (The above are trade names, manufactured by Nippon Kayaku Co., Ltd.), Epotohto (registered trademark) YH-434L (trade name, manufactured by Tohto Chemical Co., Ltd.), EHPE-3150 (trade name, manufactured by DAICEL Co., Ltd.), with Oxetanyl compounds include, for example, OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (the above are trade names, produced by Toagosei Co., Ltd.), ETERNACOLL (registered Trademarks) OXBP, ETERNACOLL OXTP (the above are trade names, produced by Ube Industries, Ltd.), etc., can be obtained from the above-mentioned companies respectively.

The thermal crosslinking agent preferably has a phenolic hydroxyl group in one molecule and has a methylol group and/or an alkoxymethyl group at both ortho-positions of the above-mentioned phenolic hydroxyl group. By adjoining a methylol group and/or an alkoxymethyl group to a phenolic hydroxyl group, the durability of the cured product can be further improved. The alkoxymethyl group includes, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group, but is not limited thereto.

The content of the thermal crosslinking agent is preferably at least 5 parts by mass, more preferably at least 10 parts by mass, and still more preferably at least 15 parts by mass, based on 100 parts by mass of the total amount of the alkali-soluble resin (B). Moreover, it is preferably at most 50 parts by mass, more preferably at most 40 parts by mass, and still more preferably at most 30 parts by mass. By setting the content of the thermal crosslinking agent to 5 parts by mass or more, the heat resistance of the cured product can be improved, and by setting the content of the thermal crosslinking agent to 50 parts by mass or less, it is possible to prevent the decrease in the elongation of the cured product.

＜Method for producing photosensitive resin composition＞ A method for producing the photosensitive resin composition of the present invention will be described. For example, it can be obtained by dissolving the polysiloxane (A)~sensitizer (C) and other components in an organic solvent (D). As a dissolution method, stirring, heating, etc. are mentioned, for example. When heating, the heating temperature is preferably within the range that does not damage the performance of the resin composition, usually 20°C to 80°C. Moreover, the dissolution order of each component is not specifically limited, For example, there is a method of dissolving in order from a compound with low solubility.

The obtained photosensitive resin composition is preferably filtered with a filter to remove impurities or particles. The filter pore size is, for example, 1 μm, 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm, etc., but is not limited thereto. The material of the filter is polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc. It is better to use polyethylene or nylon for filtering.

＜hardened material＞ The cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention. As a hardening method, the method of heat-processing the photosensitive resin composition apply|coated on the board|substrate etc. are mentioned, for example. As a method of coating a photosensitive resin composition on a board|substrate, a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method etc. are mentioned, for example. Residual solvents or components with low heat resistance can be removed by heat treatment after coating, so the heat resistance and chemical resistance of the hardened product can be improved. Also, by containing a crosslinking agent, heat treatment can be used to advance the thermal crosslinking reaction, and the heat resistance and chemical resistance of the cured product can be improved. For example, the heat treatment can be carried out by selecting a temperature and raising the temperature step by step, or by selecting a certain temperature range and continuously raising the temperature for 5 minutes to 5 hours. As an example, the method of heat-processing at 150 degreeC and 250 degreeC for 30 minutes each is mentioned. Alternatively, for example, a method of linearly raising the temperature from room temperature to 300° C. over 2 hours may be used. The heat treatment conditions in the present invention are preferably at least 180°C, more preferably at least 200°C, and still more preferably at least 230°C. Also, the heat treatment conditions are preferably at most 400°C, more preferably at most 350°C, and still more preferably at most 300°C.

The cured product of the present invention can be used in electronic components such as organic EL display devices, liquid crystal display devices, semiconductor devices, and multilayer wiring boards. Specifically, it can be suitably used as a partition wall of an organic EL element, a flattening layer of a drive circuit substrate of a display device using an organic EL element, a filter of a liquid crystal device, a black matrix of a liquid crystal device, a semiconductor device, or a semiconductor component. Interlayer insulating film between rewiring, passivation film of semiconductor, surface protective film of semiconductor element, interlayer insulating film of multilayer wiring for high-density mounting, wiring protective insulating layer of circuit board, core-mounted microlens of solid-state imaging element (on -chip microlens) or a planarization layer for various displays and solid-state imaging devices. An electronic device having a surface protective film or an interlayer insulating film on which the cured product of the present invention is disposed includes, for example, MRAM with low heat resistance. That is, the cured product of the present invention is suitable as a surface protection film of MRAM. Moreover, for example, it can be suitably used for the partition wall or insulating layer of display devices, such as LCD and organic EL. More preferably, it is suitable for use as a partition wall of a display device in which a functional ink is applied by an inkjet method in a region (pixel) surrounded by partition walls formed on a substrate.

Since the cured product of the present invention has good liquid repellency, by preventing the ink used in the inkjet method from penetrating into adjacent pixels, a display device with less occurrence of display defects can be obtained. On the other hand, the side surface of the cured product and the portion (opening) without the cured product have good ink coating properties because they do not have liquid repellency. Furthermore, since the cured product of the present invention has less outgassing at high temperature, it can be suitably used in functional layers containing at least one selected from the group consisting of organic EL light-emitting materials, hole injection materials, and hole transport materials. in organic EL display devices.

＜Laminated body＞ In the layered system of the present invention, the patterned first electrode and the cured product of the present invention are sequentially laminated on the substrate, and at least a part of the cured product located on the first electrode is opened. Since the surface of the cured product has good liquid repellency, it can be suitably used in a display device in which at least a part of the cured product on the first electrode is opened and coated with a functional ink by an inkjet method to form a functional layer middle. Also, the laminate of the present invention can be suitably used in a functional layer containing at least one compound selected from the group consisting of organic EL light-emitting materials, hole injection materials, and hole transport materials because the cured product has less outgassing at high temperatures. More than one organic EL display device.

The laminate of the present invention preferably satisfies the characteristic (v) and characteristic (vi) in the analysis of the above-mentioned cured product obtained by X-ray photoelectron spectroscopy (XPS). (v) In the above-mentioned cured product, the concentration of F atoms measured from the surface opposite to the contact surface of the first electrode and the above-mentioned cured product is not less than 8.1 atom % and not more than 30.0 atom %, and the concentration of Si atoms is: More than 1.0atom% and less than 6.0atom%. (vi) In a direction perpendicular to the contact interface between the first electrode and the hardened material and from the substrate toward the hardened material, a distance of 100 to 200 nm from the interface between the first electrode and the hardened material as the starting point The concentration of F atoms in the cured product measured at any one of the ranges is not less than 0.1 atom % and not more than 8.0 atom %.

Fig. 2 is a schematic cross-sectional view showing an example of the laminate of the present invention. On the substrate 8, the planarization layer 9, the patterned first electrode 10, and the cured product 11 of the present invention are sequentially stacked, and at least a part of the cured product 11 on the patterned first electrode 10 is opened. The characteristic (v) of the cured product analyzed by X-ray photoelectron spectroscopy (XPS) was measured from the surface 12 on the opposite side to the surface where the above-mentioned first electrode and the above-mentioned hardened product contact. Preferably, the measurement is performed anywhere within a range of 100 μm from the end of the opening of the hardened object 11 . In addition, the characteristic (vi) is perpendicular to the contact interface 13 between the first electrode and the above-mentioned cured product, and in the direction from the above-mentioned substrate toward the above-mentioned cured product, starting from the contact interface between the first electrode and the above-mentioned cured product. , from a distance of 100nm15 to be measured at any place in the range of 100nm, that is, in the direction perpendicular to the contact interface 13 between the first electrode and the above-mentioned cured product, and from the above-mentioned substrate toward the direction of the above-mentioned cured product, with the above-mentioned first electrode The interface between the electrode and the above-mentioned cured material is used as the starting point, and the measurement is made at any place within the range of 14 from 100nm to 200nm. In the opening of the patterned first electrode, as shown in FIG. The interface between the electrode and the above-mentioned cured product is generally in the range of 100 to 200 nm from the starting point, assuming that the first electrode exists, and the measurement is performed at any point in the range of 100 to 200 nm from the height of the first electrode. Also, in the case where the thickness of the first electrode varies, in the opening of the patterned first electrode, the first electrode having an average thickness at the end of the opening is provided.

In the laminate of the present invention, as a method for satisfying the characteristic (v), for example, a compound (a-1) containing a fluorinated alkyl group having a fluorine number of 7 to 21 and a carbon number of 5 to 12, and a compound (a-1) having a silicon oxide A method for forming a cured product of the photosensitive resin composition of the compound (a-2) having an alkane structure. The so-called siloxane structure refers to a structure in which silicon (Si) and oxygen (O) are alternately bonded. It may also contain two types of compound (a-1) having a fluorinated alkyl group with fluorine number 7-21 and carbon number 5-12 and compound (a-2) with siloxane structure, or it may be as polysiloxane as above Like oxane (A), it has a fluorinated alkyl group with a fluorine number of 7-21 and a carbon number of 5-12 and a siloxane structure in one compound.

As a method of making the F atom concentration of the characteristic (v) into the above-mentioned range, for example, there is a method of adjusting the compound (a-1) having a fluorinated alkyl group having 7 to 21 fluorine and 5 to 12 carbons in the photosensitive resin composition. content method. If the content is increased, the F atom concentration of the characteristic (v) can be increased; if the content is decreased, the F atom concentration of the characteristic (v) can be reduced. In addition, there is also a method of adjusting the concentration of the fluorinated alkyl group contained in the compound (a-1). If the concentration of the fluorinated alkyl group increases, the F atom concentration of the characteristic (v) can be increased; if the concentration of the fluorinated alkyl group is decreased, the F atom concentration of the characteristic (v) can be reduced.

As a method of making the Si atom concentration of the characteristic (v) into the above-mentioned range, for example, there is a method of adjusting the content of the compound (a-2) having a siloxane structure in the photosensitive resin composition. If the content is increased, the concentration of Si atoms of characteristic (v) can be increased; if the content is decreased, the concentration of Si atoms of characteristic (v) can be reduced. Moreover, there is also a method of adjusting the concentration of the siloxane structure which the compound (a-2) has. If the concentration of the siloxane structure is increased, the concentration of Si atoms of the characteristic (v) can be increased; if the concentration of the siloxane structure is decreased, the concentration of Si atoms of the characteristic (v) can be reduced.

The structure of the compound (a-1) having a fluorinated alkyl group having 7 to 21 fluorine and 5 to 12 carbon atoms is not particularly limited. For example, the group selected from 2-(perfluorobutyl)ethyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, 2-(perfluorooctyl)ethyl ( One or more copolymerized acrylic resins of the group consisting of meth)acrylates, the aforementioned polysiloxane (A), and the like. From the viewpoint of UV ozone resistance, the polysiloxane (A) described above is preferable.

The structure of the compound (a-2) having a siloxane structure is not particularly limited. Examples thereof include alkyl-modified polysiloxane, polyether-modified polysiloxane, and the aforementioned polysiloxane (A). From the viewpoint of localization on the surface of the cured product, polyether-modified polysiloxane and the aforementioned polysiloxane (A) are preferred. From the viewpoint of liquid repellency, the above polysiloxane (A) is more preferable.

Commercially available polyether-modified silicones include, for example, KF-351A, KF-352A, KF-353, KF-354L, KF-355A, and KF-642 (manufactured by Shin-Etsu Chemical Co., Ltd.), SH8400, SH8700, SF8410 (manufactured by Toray Dow Corning Co., Ltd.), BYK-300, BYK-306, BYK-307, BYK-320, BYK-325, BYK-330 (manufactured by BYK-Chemie), etc.

In the laminate of the present invention, as a method of satisfying the characteristic (vi), for example, a method of forming a cured product from a photosensitive resin composition containing an alkali-soluble resin (b-1) having a trifluoromethyl group can be mentioned. The trifluoromethyl system is weak on the surface of the hardened material, and can make F atoms stay inside the hardened material. In addition, since the trifluoromethyl group does not impart liquid repellency, it is possible to form a cured product whose surface is lyophilic by "half-exposure" described later.

As a method of making the F atom concentration of the characteristic (vi) into the above-mentioned range, for example, there is a method of adjusting the content of the alkali-soluble resin (b-1) having a trifluoromethyl group in the photosensitive resin composition. If the content is increased, the F atom concentration of the characteristic (vi) can be increased; if the content is decreased, the F atom concentration of the characteristic (vi) can be reduced. Moreover, there is also a method of adjusting the concentration of the trifluoromethyl group contained in the alkali-soluble resin (b-1). If the concentration of the trifluoromethyl group increases, the F atom concentration of the characteristic (vi) can be increased; if the concentration of the trifluoromethyl group is decreased, the F atom concentration of the characteristic (vi) can be decreased. In the alkali-soluble resin (b-1) having a trifluoromethyl group, there are no limitations on the main chain skeleton and side chain type of the polymer constituting the resin. Examples thereof include polyimide resins, polybenzoxazole resins, polyamideimide resins, acrylic resins, novolak resins, polyhydroxystyrene resins, phenol resins, and polysiloxane resins. Not limited to these. From the standpoint of heat resistance, the alkali-soluble resin (b-1) having a trifluoromethyl group preferably contains a resin selected from polyimide, polybenzoxazole, polyamideimide, any one of these One or more of the group consisting of precursors and their copolymers. Since these alkali-soluble resins have high heat resistance, if they are used in display devices, there will be less outgassing at high temperatures of 200°C or higher after heat treatment, which can improve the durability of display devices.

The hardened product analysis is described below by X-ray photoelectron spectroscopy (XPS).

The characteristic (v) is measured from the surface of the cured product on the opposite side to the contact surface of the first electrode and the cured product. Also, it is preferable to measure at any point within a range of 100 μm from the end of the opening of the cured product. By measuring this range, the liquid repellency of the hardened surface to functional ink can be analyzed.

The characteristic (v) of the laminate of the present invention is that the concentration of F atoms is preferably not less than 8.1 atom % and not more than 30.0 atom %. More preferably, it is 15.0 atom% or more and 26 atom% or less. When the concentration of F atoms is 8.1 atom % or more, liquid repellency can be imparted to the surface of the hardened material. On the other hand, when the concentration of F atoms is 30 atom % or less, aggregation of F atoms can be suppressed, and a cured product with few defects can be obtained.

In addition, in the characteristic (v) of the laminate of the present invention, the concentration of Si atoms is preferably not less than 1.0 atom % and not more than 6.0 atom %. More preferably, it is 1.5 atom% or more and 4.5 atom% or less. By making the concentration of Si atoms more than 1.0atom%, the UV ozone resistance of the hardened product is improved, and good liquid repellency can be obtained even after UV ozone treatment. In addition, since the polysiloxane skeleton exhibits good heat resistance, it will not decompose during the curing step, which can prevent liquid-repellent components from scattering toward the opening and improve the wettability of the functional ink coated on the opening. On the other hand, by making the concentration of Si atoms 6.0 atom% or less, aggregation of Si atoms can be suppressed, and a cured product with few defects can be obtained.

Characteristic (v) is preferably analyzed by an XPS device with a detector whose inclination relative to the sample surface is 45∘. With the inclination of the detector being 45∘, a region with a high concentration of polysiloxane (A) near the surface can be analyzed.

The characteristic (vi) is any value in the range of 100-200nm from the starting point of the interface between the first electrode and the cured material, which is perpendicular to the interface between the first electrode and the hardened material, and in the direction from the substrate toward the hardened material. A location measurement. When the thickness of the cured product is less than 200nm, measure the median value of the thickness of the cured product. If the cured product has F component inside, the water absorption of the cured product will decrease, so it can suppress electrode corrosion and improve the durability of the display device.

The characteristic (vi) of the laminate of the present invention is that the concentration of F atoms is preferably not less than 0.1 atom % and not more than 8.0 atom %. More preferably, it is 4.0 atom% or more and 7.5 atom% or less. When the concentration of F atoms is 0.1 atom % or more, since the water absorption of the hardened product is reduced, the durability of the display device can be improved. On the other hand, by keeping the concentration of F atoms below 8.0 atom%, the durability of the display device and the good mechanical properties of the hardened product can be taken into account.

The characteristic (vi) is preferably excavated by Ar gas ion clusters (Ar-GCIB), so that the interface between the first electrode and the hardened object is vertical, and the distance from the substrate to the hardened object is 100~ After exposure anywhere in the range of 200 nm, it was measured by X-ray photoelectron spectroscopy (XPS).

Next, in the laminated body of the present invention, a method of forming a cured product having at least a part of openings on the first electrode will be described.

The photosensitive resin composition of the present invention is coated on the substrate having the first electrode, dried to obtain a cured product. Further, the following steps (1) to (4) are performed sequentially to form a cured product on at least a part of the opening on the first electrode. (1) A step of coating a photosensitive resin composition on a substrate having a first electrode to form a dried photosensitive resin; (2) a step of exposing the dried photosensitive resin; (3) A step of developing the exposed dried photosensitive resin; (4) A step of forming a cured product by heat-treating the developed photosensitive resin dried product. First, the step of (1) coating a photosensitive resin composition on a substrate having a first electrode to form a dried photosensitive resin will be described.

As a method of coating a photosensitive resin composition on the board|substrate which has a 1st electrode, a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method etc. are mentioned, for example. Before coating, the substrate coated with the photosensitive resin composition may be pretreated with the above-mentioned adhesion improving agent. For example, using 0.5~20% by mass of the adhesion improver dissolved in isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, adipic acid A solution in a solvent such as diethyl ester to treat the surface of the substrate. As methods for treating the surface of the substrate, methods such as spin coating, slit coating, bar coating, dip coating, spray coating, and steam treatment may be mentioned.

Next, for example, if necessary, dry the coated photosensitive resin under reduced pressure, and then perform heat treatment in the range of 50°C to 180°C for 1 minute to several hours using a hot plate, oven, infrared rays, etc. , A dried photosensitive resin can be obtained.

Next, (2) the step of exposing the above-mentioned dried photosensitive resin will be described.

The dried photosensitive resin is irradiated with chemical rays through a photomask with a desired pattern. As the chemical rays used for exposure, there are ultraviolet rays, visible light, electron rays, X-rays, etc., preferably i-rays (365nm), h-rays (405nm), and g-rays (436nm) of mercury lamps are used in the present invention. After irradiating chemical rays, post-exposure baking may also be performed. By post-exposure baking, effects such as improvement in resolution after development and increase in latitude of development conditions can be expected. Baking after exposure can use an oven, a heating plate, infrared rays, a flash annealing device, a laser annealing device, or the like. The post-exposure baking temperature is preferably 50-180°C, more preferably 60-150°C. The post-exposure baking time is preferably 10 seconds to several hours. If the post-exposure baking time is within the above range, the reaction will progress favorably, and the developing time may be shortened. At this time, by using a lattice-shaped mask, a lattice-shaped cured product can be obtained.

"Half exposure" can also be used in the present invention. The so-called "half-exposure" refers to the process of leaving the base of the dried photosensitive resin in the exposed part to a certain extent when the development is completed. In other words, it refers to the process of exposing according to the way that the lower layer of the dried photosensitive resin is not sensitive to light. For example, in the case of forming the cured product of FIG. 3 from a positive-type photosensitive resin dry product, it is carried out: the thicker part of the first section 16 of the cured product is unexposed, and the thinner part becomes the cured product. The part of the second paragraph 17 of the dried photosensitive resin is exposed according to the amount of chemical rays that are not photosensitive to the lower layer of the dried photosensitive resin; it is then formed by development and heat treatment. In addition, by adjusting the amount of chemical rays irradiated on the dried photosensitive resin, the thickness of the dried photosensitive resin remaining after the development can be adjusted. Specifically, when the dried photosensitive resin is a positive type, the thickness of the dried photosensitive resin remaining after completion of development becomes thinner when the dose of chemical rays is increased. On the other hand, when the dried photosensitive resin is a negative type, the thickness of the dried photosensitive resin remaining after completion of development becomes thicker when the dose of chemical rays is increased. The amount of chemical radiation can also be adjusted by irradiating chemical radiation through a mask having two or more types of regions with different transmittances.

When the dried photosensitive resin formed by the photosensitive resin composition of the present invention is a positive type, the surface of the cured product formed by half-exposure has no liquid repellency and can have good ink coating properties. That is, a cured product with a liquid-repellent surface and a cured product with a lyophilic surface can be formed by one photolithography.

Next, (3) The step of developing the exposed dried photosensitive resin will be described.

In the step of developing the exposed dried photosensitive resin, the exposed dried photosensitive resin is developed using a developing solution, and the parts other than the exposed portion are removed. As a developing solution, tetramethylammonium hydroxide (hereinafter referred to as TMAH), diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, Ethylamine, Methylamine, Dimethylamine, Dimethylaminoethyl Acetate, Dimethylaminoethyl Ethanol, Dimethylaminoethyl Methacrylate, Cyclohexylamine, Ethylenediamine, Hexaethylene An aqueous solution of a basic compound such as methyldiamine. In addition, depending on the situation, the following can also be added to these alkaline aqueous solutions alone or in combination: N-methyl-2-pyrrolidone, N,N-dimethylformamide, N , Polar solvents such as N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, and dimethylacrylamide, alcohols such as methanol, ethanol, and isopropanol, ethyl lactate, propylene glycol monomethyl Esters such as base ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone, etc. As the developing method, methods such as spray coating, paddle, immersion, and ultrasonic wave can be used.

Next, it is preferable to rinse the pattern formed by development with distilled water. Here, alcohols such as ethanol and isopropanol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to distilled water for rinsing.

Next, (4) The step of forming a cured product by heat-treating the developed photosensitive resin dried product will be described.

A cured product is obtained through the step of heat-treating the developed photosensitive resin dried product. Since residual solvents or components with low heat resistance can be removed by heat treatment, heat resistance and chemical resistance can be improved. Moreover, by containing a crosslinking agent, thermal crosslinking reaction can be advanced by heat treatment, and heat resistance and chemical resistance can be improved. This heat treatment is carried out by selecting the temperature, increasing the temperature step by step, or selecting a certain temperature range to continuously increase the temperature, and implementing it for 5 minutes to 5 hours. As an example, the method of heat-processing for 30 minutes each at 150 degreeC and 250 degreeC is mentioned, for example. Alternatively, for example, a method of linearly raising the temperature from room temperature to 300° C. over 2 hours may be used. The heat treatment conditions in the present invention are preferably at least 180°C, more preferably at least 200°C, and still more preferably at least 230°C. Also, the heat treatment conditions are preferably at most 400°C, more preferably at most 350°C, and still more preferably at most 300°C.

In the laminate of the present invention, the thickness of the cured product is preferably 0.5 to 10 μm starting from the interface between the first electrode and the cured product. If it is more than 0.5 μm, the functional ink can easily stay in the pixel. From the viewpoint of easy processing of the photosensitive resin composition by photolithography, the thickness of the partition wall is preferably 10 μm or less.

As the substrate used in the laminate of the present invention, metal, glass, resin film, etc. suitable for supporting display devices or conveying in subsequent steps can be appropriately selected. In the case of a glass substrate, soda-lime glass, non-alkali glass, etc. can be used, and the thickness may be sufficient to maintain mechanical strength. As for the glass material, the one with less ions leached from the glass is suitable, so alkali-free glass is preferable, but soda-lime glass with shield coating such as _SiO2 is also commercially available, so it can also be used. If it is a resin film, it preferably contains a resin material selected from polyimide, polyamide, polybenzoxazole, polyamide imide, and parylene, and these resin materials can be contained alone, Combinations of plural types are also possible. For example, in the case of forming by polyimide resin, it is also possible to use polyamic acid (including partially imidized polyamic acid) which is a polyimide precursor, or soluble polyimide The amine solution is coated on the support substrate and fired.

The first electrode used in the laminate of the present invention preferably contains ITO (indium oxide‧tin) or IZO (indium oxide‧zinc), ZnO (zinc oxide), Ag, Al, and the like.

The patterning of the 1st electrode of the laminated body of this invention can be implemented by a well-known method. For example, a method of forming the first electrode on the entire surface of the substrate by sputtering, masking an arbitrary region with a photoresist, and then etching the opening.

When using the laminate of the present invention in a display device, a planarization layer may be further laminated between the substrate and the patterned first electrode. TFTs (Thin Film Transistors) and wirings located on the sides of the TFTs and connected to the TFTs are often provided on a substrate such as glass. If the first electrode follows the unevenness of the wiring, appearance defects such as uneven light emission will occur. Therefore, a planarization layer is formed on the driving circuit to cover the unevenness, and the first electrode is further provided on the planarization layer. In the planarization layer, it is preferable to contain a resin material selected from polyimide, polyamide, polybenzoxazole, polyamideimide, acrylic acid, cardo (cardo) and parylene, These resin materials may be contained alone or in combination of plural kinds. ＜Display device＞ The display device of the present invention includes the cured product of the present invention or the laminate of the present invention. As a specific example of a display device, LCD, organic EL, etc. are mentioned, for example.

The display device of the present invention preferably has a structure in which a functional layer is formed in a region surrounded by partition walls, at least a part of which is the hardened product of the present invention. Since the hardened product of the present invention has high liquid repellency on the upper surface, it is preferable to form the above-mentioned functional layer by inkjet. The partition wall made of the cured product of the present invention prevents the ink used in the inkjet method from penetrating into adjacent pixels, so that a display device with less occurrence of display defects can be obtained. Furthermore, the openings between the partitions have good wettability to the ink, so the yield of the display device can be improved. For example, by forming a coloring layer for coloring transmitted light and disposing a plurality of coloring layers having different colors for each pixel, it can be suitably used as a color filter. Furthermore, by containing quantum dots (QD) in the above-mentioned colored layer, it can be suitably used as a QD color filter.

The display device of the present invention preferably includes the laminate of the present invention. Specifically, it is preferable to sequentially laminate the patterned first electrode and the cured product of the present invention on a substrate, and to have a laminate having openings in at least a part of the cured product located on the first electrode, and to The opening of the hardened product forms the structure of the functional layer. Since the hardened product of the present invention has high liquid repellency on the upper surface, it is preferable to form the above-mentioned functional layer by inkjet. The cured product of the present invention prevents the ink used in the inkjet method from penetrating into adjacent pixels, so that a display device with less occurrence of display defects can be obtained. Furthermore, the openings between the partitions have good wettability to the ink, so the yield of the display device can be improved. For example, by forming an organic EL light-emitting layer containing at least one or more selected from organic EL light-emitting materials, hole injection materials, and hole transport materials as a functional layer, and then forming a second electrode on the functional layer, it can be suitably used As an organic EL display device.

The cured product of the display device of the present invention has less outgassing at high temperature, so it is suitable for use in a functional layer containing at least 1 selected from the group consisting of organic EL light-emitting materials, hole injection materials, and hole transport materials. More than one organic EL display device. An organic EL display device with reduced pixel reduction and excellent durability can be obtained.

When the display device of the present invention is an organic EL display device, the organic EL display device has a driving circuit, a planarization layer, a first electrode, a partition wall, an organic EL light-emitting layer, and a second electrode on the substrate, and the partition wall is preferably formed by the present invention. composed of hardened matter. Taking an active matrix display device as an example, there are TFTs on substrates such as glass or resin films, and wiring located on the side of the TFTs and connected to the TFTs, and there is a planarization layer covered with unevenness on it. Display elements are arranged on the planarization layer. The display element and wiring are connected through contact holes formed in the planarization layer.

<Manufacturing method of display device> Next, the method of manufacturing the display device of the present invention will be described. The manufacturing method of the display device of the present invention has steps (5) and (6) in sequence. (5) A first electrode and a cured product of the present invention are sequentially laminated on a substrate, and a laminate in which at least a part of the cured product located on the first electrode is opened, or in a laminate of the present invention, A step of forming a functional layer by coating a functional ink on the first electrode by an inkjet method; (6) A step of forming a second electrode on the functional layer.

In the step (5), a functional ink is applied on the first electrode of the above-mentioned laminate by an inkjet method to form a functional layer. For example, in the case of an organic EL display device, a composition containing at least one selected from the group consisting of an organic EL luminescent material, a hole injection material, and a hole transport material is used as a functional ink and dropped into a pixel , and dried to form an organic EL light-emitting layer. When drying, it is better to use a heating plate or an oven, and heat at 150°C~250°C for 0.5 minutes to 120 minutes.

In step (6), the second electrode is formed on the above-mentioned functional layer. The above-mentioned second electrode is preferably formed so as to cover the entirety of the partition walls and the functional layer. As a method of forming the above-mentioned second electrode, a sputtering method or a vapor deposition method may be mentioned, for example. Also, it is preferable to form the second electrode so that there is no disconnection and a uniform layer thickness. [Example]

The following examples are given to illustrate the present invention, but the present invention is not limited to these examples. First, the measurement method and evaluation method will be described.

(1) Determination of average molecular weight Polysiloxane P-1~P-29 synthesized according to Synthesis Example 1~28, acrylic liquid-repellent material (Ac-1) synthesized according to Synthesis Example 31, and phenol resin (d1) synthesized according to Synthesis Example 38 The molecular weight was measured using a GPC (gel permeation chromatography) apparatus (Waters 2690-996; manufactured by Nippon Waters Co., Ltd.), and the developing solvent was tetrahydrofuran, and the weight average molecular weight (Mw) was calculated in terms of polystyrene.

In addition, the molecular weights of the alkali-soluble resins (b1) to (b4) synthesized in Synthesis Examples 33 to 36 were determined using the above-mentioned GPC device, and the developing solvent was N-methyl-2-pyrrolidone (hereinafter referred to as NMP). The measurement was performed, and the number average molecular weight (Mn) was calculated in terms of polystyrene.

(2) Compatibility evaluation On a 4-inch silicon wafer, apply a photosensitive resin composition so that the thickness after pre-baking becomes 2 μm, and then use a heating plate to pre-bake at 90°C for 2 minutes to obtain a dried photosensitive resin substrate.

The obtained substrate having the dried photosensitive resin was subjected to defect inspection with a wafer surface inspection device "WM-10" manufactured by TOPCON Co., Ltd. WM-10 uses particle size standard polystyrene latex balls to correct the peak height and particle size of the signal accompanying particle detection. The number of defects of 0.5 μm or more converted from standard polystyrene latex balls with a particle size of 0.5 μm was judged as follows. A was rated as excellent, B as good, C as acceptable, and D as unacceptable. A: less than 10 B: More than 11 and less than 20 C: 21 or more and 30 or less D: 31 or more (3) Evaluation of liquid repellency In the measurement of the contact angle, 3 μL of PGMEA was dropped on the barrier rib pattern 4 in FIG. 1 formed on the substrate by the method described later, and the contact angle was measured. The measurement system uses a contact angle measuring device (DMs-401; manufactured by Kyowa Interface Science Co., Ltd.), and it measures at 23° C. by the static drop method according to JIS-R3257:1999.

The measurement results of the PGMEA contact angle on the cured product were judged as follows, A was rated as excellent, B was rated as good, C was rated as acceptable, and D was rated as unacceptable. A: The contact angle is above 45∘ B: The contact angle is 35∘ or more and less than 45∘ C: The contact angle is 25∘ or more and less than 35∘ D: The contact angle is less than 25∘

(4) Evaluation of ink wettability at the opening In the area (opening) surrounded by the barrier ribs of the substrate on which the barrier rib pattern 5 is formed in FIG. (HT-1) Ink (7% by mass), the wetting spreadability of the ink at the opening was observed. The number of ink drops required to wet and spread the ink over the entire opening was calculated. The ink used for this evaluation has a volume of 8 pl per drop. The wettability of the ink at the opening is judged according to the following criteria: if the amount of ink dropped below 2 drops, the ink will spread to the entire opening (A+), or if the amount of ink dropped to 3~4 drops, the ink will spread to the entire opening (A) set as excellent, according to the amount of 5~6 drops of ink dripping, the ink wets and spreads to the entire opening. ) is set to Yes, and if the amount of ink dripping is more than 9 drops, the ink will spread to the entire opening (D), or if the ink seeps out of the pixel is confirmed (E), then set it to No.

[chemical 17]

(5) Evaluation of UV ozone resistance The substrate subjected to the evaluation of the above (3) liquid repellency was subjected to UV ozone treatment under the following conditions. Thereafter, 3 μL of PGMEA was dropped on the partition wall pattern 4 in FIG. 1 to measure the contact angle. The measuring system uses a contact angle measuring device (DMs-401; manufactured by Kyowa Interface Science Co., Ltd.), and measures by static drop method at 23° C. in accordance with JIS-R3257.

Comparing the evaluation results of (3) liquid repellency above, if the change in contact angle is less than 10%, it is rated as A (pass), and when the change in contact angle is more than 10%, it is rated as B (failure).

‧UV ozone condition device: PL16 (manufactured by SEN LIGHTS Corp.) Illuminance: 15mW/cm ² Irradiation distance: 75mm Irradiation time: 120sec Method (XPS) for analysis of hardened products.

＜Preparation of hardened products for X-ray photoelectron spectroscopy (XPS) analysis＞ A laminate formed with the barrier rib pattern 4 in FIG. 1 was produced by the method described later, and XPS analysis was performed at any point in the barrier rib pattern 4 within a distance of 100 μm from the end of the opening of the cured product.

<Measurement method of characteristic (v) by X-ray photoelectron spectroscopy (XPS) analysis> Surface analysis of hardened products was performed by X-ray photoelectron spectroscopy (XPS). The measurement conditions and data processing conditions are described below.

‧Measurement conditions Device Quantera SXM (manufactured by PHI Corporation) Excited X-ray monochromatic Al K 1,2 rays (1486.6eV) X-ray diameter 200μm Photoelectron detection angle 45∘ (the inclination of the detector relative to the surface of the sample) ‧Data processing conditions Smoothing 9-point smoothing Correct the main peak of C1s on the horizontal axis and set (CHx, C-C, C=C) to 284.6eV.

<Measurement method of characteristic (vi) by X-ray photoelectron spectroscopy (XPS) analysis> For the partition wall pattern 4 of FIG. 1 , in the direction where the interface between the first electrode 2 and the partition wall pattern 4 is perpendicular and from the alkali-free glass substrate 1 to the partition wall pattern 4, the Ar gas ion cluster (Ar-GCIB ) to expose anywhere in the range of 100 to 200 nm from the above-mentioned interface. Thereafter, analysis by X-ray photoelectron spectroscopy (XPS) was performed where Ar-GCIB was performed. Measurement conditions and data processing are as follows.

‧Measurement conditions Device K-Alpha (manufactured by Thermo Fisher Scientific) Excited X-ray monochromatic Al K 1,2 rays (1486.6eV) X-ray diameter 400μm Photoelectron exit angle 90∘ (inclination of the detector relative to the surface of the sample) Ion etching conditions Ar gas ion clusters (Ar-GCIB) Etching rate 3.5nm/min ‧data processing Smoothing 11-point smoothing Correct the main peak of C1s on the horizontal axis and set (CHx, C-C) to 284.6eV. (7) Evaluation of durability On the substrate on which the barrier rib pattern 5 described later using a cured product of the photosensitive resin composition was formed, UV ozone treatment was performed in accordance with the evaluation conditions of the above (5) UV ozone resistance. Thereafter, as a hole injection layer, the ink of the compound (HT-1) using methyl benzoate as a solvent was dropped onto the area surrounded by the barrier ribs using an inkjet device (Litlex 142 manufactured by ULVAC Co., Ltd.), and then sprayed at 200 ℃ for firing to form a hole injection layer. Next, as the hole transport layer, a compound (HT-2) using 4-methoxytoluene as a solvent was dropped onto the region surrounded by the barrier ribs using an inkjet device, and then fired at 190°C to form a hole transport layer. Hole transport layer. Furthermore, as a light-emitting layer, a mixture of compound (GH-1) and compound (GD-1) using 4-methoxytoluene as a solvent was dropped onto the region surrounded by the partition wall using an inkjet device, and the mixture was sprayed at 130 ℃ for firing to form a light-emitting layer. Thereafter, as an electron transport material, the compound (ET-1) and the compound (LiQ) were sequentially stacked at a volume ratio of 1:1 by vacuum evaporation to form the organic EL layer 6 . Next, after vapor-depositing the compound (LiQ) for 2 nm, Mg and Ag were vapor-deposited for 10 nm at a volume ratio of 10:1 to form the second electrode 7 . Finally, an epoxy resin-based adhesive was used to seal the cover glass plate in a low-humidity nitrogen environment, and a 5mm square organic EL display device was produced on one substrate.

[chemical 18]

The organic EL display device produced by the above method was driven to emit light by direct current at 10mA/cm ² , and the initial light emitting area was observed. Furthermore, it was kept at 80°C for 500 hours, and then driven to emit light by direct current at 10mA/cm ² , and whether there was any change in the light emitting area was confirmed, and the durability was judged as follows. A is excellent, B is good, C is good, D is bad, and A, B, and C are good. A: No change in luminous area B: 90% to 99% change in luminous area C: 80% to 89% change in luminous area D: 79% or less change in luminous area

＜Alkoxysilyl＞ MTMS: Methyltrimethoxysilane HfTES: 4-(2-Hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-1-triethoxysilylbenzene PhTMS: Phenyltrimethoxysilane DPhDMS: Dimethoxydiphenylsilane NapTMS: 1-Naphthyltrimethoxysilane TMSSucA: 3-Trimethoxysilylpropylsuccinic anhydride TfTMS: Tridecafluorooctyltrimethoxysilane NfTMS: Nonafluorohexyltrimethoxysilane CfTMS: Trifluoromethylpropyltrimethoxysilane TEOS: Tetraethoxysilane ＜Crosslinking agent＞ HMOM-TPHAP: (compound represented by the following chemical formula, produced by Honshu Chemical Industry Co., Ltd.)

[chemical 19]

VG3101L: "TECHMORE" (registered trademark) VG3101L (compound represented by the following chemical formula, manufactured by Printec Co., Ltd.)

[chemical 20]

＜Organic solvent＞ PGMEA: Propylene Glycol Monomethyl Ether Acetate PGME: Propylene Glycol Monomethyl Ether MAK: 2-Heptanone IPA: Isopropyl Alcohol The compounds used in Examples and Comparative Examples are as follows.

(Synthesis Example 1) Synthesis of polysiloxane (P-1) In a 500mL three-neck flask, fill TfTMS 8.20g (0.05mol), NapTMS 43.46g (0.50mol), TMSSucA 9.18g (0.10mol), MTMS 16.68g (0.35mol), MAK 72.90g, IPA8.10g, at 40 Under stirring at °C, a phosphoric acid solution in which 19.53 g of water, 0.76 g of phosphoric acid (1.0% by mass relative to the filling monomer) and 2.70 g of IPA were mixed was added. Then, after immersing the flask in a 70 degreeC oil bath and stirring for 60 minutes, the oil bath was heated up to 130 degreeC over 15 minutes. 10 minutes after the start of heating, the inner temperature of the solution reached 100° C., and the solution was heated and stirred for 1 hour (the inner temperature was 100 to 125° C.) to obtain polysiloxane (P-1). Also, nitrogen was circulated at 0.07 l (liter)/minute during heating and stirring. The weight average molecular weight was determined by GPC, and the weight average molecular weight was 3,000.

(Synthesis Example 2~29) Polysiloxanes (P-2 to P-29) were obtained in the same procedure as in Synthesis Example 1, except that the components and filling amounts of the alkoxysilanes listed in Table 1 and Table 2 were changed. The weight average molecular weights of polysiloxanes (P-2 to P-29) are listed in Table 1 and Table 2.

[Table 1] No. (A) Raw material alkoxysilane Weight average molecular weight (Mw) The structure shown in formula (12) The structure shown in formula (13) The structure shown in formula (14) The structure shown in formula (15) Element Filling amount (mol%) Element Filling amount (mol%) Element Filling amount (mol%) Element Filling amount (mol%) Element Filling amount (mol%) Synthesis Example 1 P-1 TTMS 5 NapTMS 50 TMSSucA 10 MTMS 35 3000 Synthesis example 2 P-2 TTMS 10 NapTMS 50 TMSSucA 10 MTMS 30 2700 Synthesis example 3 P-3 TTMS 17 NapTMS 50 TMSSucA 10 MTMS twenty three 2600 Synthesis Example 4 P-4 TTMS 25 NapTMS 50 TMSSucA 10 MTMS 15 2600 Synthesis Example 5 P-5 TTMS 30 NapTMS 50 TMSSucA 10 MTMS 10 2600 Synthesis Example 6 P-6 TTMS 17 NapTMS 20 TMSSucA 10 MTMS 53 3600 Synthesis Example 7 P-7 TTMS 17 NapTMS 30 TMSSucA 10 MTMS 43 3000 Synthesis Example 8 P-8 TTMS 17 NapTMS 60 TMSSucA 10 MTMS 13 1900 Synthesis Example 9 P-9 TTMS 17 NapTMS 70 TMSSucA 3 MTMS 13 1400 Synthesis Example 10 P-10 TTMS 17 NapTMS 50 TMSSucA 2 MTMS 31 2700 Synthesis Example 11 P-11 TTMS 17 NapTMS 50 TMSSucA 5 MTMS 28 2700 Synthesis Example 12 P-12 TTMS 17 NapTMS 50 TMSSucA 20 MTMS 13 2600 Synthesis Example 13 P-13 TTMS 17 NapTMS 35 TMSSucA 30 MTMS 18 2600 Synthesis Example 14 P-14 TTMS 15 NapTMS 35 TMSSucA 40 MTMS 10 2800 Synthesis Example 15 P-15 TTMS 17 NapTMS 30 HfTES 15 TMSSucA 10 MTMS 28 3800 Synthesis Example 16 P-16 TTMS 17 NapTMS 30 PhTMS 15 TMSSucA 10 MTMS 28 3700 Synthesis Example 17 P-17 TTMS 17 DPhDMS 50 TMSSucA 10 MTMS twenty three 1700 Synthesis Example 18 P-18 CfTMS 17 NapTMS 50 TMSSucA 10 MTMS twenty three 2800 Synthesis Example 19 P-19 NapTMS 50 TMSSucA 10 MTMS 40 2600 Synthesis Example 20 P-20 TTMS 17 TMSSucA 10 MTMS 73 8000 Synthesis Example 21 P-21 TTMS 17 NapTMS 50 MTMS 33 2600

[Table 2] No. (A) Raw material alkoxysilane With respect to 100 mol parts of the repeating unit structure of (iii), the mol parts of the repeating unit structure of (vii) Weight average molecular weight (Mw) The structure shown in formula (12) The structure shown in formula (13) The structure shown in formula (14) The structure shown in formula (26) Element Filling amount (mol%) Element Filling amount (mol%) Element Filling amount (mol%) Element Filling amount (mol%) Synthesis Example 22 P-22 TTMS 17 NapTMS 50 TMSSucA 28 TEOS 5 18 2600 Synthesis Example 23 P-23 TTMS 17 NapTMS 50 TMSSucA 25 TEOS 8 32 3050 Synthesis Example 24 P-24 TTMS 17 NapTMS 50 TMSSucA 20 TEOS 13 65 3200 Synthesis Example 25 P-25 TTMS 17 NapTMS 50 TMSSucA 15 TEOS 18 120 3420 Synthesis Example 26 P-26 TTMS 17 NapTMS 50 TMSSucA 12 TEOS twenty one 175 3650 Synthesis Example 27 P-27 TTMS 17 NapTMS 50 TMSSucA 10 TEOS twenty three 230 4500 Synthesis Example 28 P-28 TTMS 17 NapTMS 50 TMSSucA 5 TEOS 28 560 6500 Synthesis Example 29 P-29 NfTMS 20 NapTMS 47 TMSSucA 15 TEOS 18 120 3920

(Synthesis Example 30) Synthesis of HfTES In order to synthesize HfTES(Hf-1), the following reactions were carried out.

[chem 21]

In a 300mL three-neck flask equipped with a reflux tube, take previously dried 2-(3-bromophenyl)-1,1,1,3,3,3-hexafluoropropanol (H-1) at room temperature 6.46g (20.0mmol), 7.38g (40.0mmol) of tetrabutylammonium iodide and 0.2280g (0.60mmol) of bis(acetonitrile)(1.5-cyclooctadiene)rhodium(I) tetrafluoroborate. Next, under an argon atmosphere, 120 mL of dehydrated N,N-dimethylformamide, 11.1 mL (80.0 mmol) of dehydrated triethylamine, and 7.40 mL (40.0 mmol) of triethoxysilane were added. ), warming up to 80°C and stirring for 4 hours. After the reaction system was naturally cooled to room temperature, the solvent N,N-dimethylformamide was distilled off, and then 200 mL of isopropyl ether was added. The generated precipitate was filtered by contacting with diatomaceous earth, the filtrate was washed three times with 100 mL of water, Na ₂ SO ₄ was added to dehydrate and dry, and the solvent was distilled off after filtration. The residue belonging to the reactant was distilled using a Kugelrohr device under the conditions of 140°C to 190°C and 200Pa to obtain HfTES (Hf-1) as a colorless liquid. The ¹ H-NMR measurement results of the obtained HfTES (Hf-1) are as follows.

¹ H-NMR (solvent CDCl ₃ (deuterated chloroform), TMS (tetramethylsilane)): δ8.03 (1H, s), 7.79 (2H, d, J=7.6Hz), 7.47 (1H, t, J=7.6Hz), 4.16(1H, s), 3.88(6H, q, J=5.0Hz), 1.24(9H, t, J=7.4Hz)

(Synthesis Example 31) Synthesis of acrylic liquid-repellent material (Ac-1) 100 g of cyclohexanone was added to a glass reaction vessel equipped with a stirring device, a reflux cooling tube, a dropping funnel, a thermometer, and a nitrogen blowing port, and the temperature was raised to 110° C. under a nitrogen atmosphere. The temperature of cyclohexanone was maintained at 110°C, and 44 g (0.65 moles) of N,N-dimethylacrylamide, 30 g (0.10 moles) of 2-(perfluorohexyl)ethyl methacrylate, A monomer mixed solution of 21 g (0.22 moles) of glycidyl methacrylate and 5 g (0.03 moles) of 3-phenoxybenzyl acrylate was dropped through the dropping funnel at a constant speed for 2 hours to prepare a monomer mixed solution . After completion|finish of dripping, the monomer solution was heated up to 115 degreeC, it was made to react for 2 hours, and the acrylic liquid-repellent material (Ac-1) was obtained. The weight average molecular weight was determined by GPC, and the weight average molecular weight was 5,500.

(Synthesis Example 32) Synthesis of hydroxyl-containing diamine compound 18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15°C. A solution in which 20.4 g (0.11 mol) of 3-nitrophenyl chloride was dissolved in 100 mL of acetone was dropped therein. After dropping, react at -15° C. for 4 hours, and then return to room temperature. The precipitated white solid was collected by filtration and vacuum-dried at 50°C.

Put 30g of the solid into a 300mL stainless steel autoclave, disperse it in 250mL of methyl cellophane, and add 2g of 5% palladium-carbon. Hydrogen is introduced into it with a balloon, and the reduction reaction is carried out at room temperature. After about 2 hours, it was confirmed that the balloon no longer deflated, and the reaction was terminated. After the reaction, the palladium compound belonging to the catalyst was removed by filtration, and concentrated by a rotary evaporator to obtain a hydroxyl-containing diamine compound represented by the following formula.

[chem 22]

(Synthesis Example 33) Synthesis of Alkali-Soluble Resin (b1) Under a dry nitrogen stream, 88.8 g (0.20 mol) of 2,2-(3,4-dicarboxyphenyl) hexafluoropropane dianhydride was dissolved in 500 g of NMP. In it, 96.7 g (0.16 mol) of the hydroxyl-containing diamine compound obtained in Synthesis Example 31, 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 100 g of NMP Add them together and react at 20°C for 1 hour, then react at 50°C for 2 hours. Next, 8.7 g (0.08 mol) of 3-aminophenol as a terminal terminator was added together with 50 g of NMP, and reacted at 50° C. for 2 hours. Thereafter, a solution obtained by diluting 47.7 g (0.40 mol) of N,N-dimethylformamide dimethyl acetal with 100 g of NMP was charged. After charging, it stirred at 50 degreeC for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and the solution was poured into 5 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain the target alkali-soluble resin (b1) which is a polyimide precursor. The number average molecular weight of the alkali-soluble resin (b1) which is a polyimide precursor is 12000.

(Synthesis Example 34) Synthesis of Alkali-Soluble Resin (b2) Under a stream of dry nitrogen, 62.0 g (0.20 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride was dissolved in 500 g of NMP. In it, 96.7 g (0.16 mol) of the hydroxyl-containing diamine compound obtained in Synthesis Example 31, 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 100 g of NMP Add them together and react at 20°C for 1 hour, then react at 50°C for 2 hours. Next, 8.7 g (0.08 mol) of 3-aminophenol as a terminal terminator was added together with 50 g of NMP, and reacted at 50° C. for 2 hours. Thereafter, a solution obtained by diluting 47.7 g (0.40 mol) of N,N-dimethylformamide dimethyl acetal with 100 g of NMP was charged. After charging, it stirred at 50 degreeC for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and the solution was poured into 5 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain the target alkali-soluble resin (b2) which is a polyimide precursor. The number average molecular weight of the alkali-soluble resin (b2) which is a polyimide precursor is 11000.

(Synthesis Example 35) Synthesis of Alkali-Soluble Resin (b3) Under a stream of dry nitrogen, 62.0 g (0.20 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride was dissolved in 500 g of NMP. In it, 44.85g (0.16 mol) of bis(3-amino-4-hydroxyphenyl)sulfone, 1.24g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane ear) and NMP100g were added together, reacted at 20°C for 1 hour, and then reacted at 50°C for 2 hours. Next, 8.7 g (0.08 mol) of 3-aminophenol as a terminal terminator was added together with 50 g of NMP, and reacted at 50° C. for 2 hours. Thereafter, a solution obtained by diluting 47.7 g (0.40 mol) of N,N-dimethylformamide dimethyl acetal with 100 g of NMP was charged. After charging, it stirred at 50 degreeC for 3 hours. After stirring, the solution was cooled to room temperature, and the solution was poured into 5 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain the target alkali-soluble resin (b3) which is a polyimide precursor. The number average molecular weight of the alkali-soluble resin (b3) which is a polyimide precursor is 11000.

(Synthesis Example 36) Synthesis of Alkali-Soluble Resin (b4) Under dry nitrogen flow, react 41.3g (0.16 mol) of diphenylether-4,4'-dicarboxylic acid with 43.2g (0.32 mol) of 1-hydroxy-1,2,3-benzotriazole A mixture of dicarboxylic acid derivatives 0.16 mol and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 73.3g (0.20 mol), 1,3-bis(3-amino Propyl) tetramethyldisiloxane 1.24g (0.005 mol) was dissolved in NMP570g, and it was made to react at 75 degreeC for 12 hours after that. Next, 13.1 g (0.08 mol) of 5-northene-2,3-dicarboxylic anhydride dissolved in 70 g of NMP was added, and the reaction was completed after stirring for 12 hours. After filtering the reaction mixture, the reaction mixture was put into a solution of water/methanol=3/1 (volume ratio) to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain the target alkali-soluble resin (b4) which is a precursor of polybenzoxazole (PBO). The number average molecular weight of the alkali-soluble resin (b4) which is a PBO precursor is 8500.

(Synthesis Example 37) Synthesis of quinone diazide compound (c2) Under a dry nitrogen stream, 21.23 g (0.05 moles) of TrisP-PA (trade name, produced by Honshu Chemical Industry Co., Ltd.) and 33.58 g (0.125 moles) of diazide 4-naphthoquinonesulfonyl chloride were dissolved in 1, 4-dioxane 450g, bring it to room temperature. 12.65 g (0.125 mol) of triethylamine mixed with 50 g of 1,4-dioxane was dropped therein so that the temperature in the reaction system would not be higher than 35°C. After dripping, it stirred at 30 degreeC for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. Thereafter, the precipitated precipitate was collected by filtration. The precipitate was dried with a vacuum dryer to obtain a quinone diazide compound (c2) belonging to the naphthoquinone diazide compound. The quinone diazide substitution rate of this naphthoquinone diazide compound was 83%.

[chem 23]

(Synthesis Example 38) Synthesis of Phenolic Resin (d1) Under dry nitrogen flow, fill m-cresol 108.0g (1.00 mole), 37 mass % formaldehyde aqueous solution 75.5g (formaldehyde 0.93 mole), oxalic acid dihydrate 0.63g (0.005 mole), methyl isobutyl ketone After 264 g, it was immersed in an oil bath, and polycondensation reaction was performed for 4 hours, recirculating the reaction liquid. Thereafter, the temperature of the oil bath was raised for 3 hours, after that, the pressure in the flask was reduced to 4.0kPa~6.7kPa, the volatile matter was removed, and the dissolved resin was cooled to room temperature to obtain a novolac-type phenolic resin. Phenolic resin (d1). The weight average molecular weight obtained by GPC was 3,500.

[Example 1~36], [Comparative Example 1~6] FIG. 1 shows a schematic diagram of a substrate used for evaluation.

On the non-alkali glass plate 1, a 10 nm ITO transparent conductive film was formed on the entire surface of the non-alkali glass plate by sputtering, and etched to form the first electrode 2. In addition, the auxiliary electrode 3 for taking out the second electrode is also formed at the same time. The obtained substrate was ultrasonically cleaned with "Semico Clean" (registered trademark) 56 (manufactured by Furuuchi Chemical Co., Ltd.) for 10 minutes, washed with ultrapure water, and dried to obtain a substrate.

Next, under a yellow light, mix the ingredients according to the formulation ratios shown in Table 3, Table 4 and Table 5, and fully stir at room temperature to dissolve them. Thereafter, the obtained solution was filtered through a filter with a pore diameter of 0.45 μm to obtain photosensitive resin compositions W1 to W42.

[table 3] Photosensitive resin composition No. (A) The amount of polysiloxane added (B) Alkali-soluble resin (C) Amount of sensitizer added (D) The amount of organic solvent added Addition of crosslinking agent Amount added Amount added W1 P-1 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W2 P-2 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W3 P-3 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W4 P-4 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W5 P-5 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W6 P-6 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W7 P-7 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W8 P-8 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W9 P-9 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W10 P-10 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W11 P-11 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W12 P-12 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W13 P-13 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W14 P-14 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W15 P-15 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W16 P-16 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W17 P-17 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W18 P-18 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W19 P-19 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W20 P-20 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W21 P-21 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass

[Table 4] Photosensitive resin composition No. (A) The amount of polysiloxane added (B) Alkali-soluble resin (C) Amount of sensitizer added (D) The amount of organic solvent added Addition of crosslinking agent Amount of other ingredients added Amount added Amount added W22 P-3 0.1 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass — W23 P-3 0.3 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass — W24 P-3 3.0 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass — W25 P-3 5.0 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass — W26 P-3 10.0 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass — W27 P-3 1.5 parts by mass b2 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass — W28 P-3 1.5 parts by mass b3 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass — W29 P-3 1.5 parts by mass b4 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass — W30 P-3 1.5 parts by mass b1 100 parts by mass — c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass — W31 P-3 1.5 parts by mass — d1 100 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass — W32 P-3 1.5 parts by mass b1 100 parts by mass — 10 parts by mass of pentaerythritol triacrylate 5 parts by mass of isobutyl benzoin ether PGMEA 400 parts by mass 400 parts by mass of PGME VG3101L 20 parts by mass — W33 — b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass Ac-1 1.5 parts by mass W34 — b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass —

[table 5] Photosensitive resin composition No. (A) The amount of polysiloxane added (B) Alkali-soluble resin (C) Sensitizer addition amount (D) The amount of organic solvent added Addition of crosslinking agent Amount added Amount added W35 P-22 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W36 P-23 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W37 P-24 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W38 P-25 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W39 P-26 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W40 P-27 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W41 P-28 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass W42 P-29 1.5 parts by mass b1 70 parts by mass d1 30 parts by mass c2 30 parts by mass — PGMEA 400 parts by mass 400 parts by mass of PGME HMOM-TPHAP 20 parts by mass

Next, (2) compatibility evaluation was performed using the obtained photosensitive resin composition W1-W42. The results are shown in Table 6, Table 7 and Table 8.

Furthermore, the obtained photosensitive resin compositions W1~W42 were coated on the above-mentioned substrate by spin coating, and pre-baked on a hot plate at 120°C for 2 minutes to form a dry coating film with a thickness of about 2 μm, and then through The photomask was irradiated with ultraviolet rays with an exposure dose of 120mJ/cm ² (h-ray conversion) according to the full wavelength of the mercury lamp, developed with a 2.38 mass% TMAH aqueous solution for 60 seconds, and rinsed with water. A partition wall pattern 4 having an opening with a width of 70 μm and a length of 260 μm is arranged; similarly, openings with a width of 70 μm and a length of 260 μm are formed on the substrate at an interval of 155 μm in the width direction and at an interval of 465 μm in the length direction, and the The respective openings expose the partition rib pattern 5 in the shape of the first electrode.

Next, the substrate on which the partition rib pattern 4 and the partition rib pattern 5 were formed was heated at 250°C for 1 hour in a nitrogen atmosphere using a dust-free furnace (manufactured by Koyo Thermo System Co., Ltd.) to harden. Using the substrate on which the barrier rib pattern 4 was formed, (3) evaluation of liquid repellency was performed; using the substrate on which the barrier rib pattern 5 was formed, (4) evaluation of ink wettability of the opening was performed. Then, (5) Evaluation of UV ozone resistance was performed. The results are shown in Table 6, Table 7 and Table 8.

[Table 6] Photosensitive resin composition No. Evaluation of Compatibility Evaluation of liquid repellency Evaluation of wettability of ink at the opening Evaluation of UV Ozone Resistance Number of defects (pcs/4 inches) determination PGMEA contact angle (∘) determination ink drops determination Contact angle of PGMEA after UV ozone treatment (∘) Change rate of PGMEA contact angle (%) determination Example 1 W1 5 A 31 C 3 A 29 6.5 A Example 2 W2 6 A 37 B 3 A 35 5.4 A Example 3 W3 7 A 46 A 4 A 44 4.3 A Example 4 W4 12 B 47 A 4 A 44 6.4 A Example 5 W5 27 C 49 A 6 B 46 6.1 A Example 6 W6 26 C 46 A 4 A 43 6.5 A Example 7 W7 17 B 46 A 4 A 44 4.3 A Example 8 W8 6 A 46 A 4 A 44 4.3 A Example 9 W9 6 A 45 A 6 B 44 2.2 A Example 10 W10 19 B 47 A 8 C 45 4.3 A Example 11 W11 12 B 47 A 5 B 45 4.3 A Example 12 W12 5 A 46 A 4 A 44 4.3 A Example 13 W13 5 A 45 A 4 A 43 4.4 A Example 14 W14 5 A 41 B 3 A 40 2.4 A Example 15 W15 5 A 47 A 4 A 44 6.4 A Example 16 W16 28 C 47 A 4 A 45 4.3 A Example 17 W17 7 A 47 A 4 A 43 8.5 A Comparative example 1 W18 7 A <5 D. Leakage to the outside of the pixel E. Not rated Comparative example 2 W19 7 A <5 D. Leakage to the outside of the pixel E. Not rated Comparative example 3 W20 55 D. 46 A 6 B 43 6.5 A Comparative example 4 W21 25 C 46 A 12 D. 43 6.5 A

[Table 7] Photosensitive resin composition No. Evaluation of Compatibility Evaluation of liquid repellency Evaluation of wettability of ink at the opening Evaluation of UV Ozone Resistance Number of defects (pcs/4 inches) determination PGMEA contact angle (∘) determination ink drops determination Contact angle of PGMEA after UV ozone treatment (∘) Change rate of PGMEA contact angle (%) determination Example 18 W22 4 A 31 C 3 A 29 6.5 A Example 19 W23 5 A 40 B 3 A 38 5.0 A Example 20 W24 8 A 47 A 4 A 45 4.3 A Example 21 W25 9 A 49 A 5 B 46 6.1 A Example 22 W26 18 B 51 A 7 C 48 5.9 A Example 23 W27 17 B 46 A 4 A 44 4.3 A Example 24 W28 27 C 46 A 4 A 44 4.3 A Example 25 W29 16 B 46 A 4 A 44 4.3 A Example 26 W30 5 A 32 C 3 A 30 6.3 A Example 27 W31 twenty one C 46 A 4 A 45 2.2 A Example 28 W32 7 A 46 A 4 A 45 2.2 A Comparative Example 5 W33 5 A 50 A 11 D. 20 60.0 B Comparative Example 6 W34 3 A <5 D. Leakage to the outside of the pixel E. Not rated

[Table 8] Photosensitive resin composition No. Evaluation of Compatibility Evaluation of liquid repellency Evaluation of wettability of ink at the opening Evaluation of UV Ozone Resistance Number of defects (pcs/4 inches) determination PGMEA contact angle (∘) determination ink drops determination Contact angle of PGMEA after UV ozone treatment (∘) Change rate of PGMEA contact angle (%) determination Example 29 W35 5 A 47 A 4 A 44 6.4 A Example 30 W36 6 A 47 A 3 A 44 6.4 A Example 31 W37 6 A 46 A 3 A 44 4.3 A Example 32 W38 7 A 47 A 2 A+ 44 6.4 A Example 33 W39 8 A 48 A 2 A+ 46 4.2 A Example 34 W40 17 B 46 A 3 A 43 6.5 A Example 35 W41 28 C 46 A 4 A 44 4.3 A Example 36 W42 5 A 42 B 2 A+ 40 4.8 A

[Example 37] According to the method described in the above <Measurement method of characteristic (v) by X-ray photoelectron spectroscopy (XPS) analysis>, XPS analysis of the cured product of photosensitive resin composition W3 was carried out, and the obtained F atoms and Si atoms The elemental concentrations (atom%) of the compounds are shown in Table 9.

Next, according to the method described in the above <Measurement method of characteristic (vi) by X-ray photoelectron spectroscopy (XPS) analysis>, the XPS analysis of the cured product of the photosensitive resin composition W3 was carried out, and the obtained F atoms and The element concentration (atom%) of Si atoms is shown in Table 9.

Next, the above (7) durability evaluation was performed using the cured product of the obtained photosensitive resin composition W3, and the evaluation results are shown in Table 9.

[Examples 38-41], [Comparative Examples 7, 8] Except having changed photosensitive resin composition W3 into any one of W23, W25, W27, W28, W33, and W34, it evaluated similarly to Example 36. The evaluation results are shown in Table 9.

[Table 9] Photosensitive resin composition No. XPS analysis XPS analysis result elemental composition (atmic%) Durability Evaluation f Si Light emitting area ratio after high temperature treatment (%) determination Example 37 W3 (v) 20.8 3.3 100% A (vi) 6.3 0.3 Example 38 W23 (v) 14.0 2.0 100% A (vi) 6.4 0.2 Example 39 W25 (v) 25.7 4.2 100% A (vi) 6.3 0.2 Example 40 W27 (v) 20.6 3.1 92% B (vi) 2.5 0.2 Example 41 W28 (v) 20.6 3.2 83% C (vi) 0 0.2 Comparative Example 7 W33 (v) 18.3 0 Leakage to the outside of the pixel (vi) 6.4 0.2 Comparative Example 8 W34 (v) 14.8 0.4 Leakage to the outside of the pixel (vi) 6.2 0.2

[Example 42, 43] A 10nm ITO transparent conductive film was formed on the entire surface of an alkali-free glass plate by sputtering, and on this alkali-free glass plate, the photosensitive resin compositions W3 and W32 were coated by spin coating, Pre-baked on a heating plate at 120°C for 2 minutes to form a dry coating film with a thickness of about 2 μm. Next, "half-exposure" was performed by irradiating ultraviolet rays with the full wavelength of a mercury lamp to half the area of the dried photosensitive resin so that the thickness after development would be 0.5 μm. For the remaining half area, the dried photosensitive resin of W3 having positive photosensitive characteristics was set as unexposed in such a way that the thickness does not decrease during the developing step. On the other hand, W32 having negative photosensitive characteristics was irradiated with ultraviolet light at an exposure amount of 120 mJ/cm ² (h-ray conversion) so that the thickness would not decrease during the developing step. Next, development was performed for 60 seconds with a 2.38% by mass TMAH aqueous solution, followed by rinsing with water to prepare a substrate having a dried photosensitive resin.

Next, the obtained substrate with dried photosensitive resin was heated at 250° C. in a dust-free furnace (manufactured by Koyo Thermo System Co., Ltd.) under a nitrogen atmosphere for 1 hour to be cured to obtain a substrate with a cured product.

Regarding the contact angle of PGMEA measured on the surface of the cured product of photosensitive resin composition W3, the unexposed part was 46∘, and the half-exposed part was 5∘ or less. In this manner, it was confirmed that the surface of the cured product obtained by half-exposing the positive-type photosensitive resin composition showed lyophilicity. That is, a cured product with a liquid-repellent surface and a cured product with a lyophilic surface can be formed by one photolithography. On the other hand, the contact angle of PGMEA measured on the surface of the cured product of the negative photosensitive resin composition W32 was 46∘ in the exposed part and 40∘ in the half-exposed part, and liquid repellency was confirmed in both regions.

1: Alkali-free glass substrate 2: 1st electrode 3: Auxiliary electrode 4: A partition pattern with an opening in the center 5: next door pattern 6: Organic EL layer 7: 2nd electrode 8: Substrate 9: Planarization layer 10: Patterned first electrode 11: Hardened 12: The surface opposite to the interface between the first electrode and the hardened material 13: The interface between the first electrode and the hardened object 14: In the direction where the interface between the first electrode and the hardened object is perpendicular and from the above-mentioned substrate toward the hardened object, the distance from the interface between the first electrode and the hardened object is 100~200nm. 15: In the direction where the interface between the first electrode and the hardened object is perpendicular and from the above-mentioned substrate toward the hardened object, the distance between the first electrode and the interface between the hardened object and the starting point is 100 16: The first stage of hardening 17: The second paragraph of the hardened object

FIG. 1 is a schematic diagram of a substrate used for evaluation in Examples. Fig. 2 is a schematic cross-sectional view of an example of a laminate. Fig. 3 is a schematic cross-sectional view of another example of a laminate.

1: Alkali-free glass substrate

2: 1st electrode

3: Auxiliary electrode

4: A partition pattern with an opening in the center

5: next door pattern

6: Organic EL layer

7: 2nd electrode

Claims (20)

A photosensitive resin composition, which contains polysiloxane (A), alkali-soluble resin (B) and photosensitizer (C); wherein, the polysiloxane (A) has (i), (ii) and (iii) repeating unit structure; (i) repeating unit structure shown in formula (1) and/or repeating unit structure shown in formula (2); (ii) repeating unit structure shown in formula (3) and/or formula Repeating unit structure shown in (4); (iii) repeating unit structure shown in formula (5) and/or repeating unit structure shown in formula (6);

(R ^f is a fluorinated alkyl group with a fluorine number of 7-21 and a carbon number of 5-12, and R ¹ is a hydrogen atom, an alkyl group with a carbon number of 1-6, an acyl group with a carbon number of 1-6, or a carbon number of 6-15 Aryl; R2 is an aryl group with ⁶ ~15 carbons, ^R3 is a single bond or an alkylene group with 1~ ⁴ carbons, Y is 1 or 2; R4 is an acidic group with 2~20 carbons organic group; ✽ means covalent bond). The photosensitive resin composition according to claim 1, wherein at least one of the above-mentioned R ² is the structure shown in formula (26) or formula (27); [Chemical 2]

(R ¹⁶ is hydroxyl, alkyl with 1 to 5 carbons, alkoxy with 1 to 5 carbons, halogenated alkyl with 1 to 5 carbons, hydroxyalkyl with 1 to 5 carbons, or 1 to 5 carbons 5 is a halogenated hydroxyalkyl group; b is an integer from 0 to 3; ✽ represents a covalent bond). The photosensitive resin composition as claimed in claim 1 or 2, wherein at least one of the above R ² is 1-naphthyl, 2-naphthyl or the structure shown in formula (7); [Chemical 3]

(a represents an integer from 1 to 3; ✽ represents a covalent bond). The photosensitive resin composition according to any one of claims 1 to 3, wherein at least one of the above-mentioned R ⁴ is an organic group with 2 to 20 carbon atoms containing a carboxyl group. The photosensitive resin composition according to any one of claims 1 to 4, wherein at least one of the above-mentioned R ⁴ is the structure shown in formula (8) or formula (9); [Chemical 4]

(R ¹⁵ is a single bond or an alkylene group with 1 to 10 carbons; ✽ represents a covalent bond). The photosensitive resin composition according to any one of claims 1 to 5, wherein, in 100 mol% of the total repeating unit structure of the polysiloxane (A), the repeating unit structure shown in formula (1) and the formula (2) The total of the repeating unit structures shown in (2) contains 5-30 mol%. The photosensitive resin composition according to any one of claims 1 to 6, wherein, in 100 mol% of the total repeating unit structure of the polysiloxane (A), the repeating unit structure shown in formula (3) and the formula (4) The total of the repeating unit structures shown in (4) contains 20-70 mol%. The photosensitive resin composition according to any one of Claims 1 to 7, wherein, in 100 mol% of the total repeating unit structure of the polysiloxane (A), the repeating unit structure shown in formula (5) and the formula (6) The total of the repeating unit structures shown in (6) contains 1-40 mol%. The photosensitive resin composition according to any one of Claims 1 to 8, wherein the polysiloxane (A) further has the repeating unit structure of (vii); (vii) the repeating unit structure represented by formula (25) [chemical 5]

(✽ denotes a covalent bond). The photosensitive resin composition according to Claim 9, wherein the polysiloxane (A) contains 30 to 300 mole parts of the repeating unit structure of the above (vii) relative to 100 mole parts of the repeating unit structure of the above (iii) Mole portion. The photosensitive resin composition according to any one of Claims 1 to 10, wherein the above-mentioned alkali-soluble resin (B) contains a compound selected from polyimide, polybenzoxazole, polyamideimide, etc. One or more species from the group consisting of any one of its precursors and copolymers thereof. Such as the photosensitive resin composition of claim 11, wherein the above-mentioned polyimide, polybenzoxazole, polyamideimide, any of these precursors and their copolymers are bound to carboxyl The residue of the acid component and/or the residue of the diamine component has the structure shown in formula (16); [Chemical 6]

(✽ denotes a covalent bond). The photosensitive resin composition according to any one of claims 1 to 12, wherein the photosensitive agent (C) contains a quinone diazide compound. The photosensitive resin composition according to claim 13, wherein the alkali-soluble resin (B) contains phenol resin and/or polyhydroxystyrene resin. The photosensitive resin composition according to any one of claims 1 to 14, wherein the content of the polysiloxane (A) is 0.1 parts by mass or more and 10 parts by mass relative to 100 parts by mass of the alkali-soluble resin (B) servings or less. A cured product obtained by curing the photosensitive resin composition in any one of Claims 1 to 15. A laminated body, in which a patterned first electrode and the cured product according to claim 16 are sequentially laminated on a substrate, and at least a part of the cured product located on the first electrode is opened. The laminated body according to claim 17, wherein the analysis of the hardened product obtained by X-ray photoelectron spectroscopy (XPS) satisfies the characteristics (v) and characteristics (vi); (v) In the cured product, the concentration of F atoms measured from at least a part of the surface opposite to the surface of the first electrode contacting the cured product is 8.1 atom % or more and 30.0 atom % or less, and Si atoms The concentration is more than 1.0atom% and less than 6.0atom%; (vi) In a direction perpendicular to the contact interface between the first electrode and the hardened material and from the substrate toward the hardened material, a distance of 100 to 200 nm from the interface between the first electrode and the hardened material as the starting point The concentration of F atoms in the cured product measured at any one of the ranges is not less than 0.1 atom % and not more than 8.0 atom %. A display device comprising the hardened product of claim 16 or the laminate of claim 17 or 18. A method of manufacturing a display device, comprising steps (5) and (6) in sequence; (5) In the laminate according to claim 17 or 18, a step of forming a functional layer by coating a functional ink on the first electrode by an inkjet method; (6) A step of forming a second electrode on the functional layer.

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