JP2011059425A - Photosensitive resin composition, cured film and method of forming the cured film, organic el display device, and liquid crystal display device - Google Patents

Abstract

The present invention provides a photosensitive resin composition that provides a cured film having excellent transparency and heat-resistant transparency, low dielectric constant, and high dielectric breakdown voltage, and excellent in transparency and heat-resistant transparency. A cured film having a low dielectric breakdown voltage and a high breakdown voltage, and a method for forming the cured film. In addition, an organic EL display device and a liquid crystal display device each including a cured film having excellent transparency and heat-resistant transparency, a low dielectric constant, and a high dielectric breakdown voltage are provided.
(A) (a) a monomer unit having a carboxystyrene skeleton, and (b) an alkali-soluble resin having a monomer unit having a cyclic ether group, (B) a photosensitive agent, and (C) a solvent. The photosensitive resin composition characterized by including.
[Selection figure] None

Description

  The present invention relates to a photosensitive resin composition, a cured film and a method for forming the same, an organic EL display device, and a liquid crystal display device.

An organic EL display device, a liquid crystal display device, and the like are provided with a patterned interlayer insulating film. In forming the interlayer insulating film, a photosensitive resin composition is widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.
The interlayer insulating film in the display device is required to have high transparency in addition to the properties of the cured film, such as excellent insulation, solvent resistance, heat resistance, and ITO sputtering resistance. For this reason, an attempt has been made to use an acrylic resin having excellent transparency as a film forming component.

For example, Patent Documents 1 and 2 are known as photosensitive resin compositions for forming an interlayer insulating film.
Patent Document 1 discloses (A) (a) an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, (b) a radical polymerizable compound having an epoxy group, and (c) another radical polymerizable compound (provided that ω- A radiation-sensitive resin composition comprising a resin soluble in an alkaline aqueous solution, which is a copolymer of aminoalkyl (meth) acrylate) and (B) a radiation-sensitive acid generating compound is disclosed. .
Patent Document 2 includes [A] (a1) an unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, (a2) a compound having an ethylenically unsaturated bond and an oxetanyl group, and (a3) the above (a1) And a radiation-sensitive resin composition comprising a copolymer obtained by copolymerizing an olefinically unsaturated compound other than (a2) and a [B] 1,2-quinonediazide compound. Yes.

Japanese Patent No. 2961722 Japanese Patent No. 3835120

The problem to be solved by the present invention is to provide a photosensitive resin composition that is excellent in transparency and heat-resistant transparency, has a low dielectric constant, and provides a cured film having a high dielectric breakdown voltage, as well as transparency and heat resistance. An object of the present invention is to provide a cured film having excellent transparency, a low dielectric constant, and a high dielectric breakdown voltage, and a method for forming the cured film.
Another problem to be solved by the present invention is an organic EL display device having a cured film having excellent transparency and heat-resistant transparency, a low dielectric constant, and a high dielectric breakdown voltage, and a liquid crystal display device. Is to provide.

The above-described problems of the present invention have been solved by means described in the following <1>, <5>, <13>, <14>, <16> and <17>. It is described below together with <2> to <4>, <6> to <12> and <15>, which are preferred embodiments.
<1> (A) (a) a monomer unit having a carboxystyrene skeleton, (b) an alkali-soluble resin having a monomer unit having a cyclic ether group, and (B) a photosensitizer. Photosensitive resin composition,
<2> The photosensitive resin composition according to <1>, wherein the cyclic ether group is an epoxy group and / or an oxetanyl group.
<3> The photosensitive resin composition according to <1> or <2>, wherein the cyclic ether group is an epoxy group,
<4> The content of the (A) alkali-soluble resin is 60% by weight to 95% by weight and the content of the (B) photosensitive agent is 5% by weight with respect to the total solid content of the photosensitive resin composition. The photosensitive resin composition according to any one of <1> to <3>, which is 40% by weight or less,
<5> (X) An alkali-soluble resin containing a monomer unit having a carboxystyrene skeleton, (B) a photosensitizing agent, (Y) a crosslinking agent having a cyclic ether group, and (C) a solvent. A photosensitive resin composition,
<6> The photosensitive resin composition according to <5>, wherein the (Y) crosslinking agent is a crosslinking agent having an epoxy group and / or an oxetanyl group,
<7> The photosensitive resin composition according to <5> or <6>, wherein the (Y) crosslinking agent is a crosslinkable resin having a cyclic ether group.
<8> The content of the (X) alkali-soluble resin is 40% by weight or more and 70% by weight or less with respect to the total solid content of the photosensitive resin composition, and the content of the (B) photosensitive agent is 5% by weight. The photosensitive resin composition according to any one of <5> to <7>, which is 40% by weight or less and the content of the (Y) crosslinking agent is 3% by weight or more and 40% by weight or less,
<9> The photosensitive resin composition according to any one of <1> to <8>, wherein the (B) photosensitive agent is a 1,2-naphthoquinonediazide compound,
<10> (D) The photosensitive resin composition according to any one of <1> to <9>, further containing a thermal radical generator,
<11> The photosensitive resin composition according to <10>, wherein the (D) thermal radical generator has a 10-hour half-life temperature of 100 ° C. or higher and 230 ° C. or lower.
<12> (E) The photosensitive resin composition according to any one of <1> to <11>, further containing a methylol-based crosslinking agent and / or an alkoxymethyl group-containing crosslinking agent,
<13> (1) The process of apply | coating the photosensitive resin composition as described in any one of <1>-<12> on a board | substrate, (2) Prebaking which removes a solvent from the apply | coated photosensitive resin composition A method for forming a cured film, comprising: a step, (3) a step of exposing with actinic radiation, (4) a step of developing with an aqueous developer, and (5) a post-baking step of thermosetting.
<14> A cured film formed by the method according to <13>,
<15> The cured film according to <14>, which is an interlayer insulating film,
<16> An organic EL display device comprising the cured film according to <14> or <15>,
<17> A liquid crystal display device comprising the cured film according to <14> or <15>.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which is excellent in transparency and heat-resistant transparency, has a low dielectric constant, and gives the cured film which has a high dielectric breakdown voltage could be provided. Furthermore, it was possible to provide a cured film having excellent transparency and heat-resistant transparency, a low dielectric constant, and a high dielectric breakdown voltage, and a method for forming the same.
Moreover, according to the present invention, an organic EL display device and a liquid crystal display device having a cured film having excellent transparency and heat-resistant transparency, a low dielectric constant, and a high breakdown voltage can be provided. .

1 shows a conceptual diagram of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type EL light emitting device is shown, and a planarizing film 4 is provided. 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. The schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.

1. Photosensitive resin composition The first photosensitive resin composition of the present invention comprises (A) (a) a monomer unit having a carboxystyrene skeleton, and (b) an alkali-soluble resin having a monomer unit having a cyclic ether group. (B) a photosensitive agent and (C) a solvent.
In addition, the second photosensitive resin composition of the present invention includes (X) an alkali-soluble resin containing a monomer unit having a carboxystyrene skeleton, (B) a photosensitive agent, and (Y) a crosslinking agent having a cyclic ether group. And (C) a solvent.
The photosensitive resin composition of the present invention can be suitably used as a positive photosensitive resin composition.
In the following description, the description of “A to B” representing a numerical range represents “A or more and B or less” unless otherwise specified. That is, a numerical range including A and B which are end points is represented.

1-1. First photosensitive resin composition (A) Alkali-soluble resin The first photosensitive resin composition of the present invention comprises (A) (a) a monomer unit having a carboxystyrene skeleton, and (b) a cyclic ether group. An alkali-soluble resin having a monomer unit (hereinafter also referred to as “component A” or “(A) alkali-soluble resin”).
Component A contains (a) a monomer unit having a carboxystyrene skeleton and (b) a monomer unit having a cyclic ether group, and if necessary, other monomers different from (a) and (b) Unit (c) may be included.
Hereinafter, the monomer units (a) to (c) will be described.

(A) Monomer unit having carboxystyrene skeleton (A) The alkali-soluble resin has a monomer unit having a carboxystyrene skeleton. The monomer unit having a carboxystyrene skeleton is a monomer unit derived from a monomer having a carboxystyrene skeleton, and is preferably represented by the following formula (1).

The substitution position of the carboxy group is not particularly limited, and may be any of the ortho position, the meta position, and the para position, but the para position is preferable from the viewpoint of availability.
R represents a monovalent substituent, and n represents 0 to 4.
R is preferably a monovalent organic group, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 carbon atom. A methyl group as a group is particularly preferred. n is preferably 0 to 2, more preferably 0 or 1, and still more preferably 0. When n is 2 or more, a plurality of R may be the same or different.

  The monomer unit having a carboxy skeleton is preferably a monomer unit derived from carboxystyrene, and more preferably a monomer unit derived from p-carboxystyrene.

  (A) Content of the monomer unit which has carboxystyrene skeleton in alkali-soluble resin is 10-80 mol% with respect to 100 mol% of all the monomer units in Component A from a viewpoint of coexistence with various tolerance and developability. Is preferable, 20-60 mol% is more preferable, and 25-55 mol% is further more preferable.

(B) Monomer unit having a cyclic ether group (A) The alkali-soluble resin has a monomer unit having a cyclic ether group. Although it does not specifically limit as a cyclic ether group, It is preferable that it is a 3-6 membered ring, It is more preferable that it is a 3-5 membered ring, It is further more preferable that it is a 3-4 membered ring, It is a 3 membered ring. It is particularly preferred. That is, the monomer unit having a cyclic ether group preferably has an epoxy group and / or an oxetanyl group, and particularly preferably has an epoxy group.
The monomer unit having a cyclic ether group may have at least one cyclic ether group in one monomer unit, and may have a plurality of cyclic ether groups, and is not particularly limited. Are preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.

The monomer unit having a cyclic ether group is preferably a monomer unit derived from a radical polymerizable compound having at least one cyclic ether group (preferably an epoxy group or oxetanyl group) and one ethylenically unsaturated group.
Examples of the monomer having at least one epoxy group and one ethylenically unsaturated group include glycidyl acrylate, glycidyl methacrylate, (3,4-epoxycyclohexyl) methyl acrylate, (3,4-epoxycyclohexyl) methyl methacrylate, and allyl glycidyl. Mention may be made of compounds such as ethers.
Among these, glycidyl acrylate, glycidyl methacrylate, (3,4-epoxycyclohexyl) methyl acrylate, and (3,4-epoxycyclohexyl) methyl methacrylate are preferable, and glycidyl methacrylate, 3,4-epoxycyclohexyl) methyl acrylate, (3, 4-Epoxycyclohexyl) methyl methacrylate is most preferred from the viewpoint of solvent resistance and heat resistance.
Examples of the monomer having one or more oxetanyl groups and one or more ethylenically unsaturated groups include (meth) acrylic acid esters having an oxetanyl group as described in JP-A-2001-330953. . Specific examples of such a monomer include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- ( Methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. have wide development latitude (process margin) of the resulting photosensitive resin composition, and chemical resistance of the resulting cured film It is preferable from the point of improving the property.

  The content of the monomer unit having a cyclic ether group is preferably 20 to 80 mol% with respect to 100 mol% of all monomer units in the (A) alkali-soluble resin, from the viewpoint of compatibility between various resistances and developability. 60 mol% is more preferable and 25-55 mol% is further more preferable.

(C) Other monomer units The other monomer units are not particularly limited as long as they have a structure different from the monomer units of (a) and (b), but other ethylenically unsaturated compounds ("ethylenic compounds"). The “unsaturated compound” is preferably a monomer unit derived from “vinyl monomer” hereinafter.

(C) Other vinyl monomers that can form monomer units include, for example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters Preferred examples thereof include (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".
Specific examples of such vinyl monomers include the following compounds.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, dodecyl (meth) acrylate , Octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2- (meth) acrylic acid 2- Ethoxyethyl, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3- (meth) acrylic acid 3- Enoxy-2-hydroxypropyl, (meth) acrylic acid benzyl, (meth) acrylic acid diethylene glycol monomethyl ether, (meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid tri Ethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, (meth) acrylic acid β-phenoxyethoxyethyl, (meth) acrylic acid nonylphenoxy polyethylene glycol, (meta ) Trifluoroethyl acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, (meth) acryl Examples include tribromophenyl acid and tribromophenyloxyethyl (meth) acrylate.

Examples of the crotonic acid esters include butyl crotonic acid and hexyl crotonic acid.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N -Phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group deprotectable by an acidic substance (for example, t-butoxycarbonyl group (t-Boc) and the like), methyl vinylbenzoate, and α-methylstyrene.

(A) The alkali-soluble resin may contain a monomer unit having an aromatic ring structure from the viewpoint of improving the developability of the photosensitive resin composition.
The monomer unit having an aromatic ring structure is preferably derived from the monomers shown below.
That is, phenyl (meth) acrylate, 3-methoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate , Tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, Hydroxystyrene protected with acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, a group that can be deprotected by an acidic substance (for example, t-Boc, etc.) , Methyl vinyl benzoate, and, alpha-methyl styrene and the like, these, (meth) acrylate, benzyl styrene is preferred.

(C) Another monomer unit may be comprised by 1 type individually, and may be comprised by 2 or more types.
The content of (c) other monomer units in Component A is 0 to 50 mol% with respect to 100 mol% of all monomer units in (A) alkali-soluble resin, from the viewpoint of compatibility between various resistances and developability. Preferably, 0 to 45 mol% is more preferable, and 0 mol% to 40 mol% is more preferable.

The synthesis method of component A is not particularly limited, and may be appropriately selected from known methods. For example, at the time of polymerization, at least (a) a monomer unit having a carboxystyrene skeleton, (b) a monomer unit having a cyclic ether group, and (c) a monomer capable of forming another monomer unit as necessary. It can be synthesized by copolymerization.
In addition, the synthesis method of component A is not limited to this, The method etc. which add the monomer (monomer) containing an epoxy ring to the carboxy group of the polymer synthesize | combined previously in an appropriate ratio can also be used.
Among these, it is preferable to synthesize | combine (A) alkali-soluble resin by copolymerization, and you may use an addition reaction together as needed.

As described above, when (A) the alkali-soluble resin is synthesized and when the addition reaction is performed, it is preferably performed in a solvent (solvent).
Any solvent may be used as long as it can dissolve the raw material monomer used for copolymerization at a necessary concentration and does not adversely affect the properties of the film formed using the resulting copolymer. May be used.
Specific examples of the solvent include water, alcohol solvents such as methanol, ethanol and propanol, ketone solvents such as acetone, alcohol acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone, ethyl acetate, butyl acetate and propylene. Ester solvents such as glycol monomethyl ether acetate, γ-butyrolactone, methyl benzoate, ether solvents such as dibutyl ether, anisole, tetrahydrofuran, toluene, xylene, mesitylene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene , Isopropylbenzene, 1,4-diisopropylbenzene, t-butylbenzene, 1,4-di-t-butylbenzene, 1,3,5-triethylbenzene, 1,3,5-tri- Aromatic hydrocarbon solvents such as -butylbenzene, 4-t-butyl-orthoxylene, 1-methylnaphthalene, 1,3,5-triisopropylbenzene, amide solvents such as N-methylpyrrolidinone and dimethylacetamide, Halogen solvents such as carbon chloride, dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane Solvents can be used.

Among these, more preferred solvents are tetrahydrofuran, γ-butyrolactone, anisole, toluene, xylene, mesitylene, isopropylbenzene, t-butylbenzene, 1,3,5-tri-t-butylbenzene, 1-methylnaphthalene, 1 Amide solvents such as 1,3,5-triisopropylbenzene, N-methylpyrrolidinone, dimethylacetamide, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, particularly preferred Is an amide solvent such as N-methylpyrrolidinone and dimethylacetamide.
These solvents may be used alone or in combination of two or more.
In addition, the boiling point of the organic solvent used for the copolymerization reaction or the addition reaction is preferably 50 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 150 ° C. or higher.
The concentration of the solute in the reaction solution used for the copolymerization reaction or addition reaction is preferably 1 to 50% by weight, more preferably 5 to 30% by weight, and 10 to 20% by weight. It is particularly preferred.

(A) Although the optimal conditions for the copolymerization reaction during the production of the alkali-soluble resin vary depending on the type and concentration of the solvent, the reaction temperature is preferably 0 ° C to 150 ° C, more preferably 30 ° C. It is -100 degreeC, More preferably, it is 50 degreeC-90 degreeC. Moreover, reaction time becomes like this. Preferably it is 1 to 50 hours, More preferably, it is 2 to 40 hours, More preferably, it is 3 to 30 hours.
Moreover, in order to suppress the oxidative decomposition of the copolymer to be synthesized, the reaction is preferably performed in an inert gas atmosphere (for example, nitrogen, argon, etc.). It is also preferable to carry out the polymerization reaction under light-shielding conditions in order to suppress unwanted photoreactions.
In the polymerization, it is preferable to use a polymerization initiator as necessary, and the polymerization initiator can be appropriately selected from known photopolymerization initiators, thermal polymerization initiators, and the like.

  The molecular weight of the (A) alkali-soluble resin is not particularly limited, but in terms of alkali dissolution rate, film physical properties, etc., the weight average molecular weight is preferably 1,000 to 500,000, and preferably 3,000 to 300,000. More preferred is 5,000 to 200,000. In the present invention, the molecular weight is measured by gel permeation chromatography and can be determined using a standard polystyrene calibration curve.

  In the first photosensitive resin composition of the present invention, the content of component A ((A) alkali-soluble resin) is 20 to 99% by weight with respect to the total solid content of the photosensitive resin composition. Preferably, it is 40 to 97% by weight, more preferably 60 to 95% by weight. When the content is in the above range, the pattern formability upon development is good.

(B) Photosensitive agent The first photosensitive resin composition of the present invention contains (B) a photosensitizer.
The photosensitive agent that can be used in the photosensitive resin composition of the present invention refers to a compound that imparts a function of forming an image by exposure to the photosensitive resin composition and / or gives the trigger.
Specific examples include a photosensitive quinonediazide compound (B1), a dihydropyridine compound (B2), and a compound that generates an acid upon exposure (photoacid generator) (B3).
Among these, a quinonediazide compound (B1) and a dihydropyridine compound (B2) are preferable, and a quinonediazide compound (B1) is more preferable.
These photosensitizers may be used alone or in combination of two or more.
In order to adjust sensitivity, a sensitizer or the like can be used in combination with the photosensitive agent.

<Quinonediazide compound (B1)>
The photosensitive resin composition of the present invention preferably contains a quinonediazide compound as the photosensitizer (B), and more preferably contains a 1,2-quinonediazide compound.
The quinonediazide compound is a compound having a quinonediazide partial structure, requires at least one quinonediazide partial structure in the molecule, and preferably has two or more partial structures.
The quinonediazide compound suppresses alkali solubility of the photosensitive resin composition coating film in the unexposed area, and improves the alkali solubility of the photosensitive resin composition coating film by generating a carboxy group in the exposed area. A positive pattern can be formed.

Examples of the quinonediazide compound include an o-quinonediazide compound (1,2-quinonediazide compound) and a p-quinonediazide compound (1,4-quinonediazide compound). Among these, from the viewpoints of sensitivity and developability, 1,2-quinonediazide compounds are preferable, and 1,2-naphthoquinonediazide compounds are particularly preferable.
A 1,2-quinonediazide compound can be obtained, for example, by subjecting 1,2-quinonediazidesulfonyl chlorides to a hydroxy compound, an amino compound, or the like in the presence of a dehydrochlorinating agent.
Examples of the 1,2-quinonediazide compound include 1,2-benzoquinonediazidesulfonic acid ester, 1,2-naphthoquinonediazidesulfonic acid ester, 1,2-benzoquinonediazidesulfonic acid amide, and 1,2-naphthoquinonediazidesulfonic acid amide. Etc. Specifically, “Light-Sensitive Systems” by J. Kosar, pp. 339-352 (1965), John Wiley & Sons (New York), WS De Forest, “Photoresist” 50 (1975), McGraw-Hill, Inc, (New York), 1,2-quinonediazide compounds, 1,2-quinonediazide compounds described in JP-A No. 2004-170566, JP-A No. 2002-40653, JP-A No. 2002-351068, JP-A No. 2004-4233, JP-A No. 2004-271975, etc. Can be mentioned. Those described in paragraphs 0066 to 0081 of JP-A-2008-224970 are also preferable.

  Among the compounds having a 1,2-naphthoquinonediazide group, compounds having the following structures can be preferably used because they have particularly high sensitivity.

  Further, the most preferable compound having a 1,2-naphthoquinonediazide group is the following compound. The ratio (molar ratio) of H and 1,2-naphthoquinonediazide group in D is preferably 50:50 to 1:99 from the viewpoint of sensitivity and transparency.

<Dihydropyridine compound (B2)>
There is no restriction | limiting in particular as a dihydropyridine compound, A well-known dihydropyridine compound can be used suitably as a photosensitive agent.
The dihydropyridine compound is preferably a 1,4-dihydropyridine compound. Further, the dihydropyridine compound preferably has a nitroaryl structure, and more preferably a 4- (o-nitroaryl) -1,4-dihydropyridine compound.
Examples of the dihydropyridine compound that can be used in the present invention include 2,6-dimethyl-3,5-diacetyl-4- (2′-nitrophenyl) -1,4-dihydropyridine and 4- (2′-nitrophenyl). ) -2,6-dimethyl-3,5-dicarboethoxy-1,4-dihydropyridine, 4- (2 ′, 4′-dinitrophenyl) -2,6-dimethyl-3,5-dicarbomethoxy-1 Preferred examples include 1,4-dihydropyridine.

<Photoacid generator (B3)>
Photoacid generators include photoinitiators of photocationic polymerization, photoinitiators of photoradical polymerization, photodecolorants of dyes, photochromic agents, irradiation of actinic rays or radiation used in microresists, etc. A known compound that generates an acid or a mixture thereof can be appropriately selected and used.

Specific examples of the photoacid generator include a diazonium salt compound, a phosphonium salt compound, a sulfonium salt compound, an iodonium salt compound, an imide sulfonate compound, an oxime sulfonate compound, a diazodisulfone compound, a disulfone compound, and an o-nitrobenzyl sulfonate compound. Can be mentioned.
As a photoacid generator, a compound that generates a sulfonic acid or an alkyl or arylcarboxylic acid substituted with an electron withdrawing group, a disulfonylimide substituted with an electron withdrawing group, or the like having a strong pKa of 2 or less as a generated acid Is preferred. Here, examples of the electron withdrawing group include a halogen atom such as an F atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.

  Further, as a photoacid generator, a group that generates an acid upon irradiation with actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of a resin, for example, US Pat. No. 3,849,137, German Patent No. 3914407, and JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452. The compounds described in JP-A-62-153853 and JP-A-63-146029 can also be used.

  Further, as a photoacid generator, compounds capable of generating an acid by light described in each specification such as US Pat. No. 3,779,778 and European Patent 126,712 can also be used.

  In the first photosensitive resin composition of the present invention, the blending amount of the photosensitive agent (B) is that of the photosensitive resin composition in terms of the difference in dissolution rate between the exposed part and the unexposed part and the allowable sensitivity range. The total solid content is preferably 1 to 80% by weight, more preferably 3 to 60% by weight, and further preferably 5 to 40% by weight.

  In the first photosensitive resin composition of the present invention, the total content of (A) the alkali-soluble resin and (B) the photosensitive agent is 50% by weight based on the total solid content of the photosensitive resin composition. Preferably, it is 60% by weight, more preferably 70% by weight, and particularly preferably 80% by weight or more. The upper limit of the content is not particularly limited as long as it is 100% by weight or less.

(C) Solvent The first photosensitive resin composition of the present invention contains (C) a solvent.
As the solvent used for the preparation of the photosensitive resin composition of the present invention, a solvent that uniformly dissolves component A and component B and other components optionally blended and does not react with these components is used. It is done.
Among these, alcohol, glycol ether, ethylene glycol alkyl ether acetate, ester, or diethylene glycol is preferably used from the viewpoints of solubility of each component, reactivity with each component, ease of film formation, and the like. Among these, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, methyl methoxypropionate or ethyl ethoxypropionate are preferred, and propylene glycol monomethyl ether acetate or diethylene glycol dimethyl ether is more preferred.

Furthermore, in order to improve the in-plane uniformity of the film thickness together with the solvent, a high boiling point solvent can be used in combination.
Examples of the high-boiling solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl. Ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, Examples thereof include phenyl cellosolve acetate. Of these, N-methylpyrrolidone, γ-butyrolactone, or N, N-dimethylacetamide is preferable.

  When a high boiling point solvent is used in combination as the solvent for preparing the first photosensitive resin composition of the present invention, the amount used is preferably 50% by weight or less, more preferably 40% by weight or less, based on the total amount of the solvent. More preferably, it can be 30% by weight or less. It is excellent in the point of the film thickness uniformity of a coating film, the sensitivity, and the remaining film rate that the usage-amount of a high boiling point solvent is the said range.

(C) A solvent may be used individually by 1 type, or what mixed 2 or more types in arbitrary ratios may be used for it.
When preparing the photosensitive resin composition of the present invention in a solution state, the solid content concentration of components other than the solvent in the solution can be arbitrarily set according to the purpose of use, the value of the desired film thickness, and the like. However, it is preferable that it is 5 to 50 weight% with respect to the total weight of the photosensitive resin composition of this invention, it is preferable that it is 10 to 40 weight%, and it is more preferable that it is 12 to 35 weight%.
The photosensitive resin composition solution thus prepared may be used after being filtered using a Millipore filter having an opening having a pore diameter of about 0.2 μm.

1-2. Second photosensitive resin composition As described above, the second photosensitive resin composition of the present invention comprises (X) an alkali-soluble resin containing a monomer unit having a carboxystyrene skeleton, (B) a photosensitive agent, Y) a crosslinking agent having a cyclic ether group, and (C) a solvent. Hereinafter, each component will be described.

(X) Alkali-soluble resin containing a monomer unit having a carboxystyrene skeleton The second photosensitive resin composition of the present invention comprises (X) an alkali-soluble resin containing a monomer unit having a carboxystyrene skeleton (hereinafter referred to as “component X”). Or “(X) Alkali-soluble resin”).
(X) The alkali-soluble resin contains (x) at least a monomer unit having a carboxystyrene skeleton, and may contain another monomer unit (y) different from (x) as necessary.

(X) Monomer unit having a carboxystyrene skeleton As the monomer unit having a carboxystyrene skeleton, those exemplified in the above (a) monomer unit having a carboxystyrene skeleton can be preferably used.
(X) The content of the monomer unit having a carboxystyrene skeleton in the alkali-soluble resin is 10 with respect to 100 mol% of all monomer units in the (X) alkali-soluble resin, from the viewpoint of achieving both various resistances and developability. -100 mol% is preferable, 20-90 mol% is more preferable, 30-80 mol% is further more preferable.

(Y) Other monomer units Examples of other monomer units include those exemplified above for (c) other monomer units, and preferred ranges are also the same.
(X) The content of (y) other monomer units in the alkali-soluble resin is 0 with respect to 100 mol% of all monomer units in the (X) alkali-soluble resin, from the viewpoint of compatibility between various resistances and developability. -90 mol% is preferable, 10-80 mol% is more preferable, 20-70 mol% is further more preferable.

  In addition, as other monomer units, a monomer unit having a cyclic ether group may be contained, but the content thereof is preferably 0 to 90 mol% with respect to 100 mol% of all monomer units in Component X, 0-80 mol% is more preferable, and 0-70 mol% is further more preferable. When the content of the monomer unit having a cyclic ether group is within the above range, the curability is improved, which is preferable.

In the second photosensitive resin composition of the present invention, the content of the (X) alkali-soluble resin is preferably 10 to 90% by weight with respect to the total solid content of the photosensitive resin composition. It is more preferably 80% by weight, and further preferably 40 to 70% by weight.
(X) It is preferable for the content of the alkali-soluble resin to be in the above range since the developability is good.

(X) The method for synthesizing the alkali-soluble resin is not particularly limited, and may be appropriately selected from known methods. For example, at the time of polymerization, at least styrene carboxylic acid and a derivative thereof (for example, alkyl-substituted product) can be used, and if necessary, polymerization can be performed by copolymerizing monomers that can form other monomer units. .
In addition, the synthesis method of (X) alkali-soluble resin is not limited to this, The method of adding the monomer containing an epoxy group to the carboxy group of the polymer synthesize | combined previously in an appropriate ratio, and the epoxy ring (for example, A method of adding a monomer containing a carboxy group such as (meth) acrylic acid to (glycidyl group) can also be used.
(X) When synthesizing an alkali-soluble resin and when an addition reaction is used, it is preferably carried out in a solvent (solvent). As the solvent, the above component A is synthesized or subjected to an addition reaction. Can be exemplified, and preferred embodiments are also the same. Moreover, the optimum conditions for the (co) polymerization reaction are the same as the conditions for the copolymerization reaction of Component A, and the preferred embodiments are also the same.

  (X) The molecular weight of the alkali-soluble resin is not particularly limited, but is preferably 3,000 to 200,000 in terms of weight average molecular weight from the viewpoint of alkali dissolution rate, film physical properties, etc., and 5,000 to 100,000. It is more preferable that it is 5,000-50,000.

(B) Photosensitive agent The second photosensitive resin composition of the present invention contains (B) a photosensitive agent.
Preferred examples of the (B) photosensitive agent include those exemplified as the (B) photosensitive agent in the first photosensitive resin composition of the present invention.

  In the 2nd photosensitive resin composition of this invention, it is preferable that content of (B) photosensitive agent is 1 to 60 weight% with respect to the total solid of the photosensitive resin composition, and 3-50 More preferably, it is 5 weight%, and it is still more preferable that it is 5-40 weight%. (B) When the content of the photosensitive agent is within the above range, the developability is good.

(Y) Crosslinking agent having a cyclic ether group The second photosensitive resin composition of the present invention contains (Y) a crosslinking agent having a cyclic ether group (hereinafter also referred to as (Y) a crosslinking agent).
The (Y) crosslinking agent is not particularly limited as long as it has a cyclic ether group, but the cyclic ether group preferably has an epoxy group and / or an oxetanyl group.

The (Y) crosslinking agent may be a low molecular compound having a cyclic ether group, but is preferably a crosslinkable resin having a cyclic ether group.
(Y) The weight average molecular weight of the crosslinking agent is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and further preferably 3,000 to 20,000. preferable. (Y) It is preferable that the weight average molecular weight of the crosslinking agent is within the above range because the developability is good.

When (Y) the crosslinking agent is a (Y ′) crosslinkable resin having a cyclic ether group (hereinafter, also referred to as (Y ′) crosslinkable resin), the crosslinkable resin contains a cyclic ether group and an ethylenically unsaturated group. A homopolymer of a monomer having a bond or a copolymer with another monomer is preferable.
(Y ′) As the monomer unit having a cyclic ether group constituting the crosslinkable resin, those exemplified as the monomer unit having (b) a cyclic ether group in the first photosensitive resin composition are preferably exemplified. .
The content of the monomer unit having a cyclic ether group in the (Y ′) crosslinkable resin is 10 to 90 mol% with respect to 100 mol% of all monomer units in the (Y ′) crosslinkable resin from the viewpoint of film strength. It is preferable, it is more preferable that it is 20-80 mol%, and it is further more preferable that it is 30-80 mol%.

(Y ′) Other monomer units constituting the crosslinkable resin are preferably exemplified by those exemplified as (c) other monomer units in the first photosensitive resin composition.
The content of other monomer units in (Y ′) crosslinkable resin is 0 to 50 mol% with respect to 100 mol% of all monomer units in (Y ′) crosslinkable resin from the viewpoint of developability and curability. It is preferable that it is 1-40 mol%, it is more preferable that it is 5-30 mol%.

The method for synthesizing (Y ′) the crosslinkable resin is not particularly limited, and it is preferable to synthesize by a (co) polymerization reaction as shown in the above (A) alkali-soluble resin and (X) alkali-soluble resin.
In addition, the preferable conditions at the time of a synthesis | combination are the same as that of what was illustrated with (A) alkali-soluble resin, and a preferable aspect is also the same.

In the 2nd photosensitive resin composition of this invention, it is preferable that content of (Y) crosslinking agent is 1 to 60 weight% with respect to the total solid of the photosensitive resin composition, and 2-50 It is more preferable that it is weight%, and it is further more preferable that it is 3-40 weight%.
(Y) It is preferable for the content of the crosslinking agent to be in the above range since the developability is good.

(C) Solvent The second photosensitive resin composition of the present invention contains (C) a solvent.
As a solvent used for the preparation of the photosensitive resin composition of the present invention, the component X, the component B and the component Y, and other components optionally blended are uniformly dissolved and do not react with these components. Things are used.
As specific examples of the solvent, those exemplified for the solvent (C) of the first photosensitive composition can be similarly exemplified, and preferred ranges thereof are also the same.

  In the second photosensitive resin composition of the present invention, the total content of (X) alkali-soluble resin, (B) photosensitive agent, and (Y) crosslinking agent is the total solid content of the photosensitive resin composition. On the other hand, it is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 70% by weight or more, and particularly preferably 80% by weight or more. Moreover, an upper limit is not specifically limited, What is necessary is just 100 weight% or less. It is preferable that the total content of (X) alkali-soluble resin, (B) photosensitizer and (Y) cross-linking agent is within the above ranges because good developability, strength of the cured film, and ITO sputtering resistance can be obtained.

In addition to the above components, the first photosensitive resin composition and the second photosensitive resin composition of the present invention include (D) a thermal radical generator, (E) other crosslinking agent, and (F) adhesion promotion. An optional component such as an agent, (G) a surfactant, and / or (H) an antioxidant may be further included.
Hereinafter, arbitrary components will be described.

(D) Thermal radical generator The photosensitive resin composition of the present invention may contain (D) a thermal radical generator.
As the thermal radical generator in the present invention, those which are different from the photosensitive agent (B) and generally known as radical generators can be used. The thermal radical generator is a compound that generates radicals by heat energy and initiates and accelerates a polymerization reaction with (A) an alkali-soluble resin or (Y) a crosslinking agent. By adding a thermal radical generator, the obtained cured film becomes tougher and heat resistance and solvent resistance are improved.

Hereinafter, although a thermal radical generator is explained in full detail, this invention is not restrict | limited by these description.
In the present invention, preferred thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, activity Examples thereof include an ester compound, a compound having a carbon halogen bond, an azo compound, and a bibenzyl compound.
In the present invention, from the viewpoint of heat resistance and solvent resistance of the obtained cured film, organic peroxides, azo compounds, and bibenzyl compounds are more preferable, and bibenzyl compounds are particularly preferable.
Specific examples of the above-described thermal radical generator are given below, but the present invention is not limited to these.

  Specific examples of these organic peroxides include Parroyl L, Perocta O, Parroyl SA, Perhexa 25O, Perhexyl O, Nipper BMT, Nipper BW, Perhexa MC, Perhexa TMH, Perhexa HC, Perhexa C, Pertetra C, Perhexyl I. Perbutyl MA, perbutyl 355, perbutyl L, perbutyl I, perbutyl E, perhexyl Z, perhexa 25Z, perbutyl A, perhexa 22, perbutyl Z, perhexa V, perbutyl P, park mill D, perhexyl D, perhexyl 25B, perbutyl C (above , Manufactured by NOF Corporation).

  Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobispropionitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2 ′. -Azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 4,4 '-Azobis (4-cyanovaleric acid), 2,2'-azobisisobutyric acid dimethyl, 2,2'-azobis (2-methylpropionamidooxime), 2,2'-azobis [2- (2-imidazoline-2 -Yl) propane], 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis [2 Methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide), 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2′-azobis (2,4,4-trimethylpentane) and the like can be mentioned.

  Moreover, as a bibenzyl compound, the compound represented by following formula (1) is preferable.

（式（１）中、複数存在するＲ³は、それぞれ独立に、水素原子、炭素数が１〜２０の炭化水素基、シアノ基、ニトロ基、炭素数１〜２０のアルコキシル基、又はハロゲン原子を表す。）

(In Formula (1), a plurality of R ³ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms, or a halogen atom. Represents.)

  Specific examples of the compound represented by the formula (1) include 2,3-dimethyl-2,3-diphenylbutane, α, α′-dimethoxy-α, α′-diphenylbibenzyl, α, α′- Diphenyl-α-methoxybibenzyl, α, α′-dimethoxy-α, α′dimethylbibenzyl, α, α′-dimethoxybibenzyl, 3,4-dimethyl-3,4-diphenyl-n-hexane, 2, 2,3,3-tetraphenyl succinic acid nitrile, dibenzyl and the like can be mentioned.

The (D) thermal radical generator used in the present invention is preferably a compound having a 10-hour half-life temperature of 100 ° C. or higher and 230 ° C. or lower, more preferably 120 ° C. or higher and 220 ° C. or lower. . When the 10-hour half-life temperature is in this temperature range, a cured film having excellent characteristics can be obtained.
The 10-hour half-life temperature of the thermal radical generator refers to a temperature at which half of the compound to be measured decomposes when left at a specific temperature for 10 hours.

As compounds having a 10-hour half-life temperature in the range of 100 ° C. or higher and 230 ° C. or lower, among the above-mentioned compounds, Perbutyl A, Perhexa 22, Perbutyl Z, Perhexa V, Perbutyl P, Park Mill D, manufactured by NOF Corporation. Perhexyl D, perhexa 25B, perbutyl C, NOFMER BC-90 (2,3-dimethyl-2,3-diphenylbutane) and the like are preferable.
The reason is not clear, but a thermal radical generator that decomposes at a higher temperature to generate radicals is preferable, and the resulting cured film has good heat resistance and solvent resistance.

(D) A thermal radical generator may be used individually by 1 type, and can also use 2 or more types together.
The content of the (D) thermal radical generator in the photosensitive resin composition of the present invention is 0.1 to 100 weights when (A) the alkali-soluble resin or (X) the alkali-soluble resin is 100 parts by weight. Part is preferred, 1 to 50 parts by weight is more preferred, and 5 to 30 parts by weight is most preferred from the viewpoint of improving film physical properties.

(E) Other crosslinking agent It is preferable that the 1st photosensitive resin composition of this invention contains a crosslinking agent. Moreover, it is preferable that the 2nd photosensitive resin composition of this invention contains the (E) other crosslinking agent other than the said Y component.
Preferred examples of the other crosslinking agent include (E-1) a methylol-based crosslinking agent and / or (E-2) a crosslinking agent containing an alkoxymethyl group (hereinafter also referred to as an alkoxymethyl group-containing crosslinking agent). (E-2) An alkoxymethyl group-containing crosslinking agent is more preferred. These crosslinking agents may be used individually by 1 type, and may use 2 or more types together.

(E-1) Methylol-based crosslinking agent The methylol-based crosslinking agent is not particularly limited as long as it is a crosslinking agent having a methylol group, and specifically, methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, and methylolated. A compound having a methylol group of urea is exemplified. Of these, methylolated melamine is preferred.

(E-2) Alkoxymethyl group-containing crosslinking agent Alkoxymethyl group-containing crosslinking agent (alkoxymethyl group-containing crosslinking agent) includes alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril and alkoxymethylated urea. Etc. are preferred. These can be obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril and methylolated urea to an alkoxymethyl group, respectively. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, and the like. preferable.
Among these crosslinkable compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are mentioned as preferable crosslinkable compounds, and alkoxymethylated glycoluril is particularly preferable from the viewpoint of transparency.
These (E-1) alkoxymethyl group-containing crosslinking agents are available as commercial products, for example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202. , 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalac Mx-750, -032, -706, -708, -40, -31, -270, -280 , -290, Nicarak Ms-11, Nicarak Mw-30HM, -100LM, -390 (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.

  The amount of addition of these (E) other crosslinking agents is preferably 0.05 to 50 parts by weight, more preferably 0.5 to 100 parts by weight of the alkali-soluble resin (A) or (X) alkali-soluble resin. ~ 20 parts by weight. By adding within this range, preferable alkali solubility during development and excellent solvent resistance of the cured film can be obtained.

(F) Adhesion promoter To the photosensitive resin composition of the present invention, if necessary, an adhesion promoter such as an organosilicon compound, a silane coupling agent, and a leveling agent is added to provide adhesion to a solid surface. May be.
Examples of these are, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryl. Trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, ureapropyltriethoxysilane, tris ( Acetylacetonate) aluminum, acetylacetate aluminum diisopropylate and the like.
When the adhesion promoter is used in the photosensitive resin composition of the present invention, the content of the adhesion promoter in the photosensitive resin composition of the present invention is (A) alkali-soluble resin or (X) alkali-soluble resin 100 weight. 0.1-20 weight part is preferable with respect to part, and 0.5-10 weight part is more preferable.

(G) Surfactant The photosensitive resin composition of the present invention can contain (G) a surfactant in order to improve coatability.
As the surfactant, a fluorine-based surfactant, a silicone-based surfactant, or a nonionic surfactant can be suitably used. For example, various surfactants described in JP-A-2001-330953 are used. Can do.
These surfactants may be used alone or in combination of two or more.
In the photosensitive resin composition of the present invention, these surfactants are 0.001 to 100 parts by weight of (A) alkali-soluble resin or (X) alkali-soluble resin from the viewpoint of improving coatability. It is preferable to use 20 parts by weight, more preferably 0.01 to 5 parts by weight, and still more preferably 0.01 to 2 parts by weight.

(H) Antioxidant Furthermore, it is also preferable to add an antioxidant to the photosensitive resin composition of the present invention.
By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented or reduction in film thickness due to decomposition can be reduced.
As the antioxidant, known antioxidants can be used. Phosphorous antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate Saccharides, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like. Among these, phenolic antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. These may be used alone or in combination.

Examples of commercially available phenolic antioxidants include ADK STAB AO-60 (manufactured by ADEKA), ADK STAB AO-80 (manufactured by ADEKA), Irganox 1098 (manufactured by Ciba Japan Co., Ltd.), and Iruga. Nox 1010 (manufactured by Ciba Japan Co., Ltd.), Sumilyzer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.) and the like.
The content of the antioxidant is preferably 0.1 to 6% by weight, more preferably 0.2 to 5% by weight, based on the total solid content of the photosensitive resin composition. 5-4% by weight is optimal. By setting it in this range, sufficient transparency of the formed film can be obtained, and sensitivity can be exhibited even during pattern formation.
In addition, as an additive other than the antioxidant, the various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun)”, metal deactivators and the like are used in the photosensitive resin composition of the present invention. You may add to.

2. Cured film and method for forming the same, organic EL display device, and liquid crystal display device <cured film and method for forming the same>
The cured film of the present invention is a cured film formed from the photosensitive resin composition of the present invention, and can be suitably used as an interlayer insulating film in an electronic device such as a semiconductor device or a display device.
In the present invention, a cured film can be formed using a photosensitive resin composition containing a solvent. In this case, it is preferable to employ the following steps as the method for forming the cured film.
(1) The process of apply | coating the photosensitive resin composition containing a solvent on a board | substrate, (2) The prebaking process of removing a solvent from the apply | coated photosensitive resin composition, (3) The process of exposing with actinic radiation, (4 ) A step of developing with an aqueous developer, and (5) a post-baking step of thermosetting.
An optional step can be included in addition to the above essential steps.
In the step (1), the substrate may be a semi-finished product obtained in the middle of the display device manufacturing process, in addition to the unprocessed semiconductor substrate such as a silicon wafer.

The cured film obtained by the above-described method for forming a cured film can be suitably used as an interlayer insulating film in an electronic device such as a semiconductor device or a display device.
The interlayer insulating film of the present invention imparts energy by actinic radiation with light to the coating film comprising the photosensitive resin composition of the present invention, improves the developability of the energy imparted region, and removes the region by development. Further, it is preferably formed by a heat curing treatment.
Such a cured film is excellent in transparency, heat resistance and insulation, and is particularly suitable as an interlayer insulating film for electronic devices. The electronic device referred to in the present invention means an organic EL display device and an electronic device for a liquid crystal display device, and the photosensitive resin composition of the present invention has an interlayer insulation for the organic EL display device and the liquid crystal display device. It is especially effective for the membrane.
The photosensitive resin composition of the present invention is applied to the following positive pattern forming method, and can be used as an interlayer insulating film as a cured film having a desired shape.

[Pattern formation method]
As a method of forming a patterned cured film using the photosensitive resin composition of the present invention, (1) the photosensitive resin composition of the present invention was applied on a suitable substrate, and (2) the coating was applied. The substrate is baked (pre-baked), (3) exposed with actinic rays or radiation, (4) developed with an aqueous developer, (5) exposed as required, and (6) thermoset (post-baked). Various processes for forming a pattern are used. By using this pattern forming method, a cured film having a desired shape (pattern) can be formed on the substrate.

  In the pattern forming method described above, the overall exposure in (5) is an optional step and may be performed as necessary.

  As in the pattern formation method described above, (1) the photosensitive resin composition of the present invention is formed on a semiconductor element so that the thickness after curing becomes a desired thickness (preferably 0.1 to 30 μm). Or after apply | coating on a glass substrate, at least (2) prebaking, (3) exposure, (4) development, and (6) pattern shape for organic EL display devices or liquid crystal display devices by thermosetting. The cured film can be formed.

Hereinafter, the pattern forming method will be described in more detail.
The photosensitive resin composition of the present invention is (1) coated on a suitable substrate.
The substrate may be selected according to the use of the cured film to be formed. For example, a semiconductor substrate such as a silicon wafer or a ceramic substrate, or a substrate made of glass, metal, or plastic is used. If the cured film is for a semiconductor device, a silicon wafer is generally used, and if the cured film is for a display device, a glass substrate is generally used.
Examples of the application method include, but are not limited to, spray coating, spin coating, slit coating, offset printing, roller coating, screen printing, extrusion coating, meniscus coating, curtain coating, and dip coating.
By this (1) coating process, a photosensitive resin composition layer is formed on the substrate.

  After the (1) coating step, (2) pre-baking is performed in order to evaporate the solvent remaining in the photosensitive resin composition layer. This (2) pre-bake is preferably performed at a temperature of 70 to 130 ° C. for 30 seconds to 30 minutes.

Next, (2) the photosensitive resin composition layer dried by pre-baking is subjected to (3) exposure using actinic radiation through a mask having a desired pattern. Exposure energy is preferably 10~1,000mJ / cm ^2, and more preferably the energy of 20~500mJ / cm ^2. As the active radiation, X-rays, electron beams, ultraviolet rays, visible rays, and the like can be used. The most preferred actinic radiation is one having a wavelength of 436 nm (g-line), 405 nm (h-line), and 365 nm (i-line). Further, exposure can be performed by a laser method such as an ultraviolet laser. By this (3) exposure step, a region that is developed with an aqueous developer and a region that is not developed are formed in the photosensitive resin composition layer on the substrate. Since the photosensitive resin composition of the present invention has a positive action, the exposed portion becomes a region to be developed with an aqueous developer.

Next, (3) the exposed photosensitive resin composition layer is developed with (4) an aqueous developer. By this development, the exposed portion of the photosensitive resin composition layer is developed with an aqueous developer, preferably an alkaline aqueous solution, and the unexposed portion remains on the substrate, thereby leaving a pattern having a desired shape. A layer is formed.
Aqueous developers include inorganic alkalis (eg, potassium hydroxide, sodium hydroxide, aqueous ammonia), primary amines (eg, ethylamine, n-propylamine), secondary amines (eg, diethylamine, di-n). -Propylamine), tertiary amines (eg, triethylamine), alcohol amines (eg, triethanolamine), quaternary ammonium salts (eg, tetramethylammonium hydroxide, tetraethylammonium hydroxide), and mixtures thereof There is an alkaline solution using The most preferred developer is one containing tetramethylammonium hydroxide. In addition, an appropriate amount of a surfactant may be added to the developer. Further, the development may be performed by dipping, spraying, paddling, or other similar development methods.

  (4) After the development step, the photosensitive resin composition layer remaining on the substrate may be rinsed using deionized water in some cases.

Further, (4) after the development step, the photosensitive resin composition layer remaining on the substrate is subjected to (5) whole surface exposure as necessary. The exposure energy for this overall exposure is preferably 100 to 1,000 mJ / cm ² . This (5) overall exposure is preferable because the transparency is improved when a cured film for a display device is formed.

Next, (4) the photosensitive resin composition layer remaining on the substrate after the development step is subjected to a post-baking step of (6) thermosetting in order to obtain a final patterned cured film.
In this post-baking step, free carboxy groups are generated from the protected carboxy groups in the entire patterned resin composition film formed in the development step, and contribute to a crosslinking reaction such as epoxy groups.
By this thermosetting, a cured film having high heat resistance, chemical resistance, and film strength is formed. When a general photosensitive polyimide precursor composition of a conventional method is used, it has been heat-cured at a temperature of about 300 to 400 ° C. On the other hand, the photosensitive resin composition of the present invention preferably has a film property equivalent to or higher than that of a conventional photosensitive polyimide precursor composition by heating at 150 ° C. to 300 ° C., more preferably 160 ° C. to 250 ° C. A membrane is obtained.

With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film physical properties, it is useful for applications of organic EL display devices and liquid crystal display devices.
The organic EL display device or liquid crystal display device of the present invention is not particularly limited except that it has a flattening film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and has various structures. Various known organic EL display devices and liquid crystal display devices can be used.

  FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate 14 is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.

  EXAMPLES Hereinafter, although this invention is explained in full detail with reference to an Example, this invention is not limited to a following example at all.

(List of abbreviations used in the synthesis example)
・ StCO ₂ H: Styrene carboxylic acid (4-Vinylbenzoic acid, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ GMA: Glycidyl methacrylate (Wako Pure Chemical Industries, Ltd.)
DCPM: dicyclopentanyl methacrylate (FA-511A, manufactured by Hitachi Chemical Co., Ltd.)
・ HEMA: Hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.)
・ MMA: Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
・ OXE-30 (Oxetane acrylate: manufactured by Osaka Organic Chemical Industry Co., Ltd.)
V-601: Dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
・ PGMEA: Methoxypropyl acetate (manufactured by Showa Denko KK)
HS-EDM: High Solve EDM (manufactured by Toho Chemical Industry Co., Ltd., diethylene glycol ethyl methyl ether)
Nicarax MX-270: Methoxymethyl crosslinking agent (manufactured by Sanwa Chemical Co., Ltd.)

(Synthesis example)
<Synthesis Example 1 (1 binder: epoxy)>
HS-DEM (54.6 g) was placed in a three-necked flask and heated to 70 ° C. in a nitrogen atmosphere. StCO ₂ H (18.52 g, 0.125 mol), GMA (17.77 g, 0.125 mol), V-65 (1.24 g, 2 mol% with respect to the monomer) and HS-EDM (54.6 g) were added to the solution. And was added dropwise over 2 hours. After completion of dropping, the mixture was stirred for 2 hours, further heated to 90 ° C. and stirred for 1 hour to complete the reaction. Thereby, the binder A was obtained.
The weight average molecular weight of the binder A was 20,000.

<Synthesis Example 2 (1 binder: epoxy)>
HS-DEM (57.5) was placed in a three-necked flask and heated to 70 ° C. in a nitrogen atmosphere. StCO ₂ H (16.67 g, 0.1125 mol), GMA (15.99 g, 0.1125 mol), DCPM (5.51 g, 0.025 mol), V-65 (1.24 g, based on monomer) 2 mol%) was dissolved in HS-EDM (57.5 g) and added dropwise over 2 hours. After completion of dropping, the mixture was stirred for 2 hours, further heated to 90 ° C. and stirred for 1 hour to complete the reaction. Thereby, Binder B was obtained.
The weight average molecular weight of the binder B was 18,000.

<Synthesis Example 3 (2 binder)>
(1) Acid polymer HS-DEM (53.5 g) was placed in a three-necked flask and heated to 70 ° C. in a nitrogen atmosphere. StCO ₂ H (18.52 g, 0.125 mol), DCPM (27.54 g, 0.125 mol), V-65 (1.24 g, 2 mol% based on monomer) were added to the solution with HS-EDM (53.5 g). And was added dropwise over 2 hours. After completion of dropping, the mixture was stirred for 2 hours, further heated to 90 ° C. and stirred for 1 hour to complete the reaction. Thereby, the binder C was obtained.
The weight average molecular weight of the binder C was 21,000.

(2) Epoxy crosslinkable resin HS-DEM (39.75g) was put into the three necked flask, and it heated up at 90 degreeC in nitrogen atmosphere. GMA (28.43 g, 0.2 mol), MMA (2.50 g, 0.0025 mol), HEMA (3.25 g, 0.0025 mol), V-601 (2.878 g, 5 mol% based on monomer) were added to the solution. ) Was dissolved in HS-EDM (39.75 g) and added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours. Thereby, a crosslinking agent A was obtained.
The weight average molecular weight of the crosslinking agent A was 11,000.

<Synthesis Example 4 (1 binder: oxetane)>
HS-DEM (50.0 g) was placed in a three-necked flask and heated to 70 ° C. in a nitrogen atmosphere. StCO ₂ H (16.67 g, 0.1125 mol), OXE-30 (20.73 g, 0.1125 mol), DCPM (5.51 g, 0.025 mol), V-65 (1.24 g, monomer) 2 mol%) was dissolved in HS-EDM (50.0 g) and added dropwise over 2 hours. After completion of dropping, the mixture was stirred for 2 hours, further heated to 90 ° C. and stirred for 1 hour to complete the reaction. Thereby, binder D was obtained.
The weight average molecular weight of the binder D was 20,000.

<Synthesis Example 5 (2 binder: oxetane)>
(1) Oxetane crosslinkable resin HS-DEM (55.5 g) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. To the solution, OXE-30 (36.64 g, 0.2 mol), DCPM (11.01 g, 0.05 mol), V-601 (5.75 g, 10 mol% based on monomer) and HS-EDM (55.5 g) were added. And was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours. Thereby, the crosslinking agent B was obtained.
The weight average molecular weight of the crosslinking agent B was 5,000.

<Comparative Synthesis Example 1>
After the atmosphere in the flask was replaced with nitrogen, 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2′-azobisisobutyronitrile was dissolved was charged. Subsequently, 22.5 g of styrene, 45.0 g of methacrylic acid, 67.5 g of dicyclopentanyl methacrylate and 90.0 g of glycidyl methacrylate were charged, and then gently stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 5 hours, and then heated at 90 ° C. for 1 hour to complete the polymerization.
Thereafter, the reaction product solution was dropped into a large amount of water to coagulate the reaction product. The coagulated product was washed with water, redissolved in 200 g of tetrahydrofuran, and coagulated again with a large amount of water.
After this re-dissolution / coagulation operation was performed three times in total, the obtained coagulated product was vacuum-dried at 60 ° C. for 48 hours to obtain the desired copolymer.
The weight average molecular weight of the copolymer was 35,000.

<Comparative Synthesis Example 2>
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 22 parts by weight of methacrylic acid, 38 parts by weight of dicyclopentanyl methacrylate, 40 parts by weight of 3- (methacryloyloxymethyl) -2-phenyloxetane and 1.5 parts by weight of α-methylstyrene dimer were charged, and the atmosphere was gradually replaced with nitrogen. Stirring was started. The temperature of the solution was raised to 70 ° C. and heated at this temperature for 5 hours to obtain a polymer solution containing the copolymer [A-1]. The obtained polymer solution had a solid content concentration of 31.2% by weight, and the copolymer [A-1] had a weight average molecular weight (Mw) of 18,500 and a molecular weight distribution (Mw / number average molecular weight ratio). ) Was 1.8. In addition, Mw and number average molecular weight are polystyrene conversion average molecular weights measured using GPC (gel permeation chromatography (HLC-8020 manufactured by Tosoh Corporation)).

(Example)
<Example 1 (1 binder: epoxy)>
-Production of photosensitive resin composition-
The following composition was dissolved and mixed, and filtered through a 0.2 μm polytetrafluoroethylene filter to obtain a photosensitive resin composition 1.
-Binder A solution obtained by the above synthesis method (solid content equivalent to 17.0 parts)
・ Photosensitive agent (TAS-200, manufactured by Toyo Gosei Co., Ltd.) 5.0 parts ・ Adhesion promoter (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts ・ Thermal radical generator (Nofmer BC-) 90, manufactured by NOF Corporation) 0.4 part, solvent (PGMEA) 77.1 part, surfactant (Megafac F172, manufactured by DIC) 0.005 part

<Example 2 (1 binder: epoxy)>
The photosensitive resin composition 2 was obtained by dissolving and mixing in the same composition except that the binder B solution was used instead of the binder A solution in Example 1.

<Example 3 (2 binder: epoxy)>
-Production of photosensitive resin composition-
The following composition was dissolved and mixed, and filtered through a 0.2 μm polytetrafluoroethylene filter to obtain a photosensitive resin composition 3.
-Binder C solution obtained by the above synthesis method (amount equivalent to 12.0 parts in solid content)
・ Photosensitive agent (TAS-200, manufactured by Toyo Gosei Co., Ltd.) 5.0 parts ・ Crosslinking agent A obtained by the above synthesis method (solid content equivalent to 5.0 parts)
-Adhesion promoter (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 part-Thermal radical generator (NOFMER BC-90 manufactured by NOF Corporation) 0.4 part-Solvent (PGMEA) 77.1 part-Interface Activator (Megafuck F172, manufactured by DIC) 0.005 parts

<Example 4 (1 binder: oxetane)>
The photosensitive resin composition 4 was obtained by dissolving and mixing with the same composition except that the binder D solution was used instead of the binder A solution in Example 1.

<Example 5 (2 binder: oxetane)>
The photosensitive resin composition 5 was obtained by dissolving and mixing in the same composition except that the crosslinking agent B solution was used instead of the crosslinking agent A solution in Example 3.

<Example 6 (2 binder: epoxy + methylol system)>
A photosensitive resin composition 6 was obtained in the same manner as in Example 3 except that Nicalak MX-270 was further added in an amount corresponding to 2% by solid content.

<Example 7>
A photosensitive resin composition 7 was obtained in the same manner as in Example 1 except that the photosensitive agent nifedipine (the following structure) was used instead of the photosensitive agent TAS-200.

<Comparative Example 1>
-Production of photosensitive resin composition-
The following composition was dissolved and mixed, and filtered through a 0.2 μm polytetrafluoroethylene filter to obtain a photosensitive resin composition 1 of a comparative example.
-Acid / epoxy binder solution obtained in Comparative Synthesis Example 1 above
(Solid content equivalent to 17.0 parts)
・ Photosensitive agent (TAS-200, manufactured by Toyo Gosei Co., Ltd.) 5.0 parts ・ Adhesion promoter (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts ・ Thermal radical generator (Nofmer BC-) 90, manufactured by NOF Corporation) 0.4 part, solvent (PGMEA) 77.1 part, surfactant (Megafac F172, manufactured by DIC) 0.005 part

<Comparative Example 2>
In the above Comparative Example 1, instead of the acid / epoxy binder solution obtained in Comparative Synthesis Example 1, the same composition was used except that the acid / oxetane binder solution obtained in Comparative Synthesis Example 2 was used. The photosensitive resin composition 2 was obtained.

(Evaluation)
The photosensitive resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were each evaluated by the following evaluation methods. The evaluation results are summarized in Table 1.

<Transparency>
Each photosensitive resin composition was applied on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)) using a spinner, and then pre-baked on a hot plate at 100 ° C. for 1 minute to volatilize the solvent. Thus, a photosensitive resin composition layer having a thickness of 3.0 μm was formed.
The obtained photosensitive resin composition layer was exposed to a cumulative irradiation amount of 300 mJ / cm ² (illuminance: 20 mW / cm ² ) with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Thereafter, the substrate was heated in an oven at 230 ° C. for 1 hour to obtain a cured film.
The light transmittance of the glass substrate having this cured film was measured at a wavelength in the range of 400 to 800 nm using a spectrophotometer “150-20 type double beam (manufactured by Hitachi, Ltd.)”.
Table 1 shows the evaluation of the minimum light transmittance at that time.

<Heat resistant transparency>
The substrate after the above transparency evaluation was further heated in an oven at 230 ° C. for 2 hours, and then the light transmittance was 400 to 800 nm using a spectrophotometer “150-20 type double beam (manufactured by Hitachi, Ltd.)”. Measured at a wavelength in the range of.
Table 1 shows the evaluation of the minimum light transmittance at that time.

<Dielectric breakdown voltage>
A photosensitive resin composition is applied onto a bare wafer (N-type low resistance) (manufactured by SUMCO) using a spinner and then prebaked on a hot plate at 90 ° C. for 2 minutes to obtain a photosensitive film having a thickness of 3.0 μm. A functional resin composition layer was formed. The obtained photosensitive resin composition was exposed to a cumulative irradiation amount of 300 mJ / cm ² (illuminance: 20 mW / cm ² ) with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. The substrate was heated in an oven at 220 ° C. for 1 hour to obtain a cured film.
About this cured film, the dielectric breakdown voltage was measured using CVmap92A (made by Four Dimensions Inc.).
The dielectric breakdown voltage is a voltage that increases the voltage applied to the cured film, breaks the insulation state without being able to withstand the voltage, and starts to flow a large current. When this value is 350 V / μm or more, it can be said that the dielectric breakdown voltage is good. The results are shown in Table 1.

<Relative permittivity (k value)>
A photosensitive resin composition was applied onto a bare wafer (N-type low resistance) (manufactured by SUMCO) using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to obtain a film thickness of 3.0 μm. A photosensitive resin composition layer was formed. The obtained photosensitive resin composition was exposed to a cumulative irradiation amount of 300 mJ / cm ² (illuminance: 20 mW / cm ² ) with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. The substrate was heated in an oven at 220 ° C. for 1 hour to obtain a cured film.
With respect to this cured film, the relative dielectric constant was measured at a measurement frequency of 1 MHz using CVmap92A (made by Four Dimensions Inc.). The results are shown in Table 1.

<Example 8>
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 1).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is used to connect the TFT 1 to the organic EL element formed between the TFTs 1 or in a later process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 1 on a substrate, pre-baking on a hot plate (90 ° C. × 2 minutes), and then applying high pressure from above the mask. After irradiating 100 mJ / cm ² (illuminance 20 mW / cm ² ) with i-line (365 nm) using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 220 ° C. for 60 minutes. The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the planarizing film 4 obtained after exposure, development, and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.

  Next, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, a first electrode 5 made of indium tin oxide (ITO) was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped using a resist stripping solution (mixed solution of monoethanolamine and dimethyl sulfoxide (DMSO)). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

  Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film 8, the photosensitive resin composition of Example 1 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.

  Furthermore, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al was formed on the entire surface above the substrate. The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.

  As described above, an active matrix type organic EL display device in which each organic EL element is connected to the TFT 1 for driving the organic EL element was obtained. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

<Example 9>
In the active matrix type liquid crystal display device shown in FIGS. 1 and 2 of Japanese Patent No. 3321003, the interlayer insulating film 17 was formed as follows, and the liquid crystal display device of Example 9 was obtained.
That is, using the photosensitive resin composition of Example 1, the interlayer insulating film 17 was formed by the same method as the method for forming the planarizing film 4 of the organic EL display device in Example 8 above.

  When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.

1: TFT
2: Wiring 3: Insulating film 4: Flattened film 5: First electrode 6: Glass substrate 7: Contact hole 8: Insulating film 10: Liquid crystal display device 12: Backlight unit 14, 15: Glass substrate 16: TFT (thin Layer film transistor)
17: Cured film 18: Contact hole 19: ITO transparent electrode 20: Liquid crystal 22: RGB color filter

Claims (17)

(A) (a) a monomer unit having a carboxystyrene skeleton, and (b) an alkali-soluble resin having a monomer unit having a cyclic ether group;
(B) a photosensitive agent;
(C) A photosensitive resin composition comprising a solvent.   The photosensitive resin composition of Claim 1 whose said cyclic ether group is an epoxy group and / or an oxetanyl group.   The photosensitive resin composition of Claim 1 or 2 whose said cyclic ether group is an epoxy group.   The content of the (A) alkali-soluble resin is 60 wt% or more and 95 wt% or less, and the content of the (B) photosensitizer is 5 wt% or more and 40 wt% with respect to the total solid content of the photosensitive resin composition. The photosensitive resin composition of any one of Claims 1-3 which is% or less. (X) an alkali-soluble resin containing a monomer unit having a carboxystyrene skeleton;
(B) a photosensitive agent;
(Y) a crosslinking agent having a cyclic ether group;
(C) A photosensitive resin composition comprising a solvent.   The photosensitive resin composition of Claim 5 whose said (Y) crosslinking agent is a crosslinking agent which has an epoxy group and / or an oxetanyl group.   The photosensitive resin composition according to claim 5 or 6, wherein the (Y) crosslinking agent is a crosslinkable resin having a cyclic ether group.   The content of the (X) alkali-soluble resin is 40% by weight or more and 70% by weight or less, and the content of the (B) photosensitive agent is 5% by weight or more and 40% by weight with respect to the total solid content of the photosensitive resin composition. The photosensitive resin composition according to claim 5, wherein the content of the (Y) crosslinking agent is 3% by weight or more and 40% by weight or less.   The photosensitive resin composition of any one of Claims 1-8 whose said (B) photosensitive agent is a 1, 2- naphthoquinone diazide compound.   (D) The photosensitive resin composition of any one of Claims 1-9 which further contains a thermal radical generator.   The photosensitive resin composition of Claim 10 whose 10-hour half life temperature of the said (D) thermal radical generator is 100 degreeC or more and 230 degrees C or less.   (E) The photosensitive resin composition of any one of Claims 1-11 which further contains a methylol type | system | group crosslinking agent and / or an alkoxymethyl group containing crosslinking agent. (1) The process of apply | coating the photosensitive resin composition of any one of Claims 1-12 on a board | substrate,
(2) a pre-baking step for removing the solvent from the applied photosensitive resin composition;
(3) a step of exposing with actinic radiation,
(4) developing with an aqueous developer, and
(5) A method for forming a cured film, comprising a post-baking step of thermosetting.   A cured film formed by the method according to claim 13.   The cured film according to claim 14, which is an interlayer insulating film.   An organic EL display device comprising the cured film according to claim 14.   A liquid crystal display device comprising the cured film according to claim 14.

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