JP2011053247A - Photosensitive resin composition, cured film and method for forming the same, organic el display device and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of giving a cured film excellent in transparency and heat-resistant transparency and having a high dielectric breakdown voltage, to provide a cured film excellent in transparency and heat-resistant transparency and having a high dielectric breakdown voltage and a method for forming the same, and to provide an organic EL display device and a liquid crystal display device each including a cured film excellent in transparency and heat-resistant transparency and having a high dielectric breakdown voltage. <P>SOLUTION: The photosensitive resin composition includes: (A) a resin having a carboxy group; (B) a photosensitizer; and (C) a resin having an ethylenically unsaturated group and/or a resin having an ethylenically unsaturated group and an oxetanyl group. The cured film is formed of the photosensitive resin composition and the method for forming the same is provided. The organic EL display device and the liquid crystal display device each include the cured film. <P>COPYRIGHT: (C)2011,JPO&INPIT

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 photosensitive resin composition comprising: a) i) an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof; ii) a hydroxy group-containing olefinic unsaturated compound iii) an olefinic system An acrylic copolymer obtained by copolymerizing an unsaturated compound and then removing unreacted monomers; b) 1,2-quinonediazide compound; c) a specific epoxy-based crosslinking agent; and d) a solvent The photosensitive resin composition characterized by including this is disclosed.

Patent Document 2 discloses a positive photosensitive resin composition containing the following component (A), component (B) and component (C).
Component (A): an alkali-soluble acrylic polymer having 3 to 16 carbon atoms and having a side chain having an unsaturated bond at the terminal and having a number average molecular weight of 2,000 to 30,000 in terms of polystyrene, B) Component: 1,2-quinonediazide compound, (C) solvent.

JP 2007-34257 A JP 2008-256974 A

The problem to be solved by the present invention is to provide a photosensitive resin composition that gives a cured film having excellent transparency and heat-resistant transparency, and having a high dielectric breakdown voltage, and excellent in transparency and heat-resistant transparency, A cured film having a high breakdown voltage and a method for forming the cured film.
Another problem to be solved by the present invention is to provide an organic EL display device and a liquid crystal display device having a cured film having excellent transparency and heat-resistant transparency and having a high dielectric breakdown voltage. .

The above-mentioned problems of the present invention have been solved by means described in the following <1>, <10>, <11>, <13> or <14>. It describes below with <2>-<9> and <12> which are preferable embodiments.
<1> a resin having (A) a carboxy group, (B) a photosensitizer, (C) a resin having an ethylenically unsaturated group and an epoxy group, and / or a resin having an ethylenically unsaturated group and an oxetanyl group And a photosensitive resin composition, comprising:
<2> (D) The photosensitive resin composition according to <1>, further including a solvent,
<3> The above (C) a resin having an ethylenically unsaturated group and an epoxy group and / or a resin having an ethylenically unsaturated group and an epoxy group as the resin having an ethylenically unsaturated group and an oxetanyl group <1> or the photosensitive resin composition as described in <2>,
<4> The photosensitive resin composition according to any one of the above <1> to <3>, wherein the ethylenically unsaturated group is a methacryloyl group or an acryloyl group,
<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the resin having a carboxy group (A) further has an ethylenically unsaturated group,
<6> The content of the resin (A) having a carboxy group is 40 to 70% by weight with respect to the total solid content of the photosensitive resin composition, and the content of the (B) photosensitive agent is 5 to 5%. <1> above, wherein the total content of (C) the resin having an ethylenically unsaturated group and an epoxy group and the resin having an ethylenically unsaturated group and an oxetanyl group is 3 to 40% by weight. ~ Photosensitive resin composition according to any one of <5>,
<7> The photosensitive resin composition according to any one of the above <1> to <6>, wherein the (B) photosensitive agent is a 1,2-naphthoquinonediazide compound,
<8> (E) The photosensitive resin composition according to any one of the above <1> to <7>, further comprising a thermal radical generator,
<9> The photosensitive resin composition according to <8>, wherein the (E) thermal radical generator has a 10-hour half-life temperature of 100 ° C. or higher and 230 ° C. or lower.
<10> (1) A step of applying the photosensitive resin composition according to any one of <2> to <8> above on a substrate, (2) removing a solvent from the applied photosensitive resin composition A cured film forming method comprising: a pre-baking 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.
<11> A cured film formed by the method according to <10> above,
<12> The cured film according to <11>, which is an interlayer insulating film,
<13> An organic EL display device comprising the cured film according to <11> or <12> above,
<14> A liquid crystal display device comprising the cured film according to <11> or <12>.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which was excellent in transparency and heat-resistant transparency, and provided the cured film which has a high dielectric breakdown voltage was able to be provided.
Moreover, according to this invention, it was excellent in transparency and heat-resistant transparency, and the cured film which has a high dielectric breakdown voltage, and its formation method were able to be provided.
Furthermore, according to the present invention, it was possible to provide an organic EL display device and a liquid crystal display device having a cured film having excellent transparency and heat-resistant transparency and having a high dielectric breakdown voltage.

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.

  Hereinafter, the present invention will be described in detail.

(Photosensitive resin composition)
The photosensitive resin composition of the present invention comprises (A) a resin having a carboxy group, (B) a photosensitive agent, (C) a resin having an ethylenically unsaturated group and an epoxy group, or an ethylenically unsaturated group and And a resin having an oxetanyl group.
The photosensitive resin composition of the present invention can be suitably used as a positive photosensitive resin composition.

(A) Resin Having Carboxy Group The photosensitive resin composition of the present invention contains (A) a resin having a carboxy group (hereinafter also referred to as “alkali-soluble resin” or “component A”).
The resin having a carboxy group is a resin having alkali solubility by containing a carboxy group, that is, an alkali-soluble resin.
Moreover, it is preferable that resin which has a carboxy group has an ethylenically unsaturated group.
The resin having a carboxy group may further contain an alicyclic structure in the molecule from the viewpoint of high transmittance and low relative dielectric constant.

<Monomer unit having carboxy group (A1)>
The resin having a carboxy group includes at least a monomer unit having a carboxy group.
The monomer unit (A1) having a carboxy group may have, for example, an ethylenically unsaturated group in addition to the carboxy group.
The resin having a carboxy group is a monomer unit having a carboxy group (A1-1) or a monomer unit having an ethylenically unsaturated group and a carboxy group (from the viewpoint of improving the solubility of the photosensitive resin composition in a developer). It is preferable that any one of A1-2) is included.

-Monomer unit having a carboxy group (A1-1)-
Examples of the monomer unit (A1-1) having a carboxy group include unsaturated carboxylic acids having at least one carboxy group in the molecule, such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated tricarboxylic acid. The monomer unit derived from is mentioned.
Examples of the unsaturated carboxylic acid used to obtain the monomer unit (A1-1) having a carboxy group include those listed below.
That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid.
Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.

Moreover, the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to obtain the monomer unit (A1-1) which has a carboxy group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid. For example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like.
Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both terminals, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate.
As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
Among these, from the viewpoint of developability, in order to form the monomer unit (A1-1) having a carboxy group, it is preferable to use acrylic acid, methacrylic acid, an unsaturated polycarboxylic acid anhydride, or the like.
The monomer unit (A1-1) having a carboxy group may be composed of one kind alone, or may be composed of two or more kinds.

-Monomer unit having an ethylenically unsaturated group and a carboxy group (A1-2)-
The monomer unit (A1-2) having an ethylenically unsaturated group and a carboxy group is a secondary hydroxyl group present in a monomer unit (A2-1) having an ethylenically unsaturated group described later, an acid anhydride, The monomer unit obtained by reacting is preferred.
As the acid anhydride, known ones can be used. Specific examples include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride. Examples include basic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and biphenyl tetracarboxylic acid anhydride. Among these, from the viewpoint of developability. Phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferred.
The reaction rate of the acid anhydride with respect to the secondary hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, from the viewpoint of developability.

The monomer unit (A1) having a carboxy group may be composed of a single monomer unit (A1-1) having a carboxy group, or a monomer unit having both an ethylenically unsaturated group and a carboxy group ( One type of A1-2) may be constituted alone, or two types of these may be mixed.
The content of the monomer unit (A1) having a carboxy group in the resin having a carboxy group is preferably 1 to 50 mol% with respect to 100 mol% of all the monomer units in the resin having a carboxy group, from the viewpoint of developability. 3-45 mol% is more preferable, and 5-40 mol% is still more preferable.

<Monomer unit other than (A1) (A2)>
The resin having a carboxy group may contain a monomer unit (A2-1) having an ethylenically unsaturated group and other monomer units (A2-2) as monomer units (A2) other than (A1). Good.

-Monomer unit having an ethylenically unsaturated group (A2-1)-
The resin having a carboxy group is preferably a resin having an ethylenically unsaturated group and a carboxy group, and a monomer unit having an ethylenically unsaturated group and a carboxy group and / or a monomer unit having an ethylenically unsaturated group (A2 -1) is more preferable.
As a monomer unit (A2-1) which has an ethylenically unsaturated group, the monomer unit derived from the monomer which has an ethylenically unsaturated group (polymerizable group) is mentioned. In particular, as the monomer unit (A2-1) having an ethylenically unsaturated group, a monomer unit having a structure in which an epoxy group in a compound containing an epoxy ring and an ethylenically unsaturated group is added to a carboxy group, or And a monomer unit having a structure in which a carboxy group in a compound containing a carboxy group and an ethylenically unsaturated group is added to an epoxy group. More specifically, a monomer unit obtained by reacting an epoxy group in a compound containing an epoxy group and an ethylenically unsaturated group with the carboxy group of the monomer unit (A1-1) having the carboxy group described above, or described later. It is preferably a monomer unit obtained by reacting a carboxy group of a compound containing a carboxy group such as (meth) acrylic acid and an ethylenically unsaturated group with an epoxy group in a monomer unit derived from a monomer having an epoxy ring. . By such a reaction, a secondary hydroxyl group is introduced into the monomer unit (A2-1) having an ethylenically unsaturated group.

The compound containing an epoxy group and an ethylenically unsaturated group may be a compound having at least one epoxy group and one ethylenically unsaturated group. For example, glycidyl acrylate, glycidyl methacrylate, (3,4-epoxy Examples thereof include compounds such as (cyclohexyl) methyl acrylate, (3,4-epoxycyclohexyl) methyl methacrylate, and allyl glycidyl ether.
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.

The monomer unit (A2-1) having an ethylenically unsaturated group may be composed of one kind alone, or may be composed of two or more kinds.
The content of the monomer unit (A2-1) having an ethylenically unsaturated group in the resin having a carboxy group is 100 mol% of all monomer units in the resin having a carboxy group from the viewpoint of compatibility between various resistances and developability. On the other hand, 0-60 mol% is preferable, 0-55 mol% is more preferable, and 0-50 mol% is still more preferable.

-Other monomer units (A2-2)-
The other monomer unit (A2-2) is not particularly limited as long as it has a structure different from those other than the monomer units (A1) and (A2-1), but other ethylenically unsaturated compounds (“ The “ethylenically unsaturated compound” is preferably a monomer unit derived from “vinyl monomer” hereinafter.

Examples of the vinyl monomer capable of forming the monomer unit (A2-2) include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, and itaconic acid. Preferable examples include diesters, (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, and (meth) acrylonitrile. 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, glycidyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid diethylene glycol monomethyl ether, (meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether , (Meth) acrylic acid triethylene 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 Nonylphenoxypolyethylene glycol, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluoroo (meth) acrylate Examples include butyl ethyl, tribromophenyl (meth) acrylate, 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.

The resin having a carboxy group 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.

Another monomer unit (A2-2) may be comprised by 1 type individually, and may be comprised by 2 or more types.
The content of the monomer unit (A2-2) in the resin having a carboxy group is from 0 to 80 with respect to 100 mol% of all monomer units in the resin having a carboxy group, from the viewpoint of compatibility between various resistances and developability. The mol% is preferable, and 0 to 75 mol% is more preferable.

The resin having a carboxy group can be synthesized, for example, by copolymerizing at least a monomer capable of forming the monomer unit (A2) as necessary during the polymerization.
Further, when the resin having a carboxy group is a resin having an ethylenically unsaturated group and a carboxy group, for example, a monomer capable of forming at least the monomer unit (A1) is copolymerized in advance. It is also possible to synthesize by using a method in which an epoxy ring in a compound containing an epoxy group and an unsaturated group is added to the carboxy group of the copolymer at an appropriate ratio. Also, for example, at least the monomer unit (A1) and a monomer capable of forming a monomer unit having an epoxy group are copolymerized in advance, and the resulting epoxy group (for example, glycidyl group) is copolymerized. Resins having an ethylenically unsaturated group and a carboxy group can also be synthesized using a method of adding a carboxy group of a compound containing a carboxy group such as (meth) acrylic acid and an ethylenically unsaturated group. Further, the secondary hydroxyl group generated by the above addition reaction is reacted with an acid anhydride such as tetrahydrophthalic anhydride to produce an ethylenically unsaturated group and a carboxyl group containing monomer units having an ethylenically unsaturated group and a carboxy group. A resin having a group may be synthesized.

As described above, when synthesizing a resin having a carboxy group or when performing an addition reaction, 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.

The optimum conditions for the copolymerization reaction during the production of the resin having a carboxy group vary depending on the type and concentration of the solvent, but the reaction temperature is preferably an internal temperature of 0 ° C to 200 ° C, more preferably 50 ° C to It is 150 degreeC, Most preferably, it is 60 to 100 degreeC. The reaction time is preferably 1 to 50 hours, more preferably 2 to 40 hours, and particularly preferably 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.

  The resin having a carboxy group is not particularly limited in molecular weight, but in terms of alkali dissolution rate and film physical properties, the weight average molecular weight is preferably 3,000 to 200,000, more preferably 5,000 to 100,000. 10,000 to 50,000 are particularly preferable. In the present invention, the molecular weight is measured by gel permeation chromatography and can be determined using a standard polystyrene calibration curve.

  The content of the resin having a carboxyl group (A) in the photosensitive resin composition of the present invention is preferably 20 to 90% by weight with respect to the total solid content of the photosensitive resin composition, and is preferably 25 to 75%. More preferably, it is 40% by weight, and still more preferably 40-70% by weight. When the content is in the above range, the pattern formability upon development is good.

(B) Photosensitive agent The 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, J. et al. Kosar, “Light-Sensitive Systems”, pp. 339-352 (1965), John Wiley & Sons (New York) and W.C. S. De Forest, “Photoresist” 50 (1975), 1,2-quinonediazide compounds described in McGraw-Hill, Inc, (New York), JP-A 2004-170566, JP-A 2002-40653, JP Examples thereof include 1,2-quinonediazide compounds described in JP-A No. 2002-351068, JP-A No. 2004-4233, JP-A No. 2004-271975, and the like. Those described in JP-A-2008-224970, 0066 to 0081 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 the 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.

The blending amount of the photosensitive agent (B) in the photosensitive resin composition of the present invention is (A) the total amount of the resin having a carboxy group in terms of the difference in dissolution rate between the exposed part and the unexposed part and the allowable sensitivity range. Is 100 parts by weight, preferably 1 to 100 parts by weight, more preferably 5 to 80 parts by weight, and most preferably 5 to 50 parts by weight.
In addition, the blending amount of the photosensitive agent (B) in the photosensitive resin composition of the present invention is the photosensitive resin composition of the present invention in terms of the difference in dissolution rate between the exposed and unexposed areas and the allowable sensitivity range. The total solid content is preferably 1 to 60% by weight, more preferably 5 to 50% by weight, and most preferably 5 to 40% by weight.

(C) Resin having an ethylenically unsaturated group and an epoxy group and / or a resin having an ethylenically unsaturated group and an oxetanyl group The photosensitive resin composition of the present invention comprises (C) an ethylenically unsaturated group and an epoxy. A resin having a group and / or a resin having an ethylenically unsaturated group and an oxetanyl group (hereinafter also referred to as “component C”).
Component C is a crosslinkable resin having an epoxy group (hereinafter also referred to as “oxiranyl group”) and / or an oxetanyl group and an ethylenically unsaturated group. Component C preferably does not have a carboxy group, and more preferably does not have an acidic group such as a carboxy group and a phenolic hydroxyl group.
Component C is preferably a polymer or copolymer of a compound having an ethylenically unsaturated group, and more preferably a (meth) acrylic resin or a copolymer thereof.

In the photosensitive resin composition of the present invention, it is preferable from the viewpoint of the storage stability of the composition that the epoxy group and the oxetanyl group are separated from the resin (A) having a carboxy group and contained in Component C.
Component C preferably has an epoxy group from the viewpoint of ease of reaction, and preferably has an oxetanyl group from the viewpoint of storage stability of the composition.

Component C may have at least one group selected from the group consisting of an epoxy group and an oxetanyl group and an ethylenically unsaturated group in different monomer units or in the same monomer unit. Good. Component C is a copolymer comprising a monomer unit (C1) having at least one group selected from the group consisting of an epoxy group and an oxetanyl group, and a monomer unit (C2) having an ethylenically unsaturated group. Preferably there is. Furthermore, (C3) other monomer units may be included as necessary.
Component C preferably has no monomer unit having a carboxy group in its structure, and preferably does not contain a monomer unit having a carboxy group and other alkali-soluble groups.

<Monomer unit (C1) having at least one group selected from the group consisting of epoxy groups and oxetanyl groups>
Component C preferably has a monomer unit (C1) having at least one group selected from the group consisting of an epoxy group and an oxetanyl group.
As the monomer unit (C1) having at least one group selected from the group consisting of an epoxy group and an oxetanyl group, the monomer unit derived from a monomer having at least one group selected from the group consisting of an epoxy group and an oxetanyl group Is mentioned.
Specific examples of the monomer having an epoxy group include glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, allyl glycidyl ether, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexyl-n-bromo (meth) acrylate, 3,4-epoxycyclohexyl-i-propyl (meth) acrylate, 1-vinyl-2,3-epoxycyclohexane, 1-vinyl-3 , 4-epoxycyclohexane, 1-allyl-2,3-epoxycyclohexane, 1-allyl-3,4-epoxycyclohexane, and the like. Among them, glycidyl (meth) acrylate, (3,4-epoxy (Cyclohexyl) methyl (meth) acryle DOO is, solvent resistance, from the viewpoint of heat resistance, glycidyl (meth) acrylate are particularly preferred.

  As a monomer which has an oxetanyl group, the (meth) acrylic acid ester which has an oxetanyl group as described in Unexamined-Japanese-Patent No. 2001-330953 etc. can be mentioned, for example. 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 monomer unit (C1) having at least one group selected from the group consisting of an epoxy group and an oxetanyl group may be composed of one kind alone, or may be composed of two or more kinds.
The content of the monomer unit (C1) having at least one group selected from the group consisting of an epoxy group and an oxetanyl group in Component C is the solvent resistance and heat resistance of a cured film formed using the photosensitive resin composition. From the standpoint of excellent properties, 20 to 98 mol% is preferable, 30 to 95 mol% is more preferable, and 40 to 90 mol% is still more preferable with respect to 100 mol% of all monomer units contained in Component C.

<Monomer unit having ethylenically unsaturated group (C2)>
Component C preferably has a monomer unit (C2) having an ethylenically unsaturated group.
The monomer unit (C2) having an ethylenically unsaturated group is not particularly limited as long as it has one or more ethylenically unsaturated groups. Although a monomer unit having an ethylenically unsaturated group may be formed by performing polymerization using a functional ethylenically unsaturated compound, it is preferable to introduce or form an ethylenically unsaturated group after polymerization.
Examples of the monomer unit (C2) having an ethylenically unsaturated group include an epoxy group and / or oxetanyl group in a monomer unit having an epoxy group and / or an oxetanyl group, a carboxy group such as (meth) acrylic acid, and ethylene. In a monomer unit obtained by reacting a carboxyl group of a compound having an ethylenically unsaturated group, or a compound containing an epoxy group and / or an oxetanyl group and an ethylenically unsaturated group in the carboxyl group of the monomer unit having a carboxyl group Preferred examples include monomer units obtained by reacting an epoxy group and / or an oxetanyl group. The epoxy group and / or oxetanyl group in the monomer unit having an epoxy group and / or an oxetanyl group may have a carboxy group and an ethylenic unsaturated group. Mono-reacted with a carboxyl group of a compound having a group Over the unit and the like and more preferably.
Since the secondary hydroxyl group is introduced into the monomer unit (C2) having an ethylenically unsaturated group by the above reaction, the monomer unit (C2) having an ethylenically unsaturated group may have a secondary hydroxyl group. preferable.
The monomer unit having an ethylenically unsaturated group may be formed by chemically converting a specific group into an ethylenically unsaturated group by a known method after polymerization.
Component C is a monomer unit represented by the following formula (Ee) obtained by reacting (meth) acrylic acid with a monomer unit derived from glycidyl (meth) acrylate as a monomer unit (C2) having an ethylenically unsaturated group, or It is particularly preferable to have at least a monomer unit represented by the following formula (Eo) obtained by reacting (meth) acrylic acid with a monomer unit derived from (3-ethyl-3-oxetanyl) methyl (meth) acrylate. Most preferably, it has at least a monomer unit represented by (Ee).

The monomer unit (C2) having an ethylenically unsaturated group may be composed of one kind alone, or may be composed of two or more kinds.
Although the monomer unit (C2) which has an ethylenically unsaturated group should just have one or more ethylenically unsaturated groups, it is preferable that it is 1-6, and it is more preferable that it is 1.
The content of the monomer unit (C2) having an ethylenically unsaturated group in Component C is that Component C has, from the viewpoint of excellent solvent resistance and heat resistance of a cured film formed using the photosensitive resin composition. 1-30 mol% is preferable with respect to 100 mol% of all monomer units, 2-25 mol% is more preferable, and 5-20 mol% is still more preferable.

<Other monomer units (C3)>
Component C includes monomer units (C1) having at least one group selected from the group consisting of epoxy groups and oxetanyl groups, and other monomer units (C3) other than monomer units (C2) having ethylenically unsaturated groups. May be included.
Although there is no limitation in particular as another monomer unit (C3), It is preferable that a hydroxyl group and a polyethylene oxide group are included from a compatible viewpoint with (A) resin which has a carboxy group.
Moreover, as another monomer unit (C3), the other monomer unit (A2-2) mentioned above can be illustrated.
Examples of vinyl monomers that can form other monomer units (C3) include vinyl monomers described in paragraph numbers 0046 to 0051 of JP-A-2009-98691.

  Among these, (meth) acrylic acid esters or styrenes are preferable. Most preferred are (meth) acrylic esters, and among (meth) acrylic esters, 2-hydroxyethyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl (meth) acrylate Ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether form pattern by development From the viewpoints of safety and transparency. Among these, methyl (meth) acrylate is particularly preferable from the viewpoint of transparency.

The other monomer unit (C3) preferably includes a monomer unit having an alicyclic structure.
Specific examples of the monomer having an alicyclic structure capable of forming a monomer unit having an alicyclic structure include cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, and dicyclo (meth) acrylate. Pentenyl, (meth) acrylic acid dicyclopentenyloxyethyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid isobonyl, etc., among others, (meth) acrylic acid cyclohexyl, (meth) acrylic acid dicyclo Pentenyl, dicyclopentenyloxyethyl (meth) acrylate, and dicyclopentanyl (meth) acrylate are preferred.

Another monomer unit (C3) may be comprised by 1 type individually, and may be comprised by 2 or more types.
The content of other monomer units (C3) in component C is 100 mol of all monomer units contained in component C from the viewpoint of excellent transparency and developability of a cured film formed using the photosensitive resin composition. % To 0 to 50 mol% is preferable, 3 to 40 mol% is more preferable, and 5 to 30 mol% is still more preferable.

  Although there is no restriction | limiting in particular in the molecular weight of component C, 2,000-50,000 are preferable at a weight average molecular weight from a viewpoint of alkali dissolution rate or film | membrane physical property, and 3,000-10,000 are more preferable.

As component C, a copolymer containing 50 to 95 mol% of a monomer unit derived from glycidyl (meth) acrylate can be mentioned as a more preferable one from the viewpoint of availability of raw materials and transparency.
Component C that can be used in the photosensitive resin composition of the present invention may be used alone or in combination of two or more.
The content of Component C in the photosensitive resin composition of the present invention is preferably 5 to 120 parts by weight, preferably 10 to 100 parts by weight, when the total amount of (A) the resin having a carboxy group is 100 parts by weight. It is more preferable that When the addition amount is within this range, the cured film formed using the photosensitive resin composition has excellent solvent resistance, heat resistance, and insulation stability.
The content of component C in the photosensitive resin composition of the present invention is preferably 1 to 50% by weight, and 3 to 40% by weight, based on the total solid content of the photosensitive resin composition of the present invention. More preferably, it is more preferably 5 to 30% by weight. When the addition amount is within this range, the cured film formed using the photosensitive resin composition has excellent solvent resistance, heat resistance, and insulation stability.

In the present invention, an epoxy group-containing compound other than the component C may be used in combination as a crosslinking agent. Specifically, for example, Celoxide 2021P, 3000, Epolide GT401, EHPE3150, EHPE3150E (manufactured by Daicel Chemical Industries, Ltd.) can be used.
When the epoxy group-containing compound other than the component C is used in combination, the addition amount is preferably 1 to 50 parts by weight when the total amount of the resin having (A) carboxy group is 100 parts by weight, and 3 to 30 More preferred are parts by weight.

The photosensitive resin composition of the present invention comprises (A) a resin having a carboxy group, (B) a photosensitive agent, and (C) a resin having an ethylenically unsaturated group and an epoxy group, and / or an ethylenically unsaturated group. In addition to a resin having a saturated group and an oxetanyl group, (D) solvent, (E) thermal radical generator, (F) adhesion promoter, (G) surfactant, and / or (H) antioxidant, etc. An optional component may be further included.
Hereinafter, arbitrary components will be described.

(D) Solvent The photosensitive resin composition of the present invention may contain (D) a solvent.
As a solvent used for the preparation of the photosensitive resin composition of the present invention, (A) a resin having a carboxy group, (B) a photosensitive agent, (C) a resin having an ethylenically unsaturated group and an epoxy group, and / or Alternatively, a resin having an ethylenically unsaturated group and an oxetanyl group, and other components that are optionally blended, and those that do not react with these components are used.
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, and ease of film formation. 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 a solvent for preparing the photosensitive resin composition of the present invention, the amount used is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably based on the total amount of the solvent. May be 30 wt% 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.

(D) 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 still 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.

(E) Thermal radical generator The photosensitive resin composition of the present invention may contain (E) 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 polymerizable compound such as (A) a resin having a carboxy group. 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 (E) thermal radical generator used in the present invention is preferably a compound having a 10-hour half-life temperature of 100 ° C. to 230 ° C., more preferably 120 ° C. to 220 ° C. . 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.

(E) One type of thermal radical generator may be used alone, or two or more types may be used in combination.
The content of the (E) thermal radical generator in the photosensitive resin composition of the present invention is preferably 0.1 to 100 parts by weight when the alkali-soluble resin (A) is 100 parts by weight. The amount is more preferably 50 parts by weight, and most preferably 5 to 30 parts by weight from the viewpoint of improving film properties.

(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 0. 0 parts by weight with respect to 100 parts by weight of the resin having (A) carboxy group. 1 to 20 parts by weight is preferable, and 0.5 to 10 parts by weight 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 may be used in an amount of 0.001 to 20 parts by weight with respect to 100 parts by weight of the resin (A) having a carboxy group, from the viewpoint of improving coatability. Preferably, 0.01 to 5 parts by weight is more preferable, and 0.01 to 2 parts by weight is most preferable.

(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.

(Curing film and method for forming the same, organic EL display device, and liquid crystal display device)
<Hardened 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, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Further, “part” represents “part by weight” unless otherwise specified.

In the following synthesis examples, the following symbols represent the following compounds, respectively.
・ MMA: Methyl methacrylic acid (Wako Pure Chemical Industries, Ltd.)
・ MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
・ GMA: Glycidyl methacrylate (Wako Pure Chemical Industries, Ltd.)
CHMA: cyclohexyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
DCPM: dicyclopentanyl methacrylate (FA-511A, manufactured by Hitachi Chemical Co., Ltd.)
-Karenz MOI: 2-methacryloyloxyisocyanate (manufactured by Showa Denko KK)
Cyclomer A: 3,4-epoxycyclohexylmethyl acrylate (manufactured by Daicel Chemical Industries)
Cyclomer P ACA200M: an acrylic copolymer containing an ethylenically unsaturated group and a carboxy group (manufactured by Daicel Cytec 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.)
AIBN: 2,2′-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.)
HS-EDM: High Solve EDM (diethylene glycol ethyl methyl ether, manufactured by Toho Chemical Industry Co., Ltd.)
・ PGMEA: Methoxypropyl acetate (manufactured by Showa Denko KK)
CL1: Epolide GT-401 (alicyclic epoxy resin, manufactured by Daicel Chemical Industries, Ltd.)
MPTS: γ-methacryloxypropyltrimethylsilane OXE-30: oxetane methacrylate ((3-ethyl-3-oxetanyl) methyl methacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.)

<Synthesis example 1 (crosslinking agent A)>
HS-DEM (33.5 parts) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. GMA (33.54 parts) and V-601 (5.76 parts, 10 mol% based on the monomer) were dissolved in HS-EDM (33.5 parts) in the solution and added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred for 4 hours to complete the polymerization reaction. Subsequently, after replacing with air, methoxyphenol (0.061 parts) and dimethyldodecylamine (0.64 parts) were added, and methacrylic acid (5.16 parts, 20 mol% based on GMA unit) was added. An addition reaction was performed at 90 ° C. for 5 hours to synthesize a crosslinking agent A having an ethylenically unsaturated group and an epoxy group. Moreover, the weight average molecular weight of the obtained crosslinking agent A was 5,000.

<Synthesis Example 2 (Crosslinking agent B)>
HS-DEM (31.5 parts) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. GMA (31.98 parts, 225 mol equivalent), DCPM (5.51 parts, 25 mol equivalent), V-601 (5.76 parts, 10 mol% based on monomer) were added to the solution with HS-EDM (31.98 parts). And was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred for 4 hours to complete the polymerization reaction. Next, after replacing with air, methoxyphenol (0.060 parts) and dimethyldodecylamine (0.32 parts) were added, and MAA (2.582 parts, 10 mol% based on GMA units) was added. An addition reaction was performed at 90 ° C./5 hours to synthesize a crosslinking agent B having an ethylenically unsaturated group and an epoxy group. Moreover, the weight average molecular weight of the obtained crosslinking agent B was 5,100.

<Synthesis Example 3 (Crosslinking agent C)>
HS-DEM (52.5 parts) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. GMA (34.1 parts, 24 mol equivalent), MMA (2.58 parts, 3 mol equivalent), HEMA (3.9 parts, 3 mol equivalent), V-601 (6.9 parts, 10 mol based on the monomer) %) Was dissolved in HS-EDM (52.5 parts) and added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred for 4 hours to complete the polymerization reaction. Next, after substituting with air, dibutyl dilaurate tin (0.060 parts) and Karenz MOI (4.65 parts, 3 mol equivalent) were added, and the addition reaction to the HEMA unit was carried out at 90 ° C./5 hours, and ethylenically unsaturated. A crosslinking agent C having a group and an epoxy group was synthesized. Moreover, the weight average molecular weight of the obtained crosslinking agent C was 5,000.

<Synthesis Example 4 (Crosslinking agent D)>
HS-DEM (31.5 parts) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. To the solution, OXE30 (31.98 parts, 225 mol equivalent), DCPM (5.51 parts, 25 mol equivalent), V-601 (5.76 parts, 10 mol% with respect to the monomer) and HS-EDM (31.98 parts). And was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred for 4 hours to complete the polymerization reaction. Subsequently, after replacing with air, methoxyphenol (0.060 parts) and dimethyldodecylamine (0.32 parts) were added, and MAA (2.582 parts, 10 mol% based on OXE10 units) was added. An addition reaction was performed at 90 ° C./5 hours to synthesize a crosslinking agent D having an ethylenically unsaturated group and an epoxy group. Moreover, the weight average molecular weight of the obtained crosslinking agent D was 5,100.

<Synthesis Example 5 (Acid Binder A)>
HS-DEM (113 parts) was placed in a three-necked flask and heated to 70 ° C. in a nitrogen atmosphere. To the solution, MAA (19.93 parts, 22 mol equivalent), MMA (78.09 parts, 78 mol equivalent), V-65 (0.931 parts, 0.4 mol% based on the monomer) and HS-EDM (113 parts) were added. 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 polymerization reaction. An acid binder A solution was obtained. Moreover, the weight average molecular weight of the obtained acid binder A was 35,000.

<Synthesis Example 6 (Acid Binder B)>
HS-DEM (35.9 parts) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. CHMA (6.00 parts, 375 mol equivalent), MAA (15.54 parts, 184 mol equivalent), MMA (8.38 parts, 873 mol equivalent), V-601 (1.03 parts, 1 mol based on the monomer) %) Was dissolved in HS-EDM (35.9 g) and added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred for 4 hours to complete the polymerization reaction. Subsequently, after replacing with air, p-methoxyphenol (0.093 parts) and dimethyldodecylamine (0.99 parts) were added, and cyclomer A (16.9 parts, 93 mol equivalent) was added. An addition reaction was carried out at 90 ° C./5 hours to synthesize acid binder B having an ethylenically unsaturated group. Moreover, the weight average molecular weight of the obtained acid binder B was 31,000.

<Comparative Synthesis Example 1 (Refer to Synthesis Example 1 of JP-A-2008-256974)>
Under a nitrogen atmosphere, PGMEA (120 parts), MAA (40 parts, 465 mol equivalents), DCPM (40 parts, 182 mol equivalents) were placed in a three-necked flask, and AIBN (2.0 parts, 122 mol equivalents, based on monomer) 1.88 mol%)) was added to cause a polymerization reaction. GMA (26.0 parts, 0.183 mol equivalent) and benzyltriethylammonium (1.1 parts) were added to 200 parts of the resulting solution to obtain comparative binder C. Moreover, the weight average molecular weight of the obtained comparative binder C was 15,000.

<Comparative Synthesis Example 2>
Acrylic copolymer 1 (Comparative Binder D) described in Example 1 of JP-A-2007-34257 was synthesized by a method similar to the method described in JP-A-2007-34257.

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.
-Acid binder A solution obtained by the above-mentioned synthesis method Amount equivalent to 12.0 parts by solid content-Photosensitizer (TAS-200 manufactured by Toyo Gosei Kogyo Co., Ltd.) 5.0 parts-Obtained by the above-mentioned synthesis method Cross-linking agent A solution in an amount equivalent to 5.0 parts by solid content, adhesion promoter (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 part, thermal radical generator (NOFMER BC- manufactured by NOF Corporation) 90, 2,3-dimethyl-2,3-diphenylbutane) 0.4 parts, solvent (PGMEA)
77.1 parts in total with HS-DEM contained in the acid binder A solution and the crosslinking agent A solution (surfactant manufactured by DIC Corporation, MegaFuck F172, fluorosurfactant)
0.005 parts

(Example 2)
A photosensitive resin composition 2 was obtained in the same manner as in Example 1 except that the crosslinking agent B solution was used instead of the crosslinking agent A solution.

(Example 3)
A photosensitive resin composition 3 was obtained in the same manner as in Example 1 except that the crosslinking agent C solution was used instead of the crosslinking agent A solution.

Example 4
A photosensitive resin composition 4 was obtained by dissolving and mixing in the same composition except that the crosslinking agent D solution was used instead of the crosslinking agent A solution in Example 1.

(Example 5)
A photosensitive resin composition 5 was obtained in the same manner as in Example 1 except that the acid binder A solution was replaced by an ethylenically unsaturated group-containing acid binder B solution.

(Example 6)
In Example 1, the photosensitive resin composition 6 was obtained by dissolving and mixing the same composition except that the photosensitive agent nifedipine (the following compound) was used instead of the photosensitive agent TAS-200.

(Example 7)
A photosensitive resin composition 7 was obtained in the same manner as in Example 1 except that the thermal radical generator (NOFMER BC-90 manufactured by NOF Corporation) was removed.

(Comparative Example 1)
In Example 1 above, the same composition was dissolved and mixed except that 5.0 parts of EPICRON 840 (bisphenol A type polymer epoxy crosslinking agent, manufactured by DIC Corporation) was used instead of the crosslinking agent A solution. Resin composition C1 was obtained.

(Comparative Example 2)
In Example 5 above, the same composition was dissolved and mixed except that 5.0 parts of EPICRON 840 (bisphenol A type polymer epoxy crosslinking agent, manufactured by DIC Corporation) was used instead of the crosslinking agent A solution. Resin composition C2 was obtained.

(Comparative Example 3)
-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 C3.
Acrylic copolymer 1 obtained in Comparative Synthesis Example 1 12.0 parts Photosensitizer (TAS-200 manufactured by Toyo Gosei Co., Ltd.) 5.0 parts EPICRON 840 (bisphenol A type polymer epoxy crosslinking agent, (Made by DIC Corporation)
5.0 parts, adhesion promoter (KBM-403, Shin-Etsu Chemical Co., Ltd.) 0.5 parts, thermal radical generator (NOFMER BC-90, NOF Corporation) 0.4 parts, solvent (PGMEA) 77.1 parts-Surfactant (DIC Corporation MegaFuck F172) 0.005 parts

  The photosensitive resin compositions 1-7 and C1-C3 obtained in Examples 1-7 and Comparative Examples 1-3 were evaluated by the following evaluation methods, respectively. 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 flattening 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 (14)

(A) a resin having a carboxy group;
(B) a photosensitive agent;
(C) A resin having an ethylenically unsaturated group and an epoxy group, and / or a resin having an ethylenically unsaturated group and an oxetanyl group.   (D) The photosensitive resin composition of Claim 1 which further contains a solvent.   The (C) the resin having an ethylenically unsaturated group and an epoxy group and / or the resin having an ethylenically unsaturated group and an oxetanyl group includes a resin having an ethylenically unsaturated group and an epoxy group. 2. The photosensitive resin composition according to 2.   The photosensitive resin composition according to claim 1, wherein the ethylenically unsaturated group is a methacryloyl group or an acryloyl group.   The photosensitive resin composition of any one of Claims 1-4 in which the resin which has the said (A) carboxy group further has an ethylenically unsaturated group. For the total solid content of the photosensitive resin composition,
The content of the resin (A) having a carboxy group is 40 to 70% by weight,
The content of the photosensitive agent (B) is 5 to 40% by weight,
6. The total content of (C) a resin having an ethylenically unsaturated group and an epoxy group, and a resin having an ethylenically unsaturated group and an oxetanyl group is 3 to 40% by weight. The photosensitive resin composition as described in 2.   The photosensitive resin composition according to claim 1, wherein the photosensitive agent (B) is a 1,2-naphthoquinonediazide compound.   (E) The photosensitive resin composition of any one of Claims 1-7 which further contains a thermal radical generator.   The photosensitive resin composition according to claim 8, wherein the (E) thermal radical generator has a 10-hour half-life temperature of 100 ° C. or higher and 230 ° C. or lower. (1) The process of apply | coating the photosensitive resin composition of any one of Claims 2-8 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 10.   The cured film according to claim 11, which is an interlayer insulating film.   An organic EL display device comprising the cured film according to claim 11.   A liquid crystal display device comprising the cured film according to claim 11.

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