JPWO2014034301A1 - Photosensitive resin composition, method for forming cured film, cured film, organic EL display device, and liquid crystal display device - Google Patents

Abstract

[A] (A1) An alkali-soluble resin obtained by copolymerizing at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride and (A2) an epoxy group-containing unsaturated compound. B] a photosensitive resin composition containing a quinonediazide compound and [C] a blocked isocyanate compound, wherein the content of the blocked isocyanate is 0.1 to 10% by mass relative to the total solid content of the photosensitive resin composition And a photosensitive resin composition which is a compound represented by the following general formula (1). (In general formula (1), R represents an organic group having 1 to 20 carbon atoms.)

Description

  The present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as “the composition of the present invention”). Furthermore, it is related with the formation method of the cured film using this photosensitive resin composition. Furthermore, it is related with the cured film formed by this formation method. The present invention also relates to an organic EL display device and a liquid crystal display device having the cured film.

  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, photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained. As a photosensitive resin composition, the thing of patent document 1 is known, for example.

JP 2012-88459 A

As a result of studying the above-mentioned Patent Document 1, in a formulation in which an alkali-soluble resin and a quinonediazide compound as described in Cited Document 1 are blended, depending on the type of curing agent to be used, the panel display of the display device finally obtained is used. It was found that unevenness may occur.
This invention solves this subject, and it aims at providing the photosensitive resin composition which was excellent also in the panel display characteristic, maintaining the sensitivity etc. which are required for a cured film.

  Based on the above-mentioned problems, the inventors of the present application have conducted intensive studies. As a result, a photosensitive resin composition having excellent panel display characteristics can be obtained by using a compound having a specific structure as a block isocyanate compound as a curing agent. As a result, the present invention was completed. Specifically, the above problem has been solved by the following means <1>, preferably by <2> to <6>.

<1> [A] (A1) Alkali-soluble by copolymerizing at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides and (A2) an epoxy group-containing unsaturated compound resin,
A photosensitive resin composition containing [B] a quinonediazide compound, and [C] a blocked isocyanate compound,
The photosensitive resin whose content of the said block isocyanate is the range of 0.1-10 mass% with respect to the total solid of this photosensitive resin composition, and is a compound represented by following General formula (1) Composition.
General formula (1)
(In general formula (1), R represents an organic group having 1 to 20 carbon atoms.)
<2> The photosensitive resin composition according to <1>, wherein R in the general formula (1) is a hydrocarbon group having 3 to 9 carbon atoms.
<3> (1) The process of apply | coating the photosensitive resin composition as described in <1> or <2> on a board | substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) a step of exposing the applied photosensitive resin composition with actinic rays;
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) A method for forming a cured film, comprising a post-baking step of thermosetting the developed photosensitive resin composition.
<4> A cured film formed by the method according to <3>.
<5> The cured film according to <4>, which is an interlayer insulating film.
<6> An organic EL display device or a liquid crystal display device having the cured film according to <4> or <5>.

  According to the present invention, it is possible to provide a photosensitive resin composition that is excellent in sensitivity and the like and excellent in panel display characteristics.

  In addition, in the description of group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). The organic EL element in the present invention refers to an organic electroluminescence element.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention comprises [A] (A1) at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and (A2) an epoxy group-containing unsaturated compound. A photosensitive resin composition comprising an alkali-soluble resin obtained by copolymerization, [B] quinonediazide compound, and [C] a blocked isocyanate compound, wherein the content of the blocked isocyanate is the total solid content of the photosensitive resin composition It is the range of 0.1-10 mass% with respect to a minute, It is a compound represented by following General formula (1), It is characterized by the above-mentioned.
General formula (1)
(In general formula (1), R represents an organic group having 1 to 20 carbon atoms.)

<[A] alkali-soluble resin>
The [A] alkali-soluble resin used in the present invention is (A1) at least one monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter referred to as “(A1) compound”). And (A2) an epoxy group-containing unsaturated compound (hereinafter sometimes referred to as “(A2) compound”).
The alkali-soluble resin is a main component of the component excluding the solvent of the photosensitive resin composition of the present invention, and preferably accounts for 60% by mass or more of the total solid content.

  [A] The alkali-soluble resin is obtained by, for example, copolymerizing a compound (A1) giving a carboxyl group-containing structural unit and a compound (A2) giving an epoxy group-containing structural unit in the presence of a polymerization initiator in a solvent. Can be manufactured. Further, (A3) a hydroxyl group-containing unsaturated compound giving a hydroxyl group-containing structural unit (hereinafter sometimes referred to as “(A3) compound”) may be further added to obtain a copolymer. Further, in the production of [A] the alkali-soluble resin, the compound (A4) (derived from the compounds (A1), (A2) and (A3)) together with the compound (A1), the compound (A2) and the compound (A3). An unsaturated compound that gives structural units other than the structural unit to be added) can be further added to form a copolymer.

[(A1) Compound]
(A1) As the compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, anhydride of unsaturated dicarboxylic acid, mono [(meth) acryloyloxyalkyl] ester of polyvalent carboxylic acid, carboxyl group and hydroxyl group at both ends And mono (meth) acrylates of polymers having an unsaturated polycyclic compound having a carboxyl group and anhydrides thereof.

Examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid and the like;
Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc .; examples of the unsaturated dicarboxylic acid anhydride include, for example, anhydrides of the compounds exemplified as the above dicarboxylic acid; Examples of acid mono [(meth) acryloyloxyalkyl] esters include succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] and the like; Examples of mono (meth) acrylates of polymers having a hydroxyl group and ω-carboxypolycaprolactone mono (meth) acrylates; unsaturated polycyclic compounds having a carboxyl group and their anhydrides include, for example, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicar Xibicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] Hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5, Examples include 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride.

  Of these, monocarboxylic acids and dicarboxylic anhydrides are preferable, and acrylic acid, methacrylic acid, and maleic anhydride are more preferable from the viewpoint of copolymerization reactivity, solubility in an aqueous alkali solution, and availability. These (A1) compounds may be used alone or in admixture of two or more.

  (A1) As a using ratio of a compound, 5-30 mass% is based on the sum total of (A1) compound and (A2) compound (arbitrary (A3) compound and (A4) compound as needed). Preferably, 10% by mass to 25% by mass is more preferable. (A1) By making the usage-amount of a compound into the said range, while optimizing the solubility with respect to the aqueous alkali solution of [A] alkali-soluble resin, the photosensitive resin composition excellent in a sensitivity is obtained.

[(A2) Compound]
The compound (A2) is an epoxy group-containing unsaturated compound. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure).

  Examples of unsaturated compounds having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 2-methyl glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, and glycidyl α-n-butyl acrylate. 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethylacrylic-6,7-epoxyheptyl, o-Vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate and the like. Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3, methacrylate 4-Epoxycyclohexyl is preferable from the viewpoint of improving the copolymerization reactivity and the solvent resistance of the cured film.

  Examples of the unsaturated compound having an oxetanyl group include 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- ( (Acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2, 2-difluorooxetane, 3- (acryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-acryloyloxy) Ethyl) oxetane, 3- 2-acryloyloxyethyl) -2-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (2-acryloyl) Oxyethyl) -2-pentafluoroethyloxetane, 3- (2-acryloyloxyethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) -2,2-difluorooxetane, 3- (2-acryloyloxy) Ethyl) -2,2,4-trifluorooxetane, 3- (2-acryloyloxyethyl) -2,2,4,4-tetrafluorooxetane and the like; 3- (methacryloyloxymethyl) oxetane, 3 -(Methacryloyloxymethyl) -2-methyloxe 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxy) Methyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2 , 2,4,4-tetrafluorooxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -2-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyl Oxetane, 3- (2-me Tacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (2-methacryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (2-methacryloyloxyethyl) -2-phenyloxetane, 3- (2- Methacryloyloxyethyl) -2,2-difluorooxetane, 3- (2-methacryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (2-methacryloyloxyethyl) -2,2,4,4- And methacrylates such as tetrafluorooxetane. These (A2) compounds may be used alone or in combination of two or more.

  The proportion of the compound (A2) used is preferably 5% by mass to 60% by mass based on the total of the compound (A1) and the compound (A2) (optional (A3) compound and (A4) compound if necessary). 10 mass%-50 mass% are more preferable. (A2) By making the usage-amount of a compound into the said range, the cured film which has the outstanding solvent resistance etc. can be formed.

[(A3) Compound]
Examples of the (A3) compound include a (meth) acrylic acid ester having a hydroxyl group, a phenolic hydroxyl group-containing unsaturated compound represented by the following formula (3), and the like.

In the above formula (3), R ¹⁷ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ^{18 to} R ²² are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms. Y is a single bond, —COO—, or —CONH—. p is an integer of 0-3. However, at least one of R ^{18 to} R ²² is a hydroxyl group.

  Examples of the (meth) acrylic acid ester having a hydroxyl group include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and polyethylene glycol. (N = 2 to 10) mono (meth) acrylate, polypropylene glycol (n = 2 to 10) mono (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-methacryloxyethylglycoside and the like. .

  Examples of the phenolic hydroxyl group-containing unsaturated compound represented by the above formula (3) include compounds represented by the following formulas (3-1) to (3-5) according to the definitions of Y and p. .

In the above formula (3-1), q is an integer of 1 to 3. R < ¹⁷ > -R < ²² > is synonymous with the said Formula (3).

In said formula (3-2), R < ¹⁷ > -R < ²² > is synonymous with the said Formula (3).

In the above formula (3-3), r is an integer of 1 to 3. R < ¹⁷ > -R < ²² > is synonymous with the said Formula (3).

In said formula (3-4), R < ¹⁷ > -R < ²² > is synonymous with the said Formula (3).

In the above formula (3-5), R ¹⁷ to R ²² is as defined in the above formula (3).

  Of these (A3) compounds, 2-hydroxyethyl methacrylate, 4-hydroxyphenyl methacrylate, o-hydroxystyrene, p-hydroxystyrene, and α-methyl-p-hydroxystyrene are preferable. These (A3) compounds may be used alone or in admixture of two or more.

  (A3) As a using ratio of a compound, 5-30 mass% is based on the sum total of (A1) compound, (A2) compound, and (A3) compound (arbitrary (A4) compound as needed). Preferably, 10% by mass to 25% by mass is more preferable. (A3) By making the usage-amount of a compound into the said range, the cured film which has the outstanding solvent resistance etc. can be formed.

[(A4) Compound]
(A4) A compound will not be restrict | limited especially if it is unsaturated compounds other than said (A1) compound, (A2) compound, and (A3) compound. As the (A4) compound, for example, methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid chain alkyl ester, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, Bicyclo unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, unsaturated compound containing skeleton represented by the following formula (4), and other unsaturated compounds Compounds and the like.

In the formula (4), R ²³ is a hydrogen atom or a methyl group. s is an integer of 1 or more.

  Examples of the chain alkyl ester of methacrylic acid include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, and n-methacrylate. Examples include lauryl, tridecyl methacrylate, and n-stearyl methacrylate.

Examples of the cyclic alkyl ester of methacrylic acid include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, and tricyclomethacrylate [5.2.1]. .0 ^2,6] decan-8-yl oxy ethyl, and isobornyl methacrylate.

  Examples of the acrylic acid chain alkyl ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, and n-acrylate. Examples include lauryl, tridecyl acrylate, and n-stearyl acrylate.

Examples of acrylic acid cyclic alkyl esters include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, and tricyclo [5.2.1.0 ^2,6. ] Decan-8-yloxyethyl acrylate, isobornyl acrylate and the like.

  Examples of the methacrylic acid aryl ester include phenyl methacrylate and benzyl methacrylate.

  Examples of the acrylic acid aryl ester include phenyl acrylate and benzyl acrylate.

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

  Examples of the bicyclo unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2.1]. Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 .1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 -Cyclohexyloxycarbonyl bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [2 2.1] Hept- -Ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2 ′ -Hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2. 2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, and the like.

  Examples of maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.

  Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene.

  Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

  Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like.

  Examples of unsaturated compounds containing a furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-ene- 2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2- Yl-hex-1-en-3-one, acrylic acid-2-furan-2-yl-1-methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-hepten-3-one, etc. Is mentioned.

  Examples of unsaturated compounds containing a tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one , 2-methacrylic acid tetrahydropyran-2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, and the like.

  Examples of unsaturated compounds containing a pyran skeleton include 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyran and 4- (1,5-dioxa-6-oxo. -7-octenyl) -6-methyl-2-pyran and the like.

  Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Among these (A4) compounds, it has a methacrylic acid chain alkyl ester, a methacrylic acid cyclic alkyl ester, a maleimide compound, a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, and a skeleton represented by the above formula (4). Unsaturated compounds, unsaturated aromatic compounds and acrylic acid cyclic alkyl esters are preferred. Among these, styrene, methyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, p-methoxystyrene, 2- Methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, 3- (meth) acryloyloxytetrahydrofuran-2-one From the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution, it is more preferable. These (A4) compounds may be used alone or in admixture of two or more.

  The proportion of the compound (A4) used is preferably 10% by mass to 70% by mass based on the sum of the compound (A1), the compound (A2) and the compound (A4) (and any (A3) compound). A mass% to 60 mass% is more preferable. (A4) By making the usage-amount of a compound into the said range, the cured film excellent in solvent resistance etc. can be formed.

<[A] Method for synthesizing alkali-soluble resin>
The synthesis of the alkali-soluble resin can be referred to the description of paragraph numbers 0067 to 0073 of JP 2012-88549 A, and the contents thereof are incorporated in the present specification.

<[B] quinonediazide compound>
The [B] quinonediazide compound used in the photosensitive resin composition of the present invention is a 1,2-quinonediazide compound that generates a carboxylic acid upon irradiation with radiation. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used.

  Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nuclei.

  Examples of trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone; examples of tetrahydroxybenzophenone include 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2 , 3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3,4,2′-tetrahydroxy-4′-methylbenzophenone, 2,3,4,4 '-Tetrahydroxy-3'-methoxybenzophenone and the like; pentahydroxybenzophenone such as 2,3,4,2', 6'-pentahydroxybenzophenone and the like; hexahydroxybenzophenone such as 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5, 3 ′, 4 ′, 5′-hexahydroxybenzophenone, etc .; (polyhydroxyphenyl) alkane includes, for example, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) ) Methane, 1,1,1-tris (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl ] Phenyl] ethylidene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3, 3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol, 2,2,4-trimethyl-7,2 ′, 4 ′ Examples of other mother nucleus include 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman and 1- [1- (3 -{1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1 -Methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene, etc. It is done.

   Among these mother nuclei, 2,3,4,4′-tetrahydroxybenzophenone, 1,1,1-tri (p-hydroxyphenyl) ethane, 4,4 ′-[1- [4- [1- [ 4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferred.

  As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable. Examples of 1,2-naphthoquinonediazide sulfonic acid chloride include 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, and the like. Of these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is more preferred.

  In the condensation reaction of the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazidesulfonic acid halide, preferably 30 to 85 moles relative to the number of OH groups in the phenolic compound or alcoholic compound. %, More preferably 1,2-naphthoquinonediazidesulfonic acid halide corresponding to 50 to 70 mol% can be used. The condensation reaction can be carried out by a known method.

  Examples of the 1,2-quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, for example, 2,3,4-triaminobenzophenone-1,2. -Naphthoquinonediazide-4-sulfonic acid amide etc. are also used suitably.

  These [B] quinonediazide compounds can be used alone or in combination of two or more. As a use ratio of the [B] quinonediazide compound in the said photosensitive resin composition, 5 mass parts-100 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 10 mass parts-50 mass parts are more. preferable. [B] By setting the use ratio of the quinonediazide compound within the above range, the difference in solubility between the irradiated portion and the unirradiated portion in the alkaline aqueous solution serving as the developer is large, the patterning performance is improved, and the obtained cured film The solvent resistance is improved.

<[C] Block isocyanate compound>
The blocked isocyanate compound used in the present invention is represented by the following general formula (1).
General formula (1)
(In general formula (1), R represents an organic group having 1 to 20 carbon atoms.)

R represents a divalent organic group, may be branched or may be an unsaturated bond, and may have an aromatic ring and / or an aliphatic ring cyclic structure. Further, some of the atoms constituting the cyclic structure may be oxygen, sulfur, or nitrogen. Furthermore, an organic group or a substituent that the organic group has may be substituted with a group containing oxygen, sulfur, nitrogen, phosphorus, boron, or a halogen atom, and these substituents may form a bond with each other. .
Three R in the general formula (1) may be the same or different.
R in the general formula (1) is preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrocarbon group having 3 to 9 carbon atoms.
The molecular weight of the compound represented by the general formula (1) is, for example, 600 to 900.

  Specific examples of R include an alkylene group, an alkenyl group, an alkynyl group, a cycloalkenyl group, an arylene group, a carbonyl group, and a group obtained by combining these. Moreover, when R contains the above-mentioned group, ether structure (-O-) and thioether structure (-S-) may be combined. R is preferably an alkylene group, an arylene group, a carbonyl group, or a group obtained by combining these.

  In this invention, if it has the said general formula, a well-known block isocyanate compound can be used without a restriction | limiting. Specific examples of the blocked isocyanate compound include Duranate 17B-60P and Duranate 17B-60PX (both manufactured by Asahi Kasei Chemicals Corporation).

The compounding quantity of the compound represented by General formula (1) in the composition of this invention is the range of 0.1-10 mass% with respect to the total solid, 0.2-7 mass% is preferable, and 0.2. 5-5 mass% is further more preferable.
The composition of the present invention may also contain a blocked isocyanate compound other than the compound represented by the general formula (1). However, the blending amount of the blocked isocyanate compound other than the compound represented by the general formula (1) in the composition of the present invention is preferably 0.001% by mass or less with respect to the total solid content. More preferably it does not contain.

<Other optional components>
In addition to the above-mentioned [A] alkali-soluble resin, [B] quinonediazide compound, and [C] blocked isocyanate, the photosensitive resin composition includes a surfactant and an adhesion assistant as necessary within a range not impairing the effects of the present invention. An optional component such as an agent, a heat resistance improver, and a heat-sensitive acid generator can be contained. These optional components may be used alone or in combination of two or more. Details of these compounds can be referred to the description of paragraph numbers 0201 to 0224 of JP2012-88459A, the contents of which are incorporated herein.

<Method for preparing photosensitive resin composition>
Each component is mixed in a predetermined ratio and by any method, stirred and dissolved to prepare a photosensitive resin composition. For example, a resin composition can be prepared by preparing a solution in which components are dissolved in a solvent in advance and then mixing them in a predetermined ratio. The composition solution prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.

  As a solvent used for the preparation of the photosensitive resin composition of the present invention, a solvent that uniformly dissolves essential components and optional components and does not react with each component is used. As such a solvent, the thing similar to what was illustrated as a solvent which can be used in order to manufacture [A] alkali-soluble resin mentioned above is mentioned.

  Among such solvents, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether from the viewpoint of solubility of each component, reactivity with each component, ease of film formation, and the like. , Ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether , Propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono -N-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. (Poly) alkylene glycol monoalkyl ethers of

Acetic acid ethylene glycol monomethyl ether, acetic acid ethylene glycol monoethyl ether, acetic acid ethylene glycol mono-n-propyl ether, acetic acid ethylene glycol mono-n-butyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid diethylene glycol mono-n-propyl Acetic acid (poly) alkylene glycol monoalkyl ethers such as ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate ;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexane-2-one;
Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, 3-methyl-3-methoxybutylpropio Nate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, 2 -Other esters such as ethyl oxobutyrate;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like.

  Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate Le acetate i- butyl, formic acid n- amyl acetate, i- amyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate are preferred. The solvent can be used alone or in combination of two or more.

  In addition to the above solvents, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, maleic acid A high boiling point solvent such as diethyl, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate may be used in combination. The said high boiling point solvent can use single or 2 types or more.

  Although it is not limited as content of a solvent, From the viewpoint of the applicability | paintability of the photosensitive resin composition obtained, stability, etc., the total density | concentration of each component except the solvent of the said photosensitive resin composition is 5 mass%-50 mass%. The amount of mass% is preferable, and the amount of 10 mass% to 40 mass% is more preferable. When the photosensitive resin composition is prepared in a solution state, the solid content concentration (components other than the solvent in the composition solution) can be set to any concentration (for example, 5 depending on the purpose of use, a desired film thickness value, etc.). Mass% to 50 mass%). A more preferable solid content concentration varies depending on a method of forming a film on the substrate, which will be described later. The composition solution thus prepared can be used after being filtered using a Millipore filter or the like having a pore diameter of about 0.5 μm.

[Method for producing cured film]
Next, the manufacturing method of the cured film of this invention is demonstrated.
The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
(1) The process of apply | coating the photosensitive resin composition of this invention on a board | substrate;
(2) A step of removing the solvent from the applied photosensitive resin composition;
(3) The process of exposing the photosensitive resin composition from which the solvent was removed with actinic rays;
(4) A step of developing the exposed photosensitive resin composition with an aqueous developer;
(5) A post-baking step of thermosetting the developed photosensitive resin composition.
Each step will be described below in order.

In the application step (1), the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent. Before applying the photosensitive resin resin composition to the substrate, it is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning, and it is more preferable to treat the substrate surface with hexamethyldisilazane after substrate cleaning. By performing this treatment, the adhesiveness of the photosensitive resin composition to the substrate tends to be improved. The method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
Examples of the substrate include inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
Resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide compound These substrates which may be mentioned are less if used while the above embodiment, normally, depending on the form of the final product, for example, multi-layered structure such as a TFT element is formed.
The coating method on the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like can be used. Furthermore, it is also possible to apply a so-called pre-wet method as described in JP 2009-145395 A.
The wet film thickness when applied is not particularly limited and can be applied with a film thickness according to the application, but it is usually used in the range of 0.5 to 10 μm.

  In the solvent removal step (2), the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are in the above ranges, the pattern adhesiveness is better and the residue tends to be further reduced.

In the exposure step (3), the substrate provided with the coating film is irradiated with actinic rays through a mask having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to produce a carboxyl group or a phenolic hydroxyl group.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, and the like can be used. Actinic rays having a wavelength of 300 nm to 450 nm, such as 405 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as “PEB”) can be performed. PEB can promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
However, since the acid-decomposable group in the present invention has low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate a carboxyl group or a phenolic hydroxyl group, PEB is not necessarily performed. A positive image can also be formed by development.

In the developing step (4), a polymer having a liberated carboxyl group or phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
The developer used in the development step preferably contains a basic compound. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
Preferred examples of the developer include 0.4% aqueous solution, 0.5% aqueous solution, 0.7% aqueous solution and 2.38% aqueous solution of tetraethylammonium hydroxide.
The pH of the developer is preferably 10.0 to 14.0.
The developing time is preferably 30 to 500 seconds, and the developing method may be any of a liquid piling method and a dipping method. After development, washing with running water is usually performed for 30 to 300 seconds to form a desired pattern.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.

In the post-baking step of (5), by heating the obtained positive image, the acid-decomposable group is thermally decomposed to generate a carboxyl group or a phenolic hydroxyl group, and then crosslinked with a crosslinkable group, a crosslinking agent or the like. A cured film can be formed. This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on a hot plate, 30 to 120 minutes for an oven. It is preferable to By proceeding with such a crosslinking reaction, it is possible to form a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like. In addition, when the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
Prior to post-baking, post-baking can be performed after baking at a relatively low temperature (addition of a middle baking step). When performing middle baking, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Moreover, middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
Prior to post-baking, the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film. As a preferable exposure amount when the post-exposure step is included, 100 to 3,000 mJ / cm ² is preferable, and 100 to 500 mJ / cm ² is particularly preferable.

  Furthermore, the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist. In the case where a cured film obtained by thermal curing in a post-baking process is used as a dry etching resist, dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.

[Curing film]
The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention.
The cured film of the present invention can be suitably used as an interlayer insulating film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.
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. For details of the organic EL display device and the liquid crystal display device, paragraphs 0209-0210 of JP2011-209681A and the description of FIGS. 1 and 2 can be referred to, and the contents thereof are incorporated in the present specification.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<[A] Synthesis of alkali-soluble resin>
[Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether. Subsequently, 16 parts by weight of methacrylic acid as the compound (A1), 40 parts by weight of glycidyl methacrylate as the compound (A2), 10 parts by weight of styrene as the compound (A4), tricyclomethacrylate [5.2.1.0 ^2,6 ] Charge 14 parts by weight of decan-8-yl and 20 parts by weight of 2-methylcyclohexyl acrylate, purge with nitrogen, raise the temperature of the solution to 70 ° C. while gently stirring, and maintain this temperature for 4 hours for polymerization. As a result, a solution containing the copolymer (A-1) was obtained. The obtained polymer solution had a solid content concentration of 34.4%, and the copolymer (A-1) had an Mw of 8,000 and a molecular weight distribution (Mw / Mn) of 2.3.

[Synthesis Example 2]
A flask equipped with a condenser and a stirrer was charged with 8 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether. Subsequently, 13 parts by weight of methacrylic acid as the (A1) compound, 40 parts by weight of glycidyl methacrylate as the (A2) compound, 10 parts by weight of α-methyl-p-hydroxystyrene as the compound (A3), and 10 parts by weight of styrene as the (A4) compound Part, 12 parts by mass of tetrahydrofurfuryl methacrylate, 15 parts by mass of N-cyclohexylmaleimide and 10 parts by mass of n-lauryl methacrylate, and after replacing with nitrogen, the temperature of the solution was raised to 70 ° C. while gently stirring. A solution containing the copolymer (A-2) was obtained by polymerization while maintaining the temperature for 5 hours. The obtained polymer solution had a solid content concentration of 31.9%, Mw of the copolymer (A-2) was 8,000, and molecular weight distribution (Mw / Mn) was 2.3.

<[B] quinonediazide compound>
B-1: 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensate B-2 with sulfonic acid chloride (2.0 mol): 1,1,1-tri (p-hydroxyphenyl) ethane and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) Condensate with

<[C] Block isocyanate compound>
C-1: Duranate 17B-60P (Asahi Kasei Chemicals)
C-2: Duranate 17B-60PX (Asahi Kasei Chemicals)
C-3: Duranate TPA-B80E (Asahi Kasei Chemicals)
C-4: Duranate MF-B60X (Asahi Kasei Chemicals)
C-5: Death module BL3175 (manufactured by Sumika Bayer Urethane)
C-6: Death module BL3272 MPA (manufactured by Sumika Bayer Urethane)
C-7: Death Module BL3475 BA / SN (manufactured by Sumika Bayer Urethane)
C-8: Death Module BL5375 MPA / SN (manufactured by Sumika Bayer Urethane)

<Preparation of each composition>
Each component shown in the following table is mixed, and after adding diethylene glycol ethyl methyl ether as a solvent so that the solid content concentration is 30% by mass, each photosensitive resin composition is filtered by a membrane filter having a pore size of 0.2 μm. A product was prepared. In addition, “-” in the column represents that the corresponding component was not used.

<Evaluation>
The following evaluation was performed about the prepared photosensitive resin composition. The results are shown in the table below.

[Storage stability]
The obtained photosensitive resin composition was left in an oven at 40 ° C. for 1 week, and the viscosity before and after heating was measured to determine the rate of change in viscosity (%). At this time, the viscosity change rate was defined as storage stability, and when it was 5% or less, the storage stability was judged to be good, and when it exceeded 5%, the storage stability was judged to be poor. The viscosity was measured at 25 ° C. using an E-type viscometer (VISCONIC ELD.R, Toki Sangyo Co., Ltd.).

[sensitivity]
After applying any of the photosensitive resin compositions prepared as Examples and Comparative Examples on a silicon substrate using a spinner, pre-baking on a hot plate at 90 ° C. for 2 minutes to apply a film thickness of 3.0 μm. A film was formed. The obtained coating film was irradiated with a predetermined amount of ultraviolet rays by a mercury lamp through a pattern mask having a line and space pattern having a width of 10 μm. Next, using a developer composed of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, development processing was carried out at 25 ° C. for 60 seconds, followed by washing with ultrapure water for 1 minute. At this time, the minimum ultraviolet irradiation amount capable of forming a line and space pattern having a width of 10 μm was measured. When this value was less than 850 J / m ² , it was judged that the sensitivity was good.

[Solvent resistance]
After applying any of the photosensitive resin compositions prepared as Examples and Comparative Examples on a silicon substrate using a spinner, pre-baking on a hot plate at 90 ° C. for 2 minutes to apply a film thickness of 3.0 μm. A film was formed. The obtained coating film was irradiated with ultraviolet rays by a mercury lamp so that the cumulative irradiation amount was 3,000 J / m ² . Next, this silicon substrate was heated at 150 ° C. for 30 minutes for Examples 1 to 13 and Comparative Examples 1 and 2 on a hot plate. Comparative Examples 3 and 4 were heated at 150 ° C. for 60 minutes. The film thickness (T1) of the obtained cured film was measured. And after immersing the silicon substrate in which this cured film was formed in dimethyl sulfoxide temperature-controlled at 70 degreeC for 20 minutes, the film thickness (t1) of the said cured film was measured, and the film thickness change rate was shown below. Calculated from the equation, this was defined as solvent resistance.
Film thickness change rate = {(t1-T1) / T1} × 100 (%)
When the absolute value of this value was less than 5%, the solvent resistance was judged to be excellent.

[Display unevenness]
(Evaluation of display unevenness in display device)
A liquid crystal display device using a thin film transistor (TFT) was produced by the following method. In the active matrix type liquid crystal display device described in FIG. 1 and FIG. 2 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows to obtain a liquid crystal display device.
That is, the bottom gate type TFT 1 was formed on the glass substrate 6, and the insulating film 3 made of Si 3 N 4 was formed so as to cover the TFT 1. Next, after forming a contact hole in the insulating film 3, a wiring 2 (height of 1.0 μm) connected to the TFT 1 through the contact hole was formed on the insulating film 3.

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 compositions of Examples 1 to 12 and Comparative Examples 1 to 8 on a substrate and prebaking (90 ° C. × 2 on a hot plate). Then, i-line (365 nm) was irradiated from the mask with 1000 mJ / cm ² (illuminance 20 mW / cm ² ) using a high-pressure mercury lamp, and then developed with an alkaline aqueous solution to form a pattern at 60 ° C. at 60 ° C. Heat treatment was performed for a minute. The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film 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.

When a driving voltage was applied to the obtained liquid crystal display device and a gray test signal was input, the gray display was visually observed, and the presence or absence of display unevenness was evaluated according to the following evaluation criteria. 0 to 2 are practical levels.
0: No unevenness at all (very good)
1: Slight unevenness is seen on the edge of the glass substrate, but there is no problem in the display (good)
2: Slight unevenness on the display, but practical level (normal)
3: The display is uneven (somewhat bad)
4: Strong unevenness in display (very bad)

  As is clear from the above results, the composition of the present invention was excellent in storage stability, high sensitivity, excellent solvent resistance, and extremely low display unevenness. In contrast, the composition of the comparative example had poor display unevenness.

Claims (6)

[A] (A1) an alkali-soluble resin obtained by copolymerizing at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride and (A2) an epoxy group-containing unsaturated compound;
A photosensitive resin composition containing [B] a quinonediazide compound, and [C] a blocked isocyanate compound,
The photosensitive resin whose content of the said block isocyanate is the range of 0.1-10 mass% with respect to the total solid of this photosensitive resin composition, and is a compound represented by following General formula (1) Composition.
General formula (1)
(In general formula (1), R represents an organic group having 1 to 20 carbon atoms.) The photosensitive resin composition of Claim 1 whose R of General formula (1) is a C3-C9 hydrocarbon group, respectively. (1) The process of apply | coating the photosensitive resin composition of Claim 1 or 2 on a board | substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) a step of exposing the applied photosensitive resin composition with actinic rays;
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) A method for forming a cured film, comprising a post-baking step of thermosetting the developed photosensitive resin composition.   A cured film formed by the method according to claim 3.   The cured film according to claim 4, which is an interlayer insulating film.   An organic EL display device or a liquid crystal display device having the cured film according to claim 4.