TW201411280A - Photo-sensitive resin composition, method for manufacturing cured film, cured film, organic EL display device, and liquid crystal display device - Google Patents

Abstract

A photo-sensitive resin composition includes: [A] an alkali-soluble resin formed by copolymerizing (A1) at least one chosen from a group consisting of unsaturated carboxylic acid and carboxylic anhydride with (A2) an unsaturated compound containing an epoxy group; [B] a quinone diazide compound; and [C] a blocked isocyanate compound, wherein a content of the blocked isocyanate is in a range of 0.1% by mass to 10% by mass relative to a total solid content of the photo-sensitive resin composition, and the blocked isocyanate is a compound represented by the following general formula (1). (In the general formula (1), R represents an organic group with a carbon number of 1 to 20 respectively.)

Description

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

The present invention relates to a photosensitive resin composition (hereinafter, simply referred to as "the composition of the present invention"). Further, the present invention relates to a method for forming a cured film using the photosensitive resin composition. Further, the present invention relates to a cured film formed by the formation method. Further, the present invention relates to an organic electroluminescence (EL) display device and a liquid crystal display device having the cured film.

An interlayer insulating film in which a pattern is formed is provided in an organic EL display device, a liquid crystal display device, or the like. The photosensitive resin composition is widely used for forming the interlayer insulating film in order to obtain a desired pattern shape with a small number of steps and to obtain sufficient flatness. For example, a photosensitive resin composition described in JP-A-2012-88459 is known as a photosensitive resin composition.

As a result of the investigation of the composition of the alkali-soluble resin and the quinonediazide compound as described in Japanese Laid-Open Patent Publication No. 2012-88459, the result of the study is as follows. The type of hardener used was uneven in the panel display of the finally obtained display device.

The invention of the present invention is an object of the present invention, and an object of the invention is to provide a photosensitive resin composition which is excellent in panel display characteristics and the like, and which is required to maintain a cured film.

As a result of intensive studies based on the above-mentioned problems, the inventors of the present invention have found that a compound having a specific structure as a blocked isocyanate compound can be used as a curing agent, whereby photosensitive properties excellent in panel display characteristics can be obtained. The resin composition thus completed the present invention. Specifically, the above problem is preferably solved by means <2> to <6> by the following means <1>.

<1> A photosensitive resin composition comprising: [A] at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and (A2) containing epoxy groups An alkali-soluble resin obtained by copolymerization of an unsaturated compound; [B] a quinonediazide compound; and a [C] blocked isocyanate compound, the content of the blocked isocyanate relative to the total solid content of the photosensitive resin composition The range of from 0.1% by mass to 10% by mass, and the blocked isocyanate is a compound represented by the following formula (1).

(In the formula (1), R represents an organic group having 1 to 20 carbon atoms, respectively)

<2> The photosensitive resin composition according to <1>, wherein R of the formula (1) is a hydrocarbon group having 3 to 9 carbon atoms, respectively.

<3> A method for forming a cured film, comprising: (1) a step of applying a photosensitive resin composition as described in <1> or <2> to a substrate; (2) a photosensitive film applied thereto a step of removing a solvent in the resin composition; (3) a step of exposing the solvent-removed photosensitive resin composition by actinic rays; and (4) developing the exposed photosensitive resin composition with an aqueous developing solution And (5) a post-baking step of thermally hardening the developed photosensitive resin composition.

<4> A cured film obtained by the method of forming a cured film according to <3> And formed.

<5> The cured film according to <4> which is an interlayer insulating film.

<6> An organic electroluminescence display device or a liquid crystal display device comprising the cured film according to <4> or <5>.

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

In addition, in the expression of the group (atomic group) in the present specification, the substituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and also a group having a substituent (atomic group). 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). Further, the organic EL element in the present invention means an organic electroluminescence element.

<Photosensitive resin composition>

The photosensitive resin composition of the present invention comprises: [A] at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and (A2) unsaturated groups containing epoxy groups. An alkali-soluble resin obtained by copolymerizing a compound; [B] a quinone diazide compound; and a [C] blocked isocyanate compound characterized by the above-mentioned blocked isocyanate with respect to the total solid content of the photosensitive resin composition The content is in the range of 0.1% by mass to 10% by mass, and the above blocked isocyanate is A compound represented by the following formula (1).

(In the formula (1), R represents an organic group having 1 to 20 carbon atoms, respectively)

<[A] alkali soluble resin>

The [A] alkali-soluble resin used in the present invention is at least one monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (hereinafter referred to as "(A1)". The compound ") is an alkali-soluble resin obtained by copolymerizing an epoxy group-containing unsaturated compound (hereinafter referred to as "(A2) compound").

The alkali-soluble resin is a main component of a component other than 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] an alkali-soluble resin, for example, a compound (A1) which provides a structural unit containing a carboxyl group and a compound (A2) which provides a structural unit containing an epoxy group in the presence of a polymerization initiator in a solvent Copolymerization is carried out to manufacture. Further, (A3) may further be added to provide a hydroxyl group-containing unsaturated member having a hydroxyl group-containing structural unit. A compound (hereinafter sometimes referred to as "(A3) compound") is used to prepare a copolymer. Further, when the [A] alkali-soluble resin is produced, the above (A1) compound, (A2) compound, (A3) compound, and (A4) compound (provided from the above (A1) compound, (A2)) may be added together. The compound and the unsaturated compound of the structural unit other than the structural unit of the (A3) compound are used to form a copolymer.

[(A1) compound]

Examples of the (A1) compound include an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an anhydride of an unsaturated dicarboxylic acid, a mono[(meth)acryloxyalkylalkyl] ester of a polyvalent carboxylic acid, and both ends. A mono(meth)acrylate having a polymer having a carboxyl group and a hydroxyl group, an unsaturated polycyclic compound having a carboxyl group, an anhydride thereof, and the like.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid; and examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, and Zhongkang. Examples of the anhydride of the unsaturated dicarboxylic acid include an anhydride of the compound exemplified as the above dicarboxylic acid; and a mono[(meth)acryloxyalkyl group as a polyvalent carboxylic acid] Examples of the ester include succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid mono [2-(methyl) propylene methoxyethyl] ester, and the like; Examples of the mono(meth)acrylate having a polymer having a carboxyl group and a hydroxyl group at the terminal include ω-carboxypolycaprolactone mono(meth)acrylate; and the unsaturated polycyclic compound having a carboxyl group and an anhydride thereof. For example, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[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-carboxyl Keto-6-ethylbicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, and the like.

Among these, a monocarboxylic acid and a dicarboxylic acid anhydride are preferred, and acrylic acid, methacrylic acid, maleic anhydride are more preferable in terms of copolymerization reactivity, solubility in an alkaline aqueous solution, and ease of availability. . These (A1) compounds may be used singly or in combination of two or more.

The ratio of use of the (A1) compound is preferably 5% by mass to 30% by mass based on the total of the (A1) compound and the (A2) compound (optionally any (A3) compound and (A4) compound). Good is 10% by mass to 25% by mass. By using the ratio of the use of the compound (A1) to the above range, the solubility of the [A] alkali-soluble resin in the alkaline aqueous solution is optimized, and a photosensitive resin composition excellent in sensitivity can be 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 the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 2-methyl glycidyl methacrylate, α-ethyl methacrylate, α- Glycidyl propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxy acrylate Heptyl ester, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, P-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate or the like. Among these, from the viewpoints of improving copolymerization reactivity and solvent resistance of the cured film, glycidyl methacrylate, 2-methylglycidyl methacrylate, and methacrylic acid-6 are preferable. 7-Epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate.

Examples of the unsaturated compound having an oxetanyl group include 3-(acryloxymethyl)oxetane and 3-(acryloxymethyl)-2-methyloxycyclohexane. Butane, 3-(acryloxymethyl)-3-ethyloxetane, 3-(acryloxymethyl)-2-trifluoromethyloxetane, 3-( Propylene methoxymethyl)-2-pentafluoroethyl oxetane, 3-(acryloxymethyl)-2-phenyl oxetane, 3-(acryloxymethyl) )-2,2-difluorooxetane, 3-(acryloxymethyl)-2,2,4-trifluorooxetane, 3-(acryloxymethyl)- 2,2,4,4-tetrafluorooxetane, 3-(2-propenyloxyethyl)oxetane, 3-(2-propenyloxyethyl)-2-ethyl Oxycyclobutane, 3-(2-propenyloxyethyl)-3-ethyloxetane, 3-(2-propenyloxyethyl)-2-trifluoromethyloxy Heterocyclic butane, 3-(2-propenyloxyethyl)-2-pentafluoroethyl oxetane, 3-(2-propenyloxyethyl)-2-phenyl oxacyclohexane Butane, 3-(2-propenyloxyethyl)-2,2-difluorooxetane, 3-(2-propenyloxyethyl)-2,2,4-trifluoroox Heterocyclic butane, 3-(2- Acrylates such as ethenyloxyethyl)-2,2,4,4-tetrafluorooxetane; 3-(methacryloxymethyl)oxetane, 3-(methyl Propylene methoxymethyl)-2-methyloxetane, 3-(methacryloxymethyl)-3-ethyloxetane, 3-(methacryloxyloxy) Methyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl)-2-pentafluoroethyloxetane, 3-(methacryloxyloxy) A 2-phenyloxybutane, 3-(methacryloxymethyl)-2,2-difluorooxetane, 3-(methacryloxymethyl) -2,2,4-trifluorooxetane, 3-(methacryloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(2-A Acryloxyethyl)oxetane, 3-(2-methylpropenyloxyethyl)-2-ethyloxetane, 3-(2-methacryloxyloxy Ethyl)-3-ethyloxetane, 3-(2-methylpropenyloxyethyl)-2-trifluoromethyloxetane, 3-(2-methylpropene oxime Oxyethyl)-2-pentafluoroethyl oxetane, 3-(2-methylpropenyloxyethyl)-2-phenyloxetane, 3-(2-methyl Propylene oxiranyl ethyl)-2,2-difluorooxetane, 3-(2-methylpropenyloxyethyl)-2,2,4-trifluorooxetane, 3 a methacrylate such as -(2-methacryloxyethyl)-2,2,4,4-tetrafluorooxetane or the like. These (A2) compounds may be used singly or in combination of two or more.

The ratio of use of the (A2) compound is preferably 5% by mass to 60% by mass based on the total of the (A1) compound and the (A2) compound (optionally any (A3) compound and (A4) compound). Good is 10% by mass to 50% by mass. By setting the use ratio of the compound (A2) to the above range, a cured film having excellent solvent resistance and the like can be formed.

[(A3) compound]

Examples of the (A3) compound include a (meth) acrylate having a hydroxyl group, an unsaturated compound containing a phenolic hydroxyl group 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 from 0 to 3. Among them, at least one of R ¹⁸ to R ²² is a hydroxyl group.

Examples of the (meth) acrylate having a hydroxyl group include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (methyl). ) 4-hydroxybutyl acrylate, polyethylene glycol (n = 2 ~ 10) mono (meth) acrylate, polypropylene glycol (n = 2 ~ 10) mono (meth) acrylate, (meth) acrylate 2 , 3-dihydroxypropyl ester, 2-methacryloxyethyl glucoside, and the like.

The phenolic hydroxyl group-containing unsaturated compound represented by the above formula (3), for example, a compound represented by the following formula (3-1) to formula (3-5), etc. .

In the above formula (3-1), q is an integer of 1 to 3. R ¹⁷ to R ^{22 have} the same meanings as in the above formula (3).

In the above formula (3-2), R ¹⁷ to R ^{22 have} the same meanings as in the above formula (3).

In the above formula (3-3), r is an integer of 1 to 3. R ¹⁷ to R ^{22 have} the same meanings as in the above formula (3).

In the above formula (3-4), R ¹⁷ to R ^{22 have} the same meanings as in the above formula (3).

In the above formula (3-5), R ¹⁷ to R ^{22 have} the same meanings as in the above formula (3).

Among 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 singly or in combination of two or more.

The ratio of use of the (A3) compound is preferably 5% by mass to 30% by mass based on the total of the (A1) compound, the (A2) compound, and the (A3) compound (optionally any (A4) compound). Good is 10% by mass to 25% by mass. By setting the use ratio of the compound (A3) to the above range, a cured film having excellent solvent resistance and the like can be formed.

[(A4) compound]

The compound (A4) is not particularly limited as long as it is an unsaturated compound other than the compound (A1), the compound (A2) and the compound (A3). Examples of the (A4) compound include a chain alkyl methacrylate, a cyclic alkyl methacrylate, a chain alkyl acrylate, a cyclic alkyl acrylate, and a methacrylic acid aryl group. Base ester, aryl acrylate, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, tetrahydrogen A pyran skeleton, a pyran skeleton, an unsaturated compound having a skeleton represented by the following formula (4), and other unsaturated compounds.

In the above 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 methacrylate include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, second butyl methacrylate, and butyl methacrylate. 2-ethylhexyl acrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, and the like.

Examples of the cyclic alkyl methacrylate include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, and tricyclo[3-methylcyclohexane [5.2.1.0 ^2,6 ]decane-8- A base ester, a tricyclo[cyclopropyl] methacrylate [5.2.1.0 ^2,6 ]decane-8-yloxyethyl ester, isobornyl methacrylate or the like.

As the chain alkyl acrylate, for example, methyl acrylate or propyl acrylate can be mentioned. Ethyl acrylate, n-butyl acrylate, second butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, n-lauryl acrylate, tridecyl acrylate, n-stearyl acrylate Ester and the like.

Examples of the cyclic alkyl acrylate include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate, and tricyclohexyl acrylate [5.2]. .1.0 ^2,6 ]decane-8-yloxyethyl ester, isobornyl acrylate, and the like.

Examples of the aryl methacrylate include phenyl methacrylate and benzyl methacrylate.

Examples of the aryl acrylate include phenyl acrylate and benzyl acrylate.

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

Examples of the bicyclic unsaturated compound include bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]heptane- 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- Cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(t-butoxycarbonyl)bicyclo[ 2.2.1] Hept-2-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-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6- Bis(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 the maleimide compound include N-phenyl maleimide, N-cyclohexyl maleimide, and N-benzyl maleimide. N-(4-hydroxyphenyl) maleimide, N-(4-hydroxybenzyl) maleimide, N-ammonium imino-3-butenylene Ammonium benzoate, N-succinimide-4-butylimide butyrate, N-succinimide-6-m-butyleneimine hexanoate, N- Amber quinone imino-3-butanediimide propionate, 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, and 2,3-dimethyl-1,3-butadiene.

Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth)acrylate, 2-methylpropenyloxy-tetrahydrofurfuryl propionate, and 3-(methyl)acryloxytetrahydrofuran. 2-ketone and the like.

Examples of the unsaturated compound containing a furan skeleton include 2-methyl-5-(3-furyl)-1-penten-3-one, decyl (meth)acrylate, and 1-furan-2- Butyl-3-en-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, 2-furan-2-yl-1-methyl-ethyl acrylate, 6-(2-furanyl) -6-methyl-1-hepten-3-one and the like.

As the unsaturated compound containing a tetrahydropyran skeleton, for example, (tetrahydropyran-2-yl)methyl methacrylate, 2,6-dimethyl-8-(tetrahydropyran-2-yloxy)-oct-1-en-3-one, 2 - tetrahydropyran-2-yl methacrylate, 1-(tetrahydropyran-2-yloxy)-butyl-3-en-2-one, and the like.

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

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

Among these (A4) compounds, a linear alkyl methacrylate, a cyclic alkyl methacrylate, a maleimide compound, a tetrahydrofuran skeleton, a furan skeleton, and a tetrahydropyran are preferred. A skeleton, a pyran skeleton, an unsaturated compound of a skeleton represented by the above formula (4), an unsaturated aromatic compound, and a cyclic alkyl acrylate. Among these, from the viewpoints of copolymerization reactivity and solubility in an aqueous alkaline solution, styrene, methyl methacrylate, butyl methacrylate, n-lauryl methacrylate, and A are more preferable. Tricyclohexyl acrylate [5.2.1.0 ^2,6 ]decane-8-yl ester, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenyl maleimide, N- Cyclohexyl maleimide, tetrahydrofurfuryl (meth)acrylate, polyethylene glycol (n=2~10) mono(meth)acrylate, 3-(meth)acryloxytetrahydrofuran -2-ketone. These (A4) compounds may be used singly or in combination of two or more.

The ratio of use of the compound (A4) is based on the total of the (A1) compound, the (A2) compound, and the (A4) compound (and any (A3) compound). Preferably, it is 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass. When the ratio of use of the compound (A4) is in the above range, a cured film excellent in solvent resistance or the like can be formed.

<[A] Synthesis method of alkali-soluble resin>

The synthesis of the alkali-soluble resin can be referred to the description of Paragraph No. 0067 to Paragraph No. 0073 of JP-A-2012-88549, the contents of which are incorporated herein by reference.

<[B] quinone diazide compound>

The [B] quinonediazide compound used in the photosensitive resin composition of the present invention is a 1,2-quinonediazide compound which generates a carboxylic acid by irradiation of radiation. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as "mother core") and 1,2-naphthoquinonediazidesulfonium halide can be used.

Examples of the mother nucleus include trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, pentahydroxydiphenyl ketone, hexahydroxydiphenyl ketone, (polyhydroxyphenyl)alkane, and other mother nucleus.

Examples of the trihydroxydiphenyl ketone include 2,3,4-trihydroxydiphenyl ketone and 2,4,6-trihydroxydiphenyl ketone; and as the tetrahydroxydiphenyl ketone, for example, : 2,2',4,4'-tetrahydroxydiphenyl ketone, 2,3,4,3'-tetrahydroxydiphenyl ketone, 2,3,4,4'-tetrahydroxydiphenyl ketone, 2,3,4,2'-tetrahydroxy-4'-methyldiphenyl ketone, 2,3,4,4'-tetrahydroxy-3'-methoxydiphenyl ketone, etc.; as pentahydroxydi Examples of the phenyl ketone include 2,3,4,2',6'-pentahydroxydiphenyl ketone; and as the hexahydroxydiphenyl ketone, for example, 2, 4, 6, 3', 4 ',5'-hexahydroxydiphenyl ketone, 3,4,5,3',4',5'-hexahydroxydiphenyl ketone And as the (polyhydroxyphenyl)alkane, 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-methyl Ethylethyl]phenyl]ethylidene]bisphenol, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl Base-1,1'-spirobi-5,6,7,5',6',7'-hexanol, 2,2,4-trimethyl-7,2',4'-trihydroxy yellow Alkanes and the like; as other parent cores, for example, 2-methyl-2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxychroman, 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-hydroxybenzene Base)-1-methylethyl}-1,3-dihydroxybenzene and the like.

Among the mother cores, preferred are 2,3,4,4'-tetrahydroxydiphenyl ketone, 1,1,1-tris(p-hydroxyphenyl)ethane, 4,4'-[1- [4-[1-[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol.

As the 1,2-naphthoquinonediazidesulfonium halide, 1,2-naphthoquinonediazidesulfonium chloride is preferred. Examples of the 1,2-naphthoquinonediazidesulfonium chloride include 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, and the like. . Among these, 1,2-naphthoquinonediazide-5-sulfonyl chloride is more preferable.

In the condensation reaction of a phenolic compound or an alcoholic compound (nuclear core) with a 1,2-naphthoquinonediazidesulfonium halide, the number of OH groups in the phenolic compound or the alcoholic compound can be used, which is equivalent to It is from 30 mol% to 85 mol%, more preferably from 50 mol% to 70 mol% of 1,2-naphthoquinonediazidesulfonium halide. The condensation reaction can be carried out by a known method The law is implemented.

Further, as the 1,2-quinonediazide compound, 1,2-naphthoquinonediazidesulfonamide which changes the ester bond of the above-exemplified nucleus to a guanamine bond can be suitably used, for example, 2 , 3,4-triaminodiphenyl ketone-1,2-naphthoquinonediazide-4-sulfonamide, and the like.

These [B] quinonediazide compounds may be used singly or in combination of two or more. The use ratio of the [B] quinone diazide compound in the photosensitive resin composition is preferably 5 parts by mass to 100 parts by mass, more preferably 10 parts by mass, per 100 parts by mass of the [A] alkali-soluble resin. ~50 parts by mass. When the ratio of use of the [B] quinone diazide compound is in the above range, the difference in solubility between the irradiated portion and the unirradiated portion of the alkaline aqueous solution serving as the developing solution is large, and the patterning performance is improved. The solvent resistance of the obtained cured film became good.

<[C] blocked isocyanate compound>

The blocked isocyanate compound used in the present invention is represented by the following formula (1).

(In the formula (1), R represents an organic group having 1 to 20 carbon atoms, respectively)

R is a divalent organic group which may be branched, may be an unsaturated bond, or may have a cyclic structure of an aromatic ring and/or an aliphatic ring. Further, a part of the atoms constituting the cyclic structure may be oxygen, sulfur, or nitrogen. Further, the substituent which the organic group or the organic group has may be substituted by a group containing oxygen, sulfur, nitrogen, phosphorus, boron, or a halogen atom, and the substituents may bond each other to each other.

The three Rs in the formula (1) may be the same or different.

R in the formula (1) is preferably a hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrocarbon group having 3 to 9 carbon atoms.

The molecular weight of the compound represented by the 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 extended aryl group, a carbonyl group, and a group in which these groups are combined. Further, when R contains the above group, an ether structure (-O-) or a thioether structure (-S-) may be combined. R is preferably an alkyl group, an aryl group, a carbonyl group, and a group in which the groups are combined.

In the present invention, as long as it has the above formula, a known blocked isocyanate compound can be used without limitation. Specific examples of the blocked isocyanate compound include Duranate 17B-60P and Duranate 17B-60PX (all manufactured by Asahi Kasei Chemicals Co., Ltd.).

The compounding amount of the compound represented by the formula (1) in the composition of the present invention is in the range of 0.1% by mass to 10% by mass, preferably 0.2% by mass to 7% by mass, based on the total solid content. It is 0.5% by mass to 5% by mass.

Further, the composition of the present invention may also contain a compound represented by the general formula (1). A blocked isocyanate compound other than the compound. However, the amount of the blocked isocyanate compound other than the compound represented by the formula (1) in the composition of the present invention is preferably 0.001% by mass or less, and more preferably substantially not contained by the total solid content. A blocked isocyanate compound other than the compound represented by the formula (1).

<Other optional ingredients>

In addition to the above [A] alkali-soluble resin, [B] quinonediazide compound, and [C] blocked isocyanate, the photosensitive resin composition may contain a surfactant, if necessary, insofar as the effect of the present invention is not impaired. Next, an optional component such as an auxiliary agent, a heat resistance improving agent, or a heat sensitive acid generator. These optional components may be used singly or in combination of two or more. For the details of these compounds, reference is made to the description of Paragraph No. 0201 to Paragraph No. 0224 of JP-A-2012-88459, the contents of which are incorporated herein by reference.

<Method for Preparing Photosensitive Resin Composition>

The components are mixed at a predetermined ratio and in an arbitrary manner, and then stirred and dissolved to prepare a photosensitive resin composition. For example, the solution may be prepared by dissolving the components in a solvent in advance to prepare a solution, and then mixing the solutions in a predetermined ratio to prepare a resin composition. The composition solution prepared as described above may be used after being filtered using a filter having a pore size of 0.2 μm or the like.

As the solvent used in the preparation of the photosensitive resin composition of the present invention, a solvent which uniformly dissolves an essential component and an optional component and does not react with each component can be used. The solvent is the same as the solvent exemplified as the solvent which can be used for producing the above-mentioned [A] alkali-soluble resin.

Among such solvents, from the viewpoints of solubility of each component, reactivity with each component, and ease of formation of a film, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol are mentioned. Alcohol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether , triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol 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) alkyl glycol monoalkyl ether; ethylene glycol monomethyl ether acetate , ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol single Ethyl acetate, diethylene glycol mono-n-propyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, acetic acid 3- Methoxybutyl ester, 3-methyl-3-methoxybutyl acetate, etc. (poly)alkylene glycol monoalkyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl Other ethers such as ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methyl pentyl) Ketones such as alkan-2-one), 4-hydroxy-4-methylhexan-2-one; propylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol Diacetate such as diacetate; alkyl lactate such as methyl lactate or ethyl lactate; Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, 3-methyl-3-methyl propionate Oxybutyl butyl ester, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, ethyl acetate Other esters such as ester, ethyl acetate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, ethyl 2-oxobutanoate; toluene, An aromatic hydrocarbon such as toluene; an amide such as N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide.

Among these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether B are preferable from the viewpoints of solubility, pigment dispersibility, and coatability. Acid ester, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone , 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -ethyl ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, Ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate. The solvent may be used singly or in combination of two or more.

Further, the above solvent may also be combined with benzyl ether, di-n-hexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl acetate, benzene. A high boiling point solvent such as ethyl formate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate or ethylene glycol monophenyl ether acetate is used in combination. These high boiling point solvents may be used singly or in combination of two or more.

The content of the solvent is not limited, and it is preferable that the total concentration of each component other than the solvent of the photosensitive resin composition becomes the viewpoint of the coating property and the stability of the photosensitive resin composition to be obtained. It is more preferable that the total concentration of each component other than the solvent of the photosensitive resin composition is 10 mass% to 40 mass%. When the photosensitive resin composition is prepared in a solution state, the solid content concentration (component other than the solvent in the composition solution) can be set to an arbitrary value depending on the purpose of use, the value of the desired film thickness, or the like. Concentration (for example, 5 mass% to 50 mass%). A more preferable solid content concentration differs depending on the method of forming the film on the substrate, and will be described later. The composition solution prepared in the above manner can be used after being filtered using a micropore filter having a pore diameter of about 0.5 μm or the like.

[Method for producing cured film]

Next, a method of producing the cured film of the present invention will be described.

The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).

(1) a step of applying the photosensitive resin composition of the present invention onto a substrate; (2) a step of removing a solvent from the applied photosensitive resin composition; and (3) removing a solvent by an actinic ray pair a step of exposing the photosensitive resin composition; (4) a step of developing the exposed photosensitive resin composition with an aqueous developing solution; and (5) a post-baking step of thermally curing the developed photosensitive resin composition.

Each step will be described in order below.

In the coating step of (1), it is preferred to apply the photosensitive resin composition of the present invention to a substrate to form a wet film containing a solvent. It is preferred to perform cleaning of the substrate such as alkali cleaning or plasma cleaning before applying the photosensitive resin composition onto the substrate, and it is more preferable to treat the surface of the substrate with hexamethyldiaziridine after the substrate is cleaned. By performing this treatment, there is a tendency that the adhesion of the photosensitive resin composition to the substrate is improved. The method of treating the surface of the substrate with hexamethyldioxane is not particularly limited, and examples thereof include a method of exposing the substrate to hexamethyldioxane vapor in advance.

Examples of the substrate include an inorganic substrate, a resin, a resin composite material, and the like.

Examples of the inorganic substrate include glass, quartz, anthrone, tantalum nitride, and a composite substrate obtained by vapor-depositing molybdenum, titanium, aluminum, copper, or the like on the substrate.

Examples of the resin include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, and polyfluorene. , polyether oxime, polyarylate, allyl diglycol carbonate, polyamine, polyimide, polyamidimide, polyether phthalimide, polybenzoxazole, polyphenyl sulphide Ether, polycycloolefin, norbornene resin, fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, fluorenone resin, ionic polymer resin, cyanate resin, crosslinked butene A substrate of a synthetic resin such as a diacid diester, a cyclic polyolefin, an aromatic ether, a maleimide-olefin, a cellulose, or an episulfide compound.

These substrates are used as they are in the above-described form. Generally, depending on the form of the final product, for example, a multilayer laminated structure such as a thin film transistor (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 cast coating method, a slit and a spin method can be used. And other methods. Further, a so-called prewet method as described in Japanese Laid-Open Patent Publication No. 2009-145395 can also be applied.

The wet film thickness at the time of coating is not particularly limited, and can be applied in a film thickness corresponding to the application, but is usually used in the range of 0.5 μm to 10 μm.

In the solvent removal step of (2), the solvent is removed from the applied film by pressure reduction (vacuum) and/or heating to form a dried coating film on the substrate. The heating condition of the solvent removal step is preferably from 70 ° C to 130 ° C for about 30 seconds to 300 seconds. When the temperature and time are in the above range, the adhesion of the pattern is further improved, and the residue tends to be further reduced.

In the exposure step of (3), the substrate on which the coating film is provided is irradiated with actinic rays through a mask having a predetermined pattern. In this step, the photoacid generator decomposes and produces an acid. The acid generated by the acid-decomposable gene contained in the coating component is hydrolyzed by a catalytic action to form a carboxyl group or a phenolic hydroxyl group.

As the exposure light source using the actinic ray, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generating device, or the like can be used, and can be preferably used. An actinic ray having a wavelength of 300 nm or more and 450 nm or less, such as g-ray (436 nm), i-ray (365 nm), and h-ray (405 nm). Further, the illumination light may be adjusted by a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter as needed.

As the exposure device, 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 the region where the acid catalyst is formed, in order to accelerate the hydrolysis reaction, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as "PEB") may be performed. The formation of a carboxyl group or a phenolic hydroxyl group derived from an acid-decomposable group can be promoted by PEB. The temperature at the time of 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, the acid-decomposable group in the present invention has a low activation energy due to acid decomposition, is easily decomposed by an acid derived from an acid generator generated by exposure, and generates a carboxyl group or a phenolic hydroxyl group, so that it is not necessary to carry out PEB. A positive image can be formed by development.

In the developing step of (4), a polymer having a free carboxyl group or a phenolic hydroxyl group is developed using an alkaline developing solution. The exposed portion region containing the resin composition having a carboxyl group or a phenolic hydroxyl group which is easily dissolved in the alkaline developing solution is removed, whereby a positive image is formed.

It is preferred that the developer used in the developing step contains a basic compound. As the basic compound, for example, an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide; an alkali metal carbonate such as sodium carbonate or potassium carbonate; or an alkali metal such as sodium bicarbonate or potassium bicarbonate can be used. Bicarbonate; ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or choline hydroxide; aqueous solution of sodium citrate or sodium metasilicate. Further, 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 aqueous solution of the above-mentioned alkali may be used as the developing solution.

Preferred examples of the developer include a 0.4% aqueous solution of tetraethylammonium hydroxide, a 0.5% aqueous solution, a 0.7% aqueous solution, and a 2.38% aqueous solution.

The pH of the developer is preferably from 10.0 to 14.0.

The development time is preferably from 30 seconds to 500 seconds, and the development method may be any one of a puddle development method and a dipping method. After development, it is usually possible to carry out running water cleaning for 30 seconds to 300 seconds to form a desired pattern.

After the development, a rinsing step can also be performed. In the elution step, the developed substrate is washed with pure water or the like, whereby the adhered developer is removed, and the development residue is removed. A known method can be used for the rinsing method. For example, spray rinsing, immersion rinsing, etc. are mentioned.

In the post-baking step of (5), by heating the obtained positive image, the acid-decomposable group can be thermally decomposed to form a carboxyl group or a phenolic hydroxyl group, and a crosslinkable group, a crosslinking agent, etc. Crosslinking is carried out to thereby form a cured film. The heating is preferably performed by using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 ° C to 250 ° C. Next, for a predetermined period of time, for example, if it is a hot plate, heat treatment is performed for 5 minutes to 90 minutes, and if it is an oven, heat treatment is performed for 30 minutes to 120 minutes. By carrying out such a crosslinking reaction, a protective film or an interlayer insulating film which is more excellent in heat resistance and hardness can be formed. Further, when the heat treatment is performed, it can also be carried out under a nitrogen atmosphere, thereby further improving the transparency.

It is also possible to perform post-baking after the post-baking and baking at a relatively low temperature (addition of the intermediate baking step). When the intermediate baking is performed, it is preferably heated at 90 ° C to 150 ° C for 1 minute to 60 minutes, and then post-baked at a high temperature of 200 ° C or higher. Further, the intermediate baking and the post-baking may be divided into three or more stages to perform heating. With this intermediate baking and post-baking design, the taper angle of the pattern can be adjusted. A known heating method such as a hot plate, an oven, or an infrared heater can be used for the heating.

Furthermore, the patterned substrate can be fully re-exposed (post-exposure) with actinic radiation before post-baking, and then post-baked, thereby being present in the photoacid generator present in the unexposed portion. The acid is generated and functions as a catalyst for promoting the crosslinking step, thereby promoting the hardening reaction of the film. The preferred exposure amount in the case of including the post-exposure step is preferably 100 mJ/cm ² to 3,000 mJ/cm ² , particularly preferably 100 mJ/cm ² to 500 mJ/cm ² .

Further, the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist. When a cured film obtained by thermally hardening by a post-baking step is used as a dry etching resist, a dry etching treatment such as ashing, plasma etching, or ozone etching may be performed as an etching treatment.

[hardened 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. Further, the cured film of the present invention is preferably a cured film obtained by the method for forming a cured film of the present invention.

According to the photosensitive resin composition of the present invention, an interlayer insulating film which is excellent in insulation and has high transparency even when baked at a high temperature can be obtained. The interlayer insulating film obtained by using the photosensitive resin composition of the present invention has high transparency and is excellent in physical properties of a cured film, and thus is useful for use in an organic EL display device or a liquid crystal display device. For details of the organic EL display device and the liquid crystal display device, reference may be made to paragraphs 0209 to 10210 of the Japanese Patent Laid-Open No. 2011-209681, and the descriptions of FIG. 1 and FIG. 2, the contents of which can be incorporated into the present application. In the manual.

Example

Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the 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]

To the flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were added. Then, 16 parts by mass of methacrylic acid as the compound (A1), 40 parts by mass of glycidyl methacrylate as the compound (A2), 10 parts by mass of styrene as the compound (A4), and tricyclic methacrylate [ 5.2.1.0 ^2,6 ] 14 parts by mass of decane-8-yl ester and 20 parts by mass of 2-methylcyclohexyl acrylate, and replaced with nitrogen, and then slowly stirred the solution to raise the temperature of the solution to 70. At ° C, the temperature was maintained for 4 hours to carry out polymerization, whereby a solution containing the copolymer (A-1) was obtained. The solid content concentration of the obtained polymer solution was 34.4%, the Mw of the copolymer (A-1) was 8,000, and the molecular weight distribution (Mw/Mn) was 2.3.

[Synthesis Example 2]

To the flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were added. Then, 13 parts by mass of methacrylic acid as the compound (A1), 40 parts by mass of glycidyl methacrylate as the compound (A2), and 10 parts by mass of α-methyl-p-hydroxystyrene as the compound (A3) were added. And 10 parts by mass of styrene as the compound (A4), 12 parts by mass of tetrahydrofurfuryl methacrylate, 15 parts by mass of N-cyclohexylmethyleneimine, and 10 parts by mass of n-lauryl methacrylate. After the nitrogen gas was replaced, the temperature of the solution was gradually increased to 70 ° C while stirring, and the temperature was maintained for 5 hours to carry out polymerization, whereby a solution containing the copolymer (A-2) was obtained. The solid content concentration of the obtained polymer solution was 31.9%, the Mw of the copolymer (A-2) was 8,000, and the molecular weight distribution (Mw/Mn) was 2.3.

<[B] quinone diazide compound>

B-1: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol Condensate of (1.0 mol) with 1,2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol) B-2: 1,1,1-tris(p-hydroxyphenyl)ethane and 1 a condensate of 2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol)

<[C] blocked isocyanate compound>

C-1: Duranate 17B-60P (made by Asahi Kasei Chemicals)

C-2: Duranate 17B-60PX (made by Asahi Kasei Chemicals)

C-3: Duranate TPA-B80E (made by Asahi Kasei Chemicals)

C-4: Duranate MF-B60X (made by Asahi Kasei Chemicals)

C-5: Desmodur BL3175 (manufactured by Sumika Bayer Urethane)

C-6: Desmodur BL3272 MPA (manufactured by Sumika Bayer Urethane)

C-7: Desmodur BL3475 BA/SN (manufactured by Sumika Bayer Urethane)

C-8: Desmodur BL5375 MPA/SN (manufactured by Sumika Bayer Urethane)

<Preparation of each composition>

The components shown in the following table were mixed, and diethylene glycol ethyl methyl ether as a solvent was added so that the solid content concentration became 30% by mass, and then filtered using a membrane filter having a pore size of 0.2 μm. This prepared each photosensitive resin composition. Furthermore, the "-" in the column indicates that the matching component is not used.

<evaluation>

The prepared photosensitive resin composition was subjected to the following evaluation. The results are shown in the following table.

[Save stability]

The obtained photosensitive resin composition was allowed to stand in an oven at 40 ° C for one week, and the viscosity before and after the temperature increase was measured, and the viscosity change rate (%) was determined. In this case, the viscosity change rate is set as the storage stability, and when the viscosity change rate is 5% or less, it is judged. In order to maintain good stability, it was judged that the storage stability was poor when the viscosity change rate exceeded 5%. The viscosity was measured at 25 ° C using an E-type viscometer (VISCONIC ELD.R, Toki Sangyo Co., Ltd.).

[Sensitivity]

Any one of the photosensitive resin compositions prepared in the examples and the comparative examples was applied onto a ruthenium substrate by a spinner, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a film thickness of 3.0 μm. Coating film. 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. Then, a developing solution containing a 2.38 mass% aqueous solution of tetramethylammonium hydroxide was used, and development treatment was carried out at 25 ° C for 60 seconds, followed by running water washing with ultrapure water for 1 minute. At this time, the minimum ultraviolet irradiation amount which can form the line-space pattern of the width of 10 micrometer was measured. When the value is less than 850 J/m ² , it is judged that the sensitivity is good.

[solvent resistance]

Any one of the photosensitive resin compositions prepared in the examples and the comparative examples was applied onto a ruthenium substrate by a spinner, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a film thickness of 3.0 μm. Coating film. The obtained coating film was irradiated with ultraviolet rays by a mercury lamp so that the cumulative irradiation amount became 3,000 J/m ² . Then, with respect to Examples 1 to 13 and Comparative Examples 1 to 2, the tantalum substrate was heated at 150 ° C for 30 minutes on a hot plate. For Comparative Example 3 and Comparative Example 4, the tantalum substrate was heated at 150 ° C for 60 minutes. The film thickness (T1) of the obtained cured film was measured. Further, the tantalum substrate on which the cured film was formed was immersed in dimethyl sulfoxide having a temperature of 70 ° C for 20 minutes, and then the film thickness (t1) of the cured film was measured, and the film thickness change rate was calculated according to the following formula. And use it as solvent resistance.

Film thickness change rate = {(t1-T1)/T1} × 100 (%)

When the absolute value of this value is less than 5%, it is judged that it is excellent in solvent resistance.

[display unevenness]

(Evaluation of display unevenness in the display device)

A liquid crystal display device using a thin film transistor (TFT) was produced by the following method. In the active matrix liquid crystal display device described in FIG. 1 and FIG. 2 of the Japanese Patent No. 3321003, the cured film 17 is formed as an interlayer insulating film in the following manner to obtain a liquid crystal display device.

That is, the bottom gate type TFT 1 is formed on the glass substrate 6, and the insulating film 3 containing Si ₃ N ₄ is formed in a state of covering the TFT 1. Then, after a contact hole is formed in the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 is formed on the insulating film 3 via the contact hole.

Further, in order to planarize the unevenness caused by the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness caused by the wiring 2 is buried. The formation of the planarizing film 4 on the insulating film 3 was performed by spin-coating each of the photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 8 onto a substrate, and pre-baking on a hot plate. After (90 ° C × 2 minutes), i-rays (365 nm) irradiated with 1000 mJ/cm ² (illuminance: 20 mW/cm ² ) were irradiated from the mask using a high-pressure mercury lamp, and then developed with an alkaline aqueous solution to form a pattern. Heat treatment was carried out at 230 ° C for 60 minutes. The coating property when the photosensitive resin composition was applied was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development, and firing. Further, the average step of the wiring 2 was 500 nm, and the thickness of the produced planarizing film 4 was 2,000 nm.

A driving voltage was applied to the obtained liquid crystal display device to visually observe the gray display when the gray test signal was input, and the presence or absence of display unevenness was evaluated based on the following evaluation criteria. 0~2 is a practical level.

0: No unevenness at all (very good)

1: The unevenness was slightly observed at the edge portion of the glass substrate, but the display portion had no problem (good).

2: Slightly see unevenness in the display section, but it is practical (normal)

3: There is unevenness in the display section (slightly worse)

4: There is strong unevenness in the display section (very bad)

As is clear from the above results, the composition of the present invention is excellent in storage stability, high in sensitivity, excellent in solvent resistance, and extremely low in display unevenness. On the other hand, the display unevenness of the composition of the comparative example was unsatisfactory.

Claims (7)

A photosensitive resin composition comprising: [A] at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and (A2) an epoxy group-containing unsaturated group An alkali-soluble resin obtained by copolymerizing a compound; [B] a quinonediazide compound; and a [C] blocked isocyanate compound, wherein the blocked isocyanate is 0.1 by mass based on the total solid content of the photosensitive resin composition The range of % to 10% by mass, and the blocked isocyanate is a compound represented by the following formula (1): (In the formula (1), R represents an organic group having 1 to 20 carbon atoms, respectively). The photosensitive resin composition according to the first aspect of the invention, wherein R of the formula (1) is a hydrocarbon group having 3 to 9 carbon atoms. A method for forming a cured film, comprising: (1) a photosensitive resin group according to claim 1 or 2 a step of applying a product onto a substrate; (2) a step of removing a solvent from the applied photosensitive resin composition; and (3) performing, by using actinic rays, the photosensitive resin composition from which the solvent is removed. a step of exposing; (4) a step of developing the exposed photosensitive resin composition with an aqueous developing solution; and (5) a post-baking step of thermally curing the developed photosensitive resin composition. A cured film formed by a method of forming a cured film according to claim 3 of the patent application. The cured film according to claim 4, which is an interlayer insulating film. An organic electroluminescence display device comprising the cured film according to item 4 of the patent application. A liquid crystal display device comprising the cured film according to item 4 of the patent application.