TW201800838A - Positive photosensitive resin composition and uses thereof - Google Patents

Abstract

The invention relates to a positive photosensitive resin composition and an overcoat produced therefrom. The overcoat is for forming a planarization film of a TFT substrate in a liquid crystal display element or organic light-emitting display device, an interlayer insulating film or an overcoat of a core material or a protective material in a waveguide, and has good insulation. The positive photosensitive resin composition comprises an alkali-soluble resin (A), an ortho-naphthoquinone diazide sulfonic acid ester (B), a compound (C) selected from the group consisting of a thermal acid generator and a thermal bas generator, a cyclic siloxane compound (D) and a solvent (E).

Description

Positive photosensitive resin composition and application thereof

The present invention relates to a positive-type positive photosensitive resin product which is applied to a flattening film for a TFT substrate, an interlayer insulating film, or a core material or a cladding material of an optical waveguide, such as a liquid crystal display device or an organic EL display device. And a protective film formed therefrom and an element having the protective film. Among them, in particular, a positive photosensitive resin composition for a protective film which is excellent in insulation after exposure and development is provided.

In recent years, in the field of liquid crystal displays, organic electroluminescent devices, and the like, in order to improve the resolution and resolution, it is generally achieved by increasing the aperture ratio of the display device (as disclosed in Japanese Patent No. 2933879). A method in which the pixel electrode and the data line are overlapped by forming a protective film on the transparent TFT substrate flattening film is a method of increasing the aperture ratio as compared with the prior art.

The material of the flattening film for a TFT substrate must have high heat resistance, high transparency, and low electric conductivity. Therefore, a combination of a quinonediazide compound and a phenol resin is generally used in the industry (as disclosed in Japanese Laid-Open Patent Publication No. 7-98502). Or a combination of a quinone diazide compound and an acrylic resin (as disclosed in Japanese Laid-Open Patent Publication No. Hei 10-153854 and No. 2001-281853), however, the heat resistance of the aforementioned materials is not satisfactory, and further, when the substrate is subjected to At the time of high temperature treatment, yellowing of the cured film also causes a problem of low transparency.

Although various positive photosensitive resin compositions for producing protective films have been proposed for the aforementioned desired characteristics, the insulating requirements of such materials have not been accepted by the industry.

For the sake of the job, the industry still needs to develop a positive-type photosensitive resin composition with good insulation properties, which is the development of liquid crystal display elements and organic display elements.

The present invention provides a positive photosensitive resin composition having excellent insulating properties by using a component which provides a specific cyclic siloxane compound.

Accordingly, the present invention provides a positive photosensitive resin composition comprising: an alkali-soluble resin (A); o-naphthoquinonediazide sulfonate (B); and a compound (C) selected from a thermal acid generator And a group consisting of a thermal base generator; a cyclic siloxane compound (D) having the structure represented by the formula (1); and a solvent (E);

In the formula (1): R ¹⁹ and R ^{20 each} represent a monovalent group or an alkyl group having an alicyclic epoxy group, wherein at least one of the t R ¹⁹ and the t R ²⁰ is at least one of system having an alicyclic epoxy group (alicyclic epoxy group) one monovalent group; and t represents an integer of 3; wherein the R ¹⁹ and R ²⁰ may be the same or different, R ¹⁹ and the plurality of the plurality of R ²⁰ may be the same or different.

The present invention also provides a method of forming a film on a substrate comprising applying the positive photosensitive resin composition described above to the substrate.

The invention further provides a film on a substrate produced by the method described above.

The invention further provides a device comprising the aforementioned film.

The present invention provides a positive photosensitive resin composition comprising: an alkali-soluble resin (A); o-naphthoquinonediazide sulfonate (B); and a compound (C) selected from a thermal acid generator and heat a group consisting of an alkali generating agent; a cyclic oxoxane compound (D) having the structure represented by the formula (1); and a solvent (E);

In the formula (1): R ¹⁹ and R ^{20 each} represent a monovalent group or an alkyl group having an alicyclic epoxy group, wherein at least one of the t R ¹⁹ and the t R ²⁰ is at least one of Is a monovalent group having an alicyclic epoxy group; and t represents an integer of 3 or more; wherein, R ¹⁹ and R ²⁰ may be the same or different, and the plurality of R ¹⁹ and the plural two R ²⁰ may be the same or different.

The respective components used in the positive photosensitive resin composition of the present invention will be described in detail below.

The alkali-soluble resin (A) of the present invention means a resin which is soluble in an aqueous alkaline solution, and the structure thereof is not particularly limited. Preferably, the alkali-soluble resin (A) may have a carboxyl group An acid-based resin or a phenol-novolac resin or the like. More preferably, the alkali-soluble resin (A) can be obtained by copolymerization of a mixture in the presence of a suitable polymerization initiator.

The mixture may comprise an unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1), an epoxy group-containing unsaturated compound (a2) and/or other unsaturated compound (a3).

The unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1) may be a compound containing a carboxylic acid group or a carboxylic acid anhydride structure, and an unsaturated bond for polymerizing the bond. The structure of the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1) is not particularly limited, and the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1) may include, but is not limited to, an unsaturated monocarboxylic acid compound, and is unsaturated. a dicarboxylic acid compound, an unsaturated acid anhydride compound, a polycyclic unsaturated carboxylic acid compound, a polycyclic unsaturated dicarboxylic acid compound or a polycyclic unsaturated acid anhydride compound.

Specific examples of the aforementioned unsaturated monocarboxylic acid compound may include, but are not limited to, (meth)acrylic acid, crotonic acid, α -chloroacrylic acid, ethacrylic acid, cinnamic acid, 2-(methyl)acrylic acid ethoxylated butyl Acid ester [2-(meth)acryloyloxyethyl succinate monoester], 2-(meth)acryloyl ethoxyethoxy hexahydrophthalate, 2-(methyl) propylene ethoxylate or omega a carboxypolycaprolactone polyol monoacrylate (which may be a product manufactured by East Asia Synthetic Co., Ltd., model number ARONIX M-5300) or the like.

Specific examples of the aforementioned unsaturated dicarboxylic acid compound may include, but are not limited to, maleic acid, fumaric acid, methyl fumaric acid, itaconic acid or citraconic acid, and the like.

The aforementioned unsaturated acid anhydride compound may be an acid anhydride compound of the unsaturated dicarboxylic acid compound.

Specific examples of the polycyclic unsaturated carboxylic acid compound may include, but are not limited to, 5-carboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2- Alkene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene or 5-carboxy-6-ethyl Bicyclo [2.2.1] hept-2-ene.

Specific examples of the polycyclic unsaturated dicarboxylic acid compound may include, but are not limited to To 5,6-dicarboxylic acid bicyclo[2.2.1]hept-2-ene.

The polycyclic unsaturated acid anhydride compound may be an acid anhydride compound of the polycyclic unsaturated dicarboxylic acid compound.

The above unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1) may be used singly or in combination of plural kinds.

Preferably, the specific example of the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1) may be acrylic acid, methacrylic acid, maleic anhydride, 2-methylpropenyl ethoxy succinate or 2-methyl Acryl decyl ethoxy hexahydrophthalic acid.

The unsaturated carboxylic acid is used in an amount of 100 parts by weight based on the total amount of the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1), and the unsaturated compound (a2) having an epoxy group described later and the other unsaturated compound (a3). The unsaturated carboxylic anhydride compound (a1) may be used in an amount of 10 parts by weight to 30 parts by weight, preferably 10 parts by weight to 25 parts by weight, and more preferably 15 parts by weight to 25 parts by weight.

The epoxy group-containing unsaturated compound (a2) may include a (meth) acrylate compound having an epoxy group, an α -alkyl acrylate compound having an epoxy group, a glycidyl ether compound, or the like.

Specifically, the epoxy group-containing (meth) acrylate compound may include, but is not limited to, glycidyl (meth) acrylate, 2-methyl propyl propyl (meth) acrylate, and (meth) acrylate 3 , 4-epoxybutyl acrylate, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate or 3,4-epoxycyclohexyl (meth)acrylate Methyl ester, etc.

Specific examples of the above-mentioned epoxy group-containing α -alkyl acrylate compound may include, but are not limited to, α -ethyl acrylate propyl acrylate, α -n-propyl propylene acrylate, α -n-butyl acrylate epoxy Propyl ester or α -ethyl acrylate 6,7-epoxyheptyl ester and the like.

Specific examples of the aforementioned glycidyl ether compound may include, but are not limited to, o-vinylbenzylglycidylether, m-vinylbenzylglycidylether or p- Vinyl benzyl methyl epoxide (p- Vinylbenzylglycidylether) and so on.

The above epoxy group-containing unsaturated compound (a2) may be used singly or in combination of plural kinds.

Preferably, the specific example of the epoxy group-containing unsaturated compound (a2) may be glycidyl methacrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, or methacrylic acid 6, 7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether or p-vinylbenzyl glycidyl ether.

Based on the total amount of the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1) and the epoxy group-containing unsaturated compound (a2), and other unsaturated compound (a3), which is 100 parts by weight, the epoxy group The ethylenically unsaturated compound (a2) may be used in an amount of from 25 parts by weight to 45 parts by weight, preferably from 25 parts by weight to 40 parts by weight, and more preferably from 30 parts by weight to 40 parts by weight.

The other unsaturated compound (a3) may be an alkyl (meth)acrylate, an alicyclic (meth)acrylate, an aryl (meth)acrylate, an unsaturated dicarboxylic acid diester, (methyl) a hydroxyalkyl acrylate, a polyether of (meth) acrylate, an aromatic vinyl compound, or other unsaturated compound other than the foregoing compounds.

Specific examples of the aforementioned alkyl (meth)acrylate may include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. , n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate or tertiary butyl (meth)acrylate.

Specific examples of the aforementioned (meth)acrylic alicyclic ester may include, but are not limited to, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, and tricyclo [5.2.1.02, 6]癸-8-yl (meth) acrylate [may also be referred to as dicyclopentyl (meth) acrylate], dicyclopentyloxy (meth) acrylate, isobornyl (meth) acrylate or ( Methyl)tetrahydrofuran acrylate or the like.

Specific examples of the aforementioned aryl (meth)acrylate may include, but are not limited to, (A) Base) phenyl acrylate or benzyl methacrylate, and the like.

Specific examples of the unsaturated dicarboxylic acid diester may include, but are not limited to, diethyl maleate, diethyl fumarate or diethyl itaconate.

Specific examples of the aforementioned hydroxyalkyl (meth)acrylate may include, but are not limited to, 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate.

Specific examples of the polyether of the (meth) acrylate may include, but are not limited to, polyethylene glycol mono(meth)acrylate or polypropylene glycol mono(meth)acrylate.

Specific examples of the above aromatic vinyl compound may include, but are not limited to, styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene or p-methoxystyrene.

Specific examples of the unsaturated compound other than the above compound may include, but are not limited to, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl ethyl ester, 1,3- Butadiene, isoprene, 2,3-dimethyl1,3-butadiene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmalay Yttrium, N-butylenediamine-3-maleimide benzoate, N-butylenediamine-4-maleimine butyrate, N-butane Imino-6-maleimide caproate, N-butylenediamine-3-maleimide propionate or N-(9-acridinyl)maleimide .

The other unsaturated compound may be used alone or in combination of plural kinds.

Specific examples of the other unsaturated compound (a3) may preferably be methyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, or tertiary (meth)acrylate. Ester, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, styrene or p-methoxystyrene.

Based on the aforementioned unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1) and the epoxy group-containing unsaturated compound (a2), and the other unsaturated compound (a3) are used in an amount of 100 parts by weight, the other unsaturated The compound (a3) can be used in an amount of 25 parts by weight to 65 parts by weight, preferably 35 parts by weight to 65 parts by weight, and more preferably 35 parts by weight to 55 parts by weight.

The solvent used in the production of the alkali-soluble resin (A) of the present invention may be an alcohol, an ether, a glycol ether, an ethylene glycol alkyl ether acetate acetate, a diethylene glycol, a dipropylene glycol, or a propylene glycol monoalkyl group. Ether, propylene glycol alkyl ether acetate acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbons, ketones or esters, and the like.

Specific examples of the alcohol solvent may include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol or 3-phenyl-1-propanol.

Specific examples of the ether solvent may include tetrahydrofuran or the like.

Specific examples of the aforementioned glycol ether may include ethylene glycol monopropyl ether, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether.

Specific examples of the ethylene glycol alkyl ether acetate may include ethylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate or ethylene glycol methyl ether acetate.

Specific examples of the diethylene glycol may include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether or diethyl Glycol methyl ether and the like.

Specific examples of the dipropylene glycol may include dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether or dipropylene glycol methyl ethyl ether.

Specific examples of the propylene glycol monoalkyl ether may include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether.

Specific examples of the propylene glycol alkyl ether acetate may include propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, or propylene glycol butyl ether acetate.

Specific examples of the propylene glycol alkyl ether propionate may include propylene glycol methyl ether propionate, propylene glycol diethyl ether propionate, propylene glycol propyl ether propionate or propylene glycol butyl ether propionate.

Specific examples of the above aromatic hydrocarbons may include toluene or xylene.

Specific examples of the ketones may include methyl ethyl ketone, cyclohexanone or diacetone alcohol.

Specific examples of the above esters may include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2. -ethyl methacrylate, methyl glycolate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate , 3-propylpropionic acid propyl ester, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate Ethyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, Butyl propoxyacetate, methyl butoxyacetate, ethyl butoxylate, propyl butoxyacetate, butyl butoxyacetate, 3-methoxybutyl acetate, 2-methoxy Methyl propyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxy Ethyl propyl propionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, Methyl 2-butoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, Propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate or Butyl 3-butoxypropionate and the like.

The solvent may be used alone or in combination of plural kinds.

Preferably, a specific example of the solvent may be diethylene glycol dimethyl ether or propylene glycol methyl ether acetate.

Specific examples of the polymerization initiator may be an azo compound, a peroxide or the like.

Specific examples of the azo compound may include, but are not limited to, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-even Nitrogen bis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 4,4'-azobis(4-cyano) Valeric acid) or 2,2'-azobis(dimethyl-2-methylpropionate) or the like.

Specific examples of the peroxide may include, but are not limited to, dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxypivalate, 1, 1- Di(tert-butylperoxycyclohexane) or hydrogen peroxide.

The polymerization initiator may be used singly or in combination of plural kinds.

The o-naphthoquinonediazide sulfonate (B) of the present invention contains o-naphthoquinonediazidesulfonate (B-1) having a structure represented by the following formula (2). Next, the o-naphthoquinonediazide sulfonate (B) may optionally contain other o-naphthoquinonediazide sulfonate (B-2).

The o-naphthoquinonediazide sulfonate (B-1) has a structure represented by the following formula (2):

In the formula (2), R ₁ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aromatic group or an alkenyl group. R ₂ each independently represents a hydrogen atom or a functional group having a quinonediazide structure. a, b, d, and e represent integers greater than or equal to 0, respectively, and the sum of f and g is an integer greater than or equal to one. When the sum of a, b, d and e is greater than 1, the plurality of R ₁ may be the same or different respectively; when the sum of f and g is greater than 1, at least one of the plurality of R ₂ has a quinonediazide structure. Functional group.

The o-naphthoquinonediazide sulfonate (B-1) having the structure represented by the formula (2) can be synthesized by using a hydrazine compound having a hydroxyl group, or by an anthrone with a phenol, a catechol or an orthobenzene. Trisphenol is obtained by reacting in the presence of thioacetic acid and acidic coal.

The o-naphthoquinonediazide sulfonate (B-1) having the structure represented by the formula (2) is an esterified product which may be completely esterified or partially esterified, preferably an o-naphthoquinonediazide The sulfonic acid or a salt thereof is obtained by reacting a hydrazine compound having a hydroxyl group, and more preferably, it is obtained by reacting o-naphthoquinonediazidesulfonic acid or a salt thereof with a hydrazine compound having a polyhydric hydroxyl group.

Specific examples of the oxime compound having a hydroxyl group may include a product manufactured by JFE Chemical Co., Ltd., and its model is BPF (shown by the following formula (I-1)) or BCF (shown by the following formula (I-2)); A product manufactured by Chemical Co., Ltd., and its model is BisP-FL (shown by the following formula (I-1)); or a compound represented by the following formula (I-3) to formula (I-5):

The o-naphthoquinonediazidesulfonic acid may include, but is not limited to, o-naphthoquinonediazide-4-sulfonic acid, o-naphthoquinonediazide-5-sulfonic acid or o-naphthoquinonediazide-6-sulfonic acid, etc. . The salt of the o-naphthoquinonediazidesulfonic acid may include, but is not limited to, an o-naphthoquinonediazidesulfonic acid halide salt, and specific examples may include an o-naphthoquinone diazide-4-sulfonic acid chloride or an o-naphthoquinone Nitrogen-5-sulfonic acid chloride.

There is no special limit on the amount of the o-naphthoquinone diazide sulfonate (B-1). The amount of the o-naphthoquinonediazide sulfonate (B-1) having the structure represented by the formula (2) is 5 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). 50 parts by weight, preferably 7 parts by weight to 45 parts by weight, and more preferably 10 parts by weight to 40 parts by weight.

When the o-naphthoquinonediazide sulfonate (B-1) having the structure represented by the formula (2) is used, the insulating property of the positive-type photosensitive resin composition can be further improved.

The o-naphthoquinonediazide sulfonate (B) may optionally have other o-naphthoquinonediazide sulfonate (B-2).

In one embodiment of the invention, the o-naphthoquinonediazide sulfonate (B-2) is an esterified ester which may be fully esterified or partially esterified. The o-naphthoquinonediazide sulfonate (B-2) is preferably prepared by reacting o-naphthoquinonediazidesulfonic acid or a salt thereof with a hydroxy compound, more preferably o-naphthoquinonediazide It is obtained by reacting an acid or a salt thereof with a polyvalent hydroxy compound.

The o-naphthoquinonediazidesulfonic acid may include, but is not limited to, o-naphthoquinonediazide-4-sulfonic acid, o-naphthoquinonediazide-5-sulfonic acid or o-naphthoquinonediazide-6-sulfonic acid, etc. . The salt of o-naphthoquinonediazidesulfonic acid may include, but is not limited to, an o-naphthoquinonediazidesulfonic acid halide salt.

The hydroxy compound may include, but is not limited to, a hydroxybenzophenone compound, a hydroxyaryl compound, a (hydroxyphenyl) hydrocarbon compound, or other aromatic hydroxy compound. The hydroxy compound may be used singly or in combination of plural kinds.

The aforementioned hydroxybenzophenone compound may include, but is not limited to, 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxy Benzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,4,2',4'-tetrahydroxybenzophenone, 2,4,6,3',4'-five Hydroxybenzophenone, 2,3,4,2',4'-pentahydroxybenzophenone, 2,3,4,2',5'-pentahydroxybenzophenone, 2,4,5, 3',5'-pentahydroxybenzophenone or 2,3,4,3',4',5'-hexahydroxybenzophenone and the like.

The aforementioned hydroxyaryl compound may have a structure represented by the following formula (II-1):

In the formula (II-1), Z ₁ to Z ₃ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and Z ₄ to Z ₉ represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, An alkoxy having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or a cycloalkyl group; Z ₁₀ and Z ₁₁ representing a hydrogen atom, a halogen atom and a carbon number An alkyl group of 1 to 6; j, k and m represent an integer of 1 to 3; h represents 0 or 1.

The hydroxyaryl compound represented by the formula (II-1) may include, but is not limited to, tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyl Phenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenyl Methane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, Bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane , bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2,4-di Hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxyphenyl)-3-methoxy-4-hydroxyl Phenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3- Cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl- 4-hydroxy-6-A Phenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6- Methylphenyl)-3,4-dihydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl) -4-hydroxyl Phenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-2-hydroxyphenylmethane , bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-3,4- Dihydroxyphenylmethane, 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene, 1-[1-(3 -Methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4-hydroxyphenyl)ethyl]benzene or 4,4'-[1-[4 [-1-(4-Hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol.

The aforementioned (hydroxyphenyl) hydrocarbon compound may have a structure represented by the following formula (II-2):

In the formula (II-2), Z ₁₂ and Z ₁₃ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and p and q represent an integer of 1 to 3.

The (hydroxyphenyl) hydrocarbon compound represented by the formula (II-2) may include, but is not limited to, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'- Trihydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(4) '-Hydroxyphenyl)propane, bis(2,3,4-trihydroxyphenyl)methane or bis(2,4-dihydroxyphenyl)methane.

The other aromatic hydroxy compounds described above may include, but are not limited to, phenol, p-methoxyphenol, dimethyl phenol, hydroquinone, bisphenol A, naphthol, catechol, 1,2,3- Pyrogallol methyl ether, 1,2,3-benzenetriol-1,3-dimethyl ether, 3,4,5-trihydroxybenzoic acid, or partially esterified or partially etherified 3,4 , 5-trihydroxybenzoic acid, and the like.

The above hydroxy compound is preferably selected from the group consisting of 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene, 2,3. , 4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone or any combination of the above.

The reaction of the o-naphthoquinonediazidesulfonic acid or a salt thereof with a hydroxy compound is usually carried out in dioxane, N-pyrrolidone or acetamide. It is carried out in an organic solvent such as (acetamide). More preferably, the above reaction is carried out by adding an alkali condensing agent such as triethanolamine, an alkali metal carbonate or an alkali metal hydrogencarbonate.

The degree of esterification of the ortho-naphthoquinonediazide sulfonate (B) is preferably at least 50%, that is, the total amount of hydroxyl groups in the hydroxy compound is 100 mole percent, and the hydroxy compound has 50 moles. More than a percentage of the hydroxyl groups are esterified with o-naphthoquinonediazidesulfonic acid or a salt thereof. The degree of esterification of the o-naphthoquinonediazide sulfonate (B) is more preferably 60% or more.

The o-naphthoquinonediazide sulfonate (B) may be used in an amount of 5 parts by weight to 60 parts by weight, preferably 7 parts by weight to 55 parts, based on 100 parts by weight of the alkali-soluble resin (A). Parts by weight, and more preferably 10 parts by weight to 50 parts by weight.

The compound (C) according to the present invention is selected from the group consisting of a thermal acid generator and a thermal base generator, and the above thermal acid generator or thermal base generator may be used singly or in combination of two or more.

The thermal acid generator according to the present invention comprises an ionic thermal acid generator and a nonionic thermal acid generator.

The ionic thermal acid generator preferably does not contain heavy metals or halogen ions.

Specific examples of the ionic thermal acid generator are sulfonium salts such as triphenylsulfonium, 1-dimethylthionaphthalene, 1-dimethylthio-4-hydroxynaphthalene, and 1-dimethylthio-4,7. -dihydroxynaphthalene, 4-hydroxyphenyldimethylhydrazine, benzyl-4-hydroxyphenylmethylhydrazine, 2-methylbenzyl-4-hydroxyphenylmethylhydrazine, 2-methylbenzyl- Methanesulfonate, trifluoromethanesulfonic acid, camphorsulfonic acid, p-toluenesulfonic acid, 4-ethylmercaptophenylmethylhydrazine, 2-methylbenzyl-4-benzylidylphenylmethylhydrazine , hexafluorophosphonate, commercially available benzyl sulfonium salts such as SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, SI-100L, SI-110L , SI-145L, SI-150L, SI-160L, SI-180L (all manufactured by Sanxin Chemical Industry Co., Ltd.).

The nonionic thermal acid generator is, for example, a halogen-containing compound, a diazomethane compound, a hydrazine compound, a sulfonate compound, a carboxylic acid ester compound, a phosphate compound, a sulfonimide compound, a sulfonated benzotriazole compound, or the like. .

The halogen-containing compound such as a halogenated hydrocarbon compound, a halogenated heterocyclic compound, and the like are preferably 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane. Alkyl, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-naphthyl-4,6-bis(trichloromethyl)-s-triazine.

The diazomethane compound such as bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-tolyl) Diazomethane, bis(2,4-dimethylsulfonyl)diazomethane, bis(p-chlorophenyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonium (1,1-dimethylethylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, phenylsulfonyl (benzhydryl)diazomethane .

The hydrazine compound such as a β-ketoxime compound, a β-sulfonyl compound, a diaryl sulfonium compound or the like; preferably 4-trityl hydrazine methyl hydrazine, trimethylphenyl benzhydryl methyl hydrazine, bis (benzene) Methanesulfonyl)methane, 4-chlorophenyl-4-methylphenylhydrazine.

The sulfonate compound, such as an alkyl sulfonate, a haloalkyl sulfonate, an aryl sulfonate, an imide sulfonate; preferably a benzoin tosylate, pyrogallol Mesylate, nitrobenzyl-9,10-diethoxyindole-2-sulfonate, sodium 2,6-dinitrobenzenesulfonate and commercially available imidosulfonates such as PAI- 101, PAI-106 (manufactured by Green Chemical Co., Ltd.), CGI-1311 (manufactured by Ciba Specialty Chemicals Co., Ltd.).

The carboxylic acid ester compound is o-nitrobenzyl carboxylic acid ester and the like.

The sulfonimide compound such as N-(trifluoromethylsulfonyloxy) succinimide (trade name: SI-105, manufactured by Green Chemical Co., Ltd.), N-(camphorsulfonyloxy) succinimide (trade name: SI-106, manufactured by Green Chemical Co., Ltd.), N-(4-methylbenzenesulfonyloxy) amber ylide (trade name: SI-101, manufactured by Green Chemical Co., Ltd.), N-(2- Trifluoromethylbenzenesulfonyloxy) succinimide, N-(4-fluorophenylsulfonyloxy) succinimide, N-(trifluoromethylsulfonyloxy)phthalic acid Imine, N-(camphorsulfonyl) phthalimide, N-(2-trifluoromethylbenzenesulfonyloxy) phthalimide, N-(2-fluorophenyl) Sulfomethoxy) phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide (trade name PI-105, Nippon Chemical Co., Ltd.), N-(camphorsulfonyloxy)diphenylmaleimide, 4-(methylbenzenesulfonyloxy)diphenylmaleimide, N-(2- Trifluoromethylbenzenesulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonate醯oxy)diphenylmaleimide, N-(phenylsulfonyloxy)bicyclo[2.2.2.1]hept-5-ene-2,3-dicarboxylimenide (trade name NDI-100) , manufactured by Green Chemical Co., Ltd.), N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimenimine (trade name NDI-101, green N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimenide (trade name: NDI-105, manufactured by Green Chemical Co., Ltd.) ), N-(nonafluorobutsulfonyloxy)bicyclo[2.2.1]hept-5-ene-diimine (trade name: NDI-109, manufactured by Green Chemical Co., Ltd.), N-(camphorsulfonate) Bis)bicyclo[2.2.1]hept-5-ene-diimine (trade name: NDI-106, manufactured by Green Chemical Co., Ltd.), N-(camphorsulfonyl)-7-oxabicyclo[2.2. 1]hept-5-ene-2,3-dicarboxylimenine, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1]g -5-ene-2,3-dicarboxyarsenine, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimenide, N-(4-methylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimenide, N-(2-trifluoromethyl Phenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimenine, N-(2-trifluoromethylbenzenesulfonyloxy)-7-oxabicyclo[ 2.2.2.1]hept-5-ene-2,3-dicarboxylimenine, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine, N-(4-fluorophenylsulfonyl)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-(trifluoro Methylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylimenide, N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane -5,6-oxy-2,3-dicarboxyarsenine N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3- Dicarboxylated imine, N-(2-trifluoromethylbenzenesulfonyloxy)bicyclo[2.2.2.1]heptane-5,6-oxy-2,3-dicarboxylimenide, N- (4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylate imine, N-(trifluoromethylsulfonyloxy) Naphthyl dicarboxy quinone imine (trade name NAI-105, manufactured by Green Chemical Co., Ltd.) N-( camphorsulfonyloxy)naphthalene diimine (trade name: NAI-106, manufactured by Green Chemical Co., Ltd.), N-(4-methylphenylsulfonyloxy)naphthyldicarboxylimine ( Product name NAI-101, greening N-(phenylsulfonyloxy)naphthylcarbodiimide (trade name: NAI-100, manufactured by Green Chemical Co., Ltd.), N-(2-trifluoromethylbenzenesulfonate) Naphthyl dicarboxy quinone imine, N-(4-fluorophenylsulfonyloxy)naphthyl dicarboxy quinone imine, N-(pentafluoroethylsulfonyloxy)naphthyl dicarboxy quinone imine , N-(heptafluoropropylsulfonyloxy)naphthyldicarboquinone imine, N-(nonafluorobutoxysulfonyloxy)naphthyldicarboximine (trade name NAI-109, green chemical formula) Manufactured by the company), N-(ethylsulfonyloxy)naphthyldicarboquinone imine, N-(propylsulfonyloxy)naphthyldicarbenium imine, N-(butylsulfonyloxy) Naphthyl dicarboxy quinone imine (trade name NAI-1004, manufactured by Green Chemical Co., Ltd.), N-(pentylsulfonyloxy)naphthyl dicarboxy quinone imine, N-(hexylsulfonyloxy)naphthyl Dicarboxylated imine, N-(heptylsulfonyloxy)naphthyldicarbenium imine, N-(octylsulfonyloxy)naphthyldicarbenium imine, N-(mercaptosulfonyloxy) Naphthyldiamine.

Other thermal acid generators such as 1-(4-n-butoxy-1-naphthalenyl)tetrahydrothiophenium trifluoromethanesulfonate, 1 -(4,7-Di-n-butoxy-1-naphthalenyl)tetrahydrothiophenium trifluoromethanesulfonate tetrahydrothiophene salt.

Specific examples of the thermal base generator according to the present invention are transition metal complexes and fluorenyl hydrazines. The transition metal complexes such as bromopentadecyl ammonium cobalt perchlorate, bromopentadecane methylamine cobalt perchlorate, bromopentadecane propylamine perchlorate, hexaammonium perchlorate, and hexa Amine cobalt perchlorate, hexabromopropylamine cobalt perchlorate and the like.

The sulfhydryl group is, for example, acetophenone acetophenone, acetophenone benzophenone oxime, acetophenone oxime, acetophenone acetophenone oxime, butyl benzophenone oxime, butyl ketone oxime, hexamethylene oxime Acetophenone oxime, hexamethylene benzophenone oxime, hexanyl acetonide oxime, propylene acetophenone oxime, propylene fluorenyl benzophenone oxime, propylene fluorenyl acetonide oxime, and the like.

On the other hand, the hot base generator according to the present invention preferably comprises a compound represented by the following formula (3) or a salt derivative thereof and/or a compound represented by the following formula (4) and/or the following formula ( 5) Compounds shown:

Wherein: r represents an integer of 2 to 6; and R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms which may have a substituent, or a carbon number of 2 To 12 alkyl dialkyl groups.

Preferably, r represents an integer from 3 to 5.

In a specific example of the present invention, R ³¹ and R ³² are independently represented by a hydrogen atom; and an alkyl group having 1 to 8 carbon atoms may be, for example but not limited to, methyl, ethyl, isopropyl, n-butyl, a tert-butyl or n-hexyl group; a hydroxyalkyl group having a carbon number of 1 to 6 which may have a substituent, such as, but not limited to, a hydrocarbon methyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 2-hydroxyisopropyl group. a 3-hydroxy-tert-butyl or 6-hydroxyhexyl group; or a dialkylamino group having 2 to 12 carbon atoms, such as, but not limited to, dimethylamino, methylethylamino, and diethyl Amino group, diisopropylamino group, tert-butylmethylamino group or di-n-hexylamino group, and the like.

Preferred specific examples of the compound represented by the formula (3) or a salt derivative thereof are 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,5-diaza Bicyclo[4.4.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 5-hydroxypropyl-1,8-diazabicyclo [5.4.0] Undec-7-ene or 5-dibutylamino-1,8-diazabicyclo[5.4.0]undec-7-ene, or product of Aporo: U- CAT® SA810, U-CAT® SA831, U-CAT® SA841, U-CAT® SA851, U-CAT® 5002; more preferably DBN, U-CAT® SA851 or U-CAT® 5002.

Wherein: R ³³ , R ³⁴ , R ³⁵ and R ³⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 8 carbon atoms which may have a substituent, and a carbon number An alkoxy group which may have a substituent of 1 to 8, an alkenyl group which may have a substituent of 2 to 8 carbon atoms, an alkynyl group which may have a substituent of 2 to 8 carbon atoms, an aryl group which may have a substituent, or may be a heterocyclic group having a substituent; R ³⁷ and R ³⁸ each independently represent a hydrogen atom, an alkyl group having a substituent of 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms which may have a substituent, and a carbon number An alkoxy group which may have a substituent of 1 to 8, an alkenyl group which may have a substituent of 2 to 8 carbon atoms, an alkynyl group which may have a substituent of 2 to 8 carbon atoms, an aryl group which may have a substituent, or may be a heterocyclic group having a substituent, or a combination of each other to form a monocyclic ring which may have a substituent, or a polycyclic ring which may have a substituent; R ³⁹ represents an alkyl group having a substituent of 1 to 12 carbon atoms, carbon a cycloalkyl group which may have a substituent of 3 to 12, an alkenyl group which may have a substituent of 2 to 12 carbon atoms, an alkynyl group which may have a substituent of 2 to 12 carbon atoms, may have a carbon number of 1 3 of alkyl group of the substituted aryl group, an alkyl group may have a number of carbon with 1 to 3 substituents of the aralkyl group may have a substituent or a heterocyclic group of the group, but the total number of carbon atoms of R ³⁹ is 12 or less.

Wherein: R ³³ , R ³⁴ , R ³⁵ and R ³⁶ , R ³⁷ and R ^{38 are} as defined in the formula (4); and R ⁴⁰ represents an alkylene group having a substituent of 1 to 12 and having a carbon number of 3 a cycloalkylene group which may have a substituent to 12, an alkenylene group which may have a substituent of 2 to 12 carbon atoms, an alkynylene group which may have a substituent of 2 to 12 carbon atoms, may have a carbon number of 1 to An arylene group of 3 alkyl substituents, an aralkyl group which may have an alkyl substituent of 1 to 3 carbon atoms or a heterocyclic group which may have a substituent, but the total number of carbon atoms of R ⁴⁰ is 12 or less.

Preferred specific examples of the compounds represented by the formulae (4) and (5) are, for example, {[(2-nitrobenzyl)oxy]carbonyl}methylamine, {[(2-nitrobenzyl)oxy [carbonyl] propylamine, {[(2-nitrobenzyl)oxy]carbonyl}hexylamine, {[(2-nitrobenzyl)oxy]carbonyl}cyclohexylamine, {[(2- Nitrobenzyl)oxy]carbonyl}aniline, {[(2-nitrobenzyl)oxy]carbonyl}piperidine, bis{[(2-nitrobenzyl)oxy]carbonyl}hexamethylenediamine, Bis{[(2-nitrobenzyl)oxy]carbonyl}phenylenediamine, bis{[(2-nitrobenzyl)oxy]carbonyl}toluenediamine, bis{[(2-nitrobenzyl) )oxy]carbonyl}-diaminodiphenylmethane, bis{[(2-nitrobenzyl)oxy]carbonyl}piperazine, {[(2,6-dinitrobenzyl)oxy] Carbonyl}-methylamine, {[(2,6-dinitrobenzyl)oxy]carbonyl}propylamine, {[(2,6-dinitrobenzyl)oxy]carbonyl}hexylamine, { [(2,6-Dinitrobenzyl)oxy]carbonyl}cyclohexylamine, {[(2,6-dinitrobenzyl)oxy]carbonyl}aniline, {[(2,6-dinitrate) Benzyl)oxy]carbonyl}piperidine, bis{[(2,6-dinitrobenzyl)oxy]carbonyl}hexanediamine, bis{[(2,6-dinitrobenzyl)oxy Carbonyl}phenylenediamine, bis{[(2,6-dinitrobenzyl)oxy]carbonyl} Toluene diamine, bis{[(2,6-dinitrobenzyl)oxy]carbonyl}diaminodiphenylmethane, bis-{[(2,6-dinitrobenzyl)oxy]carbonyl An o-nitrobenzyl carbazate such as piperazine; for example, {[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl}methylamine, {[ (α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl}propylamine, {[(α,α-dimethyl-3,5-dimethoxybenzyl) )oxy]carbonyl}hexylamine, {[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl}cyclohexylamine, {[(α,α-dimethyl) -3,5-dimethoxybenzyl)oxy]carbonyl}aniline, {[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl}piperidine, double {[(α,α-Dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl}hexanediamine, bis{[(α,α-dimethyl-3,5-dimethoxy) Benzyl)oxy]carbonyl}phenylenediamine, bis{[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl}toluenediamine, double {[(α ,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl}diaminodiphenylmethane, bis{[(α,α-dimethyl-3,5-dimethoxy α,α-dimethyl, etc., such as benzyl)oxy]carbonyl}piperazine a group of 3-, 5-dimethoxybenzyl carbamates; and, for example, N-(isopropoxycarbonyl)-2,6-dimethylpiperidine, N-(isopropoxycarbonyl)- 2,2,6,6-tetramethylpiperidine, N-(isopropoxycarbonyl)diisopropylamine, N-(isopropoxycarbonyl)pyrrolidine, N-(isopropoxycarbonyl) -2,5-dimethylpyrrolidine, N-(isopropoxycarbonyl)azetidine, N-(1-ethylpropoxycarbonyl)-2,6-dimethylpiperidine, N -(1-ethylpropoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(1-ethylpropoxycarbonyl)diisopropylamine, N-(1-ethylpropane Oxycarbonyl)pyrrolidine, N-(1-ethylpropoxycarbonyl)-2,5-dimethylpyrrolidine, N-(1-ethylpropoxycarbonyl)-azetidine, N -(1-propylbutoxycarbonyl)-2,6-dimethylpiperidine, N-(1-propylbutoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N -(1-propylbutoxycarbonyl)diisopropylamine, N-(1-propylbutoxycarbonyl)pyrrolidine, N-(1-propylbutoxycarbonyl)-2,5-di Methylpyrrolidine, N-(1-propylbutoxycarbonyl)-azetidine, N-(cyclopentyloxycarbonyl)-2,6-dimethylpiperidine, N-(cyclopentyloxy) Carbonyl)-2,2,6,6-tetramethylpiperidine, N-(cyclopentyloxycarbonyl) Propylamine, N-(cyclopentyloxycarbonyl)pyrrolidine, N-(cyclopentyloxycarbonyl)-2,5-dimethylpyrrolidine, N-(cyclopentyloxycarbonyl)-azetidine, N-(cyclohexylcarbonyl)-2,6-dimethylpiperidine, N-(cyclohexylcarbonyl)-2,2,6,6-tetramethylpiperidine, N-(cyclohexylcarbonyl)diisopropylamine , N-(cyclohexylcarbonyl)pyrrolidine, N-(cyclohexylcarbonyl)-2,5-dimethylpyrrolidine, N-(cyclohexylcarbonyl)-azetidine, N-(tert-butoxy) Carbonyl)-2,6-dimethylpiperidine, N-(tert-butoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(tert-butoxycarbonyl)diisopropylamine, N-(tert-Butoxycarbonyl)pyrrolidine, N-(tert-butoxycarbonyl)-2,5-dimethylpyrrolidine, N-(tert-butoxycarbonyl)-azetidine, N- (benzyloxycarbonyl)-2,6-dimethylpiperidine, N-(benzyloxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(benzyloxycarbonyl) diiso Propylamine, N-(benzyloxycarbonyl)pyrrolidine, N-(benzyloxycarbonyl)-2,5-dimethylpyrrolidine, N-(benzyloxycarbonyl)-azetidine or 1,4 -Bis(N,N'-diisopropylaminocarbonyloxy)cyclohexane; more preferably N-(isopropoxycarbonyl)-2,6-dimethylpiperidine, N-(1- Ethylpropoxycarbonyl) Isopropylamine, N-(cyclopentyloxycarbonyl)-2,6-dimethylpiperidine, N-(benzyloxycarbonyl)pyrrolidine or 1,4-bis(N,N'-diisopropylamine Other compounds such as carbonyloxy)cyclohexane.

Other thermal base generators such as 2-nitrobenzyl cyclohexylcarbamate or O-carbamoylhydroxyamines amide.

In a specific example of the present invention, the compound (C) is used in an amount of 0.3 to 3 parts by weight, preferably 0.4 to 2.5 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). It is 0.5 to 2 parts by weight. If the compound (C) is not used, the positive photosensitive resin composition may have a problem of poor insulation properties.

According to the cyclic siloxane compound (D) of the structure represented by the formula (1) of the present invention, the formula (1) is as follows:

Wherein: R ¹⁹ and R ²⁰ represent a monovalent group or an alkyl group having an alicyclic epoxy group, wherein at least one of the t R ¹⁹ and the t R ²⁰ is a lipid. a monovalent group of a cyclocyclic epoxy group; and t represents an integer of 3 or more, preferably an integer of 3 to 6; wherein R ¹⁹ and R ²⁰ may be the same or different, the plural R ¹⁹ and the plurality of R ²⁰ may be the same or different.

The cyclic oxoxane compound (D) includes, but is not limited to, 2,4-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,6, 8,8-hexamethyl-cyclotetraoxane alkane, 4,8-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,2,4 6,6,8-hexamethyl-cyclotetraoxane, 2,4-di[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-6,8-di Propyl-2,4,6,8-tetramethyl-cyclotetraoxane, 4,8-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2 ,6-dipropyl-2,4,6,8-tetramethyl-cyclotetraoxane, 2,4,8-tri[2-(3-{oxabicyclo[4.1.0]heptyl} Ethyl]-2,4,6,6,8-pentamethyl-cyclotetraoxane, 2,4,8-bis[2-(3-{oxabicyclo[4.1.0]g Base}) ethyl]-6-propyl-2,4,6,8-tetramethyl-cyclotetraoxane, 2,4,6,8-tetra[2-(3-{oxabicyclo[ 4.1.0] heptyl}) ethyl]-2,4,6,8-tetramethyl-cyclotetraoxane, silsesquioxane having an alicyclic epoxy group, and the like.

Specifically, specific examples of the cyclic siloxane compound (D) having the structure represented by the above formula (1) are as follows.

The cyclic siloxane compound (D) having a structure represented by the formula (1) may be used alone or in combination of two or more.

The cyclic siloxane compound (D) having a structure represented by the formula (1) is used in an amount of from 3 parts by weight to 30 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). The parts by weight to 25 parts by weight, and more preferably 5 parts by weight to 20 parts by weight.

When the cyclic siloxane compound (D) having the structure represented by the formula (1) is not used, the positive photosensitive resin composition may have a problem of poor insulation.

The solvent (E) of the present invention is completely soluble in other organic components, and its volatility must be high enough to evaporate from the dispersion with a little heat at normal pressure. Therefore, a solvent having a boiling point of less than 150 ° C at normal pressure is most often used.

The solvent (E) to which the present invention is applicable may include an aromatic solvent such as benzene, toluene or xylene; an alcohol solvent such as methanol or ethanol; ethylene glycol monopropyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and ethylene. An ether solvent such as alcohol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether or diethylene glycol butyl ether; ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate An ester solvent such as propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate or ethyl 3-ethoxypropionate; a ketone solvent such as methyl ethyl ketone or acetone.

Preferably, the solvent (E) may be a single one of diethylene glycol dimethyl ether, propylene glycol methyl ether acetate or ethyl 3-ethoxypropionate or both.

The solvent (E) is used in an amount of from 100 parts by weight to 1000 parts by weight, based on the amount of the alkali-soluble resin (A), preferably from 120 parts by weight to 800 parts by weight, and more preferably 150 parts by weight. Parts by weight to 600 parts by weight.

The resin composition according to the present invention may be optionally further added with an additive (F). Specifically, the additive (F) is, for example, a sensitizer, an adhesion auxiliary agent, or a surfactant (surfactant). ), a solubility promoter, a defoamer or a combination thereof.

The type of the sensitizer is not particularly limited. The sensitizer is preferably a compound containing a phenolic hydroxy group, for example: (1) a trisphenol type compound such as tris(4-hydroxyphenyl)methane or bis(4-hydroxyl) 3-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,3,5-trimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3, 5-dimethylphenyl)-4-hydroxybenzene Methane, bis(4-hydroxy-3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-methylphenyl)-2-hydroxyphenylmethane, Bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, bis ( 4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, double (4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxybenzene Methane, bis(4-hydroxyphenyl)-3-methoxy-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane , bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxybenzene Methane or bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenylmethane; etc.; (2) bisphenol type compound: such as double (2) , 3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2-(2,3 ,4-trihydroxyphenyl)-2-(2', 3',4'-trihydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl) )-2-(4'-hydroxyphenyl)propane, 2-(3-fluoro-4-hydroxyphenyl)-2-(3'-fluoro-4'-hydroxyphenyl)propane, 2-( 2,4-Dihydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxyphenyl)propane or 2 -(2,3,4-trihydroxyphenyl)-2-(4'-hydroxy-3',5'-dimethylphenyl)propane; (3) polynuclear branched compound : such as 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene or 1-[1-(3-methyl- 4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4-hydroxyphenyl)ethyl]benzene; (4) condensation type phenol compound : such as 1,1-bis(4-hydroxyphenyl)cyclohexane; (5) polyhydroxy benzophenone: such as 2,3,4-trihydroxybenzophenone, 2, 4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4, 4'-tetrahydroxybenzophenone, 2,4,2',4'-tetrahydroxybenzophenone, 2,4,6,3',4'-pentahydroxydiphenyl Ketone, 2,3,4,2 ', 4'-pentahydroxy benzophenone, 2,3,4,2',5'-pentahydroxybenzophenone, 2,4,6,3',4',5'-hexahydroxybenzophenone or 2,3,4,3', 4', 5'-hexahydroxybenzophenone or the like; or (6) a combination of the above various compounds containing a phenolic hydroxyl group.

The sensitizer is used in an amount of 5 to 50 parts by weight, preferably 8 parts by weight to 40 parts by weight, and more preferably 10 parts by weight to 35 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). Parts by weight.

The adhesion aid is, for example, a melamine compound or a decane compound. The adhesion aid functions to increase the adhesion between the protective film formed of the positive photosensitive resin composition and the member to be protected.

Commercially available products of melamine are, for example, those manufactured by Mitsui Chemicals under the trade name of Cymel-300 or Cymel-303; or manufactured by Sanwa Chemical under the trade names of MW-30MH, MW-30, MS-11, MS-001, MX-750 or MX-706, etc.

When the melamine compound is used as the adhesion aid, the amount of the alkali-soluble resin (A) used is 100 parts by weight, and the melamine compound is used in an amount of 0 parts by weight to 20 parts by weight; preferably 0.5 parts by weight to 18 parts by weight. Parts by weight; and more preferably from 1.0 part by weight to 15 parts by weight.

The decane-based compound is, for example, vinyltrimethoxydecane, vinyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, vinyltris(2-methoxyethoxy)decane, nitrogen- (2-Aminoethyl)-3-aminopropylmethyldimethoxydecane, nitrogen-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyl Triethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyldimethylmethoxydecane, 2-(3,4-epoxycyclohexyl)B Trimethoxy decane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxy A quinone or a commercially available product (trade name such as KBM403) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

When a decane compound is used as a binding aid, based on the alkali solubility The resin (A) is used in an amount of 100 parts by weight, and the decane-based compound is used in an amount of from 0 part by weight to 2 parts by weight; preferably from 0.05 part by weight to 1 part by weight; and more preferably from 0.1 part by weight to 0.8 part by weight. .

The surfactant is, for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, a polyoxyalkylene surfactant, a fluorine surfactant, or a combination thereof.

Examples of the surfactant include (1) polyoxyethylene alkyl ethers: polyethylene oxide lauryl ether, and the like; (2) polyethylene oxide alkylphenyl ethers (polyoxyethylene phenyl ethers): polyethylene oxide octyl phenyl ether, polyethylene oxide nonyl phenyl ether, etc.; (3) polyethylene glycol diesters (polyethylene glycol diesters): polyethylene glycol II Lauric acid ester, polyethylene glycol distearate, etc.; (4) sorbitan fatty acid esters; and (5) fatty acid modified poly esters And (6) tertiary amine modified polyurethanes modified by tertiary amines. Commercially available products of surfactants are, for example, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), SF-8427 (manufactured by Dow Corning Toray Silicone Co., Ltd.), and Polyflow (from a total of Rongshe Oil Chemical Industry Co., Ltd.), F-Top (manufactured by Tochem Products Co., Ltd.), Megaface (manufactured by Dainippon Chemical Industry (DIC)), Fluorade (by Sumitomo 3M Co., Ltd. (manufactured by Sumitomo 3M Ltd.), Surflon (manufactured by Asahi Glass), SINOPOL E8008 (manufactured by Sino-Japanese Synthetic Chemicals), F-475 (manufactured by Dainippon Ink Chemical Industries), or a combination thereof.

The surfactant is used in an amount of from 0.5 part by weight to 50 parts by weight, based on the amount of the alkali-soluble resin (A), preferably from 1 part by weight to 40 parts by weight; more preferably from 3 to 30 parts by weight. Parts by weight.

Examples of antifoaming agents include Surfynol MD-20, Surfynol MD-30, EnviroGem AD01, EnviroGem AE01, EnviroGem AE02, Surfynol DF110D, Surfynol 104E, Surfynol 420, Surfynol DF37, Surfynol DF58, Surfynol DF66, Surfynol DF70, and Surfynol DF210 (manufactured by Air Products), and the like.

The antifoaming agent is used in an amount of from 1 part by weight to 10 parts by weight, based on the amount of the alkali-soluble resin (A), preferably from 2 parts by weight to 9 parts by weight, and more preferably 3 parts by weight. Up to 8 parts by weight.

Examples of the dissolution promoter include a nitrogen-hydroxydicarboxylic imide compound and a compound having a phenolic hydroxyl group.

The dissolution promoter is used in an amount of 1 part by weight to 20 parts by weight, based on the amount of the alkali-soluble resin (A), and is preferably 2 parts by weight to 15 parts by weight; and more preferably 3 parts by weight. Up to 10 parts by weight.

The positive photosensitive resin composition according to the present invention is prepared, for example, in the following manner: an alkali-soluble resin (A), an o-naphthoquinonediazide sulfonate (B), a compound (C), a cyclic oxirane The compound (D) and the solvent (E) are placed in a stirrer and stirred to be uniformly mixed into a solution state, and if necessary, an additive (F) may be added.

The present invention also provides a method of forming a film on a substrate comprising applying the positive photosensitive resin composition described above to the substrate.

The invention further provides a film on a substrate produced by the method described above.

The film according to the present invention is preferably a flat film of a TFT substrate, an interlayer insulating film or a protective film of a core material or a cladding material for a TFT substrate in a liquid crystal display element or an organic electroluminescence display.

The invention further provides a device comprising the aforementioned film.

Hereinafter, a method of forming a protective film will be described in detail, which includes sequentially forming a pre-baked coating film using a positive photosensitive resin composition, patterning exposure of the prebaked coating film, and removing an exposed region by alkali development to form Pattern; and post-baking to form Protective film.

Forming a pre-baked film

A positive photosensitive resin composition in a solution state is applied onto a protected member (hereinafter referred to as a substrate) by a coating method such as spin coating, cast coating, or roll coating to form a coating film.

The substrate may be an alkali-free glass, a soda-lime glass, a hard glass (Pyrus glass), a quartz glass, a glass to which a transparent conductive film is attached, or a photoelectric conversion device (for example, for a liquid crystal display device). A substrate (such as a tantalum substrate) of a solid-state imaging device.

After the coating film is formed, most of the organic solvent of the positive photosensitive resin composition is removed by vacuum drying, and then the residual organic solvent is completely removed by pre-bake to form a prebaked coating film.

The operating conditions of the above-described reduced-pressure drying and pre-baking may vary depending on the type and blending ratio of each component. In general, the drying under reduced pressure is carried out at a pressure of from 0 torr to 200 Torr for 1 second to 60 seconds, and the prebaking is carried out at a temperature of 70 ° C to 110 ° C for 1 minute to 15 minutes.

Patterned exposure

The prebaked coating film is exposed in a mask having a specific pattern. The light used in the exposure process is preferably ultraviolet rays such as g-line, h-line or i-line, and the device for providing ultraviolet rays may be a (ultra) high pressure mercury lamp or a metal halide lamp.

development

The exposed prebaked coating film is immersed in a developing solution having a temperature of 23±2° C. for about 15 seconds to 5 minutes to remove unnecessary portions of the exposed prebaked coating film, that is, The exposed area is dissolved in the developer, and the unexposed areas are retained, whereby a semi-finished product having a protective film of a predetermined pattern can be formed on the substrate. Specific examples of the developer include, but are not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methylsilicate, aqueous ammonia, Ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide (THAM), tetraethylammonium hydroxide, choline, pyrrole, acridine or 1,8-diazabicyclo[5.4.0]-7 a basic compound such as undecene.

It is worth mentioning that if the concentration of the developer is too high, the specific pattern may be damaged or the resolution of the specific pattern may be deteriorated; if the concentration is too low, the development may be poor, resulting in the failure of the specific pattern to be formed or the composition of the exposed portion remaining. Therefore, the amount of concentration affects the formation of a specific pattern of the subsequent positive photosensitive resin composition after exposure. The concentration of the developer is preferably in the range of 0.001% by weight to 10% by weight; more preferably 0.005% by weight to 5% by weight; still more preferably 0.01% by weight to 1% by weight. An embodiment of the present invention is a developer using 2.38 wt% of tetramethylammonium hydroxide. It is worth mentioning that the positive-type photosensitive resin composition of the present invention can form a good fine pattern even when a developer having a lower concentration is used.

Post-bake treatment

The substrate (the semi-finished product of the protective film having a predetermined pattern on the substrate) is washed with water to remove unnecessary portions of the exposed pre-baked film. Then, the semi-finished product of the above protective film having a predetermined pattern is dried with compressed air or compressed nitrogen. Finally, the semi-finished product of the above-mentioned protective film having a predetermined pattern is subjected to a post-bake treatment by a heating means such as a hot plate or an oven. The heating temperature is set between 100 ° C and 250 ° C, the heating time when using the hot plate is 1 minute to 60 minutes, and the heating time when using the oven is 5 minutes to 90 minutes. Thereby, the pattern of the semi-finished product of the protective film having the predetermined pattern described above can be fixed to form a protective film.

The invention is illustrated by the following examples, which are not intended to be limited to the scope of the invention.

Synthesis of alkali soluble resin (A)

<Synthesis Example A-1>

A nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer were placed on a four-necked cone of 1000 ml volume. After introducing nitrogen, 20 parts by weight of methyl propyl was added. Eleic acid (hereinafter abbreviated as MAA), 35 parts by weight of glycidyl methacrylate (hereinafter abbreviated as GMA), 30 parts by weight of dicyclopentanyl methacrylate (hereinafter abbreviated as FA-513M), 15 parts by weight Styrene (hereinafter abbreviated as SM), 5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) (hereinafter abbreviated as ADVN) and 300 parts by weight of diethylene glycol dimethyl ether (hereinafter referred to as Diglyme) to the reaction bottle. Next, the above ingredients were slowly stirred, and the solution was heated to 70 °C. After the polycondensation reaction was carried out for 4 hours, the solvent was devolatilized to obtain an alkali-soluble resin (A-1) of Synthesis Example A-1.

<Synthesis Example A-2 to Synthesis Example A-5>

Synthesis Example A-2 to Synthesis Example A-5 were prepared in the same manner as in Synthesis Example A-1, and the difference was that Synthesis Example A-2 to Synthesis Example A-5 changed the kind of the raw material in the alkali-soluble resin. And the amount of use and its polymerization conditions, and its formulation and polymerization conditions are shown in Table 1, and will not be further described herein.

Synthesis of o-naphthoquinonediazide sulfonate compound (B-1) having the structure represented by formula (2)

<Synthesis Example B-1-1>

In a dry nitrogen atmosphere, 0.1 mole of the oxime compound having a hydroxyl group represented by the above formula (I-1) and 0.13 mol of o-naphthoquinonediazide-5-sulfonic acid chloride are added to 450 g of γ-butane. In the ester.

Then, 0.14 mol of triethylamine was dissolved in 50 g of 1,4-dioxane to configure a mixed solution. The mixed solution was added dropwise to the aforementioned γ-butyrolactone solution, and the temperature of the solution was prevented from exceeding 35 °C.

After stirring at 30 ° C for 2 hours, the precipitated triethylamine salt was filtered, and the filtrate was poured into water.

Then, the precipitate was collected by filtration, and the precipitate was dried by a vacuum dryer to obtain Synthesis Example B-1-1 having the structure represented by the following formula (I-1-1) and having an esterification ratio of 65%. :

或氫原子，且兩者之比值為 1.3：0.7。 In the formula (I-1-1), Q ₁ represents

Or a hydrogen atom, and the ratio of the two is 1.3:0.7.

<Synthesis Example B-1-2>

In a dry nitrogen atmosphere, 0.1 mole of the oxime compound having a hydroxyl group represented by the above formula (I-2) and 0.14 mol of o-naphthoquinonediazide-5-sulfonic acid chloride are added to 450 g of γ-butane. In the ester.

Then, 0.154 mol of triethylamine was dissolved in 50 g of 1,4-dioxane to configure a mixed solution. The mixed solution is added dropwise to the aforementioned γ-butyrolactone solution In the liquid, and avoid the temperature of the solution exceeds 35 °C.

After stirring at 30 ° C for 2 hours, the precipitated triethylamine salt was filtered, and the filtrate was poured into water.

Then, the precipitate was collected by filtration, and the precipitate was dried by a vacuum dryer to obtain Synthesis Example B-1-2 having the structure represented by the following formula (I-2-1) and having an esterification ratio of 70. %:

或氫原子，且兩者之比值為 1.4：0.6。 In the formula (I-2-1), Q ₂ represents

Or a hydrogen atom, and the ratio of the two is 1.4:0.6.

<Synthesis Example B-1-3>

In a dry nitrogen atmosphere, 0.1 mole of the oxime compound having a hydroxyl group represented by the above formula (I-3) and 0.26 mol of o-naphthoquinonediazide-5-sulfonic acid chloride were added to 450 g of γ-butane. In the ester.

Then, 0.28 mol of triethylamine was dissolved in 50 g of 1,4-dioxane to configure a mixed solution. The mixed solution was added dropwise to the aforementioned γ-butyrolactone solution, and the temperature of the solution was prevented from exceeding 35 °C.

After stirring at 30 ° C for 2 hours, the precipitated triethylamine salt was filtered, and the filtrate was poured into water.

Then, the precipitate was collected by filtration, and the precipitate was dried by a vacuum dryer to obtain Synthesis Example B-1-3 having the structure represented by the following formula (I-3-1), and the esterification ratio thereof was obtained. 65%:

或氫原子，且兩者之比值為 1.3：0.7。 In the formula (I-3-1), Q ₃ represents

Or a hydrogen atom, and the ratio of the two is 1.3:0.7.

<Synthesis Example B-1-4>

In a dry nitrogen atmosphere, 0.1 mole of the oxime compound having a hydroxyl group represented by the above formula (I-3) and 0.28 mol of o-naphthoquinonediazide-5-sulfonic acid chloride were added to 450 g of γ-butane. In the ester.

Then, 0.33 mol of triethylamine was dissolved in 50 g of 1,4-dioxane to configure a mixed solution. The mixed solution was added dropwise to the aforementioned γ-butyrolactone solution, and the temperature of the solution was prevented from exceeding 35 °C.

After stirring at 30 ° C for 2 hours, the precipitated triethylamine salt was filtered, and the filtrate was poured into water.

Then, the precipitate was collected by filtration, and the precipitate was dried by a vacuum dryer to obtain Synthesis Example B-1-4 having the structure represented by the following formula (I-4-1) and having an esterification ratio of 70. %:

或氫原子，且兩者之比值為 1.4：0.6。 In the formula (I-4-1), Q ₄ represents

Or a hydrogen atom, and the ratio of the two is 1.4:0.6.

Preparation of positive photosensitive resin composition

<Example 1>

100 parts by weight of 5 parts by weight of the alkali-soluble resin (A-1) obtained in the above Synthesis Example A-1, and 5 parts by weight of the o-naphthoquinonediazidesulfonate obtained in the above Synthesis Example B-1-1 (B) -1-1), 0.5 parts by weight of NDI-105 (hereinafter referred to as C-1), 3 parts by weight of the structure shown by D-1 in Table 2, and 1 part by weight of SF-8427 (hereinafter referred to as F-1) After adding 100 parts by weight of the solvent propylene glycol methyl ether acetate (hereinafter referred to as E-1), the mixture is dissolved and mixed by a shaker to obtain a positive photosensitive resin composition, and the positive photosensitive resin composition is obtained. Each measurement evaluation method described below was evaluated, and the results obtained are shown in Table 2.

<Example 2 to Example 10>

The positive photosensitive resin compositions of Examples 2 to 10 were separately prepared in the same manner as in Example 1, and were different in that the kinds of the components and the amounts thereof were changed, as shown in Table 2. The evaluation methods of the positive photosensitive resin compositions obtained in Examples 2 to 10 were evaluated in the following manner, and the results are shown in Table 2.

<Comparative Example 1 to Comparative Example 3>

The positive photosensitive resin compositions of Comparative Examples 1 to 3 were separately prepared in the same manner as in Example 1, and were different in that the kinds of the components and the amounts thereof were changed, as shown in Table 2. The evaluation methods of the positive photosensitive resin compositions obtained in Comparative Examples 1 to 3 were evaluated in the following manner. Table 2 shows the results.

B-1-1 Synthesis Example B-1-1

B-1-2 Synthesis Example B-1-2

B-1-3 Synthesis Example B-1-3

B-1-4 Synthesis Example B-1-4

B-2-1 1-[1-(4-Hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene and o-naphthoquinonediazide-5 - o-naphthoquinone diazide sulfonate formed by sulfonic acid

B-2-2 2,3,4-trihydroxybenzophenone and o-naphthoquinone diazide sulfonate formed by o-naphthoquinonediazide-5-sulfonic acid

B-2-3 2,3,4,4'-tetrahydroxybenzophenone and o-naphthoquinonediazide-5-sulfonic acid formed o-naphthoquinone diazide sulfonate

C-1 NDI-105 (manufactured by Green Chemical Co., Ltd.)

C-2 SI-105 (manufactured by Green Chemical Co., Ltd.)

C-3 PAI-106 (manufactured by Green Chemical Co., Ltd.)

C-4 SI-100 (Sanshin Chemical)

C-5 SI-150 (Sanshin Chemical)

C-6 {[(2-nitrobenzyl)oxy]carbonyl}methylamine

C-7 {[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl}hexylamine

C-8 propylene benzophenone oxime

C-9 U-CAT® 5002

C-10 N-(isopropoxycarbonyl)-2,6-dimethylpiperidine

D-1

D-2

D-3

D-4

D-5

D-6

E-1 propylene glycol methyl ether acetate

E-2 diethylene glycol dimethyl ether

E-3 3-ethoxypropionate ethyl ester

F-1 SF-8427

F-2 3-glycidoxypropyltrimethoxydecane (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.)

Evaluation method

<insulation>

The positive photosensitive resin composition was applied onto a SUS substrate by spin coating to obtain a precoat film having a thickness of about 2 μm, and then prebaked at 110 ° C for 2 minutes, and then exposed to an exposure machine (AG500-4N; manufactured by M&R Nano Technology). The pre-coated film is irradiated with ultraviolet light having an energy of 200 J/cm ² , and then the developed film is directly irradiated with an exposure machine at an energy of 300 mJ/cm ² , and finally, baked at 230 ° C for 60 minutes. An insulating film on the SUS substrate was obtained. A Pt/Pd electrode pattern was formed on the insulating film by a vapor deposition method to prepare a sample for measurement, and then a dielectric was measured by a CV method using a Precision LCR meter (Yokogawa Hewlett Packard "HP4284A") at a frequency of 10 kHz. constant.

◎: dielectric constant ≦ 3.3

○: 3.3 <dielectric constant ≦ 3.6

△: 3.6 < dielectric constant ≦ 3.9

×: dielectric constant > 3.9

The above-described embodiments are merely illustrative of the principles and effects of the invention, and are not intended to limit the invention. Modifications and variations of the embodiments described above will be apparent to those skilled in the art without departing from the spirit of the invention. The scope of the invention should be as set forth in the appended claims.

Claims (11)

A positive photosensitive resin composition comprising: an alkali-soluble resin (A); o-naphthoquinonediazide sulfonate (B); and a compound (C) selected from the group consisting of a thermal acid generator and a thermal base generator a group consisting of a cyclic siloxane compound (D) having the structure represented by the formula (1); and a solvent (E); In the formula (1): R ¹⁹ and R ^{20 each} represent a monovalent group or an alkyl group having an alicyclic epoxy group, wherein at least one of the t R ¹⁹ and the t R ²⁰ is at least one of Is a monovalent group having an alicyclic epoxy group; and t represents an integer of 3 or more; wherein, R ¹⁹ and R ²⁰ may be the same or different, and the plurality of R ¹⁹ and the plural R ²⁰ may be the same or different. The positive photosensitive resin composition according to Item 1, wherein the alkali-soluble resin (A) is an unsaturated carboxylic acid or an unsaturated carboxylic anhydride compound (a1) or an epoxy group-containing unsaturated monomer ( A2) is obtained by copolymerization of other unsaturated monomers (a3). The positive photosensitive resin composition according to Item 1, wherein the amount of the o-naphthoquinone diazide sulfonate (B) used is 100 parts by weight based on the amount of the alkali-soluble resin (A). 5 to 60 parts by weight; the compound (C) is used in an amount of 0.3 to 3 parts by weight The cyclic oxirane compound (D) of the structure represented by the formula (1) is used in an amount of 3 to 30 parts by weight; and the solvent (E) is used in an amount of 100 to 1000 parts by weight. According to the positive photosensitive resin composition of claim 1, the o-naphthoquinonediazide sulfonate (B) comprises an o-naphthoquinonediazide sulfonate compound having a structure represented by the formula (2) (B) -1): In the formula (2): R ₁ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group or an alkenyl group; and R ₂ each independently represents a hydrogen atom or a functional group having a quinonediazide structure; , b, d, and e respectively represent integers greater than or equal to 0, and the sum of f and g is an integer greater than or equal to 1; when the sum of a, b, d, and e is greater than 1, the plurality of R ₁ are respectively the same Or different; when the sum of f and the g is greater than 1, at least one of the plurality of R ₂ has a functional group of a quinonediazide structure. The positive-type photosensitive resin composition of claim 4, wherein the amount of the alkali-soluble resin (A) used is 100 parts by weight, and the o-naphthoquinonediazidesulfonic acid having the structure represented by the formula (2) The ester compound (B-1) is used in an amount of 5 to 50 parts by weight. The positive photosensitive resin composition according to claim 1, wherein the thermal acid generating agent is selected from the group consisting of a phosphonium salt, a halogen-containing compound, a diazomethane compound, a hydrazine compound, a sulfonate compound, a carboxylate compound, and a phosphate compound. a group consisting of a sulfonium imine compound, a sulfonated benzotriazole compound, and a combination thereof. The positive photosensitive resin composition according to claim 1, wherein the thermal base generating agent is selected from the group consisting of transition metal complexes, fluorenyl hydrazines, compounds represented by the following formula (3) or salts thereof a group consisting of a compound of the structure represented by the following formula (4), a compound of the structure represented by the following formula (5), and a combination thereof: Wherein: m represents an integer of 2 to 6; and R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having a carbon number of 1 to 6 or a carbon number of 2 Dialkylamino group to 12; Wherein: R ³³ , R ³⁴ , R ³⁵ and R ³⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 8 carbon atoms which may have a substituent, and carbon An alkoxy group having a substituent of 1 to 8, an alkenyl group having 2 to 8 carbon atoms which may have a substituent, an alkynyl group having 2 to 8 carbon atoms which may have a substituent, an aryl group which may have a substituent or a heterocyclic group which may have a substituent; R ³⁷ and R ³⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 8 carbon atoms which may have a substituent, An alkoxy group having a carbon number of 1 to 8 which may have a substituent, an alkenyl group having 2 to 8 carbon atoms which may have a substituent, an alkynyl group having 2 to 8 carbon atoms which may have a substituent, and an aryl group which may have a substituent Or a heterocyclic group which may have a substituent, or a single ring which may have a substituent, or a polycyclic ring which may have a substituent; and R ³⁹ represents an alkyl group which may have a substituent of 1 to 12 carbon atoms; a cycloalkyl group which may have a substituent of 3 to 12 carbon atoms, an alkenyl group which may have a substituent of 2 to 12 carbon atoms, an alkynyl group which may have a substituent of 2 to 12 carbon atoms, may have The alkyl group with 1 to 3 substituents of the aryl group may be an alkyl group having a carbon number of from 1 to 3 substituents of the aralkyl group may have a substituent or a heterocyclic group of, but the total number of carbon atoms of R ³⁹ to 12 the following; Wherein: R ³³ , R ³⁴ , R ³⁵ and R ³⁶ , R ³⁷ and R ^{38 are} as defined in the formula (4); and R ⁴⁰ represents an alkylene group having a carbon number of 1 to 12 and a carbon number. a cycloalkylene group which may have a substituent of 3 to 12, an alkenylene group which may have a substituent of 2 to 12 carbon atoms, an alkynylene group which may have a substituent of 2 to 12 carbon atoms, may have a carbon number of 1 An arylene group having an alkyl substituent of 3, an aralkyl group which may have an alkyl substituent of 1 to 3 carbon atoms or a heterocyclic group which may have a substituent, but the total number of carbon atoms of R ⁴⁰ is 12 or less . A method of forming a film on a substrate, which comprises applying the positive photosensitive resin composition according to any one of claims 1 to 7 to the substrate. A film on a substrate produced by the method of claim 8. The film according to claim 9 which is a flat film of a thin film transistor substrate, an interlayer insulating film or a protective film of a core material or a cladding material of the optical waveguide in the liquid crystal display element or the organic electroluminescent display. A device comprising a film according to claim 9 or 10.