KR101842891B1 - Photosensitive composition, cured film formed from same, and element having cured film - Google Patents

Abstract

(A) an alkali-soluble resin, (B) a naphthoquinone diazide compound, (C) a solvent, and (D) a metal chelate compound, wherein the metal chelate compound (D) ), Wherein the content of the metal chelate compound (D) is 0.1 to 5 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). Provided is a positive photosensitive composition which has characteristics of high heat resistance and high transparency and is excellent in developing adhesion and wet heat resistance.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive composition, a cured film formed therefrom, and a device having the cured film.

The present invention relates to a planarizing film for a thin film transistor (TFT) substrate such as a liquid crystal display element or an organic EL display element, a protective film or insulating film for a touch panel, an interlayer insulating film of a semiconductor element, a planarization film or a micro lens array pattern for a solid- A photosensitive composition for forming a core or clad material of an optical waveguide, a cured film formed therefrom, and a device having the cured film.

In recent years, it is demanded to realize a higher precision and a higher resolution in a liquid crystal display, an organic EL display, and the like.

In recent years, the adoption of touch panels in liquid crystal displays and the like has been actively promoted. Particularly, attention has been paid to capacitive touch panels, and in order to improve the transparency and functionality of touch panels, high transparency of ITO, Insulating films are also required to have high heat resistance to heat treatment.

For example, Patent Document 1 discloses a method of increasing the aperture ratio of a display device as a method of achieving a higher precision and a higher resolution in a liquid crystal display, an organic EL display, and the like. This is a method of increasing the aperture ratio as compared with the conventional technique by making it possible to overlap the data line and the pixel electrode by providing a transparent planarization film as a protective film on the TFT substrate.

As a material for the TFT substrate flattening film, it is necessary to form a hole pattern having a thickness of several mu m to 50 mu m in order to connect the TFT substrate electrode and the ITO electrode with high heat resistance and high transparency. Generally, Material is used.

Patent Documents 2, 3, and 4 describe a material in which a quinone diazide compound is combined with an acrylic resin as a typical example of a positive photosensitive material.

On the other hand, a polysiloxane is known as a material having high heat resistance and high transparency, and Patent Documents 5 and 6 disclose a material in which a quinone diazide compound is combined to impart a positive photosensitivity thereto. A high transparency cured film can be obtained without causing defects such as cracks even by high temperature treatment.

Patent Document 7 discloses a method of adding a metal chelating agent to a polysiloxane as a method for improving the heat and humidity resistance. This is thought to be a mechanism by which the titanium or zirconium chelating agent promotes the crosslinking of the siloxane and improves resistance to moisture and humidity.

Patent Document 8 discloses a negative-working photosensitive material containing an organic metal chelate compound.

Patent Document 9 discloses a positive photosensitive material to which a metal particle is added to a siloxane.

In addition, Patent Document 10 reports on improvement in coating unevenness of a siloxane composition containing a specific solvent. Among them, the addition of naphthoquine diazide and the addition of a chelate compound are separately described as examples of positive photosensitivity.

Japanese Patent Laid-Open No. 9-152625 (Claim 1) Japanese Patent Laid-Open No. 2001-281853 (Claim 1) Japanese Unexamined Patent Application Publication No. 5-165214 (Claim 1) Japanese Patent Laid-Open No. 2002-341521 (Claim 1) Japanese Patent Application Laid-Open No. 2006-178436 (Claim 1) Japanese Patent Application Laid-Open No. 2009-211033 (Claim 1) Japanese Patent Laid-Open No. 07-331173 (Claim 1) Japanese Patent Application Laid-Open No. 2007-308688 (Claim 1) Japanese Patent Application Laid-Open No. 2007-246877 (Claims 1 to 6) WO 2007-049440 (paragraphs 0040-0041 and 0054)

However, since the transparent planarizing film of Patent Document 1 uses an acrylic resin material, the heat resistance is insufficient.

The acrylic resin as a material described in Patent Documents 2, 3 and 4 is insufficient in heat resistance and chemical resistance, and the cured film is colored due to high-temperature processing of the substrate, high-temperature film formation such as a transparent electrode, , There is a problem that the conductivity of the electrode is lowered by degassing in the high-temperature film. In addition, since these acrylic materials generally have low sensitivity, productivity is low and materials with higher sensitivity are required. In addition, according to the progress of the display, the opening dimensions such as the hole pattern are made fine every year, and in some cases, fine pattern formation of 3 탆 or less is required, but the resolution of the acrylic material is insufficient.

The polysiloxane materials described in Patent Documents 5 and 6 have high heat resistance and high transparency. However, even in this material, the adhesion between the film formed on the pattern at the time of development and the substrate (hereinafter referred to as developing adhesion) The fine pattern is peeled together with the developer or the rinsing liquid. Therefore, there is a strong demand for a positive photosensitive material having better developing adhesion.

In general, in order to improve the developing adhesion, a prebaking temperature after coating is increased. However, since the photosensitizer is inactivated by increasing the prebaking temperature, the sensitivity is lowered. On the contrary, if the prebaking temperature is set to a low value, the residual agent in the film becomes large and the developing adhesion is degraded.

In addition, it is not always sufficient for the resistance to moisture and humidity, and a positive-type photosensitive material with better heat and humidity resistance is strongly demanded.

There is no mention of how much chelating agent should be added to the photosensitive composition described in Patent Document 7. [

In Patent Document 8, firing is performed in order to form a conductive film, and an insulating organic film is not left.

Patent Document 9 does not mention moisture resistance.

Patent Document 10 discloses that there is no description related to the use of naphthoquinone diazide and chelate compound at the same time, and that both of them are used at the same time to have both positive heat-sensitive characteristics, There is no substrate that can be easily inferred.

As described above, a positive-type photosensitive material having high transparency and high moisture-and-heat resistance and having good developing adhesion is required, but the technique has not been established so far.

SUMMARY OF THE INVENTION The present invention has been accomplished on the basis of the above-described circumstances, and it is an object of the present invention to provide a photosensitive composition having high heat resistance, high transparency, and excellent developing adhesion and moist heat resistance. Another object of the present invention is to provide a method for manufacturing a semiconductor device, which comprises forming a planarizing film for a TFT substrate, an interlayer insulating film, a protective film or insulating film for a touch panel, a core or a clad material, a cured film as a lens material, , A solid-state image pickup device, and an optical waveguide.

In order to solve the above problems, the positive photosensitive composition of the present invention has the following constitution. That is, a photosensitive composition containing (A) an alkali-soluble polysiloxane and / or alkali-soluble acrylic resin, (B) a naphthoquinone diazide compound, (C) a solvent, and (D) a metal chelate compound, (A) an alkali-soluble polysiloxane and / or an alkali-soluble acrylic resin (hereinafter sometimes referred to as an " alkali-soluble resin " ) Is 0.1 to 5 parts by weight based on 100 parts by weight of the positive photosensitive composition.

(In the metal chelate compound represented by formula (1) M is a metal atom. R ¹ are the same or different, each represent a hydrogen, an alkyl group, an aryl group, an alkenyl group, and these substituents. R ^2, R ³ may be the same or different and each represents hydrogen, an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a substituent thereof, j represents a valence of the metal atom M, and k represents an integer of 0 to j)

Further, the cured film of the present invention has any one of the following constitutions (1) and (2). In other words,

(1) A cured film formed from the above positive-working photosensitive composition, wherein the cured film has a light transmittance of 85% or more per 3 m of film thickness at a wavelength of 400 nm, or

(2) A cured film formed from the above positive photosensitive composition, wherein the cured film is formed of at least one selected from the group consisting of titanium, zirconium, aluminum, zinc, cobalt, molybdenum, lanthanum, barium, strontium, magnesium, And calcium is 0.005 to 1 part by weight.

The device of the present invention has the following configuration. In other words,

And the cured film.

(Effects of the Invention)

The positive photosensitive composition of the present invention has high heat resistance and high transparency, and is excellent in developing adhesion and wet heat resistance. Further, the obtained cured film can be preferably used as a flattening film for a TFT substrate, an interlayer insulating film, a protective film / insulating film for a touch panel, and a core / clad material for an optical waveguide.

The positive photosensitive composition of the present invention is a positive photosensitive composition containing (A) an alkali-soluble resin, (B) a naphthoquinone diazide compound, (C) a solvent, and (D) a metal chelate compound, The chelate compound has a structure represented by the following general formula (1), and the content of the metal chelate compound (D) is 0.1 to 5 parts by weight based on 100 parts by weight of the alkali-soluble resin (A).

(In the metal chelate compound represented by formula (1) M is a metal atom. R ¹ are the same or different, each represent a hydrogen, an alkyl group, an aryl group, an alkenyl group, and these substituents. R ^2, R ³ may be the same or different and each represents hydrogen, an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a substituent thereof, j represents a valence of the metal atom M, and k represents an integer of 0 to j)

The alkali-soluble resin (A) used in the present invention is a polysiloxane and / or an acrylic resin and is a resin dissolved in an aqueous alkaline solution having a pH of 8 or more. The resin has at least one of an acidic functional group, for example, a silanol group, a carboxylic acid group, and a phenolic group, in order to exhibit alkali solubility. Preferable examples of the resin include acrylic resins and polysiloxanes having the aforementioned acidic functional groups. And is preferably polysiloxane in terms of heat resistance.

The alkali-soluble acrylic resin used in the present invention is obtained by polymerizing a polymerized unit of an unsaturated carboxylic acid (a-1), and other radical polymerizable compound capable of copolymerizing with the unsaturated carboxylic acid (a-1) Other radical polymerizable compound ") (a-2) as a copolymerization component.

The unsaturated carboxylic acid (a-1) used in the present invention is preferably an unsaturated carboxylic acid having an ethylenically unsaturated double bond.

Specific examples of such an unsaturated carboxylic acid (a-1) include monocarboxylic acids such as methacrylic acid, acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid and p-vinylbenzoic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 1,4-cyclohexene dicarboxylic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, methyl-5-norbornene-2,3-dicar Dicarboxylic acids such as dicarboxylic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, and dimethyltetrahydrophthalic acid. Of these, methacrylic acid, acrylic acid, itaconic acid and the like are preferably used.

In the present invention, the unsaturated carboxylic acid (a-1) may be a partially esterified product or a partially-amidated product of the unsaturated carboxylic acid remaining as a part of the carboxylic acid group in a free state, for example, unsaturated dicarboxylic acid Lt; / RTI > may be used. As the half ester or half amide of such an unsaturated carboxylic acid, monomethyl itaconate, monobutyl itaconate and the like are preferably used. These unsaturated carboxylic acids may be used alone or in combination of two or more.

Specific examples of the other radically polymerizable compound (a-2) used in the present invention include glycidyl (meth) acrylate, glycidyl (meth) acrylate, glycidyl (meth) acrylate, glycidyl epoxy (meth) acrylate, 3,4-epoxyheptyl (meth) acrylate,? -ethyl-6,7-epoxyheptyl (meth) Acrylate, allyl glycidyl ether, vinyl glycidyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and 3-vinyl cyclohexene oxide Epoxy group-containing radically polymerizable compounds; (Meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, lauryl (meth) acrylate, (Meth) acrylic acid propyl, (meth) acrylic acid phenyl, (meth) acrylate, (meth) acrylate, isopropyl (Meth) acrylate, naphthyl acrylate, anthracenyl (meth) acrylate, cyclopentyl methacrylate, furyl methacrylate, tetrahydrofuryl methacrylate, pyranyl (meth) acrylate, benzyl Phenesil, cresyl (meth) acrylate, 1,1,1-tris (meth) acrylate Perfluoro (meth) acrylate, perfluoro (meth) acrylate, perfluoro (meth) acrylate, perfluoroisopropyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (Meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid- (Meth) acryloyl group-containing radically polymerizable compounds such as (meth) acrylic acid-anilide, (meth) acrylonitrile, and tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate; Acrolein, vinyl chloride, vinylidene chloride, N-vinylpyrrolidone, vinyl acetate, styrene,? -Methylstyrene, omethylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p- Butoxystyrene, chloromethylstyrene, butadiene, 2,3-dimethylbutadiene, isoprene, o-vinylbenzylmethylether, m-vinylbenzylmethylether, p-vinylbenzylmethylether, o-vinylbenzyl Vinyl-containing radically polymerizable compounds such as ethyl ether, m-vinylbenzyl ethyl ether and p-vinylbenzyl ethyl ether; And unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate.

Of these, glycidyl (meth) acrylate, styrene,? -Methylstyrene, pt-butoxystyrene, dicyclopentanyl methacrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, Vinylbenzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl ethyl ether, m-vinyl benzyl ethyl ether, p-vinyl benzyl ethyl ether and the like are preferably used do. By using these compounds as a copolymerization component, it is possible to control the alkali solubility, glass transition temperature, dielectric constant and the like of the polymer, and as a result, performance as a resist such as resolution and residual film ratio and performance as a permanent film such as transparency and heat resistance . These compounds may be used alone or in combination of two or more as a copolymerization component.

The alkali-soluble acrylic resin used in the present invention is obtained by copolymerizing the respective compounds. The alkali-soluble acrylic resin contains the polymerization unit of the unsaturated carboxylic acid (a-1) in an amount of preferably 5 to 50% by weight, particularly preferably 10 to 40% by weight. The alkali-soluble acrylic resin contains the polymerization units of the other radical polymerizable compound (a-2) in an amount of preferably 90% by weight or less, particularly preferably 20 to 60% by weight.

When the content of the polymerized units of the unsaturated carboxylic acid (a-1) in the alkali-soluble acrylic resin is within the above-described preferable range, the resulting coating film has high solubility in a developer composed of an aqueous alkali solution and is excellent in developability and sensitivity. On the other hand, the resulting film does not excessively increase the solubility in an aqueous alkali solution, and the residual film ratio of the obtained resist pattern is not deteriorated. When the content of the polymerized units of the other radical polymerizable compound (a-2) in the alkali-soluble acrylic resin is in the above-described preferable range, the balance of solubility in a developer comprising an alkali aqueous solution of the polymer is good and patterning is easy.

The alkali-soluble acrylic resin used in the present invention preferably has a weight average molecular weight (hereinafter referred to as "Mw") in terms of polystyrene of 2 × 10 ^{3 to} 1 × 10 ⁵ , more preferably 5 × 10 ^{3 to} 5 × 10 ⁴ More preferable. When the Mw is within the above-mentioned preferable range, the resulting film does not deteriorate developability, residual film ratio, etc., and is excellent in pattern shape, heat resistance and the like. On the other hand, there is no case where the sensitivity is lowered or the pattern shape is lowered. In addition, the acrylic resin used in the present invention is alkali-soluble. The acid value of the acrylic resin is preferably 50 to 150 mgKOH / g, more preferably 70 to 130 mgKOH / g. When the acid value of the acrylic resin is within the above-mentioned preferable range, dissolution residue is hardly generated at the time of development. On the other hand, the film thickness of the unexposed portion during development is not increased.

The acrylic resin used in the present invention is obtained by copolymerizing the unsaturated carboxylic acid (a-1) and the other radically polymerizable compound (a-2) by various polymerization methods. Is preferred.

Specific examples of the solvent used for copolymerization include alcohols such as methanol, ethanol, propanol and butanol; Cyclic ethers such as tetrahydrofuran and dioxane; Cellosolve esters such as methyl cellosolve acetate and ethyl cellosolve acetate; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as benzene, toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 4-hydroxy-4-methyl-2-pentanone; Ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy- , Esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, ethyl acetate and butyl acetate; And aprotic polar solvents such as dimethylformamide and N-methyl-2-pyrrolidone. These solvents are used in an amount of usually 20 to 1,000 parts by weight based on 100 parts by weight of the total of the polymerizable compounds [(a-1) and (a-2)].

As the catalyst, those generally known as radical polymerization initiators can be widely used. For example, 2,2'-azobisisobutylonitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) , Azo compounds such as 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxy pivalate and 1,1'-bis (t-butylperoxy) cyclohexane, hydrogen peroxide and the like can be used. When a peroxide is used as the radical polymerization initiator, a peroxide may be used together with a reducing agent to form a redox type polymerization initiator. In the copolymerization, a molecular weight modifier such as? -Methylstyrene dimer may be added.

The acrylic resin has a suitable solubility in an aqueous alkali solution and gives a radiation-sensitive resin composition excellent in high sensitivity, high stickiness rate, developability and the like. The resist pattern obtained by using the acrylic resin is excellent in various properties such as heat resistance, adhesion with a substrate, transparency in visible light range, and chemical resistance.

The alkali-soluble polysiloxane used in the present invention can be obtained by reacting (a-3) at least one organosilane represented by the following formula (2) and / or (a-4) at least one organosilane represented by the following formula And a polysiloxane which is synthesized by hydrolysis and condensation of at least one of them.

In the organosilane represented by the general formula (2) R ⁴ is hydrogen, and represents any one of an aryl group an alkenyl group, a 6 to 15 carbon atoms in the alkyl group of 1 to 10 carbon atoms, having 2 to 10 carbon atoms, plural R ⁴ May be the same or different. These alkyl groups, alkenyl groups and aryl groups may all be either unsubstituted or substituted, and may be selected depending on the characteristics of the composition. Specific examples of the alkyl group and the substituent thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a n-hexyl group, a n-decyl group, a trifluoromethyl group, (3-ethyl-3-oxetanyl) methoxy) propyl group, 1-carboxy-propyl group, 2-carboxypentyl group, 3-aminopropyl group, 3-mercaptopropyl group and 3-isocyanatepropyl group. Specific examples of the alkenyl group and its substituent include vinyl group, 3-acryloxypropyl group and 3-methacryloxypropyl group. Specific examples of the aryl group and its substituent include a phenyl group, a tolyl group, a p-hydroxyphenyl group, a 1- (p-hydroxyphenyl) ethyl group, a 2- (p- - hydroxyphenylcarbonyloxy) pentyl group, and naphthyl group.

R ⁵ in the general formula (2) represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and the plurality of R ^{2 s} may be the same or different. These alkyl groups, acyl groups and aryl groups may all be either unsubstituted or substituted, and may be selected depending on the characteristics of the composition. Specific examples of the alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group. A specific example of the acyl group includes an acetyl group. Specific examples of the aryl group include a phenyl group.

N in the general formula (2) represents an integer of 1 to 3. When n = 1, it is a trifunctional silane, when n = 2, it is a bifunctional silane, and when n = 3, it is a monofunctional silane.

Specific examples of the organosilane represented by the general formula (2) include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, phenyltrimethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ethyltrimethoxysilane, Silane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p- Trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propyltrimethoxysilane, [ 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic acid, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, etc. Trifunctional silane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyl Bifunctional silanes such as methoxysilane, (3-glycidoxypropyl) methyldimethoxysilane and (3-glycidoxypropyl) methyldiethoxysilane, trimethylmethoxysilane, tri-n-butylethoxysilane, (3 (Glycidoxypropyl) dimethylmethoxysilane, and (3-glycidoxypropyl) dimethylethoxysilane. These organosilanes may be used singly or in combination of two or more kinds. Of these organosilanes, trifunctional silanes are preferably used in terms of crack resistance and hardness of the cured film.

In the organosilane represented by the general formula (3), each of R ⁶ to R ⁹ independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms Represents either one. These alkyl groups, acyl groups and aryl groups may all be either unsubstituted or substituted, and may be selected depending on the characteristics of the composition. Specific examples of the alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group. A specific example of the acyl group includes an acetyl group. Specific examples of the aryl group include a phenyl group. M in the general formula (3) is an integer of 1 to 8;

By using the organosilane represented by the general formula (3), a positive photosensitive composition excellent in sensitivity and resolution can be obtained while maintaining high heat resistance and transparency.

In the polysiloxane used in the present invention, the content ratio of the organosilane represented by the general formula (3) is preferably 50% or less based on the molar ratio of Si atom to the total number of Si atoms in the polysiloxane. When the content ratio of the organosilane represented by the general formula (3) in the polysiloxane is within the above-mentioned range of the mole ratio of Si atom to the total number of Si atoms in the polysiloxane, the compatibility of the polysiloxane and the naphthoquinone diazide compound is good, The transparency of the film is excellent. The content ratio of the organosilane represented by the general formula (3) can be obtained by combining ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NMR, IR, TOF-MS, elemental analysis and batch measurement.

Specific examples of the organosilane represented by the general formula (3) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraacetoxysilane , Methyl silicate 51 (manufactured by FUSO KAGAKU KOGYO KABUSHIKI K.K.), M silicate 51, silicate 40, silicate 45 (manufactured by DAMARAKA Kagaku Kogyo K.K.), methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48 (Manufactured by Gorokoto K.K.) and the like.

As the form of the polysiloxane used in the present invention, at least one organosilane represented by the above-mentioned general formula (2) and / or at least one organosilane represented by the general formula (3) Polysiloxane synthesized by reaction may be used. The pattern resolution is improved by reacting the silica particles. This is believed to be because the glass transition temperature of the film is increased by the incorporation of silica particles into the polysiloxane and the reflow of the pattern during thermal curing is suppressed.

The number average particle diameter of the silica particles is preferably from 2 nm to 200 nm, and more preferably from 5 nm to 70 nm. When the number average particle diameter of the silica particles is in the above-mentioned preferable range, the effect of improving the pattern resolution is sufficient. On the other hand, the cured film is hardly light-scattered and excellent in transparency. Here, when the number average particle diameter of the silica particles is used, the silica particles are calcined after drying, the specific surface area of the obtained particles is measured, and the particle diameter is determined from the specific surface area on the assumption that the particles are spherical. The average particle diameter is obtained as the number average. The equipment to be used is not particularly limited, but "ASAP" 2020 (trade name, manufactured by Micromeritics) can be used.

As specific examples of the silica particles, IPA-ST having a particle diameter of 12 nm in which isopropanol is used as a dispersion medium, MIBK-ST having a particle diameter of 12 nm using methylisobutylketone as a dispersion medium, IPA-ST-L having a particle diameter of 45 nm in isopropanol as a dispersion medium, IPA-ST-ZL having a particle size of 100 nm as a dispersion medium, PGM-ST (trade name, manufactured by Nissan Kagaku Kogyo K.K.) having a particle diameter of 15 nm and using propylene glycol monomethyl ether as a dispersion medium and? -Butyrolactone "Oscar" 101 having a particle diameter of 12 nm, "Oscal" 105 having a particle diameter of 60 nm made of γ-butyrolactone as a dispersion medium, "Oscal" 106 having a particle diameter of 120 nm made of a diacetone alcohol as a dispersion medium, "Qataron" -S (trade name, manufactured by Shokuba Kasei Kogyo Co., Ltd.) having a particle diameter of 5 to 80 nm, "Qwatron" PL-2L-PGME having a particle diameter of 16 nm and propylene glycol monomethyl ether as a dispersion medium, - a "quartz particle " having a particle size of 17 nm, Quot; PL-2L-BL ", PL-2L-BL, "Qwatron" PL-2L-DAA having a particle size of 17 nm and diacetone alcohol as a dispersion medium, " (over trade name, manufactured by Fuso Kagaku Kogyo (Co., Ltd.)), a particle size of 100nm in silica (SiO ₂₎ SG-SO100 (trade name, manufactured by Kyoritsu mate rial (Ltd.)), particle size of 5~50nm "Leo (Trade name, manufactured by Tokuyama Corporation), and the like. These silica particles may be used alone or in combination of two or more.

The mixing ratio when the silica particles are used is not particularly limited, but is preferably 70% or less by mole of Si atom relative to the number of moles of Si atoms in the whole polysiloxane. When the mixing ratio in the case of using the silica particles is in the above-mentioned range of the mole ratio of Si to the number of moles of Si atoms in the whole polysiloxane, the compatibility of the polysiloxane and the naphthoquinone diazide compound is good, and the transparency of the cured film is excellent.

In order to secure sufficient compatibility with the naphthoquinone diazide compound and the like to be described later in the polysiloxane used in the present invention and to form a uniform cured film without phase separation, the content of phenyl groups in the polysiloxane is preferably 5 Mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, particularly preferably 40 mol% or more. When the content of the phenyl group is within the above-mentioned preferable range, the polysiloxane and the naphthoquinone diazide compound hardly cause phase separation during coating, drying, thermosetting, etc., so that the film is not cloudy and the permeability of the cured film is excellent. The content of the phenyl group is preferably 70 mol% or less, more preferably 60 mol% or less, and still more preferably 50 mol% or less. When the content of the phenyl group is within the above-mentioned preferable range, crosslinking at the time of thermosetting sufficiently occurs and the chemical resistance of the cured film is excellent. The content of the phenyl group can be determined, for example, from ²⁹ Si-NMR measurement of the polysiloxane and the ratio of the peak area of Si bonded to the phenyl group to the peak area of Si not bonded to the phenyl group.

In the polysiloxane used in the present invention, the content of the epoxy group and / or vinyl group in the polysiloxane is preferably at least 1 mol%, more preferably at least 3 mol%, still more preferably at least 5 mol% Or more, particularly preferably 10 mol% or more. When the content of the epoxy group and / or vinyl group is within the above-mentioned preferable range, the solvent resistance of the photosensitive resin composition is excellent. The content of the epoxy group and / or vinyl group is preferably 70 mol% or less, more preferably 50 mol% or less. When the content of the epoxy group and / or vinyl group is within the above-mentioned preferable range, the polysiloxane and the naphthoquinone diazide compound hardly cause phase separation during coating, drying, thermosetting, etc., so that the film is not cloudy and the cured film has excellent transmittance. The content of the epoxy group and / or vinyl group can be determined, for example, from ²⁹ Si-NMR of the polysiloxane, the ratio of the peak area of Si bonded with the epoxy group and / or vinyl group to the peak area of Si not bonded with epoxy group and / Or the content of an epoxy group and / or a vinyl group can be obtained by measuring the content of epoxy group and / or vinyl group by measurement of ¹ H-NMR and ¹³ C-NMR and combining with the measurement of ²⁹ Si-NMR have.

The weight average molecular weight (Mw) of the polysiloxane used in the present invention is not particularly limited, but is preferably 500 to 100,000, more preferably 1,000 to 50,000 in terms of polystyrene measured by GPC (gel permeation chromatography) . When the Mw of the polysiloxane is in the above-mentioned preferable range, the coating film is good and the solubility in the developer at the time of pattern formation is good.

The polysiloxane in the present invention is synthesized by hydrolysis and partial condensation of monomers such as organosilanes represented by the general formulas (2) and / or (3). General methods can be used for hydrolysis and partial condensation. For example, a solvent is added to the mixture, if necessary, and the mixture is heated and stirred at 50 to 150 캜, preferably 90 to 130 캜 for 0.5 to 100 hours. The hydrolysis by-products (alcohol such as methanol) and condensation by-products (water) may be distilled off by distillation as necessary during stirring.

The reaction solvent is not particularly limited, but usually used is the same solvent as the (C) solvent described later. The amount of the solvent to be added is preferably 10 to 1,000 parts by weight based on 100 parts by weight of the monomer such as organosilane. The amount of water to be used for the hydrolysis reaction is preferably 0.5 to 2 moles relative to 1 mole of the hydrolyzable group.

The catalyst to be added as needed is not particularly limited, but an acid catalyst and a base catalyst are preferably used. Specific examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid or an anhydride thereof and ion exchange resins. Specific examples of the base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, An alkoxysilane having an amino group, and an ion exchange resin. The addition amount of the catalyst is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the monomer such as organosilane.

From the viewpoint of the storage stability of the composition, it is preferable that the polysiloxane solution after the hydrolysis and partial condensation contains no catalyst, and the catalyst can be removed if necessary. The method of removing the catalyst is not particularly limited, but water washing and / or treatment with an ion exchange resin is preferred from the viewpoints of simplicity of operation and removability. The water washing is a method of diluting a polysiloxane solution with an appropriate hydrophobic solvent, washing it several times with water, and concentrating the obtained organic layer with an evaporator or the like. Treatment with an ion exchange resin is a method in which a polysiloxane solution is contacted with an appropriate ion exchange resin.

The positive photosensitive composition of the present invention contains (B) a naphthoquinone diazide compound. A positive photosensitive composition containing a naphthoquinone diazide compound forms a positive type in which an exposed portion is removed by a developer. The naphthoquinone diazide compound to be used is not particularly limited, but a compound in which a naphthoquinone diazide sulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group, and the ortho position and para position of the phenolic hydroxyl group of the compound are independently A hydrogen, a hydroxyl group, or a substituent represented by any one of formulas (4) to (5) is preferably used.

In the formulas, R ¹⁰ , R ¹¹ and R ¹² each independently represents any one of an alkyl group, a carboxyl group, a phenyl group and a substituted phenyl group having 1 to 10 carbon atoms. R ¹⁰ , R ¹¹ and R ¹² may form a ring. The alkyl group may be either non-substituted or substituted, and may be selected depending on the characteristics of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, A trifluoromethyl group, and a 2-carboxyethyl group. Examples of the substituent on the phenyl group include a hydroxyl group and a methoxy group. Specific examples of the ring formed by R ¹⁰ , R ¹¹ and R ¹² include a cyclopentane ring, a cyclohexane ring, an adamantane ring, and a fluorene ring.

When the ortho position and the para position of the phenolic hydroxyl group are the above preferable substituents, oxidative decomposition is hardly caused even by thermosetting, and it is difficult to form a conjugated system compound represented by a quinoid structure. Therefore, the cured film is hardly colored, maintain. These naphthoquinone diazide compounds can be synthesized by a known esterification reaction of a compound having a phenolic hydroxyl group and naphthoquinonediazidesulfonyl chloride.

Specific examples of the compound having a phenolic hydroxyl group include the following compounds (all manufactured by Honshu Kagaku Kogyo Co., Ltd.).

As the naphthoquinonediazide sulfonic chloride as a raw material, 4-naphthoquinonediazidesulfonic chloride or 5-naphthoquinonediazidesulfonic chloride can be used. The 4-naphthoquinone diazidesulfonic acid ester compound is suitable for i-line exposure since it absorbs in the i-line (wavelength 365 nm) region. In addition, the 5-naphthoquinone diazidesulfonic acid ester compound is suitable for exposure at a wide range of wavelengths because of absorption in a wide wavelength range. It is preferable to select a 4-naphthoquinone diazide sulfonic acid ester compound and a 5-naphthoquinone diazide sulfonic acid ester compound by the wavelength to be exposed. A 4-naphthoquinone diazidesulfonic acid ester compound and a 5-naphthoquinone diazidesulfonic acid ester compound may be mixed and used.

As the naphthoquinone diazide compound preferably used in the present invention, there may be mentioned a compound represented by the following general formula (6).

In the formulas, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ represent any one of a hydrogen atom, an alkyl group, an alkoxyl group, a carboxyl group and an ester group selected from 1 to 8 carbon atoms. Each of R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different. R ¹⁷ represents hydrogen or an alkyl or aryl group selected from 1 to 8 carbon atoms. Q represents any one of a 5-naphthoquinonediazidesulfonyl group and a hydrogen atom, and Q is not a hydrogen atom at all. a, b, c, d, e,?,?,?, and? However,? +? +? +?? 2. By using the naphthoquinone diazide compound represented by the general formula (6), sensitivity and resolution in pattern processing are improved.

The amount of the naphthoquinone diazide compound to be added is not particularly limited, but is preferably 2 to 30 parts by weight, more preferably 3 to 15 parts by weight, per 100 parts by weight of the alkali-soluble resin.

When the addition amount of the naphthoquinone diazide compound is in the above preferable range, the dissolution contrast between the exposed portion and the unexposed portion is sufficiently high and sufficient photosensitivity can be exhibited for practical use. On the other hand, compatibility of the polysiloxane with the naphthoquinone diazide compound It is difficult to cause bleaching of the coating film, and coloration due to decomposition of the quinone diazide compound during thermal curing is difficult to occur, so that the colorless transparency of the cured film is maintained. Further, in order to obtain a better dissolution contrast, 5 parts by weight or more is more preferable. Further, in order to obtain a film with higher transparency, it is more preferably 20 parts by weight or less, particularly preferably 15 parts by weight or less, and most preferably 10 parts by weight or less.

The positive photosensitive composition of the present invention contains (C) a solvent. The solvent to be used is not particularly limited, but a compound having an alcoholic hydroxyl group is preferably used. When these solvents are used, the alkali-soluble resin and the quinone diazide compound are uniformly dissolved, and even when the composition is coated, the film is not whitened and high transparency can be achieved.

The compound having an alcoholic hydroxyl group is not particularly limited, but is preferably a compound having a boiling point at atmospheric pressure of 110 to 250 캜. When the boiling point is in the above-mentioned preferable range, drying at the coating film is not too fast, the film surface is hard to be roughened and the film property is good, while the amount of the residual solvent in the film is small and the film shrinkage during curing is small and excellent flatness is obtained.

Specific examples of the compound having an alcoholic hydroxyl group include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy- (Diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono n- Butyl ether, propylene glycol mono t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 3-methoxy- Methyl-3-methoxy-1-butanol, and the like. These compounds having an alcoholic hydroxyl group may be used alone or in combination of two or more.

The positive photosensitive composition of the present invention may contain other solvents as long as the effect of the present invention is not impaired. Examples of the other solvent include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1 -butylacetate, Butyl acetate, and ethyl acetoacetate; ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone and acetylacetone; ketones such as diethyl ether, diisopropyl ether, di-n-butyl ether, Examples of the solvent include ethers such as diphenyl ether, diethylene glycol ethyl methyl ether and diethylene glycol dimethyl ether,? -Butyrolactone,? -Valerolactone,? -Valerolactone, propylene carbonate, N-methylpyrrolidone, Pentanone, cyclohexanone, cycloheptanone, and the like.

The amount of the solvent to be added is not particularly limited, but is preferably in the range of 100 to 2,000 parts by weight based on 100 parts by weight of the alkali-soluble resin.

The photosensitive resin composition of the present invention (D) contains a metal chelate compound represented by the following general formula (1).

In the metal chelate compound represented by the general formula (1), M is a metal atom. R ¹ may be the same or different and each represents hydrogen, an alkyl group, an aryl group, an alkenyl group, and a substituent thereof. R ² and R ³ may be the same or different and each represents hydrogen, an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a substituent thereof. j represents a valence of a metal atom M, and k represents an integer of 0 to j.

By containing the metal chelate compound used in the present invention, the development adhesion and the wet heat resistance of the resulting cured film are improved.

In the general formula (1), M is a metal atom, and although not particularly limited, metal atoms such as titanium, zirconium, aluminum, zinc, cobalt, molybdenum, lanthanum, barium, strontium, . And is preferably a metal atom of zirconium or aluminum from the viewpoints of adhesion and wet heat resistance.

R ¹ is a group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decanyl group, A vinyl group, an allyl group, and an oleyl group. Among them, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n- An octadecyl group, and a phenyl group are preferable. R ² and R ³ are each independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, N-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n- An octadecyl group, and a benzyloxy group. Of these, a methyl group, a t-butyl group, a phenyl group, a methoxy group, an ethoxy group and an n-octadecyl group are preferable in that synthesis is easy and the compound is stable.

Examples of the compound represented by the general formula (1) include zirconium tetra n-propoxide, zirconium tetra n-butoxide, zirconium tetra sec-butoxide, zirconium tetraphenoxide, zirconium tetraacetylacetonate, (2,2,6,6-tetramethyl-3,5-heptanedionate), zirconium tetramethylacetoacetate, zirconium tetraethylacetoacetate, zirconium tetramethylmalonate, zirconium tetraethylmalonate, zirconium tetrabenzoyl acetone (Acetylacetonate), zirconium mono-n-butoxytris (acetyl acetonate), zirconium mono-n-butoxyethylacetoacetate bis Acetonate), zirconium mono n-butoxytris (acetylacetonate) (Ethyl malonate), zirconium di (n-butoxy) bis (ethyl acetoacetate), zirconium di (n-butoxy) -Butoxy) bis (benzoyl acetonate), and zirconium di (n-butoxy) bis (dibenzoylmethanate).

Examples of the aluminum compound include aluminum tris isopropoxide, aluminum tris n-propoxide, aluminum tris sec-butoxide, aluminum tris n-butoxide, aluminum trisphenoxide, aluminum trisacetylacetonate, aluminum tris , 6,6-tetramethyl-3,5-heptanedionate), aluminum tris ethyl acetoacetate, aluminum tris methylacetoacetate, aluminum trismethyl malonate, aluminum tris ethyl malonate, aluminum ethyl acetate di (isopropoxide ), Aluminum acetylacetonate di (isopropoxide), aluminum methyl acetoacetate di (isopropoxide), aluminum octadecyl acetoacetate di (isopropylate), aluminum monoacetylacetonate bis (ethylacetoacetate) And the like.

Examples of the titanium compound include titanium tetra n-propoxide, titanium tetra n-butoxide, titanium tetra-butoxide, titanium tetra phenoxide, titanium tetraacetylacetonate, titanium tetra (2,2,6,6- Heptanedionate), titanium tetramethylacetoacetate, titanium tetraethylacetoacetate, titanium tetramethylmalonate, titanium tetraethylmalonate, titanium tetrabenzoyl acetonate, titanium tetradibenzoylmethanate, titanium mono n- Butoxyethylacetonate bis (ethylacetoacetate), titanium mono-n-butoxyethylacetoacetate bis (acetylacetonate), titaniummono-n-butoxytris (acetylacetonate), titaniummono-n-butoxytris Acetonate), titanium di (n-butoxy) bis (ethylacetoacetate), titanium di (n-butoxy) bis (N-butoxy) bis (ethyl malonate), titanium di (n-butoxy) bis (benzoyl acetonate), titanium di Tetra-2-ethylhexyloxide and the like.

Among them, zirconium tetra n-propoxide, zirconium tetra n-butoxide, zirconium tetraphenoxide, zirconium tetraacetylacetonate, zirconium tetra (2,2,6 , 6-tetramethyl-3,5-heptanedionate), zirconium tetramethylmalonate, zirconium tetraethyl malonate, zirconium tetraethylacetoacetate, zirconium di n-butoxybis (ethylacetoacetate) Butoxyacetyl acetonate bis (ethylacetoacetate), titanium tetra n-propoxide, titanium tetra n-butoxide, titanium tetra phenoxide, titanium tetraacetylacetonate, titanium tetra (2,2,6,6-tetra Methyl-3,5-heptanedionate), titanium tetramethylmalonate, titanium tetraethyl malonate, titanium tetraethyl acetoacetate, titanium butoxybis (ethylacetoacetate), and titanium mono n-butoxyacetylacetonate bis (ethylacetoacetate), aluminum trisacetylacetonate, aluminum tris (2,2,6,6-tetramethyl-3,5 Aluminum tris (meth) acrylate, aluminum tris (acetoacetate), aluminum (tris (meth) acrylate, (Methoxyacetate), aluminum methacetoacetate di (isopropoxide), aluminum octadecyl acetoacetate di (isopropylate) and aluminum monoacetylacetonate bis (ethylacetoacetate) are more preferable, .

In the photosensitive resin composition of the present invention, the content of the metal chelate compound (D) is 0.1-5 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). When the content of the metal chelate compound (D) is less than 0.1 parts by weight based on 100 parts by weight of the alkali-soluble resin (A), there is a problem that the resistance to wet heat and heat is poor. When the amount is more than 5 parts by weight, the unexposed portions to be dissolved in the developer do not dissolve and the photosensitive characteristics deteriorate.

The content of the metal chelate compound (D) is preferably 0.3 to 4 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). However, when the metal having high catalytic activity, for example, the metal atom (M) is aluminum, the amount is preferably 0.1 to 1.5 parts by weight, more preferably 0.3 to 1.0 parts by weight.

The content of the metal chelate compound according to the fluorescent X-ray analysis, inductively coupled plasma mass spectrometry (ICP-MS) and the metal quantitative analysis by the atomic absorption spectrometry, gas chromatography, liquid ^{chromatography, 1 H-NMR, 13 C} -NMR It is possible to identify and quantify it by performing organic analysis. Zirconium, aluminum, zinc, cobalt, molybdenum, lanthanum, barium, strontium, magnesium and the like can be formed from the photosensitive resin composition or the cured film by fluorescent X-ray analysis, inductively coupled plasma mass spectrometry (ICP- , And calcium can be analyzed. The metal is contained in an amount of 0.005 to 1 part by weight based on 100 parts by weight of the alkali-soluble resin composition.

The positive photosensitive composition of the present invention may contain additives such as a dissolution accelerator, a silane coupling agent, a crosslinking agent, a crosslinking accelerator, a sensitizer, a heat radical generator, a dissolution inhibiting agent, a surfactant, have.

In particular, the positive photosensitive composition of the present invention preferably contains a dissolution accelerator for adjusting the solubility in an alkali developing solution. As the dissolution promoter, specific examples of the above-mentioned compounds having a phenolic hydroxyl group include phenolic compounds and N-hydroxyimide compounds of the above-mentioned short-chain. An example of the N-hydroxyimide compound is N-hydroxy-5-norbornene-2,3-hydroxyimide.

The phenolic compound is not particularly limited, but from the viewpoint of transparency, a phenol compound used as a raw material of the naphthoquinone diazide compound described above is preferable. That is, a phenolic compound having 2 to 6 benzene rings and 2 to 4 phenolic hydroxyl groups in the molecule is preferable. In addition, from the viewpoints of heat resistance and heat resistance, phenol compounds containing no secondary carbon (-CH ₂ -), tertiary carbon (-CH =), or cycloalkane groups are preferable. Examples of preferred phenolic compounds are shown below.

Surprisingly, the addition of a phenol compound to the photosensitive resin composition of the present invention drastically improves resistance to moisture and humidity. It can be inferred that the heat and humidity resistance is improved due to the hydrophobic barrier effect expressed by the packing property between the aromatic rings of the phenol compound. The content of the phenol compound is preferably 1 to 30 parts by weight, more preferably 3 to 15 parts by weight, based on 100 parts by weight of the alkali-soluble resin. If the content of the phenol compound is within the above-mentioned preferable range with respect to 100 parts by weight of the alkali-soluble resin, the effect of moisture and heat resistance is sufficient, while the effect of promoting dissolution is not excessively increased.

The positive photosensitive composition of the present invention preferably contains a crosslinking agent. The crosslinking agent is a compound which is crosslinked with an alkali-soluble resin, a dissolution accelerator or the like used in the present invention at the time of thermal curing and is introduced into the resin, and the crosslinking degree of the cured film is increased by inclusion thereof. As a result, the chemical resistance and moisture resistance of the cured film are improved, and the pattern resolution due to pattern reflow during thermal curing is suppressed from being lowered.

The crosslinking agent is not particularly limited, but preferably includes compounds having two or more structures selected from the group consisting of a methylol-based structure, an epoxy structure and an oxetane structure represented by the general formula (7). The combination of the above structures is not particularly limited, but the structures selected are preferably the same.

In the methylol compounds having two or more methylol-based structures represented by the general formula (7), R ¹⁸ represents any one of hydrogen and alkyl groups having 1 to 10 carbon atoms. The plurality of R < ¹⁸ > in the compound may be the same or different. Specific examples of the alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group and n-decyl group.

Specific examples of methylol-based compounds having two or more methylol-based structures include DM-BI25X-F, 46DMOC, 46DMOIPP and 46DMOEP (trade names, available from Asahi Yuki Kagaku Kogyo Co., Ltd.) DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, Dimethylol- DML-Bis25X-PCHP (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd., trade name; product of Dainippon Ink and Chemicals, Inc.) (Trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p- , 6-diacetoxymethyl-p-cresol, and the like. TriML-P, TriML-35XL and TriML-TrisCR-HAP (all trade names, manufactured by Honshu Kagaku Kogyo Co., Ltd.) having three methylol structures are exemplified. TML-BP, TML-BPA, TMOM-BP (manufactured by Asahi Yuki Kagaku Kogyo Co., Ltd.), TML-BP, TML-HQ, (Trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), NIKARAK MX-280 and NIKARAK MX-270 (trade names, available from Sanwa Chemical Co., Ltd.). HML-TPHAP, HML-TPHAP, HMOM-TPPHBA and HMOM-TPHAP (trade names, manufactured by Honshu Kagaku Kogyo K.K.), NIKARAK MW-390, NIKARAK MW-100LM , NIKARAK 30-HM (trade name, manufactured by SANWA CHEMICAL Co., Ltd.), and the like.

Of these, in the present invention, it is preferable to contain at least two heat-crosslinkable groups, particularly preferably 46DMOC, 46DMOEP, DML-MBPC, DML-MBOC, DML-OCHP, DML- PML, DML-PSBP, DML-MTrisPC, NIKARAK MX-290, Ba-type benzoquinone, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML- Dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, TML-BP, TML-BPA, TMML-BP, TML-BP, and TML-BP, which have three crosslinkable groups and have four thermal crosslinking groups such as TriML-P and TriML- HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA and HMOM-TPHAP, which have six thermally crosslinkable groups such as "NIKARAK" MX-280 and "NIKARAK" MX-270. More preferred examples include "NIKARAK MX-280," NIKARAK MX-270, NIKARAK MW-100LM, NIKARAK MW-390, NIKARAK 30HM (trade name, ), And the like.

Among the crosslinking agents (e), for example, a compound having a methylol group or a methylol group substituted with a hydrogen atom of an alcoholic hydroxyl group is crosslinked by a reaction mechanism added directly to the benzene ring as described below.

The structure of a typical thermally crosslinkable compound particularly preferably used in the photosensitive resin composition of the present invention is shown below. In particular, when the methylol-based compound and the above-mentioned phenol compound are combined with the positive photosensitive composition of the present invention, the heat and humidity resistance of the cured film is remarkably improved.

Specific examples of the compound having two or more epoxy structures or oxetane structures include "Epolite" 40E, Copper 100E, Copper 200E, Copper 400E, Copper 70P, Copper 200P, Copper 400P, Copper 1500NP, Copper 80MF, Copper 4000, Copper 3002 EX-214L, EX-216L, EX-850L and EX-321L (trade names, available from Nagase Chemtex Co., Ltd., trade name, available from Kyoeisha Chemical Co., GAN, GOT, EPPN502H, NC3000, NC6000 (trade names, manufactured by Nippon Kayaku), "Epicoat" 828, 1002, 1750, 1007, YX8100-BH30, E1256, E4250 , E4275 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), "Epiclon" EXA-9583, Copper HP4032, Copper N695, Copper HP7200 (trade names, manufactured by Dainippon Ink and Chemicals, S, copper G and copper P (trade names, manufactured by Nissan Chemical Industries, Ltd.) and "Ecototo" YH-434L (trade names, manufactured by TOKO KASEI CO., LTD.).

The crosslinking agent may be used alone or in combination of two or more.

The amount of the crosslinking agent to be added is not particularly limited, but is preferably in the range of 0.1 to 20 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the addition amount of the crosslinking agent is within the above-mentioned preferable range, the crosslinking effect of the resin is sufficient, while the colorless transparency of the cured film is maintained, and the storage stability of the composition is also excellent.

The positive photosensitive composition of the present invention may contain a silane coupling agent. The incorporation of the silane coupling agent improves the adhesion to the substrate.

Specific examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n- Propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinyltrimethoxy Silane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxy Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) Propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-gly Glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- Ethyl-3-oxetanyl) methoxy] propyltrimethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxy Silyl propyl succinic acid, Nt-butyl-3- (3-trimethoxysilylpropyl) succinic acid imide, and organosilanes represented by the general formula (3).

(In the organosilane represented by the general formula (3), R ⁶ to R ⁹ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms , And these alkyl groups, acyl groups, and aryl groups may all be either unsubstituted or substituted)

Specific examples of the organosilane represented by the general formula (3) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraacetoxysilane , Methyl silicate 51 (manufactured by FUSO KAGAKU KOGYO KABUSHIKI K.K.), M silicate 51, silicate 40, silicate 45 (manufactured by DAMARAKA Kagaku Kogyo K.K.), methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48 (Manufactured by Gorokoto K.K.) and the like.

Preferred examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-ureidopropyltriethoxysilane, Nt-butyl-3- (3-trimethoxysilylpropyl) succinic acid imide, tetra Methoxy silane, tetraethoxy silane, tetra-n-propoxy silane, tetraisopropoxy silane, tetra-n-butoxy silane, tetraacetoxy silane, methyl silicate 51 (manufactured by Fusokagaku Kogyo K.K.) Methyl silicate 51, methyl silicate 53A, ethyl silicate 40 and ethyl silicate 48 (manufactured by Gorukoto K.K.) are used as the silicate 51, the silicate 40, and the silicate 45 (manufactured by Tama Kagaku Kogyo K.K.).

The amount of the silane coupling agent to be added is not particularly limited, but is preferably in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the added amount of the silane coupling agent is in the above-mentioned preferable range, the effect of improving the adhesion is sufficient, and on the other hand, the silane coupling agents are difficult to condense with each other during storage, so that no dissolution residue at the time of development occurs.

The positive photosensitive composition of the present invention may contain a surfactant. By containing a surfactant, coating unevenness is improved, and a uniform coating film is obtained. Fluorine-based surfactants and silicone-based surfactants are preferably used.

Specific examples of the fluorine-based surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octa Ethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di , 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2- 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N- [3- (perfluorooctanesulfonamide) propyl ] -N, N'-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidepropyltrimethylammonium salt, perfluoroalkyl-N-ethylsulfonylglycine salt, bisphosphate (N-perfluorooctylsulfur N-ethylaminoethyl), monoperfluoroalkylethylphosphoric acid esters and the like A fluorine-based surfactant comprising a compound having at least one of a terminal, a main chain and a side chain and having a fluoroalkyl or fluoroalkylene group. As commercial products, "Megapack" F142D, copper F172, copper F173, copper F183, copper F444, copper 445, copper F475, copper 477 (manufactured by Dainippon Ink and Chemicals, Inc.) 430, Copper-431 (manufactured by Sumitomo Heavy Industries, Ltd.)), "Asahi Guard" AG710, "Surfron" S (Manufactured by Asahi Glass Co., Ltd.), BM-1000, BM-1100 (manufactured by Asahi Kasei Corporation), SC-101, SC-102, SC-103, SC- Fluorochemical surfactants such as NBX-15, FTX-218 and DFX-218 (manufactured by Neos Co., Ltd.).

Examples of commercially available silicone surfactants include SH28PA, SH7PA, SH21PA, SH30PA and ST94PA (both manufactured by Toray Dow Corning Silicone Co., Ltd.) and BYK-333 (manufactured by Big Chem Japan Co., Ltd.).

The content of the surfactant is generally preferably 0.0001 to 1% by weight in the photosensitive composition.

The positive photosensitive composition of the present invention may contain a crosslinking accelerator. The crosslinking accelerator is a compound that promotes crosslinking of the alkali-soluble resin upon thermal curing. A thermal acid generator that generates an acid at the time of thermal curing or a photo acid generator that generates acid at the time of bleaching exposure prior to thermosetting is used. The presence of an acid in the film during thermal curing accelerates the condensation reaction of the unreacted silanol group and the epoxy group in the alkali-soluble resin and increases the degree of crosslinking of the cured film. As a result, the chemical resistance of the cured film is improved, the pattern resolution is prevented from lowering due to pattern reflow during thermal curing, and the chemical resistance is improved.

The thermal acid generator preferably used in the present invention is a compound which generates an acid upon thermal curing and preferably does not generate an acid or only a small amount at the time of prebaking after application of the composition. Therefore, the compound is preferably a compound which generates an acid at a temperature higher than the prebaking temperature, for example, 100 占 폚 or higher. If the compound generates an acid at a temperature higher than the prebaking temperature, the alkali-soluble resin does not cross-link at the time of prebaking, so that the sensitivity is not lowered and no residues are generated at the time of development.

Specific examples of the preferable thermal acid generators are "Sun Aid" SI-60, SI-80, SI-100, SI-200, SI-110, SI- SI-160L, SI-180L (trade name, available from Sanxin Kagaku Kogyo Co., Ltd.), 4-hydroxyphenyldimethylsulfonium trifluoromethanesulfo Benzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenyldimethylsulfoniumtrifluoro Methoxycarbonyloxyphenyldimethylsulfonium trifluoromethanesulfonate, benzyl-4-methoxycarbonyloxyphenylmethylsulfate, benzyl-4-methoxycarbonyloxyphenylmethylsulfonate, 4-methoxybenzylsulfonium trifluoromethanesulfonate, Sulfonium trifluoromethanesulfonate (the above, manufactured by SANSHIN KAGAKU KOGYO CO., LTD.), And the like. These compounds may be used alone or in combination of two or more.

The photoacid generator preferably used in the present invention is an acid generating compound at the time of briquetting exposure and is a compound which generates acid upon exposure to light having an exposure wavelength of 365 nm (i line), 405 nm (h line), 436 nm (g line) Is a compound which generates an acid. Therefore, although acid exposure may occur even in the case of pattern exposure using the same light source, pattern exposure does not occur only in a small amount of acid because it has a small exposure amount as compared with the britting exposure. The acid to be generated is preferably a strong acid such as perfluoroalkylsulfonic acid or p-toluenesulfonic acid, and the quinone diazide compound in which a carboxylic acid is generated does not have the function of the photoacid generator described above. And does not function as a crosslinking accelerator.

Specific examples of the photoacid generator that is preferably used include SI-100, SI-101, SI-105, SI-106, SI-109, PI-105, PI-106, PI-109, NAI- NAI-1003, NAI-1004, NAI-101, NAI-105, NAI-106, NAI-109, NDI-101, NDI-105, NDI-106, NDI-109, PAI- (Trade name, manufactured by ADEKA), TPS-PFBS (trade name, manufactured by TOYO KASEI KOGYO CO., LTD.), PA-1001 (trade name, manufactured by Midori Kagaku Co., Ltd.), SP- ), CGI-MDT, CGI-NIT (trade names, manufactured by Chiba Japan), WPAG-281, WPAG-336, WPAG-339, WPAG-342, WPAG-344, WPAG- -372, WPAG-449, WPAG-469, WPAG-505 and WPAG-506 (all trade names, manufactured by Wako Pure Chemical Industries, Ltd.). These compounds may be used alone or in combination of two or more.

It is also possible to use the thermal acid generator and the photo acid generator described above as a crosslinking accelerator in combination. The amount of the crosslinking accelerator to be added is not particularly limited, but is preferably in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the addition amount is within the above-mentioned preferable range, the effect of accelerating the crosslinking is sufficient, and on the other hand, crosslinking of the polysiloxane is hard to occur during prebaking or pattern exposure.

The positive photosensitive composition of the present invention may contain a sensitizer. The inclusion of the sensitizer accelerates the reaction of the naphthoquinone diazide compound, which is a photosensitizer, thereby improving the sensitivity. In addition, when the photoacid generator is contained as a crosslinking accelerator, the reaction during the brittic exposure is promoted, .

The sensitizer used in the present invention is not particularly limited, but a sensitizer that is vaporized by heat treatment and / or a sensitizer that is discolored by light irradiation is used. This sensitizer is required to have absorption at 365 nm (i line), 405 nm (h line), and 436 nm (g line), which are the wavelengths of the light source in the pattern exposure or the brizing exposure, There is a case where the colorless transparency is lowered because of the absorption in the visible light region. Therefore, the sensitizer used for preventing the deterioration of the colorless transparency due to the sensitizer is a compound (sensitizer) that is vaporized by light irradiation such as a compound (sensitizer) vaporized by heat treatment such as thermal curing and / .

Specific examples of the sensitizer that is vaporized by the heat treatment and / or the sensitizer that is discolored by light irradiation include coumarin such as 3,3'-carbonylbis (diethylaminocoumarin), anthraquinone such as 9,10- , Aromatic ketones such as benzophenone, 4,4'-dimethoxybenzophenone, acetophenone, 4-methoxyacetophenone and benzaldehyde, biphenyl, 1,4-dimethylnaphthalene, 9-fluorenone, fluorene, phenanthrene , Triphenylene, pyrene, anthracene, 9-phenylanthracene, 9-methoxyanthracene, 9,10-diphenylanthracene, 9,10-bis (4-methoxyphenyl) anthracene, 9,10- Silane) anthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, Butyl-9,10-dibutoxyanthracene, and 9,10-bis (trimethylsilylethynyl) anthracene.

Among these sensitizers, the sensitizer which is vaporized by the heat treatment is preferably a sensitizer that sublimates, evaporates, or sublimates or pyrolyses pyrolysis products by thermal treatment. The vaporization temperature of the sensitizer is preferably 130 to 400 캜. When the vaporization temperature of the sensitizer is within the above-described preferable range, the sensitizer can be maintained at a high level since it is present in the exposure process without vaporization during prebaking, while the sensitizer does not remain in the cured film due to vaporization during thermal curing, . In order to suppress vaporization during prebaking as much as possible, the vaporization temperature of the sensitizer is more preferably 150 ° C or higher. Further, in order to vaporize sufficiently during thermal curing, the vaporization temperature of the sensitizer is preferably 250 DEG C or less.

On the other hand, from the viewpoint of transparency, the sensitizer that fades by light irradiation is preferably a sensitizer whose absorption in the visible light region is discolored by light irradiation. Further, the compound which discolors upon further light irradiation is a compound which is dimerized by light irradiation. By diminution by light irradiation, the molecular weight is increased to insolubilize, so that the effect of improving chemical resistance, heat resistance, and reducing the extract from the transparent cured film can be obtained.

Further, in addition to being capable of achieving high sensitivity, the sensitizer is preferably an anthracene-based compound in that it is dimerized by light irradiation and is discolored. Further, since the 9,10-2 substituted anthracene compound is stable to heat Do. Further, 9,10-dialkoxy anthracene-based compounds represented by the general formula (8) are more preferred from the viewpoint of improvement of the solubility of the sensitizer and reactivity of the photo-dimerization reaction.

R ¹⁹ to R ²⁶ in the general formula (8) each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group, an aryl group, an acyl group, and an organic group substituted with any of them. Specific examples of the alkyl group include a methyl group, an ethyl group and an n-propyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentyloxy group. Specific examples of the alkenyl group include a vinyl group, an acryloxypropyl group, and a methacryloxypropyl group. Specific examples of the aryl group include a phenyl group, a tolyl group and a naphthyl group. A specific example of the acyl group includes an acetyl group. R ¹⁹ to R ²⁶ are preferably hydrogen or an organic group having 1 to 6 carbon atoms in view of the vaporization property of the compound and the reactivity of photo-dimerization. More preferably, R ¹⁹ , R ²² , R ²³ and R ²⁶ are preferably hydrogen.

R ²⁷ and R ²⁸ in the general formula (8) represent an alkoxy group having 1 to 20 carbon atoms, and an organic group substituted by R ²⁷ and R ²⁸ . Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentyloxy group, but a propoxy group and a butoxy group are preferable from the viewpoint of the solubility of the compound and the discoloration reaction due to optical dimerization.

The amount of the sensitizer to be added is not particularly limited, but it is preferably added in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the addition amount of the sensitizer is in the above-mentioned preferable range, the transparency is not lowered or the sensitivity is not lowered.

A method of forming a cured film using the positive photosensitive composition of the present invention will be described. The positive photosensitive composition of the present invention is coated on a base substrate by a known method such as a spinner or a slit and is prebaked by a heating apparatus such as a hot plate or oven. The prebaking is preferably performed at a temperature in the range of 50 to 150 占 폚 for 30 seconds to 30 minutes, and the film thickness after prebaking is preferably 0.1 to 15 占 퐉.

After prebaking, an ultraviolet visible light exposure apparatus such as a stepper, a mirror projection mask aligner (MPA), a paralelite light mask aligner (PLA), or the like is used and the exposure amount is adjusted to 10 to 4,000 J / m ² Pattern exposure through a mask.

After exposure, the exposed portions are dissolved by development, and a positive pattern can be obtained. As the developing method, it is preferable to immerse the developing solution for 5 seconds to 10 minutes by a method such as shower, dip or paddle. As the developer, a known alkali developer can be used. Specific examples thereof include inorganic alkalis such as hydroxides, carbonates, phosphates, silicates and borates of alkali metals, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and choline, And aqueous solutions containing two or more species. After development, it is preferable to rinse with water. If necessary, dehydration and drying baking may be performed in a range of 50 to 150 캜 by a heating device such as a hot plate or an oven.

After that, it is preferable to perform brittleness exposure. By performing the brittic exposure, the unreacted naphthoquinone diazide compound remaining in the film is photolyzed to further improve the optical transparency of the film. As a method of brittleness exposure, an ultraviolet visible light exposure apparatus such as PLA is used and exposed to the front surface at about 100 to 20,000 J / m ² (wavelength 365 nm in terms of exposure dose).

When a brieching exposed film is required, soft baking is performed in a temperature range of 50 to 150 占 폚 for 30 seconds to 30 minutes by a heating apparatus such as a hot plate or an oven, and the resultant is heated in a heating apparatus such as a hot plate or oven at 150 to 450 占 폚 Curing is performed for about 1 hour to form a planarizing film for a TFT in a display element, an interlayer insulating film in a semiconductor element, or a cured film called a core or clad material in an optical waveguide.

The cured film produced using the positive photosensitive composition of the present invention has a light transmittance of 85% or more, more preferably 90% or more, per 3 m of the film thickness at a wavelength of 400 nm. When the light transmittance is lower than 85%, when used as a flattening film for a TFT substrate of a liquid crystal display element, a color change occurs when the backlight passes and the white display is yellowish.

The transmittance per 3 m of the film thickness at the wavelength of 400 nm is obtained by the following method. The composition is spin-coated on a Tampax glass plate using a spin coater at an arbitrary number of revolutions, and pre-baked at 100 DEG C for 2 minutes using a hot plate. Thereafter, PLA was used as a britting exposure, and an ultra-high pressure mercury lamp was exposed at an exposure dose of 3,000 J / m ² (365 nm in terms of exposure dose) onto the entire surface of the film. The film was thermally cured at 220 캜 for one hour in the air using an oven, Of the cured film. The ultraviolet visible absorption spectrum of the obtained cured film was measured using MultiSpec-1500 manufactured by Shimadzu Corporation, and the transmittance at a wavelength of 400 nm was determined.

This cured film is preferably used for a flattening film for a TFT in a display element, an interlayer insulating film in a semiconductor element, an insulating film or a protective film for a touch panel, or a core or clad material in an optical waveguide.

The element in the present invention refers to a display element, a semiconductor element, or an optical waveguide material having a cured film of high heat resistance and high transparency as described above, and particularly relates to a liquid crystal as a planarization film for a TFT, And is preferable for a display element having a panel function.

Example

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples. On the other hand, the abbreviations of the used compounds are shown below.

DAA: diacetone alcohol

PGMEA: Propylene glycol monomethyl ether acetate

GBL:? -Butyrolactone

EDM: diethylene glycol methyl ethyl ether

DPM: dipropylene glycol monoether methyl.

The solid content concentration of the polysiloxane solution, the acrylic resin solution, and the weight average molecular weight (Mw) of the polysiloxane and acrylic resin were determined as follows.

(1) Solid concentration

1 g of the polysiloxane solution or acrylic resin solution was weighed in an aluminum cup and heated at 250 DEG C for 30 minutes using a hot plate to evaporate the liquid content. The solid content remaining in the aluminum cup after heating was weighed to determine the solid content concentration of the polysiloxane solution or acrylic resin.

(2) Weight average molecular weight

The weight average molecular weight was determined by GPC (410 type RI detector manufactured by Waters, fluidized bed: tetrahydrofuran) in terms of polystyrene.

(3) the ratio of the organosilane structure represented by the general formula (2) and the general formula (3) in the polysiloxane

²⁹ Si-NMR was measured, and the ratio of the integral value to each organosilane was calculated from the total integrated value, and the ratio was calculated.

The sample (liquid) was injected into a 10 mm diameter Teflon (registered trademark) NMR sample tube and used for the measurement. ²⁹ Si-NMR measurement conditions are shown below.

Apparatus: JNM GX-270 manufactured by JEOL Ltd. Measuring method: gated decoupling method

Measurement nuclear frequency: 53.6693 MHz ( ²⁹ Si nuclei), spectrum width: 20000 Hz

Pulse width: 12 占 sec (45 占 pulse), pulse repetition time: 30.0 sec

Solvent: acetone-D6, reference material: tetramethylsilane

Measurement temperature: room temperature, sample rotation speed: 0.0 Hz.

Synthesis Example 1: Synthesis of polysiloxane solution (A1-a)

(0.60 mol) of methyltrimethoxysilane, 59.49 g (0.30 mol) of phenyltrimethoxysilane, (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (0.10 mol) of DAA and 163.1 g of DAA were added, and an aqueous phosphoric acid solution in which 0.54 g of phosphoric acid (0.3% by weight based on the input monomer) was dissolved in 55.8 g of water was added over 10 minutes while stirring at room temperature. Was immersed in an oil bath at 40 DEG C and stirred for 30 minutes, and then the temperature of the oil bath was elevated to 115 DEG C over 30 minutes. After 1 hour from the start of heating, the inner temperature of the solution reached 100 DEG C, The inside temperature was 100 to 110 占 폚) to obtain a polysiloxane solution (A1-a). Nitrogen was flowed at 0.05 L / min during heating and stirring.

The solids concentration of the obtained polysiloxane solution (A1-a) was 43% by weight, and the weight average molecular weight of the polysiloxane was 4,200. The content ratio of the phenyl group-substituted silane in the polysiloxane was 30% by mol of the Si atom.

Synthesis Example 2: Synthesis of polysiloxane solution (A1-b)

A 500-mL three-necked flask was charged with 54.48 g (0.40 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (0.1 mol) of DAA and 179.5 g of DAA were added, and while stirring at room temperature, an aqueous phosphoric acid solution of 0.54 g (0.3% by weight based on the input monomer) of phosphoric acid was added to 55.8 g of water over 10 minutes. Was immersed in an oil bath at 40 DEG C and stirred for 30 minutes. Thereafter, the oil bath was heated to 115 DEG C over 30 minutes. After 1 hour from the start of the temperature rise, the inner temperature of the solution reached 100 DEG C, (At an internal temperature of 100 to 110 DEG C) to obtain a polysiloxane solution (A1-b), and nitrogen was flowed at 0.05 L / min during heating and stirring.

The solids concentration of the obtained polysiloxane solution (A1-b) was 42% by weight, and the weight average molecular weight of the polysiloxane was 3,200. The content ratio of the phenyl group-substituted silane in the polysiloxane was 50% in terms of the molar ratio of Si atoms.

Synthesis Example 3: Synthesis of polysiloxane solution (A1-c)

Into a 500 mL three-necked flask, 27.24 g (0.20 mol) of methyltrimethoxysilane, 138.81 g (0.70 mol) of phenyltrimethoxysilane, (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (0.1 mol) of DAA and 195.89 g of DAA, and while stirring at room temperature, an aqueous solution of phosphoric acid in which 0.54 g (0.3% by weight based on the input monomer) of phosphoric acid was dissolved in 55.8 g of water was added over 10 minutes. Was immersed in an oil bath at 40 DEG C and stirred for 30 minutes. Thereafter, the oil bath was heated to 115 DEG C over 30 minutes. After 1 hour from the start of the temperature rise, the inner temperature of the solution reached 100 DEG C, (100-110 占 폚), and a polysiloxane solution (A1-c) were also obtained. During the heating and stirring, nitrogen was flowed at 0.05 L / min.

The solid content concentration of the obtained polysiloxane solution (A1-c) was 41% by weight, and the weight average molecular weight of the polysiloxane was 3,000. The content ratio of the phenyl group-substituted silane in the polysiloxane was 70% in terms of the molar ratio of Si atoms.

Synthesis Example 4: Synthesis of polysiloxane solution (A1-d)

40.86 g (0.30 mol) of methyltrimethoxysilane, 99.15 g (0.5 mol) of phenyltrimethoxysilane, (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 17.63 g (0.15 mol) of M silicate 51 (manufactured by Tamakagaku Kogyo K.K.) and 170.77 g of PGMEA were charged, and while stirring at room temperature, 53.55 g of water and 0.51 g of phosphoric acid The flask was immersed in an oil bath at 40 DEG C and stirred for 30 minutes, and then the oil bath was heated to 115 DEG C over a period of 30 minutes. After 1 hour from the start, the inside temperature of the solution reached 100 占 폚, and thereafter the mixture was heated and stirred for 2 hours (with an internal temperature of 100 to 110 占 폚) to obtain a polysiloxane solution (A1-d) min. During the reaction, a total of 125 g of the by-product methanol and water were distilled.

The solids concentration of the obtained polysiloxane solution (A1-d) was 43% by weight, and the weight average molecular weight of the polysiloxane was 8,500. The content ratio of the phenyl group-substituted silane in the polysiloxane was 50% in terms of the molar ratio of Si atoms.

Synthesis Example 5: Synthesis of polysiloxane solution (A1-e)

24.52 g (0.18 mol) of methyltrimethoxysilane, 118.98 g (0.60 mol) of phenyltrimethoxysilane, (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 42.30 g (0.36 mol) of M silicate 51 (0.36 mol) and 181.89 g of PGMEA were charged, and while stirring at room temperature, 62.64 g of water and 0.60 g of phosphoric acid (added to the charging monomer The flask was immersed in an oil bath at 40 DEG C and stirred for 30 minutes, and then the oil bath was heated to 115 DEG C over a period of 30 minutes. After 1 hour from the initiation of the reaction, the internal temperature of the solution reached 100 占 폚, followed by stirring with heating for 2 hours (internal temperature of 100 to 110 占 폚) to obtain a polysiloxane solution (A1-e) min. During the reaction, a total of 150 g of the by-product methanol and water were distilled.

The solids concentration of the obtained polysiloxane solution (A1-e) was 44% by weight, and the weight average molecular weight of the polysiloxane was 11,400. The content ratio of the phenyl group-substituted silane in the polysiloxane was 50% in terms of the molar ratio of Si atoms.

Synthesis Example 6: Synthesis of polysiloxane solution (A1-f)

40.86 g (0.30 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Aqueous solution of phosphoric acid in which 0.57 g of phosphoric acid (0.3 wt% based on the input monomer) was dissolved in 57.60 g of water was added over 10 minutes while stirring at room temperature. Then, Was immersed in an oil bath at 40 DEG C and stirred for 30 minutes. Thereafter, the oil bath was heated to 115 DEG C over 30 minutes. After 1 hour from the start of the temperature rise, the inner temperature of the solution reached 100 DEG C, (100 ° C to 110 ° C), and a polysiloxane solution (Al-f) were obtained in the same manner as in Example 1. Further, nitrogen was flowed at 0.05 L / min during heating and stirring.

The solids concentration of the obtained polysiloxane solution (A1-f) was 43% by weight, and the weight average molecular weight of the polysiloxane was 8,000. The content ratio of the phenyl group-substituted silane in the polysiloxane was 50% in terms of the molar ratio of Si atoms.

Synthesis Example 7: Synthesis of polysiloxane solution (A1-g)

20.43 g (0.15 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 17.63 g (0.15 mol) of M silicate 51 (manufactured by Tamakagaku Kogyo K.K.) and 170.90 g of PGMEA were charged, and while stirring at room temperature, to 56.25 g of water, 0.56 g of phosphoric acid The flask was immersed in an oil bath at 40 DEG C and stirred for 30 minutes, and then the oil bath was heated to 115 DEG C over a period of 30 minutes. After 1 hour from the initiation of the reaction, the internal temperature of the solution reached 100 占 폚, and the resulting mixture was heated and stirred for 2 hours (with an internal temperature of 100 to 110 占 폚) to obtain a polysiloxane solution (A1- min. During the reaction, 139 g of methanol and water, which are by-products, were distilled out in total.

The solids concentration of the obtained polysiloxane solution (A1-g) was 43 wt%, and the weight average molecular weight of the polysiloxane was 9,500. The content ratio of the phenyl group-substituted silane in the polysiloxane was 50% in terms of the molar ratio of Si atoms.

Synthesis Example 8: Synthesis of polysiloxane solution (A1-h)

27.24 g (0.20 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane And 173.02 g of PGMEA were added thereto and an aqueous phosphoric acid solution in which 0.60 g of phosphoric acid (0.3% by weight based on the input monomer) was dissolved in 59.40 g of water was added over 10 minutes while stirring at room temperature. Was immersed in an oil bath at 40 DEG C and stirred for 30 minutes. Thereafter, the oil bath was heated to 115 DEG C over 30 minutes. After 1 hour from the start of the temperature rise, the inner temperature of the solution reached 100 DEG C, (Temperature of 100-110 deg. C), and a polysiloxane solution (A1-h) were obtained in the same manner as in Example 1. Further, nitrogen was flowed at 0.05 L / min during heating and stirring.

The solids concentration of the obtained polysiloxane solution (A1-h) was 43% by weight, and the weight average molecular weight of the polysiloxane was 9,500. The content ratio of the phenyl group-substituted silane in the polysiloxane was 50% in terms of the molar ratio of Si atoms.

Synthesis Example 9: Synthesis of polysiloxane solution (A1-i)

27.24 g (0.20 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 29.65 g (0.20 mol) of vinyltrimethoxysilane and 164.40 g of PGMEA were charged, and while stirring at room temperature, 0.54 g of phosphoric acid (0.3% by weight based on the input monomer) was dissolved in 55.80 g of water The flask was immersed in an oil bath at 40 DEG C and stirred for 30 minutes, and then the oil bath was heated to 115 DEG C over a period of 30 minutes. After 1 hour from the start of the heating, And the resulting solution was heated and stirred for 2 hours with stirring to obtain a polysiloxane solution (A1-i) at a temperature of 100 to 110 DEG C. Nitrogen was flowed at 0.05 L / min during heating and stirring. Methanol and water were distilled in a total amount of 139 g.

The solids concentration of the obtained polysiloxane solution (A1-i) was 43% by weight, and the weight average molecular weight of the polysiloxane was 8,800. The content ratio of the phenyl group-substituted silane in the polysiloxane was 50% in terms of the molar ratio of Si atoms.

Synthesis Example 10: Synthesis of polysiloxane solution (A1-j)

68.10 g (0.50 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane and 150.40 g of PGMEA were added to a 500-mL three-necked flask, and while stirring at room temperature, 0.50 g (0.3% by weight based on the input monomer) dissolved therein was added over 10 minutes. Thereafter, the flask was immersed in an oil bath at 40 DEG C and stirred for 30 minutes, and then the oil bath was heated to 115 DEG C over 30 minutes. After 1 hour from the start of raising the temperature, the internal temperature of the solution reached 100 占 폚, and thereafter the mixture was heated and stirred for 2 hours (with an internal temperature of 100 to 110 占 폚) to obtain a polysiloxane solution (A1-j). Further, nitrogen was flowed at 0.05 L / min during heating and stirring. During the reaction, 137 g of methanol and water as a by-product were distilled.

The solids concentration of the obtained polysiloxane solution (A1-j) was 43% by weight, and the weight average molecular weight of the polysiloxane was 7,000. The content ratio of the phenyl group-substituted silane in the polysiloxane was 50% in terms of the molar ratio of Si atoms.

Synthesis Example 11: Synthesis of acrylic resin solution (A2-a)

5 g of 2,2'-azobis (isobutyronitrile), 5 g of t-dodecanethiol, and 180 g of PGMEA were placed in a 500 mL flask. Thereafter, 40 g of methacrylic acid, 35 g of benzyl methacrylate and 35 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were added, stirred at room temperature, and the inside of the flask was purged with nitrogen , And the mixture was heated and stirred at 70 占 폚 for 5 hours. 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine and 0.2 g of p-methoxyphenol were added to the obtained solution, and the mixture was heated and stirred at 90 占 폚 for 4 hours to obtain an acrylic resin solution (A2-a) .

The solid content concentration of the obtained acrylic resin solution (A2-a) was 40% by weight, the weight average molecular weight of the acrylic resin was 12,000, and the acid value was 91 mgKOH / g.

Synthesis Example 12: Synthesis of naphthoquinone diazide compound (B-a)

21.23 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Kagaku Kogyo K.K.) and 37.62 g (0.14 mol) of 5-naphthoquinonediazide sulfonyl chloride were added to a 1,4-di And dissolved in 450 g of oxalic acid, to room temperature. 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise to prevent the temperature from exceeding 35 占 폚. After dropwise addition, the mixture was stirred at 30 ° C for 2 hours. The triethylamine salt was filtered off and the filtrate was poured into water. Thereafter, the precipitated precipitate was collected by filtration. This precipitate was dried with a vacuum drier to obtain a naphthoquinone diazide compound (B-a) having the following structure.

Synthesis Example 13: Synthesis of naphthoquinone diazide compound (B-b)

(0.05 mol) of TrisP-HAP (trade name, manufactured by Honshu Kagaku Kogyo K.K.) and 26.87 g (0.1 mol) of 5-naphthoquinonediazide sulfonyl chloride were added to a 1,4-di And dissolved in 450 g of oxalic acid, to room temperature. Then, 11.13 g (0.11 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise to prevent the temperature from exceeding 35 占 폚. After dropwise addition, the mixture was stirred at 30 ° C for 2 hours. The triethylamine salt was filtered off and the filtrate was poured into water. Thereafter, the precipitated precipitate was collected by filtration. This precipitate was dried with a vacuum drier to obtain a naphthoquinone diazide compound (B-b) having the following structure.

Synthesis Example 14: Synthesis of naphthoquinone diazide compound (B-c)

15.32 g (0.05 mol) of Ph-cc-AP (trade name, manufactured by Honshu Kagaku Kogyo K.K.) and 37.62 g (0.14 mol) of 5-naphthoquinonediazide sulfonyl chloride were added to a 1,4- - dioxane (450 g), and the solution was cooled to room temperature. 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise to prevent the temperature from exceeding 35 占 폚. After dropwise addition, the mixture was stirred at 30 ° C for 2 hours. The triethylamine salt was filtered off and the filtrate was poured into water. Thereafter, the precipitated precipitate was collected by filtration. This precipitate was dried with a vacuum drier to obtain a naphthoquinone diazide compound (B-c) having the following structure.

Synthesis Example 15: Synthesis of naphthoquinone diazide compound (B-d)

A naphthoquinone diazide compound (B-d) having the following structure was obtained in the same manner as in Synthesis Example 10, except that the amount of 5-naphthoquinone diazidesulfonyl chloride was changed to 33.59 g (0.125 mol).

(Example 1)

15.43 g of the polysiloxane solution (A1-a) obtained in Synthesis Example 1, 0.59 g of the naphthoquinone diazide compound (Ba) obtained in Synthesis Example 7, 3.73 g of DAA as a solvent and 9.84 g of PGMEA were mixed and stirred under yellow light The mixture was made into a homogeneous solution and filtered through a 0.45 탆 filter to prepare Composition 1.

Using a spin coater (1H-360S manufactured by Mikasa), the composition 1 was applied to a glass substrate having a silicon wafer and an OA-10 glass plate (manufactured by Nippon Denshikarasu Co., Ltd.) and a molybdenum film, , And then pre-baked at 90 ° C for 2 minutes using a hot plate (SCW-636, manufactured by Dainippon Screen Shoji Co., Ltd.) to prepare a film having a thickness of 3 μm. The film thus formed was subjected to pattern exposure through a gray scale mask for sensitivity measurement using a paralelite light mask aligner (hereinafter abbreviated as PLA) (PLA-501F manufactured by Canon Inc.) (Manufactured by Mitsubishi Gas Kagaku Co., Ltd.), which is a 2.38 wt% tetramethylammonium hydroxide aqueous solution, using an apparatus (AD-2000 manufactured by Takikazawa Sangyo Co., Ltd.) for 60 seconds, Rinse. Thereafter, PLA (PLA-501F, manufactured by Canon Inc.) was used as a britting exposure, and an ultrahigh-pressure mercury lamp was exposed to the entire surface of the film at 3,000 J / m ² (at a wavelength of 365 nm in terms of exposure dose).

Thereafter, soft baking was performed at 110 DEG C for 2 minutes using a hot plate, and then cured at 230 DEG C in the air for 1 hour by using an oven (IHPS-222 manufactured by TBA Co., Ltd.) to prepare a cured film.

The evaluation results of the photosensitive characteristics and the cured film properties are shown in Table 5. The photosensitive characteristics and the cured film characteristics were evaluated by the following methods. The evaluations of (9) to (8) below were performed on a silicon wafer substrate, the evaluation of (9) was performed on an OA-10 glass plate and the evaluations of (10) to (11) were performed using a glass substrate on which a molybdenum sputter film was formed I did.

(4) Measurement of film thickness

The measurement was carried out at a refractive index of 1.50 using Lamuda Ace STM-602 (trade name, manufactured by Dainippon Screen).

(5) Decrease in film thickness of unexposed portion during development

The film thickness reduction of the unexposed portion at the time of development was calculated according to the following formula.

Film thickness reduction of unexposed portion = film thickness before development-film thickness after development of unexposed portion

(6) Calculation of sensitivity

The amount of exposure (hereinafter referred to as optimal exposure amount) for forming a line-and-space pattern of 10 mu m after exposure and development with a width of 1: 1 was taken as sensitivity.

(7) Calculation of resolution

The minimum pattern size after development in the optimum exposure amount was set as the post-development resolution, and the minimum pattern size after curing was set as the post-cure resolution.

(8) Heat resistance

The cured film prepared by the method described in Example 1 was removed from the substrate, about 10 mg of the cured film was put into an aluminum cell, and a thermogravimetric analyzer (TGA-50, manufactured by Shimadzu Corporation) Heated to 150 ° C / min and held at 150 ° C for 1 hour, and then heated to 400 ° C at a heating rate of 10 ° C / min. At this time, a temperature Td1% at which the weight loss was 1% was measured and compared. The higher the Td1%, the better the heat resistance.

(9) Measurement of light transmittance

First, only the OA-10 glass plate was measured using MultiSpec-1500 (trade name, Shimadzu Corporation), and the ultraviolet visible absorption spectrum thereof was taken as a reference. Then, a cured film of the composition was formed on the OA-10 glass plate (pattern exposure was not performed), and the sample was measured with a single beam to determine the light transmittance at a wavelength of 400 nm per 3 m, Respectively.

(10) Developing adhesion

The minimum pattern size remaining on the substrate after the development of the film residue pattern produced by the method described in (1) above on the glass substrate on which the molybdenum sputter film was formed was defined as the developing adhesion. The finer the pattern, the easier it is to peel off at the time of development, and the smaller the value, the better the adhesion to the development.

(11) Humidity Resistance

A cured film was formed on the glass substrate on which the molybdenum sputter film was formed by the method described in the above (1), and then a chamber ("HAST CAHMBER EHS-221MD (trade name)", manufactured by Espace Kabushiki Kaisha) having a humidity of 100% &Quot;) for 10 hours or 24 hours, and then the degree of discoloration of molybdenum was evaluated. Further, the glass substrates of only the molybdenum sputter film were tested at the same time, and determined as an index of the degree of discoloration before and after the test.

5: No discoloration of molybdenum under the curing membrane is observed before and after the test.

4: An area of about 1% was discolored before and after the test as compared with the case where molybdenum under the curing membrane was not covered with the cured film.

3: An area of about 2% was discolored before and after the test compared with the case where molybdenum under the curing membrane was not covered with the cured film.

2: An area of about 4% was discolored before and after the test as compared with the case where molybdenum under the curing membrane was not covered with the cured film.

1: As compared with the case where molybdenum under the curing membrane was not covered with the cured film before and after the test, an area of about 6% or more was discolored.

(Examples 2 to 40 and Comparative Examples 1 to 4)

Compositions 2 to 35 were prepared in the same compositions as shown in Tables 1 to 4 as in Composition 1. KBM303 used as a silane coupling agent is (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Phenol compounds Phcc-AP and TrisP-PA , NIKARAK MW-390 and NIKARAK-MX270 (trade names, manufactured by Sanwa Chemical Co., Ltd.) used as a crosslinking agent are compounds having the structures shown below.

Further, CGI-MDT (trade name, manufactured by Chiba Japan K.K.) used as a crosslinking accelerator and WPAG-469 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) were prepared by reacting 4-methylphenyldiphenylsulfonium parafluorobutanesulfonate 20% PGMEA solution, and DPA (trade name, manufactured by Kawasaki Kasei Kogyo Co., Ltd.) used as a sensitizer were 9,10-dipropoxyanthracene.

Each of the obtained compositions was used to evaluate each composition in the same manner as in Example 1. However, in the evaluation of the acrylic resin, development was carried out by showering with 0.4 wt% aqueous solution of tetramethylammonium hydroxide for 60 seconds. The results are shown in Tables 5 and 6. In Comparative Example 4, the amount of the chelate compound to be added was too large, so that even when an exposure amount of 3,000 J / m ² was irradiated, the resolution did not occur.

(Industrial availability)

The positive photosensitive composition of the present invention can be suitably used for a planarizing film for a thin film transistor (TFT) substrate such as a liquid crystal display element or an organic EL display element, a protective film or insulating film for a touch panel, an interlayer insulating film for a semiconductor element, A lens array pattern, or a core or clad material of an optical waveguide.

Claims (16)

1. A positive photosensitive composition comprising (A) an alkali-soluble polysiloxane, (B) a naphthoquinone diazide compound, (C) a solvent, and (D) a metal chelate compound,
The metal chelate compound (D) has a structure represented by the following general formula (1), and the content of the metal chelate compound (D) is 0.3 to 4 parts by weight based on 100 parts by weight of the alkali-soluble polysiloxane (A)
Wherein the content of the phenyl group in the alkali-soluble polysiloxane (A) is 5 mol% or more and 60 mol% or less based on Si atoms.

[In the metal chelate compound represented by the general formula (1), M is a zirconium metal atom. R ¹ may be the same or different and each represents hydrogen, an alkyl group, an aryl group, an alkenyl group, or a substituent thereof. R ² and R ³ may be the same or different and each represents hydrogen, an alkyl group, an aryl group, an alkenyl group, an alkoxy group, or a substituent thereof. j is a valence of a zirconium metal atom M, and k is an integer of 0 to j. delete delete delete delete delete The method according to claim 1,
Wherein the content of the epoxy group and / or vinyl group in the alkali-soluble polysiloxane (A) is 1 mol% or more and 50 mol% or less based on Si atoms. The method according to claim 1,
Wherein the positive photosensitive composition further contains an organosilane represented by the general formula (3) as a silane coupling agent.

[In the organosilane represented by the general formula (3), each of R ⁶ to R ⁹ independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms ≪ / RTI > These alkyl groups, acyl groups, and aryl groups may all be either unsubstituted or substituted. and m is an integer of 1 to 8.] The method according to claim 1,
A positive photosensitive composition according to claim 1, further comprising a dissolution promoting agent. 10. The method of claim 9,
Wherein the dissolution-promoting agent is a phenol compound. The method according to claim 1,
Wherein the positive photosensitive composition further comprises a crosslinking agent. 12. The method of claim 11,
Wherein the cross-linking agent comprises a methylol-based compound. A cured film formed from the positive photosensitive composition according to claim 1, wherein the cured film has a light transmittance of 3% or more at a wavelength of 400 nm of 85% or more. A cured film formed from the positive photosensitive composition according to claim 1, wherein the cured film has a zirconium metal content of 0.005 to 1 part by weight based on 100 parts by weight of the alkali-soluble polysiloxane. An element comprising the cured film according to claim 13. delete