CN108693710B - Positive photosensitive polysiloxane composition - Google Patents

Abstract

The present invention relates to a positive photosensitive polysiloxane composition, which is used for forming a planarization film or an interlayer insulating film of a TFT substrate, or a protective film of an optical waveguide core material or a coating material, and has excellent chemical resistance. The positive photosensitive siloxane composition comprises polysiloxane (A), o-naphthoquinone diazide sulfonic ester (B), solvent (C) and silane compound (D).

Description

Positive Photosensitive Polysiloxane Composition

technical field

The present invention relates to a positive photosensitive film suitable for flattening films or interlayer insulating films of TFT substrates such as liquid crystal display components and organic electroluminescent display components, or protective films of core materials or cladding materials of optical waveguides. A silicone composition, a thin film formed therefrom, and a device having the thin film. In particular, a positive photosensitive polysiloxane composition with good chemical resistance, a film formed therefrom, and a device having the film are provided.

Background technique

In recent years, in the field of semiconductor industry, liquid crystal display or organic electroluminescent display, etc., with the shrinking size, the demand for miniaturization of patterns required in the lithography process is also increasing. In order to achieve miniaturized patterns, it is generally formed by exposing and developing positive-type photosensitive materials with high resolution and high sensitivity. Among them, the positive-type photosensitive materials composed of polysiloxane polymers have gradually become the industry's most widely used mainstream.

In a liquid crystal display or an organic electroluminescent display, an interlayer insulating film is usually disposed between layered wirings as insulation. Positive-type photosensitive materials are widely used as materials for forming interlayer insulating films because the number of necessary steps to obtain a pattern shape is small, and at the same time, the obtained insulating film has good flatness.

For example, for an interlayer insulating film used in a liquid crystal display, it is necessary to form a pattern of contact holes for fine wiring. In fact, it is very difficult for the contact hole formed by the negative photosensitive composition to reach the usable level. Therefore, the industry widely uses the positive photosensitive composition to form the interlayer insulating film of the liquid crystal display module (such as Japan Special Technology Co., Ltd. Open No. 2001-354822).

Generally, the main component of a positive-type photosensitive composition for forming an interlayer insulating film is an acrylic resin, but the photosensitive composition using silicone-based materials has better heat resistance and transparency than those using acrylic resin materials. A photosensitive composition is preferable (as disclosed in Japanese Patent Laid-Open No. 2000-1648).

However, silane compounds or polysiloxane-based materials of polysiloxane are prone to hydrolysis and condensation reactions with the same or different types of compounds. When preparing the positive photosensitive composition, the occurrence of these side reactions will lead to the deterioration of the storage stability of the positive photosensitive composition, and the life of the product will also be shortened.

In order to suppress the above-mentioned condensation reaction, the industry has developed to suppress the condensation reaction by controlling the molecular weight and branched structure of polysiloxane. Japanese Patent Laid-Open No. 2003-163209 discloses that polysiloxanes with different molecular weights can be obtained through the action of acid catalysts, metal chelates and base catalysts to control the structure of the polysiloxanes. However, although the above publications disclose various molecular weights of polysiloxanes, they do not take into account the photosensitive properties of the polysiloxanes; nor do they consider various properties of the interlayer insulating film other than the dielectric constant.

Under such circumstances, Japanese Patent Application Laid-Open No. 2011-123450 discloses a positive photosensitive polysiloxane composition, which has excellent photosensitivity, storage stability and melt flow resistance. However, the positive photosensitive The chemical resistance of the polysiloxane composition is not good, so it cannot be accepted by the industry.

Therefore, how to simultaneously meet the current industrial requirements for chemical resistance is the goal of diligent research in the technical field of the present invention.

Contents of the invention

In the present invention, a positive-type photosensitive polysiloxane composition with good chemical resistance is obtained by using components that provide special silane compounds.

Therefore, the present invention provides a kind of positive photosensitive polysiloxane composition, it comprises:

Polysiloxane (A);

o-naphthoquinone diazide sulfonate (B);

solvent (C); and

Silane compound (D);

Wherein, the silane compound (D) has a structure shown in formula (D-1):

In formula (D-1):

R represents an unsubstituted or substituted alkyl group with ¹ to 10 carbons, or an unsubstituted or substituted aryl group with 6 to 10 carbons;

Each of R2 independently represents an unsubstituted or substituted alkyl group with ¹ to 20 carbon atoms, an unsubstituted or substituted aryl group with 6 to 10 carbon atoms, or an unsubstituted or substituted aryl group with 7 to 10 carbon atoms Aralkyl, unsubstituted or substituted alkenyl with 2 to 10 carbons, or unsubstituted or substituted organooxy with 1 to 20 carbons;

R ³ represents an unsubstituted or substituted alkyl group with 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group with 6 to 10 carbon atoms;

n is an integer from 1 to 3; and

m is an integer of 1 to 3.

The present invention also provides a method for forming a thin film on a substrate, which includes applying the aforementioned positive photosensitive polysiloxane composition to the substrate.

The present invention further provides a thin film on a substrate, which is prepared by the aforementioned method.

The present invention also provides a flattening film or an interlayer insulating film of a TFT substrate in a liquid crystal display component or an organic electroluminescence display, or a protective film of an optical waveguide core material or a cladding material, which is produced by the aforementioned method have to.

The present invention further provides a device comprising the aforementioned thin film.

The present invention further provides a device, which comprises the planarization film or interlayer insulating film of the TFT substrate in the aforementioned liquid crystal display assembly or organic electroluminescent display, or the protective film of the core material or cladding material of the optical waveguide

Detailed ways

Therefore, the present invention provides a kind of positive photosensitive polysiloxane composition, it comprises:

Polysiloxane (A);

o-naphthoquinone diazide sulfonate (B);

solvent (C); and

Silane compound (D);

Wherein, the silane compound (D) has a structure shown in formula (D-1):

In formula (D-1):

R represents an unsubstituted or substituted alkyl group with ¹ to 10 carbons, or an unsubstituted or substituted aryl group with 6 to 10 carbons;

Each of R2 independently represents an unsubstituted or substituted alkyl group with ¹ to 20 carbon atoms, an unsubstituted or substituted aryl group with 6 to 10 carbon atoms, or an unsubstituted or substituted aryl group with 7 to 10 carbon atoms Aralkyl, unsubstituted or substituted alkenyl with 2 to 10 carbons, or unsubstituted or substituted organooxy with 1 to 20 carbons;

R ³ represents an unsubstituted or substituted alkyl group with 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group with 6 to 10 carbon atoms;

n is an integer from 1 to 3; and

m is an integer of 1 to 3.

Each component of the positive photosensitive polysiloxane composition used in the present invention will be described in detail below.

It is explained here that (meth)acrylic acid is used to represent acrylic acid and/or methacrylic acid, and (meth)acrylate is used to represent acrylate and/or methacrylate; similarly, (meth) Acryloyl represents acryloyl and/or methacryloyl.

The type of polysiloxane (A) according to the present invention is not particularly limited as long as the object of the present invention can be achieved. Polysiloxane (A) can be synthesized by polycondensation (ie, hydrolysis and partial condensation) of silane monomers, or by polycondensation of silane monomers and other polymerizable compounds.

The silane monomer includes silane monomer (a-1) and silane monomer (a-2); other polymerizable compounds include siloxane prepolymer (a-3), silica particles (a-4) , or a combination thereof. Hereinafter, each component and the reaction steps and conditions of polycondensation will be further described.

The silane monomer (a-1) is a compound represented by the formula (I-1): Si(R ^a ) _w (OR ^b ) _4-w

Formula (I-1)

In the formula (I-1), R ^a each independently represents a hydrogen atom, an alkyl group with a carbon number of 1 to 10, an alkenyl group with a carbon number of 2 to 10, an aromatic group with a carbon number of 6 to 15, an acid anhydride group-containing An alkyl group with a carbon number of 1 to 10, an alkyl group with an epoxy group with a carbon number of 1 to 10 or an alkoxy group with an epoxy group, at least one R ^a represents an acid anhydride group with a carbon number of 1 to 10 An alkyl group, an alkyl group containing an epoxy group with a carbon number of 1 to 10, or an alkoxy group containing an epoxy group;

R ^b each independently represent a hydrogen atom, an alkyl group with 1 to 6 carbons, an acyl group with 1 to 6 carbons or an aromatic group with 6 to 15 carbons; and

w represents an integer of 1 to 3.

More specifically, when R ^a in the formula (I-1) represents an alkyl group having 1 to 10 carbon atoms, specifically, R ^a is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl or n-decyl. R ^a can also be an alkyl group with other substituents on the alkyl group. Specifically, R ^a is, for example, trifluoromethyl, 3,3,3-trifluoropropyl, 3-aminopropyl, 3-mercaptopropane group or 3-isocyanatopropyl group.

When R ^a in the formula (I-1) represents an alkenyl group having a carbon number of 2 to 10, specifically, R ^a is, for example, a vinyl group. R ^a may be an alkenyl group having other substituents on the alkenyl group. Specifically, R ^a is, for example, 3-acryloyloxypropyl or 3-methacryloyloxypropyl.

When R ^a in formula (I-1) represents an aromatic group having 6 to 15 carbon atoms, specifically, R ^a is, for example, phenyl, tolyl or naphthyl. R ^a can also be an aryl group with other substituents on the aryl group. Specifically, R ^a is, for example, p-hydroxyphenyl (o-hydroxyphenyl), 1-(p-hydroxyphenyl) ethyl (1-( o-hydroxyphenyl)ethyl), 2-(p-hydroxyphenyl)ethyl (2-(o-hydroxyphenyl)ethyl) or 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl (4- hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl).

In addition, R ^a in formula (I-1) represents an alkyl group containing an acid anhydride group, wherein the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. Specifically, the alkyl group containing an acid anhydride group is, for example, ethyl succinic anhydride shown in formula (I-1-1), propyl succinic anhydride shown in formula (I-1-2) or formula ( Propyl glutaric anhydride shown in I-1-3). It is worth mentioning that the acid anhydride group is a group formed by intramolecular dehydration of dicarboxylic acid, such as succinic acid or glutaric acid.

Furthermore, R ^a in the formula (I-1) represents an alkyl group containing an epoxy group, wherein the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. Specifically, the alkyl group containing epoxy group is, for example, oxetanylpentyl (oxetanylpentyl) or 2-(3,4-epoxycyclohexyl) ethyl (2-(3,4-epoxycyclohexyl)ethyl ). It is worth mentioning that the epoxy group is a group formed by intramolecular dehydration of a diol, such as propylene glycol, butanediol or pentanediol.

R ^a in formula (I-1) represents an alkoxy group containing an epoxy group, wherein the alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms. Specifically, the epoxy-containing alkoxy group is, for example, glycidoxypropyl or 2-oxetanylbutoxy.

In addition, when R ^b in formula (I-1) represents an alkyl group having 1 to 6 carbon atoms, specifically, R ^b is, for example, methyl, ethyl, n-propyl, isopropyl or n-butyl. When R ^b in formula (I-1) represents an acyl group having 1 to 6 carbon atoms, specifically, R ^b is, for example, an acetyl group. When R ^b in the formula (I-1) represents an aromatic group having 6 to 15 carbon atoms, specifically, R ^b is, for example, a phenyl group.

In formula (I-1), w represents an integer of 1 to 3. When w represents 2 or 3, multiple R ^a may be the same or different; when w represents 1 or 2, multiple R ^b may be the same or different.

Specific examples of the silane monomer (a-1) include: 3-glycidoxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane, GPTMS for short), 3-glycidoxypropyltriethoxysilane (3-glycidoxypropyltriethoxysilane), 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane (2-(3,4-epoxycyclohexyl)ethyl trimethoxy silane), 2-epoxypropylbutoxypropyl Triphenoxysilane (2-oxetanylbutoxypropyl triphenoxysilane), a commercial product manufactured by Toagosei Co., Ltd.: 2-oxetanylbutoxypropyltrimethoxysilane (2-oxetanylbutoxypropyltrimethoxysilane, trade name TMSOX-D), 2 -Glycidylbutoxypropyltriethoxysilane (2-oxetanylbutoxypropyltriethoxysilane, trade name TESOX-D), 3-(triphenoxysilyl)propylsuccinic anhydride, commercially available from Shin-Etsu Chemical Co., Ltd. Commercial product: 3-(trimethoxysilyl)propyl succinic anhydride (trade name X-12-967), commercial product manufactured by WACKER: 3-(triethoxysilyl)propyl butyl Diacid anhydride (trade name GF-20), 3-(trimethoxysilyl)propylglutaric anhydride (TMSG for short), 3-(triethoxysilyl)propylglutaric anhydride, 3-(triphenyl Oxysilyl) propylglutaric anhydride, diisopropoxy-di(2-epoxypropyl butoxypropyl) silane (diisopropoxy-di(2-oxetanylbutoxypropyl) silane, referred to as DIDOS), two ( 3-epoxypropyl pentyl) dimethoxysilane (di(3-oxetanylpentyl) dimethoxy silane), (di-n-butoxysilyl) bis(propyl succinic anhydride), (dimethoxysilyl ) bis(ethylsuccinic anhydride), 3-glycidoxypropyldimethylmethoxysilane (3-glycidoxypropyldimethylmethoxysilane), 3-glycidoxypropyldimethylethoxysilane (3 -glycidoxypropyl dimethylethoxysilane), two (2-epoxypropylene butoxypentyl) -2-epoxypropylene pentylethoxysilane (di (2-oxetanylbutoxypentyl) -2-oxetanyl pentylethoxysilane), three (2- Tri(2-oxetanylpentyl)methoxy sil ane), (phenoxysilyl)tris(propylsuccinic anhydride), (methylmethoxysilyl)bis(ethylsuccinic anhydride), or combinations thereof.

The said silane monomer (a-1) can be used individually or in combination of multiple types.

Specific examples of the silane monomer (a-1) preferably include 3-(triethoxysilyl)propylsuccinic anhydride, 3-(trimethoxysilyl)propylsuccinic anhydride, 3-cyclo Oxypropoxypropyltrimethoxysilane, 3-(trimethoxysilyl)propylglutaric anhydride, (dimethoxysilyl)bis(ethylsuccinic anhydride), 2-epoxypropylbutane Oxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-epoxypropylbutoxypropyltriethoxysilane, or combinations of the above compounds.

In the polycondensation reaction of the polysiloxane (A), if the silane monomer (a-1) represented by the formula (I-1) is used, the positive photosensitive polysiloxane composition can be further improved chemical resistance.

The silane monomer (a-2) is a compound represented by formula (I-2):

Si(R ^c ) _u (OR ^d ) _4-u formula (I-2)

In formula (I-2), R ^c each independently represents a hydrogen atom, an alkyl group with a carbon number of 1 to 10, an alkenyl group with a carbon number of 2 to 10, or an aromatic group with a carbon number of 6 to 15; R ^d each independently represents a hydrogen atom, an alkyl group with 1 to 6 carbons, an acyl group with 1 to 6 carbons or an aryl group with 6 to 15 carbons; and

u represents an integer of 0 to 3.

In more detail, when R ^c in formula (I-2) represents an alkyl group having 1 to 10 carbon atoms, specifically, R ^c is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl or n-decyl. R ^c can also be an alkyl group with other substituents on the alkyl group. Specifically, R ^c is, for example, trifluoromethyl, 3,3,3-trifluoropropyl, 3-aminopropyl, 3-mercaptopropane group or 3-isocyanatopropyl group.

When R ^c in the formula (I-2) represents an alkenyl group having a carbon number of 2 to 10, specifically, R ^c is, for example, a vinyl group. R ^c may also be an alkenyl group having other substituents on the alkenyl group. Specifically, R ^c is, for example, 3-acryloyloxypropyl or 3-methacryloyloxypropyl.

When R ^c in formula (I-2) represents an aromatic group having 6 to 15 carbon atoms, specifically, R ^c is, for example, phenyl, tolyl or naphthyl. R ^c can also be an aryl group with other substituents on the aryl group. Specifically, R ^c is, for example, p-hydroxyphenyl (o-hydroxyphenyl), 1-(p-hydroxyphenyl) ethyl (1-( o-hydroxyphenyl)ethyl), 2-(p-hydroxyphenyl)ethyl (2-(o-hydroxyphenyl)ethyl) or 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl (4- hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl).

In addition, when ^Rd in the formula (I-2) represents an alkyl group having 1 to 6 carbon atoms, specifically, ^Rd is, for example, methyl, ethyl, n-propyl, isopropyl or n-butyl. When R ^d in the formula (I-2) represents an acyl group having 1 to 6 carbon atoms, specifically, R ^d is, for example, an acetyl group. When R ^d in the formula (I-2) represents an aromatic group having 6 to 15 carbon atoms, specifically, R ^d is, for example, a phenyl group.

In formula (I-2), u is an integer of 0 to 3. When u represents 2 or 3, multiple R ^c may be the same or different; when u represents 0, 1 or 2, multiple R ^d may be the same or different.

In formula (I-2), when u=0, it means that the silane monomer is a tetrafunctional silane monomer (that is, a silane monomer with four hydrolyzable groups); when u=1, it means that the silane The monomer is a trifunctional silane monomer (that is, a silane monomer with three hydrolyzable groups); when u=2, it means that the silane monomer is a difunctional silane monomer (that is, a silane monomer with two hydrolyzable groups). group of silane monomers); and when u=3, it means that the silane monomer is a monofunctional silane monomer (that is, a silane monomer with one hydrolyzable group). It is worth mentioning that the hydrolyzable group refers to a group that can undergo a hydrolysis reaction and is bonded to silicon. For example, the hydrolyzable group is an alkoxy group, an acyloxy group or a phenoxy group Base (phenoxygroup).

Specific examples of silane monomers represented by formula (I-2) include, but are not limited to: (1) tetrafunctional silane monomers: tetramethoxysilane (tetramethoxysilane), tetraethoxysilane (tetraethoxysilane), tetraacetyl Oxysilane (tetraacetoxysilane) or tetraphenoxysilane (tetraphenoxy silane); (2) trifunctional silane monomer: methyltrimethoxysilane (methyltrimethoxysilane, referred to as MTMS), methyltriethoxysilane (methyltriethoxysilane) ), methyltriisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane , ethyltriisopropoxysilane (ethyltriisopropoxysilane), ethyltri-n-butoxysilane (ethyltri-n-butoxysilane), n-propyltrimethoxysilane (n-propyltrimethoxysilane), n-propyltriethoxysilane (n-propyltriethoxysilane), n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane (PTMS) , phenyltriethoxysilane (phenyltriethoxysilane, PTES), p-hydroxyphenyltrimethoxysilane (p-hydroxyphenyltrimethoxysilane), 1-(p-hydroxyphenyl) ethyltrimethoxysilane (1-(p- hydroxyphenyl)ethyltrimethoxysilane), 2-(p-hydroxyphenyl)ethyltrimethoxysilane (2-(p-hydroxyphenyl)ethyltrimethoxysilane), 4-hydroxy-5-(p-hydroxyphenyl 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane , 3,3,3-trifluoropropyltrimethoxysilane (3,3,3-trifluoropropyltrimethoxysilane), 3-aminopropyltrimethoxysilane (3-aminopropyltrimethoxysilane), 3-aminopropyltriethoxysilane (3-aminopropyltriethoxysilane), 3-mercaptopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane or 3-methacryloyl Oxypropyltriethoxysilane; (3) Difunctional silane monomers: dimethyldimethoxysilane (DMDMS for short), dimethyldiethoxysilane (dimethyldiethoxysilane), dimethyl Diacetyloxysilane (dimethyldiaacetyloxysilane), di-n-butyldimethoxysilane (di-n-butyldimethoxysilane) or diphenyldimethoxysilane (diphenyldimethoxysilane); or (4) monofunctional silane monomer: three Methylmethoxysilane (trimethylmethoxysilane) or tri-n-butylethoxysilane (tri-n-butylethoxysilane), etc.

The various silane monomers described above can be used alone or in combination.

This siloxane prepolymer (a-3) is a compound represented by formula (I-3).

In formula (I-3), R ^e , R ^f , R ^g and ^Rh independently represent a hydrogen atom, an alkyl group with 1 to 10 carbons, an alkenyl group with 2 to 6 carbons, or an alkenyl group with 6 to 6 carbons. The aryl group of 15, wherein any one of the alkyl group, alkenyl group and aryl group may optionally contain a substituent; R ⁱ and R ^j each independently represent a hydrogen atom, an alkyl group with a carbon number of 1 to 6, and a carbon number of an acyl group of 1 to 6 or an aryl group having a carbon number of 6 to 15, wherein any one of the alkyl group, acyl group and aryl group may optionally contain a substituent; and S represents an integer of 1 to 1000.

More specifically, when R ^e , R ^f , R ^g and ^Rh in formula (I-3) each independently represent an alkyl group with 1 to 10 carbon atoms, specifically, ^Re , R ^f , R ^g and ^Rh are, for example, each independently methyl, ethyl or n-propyl. When R ^e , R ^f , R ^g and ^Rh in formula (I-3) each independently represent an alkenyl group with a carbon number of 2 to 10, specifically, ^Re , R ^f , R ^g and ^Rh are, for example Each is independently a vinyl group, an acryloxypropyl group or a methacryloxypropyl group. When R ^e , R ^f , R ^g and ^Rh in formula (I-3) each independently represent an aromatic group with a carbon number of 6 to 15, specifically, ^Re , R ^f , R ^g and ^Rh are, for example Each is independently phenyl, tolyl or naphthyl. Any of the above-mentioned alkyl groups, alkenyl groups and aryl groups may have other substituents.

In addition, when R ⁱ and R ^j of the formula (I-3) each independently represent an alkyl group with a carbon number of 1 to 6, specifically, R ⁱ and R ^j are, for example, each independently methyl, ethyl, n-propyl base, isopropyl or n-butyl. When R ⁱ and R ^j in formula (I-3) each independently represent an acyl group having 1 to 6 carbon atoms, specifically, R ⁱ and R ^j are, for example, acetyl. When R ⁱ and R ^j in formula (I-3) each independently represent an aromatic group having 6 to 15 carbon atoms, specifically, R ⁱ and R ^j are, for example, phenyl. However, any of the above-mentioned alkyl groups, acyl groups, and aryl groups may optionally have a substituent.

In formula (I-3), S may be an integer of 1 to 1000, preferably an integer of 3 to 300, more preferably an integer of 5 to 200. When S is an integer of 2 to 1000, each of R ^e is the same or different group, and each of R ^f is the same or different group.

Specific examples of the siloxane prepolymer (a-3) include, but are not limited to: 1,1,3,3-tetramethyl-1,3-dimethoxydisiloxane, 1,1,3 , 3-tetramethyl-1,3-diethoxydisiloxane, 1,1,3,3-tetraethyl-1,3-diethoxydisiloxane or by Gilester ( Commercially available products (such as DMS-S12 (molecular weight: 400 to 700), DMS-S15 (molecular weight: 1500 to 2000), DMS-S21 (molecular weight: 400 to 700), DMS-S21 (molecular weight: 4200), DMS-S27 (molecular weight 18000), DMS-S31 (molecular weight 26000), DMS-S32 (molecular weight 36000), DMS-S33 (molecular weight 43500), DMS-S35 (molecular weight 49000), DMS-S38 (molecular weight 58000) , DMS-S42 (molecular weight 77000) or PDS-9931 (molecular weight 1000 to 1400)).

This siloxane prepolymer (a-3) can be used individually or in combination of several types.

The average particle diameter of the silica particles (a-4) is not particularly limited. The average particle size ranges from 2 nm to 250 nm, preferably from 5 nm to 200 nm, and more preferably from 10 nm to 100 nm.

Specific examples of the silica particles (a-4) include, but are not limited to: commercially available products manufactured by Catalyst Chemicals, with trade names such as OSCAR 1132 (particle diameter 12nm; dispersant is methanol), OSCAR 1332 (particle diameter 12nm; dispersant is n-propanol), OSCAR 105 (particle size 60nm; dispersant is γ-butyrolactone), OSCAR 106 (particle size 120nm; dispersant is diacetone alcohol), etc., manufactured by Fuso Chemical Co., Ltd. Commercially available products, trade names such as QuartronPL-1-IPA (particle size 13nm; dispersant is isopropyl ketone), Quartron PL-1-TOL (particle size 13nm; dispersant is toluene), Quartron PL-2L-PGME (particle size 18nm; dispersant is propylene glycol monomethyl ether) or QuartronPL-2L-MEK (particle size 18nm; dispersant is methyl ethyl ketone), etc., or commercially available products manufactured by Nissan Chemical Co., Ltd., trade names such as IPA-ST (particle size 12nm ; dispersant is isopropanol), EG-ST (particle size 12nm; dispersant is ethylene glycol), IPA-ST-L (particle size 45nm; dispersant is isopropanol) or IPA-ST-ZL (particle size Diameter 100nm; dispersant is isopropanol). Silica particles can be used alone or in combination.

The polysiloxane (A) can be synthesized by polycondensation using a silane monomer, or can be synthesized by polycondensing a silane monomer and other polymerizable compounds. Generally speaking, the above polycondensation reaction is carried out in the following steps: adding solvent, water, or optionally adding a catalyst (catalyst) to the silane monomer; and heating and stirring at 50° C. to 150° C. Hours, and by-products (alcohols, water, etc.) can be further removed by distillation.

The solvent used for the polycondensation reaction is not particularly limited, and the solvent may be the same as or different from the solvent (C) included in the positive photosensitive polysiloxane composition of the present invention. Based on the total amount of silane monomer (a-1) and silane monomer (a-2) being 1 mole, the amount of solvent used is preferably from 20 grams to 1000 grams; more preferably from 30 grams to 800 grams; more preferably From 50 grams to 600 grams.

Based on 1 mole of hydrolyzable groups of silane monomers, the amount of water used in the polycondensation reaction (that is, water used for hydrolysis) is preferably 10 grams to 500 grams; more preferably 15 grams to 400 grams; Further more preferably, it is 20 g to 300 g.

The catalyst used for the polycondensation reaction is not particularly limited, and is preferably selected from acid catalysts or base catalysts. Specific examples of acid catalysts include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acids or their anhydrides, or ion exchange resins. Specific examples of base catalysts include, but are not limited to, diethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethanolamine, triethanolamine, sodium hydroxide, Potassium hydroxide, silanes with alkoxy groups containing amine groups, ion exchange resins, etc.

Based on the total amount of silane monomer (a-1) and silane monomer (a-2) being 1 mole, the amount of catalyst used is preferably from 0.05 g to 5 g; more preferably from 0.07 g to 4 g; even more preferably 0.1 g to 3 g.

From the viewpoint of stability, the polysiloxane (A) preferably does not contain by-products (such as alcohols or water) and catalysts. Therefore, the polysiloxane (A) can be obtained by selectively purifying the reaction mixture after the polycondensation reaction. The method of purification is not particularly limited, preferably, the reaction mixture can be diluted with a hydrophobic solvent. Next, the hydrophobic solvent and the reaction mixture were transferred to a separation funnel. Then, the organic layer was washed several times with water, and the organic layer was concentrated with a rotary evaporator to remove alcohol or water. Alternatively, ion exchange resins can be used to remove the catalyst.

This polysiloxane (A) can use other alkali-soluble resin together. The types of other alkali-soluble resins are not particularly limited, and may include but not limited to resins containing carboxylic acid groups or hydroxyl groups. Specific examples of other alkali-soluble resins include acrylic resins, fluorene resins, urethane resins, and novolac resins.

The acrylic resin is preferably obtained by copolymerizing one or more unsaturated carboxylic acid or unsaturated carboxylic acid anhydride compounds and/or other unsaturated compounds in a solvent in the presence of a suitable polymerization initiator.

Specific examples of the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound include acrylic acid, methacrylic acid, crotonic acid, 2-chloroacrylic acid, ethacrylic acid, cinnamic acid, 2-acryloylethoxysuccinate, Unsaturated monocarboxylic acids such as 2-methacryloylethoxysuccinate or 2-methacryloylethoxysuccinate; maleic acid, maleic anhydride, fumaric acid, itaconic acid, Itaconic anhydride, citraconic acid or citraconic anhydride, etc., unsaturated dibasic carboxylic acids (anhydrides), unsaturated polycarboxylic acids (anhydrides) with more than three valences; preferably, the unsaturated carboxylic acid or unsaturated The carboxylic anhydride compound is acrylic acid, methacrylic acid, 2-acryloylethoxysuccinate, 2-methacryloylethoxysuccinate or 2-methacryloylethoxysuccinate. The above-mentioned compounds containing one or more unsaturated carboxylic acids or unsaturated carboxylic acid anhydrides can be used alone or in combination to improve pigment dispersibility, increase developing speed and reduce residue.

Specific examples of other unsaturated compounds include: aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, methoxystyrene; N-phenylmaleyl Imine, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenyl Maleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N -m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide, N-cyclohexylmaleimide and other maleimides; methyl acrylate, Methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate ester, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-methacrylate -Hydroxyethyl acrylate, 2-Hydroxypropyl acrylate, 2-Hydroxypropyl methacrylate, 3-Hydroxypropyl acrylate, 3-Hydroxypropyl methacrylate, 2-Hydroxybutyl acrylate, 2-Hydroxy methacrylate Butyl, 3-Hydroxybutyl Acrylate, 3-Hydroxybutyl Methacrylate, 4-Hydroxybutyl Acrylate, 4-Hydroxybutyl Methacrylate, Allyl Acrylate, Allyl Methacrylate, Benzyl Acrylate ester, benzyl methacrylate (BzMA), phenyl acrylate, phenyl methacrylate, triethylene glycol methoxy acrylate, triethylene glycol methoxy methacrylate, lauryl methacrylate , myristyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, eicosyl methacrylate, behenyl methacrylate, dicyclopentanyl acrylate Unsaturated carboxylic acid esters such as dicyclopentenyloxyethyl acrylate (DCPOA); N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, N , N-diethylaminopropyl methacrylate, N,N-dimethylaminopropyl methacrylate, N,N-dibutylaminopropyl acrylate, N-isobutylaminopropyl methacrylate esters; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; vinyl carboxylate esters such as vinyl acetate, vinyl propionate, and vinyl butyrate; Vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, methallyl glycidyl ether and other unsaturated ethers; acrylonitrile, methacrylonitrile, 2-chloroacrylonitrile, cyanide Vinyl cyanide compounds such as vinylidene; unsaturated amides of acrylamide, methacrylamide, 2-chloroacrylamide, N-hydroxyethylacrylamide, N-hydroxyethylmethacrylamide, etc.; 1,3 - Aliphatic conjugated dienes such as butadiene, isopentene, and chlorinated butadiene.

Specific examples of the above-mentioned fennel-based resins include V259ME, V259MEGTS, or V500MEGT (manufactured by Nippon Steel Chemical Co., Ltd.), and the above-mentioned fennel-based resins may be used alone or in combination.

Specific examples of the urethane-based resin include UN-904, UN-952, UN-333, or UN1255 (manufactured by Negami Industry Co., Ltd.), and the urethane-based resin can be used alone or in combination. .

Specific examples of the novolak-type resin include EP4020G, EP4080G, TR40B45G, or EP30B50 (manufactured by Asahi Organic Materials Co., Ltd.), and the novolak-type resin may be used alone or in combination.

The polysiloxane (A) has a weight average molecular weight of 5,000 to 60,000, preferably 7,000 to 55,000, more preferably 9,000 to 50,000.

The kind of o-naphthoquinone diazide sulfonate (B) according to the present invention is not particularly limited, and the commonly used o-naphthoquinone diazide sulfonate can be used as long as the purpose sought by the present invention can be achieved . The o-naphthoquinone diazide sulfonate (B) may be a completely esterified or partially esterified ester-based compound.

The o-naphthoquinonediazidesulfonic acid ester (B) is preferably prepared by reacting o-naphthoquinonediazidesulfonic acid or its salts with a hydroxyl compound. The o-naphthoquinonediazidesulfonic acid ester (B) is more preferably prepared by reacting o-naphthoquinonediazidesulfonic acid or its salts with polyhydroxy compounds.

Specific examples of the o-naphthoquinonediazide sulfonic acid (B) include but are not limited to o-naphthoquinonediazide-4-sulfonic acid, o-naphthoquinonediazide-5-sulfonic acid or o-naphthoquinonediazide- 6-sulfonic acid, etc. In addition, salts of diazonaphthoquinone sulfonyl halide are, for example, diazonaphthoquinone sulfonyl halide.

Specific examples of the hydroxy compound include, but are not limited to, hydroxybenzophenone compounds, hydroxyaryl compounds, (hydroxyphenyl) hydrocarbon compounds, other aromatic hydroxy compounds, or combinations of the above compounds.

Specific examples of the hydroxybenzophenone-based compound include, but are not limited to, 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2, 4,6-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,4,2',4'-tetrahydroxybenzophenone, 2,4,6, 3',4'-pentahydroxybenzophenone, 2,3,4,2',4'-pentahydroxybenzophenone, 2,3,4,2',5'-pentahydroxybenzophenone , 2,4,5,3',5'-pentahydroxybenzophenone or 2,3,4,3',4',5'-hexahydroxybenzophenone, etc.

Specific examples of the hydroxyaryl-based compound include, but are not limited to, hydroxyaryl-based compounds represented by formula (b-1).

In formula (b-1), B ¹ and B ² each independently represent a hydrogen atom, a halogen atom or an alkyl group with a carbon number of 1 to 6; B ³ , B ⁴ and B ⁷ each independently represent a hydrogen atom or a carbon number of 1 to 6 6 alkyl; B ⁵ , B ⁶ , B ⁸ , B ⁹ , B ¹⁰ and B ¹¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbons, and an alkoxy group with 1 to 6 carbons and h, i and j each independently represent an integer of 1 to 3; k represents 0 or 1.

Specifically, specific examples of hydroxyaryl compounds represented by formula (b-1) include, but are not limited to, tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl )-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)- 2-Hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3- Hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4- Dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)- 2,4-Dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxyphenyl)-3-methoxy Base-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane , bis(3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-2-hydroxyphenylmethane, bis( 3-cyclohexyl-4-hydroxy-6-methylphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-4-hydroxyphenylmethane, Bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-3,4-dihydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)-3-hydroxyphenylmethane, Bis(3-cyclohexyl-6-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-6 -Hydroxy-4-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl -6-hydroxy-4-methylphenyl)-3,4-dihydroxyphenylmethane, 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4 -Hydroxyphenyl)ethyl]benzene, 1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4-hydroxyphenyl) base) ethyl] benzene, or a combination of the above compounds.

Specific examples of the (hydroxyphenyl)hydrocarbon compound include, but are not limited to, (hydroxyphenyl)hydrocarbon compounds represented by formula (b-2).

In formula (b-2), B ¹² and B ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbons; and m and n each independently represent an integer of 1 to 3.

Specifically, specific examples of (hydroxyphenyl) hydrocarbon compounds represented by formula (b-2) include, but are not limited to, 2-(2,3,4-trihydroxyphenyl)-2-(2',3 ',4'-trihydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl) -2-(4'-hydroxyphenyl)propane, bis(2,3,4-trihydroxyphenyl)methane or bis(2,4-dihydroxyphenyl)methane, etc.

Specific examples of the other aromatic hydroxy compounds include, but are not limited to, phenol (phenol), p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol A, naphthol, catechol, 1, 2,3-Glycinol methyl ether, 1,2,3-Glycinol-1,3-dimethyl ether, 3,4,5-trihydroxybenzoic acid, 4,4'-[1-[4 [-1-(4-Hydroxyphenyl)-1-methylethyl]phenyl]ethylene]bisphenol, or partially esterified or partially etherified 3,4,5-trihydroxybenzene formic acid etc.

The hydroxy compound is preferably 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene, 2,3,4- Trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, or combinations thereof. A hydroxy compound can be used individually or in combination of multiple types.

The reaction of the o-naphthoquinone diazide sulfonic acid or its salts with the hydroxyl compound is usually carried out in an organic solvent such as dioxane, N-pyrrolidone or acetamide. In addition, the above reaction is preferably carried out with a basic condensing agent (condensing agent) such as triethanolamine, alkali metal carbonate or alkali metal bicarbonate.

The degree of esterification (degree of esterification) of the o-naphthoquinone diazide sulfonate (B) is preferably more than 50%, that is, based on the total amount of hydroxyl groups in the hydroxyl compound being 100 mole percent (mol%), the hydroxyl compound More than 50 mol% of the hydroxyl groups in the product undergo esterification reaction with o-naphthoquinone diazide sulfonic acid or its salts. The degree of esterification of o-naphthoquinone diazide sulfonate (B) is more preferably 60% or more.

The specific example of the o-naphthoquinone diazide sulfonate (B) is preferably composed of 4,4'-[1-[4[-1-(4-hydroxyphenyl)-1-methylethyl]benzene Base] ethylene] bisphenol and o-naphthoquinone diazide-5-sulfonic acid formed o-naphthoquinone diazide sulfonate, 2,3,4-trihydroxybenzophenone and o-naphthoquinone two O-naphthoquinone diazide sulfonate formed from azide-5-sulfonic acid and 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxybenzene base) propane and o-naphthoquinonediazide-5-sulfonic acid formed o-naphthoquinone diazide sulfonate, but not limited thereto.

Based on the polysiloxane (A) used in an amount of 100 parts by weight, the used amount of the o-naphthoquinone diazide sulfonate (B) is 8 to 48 parts by weight; preferably 10 to 44 parts by weight ; And more preferably 12 to 40 parts by weight.

The kind of solvent (C) according to the present invention is not particularly limited. The solvent (C) is, for example, a compound containing an alcoholic hydroxyl group or a cyclic compound containing a carbonyl group.

The specific example of the compound containing alcoholic hydroxyl group includes but not limited to acetol (acetol), 3-hydroxyl-3-methyl-2-butanone (3-hydroxy-3-methyl-2-butanone), 4- Hydroxy-3-methyl-2-butanone (4-hydroxy-3-methyl-2-butanone), 5-hydroxy-2-pentanone (5-hydroxy-2-pentanone), 4-hydroxy-4-methanone 4-hydroxy-4-methyl-2-pentanone (also known as diacetone alcohol (DAA)), ethyl lactate (ethyl lactate), butyl lactate (butyl lactate), Propylene glycol monomethyl ether (propylene glycol monomethyl ether), propylene glycol monoethyl ether (PGEE), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol mono-n-propyl ether (propylene glycol mono-n-propyl ether) ether), propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, 3-methoxy-1-butanol (3-methoxy- 1-butanol), 3-methyl-3-methoxy-1-butanol (3-methyl-3-methoxy-1-butanol), or a combination thereof. It should be noted that the compound containing alcoholic hydroxyl group is preferably diacetone alcohol, ethyl lactate, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate or a combination thereof. The alcoholic hydroxyl group-containing compound can be used alone or in combination.

Specific examples of the carbonyl-containing cyclic compound include but are not limited to γ-butyrolactone (γ-butyrolactone), γ-valerolactone (γ-valerolactone), δ-valerolactone (δ-valerolactone), propylene carbonate Ester (propylene carbonate), nitrogen-methyl pyrrolidone (N-methyl pyrrolidone), cyclohexanone (cyclohexanone) or cycloheptanone (cycloheptanone), etc. It should be noted that the carbonyl-containing cyclic compound is preferably γ-butyrolactone, nitrogen-methylpyrrolidone, cyclohexanone or a combination thereof. The carbonyl group-containing cyclic compound can be used alone or in combination.

The alcoholic hydroxyl-containing compound may be used in combination with the carbonyl-containing cyclic compound, and the weight ratio thereof is not particularly limited. The weight ratio of the alcoholic hydroxyl-containing compound to the carbonyl-containing cyclic compound is preferably 99/1 to 50/50; more preferably 95/5 to 60/40. It is worth mentioning that when the weight ratio of the alcoholic hydroxyl-containing compound to the carbonyl-containing cyclic compound in the solvent (C) is 99/1 to 50/50, no reaction in the polysiloxane (A) The silanol (Si-OH) group is not easy to produce condensation reaction and reduce the storage stability (storage stability). In addition, due to the good compatibility between alcoholic hydroxyl-containing compounds and carbonyl-containing cyclic compounds and o-naphthoquinone diazide sulfonate (B), it is not easy to have whitening phenomenon when coating and forming a film, and can maintain protection. film transparency.

This solvent (C) may contain other solvents in the range which does not impair the effect of this invention. The other solvents are, for example: (1) esters: ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy- 1-butyl acetate, 3-ethoxy ethyl propionate or 3-methyl-3-methoxy-1-butyl acetate, etc.; (2) Ketones: acetone, methyl ethyl ketone, methyl Propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl n-hexyl ketone, diethyl ketone, diisopropyl ketone, diisobutyl ketone, cyclopentanone , cyclohexanone, cycloheptanone, methylcyclohexanone, acetylacetone, diacetone alcohol or cyclohexen-1-one, etc.; or (3) ethers: diethyl ether, diisopropyl ether, di-n-butyl ether , Diethylene glycol dimethyl ether or diphenyl ether, etc.

This solvent (C) can be used individually or in combination of several types.

Based on the polysiloxane (A) used in an amount of 100 parts by weight, the solvent (C) used in an amount of 100 to 700 parts by weight; preferably 120 to 650 parts by weight; and more preferably 150 to 600 parts by weight .

The silane compound of the present invention is characterized by, for example, having both a hydrolyzable silyl group and a sulfur-silicon bond.

The silane compound of the present invention is represented by the following formula (D-1), and has a series of structures of the above-mentioned hydrolyzable silyl group and sulfur-silicon bond.

In formula (D-1):

R represents an unsubstituted or substituted alkyl group with ¹ to 10 carbons, or an unsubstituted or substituted aryl group with 6 to 10 carbons;

Each of R2 independently represents an unsubstituted or substituted alkyl group with ¹ to 20 carbon atoms, an unsubstituted or substituted aryl group with 6 to 10 carbon atoms, or an unsubstituted or substituted aryl group with 7 to 10 carbon atoms Aralkyl, unsubstituted or substituted alkenyl with 2 to 10 carbons, or unsubstituted or substituted organooxy with 1 to 20 carbons;

R ³ represents an unsubstituted or substituted alkyl group with 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group with 6 to 10 carbon atoms;

n is an integer from 1 to 3; and

m is an integer of 1 to 3.

The above structure can be specifically shown in the following formula (D-2) or formula (D-3).

In formula (D-2):

R ¹ and n are the same as above; each of R ⁴ independently represents an unsubstituted or substituted alkyl group with 1 to 20 carbon atoms, an unsubstituted or substituted aryl group with 6 to 10 carbon atoms, an unsubstituted or substituted Substituted aralkyl with 7 to 10 carbons, unsubstituted or substituted alkenyl with 2 to 10 carbons or unsubstituted or substituted organooxy with 1 to 20 carbons; Me represents methyl ; Ph represents phenyl.

In formula (D-3):

R ¹ , n, R ⁴ , and Me are the same as above; R ⁵ represents an unsubstituted or substituted alkyl group with 1 to 20 carbons, an unsubstituted or substituted aryl group with 6 to 10 carbons, unsubstituted A substituted or substituted aralkyl group having 7 to 10 carbons or an unsubstituted or substituted alkenyl group having 2 to 10 carbons.

More specifically, it can be represented by the following formula (D-4) to formula (D-9).

In formula (D-5) to formula (D-9):

R ¹ , n, Me, and Ph are the same as above; Et represents an ethyl group.

More specifically, R ¹ in formula (D-1) to formula (D-9) represents an ethyl group.

^Alkyl and aryl groups for R1, such as methyl, ethyl, propyl, butyl, phenyl, etc.; methyl and ethyl are preferred, and ethyl is more preferred. ^The alkyl of R2, such as methyl, ethyl, tert-butyl, octyl, decyl, dodecyl, etc.; aryl, such as phenyl, xylyl, tolyl, etc.; aralkyl, such as benzyl etc., alkenyl such as vinyl, propenyl, pentenyl, etc.; organic oxygen such as methoxy, ethoxy, propoxy, butoxy, octyloxy, dodecyloxy, etc., alkoxy , aryloxy such as phenoxy, ethyleneoxy, propyleneoxy, pentenyloxy and other alkenyloxy; alkyl with 1 to 6 carbons, phenyl, alkoxy with 1 to 20 carbons Preferable; more preferably an alkyl group with 1 to 4 carbons, a phenyl group, and an alkoxy group with 1 to 12 carbons. The alkyl or aryl group of ^R3 , such as methyl, ethyl, phenyl, etc.; preferably methyl. ^The alkyl of R4 is such as methyl, ethyl, tert-butyl, octyl, decyl, dodecyl, etc.; the aryl is such as phenyl, xylyl, tolyl, etc.; the aralkyl is such as benzyl, etc. ; alkenyl such as vinyl, propenyl, pentenyl, etc.; organic oxygen such as methoxy, ethoxy, propoxy, butoxy, octyloxy, dodecyloxy, etc. Aryloxy such as phenoxy, ethyleneoxy, propyleneoxy, and alkenyloxy such as pentenyloxy ^; the same as R2 is preferred. Alkyl, aryl, aralkyl, alkenyl for R5, such as methyl, ethyl, propyl, butyl, tert ^- butyl, octyl, decyl, dodecyl, phenyl, benzyl , vinyl, propenyl, pentenyl, etc.; preferably an alkyl group with 1 to 12 carbons.

The silane compound (D) of the present invention is produced, for example, by dehydrogenating a silane compound having one or more mercapto groups and a silane compound having one or more Si-H bonds in the presence of a catalyst.

Since the by-product of the above-mentioned production method of the present invention is hydrogen, there is no filtrate, and the reaction can proceed favorably under solvent-free conditions, which is an extremely high-productivity production method.

When producing the silane compound (D) of the present invention, a solvent may be used as necessary. The solvent is not particularly limited as long as it is non-reactive with the silane compound having a mercapto group or the silane compound having a Si-H bond as the raw material, and specifically, pentane, hexane, heptane, decane, etc. Aliphatic hydrocarbon solvents, ether solvents such as diethyl ether, tetrahydrofuran, and 1,4-dioxane, amide solvents such as dimethylformamide and N-methylpyrrolidone, benzene, toluene, xylene, etc. Aromatic hydrocarbon solvents, etc.

At this time, regarding the manufacture of the silane compound (D) of the above-mentioned formulas (1) to (9), in the presence of a catalyst, the silane compound having a mercapto group represented by the following formula (D-i) can be combined with the silane compound having a mercapto group represented by the following formula (D- The silane compounds having Si-H bonds shown in ii) react to form sulfur-silicon bonds.

In formula (D-i) and formula (D-ii):

R ¹ , R ² , R ³ , n, and m are the same as above.

When producing the silane compound (D) of the present invention, among the necessary raw materials, specific examples of the silane compound having a mercapto group include α-mercaptomethyltrimethoxysilane, α-mercaptomethylmethyldimethoxysilane, α -Mercaptomethyldimethylmethoxysilane, α-Mercaptomethyltriethoxysilane, α-Mercaptomethyldiethoxysilane, α-Mercaptomethyldimethylethoxysilane, γ -Mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyldimethylmethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyl methyldiethoxysilane, γ-mercaptopropyldimethylethoxysilane, etc., but not limited thereto.

When producing the silane compound (D) of the present invention, among the necessary raw materials, specific examples of organic compounds having Si-H bonds include trimethylsilane, ethyldimethylsilane, diethylmethylsilane, triethylsilane, butylsilane, tert-butyldimethylsilane, tert-butyldiphenylsilane, triisopropylsilane, tri-n-butylsilane, triisobutylsilane, dimethylphenylsilane, diphenylmethylsilane Silane, Dimethyl-n-octylsilane, Decyldimethylsilane, Dodecyldimethylsilane, Dimethylvinylsilane, Triphenylsilane, Trimethoxysilane, Triethoxysilane, Tributoxysilane, dimethylethoxysilane, dimethylbutoxysilane, dimethyloctoxysilane, dimethyldodecyloxysilane, etc., but not limited thereto.

When producing the silane compound (D) of the present invention, necessary catalysts, such as transition metal catalysts or Lewis acid catalysts, transition metal catalysts such as ruthenium catalysts, rhodium catalysts, palladium catalysts, iridium catalysts, platinum catalysts, gold catalysts, etc., especially The rhodium catalyst is preferred, and the RhCl(PPh ₃ ) ₃ catalyst is more preferred.

In addition, Lewis acid catalysts such as aluminum chloride, aluminum sulfate, tin chloride, tin chloride sulfate, ferric chloride, boron trifluoride, pentafluorophenyl boric acid, etc., especially pentafluorophenyl boric acid are preferred.

When producing the silane compound (D) of the present invention, in terms of reactivity and productivity, the compounding ratio of the silane compound having a mercapto group to the organosilicon compound having a Si-H bond is Si The -H bond is preferably reacted in the range of 0.5 to 1.5 moles, especially 0.9 to 1.1 moles.

When producing the silane compound (D) of the present invention, in terms of reactivity and productivity, the compounding ratio of the silane compound having a mercapto group to the catalyst is 0.000001 to 0.1 mole of the catalyst relative to 1 mole of the mercapto group, especially It is preferable to carry out the reaction in the range of 0.000001 to 0.001 mole.

When producing the silane compound (D) of the present invention, the reaction temperature is not particularly limited, usually room temperature to below the boiling point of the reaction raw material or organic solvent, preferably 50 to 150°C, more preferably 60 to 120°C range to react. The reaction time is not particularly limited as long as the reaction can proceed sufficiently, and is preferably about 30 minutes to 24 hours, and more preferably about 1 to 10 hours.

Based on 100 parts by weight of the polysiloxane (A), the usage amount of the silane compound (D) is 1 to 15 parts by weight; preferably 1.5 to 13 parts by weight; and more preferably 2 to 11 parts by weight share.

When the silane compound (D) is not used, the positive photosensitive polysiloxane composition has a problem of poor chemical resistance.

The positive photosensitive polysiloxane composition of the present invention may further contain a cyclic siloxane compound (E) represented by the following formula (E-1):

In formula (E-1):

R ¹⁹ and R ²⁰ represent a monovalent group or an alkyl group having an alicyclic epoxy group, wherein, at least one of the t R ¹⁹ and t R ²⁰ has an alicyclic ring a monovalent radical of an alicyclic epoxy group; and

t represents an integer greater than 3;

Wherein, the R ¹⁹ and R ²⁰ can be the same or different, and the multiple R ¹⁹ and the multiple R ²⁰ can be the same or different, respectively.

The cyclic siloxane compound (E) may include but not limited to 2,4-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,6 ,8,8-Hexamethyl-cyclotetrasiloxane siloxane, 4,8-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,2, 4,6,6,8-Hexamethyl-cyclotetrasiloxane, 2,4-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-6,8- Dipropyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 4,8-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]- 2,6-dipropyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 2,4,8-tris[2-(3-{oxabicyclo[4.1.0]heptyl })ethyl]-2,4,6,6,8-pentamethyl-cyclotetrasiloxane, 2,4,8-bis[2-(3-{oxabicyclo[4.1.0]heptyl })ethyl]-6-propyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 2,4,6,8-tetra[2-(3-{oxabicyclo[4.1 .0]heptyl})ethyl]-2,4,6,8-tetramethyl-cyclotetrasiloxane, silsesquioxane having an alicyclic epoxy group, and the like.

Specifically, specific examples of the cyclic siloxane compound (E) represented by the above formula (E-1) can be shown below.

The cyclic siloxane compound (E) represented by this formula (E-1) can be used individually by 1 type or in mixture of 2 or more types.

Based on the polysiloxane (A) used in an amount of 100 parts by weight, the amount of the cyclic siloxane compound (E) represented by the formula (E-1) is 4 to 24 parts by weight, preferably 5 parts by weight to 22 parts by weight, and more preferably 6 parts by weight to 20 parts by weight.

When the cyclic siloxane compound (E) is used, the chemical resistance of the positive photosensitive polysiloxane composition can be further improved.

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

The type of the sensitizer is not particularly limited. The sensitizer is preferably a compound containing phenolic hydroxyl (phenolic hydroxy), wherein specific examples of compounds containing phenolic hydroxyl include but are not limited to triphenol-type compounds, bisphenol-type compounds, polynuclear branched compounds, condensed phenol Compounds, polyhydroxybenzophenones, or combinations of the above compounds.

Specific examples of the trisphenol type compound (trisphenol type compound) include but are not limited to three (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenyl methane, bis ( 4-Hydroxy-2,3,5-trimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis( 4-Hydroxy-3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy -2,5-Dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-2 ,5-Dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy- 2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis( 4-hydroxyphenyl)-3-methoxy-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(5- Cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane or bis( 5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenylmethane.

Specific examples of the bisphenol type compound include, but are not limited to, bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)methane, 2,3,4 -Trihydroxyphenyl-4'-hydroxyphenylmethane, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 2- (2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2 -(3-fluoro-4-hydroxyphenyl)-2-(3'-fluoro-4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(4' -Hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxyphenyl)propane or 2-(2,3,4-trihydroxyphenyl)-2 -(4'-hydroxy-3',5'-dimethylphenyl)propane, etc.

Specific examples of the polynuclear branched compound include, but are not limited to, 1-[1-(4-hydroxyphenyl) isopropyl]-4-[1,1-bis(4-hydroxyphenyl) Ethyl]benzene or 1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4-hydroxyphenyl)ethyl] Benzene etc.

Specific examples of the condensation type phenol compound include, but are not limited to, 1,1-bis(4-hydroxyphenyl)cyclohexane and the like.

Specific examples of the polyhydroxy benzophenone (polyhydroxy benzophenone) include but are not limited to 2,3,4-trihydroxy benzophenone, 2,4,4'-trihydroxy benzophenone, 2,4, 6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,4,2' ,4'-tetrahydroxybenzophenone, 2,4,6,3',4'-pentahydroxybenzophenone, 2,3,4,2',4'-pentahydroxybenzophenone, 2 ,3,4,2',5'-pentahydroxybenzophenone, 2,4,6,3',4',5'-hexahydroxybenzophenone or 2,3,4,3',4 ',5'-Hexahydroxybenzophenone etc.

Specific examples of the adhesion aid include melamine compounds, silane compounds, and the like. The role of the adhesion aid is to increase the adhesion between the protective film formed from the positive photosensitive polysiloxane composition and the component to be protected.

Specific examples of commercially available products of this melamine include trade names Cymel-300 or Cymel-303 manufactured by Mitsui Chemicals; or trade names MW-30MH, MW-30, MS-11, and MS manufactured by Sanwa Chemicals. -001, MX-750 or MX-706 etc.

Specific examples of the silane-based compound include vinyltrimethoxysilane, vinyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane , Nitrogen-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, nitrogen-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 2-(3,4-epoxy Hexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropane Trimethoxysilane or a commercial product manufactured by Shin-Etsu Chemical Co., Ltd. (trade name such as KBM403) and the like.

Specific examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxane-based surfactants, fluorine-based surfactants, or combinations thereof.

Specific examples of the surfactant include but are not limited to (1) polyethylene oxide alkyl ethers (polyoxyethylenealkyl ethers): polyethylene oxide lauryl ether, etc.; (2) polyethylene oxide alkyl ethers; Phenyl ethers (polyoxyethylene phenyl ethers): polyethylene oxide octyl phenyl ether, polyethylene oxide nonyl phenyl ether, etc.; (3) polyethylene glycol diesters (polyethylene glycol diesters): poly Ethylene glycol dilaurate, polyethylene glycol distearate, etc.; (4) sorbitan fatty acid esters; (5) fatty acid modified polyesters poly esters); and (6) tertiary amine modified polyurethanes (tertiary amine modified polyurethanes), etc. Specific examples of commercially available surfactants include KP (manufactured by Shin-Etsu Chemical Industry), SF-8427 (manufactured by Dow Corning Toray Silicone Co., Ltd.), Polyflow (manufactured by Kyoeisha Oleochemical Industry), F-Top (manufactured by Tochem Products Co., Ltd.), Megaface (manufactured by Dainippon Ink Chemical Industry (DIC)), Fluorade ( Manufactured by Sumitomo 3M Ltd.), Surflon (manufactured by Asahi Glass), SINOPOL E8008 (manufactured by Sino-Nippon Gosei Chemical), F-475 (manufactured by Dainippon Ink Chemical Industry), or a combination thereof.

Specific examples of the antifoaming agent include Surfynol MD-20, Surfynol MD-30, EnviroGem AD01, EnviroGem AE01, EnviroGem AE02, Surfynol DF110D, Surfynol 104E, Surfynol 420, Surfynol DF37, Surfynolur DF58, Surfynol DF2F070 and Surfynol (manufactured by Air products), etc.

Specific examples of the dissolution accelerator include nitrogen-hydroxydicarboxylic imide compounds (N-hydroxydicarboxylic imide) and phenolic hydroxyl-containing compounds. The dissolution accelerator is, for example, a phenolic hydroxyl group-containing compound used for o-naphthoquinonediazidesulfonate (B).

The preparation method of the positive photosensitive polysiloxane composition of the present invention is for example: polysiloxane (A), o-naphthoquinone diazide sulfonate (B), solvent (C), silane compound (D) And the optional cyclic siloxane compound (E) is placed in a stirrer and stirred to make it uniformly mixed into a solution state. If necessary, the additive (F) can also be added. After being uniformly mixed, the normal solution state can be obtained. Type photosensitive polysiloxane composition.

The present invention also provides a method for forming a thin film on a substrate, which includes applying the aforementioned positive photosensitive polysiloxane composition to the substrate.

The present invention further provides a thin film on a substrate, which is prepared by the aforementioned method.

The present invention also provides a flattening film or an interlayer insulating film of a TFT substrate in a liquid crystal display component or an organic electroluminescence display, or a protective film of an optical waveguide core material or a cladding material, which is produced by the aforementioned method have to.

The present invention further provides a device comprising the aforementioned thin film.

The present invention further provides a device, which comprises the planarization film or interlayer insulating film of the TFT substrate in the aforementioned liquid crystal display assembly or organic electroluminescent display, or the protective film of the core material or cladding material of the optical waveguide

The method for forming a protective film will be described in detail below, which sequentially includes: using a positive photosensitive polysiloxane composition to form a pre-baked coating film, patterning the pre-baked coating film, and removing the exposed area by alkali development. to form a pattern; and post-baking to form a protective film.

pre-baked coating

By rotary coating, casting coating or roll coating and other coating methods, the positive photosensitive polysiloxane composition in the solution state is coated on the protected component (hereinafter referred to as the substrate) to form coating film.

The substrate may be alkali-free glass, soda-lime glass, hard glass (Pileus glass), quartz glass, such glass with a transparent conductive film attached thereto for liquid crystal display devices, or for photoelectric conversion devices ( Substrates such as solid-state imaging devices (such as silicon substrates).

After the coating film is formed, most of the organic solvent of the positive photosensitive polysiloxane composition is removed by drying under reduced pressure, and then the remaining organic solvent is completely removed by pre-bake to form a pre-bake coating film.

The operating conditions of the above-mentioned reduced-pressure drying and pre-baking may vary depending on the types and compounding ratios of the components. Generally speaking, the vacuum drying is carried out at a pressure of 0 torr to 200 torr for 1 second to 60 seconds, and the prebaking is carried out at a temperature of 70° C. to 110° C. for 1 minute to 15 minutes.

patterned exposure

The above-mentioned prebaked coating film is exposed with a photomask having a specific pattern. The light used in the exposure process is preferably ultraviolet light such as g-line, h-line or i-line, and the equipment used to provide ultraviolet light can be (ultra) high pressure mercury lamp or metal halide lamp.

development

Dip the exposed pre-baked coating film in a developer at a temperature of 23±2°C, and develop it for about 15 seconds to 5 minutes to remove the unnecessary part of the exposed pre-baked coating film, that is, the exposed pre-baked coating film The exposed area is dissolved in the developer solution, and the unexposed area is left, whereby a semi-finished product of a protective film having a predetermined pattern can be formed on the substrate. Specific examples of the developer include, but are not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methylsilicate (sodium methylsilicate), ammonia water, ethylamine, Diethylamine, dimethylethanolamine, tetramethylammonium hydroxide (THAM), tetraethylammonium hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo[5.4.0]-7-undeca Alkenes and other basic compounds.

It is worth mentioning that if the concentration of the developer is too high, the specific pattern will be damaged or the resolution of the specific pattern will be deteriorated; if the concentration is too low, the development will be poor, resulting in failure to form the specific pattern or the composition of the exposed part will remain. Therefore, the amount of the concentration will affect the subsequent formation of a specific pattern of the positive photosensitive polysiloxane composition after exposure. The concentration range of the developer is preferably 0.001wt% to 10wt%; more preferably 0.005wt% to 5wt%; more preferably 0.01wt% to 1wt%. The embodiment of the present invention uses 2.38wt% tetramethylammonium hydroxide developer. It is worth mentioning that the positive photosensitive polysiloxane composition of the present invention can form a good miniaturized pattern even if a developer solution with a lower concentration is used.

post roasting

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

For example, the protective film is formed by the following steps. First, the positive photosensitive polysiloxane composition was spin-coated on a plain glass substrate (100×100×0.7 mm) to form a coating film with a thickness of about 2 μm. After pre-baking at 110° C. for 2 minutes, the coating film was placed under the exposure machine. Next, a photomask for positive photoresist is placed between the exposure machine and the coating film, and the pre-bake coating film is irradiated with ultraviolet light from the exposure machine, and the energy is 100 mJ/cm ² . The exposed prebaked coating film was dipped in a 2.38% TMAH aqueous solution at 23° C. for 60 seconds to remove the exposed portion. Next, after washing with clean water, the developed coating film was directly irradiated with an exposure machine at an energy of 200 mJ/cm ² . Finally, after baking at 230°C for 60 minutes, a plain glass substrate with a protective film formed thereon can be obtained.

The following examples are used to describe the present invention in detail, but it does not mean that the present invention is limited to the content disclosed in these examples.

Preparation of polysiloxane (A)

<Preparation Example 1>

In a three-necked flask with a volume of 500 ml, add 0.01 mole of 3-(triethoxysilyl) propyl succinic anhydride (hereinafter referred to as GF-20), 0.15 mole of methyltrimethoxysilane (hereinafter referred to as MTMS), 0.4 moles of phenyltrimethoxysilane (hereinafter referred to as PTMS), 0.44 moles of tetraethoxysilane (hereinafter referred to as TEOS), and 200 grams of 4-hydroxy-4-methyl-2-pentanone (hereinafter referred to as DAA for short), and an aqueous phosphoric acid solution (0.3 g phosphoric acid/75 g water) was added within 30 minutes while stirring at room temperature. Next, the flask was immersed in a 30° C. oil bath and stirred for 30 minutes. Then, the temperature of the oil bath was raised to 120° C. over 30 minutes. When the temperature of the solution dropped to 110° C. (ie, the reaction temperature), the polymerization was carried out with continuous heating and stirring for 9 hours (ie, the polycondensation time). Then, the solvent is removed by distillation to obtain polysiloxane (A-1). Table 1 shows the types and amounts of the components of the polysiloxane (A-1).

<Preparation Example 2 to Preparation Example 6>

The polysiloxane (A) of Preparation Example 2 to Preparation Example 6 is prepared in the same steps as Preparation Example 1, and the difference lies in: changing the composition type and usage amount of polysiloxane (A), the reaction Temperature and polycondensation time (as shown in Table 1).

in FIG. 1:

Preparation of positive photosensitive polysiloxane composition

<Example 1>

100 parts by weight of the polysiloxane (A-1) of Preparation Example 1, 8 parts by weight of 4,4'-[1-[4[-1-(4-hydroxyphenyl)-1-methylethyl ] phenyl] ethylene] bisphenol and o-naphthoquinonediazide-5-sulfonic acid formed o-naphthoquinone diazide sulfonate (B-1) and 5 parts by weight as shown in the following table 2 (D-1) was added in 100 parts by weight of propylene glycol methyl ether acetate (C-1), and after stirring evenly with a shaking type stirrer (shaking type stirrer), the positive photosensitive polymer of Example 1 could be obtained. Silicone composition. Table 2 shows the results of evaluating the positive photosensitive polysiloxane composition of Example 1 by the evaluation method described later.

<Example 2 to Example 10>

The positive photosensitive polysiloxane compositions of Examples 2 to 10 were prepared in the same steps as in Example 1, and the difference is that the types and amounts of ingredients were changed, as shown in Table 2 . The positive photosensitive polysiloxane compositions prepared in Examples 2 to 10 were evaluated in the following evaluation manner, and the results are shown in Table 2.

<Comparative example 1 to comparative example 2>

The positive-type photosensitive polysiloxane compositions of Comparative Example 1 to Comparative Example 2 were prepared in the same steps as in Example 1, and the difference was that the types and amounts of ingredients were changed, as shown in Table 2 . The positive photosensitive polysiloxane compositions prepared in Comparative Example 1 to Comparative Example 2 were evaluated in the following evaluation manner, and the results are shown in Table 2.

Table 2:

Evaluation method (chemical resistance):

The photosensitive polysiloxane composition is coated on the glass substrate by spin coating to form a coating film. Next, the coating film was prebaked at 100° C. for 2 minutes to form a prebaked coating film with a thickness of about 2 μm. Then, a photomask (manufactured by NIPPON FILCON) of lines and spaces (line and space) is inserted between the exposure machine and the pre-baked coating film, and 300mJ/ ^cm2 of ultraviolet light is used to make the pre-baked coating The film was exposed (exposure machine model is AG500-4N, manufactured by M&R Nanotechnology). Then, the substrate with the exposed pre-baked coating film was developed at 23° C. with 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds to remove the exposed part of the coating film on the glass substrate, and then After washing with pure water. Then, the developed coating film was directly irradiated with an exposure machine, and the exposure energy was 200 mJ/cm ² . Finally, the coating film is post-baked in an oven at 130° C. for 60 minutes to obtain a patterned protective film. Next, soak the above protective film in a 3.4% oxalic acid solution at 60° C. for 10 minutes, then observe and record the minimum line width without peeling off. The evaluation criteria of chemical resistance are as follows, wherein the smaller the line width without peeling, the better the chemical resistance.

◎: Line width without peeling ≦12μm;

○: 12μm < line width without peeling ≦ 20μm;

△: 20μm < line width without peeling ≦ 40μm;

╳: Line width without peeling > 40 μm.

The above-mentioned embodiments are only to illustrate the principles and effects of the present invention, but not to limit the present invention. Modifications and changes made by those skilled in the art to the above embodiments still do not violate the spirit of the present invention. The scope of the present invention should be as listed in the scope of application.

Claims (10)

1. A positive photosensitive polysiloxane composition comprising:

a polysiloxane (A);

o-naphthoquinone diazide sulfonate (B);

a solvent (C); and

a silane compound (D);

wherein the silane compound (D) has a structure represented by the formula (D-1):

in the formula (D-1):

R ¹ represents an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms;

R ² each independently represents an unsubstituted or substituted alkyl group having a carbon number of 1 to 20, an unsubstituted or substituted aryl group having a carbon number of 6 to 10, an unsubstituted or substituted aralkyl group having a carbon number of 7 to 10, an unsubstituted or substituted alkenyl group having a carbon number of 2 to 10, or an unsubstituted or substituted organoxy group having a carbon number of 1 to 20;

R ³ represents an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms;

n is an integer of 1 to 3; and is

m is an integer of 1 to 3;

wherein the silane compound (D) is used in an amount of 1 to 15 parts by weight based on 100 parts by weight of the polysiloxane (A).

2. The positive photosensitive polysiloxane composition according to claim 1, wherein the polysiloxane (a) is obtained by at least polycondensing a silane monomer (a-1) represented by the formula (I-1):

Si(R ^a ) _w (OR ^b ) _4-w formula (I-1)

In the formula (I-1):

R ^a each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkyl group having 1 to 10 carbon atoms and containing an acid anhydride group, an alkyl group having 1 to 10 carbon atoms and containing an epoxy group, or an alkoxy group containing an epoxy group, and at least one R ^a Represents an alkyl group having 1 to 10 carbon atoms and containing an acid anhydride group, an alkyl group having 1 to 10 carbon atoms and containing an epoxy group, or an alkoxy group containing an epoxy group;

R ^b each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms; and

w represents an integer of 1 to 3.

3. The positive photosensitive polysiloxane composition according to claim 1, further comprising a cyclic siloxane compound (E) represented by formula (E-1):

in the formula (E-1):

R ¹⁹ and R ²⁰ Represents a monovalent group having an alicyclic epoxy group (or an alkyl group), wherein the t R' s ¹⁹ And t R ²⁰ At least one of them is a monovalent group having an alicyclic epoxy group; and

t represents an integer of 3 or more;

wherein R is ¹⁹ And R ²⁰ May be the same or different, the plurality of R ¹⁹ And the plurality of R ²⁰ Each may be the same or different.

4. The positive photosensitive polysiloxane composition according to claim 1, wherein the o-naphthoquinone diazide sulfonate ester (B) is used in an amount of 8 to 24 parts by weight, based on 100 parts by weight of the polysiloxane (a); the solvent (C) is used in an amount of 100 to 700 parts by weight.

5. The positive photosensitive polysiloxane composition according to claim 3, wherein the cyclic siloxane compound (E) is used in an amount of 4 to 24 parts by weight based on 100 parts by weight of the polysiloxane (A).

6. A method for forming a thin film on a substrate, comprising applying the positive-type photosensitive polysiloxane composition according to any one of claims 1 to 5 onto the substrate.

7. A thin film on a substrate made by the method of claim 6.

8. A liquid crystal display element or an organic electroluminescence display or an optical waveguide device comprising the film according to claim 7.

9. A planarization film or an interlayer insulating film of a TFT substrate, or an optical waveguide core material or a protective film of a clad material in a liquid crystal display element or an organic electroluminescent display, which is obtained by the method according to claim 6.

10. A liquid crystal display element or an organic electroluminescence display or an optical waveguide device, comprising the planarization film or the interlayer insulating film of the TFT substrate, or the protective film of the optical waveguide core material or the coating material in the liquid crystal display element or the organic electroluminescence display according to claim 9.