TW201837086A - Positive photosensitive polysiloxane composition - Google Patents

Abstract

The invention relates to a positive photosensitive polysiloxane composition for forming a planarization film or an interlayer insulating film of a TFT substrate in a liquid crystal display element or organic light-emitting display device, or a protective film of an overcoat or a core material in a waveguide, which has the characteristic of excellent chemical resistance. The positive photosensitive polysiloxane composition comprises a polysiloxane (A), an ortho-naphthoquinone diazide sulfonic acid ester (B), a solvent (C), and a silane compound (D).

Description

Positive photosensitive polysiloxane composition

The present invention relates to a positive-type photosensitivity of a flattening film or an interlayer insulating film suitable for a TFT substrate of a liquid crystal display element, an organic electroluminescent display element, or the like, or a protective film for a core material or a covering material of an optical waveguide. Siloxane composition, thin film formed therefrom, and device having the same. In particular, a positive-type photosensitive polysiloxane composition having excellent chemical resistance, a thin film formed therefrom, and a device having the thin film are provided.

In recent years, in the fields of the semiconductor industry, liquid crystal displays, or organic electroluminescence displays, as the size has become smaller, the miniaturization of the patterns required in the lithography process has become increasingly demanding. In order to achieve a miniaturized pattern, it is generally formed by exposing and developing a positive-type photosensitive material with high resolution and high sensitivity. Among them, a positive-type photosensitive material composed of a polysiloxane polymer is gradually used in the industry. Mainstream.

In a liquid crystal display or an organic electroluminescence display, an interlayer insulating film is usually disposed as insulation in a layered wiring room. The positive type photosensitive material is widely used as a material for forming an interlayer insulating film because the number of steps necessary to obtain a pattern shape is small and the obtained insulating film has good flatness.

For example, an interlayer insulating film for a liquid crystal display is necessary to form a pattern of contact holes for fine wiring. In fact, it is very difficult to achieve a standard pore size for the contact holes formed by the negative-type photosensitive composition. Therefore, the positive-type photosensitive composition is widely used in the industry to form an interlayer insulating film of a liquid crystal display element (such as Japanese Patent Application Laid-Open). 2001-354822).

Generally, the main component of a positive-type photosensitive composition forming an interlayer insulating film is an acrylic resin, but a photosensitive composition using a siloxane-based material has higher heat resistance and transparency than the photosensitive property using an acrylic resin material. The composition is good (as shown in Japanese Patent Laid-Open No. 2000-1648).

However, silane compounds or polysiloxane materials such as polysiloxanes are prone to hydrolytic condensation reactions with similar or different types of compounds. When a positive-type photosensitive composition is prepared, the occurrence of these side reactions causes the storage stability of the positive-type photosensitive composition to be deteriorated, and the life of the product is also shortened.

In order to suppress the above-mentioned condensation reaction, the industry has developed to control the condensation reaction by controlling the molecular weight and branching structure of polysiloxane. Japanese Patent Application Laid-Open No. 2003-163209 discloses that polysiloxanes of different molecular weights can be obtained through the action of an acid catalyst, a metal chelate, and an alkali catalyst to control the structure of the polysiloxane. However, although the above-mentioned publication discloses various molecular weights of polysiloxane, it does not take into account the photosensitive characteristics of the polysiloxane; in addition to the dielectric constant, it also does not take into account the various characteristics of the interlayer insulating film.

In this case, Japanese Patent Application Laid-Open No. 2011-123450 discloses a positive-type photosensitive polysiloxane composition having excellent photosensitivity, storage stability, and melt flow resistance. However, the positive-type photosensitive polysiloxane composition Siloxane composition has poor chemical resistance, so it cannot be accepted by the industry.

Therefore, how to simultaneously meet the current chemical resistance requirements of the industry is the goal of hard research in the technical field to which the present invention belongs.

The present invention uses a component that provides a special silane compound to obtain a positive-type photosensitive polysiloxane composition with excellent chemical resistance.

Therefore, the present invention provides a positive-type photosensitive polysiloxane composition comprising: polysiloxane (A); o-naphthoquinonediazide sulfonate (B); a solvent (C); and a silane compound ( D); wherein the silane compound (D) has a structure represented by formula (D-1): Formula (D-1) In 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 1 to 20 carbon atoms, an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, and an unsubstituted or substituted carbon number 7 Aryl to 10, unsubstituted or substituted alkenyl having 2 to 10 carbons, or unsubstituted or substituted organic oxy having 1 to 20 carbons; R ³ means unsubstituted or substituted A substituted alkyl group having 1 to 10 carbons, or an unsubstituted or substituted aryl group having 6 to 10 carbons; n is an integer of 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 comprises applying the aforementioned positive-type photosensitive polysiloxane composition to the substrate.

The present invention also 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 element or an organic electroluminescent display, or a protective film of an optical waveguide core material or a covering material, which is prepared by the aforementioned method.

The invention further provides a device comprising the aforementioned film.

The present invention further provides a device comprising the aforementioned flattening film or interlayer insulating film of a TFT substrate in a liquid crystal display element or an organic electroluminescent display, or a protective film of an optical waveguide core material or a covering material.

Therefore, the present invention provides a positive-type photosensitive polysiloxane composition comprising: polysiloxane (A); o-naphthoquinonediazide sulfonate (B); a solvent (C); and a silane compound ( D); wherein the silane compound (D) has a structure represented by formula (D-1): Formula (D-1) In 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 1 to 20 carbon atoms, an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, and an unsubstituted or substituted carbon number 7 Aryl to 10, unsubstituted or substituted alkenyl having 2 to 10 carbons, or unsubstituted or substituted organic oxy having 1 to 20 carbons; R ³ means unsubstituted or substituted A substituted alkyl group having 1 to 10 carbons, or an unsubstituted or substituted aryl group having 6 to 10 carbons; n is an integer of 1 to 3; and m is an integer of 1 to 3.

Hereinafter, each component of the positive-type photosensitive polysiloxane composition used in the present invention will be described in detail.

Here, it is explained that acrylic acid and / or methacrylic acid are represented by (meth) acrylic acid, and acrylate and / or methacrylic acid ester are represented by (meth) acrylic acid ester; similarly, (meth) Acrylofluorenyl means acrylfluorenyl and / or methacrylfluorenyl.

The kind of the 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) using a silane monomer, or by polycondensation using a silane monomer and other polymerizable compounds.

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

This silane monomer (a-1) is a compound represented by formula (I-1): Si (R ^a ) _w (OR ^b ) _4-w formula (I-1) In 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 aromatic group having 6 to 15 carbon atoms, an alkyl group having 1 to 10 carbon atoms containing an acid anhydride group, An alkyl group having 1 to 10 carbons 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 carbons containing an acid anhydride group, and an epoxy group-containing carbon number Is an alkyl group having 1 to 10 or an alkoxy group having an epoxy group; R ^b each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms or 6 to 6 carbon atoms An aromatic group of 15; 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, third butyl, n-hexyl or n-decyl. R ^a may be an alkyl group having another substituent on the alkyl group. Specifically, R ^{a is,} for example, trifluoromethyl, 3,3,3-trifluoropropyl, 3-aminopropyl, 3- Thiopropyl or 3-isocyanatopropyl.

When R ^a in the formula (I-1) represents an alkenyl group having 2 to 10 carbon atoms, specifically, R ^{a is,} for example, a vinyl group. R ^a may be an alkenyl group having another substituent on the alkenyl group. Specifically, R ^{a is,} for example, 3-propenyloxypropyl group or 3-methacryloxypropyl group.

When the formula R ^{(I-1), a} represents an aromatic group having a carbon number of 6 to 15, in particular, R ^a, for example, phenyl, tolyl (tolyl) or naphthyl group (naphthyl). R ^a may be an aromatic group having another substituent on the aromatic group. Specifically, R ^a is, for example, p-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, the formula R ^{(I-1), a} represents an alkyl group containing an acid anhydride group, wherein the alkyl group is preferably an alkyl group having a carbon number of 1 to 10. Specifically, the acid-anhydride-containing alkyl group is, for example, ethylsuccinic anhydride represented by formula (I-1-1), propylsuccinic anhydride represented by formula (I-1-2), or formula ( I-1-3) shown by propylglutaric anhydride. It is worth mentioning that the acid anhydride group is a group formed by dicarboxylic acid by intramolecular dehydration. The dicarboxylic acid is, for example, succinic acid or glutaric acid. Formula (I-1-1) Formula (I-1-2) Formula (I-1-3)

In addition, R ^a in the formula (I-1) represents an epoxy-containing alkyl group, and the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. Specifically, the epoxy-containing alkyl group is, for example, 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 the intramolecular dehydration of a diol, wherein the diol is, for example, propylene glycol, butanediol, or pentanediol.

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

In addition, when R ^{b of the} formula (I-1) represents an alkyl group having 1 to 6 carbon atoms, specifically, R ^b is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or an n-butyl group. When R ^b in the formula (I-1) represents a fluorenyl group having 1 to 6 carbon atoms, specifically, R ^{b is,} for example, an ethenyl 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 (GPTMS), 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane (3-glycidoxypropyltriethoxysilane), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl trimethoxy silane, 2-epoxypropylalkylbutoxypropyl 2-oxetanylbutoxypropyl triphenoxysilane, a commercially available product manufactured by Toa Synthesis: 2-oxetanylbutoxypropyltrimethoxysilane (trade name TMSOX-D), 2 -Glycidyl butoxypropyltriethoxysilane (2-oxetanylbutoxypropyltriethoxysilane, trade name TESOX-D), 3- (triphenoxysilyl) propylsuccinic anhydride, marketed by Shin-Etsu Chemical Co., Ltd. Sales product: 3- (trimethoxysilyl) propylsuccinic anhydride (trade name X-12-967), commercially available product manufactured by WACKER Corporation: 3- (triethoxysilyl) propylbutyl Diacid anhydride (trade name GF-20), 3- (trimethoxysilyl) propylglutaric anhydride (TMSG), 3- (triethoxysilyl) propylglutaric acid Anhydride, 3- (triphenoxysilyl) propylglutaric anhydride, diisopropoxy-di (2-oxetanylbutoxypropyl) silane , Referred to as DIDOS), di (3-oxetanylpentyl) dimethoxy silane, (di-n-butoxysilyl) bis (propylsuccinic anhydride), (Dimethoxysilyl) bis (ethylsuccinic anhydride), 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylmethoxysilane 3-glycidoxypropyl dimethylethoxysilane, di (2-oxetanylbutoxypentyl) di (2-oxetanylbutoxypentyl) -2-oxetanyl pentylethoxy silane), tri (2-oxetanylpentyl) methoxy silane, (phenoxysilyl) tris (propylsuccinic anhydride), (methyl methyl Oxysilyl) bis (ethylsuccinic anhydride), or a combination 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) include 3- (triethoxysilyl) propylsuccinic anhydride, 3- (trimethoxysilyl) propylsuccinic anhydride, and 3-cyclo Oxypropoxypropyltrimethoxysilane, 3- (trimethoxysilyl) propylglutaric anhydride, (dimethoxysilyl) bis (ethylsuccinic anhydride), 2-glycidylbutyl Oxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-glycidylbutoxypropyltriethoxysilane, or a combination thereof.

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

This 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 having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an aromatic group having 6 to 15 carbon atoms; and R ^d each independently represents a hydrogen atom and 1 to 6 carbon atoms An alkyl group, a fluorenyl group having 1 to 6 carbons, or an aromatic group having 6 to 15 carbons; and u represents an integer of 0 to 3.

More specifically, when R ^c in the 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, third butyl, n-hexyl or n-decyl. R ^c may be an alkyl group having another substituent on the alkyl group. Specifically, R ^{c is,} for example, trifluoromethyl, 3,3,3-trifluoropropyl, 3-aminopropyl, 3- Thiopropyl or 3-isocyanatopropyl.

When R ^c in the formula (I-2) represents an alkenyl group having 2 to 10 carbon atoms, specifically, R ^{c is,} for example, a vinyl group. R ^c may be an alkenyl group having another substituent on the alkenyl group. Specifically, R ^{c is,} for example, 3-propenyloxypropyl or 3-methacryloxypropyl.

When R ^c in the formula (I-2) represents an aromatic group having 6 to 15 carbon atoms, specifically, R ^c is, for example, a phenyl group, a tolyl group, or a naphthyl group. R ^c may be an aromatic group having another substituent on the aromatic group. Specifically, R ^c is, for example, p-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} 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 ^Rd in the formula (I-2) represents a fluorenyl group having 1 to 6 carbon atoms, specifically, R ^{d is,} for example, an ethylfluorenyl group. When ^Rd in Formula (I-2) represents an aromatic group having 6 to 15 carbon atoms, specifically, ^{Rd 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 having four hydrolyzable groups); when u = 1, it indicates that the silane is a silane The monomer is a trifunctional silane monomer (that is, a silane monomer having three hydrolyzable groups); when u = 2, it means that the silane monomer is a difunctional silane monomer (that is, two hydrolyzable monomers) Silane monomer); and when u = 3, it means that the silane monomer is a monofunctional silane monomer (that is, a silane monomer having a 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, for example, an alkoxy group, an acyloxy group, or a benzene group. Oxy (phenoxy group).

Specific examples of the silane monomer represented by the formula (I-2) include, but are not limited to: (1) tetrafunctional silane monomer: tetramethoxysilane, tetraethoxysilane, tetraethoxysilane Tetraacetoxysilane or tetraphenoxy silane; (2) trifunctional silane monomers: methyltrimethoxysilane (MTMS), methyltriethoxysilane ( methyltriethoxysilane), methyltriisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane ), Ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane Silane (n-propyltriethoxysilane), n-butyltrimethoxysilane (n-butyltrimethoxysilane), n-butyltriethoxysilane (n-butyltriethoxysilane), n-hexyltrimethoxysilane (n-hexyltrimethoxysilane) ane), n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethylsilane Phenyltrimethoxysilane (PTMS), phenyltriethoxysilane (PTES), p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ethyltrimethoxy 1- (p-hydroxyphenyl) ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxybenzene Carbonyloxy) pentyltrimethoxysilane (4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane), trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane , 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-propenyloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, or 3-methyl Propylene methoxypropyltriethoxysilane; (3) Difunctional silane monomer: dimethyldimethoxysilane (DMDMS), dimethyldiethoxysilane, dimethyldiethoxysilane, Dimethyldiacetyloxysilane, di-n-butyldimethoxysilane or diphenyldimethoxysilane; or (4) monofunctional silane monosilane Body: trimethylmethoxysilane (trimethylmethoxysilane) or tri-n-butylethoxysilane (tri-n-butylethoxysilane), etc.

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

The siloxane prepolymer (a-3) is a compound represented by the formula (I-3). In the formula (I-3) of formula ^{(I-3), R e} , R f, R g , and R ^h each independently represents a hydrogen atom, alkyl having 1 to 10 carbons, alkenyl having 2 to 6 Or an aromatic group having 6 to 15 carbon atoms, wherein any one of the alkyl group, alkenyl group, and aromatic group optionally contains a substituent; R ⁱ and R ^j each independently represent a hydrogen atom, and having 1 to 6 carbon atoms An alkyl group, a fluorenyl group having 1 to 6 carbons, or an aromatic group having 6 to 15 carbon atoms, wherein any one of the alkyl group, fluorenyl group, and aromatic group optionally contains a substituent; and s represents 1 to 1000 Integer.

More specifically when, in formula ^{(I-3) R e,} R f, R g , and R ^h each independently represent an alkyl group having a carbon number of 1 to 10, specifically, R ^e, R ^f, R ^g and R ^h are each independently methyl, ethyl or n-propyl. In the formula ^{(I-3) R e,} R f, R g , and R ^h each independently is a C 2-10 alkenyl group, ^{specifically, R e, R f, R} g and R ^h e.g. Each is independently a vinyl, acryloxypropyl or methacryloxypropyl. In the formula ^{(I-3) R e,} R f, R g , and R ^h each independently represents an aromatic group having a carbon number is 6 to 15, ^{specifically, R e, R f, R} g and R ^h e.g. Each is independently phenyl, tolyl or naphthyl. In addition, any of the alkyl group, alkenyl group, and aromatic group may have another substituent.

Further, when the formula (I-3) is R ⁱ and R ^j each independently represent an alkyl group having a carbon number of time of 1 to 6, specifically, for example, R ⁱ and R ^j are each independently methyl, ethyl, n-propyl Base, isopropyl or n-butyl. When R ⁱ and R ^{j in} formula (I-3) each independently represent a fluorenyl group having 1 to 6 carbon atoms, specifically, R ⁱ and R ^{j are,} for example, an ethenyl group. When R ⁱ and R ^j in the formula (I-3) each independently represent an aromatic group having 6 to 15 carbon atoms, specifically, R ⁱ and R ^{j are,} for example, a phenyl group. Among them, any of the alkyl group, fluorenyl group, and aromatic group may optionally have a substituent.

In the formula (I-3), s may be an integer of 1 to 1,000, preferably an integer of 3 to 300, more preferably an integer of 5 to 200. When s is an integer from 2 to 1000, R ^{e is} each the same or different group, and R ^{f is} each 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-diethoxydisilaxane, 1,1,3,3-tetraethyl-1,3-diethoxydisilaxane or by Gilester ( Commercial products (Silanol terminated polydimethylsiloxane) with silanol terminated polydimethylsiloxane manufactured by Gelest) (trade names such as DMS-S12 (molecular weight 400 to 700), DMS-S15 (molecular weight 1500 to 2000), 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)).

The siloxane prepolymer (a-3) can be used alone or in combination.

The average particle diameter of the silicon dioxide particles (a-4) is not particularly limited. The average particle diameter 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 silicon dioxide particles (a-4) include, but are not limited to, commercially available products manufactured by Catalytic Chemicals, such as OSCAR 1132 (particle diameter 12 nm; dispersant is methanol), OSCAR 1332 (particles) Diameter 12nm; dispersant is n-propanol), OSCAR 105 (particle diameter 60nm; dispersant is γ-butyrolactone), OSCAR 106 (particle diameter 120nm; dispersant is diacetone alcohol), etc., manufactured by Fuso Chemical Company Commercially available products, such as Quartron PL-1-IPA (particle diameter 13nm; dispersant is isoacetone), Quartron PL-1-TOL (particle diameter 13nm; dispersant is toluene), Quartron PL-2L-PGME ( Particle diameter 18nm; dispersant is propylene glycol monomethyl ether) or Quartron PL-2L-MEK (particle diameter 18nm; dispersant is methyl ethyl ketone), etc., or a commercially available product manufactured by Nissan Chemical Co., Ltd. under the trade name IPA-ST ( Particle diameter 12nm; dispersant is isopropanol), EG-ST (particle diameter 12nm; dispersant is ethylene glycol), IPA-ST-L (particle diameter 45nm; dispersant is isopropanol) or IPA-ST- ZL (particle diameter 100 nm; dispersant is isopropanol). The 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 polycondensation using a silane monomer and other polymerizable compounds. Generally speaking, the above-mentioned polycondensation reaction is performed by the following steps: adding a solvent, water, or optionally a catalyst to a silane monomer; and heating and stirring at 50 ° C to 150 ° C for 0.5 Hours to 120 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-type photosensitive polysiloxane composition of the present invention. Based on the total amount of the silane monomer (a-1) and the silane monomer (a-2) being 1 mole, the use amount of the solvent is preferably from 20 g to 1,000 g; more preferably from 30 g to 800 g; further more It is preferably 50 grams to 600 grams.

The hydrolyzable group based on the silane monomer is 1 mole, and the amount of water used for the polycondensation reaction (that is, water used for hydrolysis) is preferably 10 to 500 g; more preferably 15 to 400 g And further more preferably from 20 g to 300 g.

The catalyst used for the polycondensation reaction is not particularly limited, and is preferably selected from an acid catalyst or an alkali catalyst. Specific examples of the acid catalyst 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 the base catalyst include, but are not limited to, diethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethanolamine, triethanolamine, sodium hydroxide , Potassium hydroxide, amine-containing alkoxy-containing silane or ion exchange resin, and the like.

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

From the standpoint of stability, the polysiloxane (A) is preferably free of 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 purification method is not particularly limited, and it is preferred that 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 then the organic layer was concentrated with a rotary evaporator to remove alcohol or water. In addition, the catalyst can be removed using an ion exchange resin.

The polysiloxane (A) may be used in combination with another alkali-soluble resin. The kind of the other alkali-soluble resin is not particularly limited, and may include, but is not limited to, a resin containing a carboxylic acid group or a hydroxyl group. Specific examples of the other alkali-soluble resin include an acrylic resin, a fluorene resin, a urethane resin, or a novolac resin.

The acrylic resin is preferably obtained by copolymerizing one or more unsaturated carboxylic acids or unsaturated carboxylic 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, butene acid, 2-chloroacrylic acid, ethacrylic acid, cinnamic acid, 2-acrylic acid, ethoxysuccinate, Unsaturated monocarboxylic acids such as 2-methacrylic acid ethoxysuccinate or 2-isobutylene ethoxysuccinate; maleic acid, maleic anhydride, fumaric acid, itaconic acid, clothing Conic anhydride, citraconic acid or citraconic anhydride, etc., unsaturated dicarboxylic acids (anhydrides), trivalent or more unsaturated polycarboxylic acids (anhydrides); preferably, the unsaturated carboxylic acid or unsaturated carboxylic acid The acid anhydride compound is acrylic acid, methacrylic acid, 2-acrylic acid ethoxy succinate, 2-methacrylic acid ethoxy succinate, or 2-isobutylene ethoxy succinate. The above-mentioned one or more unsaturated carboxylic acid or unsaturated carboxylic anhydride compounds may be used alone or in combination to improve the pigment dispersibility, the development speed, and the occurrence of residues.

Specific examples of the other unsaturated compounds include: aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, and methoxystyrene; N-phenylmaleic acid 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, second butyl acrylate, second butyl methacrylate, third butyl acrylate, third butyl methacrylate, 2-hydroxyethyl acrylate, methyl formate base 2-hydroxyethyl enoate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, methacrylic acid 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, Benzyl acrylate, benzyl methacrylate (BzMA), phenyl acrylate, phenyl methacrylate, triethylene glycol methacrylate, triethylene glycol methacrylate, twelve methacrylic acid Alkyl ester, tetradecyl methacrylate, cetyl methacrylate, octadecyl methacrylate, eicosyl methacrylate, behenyl methacrylate, Unsaturated carboxylic acid esters such as dicyclopentenyloxyethyl acrylate (DCPOA); N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate , N, N-diethylaminopropyl acrylate, N, N-dimethylaminopropyl methacrylate, N, N-dibutylaminopropyl acrylate, N, iso-butylaminoethyl methacrylate; Glycidyl acrylate, Glycidyl methacrylate, etc. Base esters; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, etc .; vinyl methyl ether, vinyl ether, allyl epoxy propyl ether, methallyl epoxy Unsaturated ethers such as propyl ether; Acrylonitrile, methacrylonitrile, 2-chloroacrylonitrile, vinyl cyanide compounds such as vinyl cyanide; acrylamide, methacrylamide, 2-chloroacryl Unsaturated amines such as amines, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, etc .; aliphatic copolymers of 1,3-butadiene, isopentene, butadiene chloride, etc. Conjugated diene.

Specific examples of the samarium-based resin include V259ME, V259MEGTS, or V500MEGT (manufactured by Nippon Steel Chemical Co., Ltd.). The samarium-based resin may be used alone or in combination.

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

Specific examples of the novolak resin include EP4020G, EP4080G, TR40B45G, or EP30B50 (produced by Asahi Organic Materials Industry Co., Ltd.). The novolak resin can be used alone or in combination.

The weight-average molecular weight of the polysiloxane (A) is 5,000 to 60,000, preferably 7,000 to 55,000, and more preferably 9,000 to 50,000.

According to the present invention, the type of the o-naphthoquinonediazide sulfonate (B) is not particularly limited, and the o-naphthoquinonediazide sulfonate generally used can be used, but it can achieve the object claimed in the present invention. . The o-naphthoquinonediazide 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 a salt thereof with a hydroxy compound. P-naphthoquinonediazidesulfonate (B) is more preferably prepared by reacting p-naphthoquinonediazidesulfonic acid or a salt thereof with a polyhydroxy compound.

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

Specific examples of the hydroxy compound include, but are not limited to, a hydroxybenzophenone-based compound, a hydroxyaryl-based compound, a (hydroxyphenyl) hydrocarbon-based compound, other aromatic hydroxy-based compounds, or a combination thereof.

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, a hydroxyaryl-based compound represented by the formula (b-1). Formula (b-1) In formula (b-1), B ¹ and B ² each independently represent a hydrogen atom, a halogen atom, or a carbon number of 1 to 6 alkyl groups; B ³ , B ^4, and B ⁷ each independently represent a hydrogen atom Or an alkyl group having 1 to 6 carbon atoms; 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 having 1 to 6 carbon atoms, and a carbon number of An alkoxy group of 1 to 6, an alkenyl group or a cycloalkyl group having 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 the hydroxyaryl-based compound represented by the 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 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-ring Hexyl-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-hydroxybenzene ) Ethyl] benzene, 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl] -4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl Group] benzene, or a combination thereof.

Specific examples of the (hydroxyphenyl) hydrocarbon compound include, but are not limited to, the (hydroxyphenyl) hydrocarbon compound represented by the formula (b-2). 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 carbon atoms; and m and n each independently represent an integer of 1 to 3.

Specifically, specific examples of the (hydroxyphenyl) hydrocarbon compound represented by the 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, and the like.

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

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 a combination thereof. The hydroxy compound may be used alone or in combination.

The reaction of the o-naphthoquinonediazidesulfonic acid or a salt thereof with a hydroxy compound is usually performed in an organic solvent such as dioxane, N-pyrrolidone, or acetamide. . The above reaction is preferably performed with a basic condensing agent such as triethanolamine, an alkali metal carbonate or an alkali metal bicarbonate.

The degree of esterification of the o-naphthoquinonediazide sulfonate (B) is preferably more than 50%, that is, based on the total number of hydroxy groups in the hydroxy compound being 100 mole percent (mol%), the hydroxy group More than 50 mol% of the hydroxyl groups in the compound are esterified with o-naphthoquinonediazidesulfonic acid or a salt thereof. The degree of esterification of the o-naphthoquinonediazide sulfonate (B) is more preferably 60% or more.

Specific examples of the o-naphthoquinonediazide sulfonate (B) are preferably 4,4 '-[1- [4 [-1- (4-hydroxyphenyl) -1-methylethyl] benzene O-naphthoquinonediazidesulfonate, 2,3,4-trihydroxybenzophenone and o-naphthoquinone di O-naphthoquinonediazidesulfonate and 2- (2,3,4-trihydroxyphenyl) -2- (2 ', 3', 4'-trihydroxybenzene O-naphthoquinonediazidesulfonic acid ester formed from propane and o-naphthoquinonediazide-5-sulfonic acid, but it is not limited thereto.

Based on the use amount of the polysiloxane (A) being 100 parts by weight, the use amount of the o-naphthoquinonediazide 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 the solvent (C) according to the present invention is not particularly limited. The solvent (C) is, for example, an alcoholic hydroxy-containing compound or a carbonyl group-containing cyclic compound.

Specific examples of the alcoholic hydroxyl-containing compound include, but are not limited to, acetol, 3-hydroxy-3-methyl-2-butanone, 4- 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl 4-hydroxy-4-methyl-2-pentanone (also known as diacetone alcohol (DAA)), ethyl lactate, butyl lactate, Propylene glycol monomethyl ether, propylene glycol monoethyl ether (PGEE), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol mono-n-propyl ether propyl 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, or a combination thereof. It is worth noting that the alcoholic hydroxyl group-containing compound 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 may be used alone or in combination.

Specific examples of the carbonyl-containing cyclic compound include, but are not limited to, γ-butyrolactone, γ-valerolactone, δ-valerolactone, and propylene carbonate Esters (propylene carbonate), nitrogen-methyl pyrrolidone (N-methyl pyrrolidone), cyclohexanone (cycloheptanone) and the like. It is worth noting that the carbonyl-containing cyclic compound is preferably γ-butyrolactone, nitrogen-methylpyrrolidone, cyclohexanone, or a combination thereof. The carbonyl-containing cyclic compound may be used alone or in combination.

The alcoholic hydroxyl group-containing compound may be used in combination with a carbonyl group-containing cyclic compound, and its weight ratio is not particularly limited. The weight ratio of the alcoholic hydroxyl group-containing compound to the carbonyl group-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, the polysiloxane (A) is not reacted. Silanol (Si-OH) groups are less prone to condensation reactions and reduce storage stability. In addition, since the alcoholic hydroxyl group-containing compound and the carbonyl group-containing cyclic compound have good compatibility with o-naphthoquinonediazide sulfonate (B), it is difficult to have whitening phenomenon during coating and film formation, and can be maintained. The transparency of the protective film.

As long as the effect of the present invention is not impaired, the solvent (C) may contain other solvents. 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, ethyl 3-ethoxypropionate 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, acetoacetone, diacetone alcohol, or cyclohexen-1-one, etc .; or (3) ethers: diethyl ether, diisopropyl ether, di-n-butane Ether, diethylene glycol dimethyl ether or diphenyl ether.

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

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

A feature of the silane compound of the present invention is, for example, that it has 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. Formula (D-1) In 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 1 to 20 carbon atoms, an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, and an unsubstituted or substituted carbon number 7 Aryl to 10, unsubstituted or substituted alkenyl having 2 to 10 carbons, or unsubstituted or substituted organic oxy having 1 to 20 carbons; R ³ means unsubstituted or substituted A substituted alkyl group having 1 to 10 carbons, or an unsubstituted or substituted aryl group having 6 to 10 carbons; n is an integer of 1 to 3; and m is an integer of 1 to 3.

The structure described above can be specifically expressed by the following formula (D-2) or (D-3). Formula (D-2) In formula (D-2): R ¹ and n are the same as above; R ⁴ each independently represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, unsubstituted or Substituted aryls having 6 to 10 carbons, unsubstituted or substituted aralkyls having 7 to 10 carbons, unsubstituted or substituted alkenyls having 2 to 10 carbons or unsubstituted or substituted Substituted organic oxygen groups having 1 to 20 carbon atoms; Me represents a methyl group; Ph represents a phenyl group. Formula (D-3) In formula (D-3): R ¹ , n, R ⁴ , and Me are the same as above; R ⁵ is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, Substituted or substituted aryl having 6 to 10 carbons, unsubstituted or substituted aralkyl having 7 to 10 carbons or unsubstituted or substituted alkenyl having 2 to 10 carbons.

More specifically, it can be represented by the following formula (D-4) to (D-9). Formula (D-4) Formula (D-5) Formula (D-6) Formula (D-7) Formula (D-8) Formula (D-9) In formulas (D-5) to (D-9): R ¹ , n, Me, and Ph are the same as above; Et represents ethyl.

More specifically, R ^{1 in} Formula (D-1) to Formula (D-9) represents an ethyl group.

The alkyl and aryl groups of R ^{1 are} , for example, methyl, ethyl, propyl, butyl, phenyl, etc .; methyl and ethyl are preferred, and ethyl is more preferred. R ² alkyl, such as methyl, ethyl, 3-butyl, octyl, decyl, dodecyl, etc .; aryl, such as phenyl, xylyl, tolyl, etc .; aralkyl, such as benzene Methyl, etc., alkenyl such as vinyl, propenyl, pentenyl, etc .; organic oxy such as methoxy, ethoxy, propoxy, butoxy, octyloxy, dodecyloxy, etc. Aryloxy, ethoxy, ethoxy, ethoxy, vinyloxy, propyleneoxy, pentenyloxy, etc. alkenyloxy; alkyl with 1 to 6 carbons, phenyl, 1 to 20 carbons An oxygen group is preferred; an alkyl group having 1 to 4 carbon atoms, a phenyl group, and an alkoxy group having 1 to 12 carbon atoms are more preferred. R ³ is an alkyl or aryl group, such as methyl, ethyl, phenyl, etc .; methyl is preferred. R ⁴ alkyl groups such as methyl, ethyl, 3-butyl, octyl, decyl, dodecyl, etc .; aryl groups such as phenyl, xylyl, tolyl, etc .; aralkyl groups such as benzyl Alkenyl, such as vinyl, propenyl, pentenyl, etc .; organic oxy, such as methoxy, ethoxy, propoxy, butoxy, octyloxy, dodecyloxy, etc. And aryloxy groups such as aryloxy, vinyloxy, propyleneoxy, and pentenyloxy; preferably the same as R ² . R ⁵ alkyl, aryl, aralkyl, alkenyl, such as methyl, ethyl, propyl, butyl, 3-butyl, octyl, decyl, dodecyl, phenyl, benzene Methyl, vinyl, propenyl, pentenyl and the like; alkyl groups having 1 to 12 carbons are preferred.

The silane compound (D) of the present invention is prepared, for example, by a dehydrogenation reaction of 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 filter substance, and the reaction can be performed favorably under the condition of no solvent, which is a highly productive production method.

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

At this time, regarding the production of the silane compound (D) of the above formulas (1) to (9), a silane compound having a mercapto group represented by the following formula (Di) and a formula ( The silane compound with Si-H bond shown in D-ii) reacts to form a sulfur-silicon bond. Formula (Di) In formula (D-ii) In formula (Di) and formula (D-ii): R ¹ , R ² , R ³ , n, and m are the same as described above.

Specific examples of the silane compound having a mercapto group among the necessary raw materials when producing the silane compound (D) of the present invention include α-mercaptomethyltrimethoxysilane, α-mercaptomethylmethyldimethoxysilane, α -Mercaptomethyldimethylmethoxysilane, α-mercaptomethyltriethoxysilane, α-mercaptomethylmethyldiethoxysilane, α-mercaptomethyldimethylethoxysilane, γ -Mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyldimethylmethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyl Butylmethyldiethoxysilane, γ-mercaptopropyldimethylethoxysilane, and the like are not limited thereto.

In the production of the silane compound (D) of the present invention, specific examples of the organic compound having a Si-H bond among trimethylsilane, ethyldimethylsilane, diethylmethylsilane, and triethyl Silane, 3-butyldimethylsilane, 3-butyldiphenylsilane, triisopropylsilane, tri-n-butylsilane, triisobutylsilane, dimethylphenylsilane, Phenylmethylsilane, dimethyl-n-octylsilane, decyldimethylsilane, dodecyldimethylsilane, dimethylvinylsilane, triphenylsilane, trimethoxysilane, triethyl Oxysilane, tributoxysilane, dimethylethoxysilane, dimethylbutoxysilane, dimethyloctyloxysilane, dimethyldodecyloxysilane, and the like, but are not limited thereto.

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

In addition, Lewis acid catalysts such as aluminum chloride, aluminum sulfate, tin chloride, tin chloride sulfate, iron chloride, boron trifluoride, pentafluorophenylboronic acid and the like are preferred, and pentafluorophenylboronic acid is particularly preferred.

In the production of 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 and the organic silicon compound having a Si-H bond is 1 mole relative to the thio group, The Si-H bond is preferably reacted in the range of 0.5 to 1.5 mol, especially 0.9 to 1.1 mol.

In the production of 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 0.00001 to 0.1 with respect to 1 mole of the mercapto group. It is preferable to carry out the reaction in the range of mol, especially 0.000001 to 0.001 mol.

In the production of the silane compound (D) of the present invention, the reaction temperature is not particularly limited, and is usually from room temperature to the boiling point of the reaction raw material or organic solvent, preferably 50 to 150 ° C, and more preferably 60 to 120 ° C. Range of reaction. The reaction time is not particularly limited as long as the reaction time is sufficient, and is preferably about 30 minutes to 24 hours, and more preferably about 1 to 10 hours.

Based on the used amount of the polysiloxane (A) being 100 parts by weight, the used 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 Serving.

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

The positive-type photosensitive polysiloxane composition of the present invention may further contain a cyclic siloxane compound (E) represented by the following formula (E-1): 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 t t R ¹⁹ and t At least one of each R ²⁰ is a monovalent group having an alicyclic epoxy group; and t represents an integer of 3 or more; wherein R ¹⁹ and R ²⁰ may be the same or different, The plurality of R ¹⁹ and the plurality of R ²⁰ may be the same or different, respectively.

The cyclic siloxane compound (E) may include, but is not limited to, 2,4-bis [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,4,6,6 , 8,8-hexamethyl-cyclotetrasiloxane silanol, 4,8-bis [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,2, 4,6,6,8-hexamethyl-cyclotetrasiloxane, 2,4-di [2- (3- {oxebicyclo [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-tri [2- (3- {oxabicyclo [4.1.0] heptyl }) Ethyl] -2,4,6,6,8-pentamethyl-cyclotetrasiloxane, 2,4,8-di [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 formula (E-1) can be shown below.

The cyclic siloxane compound (E) represented by the formula (E-1) may be used alone or in combination of two or more.

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

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

The positive-type photosensitive polysiloxane composition according to the present invention may optionally further contain 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 defoamer. Its combination.

The kind of the sensitizer is not particularly limited. The sensitizer is preferably a compound containing a phenolic hydroxy group. Specific examples of the compound containing a phenolic hydroxy group include, but are not limited to, a triphenol type compound, a bisphenol type compound, a multinuclear branched type compound, and a condensation type. A phenol compound, a polyhydroxybenzophenone, or a combination thereof.

Specific examples of the trisphenol type compound include, but are not limited to, tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, and 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-ring Hexyl-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 and the like.

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 benzophenones include, but are not limited to, 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4, 6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,4,2 ' , 4'-tetrahydroxybenzophenone, 2,4,6,3 ', 4'-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 and the like.

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

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

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

Specific examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, a polysiloxane surfactant, a fluorine surfactant, or a combination thereof.

Specific examples of the surfactant include, but are not limited to (1) polyethylene oxide alkyl ethers: polyethylene oxide dodecyl ether, etc .; (2) polyethylene oxide alkyl Polyoxyethylene phenyl ethers: polyethylene oxide octylphenyl ether, polyethylene oxide nonylphenyl ether, etc .; (3) polyethylene glycol diesters: Polyethylene glycol dilaurate, polyethylene glycol distearate, etc .; (4) sorbitan fatty acid esters (sorbitan fatty acid esters); (5) fatty acids modified polyesters (fatty acid modified poly esters); and (6) tertiary amine modified polyurethanes modified with tertiary amines. Specific examples of commercially available surfactants include KP (manufactured by Shin-Etsu Chemical Industries), SF-8427 (manufactured by Dow Corning Toray Silicone Co., Ltd.), Polyflow ( (Manufactured by Kyoeisha Oil Chemical 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-Japan Synthetic Chemicals), F-475 (manufactured by Dainippon Ink Chemical Industry), or a combination thereof .

Specific examples of the defoaming agent include Surfynol MD-20, Surfynol MD-30, EnviroGem AD01, EnviroGem AE01, EnviroGem AE02, Surfynol DF110D, Surfynol 104E, Surfynol 420, Surfynol DF37, SurfynolDFDFol, Surfynol DF58, Surf66, Surffol70, Surf66 (Manufactured by Air products), etc.

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

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

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

The present invention also 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 element or an organic electroluminescent display, or a protective film of an optical waveguide core material or a covering material, which is prepared by the aforementioned method.

The invention further provides a device comprising the aforementioned film.

The present invention further provides a device comprising the aforementioned flattening film or interlayer insulating film of a TFT substrate in a liquid crystal display element or an organic electroluminescent display, or a protective film of an optical waveguide core material or a covering material.

The method of forming the protective film will be described in detail below, which includes: forming a pre-bake coating film using a positive photosensitive polysiloxane composition, patterning the pre-baking coating film, and removing the exposure by alkali development Area to form a pattern; and post-bake treatment to form a protective film. Form a pre-bake coating

By a coating method such as spin coating, cast coating, or roll coating, a positive photosensitive polysiloxane composition in a solution state is coated on a protected element (hereinafter referred to as a substrate) to form a coating film.

The substrate may be alkali-free glass, soda-lime glass, hard glass (Pales glass), quartz glass, such glass with a transparent conductive film attached to the liquid crystal display device, or a photoelectric conversion device such as Solid-state imaging device) substrate (such as silicon substrate).

After the coating film is formed, most of the organic solvents of the positive photosensitive polysiloxane composition are removed by drying under reduced pressure, and then the remaining organic solvents are completely removed by a pre-bake method 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 type of each component and the blending ratio. Generally, reduced pressure drying is performed at a pressure of 0 torr to 200 torr for 1 second to 60 seconds, and pre-baking is performed at a temperature of 70 ° C to 110 ° C for 1 minute to 15 minutes. Patterned exposure

The pre-baking coating film is exposed with a photomask having a specific pattern. The light used in the exposure process is preferably ultraviolet rays such as g-line, h-line or i-line, and the equipment used to provide ultraviolet light may be (ultra-high pressure) mercury lamps or metal halide lamps. development

The exposed pre-baked coating film is immersed in a developing solution at a temperature of 23 ± 2 ° C. and developed for about 15 seconds to 5 minutes to remove the unnecessary part of the exposed pre-baked coating film, that is, the The exposed areas are dissolved in the developing solution, and the unexposed areas remain, thereby forming a semi-finished product with a protective film having a predetermined pattern on the substrate. Specific examples of the developing solution include, but are not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methylsilicate, ammonia water, ethylamine, Diethylamine, dimethylethanolamine, tetramethylammonium hydroxide (THAM), tetraethylammonium hydroxide, choline, pyrrole, pyridine, or 1,8-diazabicyclo [5.4.0] -7-11 Basic compounds such as alkenes.

It is worth mentioning that too high a concentration of the developing solution may cause damage to a specific pattern or worsen the resolution of the specific pattern; too low a concentration may cause poor development, resulting in the failure of molding of the specific pattern or the composition of the exposed portion. Therefore, the concentration will affect the formation of a specific pattern after the subsequent positive photosensitive polysiloxane composition is exposed. The concentration range of the developer is preferably 0.001 wt% to 10 wt%; more preferably 0.005 wt% to 5 wt%; still more preferably 0.01 wt% to 1 wt%. The embodiment of the present invention is a developer using 2.38 wt% tetramethylammonium hydroxide. It is worth mentioning that even if a developing solution with a lower concentration is used, the positive photosensitive polysiloxane composition of the present invention can form a good fine pattern. Post-bake treatment

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

For example, the protective film is formed in the following steps, for example. First, a positive-type photosensitive polysiloxane composition was spin-coated onto a plain glass substrate (100 × 100 × 0.7 mm) to form a coating film of about 2 μm. After pre-baking at 110 ° C for 2 minutes, the coating film was placed under an exposure machine. Next, a positive photoresist mask was placed between the exposure machine and the coating film, and the pre-baking coating film was irradiated with the ultraviolet light of the exposure machine, and its energy was 100 mJ / cm ² . The exposed pre-baked coating film was immersed in a 2.38% TMAH aqueous solution at 23 ° C. for 60 seconds to remove the exposed portion. Next, after washing with water, the developed coating film was directly irradiated with an exposure machine, and its energy was 200 mJ / cm ² . Finally, 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 explain the present invention in detail, but it is not meant to limit the present invention to the contents disclosed in these examples. Preparation of polysiloxane (A) <Preparation Example 1>

In a 500 ml three-necked flask, 0.01 mol of 3- (triethoxysilyl) propylsuccinic anhydride (hereinafter referred to as GF-20) and 0.15 mol of methyltrimethoxysilane ( MTMS), 0.4 mol of phenyltrimethoxysilane (hereinafter referred to as PTMS), 0.44 mol of tetraethoxysilane (hereinafter referred to as TEOS), and 200 grams of 4-hydroxy-4-methyl-2- Amyl ketone (hereinafter referred to as DAA), 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 an oil bath at 30 ° C and stirred for 30 minutes. Then, the oil bath was heated to 120 ° C within 30 minutes. When the temperature of the solution is reduced to 110 ° C (that is, the reaction temperature), polymerization is continued for 9 hours (that is, the polycondensation time) by continuously heating and stirring. Then, the solvent is removed by distillation to obtain polysiloxane (A-1). Table 1 shows the types of components of the polysiloxane (A-1) and the amounts used. <Preparation Example 2 to Preparation Example 6>

The polysiloxanes (A) of Preparation Examples 2 to 6 were prepared by the same steps as those of Preparation Example 1, and the difference was that the types of components of polysiloxane (A), the amount of use, and the reaction were changed. Temperature and polycondensation time (as shown in Table 1). Table 1: Preparation of Positive Photosensitive Polysiloxane Composition <Example 1>

100 parts by weight of the polysiloxane (A-1) in Preparation Example 1 and 8 parts by weight of 4,4 '-[1- [4 [-1- (4-hydroxyphenyl) -1-methylethyl ] Phenyl] ethylene] bisphenol and o-naphthoquinonediazide-5-sulfonic acid, and 5 parts by weight of o-naphthoquinonediazidesulfonate (B-1) is shown in Table 2 below. (D-1) After 100 parts by weight of propylene glycol methyl ether acetate (C-1) is added and stirred with a shaking type stirrer, the positive photosensitive polymer of Example 1 can be obtained. Siloxane composition. The positive photosensitive polysiloxane composition of Example 1 was evaluated by an evaluation method described later, and the results are shown in Table 2. <Example 2 to Example 10>

The positive-type photosensitive polysiloxane compositions of Examples 2 to 10 were separately prepared in the same steps as in Example 1, and the difference was that the types of ingredients and their amounts of use were changed, as shown in Table 2. . The positive-type photosensitive polysiloxane composition prepared in Examples 2 to 10 was evaluated by the evaluation method described later, and the results are shown in Table 2. <Comparative Example 1 to Comparative Example 2>

The positive-type photosensitive polysiloxane compositions of Comparative Examples 1 to 2 were prepared separately in the same steps as in Example 1, and the difference was that the type of the ingredients and the amount of use were changed, as shown in Table 2. . The positive-type photosensitive polysiloxane composition prepared in Comparative Examples 1 to 2 was evaluated by an evaluation method described later, and the results are shown in Table 2. Table 2: Evaluation method ( chemical resistance ) :

The photosensitive polysiloxane composition is spin-coated on a glass substrate to form a coating film. Next, the coating film was pre-baked at 100 ° C. for 2 minutes to form a pre-baked coating film having a thickness of about 2 μm. Then, a line and space mask (manufactured by NIPPON FILCON) was placed between the exposure machine and the pre-bake coating film, and the pre-bake was performed with 300 mJ / cm ² of ultraviolet light. The coating film is exposed (the exposure machine model is AG500-4N, manufactured by M & R Nano Technology). Next, the substrate with the exposed pre-baked coating film developed at 23 ° C. with a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds to remove the exposed 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 at 130 ° C for 60 minutes to obtain a patterned protective film. Next, the protective film was immersed in a 3.4% oxalic acid solution at 60 ° C for 10 minutes, and then the minimum line width without peeling was observed and recorded. The evaluation criteria for chemical resistance are shown below. The smaller the line width without spalling, the better the chemical resistance. ◎: Line width without peeling ≦ 12 μm; ○: 12 μm <line width without peeling ≦ 20 μm; Δ: 20 μm <line width without peeling ≦ 40 μm; ╳: line width without peeling> 40 μm.

The above embodiments are only for explaining the principle of the present invention and its effects, but not for limiting 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 rights of the present invention should be listed in the scope of patent application described later.

Claims (10)

A positive-type photosensitive polysiloxane composition, comprising: polysiloxane (A); o-naphthoquinonediazidesulfonate (B); a solvent (C); and a silane compound (D); wherein, The silane compound (D) has a structure represented by the formula (D-1): Formula (D-1) In 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 1 to 20 carbon atoms, an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, and an unsubstituted or substituted carbon number 7 Aryl to 10, unsubstituted or substituted alkenyl having 2 to 10 carbons, or unsubstituted or substituted organic oxy having 1 to 20 carbons; R ³ means unsubstituted or substituted A substituted alkyl group having 1 to 10 carbons, or an unsubstituted or substituted aryl group having 6 to 10 carbons; n is an integer of 1 to 3; and m is an integer of 1 to 3. The positive-type photosensitive polysiloxane composition according to claim 1, wherein the polysiloxane (A) is a polycondensation of at least the silane monomer (a-1) represented by the formula (I-1) Thus: Si (R ^a ) _w (OR ^b ) _4-w Formula (I-1) In formula (I-1): R ^a each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a carbon number Alkenyl groups of 2 to 10, aromatic groups of 6 to 15 carbons, alkyl groups of 1 to 10 carbons containing acid anhydride groups, alkyl groups of 1 to 10 carbons containing epoxy groups, or epoxy resins An alkoxy group of at least one, and at least one R ^a represents an alkyl group having 1 to 10 carbon atoms containing an acid anhydride group, an alkyl group having 1 to 10 carbon atoms containing epoxy group, or an alkoxy group containing epoxy group; R ^b each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 15 carbon atoms; and w represents an integer of 1 to 3. The positive-type photosensitive polysiloxane composition according to claim 1, further comprising a cyclic silicone compound (E) represented by the formula (E-1): 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 t t R ¹⁹ and t At least one of each R ²⁰ is a monovalent group having an alicyclic epoxy group; and t represents an integer of 3 or more; wherein R ¹⁹ and R ²⁰ may be the same or different, The plurality of R ¹⁹ and the plurality of R ²⁰ may be the same or different, respectively. The positive-type photosensitive polysiloxane composition according to claim 1, wherein the o-naphthoquinonediazide sulfonate (B) is based on 100 parts by weight of the used amount of the polysiloxane (A) The use amount is 8 to 24 parts by weight; the use amount of the solvent (C) is 100 to 700 parts by weight; and the use amount of the silane compound (D) is 1 to 15 parts by weight. The positive-type photosensitive polysiloxane composition according to claim 3, wherein the amount of the cyclic siloxane compound (E) used is 100 parts by weight based on the amount of the polysiloxane (A) used It is 4 to 24 parts by weight. A method for forming a thin film on a substrate, the method comprising applying to the substrate a positive-type photosensitive polysiloxane composition according to any one of claims 1 to 5. A thin film on a substrate, which is produced by the method according to claim 6. A device comprising a film according to claim 7. A flattening film or interlayer insulating film for a TFT substrate in a liquid crystal display element or an organic electroluminescent display, or a protective film for a core material or a covering material of an optical waveguide, which is prepared by the method according to claim 6. A device comprising a flattening film or an interlayer insulating film of a TFT substrate in a liquid crystal display element or an organic electroluminescent display according to claim 9, or a protective film of a core material or a covering material of an optical waveguide.