TWI721145B - 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 photosensitive property suitable for flattening film or interlayer insulating film of TFT substrate of liquid crystal display element, organic electroluminescent display element, etc., or protective film of core material or cladding material of optical waveguide. Silicone composition, a thin film formed therefrom, and a device having the thin film. In particular, it provides a positive photosensitive polysiloxane composition with good chemical resistance, a thin film formed therefrom, and a device having the thin film.

In recent years, in the fields of semiconductor industry, liquid crystal displays, or organic electroluminescent displays, with the ever-decreasing size, the requirements for the miniaturization of patterns required in the lithography process are also increasing. In order to achieve a finer pattern, it is generally formed by exposing and developing a positive photosensitive material with high resolution and high sensitivity. Among them, positive photosensitive materials with polysiloxane polymers are gradually becoming used in the industry. The mainstream.

In a liquid crystal display or an organic electroluminescent display, an interlayer insulating film is usually arranged between the layered wirings as insulation. The positive photosensitive material is widely used as a material for forming an interlayer insulating film because it requires a small number of steps to obtain a pattern shape, and at the same time, the obtained insulating film has good flatness.

For example, in the interlayer insulating film used for liquid crystal displays, it is necessary to form the pattern of the contact hole of the fine wiring. In fact, it is very difficult for the contact hole formed by the negative photosensitive composition to reach the usable aperture. Therefore, the positive photosensitive composition is widely used in the industry to form the interlayer insulating film of the liquid crystal display element (such as Japanese Patent Application 2001-354822).

Generally, the main component of the positive photosensitive composition used to form the interlayer insulating film is acrylic resin, but the photosensitive composition using silicone materials has better heat resistance and transparency than the photosensitive composition using acrylic resin materials. The composition is good (as shown in JP 2000-1648).

However, silane compounds or polysiloxane materials such as polysiloxanes are prone to hydrolysis and condensation reactions with similar or different types of compounds. When the positive photosensitive composition is prepared, the occurrence of these side reactions will cause the storage stability of the positive photosensitive composition to deteriorate, and the life of the product will also be shortened.

In order to inhibit the above-mentioned condensation reaction, the industry has developed to control the molecular weight and branch structure of polysiloxane to inhibit the condensation reaction. Japanese Patent Laid-Open No. 2003-163209 discloses that polysiloxanes of different molecular weights can be obtained by the action of acid catalysts, metal chelate compounds and alkali catalysts to control the structure of the polysiloxanes. However, although the above publication discloses various molecular weights of polysiloxane, it does not consider the photosensitive properties of the polysiloxane; in addition to the dielectric constant, it does not take into account the various properties of the interlayer insulating film.

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

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

The present invention uses the components of the special silane compound to obtain a positive photosensitive polysiloxane composition with good chemical resistance.

式(D-1) 式(D-1)中： R¹ 係表示未經取代或經取代的碳數1至10之烷基，或未經取代或經取代的碳數6至10之芳基； R² 係各獨立地表示未經取代或經取代的碳數1至20之烷基、未經取代或經取代的碳數6至10之芳基、未經取代或經取代的碳數7至10之芳烷基、未經取代或經取代的碳數2至10之烯基，或未經取代或經取代的碳數1至20之有機氧基； R³ 係表示未經取代或經取代的碳數1至10之烷基，或未經取代或經取代的碳數6至10之芳基； n係1至3之整數；且 m係1至3之整數。Therefore, the present invention provides a positive photosensitive polysiloxane composition comprising: polysiloxane (A); o-naphthoquinone diazide sulfonate (B); solvent (C); and silane compound ( D); Wherein, the silane compound (D) has the structure shown in formula (D-1):

Formula (D-1) In formula (D-1): R ¹ represents an unsubstituted or substituted alkyl group with 1 to 10 carbons, or an unsubstituted or substituted aryl group with 6 to 10 carbons ; R ² is each independently an unsubstituted or substituted alkyl group having 1 to 20 carbons, an unsubstituted or substituted aryl group having 6 to 10 carbons, and an unsubstituted or substituted carbon number 7 To 10 aralkyl, unsubstituted or substituted alkenyl with 2 to 10 carbons, or unsubstituted or substituted organic oxy with 1 to 20 carbons; R ³ represents 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 of forming a thin film on a substrate, which comprises applying the aforementioned positive photosensitive polysiloxane composition to the substrate.

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

The present invention also provides a 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 cladding material, which is produced by the aforementioned method.

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

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

式(D-1) 式(D-1)中： R¹ 係表示未經取代或經取代的碳數1至10之烷基，或未經取代或經取代的碳數6至10之芳基； R² 係各獨立地表示未經取代或經取代的碳數1至20之烷基、未經取代或經取代的碳數6至10之芳基、未經取代或經取代的碳數7至10之芳烷基、未經取代或經取代的碳數2至10之烯基，或未經取代或經取代的碳數1至20之有機氧基； R³ 係表示未經取代或經取代的碳數1至10之烷基，或未經取代或經取代的碳數6至10之芳基； n係1至3之整數；且 m係1至3之整數。Therefore, the present invention provides a positive photosensitive polysiloxane composition comprising: polysiloxane (A); o-naphthoquinone diazide sulfonate (B); solvent (C); and silane compound ( D); Wherein, the silane compound (D) has the structure shown in formula (D-1):

Formula (D-1) In formula (D-1): R ¹ represents an unsubstituted or substituted alkyl group with 1 to 10 carbons, or an unsubstituted or substituted aryl group with 6 to 10 carbons ; R ² is each independently an unsubstituted or substituted alkyl group having 1 to 20 carbons, an unsubstituted or substituted aryl group having 6 to 10 carbons, and an unsubstituted or substituted carbon number 7 To 10 aralkyl, unsubstituted or substituted alkenyl with 2 to 10 carbons, or unsubstituted or substituted organic oxy with 1 to 20 carbons; R ³ represents 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 photosensitive polysiloxane composition used in the present invention will be described in detail.

It is explained here that (meth)acrylic acid is used to refer to acrylic acid and/or methacrylic acid, and (meth)acrylate is used to refer to acrylate and/or methacrylate; similarly, (meth)acrylic acid is used to refer to acrylic acid and/or methacrylic acid. The acryloyl group means an acryloyl group and/or a methacryloyl group.

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) using silane monomer, or by polycondensation using silane monomer 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), silicon dioxide particles (a-4) , Or a combination thereof. Hereinafter, the reaction steps and conditions of each component and polycondensation are further explained.

The Silane monomer (a-1) a compound represented by formula (I-1): in the _{^{Si (R a) w (OR}} b) (I-1) _4-w formula of formula (I-1), R ^a Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbons, an alkenyl group having 2 to 10 carbons, an aromatic group having 6 to 15 carbons, an alkyl group having 1 to 10 carbons containing an acid anhydride group, carbon atoms, an epoxy group-containing alkyl group having 1 to 10 or an alkoxy group-containing epoxy groups, at least one of R ^a represents a carbon number of acid anhydride group-containing alkyl group having 1 to 10 carbon atoms containing an epoxy group Is an alkyl group of 1 to 10 or an alkoxy group containing an epoxy group; R ^b each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbons, an acyl group having 1 to 6 carbons, or a carbon number of 6 to 6 15 is an aromatic group; and w represents an integer from 1 to 3.

When More specifically, when the formula R ^{(I-1), a} represents an alkyl group having a carbon number of 1 to 10, in particular, R ^a, for example, methyl, ethyl, n-propyl, isopropyl, N-butyl, tert-butyl, n-hexyl or n-decyl. In addition, R ^a may be an alkyl group having other substituents on the alkyl group. Specifically, R ^{a is,} for example, trifluoromethyl, 3,3,3-trifluoropropyl, 3-aminopropyl, 3- Mercaptopropyl or 3-isocyanatopropyl.

When the formula R ^{(I-1), a} represents an alkenyl group having a carbon number of 2 to 10, in particular, R ^a, for example, vinyl. And, R ^a may be an alkenyl group having other substituents on the alkenyl group, particularly, R ^a, for example, 3-methyl-Bing Xixi Bing Xixi group or a propyl 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). And, R ^a may be an aromatic group having a substituent on another aryl group, particularly, R ^a is for example - hydroxyphenyl (o-hydroxyphenyl), 1- (to - 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).

式(I-1-1)

式(I-1-2)

式(I-1-3)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 alkyl group containing an acid anhydride group is, for example, ethyl succinic anhydride represented by formula (I-1-1), propyl succinic anhydride represented by formula (I-1-2) or formula ( I-1-3) Propylglutaric anhydride shown in. It is worth mentioning that the acid anhydride group is a group formed by intramolecular dehydration of dicarboxylic acid, where the dicarboxylic acid is, for example, succinic acid or glutaric acid.

Formula (I-1-1)

Formula (I-1-2)

Formula (I-1-3)

Further, the formula R ^{(I-1), a} represents an alkyl group containing an epoxy group, wherein the alkyl group is preferably an alkyl group having a carbon number of 1 to 10. 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 intramolecular dehydration of a diol (diol), where the diol is, for example, propylene glycol, butylene glycol or pentanediol.

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

^{In addition, when R b in the} formula (I-1) represents an alkyl group having a carbon number of 1 to 6, specifically, R ^b is, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, or a n-butyl group. ^{When R b} in the formula (I-1) represents an acyl group having a carbon number of 1 to 6, specifically, R ^{b is,} for example, an acetyl group. ^{When R b} in the formula (I-1) represents an aromatic group having a carbon number of 6 to 15, 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) and 3-glycidoxypropyltrimethoxysilane (3-glycidoxypropyltriethoxysilane), 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane (2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane), 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 2-epoxypropyltriethoxysilane 2-oxetanylbutoxypropyl triphenoxysilane (2-oxetanylbutoxypropyl triphenoxysilane), a commercial product manufactured by Tohya Synthesis: 2-oxetanylbutoxypropyltrimethoxysilane (trade name TMSOX-D), 2 -Oxetanylbutoxypropyltriethoxysilane (2-oxetanylbutoxypropyltriethoxysilane, trade name TESOX-D), 3-(triphenoxysilyl)propyl succinic anhydride, manufactured by Shin-Etsu Chemical Sale product: 3-(trimethoxysilyl)propyl succinic anhydride (trade name X-12-967), commercial product manufactured by WACKER company: 3-(triethoxysilyl)propyl butyl Diacid anhydride (trade name GF-20), 3-(trimethoxysilyl)propylglutaric anhydride (abbreviated as TMSG), 3-(triethoxysilyl)propylglutaric anhydride, 3-(triphenyl) Oxysilyl) propyl glutaric anhydride, diisopropoxy-di(2-oxetanylbutoxy propyl)silane (diisopropoxy-di(2-oxetanylbutoxy propyl)silane, referred to as DIDOS), di( 3-oxetanylpentyl) dimethoxy silane (di(3-oxetanylpentyl)dimethoxy silane), (di-n-butoxysilyl) bis(propyl succinic anhydride), (dimethoxysilyl) )Bis(ethylsuccinic anhydride), 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylmethoxysilane (3 -glycidoxypropyl dimethylethoxysilane), di(2-oxetanylbutoxypentyl)-2-oxetanyl pentylethoxy silane), di(2-oxetanylbutoxypentyl)-2-oxetanyl pentylethoxy silane), tri(2 -Oxetanylpentyl)methoxysilane (tri(2-oxetanylpentyl)methoxy s ilane), (phenoxysilyl)tris(propyl succinic anhydride), (methylmethoxysilyl)bis(ethylsuccinic anhydride), or a combination of the above compounds.

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

Specific examples of the silane monomer (a-1) preferably include 3-(triethoxysilyl) propyl succinic anhydride, 3-(trimethoxysilyl) propyl succinic anhydride, 3-ring Oxypropoxypropyl trimethoxysilane, 3-(trimethoxysilyl)propyl glutaric anhydride, (dimethoxysilyl)bis(ethylsuccinic anhydride), 2-propylene oxide butane Oxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-glycidylbutoxypropyltriethoxysilane, or a combination of the foregoing 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 The 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 having 1 to 10 carbons, an alkenyl group having 2 to 10 carbons, or an aromatic group having 6 to 15 carbons; R ^d each independently represents a hydrogen atom, and the carbon number is 1 to 6. The alkyl group, the acyl group having 1 to 6 carbons, or the aromatic group having 6 to 15 carbons; and u represents an integer of 0 to 3.

^{In more detail, 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, tert-butyl, n-hexyl or n-decyl. In addition, R ^c may be an alkyl group having other substituents on the alkyl group. Specifically, R ^{c is,} for example, trifluoromethyl, 3,3,3-trifluoropropyl, 3-aminopropyl, 3- Mercaptopropyl or 3-isocyanatopropyl.

^{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. In addition, R ^c may be an alkenyl group having other substituents on the alkenyl group. Specifically, R ^{c is,} for example, 3-propenoxypropyl or 3-methacryloxypropyl.

^{When R c} in the formula (I-2) represents an aromatic group having a carbon number of 6 to 15, specifically, R ^c is, for example, a phenyl group, a tolyl group, or a naphthyl group. In addition, R ^c may be an aromatic group having other substituents on the aromatic 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 R d in the} formula (I-2) represents an alkyl group having a carbon number of 1 to 6, specifically, R ^d is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or an n-butyl group. ^{When R d} in the formula (I-2) represents an acyl group having a carbon number of 1 to 6, specifically, R ^{d is,} for example, an acetyl group. ^{When R d} in the formula (I-2) represents an aromatic group having a carbon number of 6 to 15, specifically, R ^{d is,} for example, a phenyl group.

In formula (I-2), u is an integer from 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 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, it has two hydrolyzable groups). When u=3, it means that the silane monomer is a monofunctional silane monomer (that is, a silane monomer with a hydrolyzable group). It is worth mentioning that the hydrolyzable group refers to a group that can undergo a hydrolysis reaction and bond with silicon. For example, the hydrolyzable group is, for example, an alkoxy group, an acyloxy group or a benzene group. Phenoxy group.

Specific examples of the silane monomer represented by 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-propyltriethoxy Silane (n-propyltriethoxysilane), n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltrimethoxysilane N-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane (PTMS) ), phenyltriethoxysilane (PTES), p-hydroxyphenyltrimethoxysilane, 1-(p-hydroxyphenyl) ethyl trimethoxysilane (1-(p -hydroxyphenyl)ethyltrimethoxysilane), 2-(p-hydroxyphenyl)ethyltrimethoxysilane (2-(p-hydroxyphenyl)ethyltrimethoxysilane), 4-hydroxy-5-(p-hydroxybenzene) 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane , 3,3,3-Trifluoropropyltrimethoxysilane (3,3,3-trifluoropropyltrimethoxysilane), 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane (3-aminopropyltriethoxysilane), 3-mercaptopropyltriethoxysilane, 3-propenyloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane or 3-methacrylic acid Oxypropyl triethoxysilane; (3) difunctional silane monomer: dimethyldimethoxysilane (DMDMS), dimethyldiethoxysilane (dimethyldiethoxysilane), dimethyl Diacetyloxysilane (dimethyldiacetyloxysilane), di-n-butyldimethoxysilane (di-n-butyldimethoxysilane) or diphenyldimethoxysilane (diphenyldimethoxysilane); or (4) Monofunctional silane monomer: Trimethylmethoxysilane or tri-n-butylethoxysilane, etc.

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

式(I-3) 式(I-3)中，R^e 、R^f 、R^g 及R^h 各自獨立表示氫原子、碳數為1至10的烷基、碳數為2至6的烯基或碳數為6至15的芳香基，其中該烷基、烯基及芳香基中任一者可選擇地含有取代基；Rⁱ 與R^j 各自獨立表示氫原子、碳數為1至6的烷基、碳數為1至6的醯基或碳數為6至15的芳香基，其中該烷基、醯基及芳香基中任一者可選擇地含有取代基；及s表示1至1000的整數。The silicone prepolymer (a-3) is a compound represented by formula (I-3).

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

^{In more detail, when R e} , R ^f , R ^g and R ^h in the formula (I-3) each independently represent an alkyl group having 1 to 10 carbon atoms, specifically, R ^e , R ^f , R ^{For example, g} and R ^h are each independently a methyl group, an ethyl group, or an n-propyl group. ^{When R e} , R ^f , R ^g and R ^h in the formula (I-3) each independently represent an alkenyl group having a carbon number of 2 to 10, specifically, R ^e , R ^f , R ^g and R ^{h are} for example Each is independently vinyl, acryloxypropyl or methacryloxypropyl. ^{When R e} , R ^f , R ^g and R ^h in the formula (I-3) each independently represent an aromatic group having 6 to 15 carbon atoms, specifically, R ^e , R ^f , R ^g and R ^{h are} for example Each is independently phenyl, tolyl or naphthyl. In addition, any of the alkyl group, alkenyl group, and aryl group may have other substituents.

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

In formula (I-3), s may be an integer from 1 to 1000, preferably an integer from 3 to 300, and more preferably an integer from 5 to 200. When s is an integer from 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 silicone 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 Gelesta ( Gelest) is a commercial product of Silanol terminated polydimethylsiloxane manufactured by the company (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 silicone prepolymer (a-3) can be used alone or in combination of multiple types.

The average particle diameter of the silica 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 silica particles (a-4) include, but are not limited to: commercial products manufactured by Catalytic Chemicals, with trade names such as OSCAR 1132 (particle size 12nm; dispersant is methanol), OSCAR 1332 (particles) 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 Company Commercial products of Quartron PL-1-IPA (particle size 13nm; dispersant is isoacetone), Quartron PL-1-TOL (particle size 13nm; dispersant is toluene), Quartron PL-2L-PGME ( The particle size is 18nm; the dispersing agent is propylene glycol monomethyl ether) or Quartron PL-2L-MEK (the particle size is 18nm; the dispersing agent is methyl ethyl ketone), etc., or commercially available products manufactured by Nissan Chemical Company, with 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 100nm; dispersant is isopropanol). The silicon dioxide particles can be used alone or in combination of multiple types.

The polysiloxane (A) can be synthesized by polycondensation using silane monomers, or synthesized by polycondensation using silane monomers and other polymerizable compounds. Generally speaking, the above-mentioned polycondensation reaction is carried out in the following steps: adding solvent, water, or optionally catalyst to the silane monomer; and heating and stirring at 50°C to 150°C for 0.5 Hours to 120 hours, and the by-products (alcohols, water, etc.) can be further removed by distillation.

The solvent used in 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 the silane monomer (a-1) and the silane monomer (a-2) being 1 mol, the usage amount of the solvent is preferably 20 g to 1000 g; more preferably 30 g to 800 g; Preferably, it is 50 g to 600 g.

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

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

Based on the total amount of the silane monomer (a-1) and the silane monomer (a-2) being 1 mol, the usage amount of the catalyst is preferably 0.05 g to 5 g; more preferably 0.07 g to 4 g; More preferably, it is 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 reaction mixture after the polycondensation reaction can be selectively purified to obtain the polysiloxane (A). The method of purification is not particularly limited, and it is preferable to use a hydrophobic solvent to dilute the reaction mixture. Next, the hydrophobic solvent and the reaction mixture are transferred to a separation funnel. Then, the organic layer was washed with water several times, and then the organic layer was concentrated with a rotary evaporator to remove alcohol or water. In addition, ion exchange resins can be used to remove the catalyst.

This polysiloxane (A) can be used in combination with other alkali-soluble resins. The types of the other alkali-soluble resins are not particularly limited, and may include, but are 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, or novolac resins.

The acrylic resin is preferably obtained by copolymerizing one or more unsaturated carboxylic acid 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, crotonic acid, 2-chloroacrylic acid, ethacrylic acid, cinnamic acid, 2-acrylic acid ethoxy succinate, Unsaturated monocarboxylic acids such as 2-methacrylic acid ethoxy succinate or 2-isobutylene ethoxy succinate; maleic acid, maleic anhydride, fumaric acid, itaconic acid, coating Conic acid anhydride, citraconic acid or citraconic acid anhydride, etc., unsaturated dicarboxylic acids (anhydrides), and unsaturated polycarboxylic acids (anhydrides) with more than trivalent; 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 compounds containing one or more unsaturated carboxylic acids or unsaturated carboxylic anhydrides can be used alone or in combination of multiples to improve pigment dispersibility, increase development speed and reduce the occurrence of residues.

Specific examples of the other unsaturated compounds include: aromatic vinyl compounds such as styrene, α-methylstyrene, vinyl toluene, 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 -Maleimines such as meta-methoxyphenyl maleimines, N-p-methoxyphenyl maleimines, N-cyclohexyl maleimines; 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 acrylate 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, methacrylic acid 2-hydroxybutyl, 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 methoxy acrylate, triethylene glycol methoxy methacrylate, twelve methacrylate Alkyl esters, tetradecyl methacrylate, cetyl methacrylate, stearyl 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-butyl methacrylate Ethyl amino ethyl; glycidyl esters of unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate; carboxylic acids such as vinyl acetate, vinyl propionate, vinyl butyrate, etc. Vinyl esters; vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, methallyl glycidyl ether and other unsaturated ethers; acrylonitrile, methacrylonitrile, 2-chloropropene Vinyl cyanide compounds such as nitrile and vinylidene cyanide; acrylamide, methacrylamide, 2-chloroacrylamide, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide Such as unsaturated amines; 1,3-butadiene, isoamylene, chlorinated butadiene and other aliphatic conjugated dienes.

Specific examples of the tea-based resin include V259ME, V259MEGTS, or V500MEGT (manufactured by Nippon Steel Chemical Co., Ltd.), and the tea-based resin can be used alone or in combination of multiple types.

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

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 can be used alone or in combination of multiple types.

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

The type of o-naphthoquinone diazide sulfonate (B) according to the present invention is not particularly limited. Ortho-naphthoquinone diazide sulfonate generally used can be used, as long as it can achieve the purpose claimed by the present invention. . The o-naphthoquinone diazide sulfonate (B) may be a completely esterified or partially esterified ester-based compound.

The o-naphthoquinonediazidesulfonic acid (B) is preferably prepared by reacting o-naphthoquinonediazidesulfonic acid or a salt thereof with a hydroxyl compound. The o-naphthoquinone diazide sulfonate (B) is more preferably prepared by reacting o-naphthoquinone diazide sulfonic acid or its salts with a polyhydroxy compound.

Specific examples of the o-naphthoquinone diazide sulfonic acid (B) include, but are not limited to, o-naphthoquinone diazide-4-sulfonic acid, o-naphthoquinone diazide-5-sulfonic acid or o-naphthoquinone diazide- 6-sulfonic acid and so on. In addition, the salt of o-naphthoquinone diazide sulfonic acid is, for example, o-naphthoquinone sulfonyl halide (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 a combination of the foregoing 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.

式(b-1) 式(b-1)中，B¹ 及B² 各自獨立表示氫原子、鹵素原子或碳數為1至6烷基；B³ 、B⁴ 及B⁷ 各自獨立表示氫原子或碳數為1至6的烷基；B⁵ 、B⁶ 、B⁸ 、B⁹ 、B¹⁰ 及B¹¹ 各自獨立表示氫原子、鹵素原子、碳數為1至6的烷基、碳數為1至6的烷氧基、碳數為1至6的烯基或環烷基(cycloalkyl)；及h、i及j各自獨立表示1至3的整數；k表示0或1。Specific examples of the hydroxyaryl-based compound include, but are not limited to, the hydroxyaryl-based compound represented by 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 an alkyl group having 1 to 6 carbon atoms; B ³ , B ⁴ and B ⁷ each independently represent a hydrogen atom Or an alkyl group with a carbon number of 1 to 6; 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 a carbon number of 1 to 6, and the carbon number is An alkoxy group of 1 to 6, an alkenyl group or a cycloalkyl group having a carbon number of 1 to 6; 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 compound 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 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-hydroxybenzene Yl)ethyl]benzene, or a combination of the above-mentioned compounds.

式(b-2) 式(b-2)中，B¹² 與B¹³ 各自獨立表示氫原子或碳數為1至6的烷基；及m及n各自獨立表示1至3的整數。Specific examples of the (hydroxyphenyl)hydrocarbon compound include, but are not limited to, the (hydroxyphenyl)hydrocarbon compound represented by 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, etc.

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 partially esterified or partially etherified 3,4,5-trihydroxybenzene 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 can be used alone or in combination of multiple types.

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

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

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

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

The type of 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 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), 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 an 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 of multiple types.

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) and so on. It is worth noting 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 of multiple types.

The alcoholic hydroxyl group-containing compound can be used in combination with a carbonyl group-containing cyclic compound, and the weight ratio 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 is 99/1 to 50/50 in the solvent (C), there is no reaction in the polysiloxane (A) The silanol (Si-OH) group is not easy to produce condensation reaction and reduce storage stability (storage stability). In addition, because the alcoholic hydroxyl group-containing compound and the carbonyl group-containing cyclic compound have good compatibility with o-naphthoquinone diazide sulfonate (B), it is not easy to whiten during coating and film formation, and can maintain The transparency of the protective film.

The solvent (C) may contain other solvents within a range that does not impair the effects of the present 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, acetone, 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.

The solvent (C) can be used alone or in combination of multiple types.

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

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

式(D-1) 式(D-1)中： R¹ 係表示未經取代或經取代的碳數1至10之烷基，或未經取代或經取代的碳數6至10之芳基； R² 係各獨立地表示未經取代或經取代的碳數1至20之烷基、未經取代或經取代的碳數6至10之芳基、未經取代或經取代的碳數7至10之芳烷基、未經取代或經取代的碳數2至10之烯基，或未經取代或經取代的碳數1至20之有機氧基； R³ 係表示未經取代或經取代的碳數1至10之烷基，或未經取代或經取代的碳數6至10之芳基； n係1至3之整數；且 m係1至3之整數。The silane compound of the present invention is represented by the following formula (D-1), and simultaneously has a series of structures of the hydrolyzable silyl group and the sulfur-silicon bond.

Formula (D-1) In formula (D-1): R ¹ represents an unsubstituted or substituted alkyl group with 1 to 10 carbons, or an unsubstituted or substituted aryl group with 6 to 10 carbons ; R ² is each independently an unsubstituted or substituted alkyl group having 1 to 20 carbons, an unsubstituted or substituted aryl group having 6 to 10 carbons, and an unsubstituted or substituted carbon number 7 To 10 aralkyl, unsubstituted or substituted alkenyl with 2 to 10 carbons, or unsubstituted or substituted organic oxy with 1 to 20 carbons; R ³ represents 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.

式(D-2) 式(D-2)中： R¹ 、n係與上述相同；R⁴ 係各獨立地表示未經取代或經取代的碳數1至20之烷基、未經取代或經取代的碳數6至10之芳基、未經取代或經取代的碳數7至10之芳烷基、未經取代或經取代的碳數2至10之烯基或未經取代或經取代的碳數1至20之有機氧基；Me係表示甲基；Ph係表示苯基。

式(D-3) 式(D-3)中： R¹ 、n、R⁴ 、Me係與上述相同；R⁵ 係表示未經取代或經取代的碳數1至20之烷基、未經取代或經取代的碳數6至10之芳基、未經取代或經取代的碳數7至10之芳烷基或未經取代或經取代的碳數2至10之烯基。The above-mentioned structure can be specifically represented by the following formula (D-2) or formula (D-3).

Formula (D-2) In formula (D-2): R ¹ and n are the same as above; R ⁴ is each independently an unsubstituted or substituted alkyl group with 1 to 20 carbons, unsubstituted or Substituted aryl group with 6 to 10 carbons, unsubstituted or substituted aralkyl with 7 to 10 carbons, unsubstituted or substituted alkenyl with 2 to 10 carbons, or unsubstituted or substituted The substituted organic oxy group 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 with 1 to 20 carbons, unsubstituted A substituted or substituted aryl group having 6 to 10 carbons, an unsubstituted or substituted aralkyl group having 7 to 10 carbons, or an unsubstituted or substituted alkenyl group having 2 to 10 carbons.

式(D-4)

式(D-5)

式(D-6)

式(D-7)

式(D-8)

式(D-9) 式(D-5)至式(D-9)中： R¹ 、n、Me、Ph係與上述相同；Et係表示乙基。More specifically, it can be represented by the following formula (D-4) to formula (D-9).

Formula (D-4)

Formula (D-5)

Formula (D-6)

Formula (D-7)

Formula (D-8)

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.

The alkyl group and aryl group 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. Alkyloxy such as oxy, phenoxy, etc., vinyloxy, propyleneoxy, pentenoxy, etc.; alkyl with 1 to 6 carbons, phenyl, and alkane with 1 to 20 carbons An oxy group is preferable; an alkyl group having 1 to 4 carbons, a phenyl group, and an alkoxy group having 1 to 12 carbons are more preferable. The alkyl or aryl group of R ³ is, for example, 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 groups such as vinyl, propenyl, pentenyl, etc.; organic oxygen groups such as methoxy, ethoxy, propoxy, butoxy, octyloxy, dodecyloxy, etc. Alkenyloxy groups such as aryloxy group, phenoxy group, vinyloxy group, propyleneoxy group, pentenoxy group, etc.; 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, etc.; preferably alkyl having 1 to 12 carbons.

The silane compound (D) of the present invention can be prepared, for example, by dehydrogenating a silane compound having more than one mercapto group and a silane compound having more than one Si-H bond 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 be carried out satisfactorily under solvent-free conditions, which is an extremely productive production method.

When manufacturing the silane compound (D) of the present invention, a solvent may be used as needed. 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 of the raw material. Specifically, it includes 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 And other aromatic hydrocarbon solvents.

式(D-i)

式(D-ii) 式(D-i)及式(D-ii)中： R¹ 、R² 、R³ 、n、m係與上述相同。At this time, with regard to the production of the silane compound (D) of the above formulas (1) to (9), in the presence of a catalyst, a silane compound having a mercapto group represented by the following formula (Di) can be combined with the following formula ( The silane compound with Si-H bond shown in D-ii) reacts to form a sulfur-silicon bond.

Formula (Di)

Formula (D-ii) In Formula (Di) 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, and α-mercaptomethylmethyldimethoxysilane. -Mercaptomethyldimethylmethoxysilane, α-mercaptomethyltriethoxysilane, α-mercaptomethylmethyldiethoxysilane, α-mercaptomethyldimethylethoxysilane, γ -Mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyldimethylmethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropane But not limited to, methyldiethoxysilane, γ-mercaptopropyldimethylethoxysilane, etc.

In the production of 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, and triethyl Base silane, 3-butyldimethyl silane, 3-butyl diphenyl silane, triisopropyl silane, tri-n-butyl silane, triisobutyl silane, dimethyl phenyl silane, two Phenyl methyl silane, dimethyl-n-octyl silane, decyl dimethyl silane, dodecyl dimethyl silane, dimethyl vinyl silane, triphenyl silane, trimethoxy silane, triethyl Oxysilane, tributoxysilane, dimethylethoxysilane, dimethylbutoxysilane, dimethyloctoxysilane, dimethyldodecyloxysilane, etc., but not limited thereto.

When manufacturing 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 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 include aluminum chloride, aluminum sulfate, tin chloride, tin chloride sulfate, iron chloride, boron trifluoride, pentafluorophenylboric acid, etc., and pentafluorophenylboronic acid is particularly preferred.

When manufacturing the silane compound (D) of the present invention, in terms of reactivity and productivity, the mixing ratio of the silane compound having a mercapto group and the organosilicon compound having a Si-H bond is relative to 1 mole of the mercapto group, The Si-H bond is preferably in the range of 0.5 to 1.5 mol, particularly 0.9 to 1.1 mol.

When manufacturing the silane compound (D) of the present invention, in terms of reactivity and productivity, the mixing ratio of the mercapto group-containing silane compound to the catalyst is 0.000001 to 0.1 in terms of 1 mole of mercapto group. The reaction is preferably carried out 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 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 The scope of the reaction. The reaction time is not particularly limited as long as the reaction can proceed sufficiently, and it is preferably about 30 minutes to 24 hours, and more preferably about 1 to 10 hours.

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

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

式(E-1) 式(E-1)中： R¹⁹ 及R²⁰ 表示具有脂環式環氧基(alicyclic epoxy group)之一價基團或烷基，其中，該t個R¹⁹ 及t個R²⁰ 中，至少有一者係為具有脂環式環氧基(alicyclic epoxy group)之一價基團；及 t表示3以上之整數； 其中，該R¹⁹ 及R²⁰ 可為相同或不同，該複數個R¹⁹ 及該複數個R²⁰ 分別可為相同或不同。The positive 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 the t R ¹⁹ and t At least one of 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.

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 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 with alicyclic epoxy group, etc.

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

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

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

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

According to the positive photosensitive polysiloxane composition of the present invention, an additive (F) can optionally be further added. Specifically, the additive (F) is, for example, a sensitizer, adhesion auxiliary agent, surfactant, solubility promoter, defoamer, or Its combination.

The type 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, triphenol type compounds, bisphenol type compounds, multinuclear branch type compounds, and condensation type compounds. Phenol compounds, polyhydroxy benzophenones, or a combination of the above compounds.

Specific examples of the trisphenol type compound include, but are not limited to, tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, 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-hydroxyl -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 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 (polyhydroxy benzophenone) 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 so on.

Specific examples of the adhesion aid include melamine compounds, silane-based compounds, and the like. The role of the adhesion assistant is to increase the adhesion between the protective film formed by the positive photosensitive polysiloxane composition and the protected element.

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

Specific examples of the silane-based compound include vinyl trimethoxy silane, vinyl triethoxy silane, 3-propenoxy propyl trimethoxy silane, vinyl tris (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) ethyl trimethoxysilane, 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., etc.

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

Specific examples of the surfactant include but are not limited to (1) polyethylene oxide alkyl ethers (polyoxyethylene alkyl ethers): polyethylene oxide lauryl ether, etc.; (2) polyethylene oxide Polyoxyethylene phenyl ethers: polyethylene oxide octyl phenyl ether, polyethylene oxide nonyl phenyl ether, etc.; (3) polyethylene glycol diesters: Polyethylene glycol dilaurate, polyethylene glycol distearate, etc.; (4) sorbitan fatty acid esters; (5) fatty acid modified polyesters (fatty acid modified poly esters); and (6) tertiary amine modified polyurethanes modified by tertiary amines, etc. Specific examples of commercially available products of surfactants include KP (manufactured by Shin-Etsu Chemical Industry), SF-8427 (manufactured by Dow Corning Toray Silicone Co., Ltd.), Polyflow (manufactured by Dow Corning Toray Silicone Co., Ltd.) 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 Zhongnichi Synthetic Chemical), 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, Surfynol DF66, Surfynol DF58, Surfynol DF66, Surfynol DF58, Surfynol 210 (Manufactured by Air products) etc.

Specific examples of the dissolution accelerator include N-hydroxydicarboxylic imide compounds and compounds containing phenolic hydroxyl groups. The dissolution accelerator is, for example, the phenolic hydroxyl group-containing compound used in o-naphthoquinone diazide sulfonate (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 if necessary, the cyclic silicone compound (E) is placed in a stirrer and stirred to make it uniformly mixed into a solution state. If necessary, additives (F) can also be added. After uniformly mixing, the normal state of the solution can be obtained. Type photosensitive polysiloxane composition.

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

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

The present invention also provides a 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 cladding material, which is produced by the aforementioned method.

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

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

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

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

The substrate can be alkali-free glass, soda-lime glass, hard glass (Pyles glass), quartz glass, transparent conductive film attached to these glasses used in liquid crystal display devices, or used in photoelectric conversion devices (such as Solid-state photography device) substrate (such as: silicon substrate).

After the coating film is formed, most of the organic solvent of the positive photosensitive polysiloxane composition is removed by a vacuum drying method, and then the remaining organic solvent is completely removed by a pre-bake method to form a pre-bake涂膜。 Coating.

The operating conditions of the above-mentioned reduced-pressure drying and pre-baking may vary according to the types and mixing ratios of the ingredients. Generally speaking, the reduced-pressure drying is performed at a pressure of 0 torr to 200 torr for 1 second to 60 seconds, and the pre-bake is performed at a temperature of 70°C to 110°C for 1 minute to 15 minutes. Patterned exposure

Expose the pre-baked coating film with a photomask with 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 rays can 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 unnecessary parts of the exposed pre-baked coating film, that is, the The exposed area is dissolved in the developer, and the unexposed area remains, so that a semi-finished product with a predetermined pattern of protective film can be formed on the substrate. Specific examples of developing solutions 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, ethylamine, Diethylamine, dimethylethanolamine, tetramethylammonium hydroxide (THAM), tetraethylammonium hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo[5.4.0]-7-eleven Alkene 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, it will cause poor development, resulting in the failure of the specific pattern to be formed or the remaining components of the exposed part. Therefore, 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 0.001 wt% to 10 wt%; more preferably 0.005 wt% to 5 wt%; still more preferably 0.01 wt% to 1 wt%. The example of the present invention uses 2.38 wt% tetramethylammonium hydroxide developer. It is worth mentioning that even if a developer with a lower concentration is used, the positive photosensitive polysiloxane composition of the present invention can form a good fine-grained pattern. Post-bake treatment

The substrate (the semi-finished product of the protective film with a predetermined pattern on the substrate) is washed with water to remove the unnecessary part of the exposed pre-baked coating film. Then, the semi-finished product of the protective film with the predetermined pattern is dried with compressed air or compressed nitrogen. Finally, a heating device such as a heating plate or an oven is used to post-bake the semi-finished product of the protective film with a predetermined pattern. 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 with the predetermined pattern can be fixed to form the protective film.

For example, the protective film is formed in the following steps, for example. First, the positive photosensitive polysiloxane composition was spin-coated on a plain glass substrate (100 × 100 × 0.7 mm) to form a coating film of approximately 2 μm. After pre-bake at 110°C for 2 minutes, put the coating film under the exposure machine. Then, a positive photoresist mask is placed between the exposure machine and the coating film, and the pre-baked coating film is irradiated with ultraviolet light from the exposure machine with an energy of 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 part. Then, after washing with clean water, the developed coating film is directly irradiated with an exposure machine with 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 on it can be obtained.

The following examples are used to illustrate the present invention in detail, but it does not mean that the present invention is limited to the content disclosed by these examples. Preparation of polysiloxane (A) <Preparation Example 1>

In a three-necked flask with a volume of 500 ml, add 0.01 mol of 3-(triethoxysilyl)propyl succinic anhydride (hereinafter referred to as GF-20) and 0.15 mol of methyl trimethoxysilane ( (Hereinafter referred to as 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- Pentanone (hereinafter referred to as DAA), and while stirring at room temperature, add phosphoric acid aqueous solution (0.3 g phosphoric acid/75 g water) within 30 minutes. 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 drops to 110°C (that is, the reaction temperature), continue heating and stirring for polymerization for 9 hours (that is, the polycondensation time). 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>

正型感光性聚矽氧烷組成物之製備 ＜實施例1＞The polysiloxane (A) of Preparation Example 2 to Preparation Example 6 is prepared by the same steps as Preparation Example 1, and the difference lies in: changing the type of polysiloxane (A) component, its usage, and reaction 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) of Preparation Example 1 and 8 parts by weight of 4,4'-[1-[4[-1-(4-hydroxyphenyl)-1-methylethyl ]Phenyl]ethylene]bisphenol and o-naphthoquinone diazide-5-sulfonic acid form o-naphthoquinone diazide sulfonate (B-1) and 5 parts by weight as shown in Table 2 below (D-1) After adding 100 parts by weight of propylene glycol methyl ether acetate (C-1), and stirring uniformly with a shaking type stirrer, the positive photosensitive polymer of Example 1 can be obtained. Silicone composition. The positive photosensitive polysiloxane composition of Example 1 was evaluated in the following evaluation method. The results are shown in Table 2. <Example 2 to Example 10>

The positive photosensitive polysiloxane compositions of Example 2 to Example 10 were prepared separately in the same steps as in Example 1, and the difference lies in: changing the types of ingredients and their usage amounts, as shown in Table 2. . The positive photosensitive polysiloxane compositions prepared in Examples 2 to 10 were evaluated in the following evaluation methods. The results are shown in Table 2. <Comparative Example 1 to Comparative Example 2>

評價方式 ( 耐化學性 ) ： The positive photosensitive polysiloxane compositions of Comparative Example 1 to Comparative Example 2 were prepared by the same steps as in Example 1, and the difference lies in: changing the types of components and their usage amounts, as shown in Table 2. . The positive photosensitive polysiloxane compositions prepared in Comparative Examples 1 to 2 were evaluated in the following evaluation methods. The results are shown in Table 2. Table 2:

Evaluation method ( chemical resistance ) :

The photosensitive polysiloxane composition is applied on the glass substrate by spin coating 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 with a thickness of about 2 μm. Then, a line and space mask (manufactured by NIPPON FILCON) is placed between the exposure machine and the pre-baked coating film, and the pre-baking is performed using 300 mJ/cm ² ultraviolet light. The coating film is exposed (the exposure machine model is AG500-4N, manufactured by M&R Nanotechnology). Next, the substrate with the exposed pre-baked coating film on it was developed with a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution at 23°C 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, post-bake the coating film in an oven at 130°C for 60 minutes to obtain a patterned protective film. Next, soak the protective film in a 3.4% oxalic acid solution at 60°C for 10 minutes, and then observe and record the minimum line width without peeling. The evaluation criteria of chemical resistance are as follows. Among them, the smaller the line width without peeling, the better the chemical resistance. ◎: Line width without peeling ≦ 12 μm; ○: 12 μm <Line width without peeling ≦ 20 μm; △: 20 μm <Line width without peeling ≦ 40 μm; ╳: Line width without peeling> 40 μm.

The above-mentioned embodiments only illustrate the principles and effects of the present invention, but do not limit the present invention. Modifications and changes made by those skilled in the art to the above-mentioned 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.

(no)

Claims (10)

A positive photosensitive polysiloxane composition comprising: polysiloxane (A); o-naphthoquinone diazide sulfonate (B); solvent (C); and silane compound (D); wherein, The silane compound (D) has the structure shown in formula (D-1):

In formula (D-1): R ¹ represents an unsubstituted or substituted alkyl group with 1 to 10 carbons, or an unsubstituted or substituted aryl group with 6 to 10 carbons; R ² is each independently地 means unsubstituted or substituted alkyl with 1 to 20 carbons, unsubstituted or substituted aryl with 6 to 10 carbons, unsubstituted or substituted aralkyl with 7 to 10 carbons , Unsubstituted or substituted alkenyl with 2 to 10 carbons, or unsubstituted or substituted organic oxy with 1 to 20 carbons; R ³ represents an unsubstituted or substituted with 1 to 20 carbons 10 alkyl group, or unsubstituted or substituted aryl group with 6 to 10 carbon atoms; n is an integer from 1 to 3; and m is an integer from 1 to 3; wherein, based on the polysiloxane (A) The usage amount is 100 parts by weight, and the usage amount of the silane compound (D) is 3 to 15 parts by weight. The positive photosensitive polysiloxane composition according to claim 1, wherein the polysiloxane (A) is at least polycondensed with the silane monomer (a-1) represented by formula (I-1) obtained: the _{^{Si (R a) w (OR}} b) 4-w of formula (I-1) of formula (I-1): R ^a each independently represent a hydrogen atom, an alkyl group having a carbon number of 1 to 10 carbon atoms It is an alkenyl group with 2 to 10, an aromatic group with a carbon number of 6 to 15, an alkyl group with a carbon number of 1 to 10 containing an anhydride group, an alkyl group with a carbon number of 1 to 10 containing an epoxy group or an epoxy the alkoxy group, and R ^a represents at least one acid anhydride group having a carbon number of an alkyl group of 1 to 10 carbon atoms containing an epoxy group of an alkyl group of 1 to 10 or an alkoxy group-containing epoxy groups; R ^b each independently represents a hydrogen atom, an alkyl group with a carbon number of 1 to 6, an acyl group with a carbon number of 1 to 6, or an aromatic group with a carbon number of 6 to 15; and w represents an integer of 1 to 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 represent a monovalent group or an alkyl group having an alicyclic epoxy group, wherein among the t R ¹⁹ and t R ²⁰ , at least One is a monovalent group having an alicyclic epoxy group; and t represents an integer of 3 or more; wherein, the R ¹⁹ and R ²⁰ may be the same or different, and the plural R ¹⁹ and The plurality of R ²⁰ may be the same or different. The positive photosensitive polysiloxane composition according to claim 1, wherein, based on 100 parts by weight of the polysiloxane (A), the ortho-naphthoquinone diazide sulfonate (B) The usage amount is 8 to 48 parts by weight; and the usage amount of the solvent (C) is 100 to 700 parts by weight. The positive photosensitive polysiloxane composition according to claim 3, wherein the use amount of the cyclic siloxane compound (E) is 100 parts by weight based on the use amount of the polysiloxane (A) It is 4 to 24 parts by weight. A method of forming a thin film on a substrate, which comprises applying the positive photosensitive polysiloxane composition according to any one of claims 1 to 5 to the substrate. A thin film on a substrate, which is produced by the method according to claim 6. A liquid crystal display element, an organic electroluminescence display or an optical waveguide device, which comprises the film according to claim 7. A 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 cladding material, which is produced by the method according to claim 6. A liquid crystal display element, an organic electroluminescent display or an optical waveguide device, which comprises 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 an optical waveguide core material Or the protective film of the covering material.