JP2014119643A - Positive photosensitive resin composition, method for producing cured pattern using the same, projection pattern substrate obtained from the same, and light-emitting element obtained from the substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition suitable for obtaining a projection pattern of SiO, that is, the resin composition having good development adhesiveness during development and capable of maintaining a fine pattern without causing reflow after baking.SOLUTION: The positive photosensitive resin composition comprises: (a) a polysiloxane synthesized by hydrolyzing and condensing organosilane containing a silane compound expressed by general formula (1) described below and a silane compound expressed by general formula (2) described below; (b) a naphthoquinone diazide compound; and (c) a solvent.

Description

The present invention relates to a positive photosensitive resin composition suitable for creating a SiO ₂ pattern formed on a high-intensity LED (Light Emitting Diodes) or the like. The patterning of the sapphire layer and the GaN layer, when performed through the SiO ₂ pattern, relates to a positive photosensitive resin composition suitable as a composition for the SiO ₂ pattern.

  Light emitting diodes (LEDs) are a type of EL (Electro Luminescence) element that converts electrical energy into light energy using the characteristics of a compound. Since LEDs have good energy conversion efficiency and long life, they are widely used as electronic devices such as various lighting devices, illuminations, and displays. For this reason, in recent years, there has been a demand for higher brightness of light emitting elements used in LEDs.

  A light emitting element used for such an LED is composed of a sapphire substrate and layers such as an n-GaN layer, an InGaN layer, and a p-GaN layer formed thereon.

  However, when the GaN layer is formed on the sapphire substrate, there is a difference between the lattice constant of sapphire and the lattice constant of GaN, which causes a problem that crystal dislocation occurs and a defect occurs. That is, there is a problem that the light extraction efficiency is reduced due to this defect. In addition, the light generated in the light emitting layer such as the InGaN layer is totally reflected at the interface with the sapphire substrate, and a part of the energy is converted into heat, and the heat extraction caused thereby reduces the light extraction efficiency. It was.

  As a method for improving this, a method of forming a fine convex pattern on the surface of the sapphire substrate is known (for example, Patent Document 1). That is, in Patent Document 1, by performing fine convex processing on the GaN layer forming surface of the sapphire substrate, crystal dislocation proceeds along the convex pattern when forming the GaN layer, and thus when a smooth sapphire substrate is used. It is described that dislocation defects in the GaN layer are reduced as compared. Furthermore, it is described that the total reflection of light is suppressed and the light extraction efficiency is improved.

  Here, a dry etching method is known as a method of forming a fine convex pattern on the surface of the sapphire substrate. The dry etching method is a method of processing the surface of the sapphire substrate by forming a photoresist pattern on the sapphire substrate, and then reacting the sapphire with a reactive gas that has been turned into plasma using a dry etching apparatus. is there.

  However, in recent years, the size of the sapphire substrate has been increased with the spread of LEDs, and a large dry etching apparatus has become necessary. Therefore, there was a problem that the equipment cost increased. Further, as described above, in the dry etching method, the surface processing of the sapphire substrate is performed by using the reaction between the reactive gas and sapphire, which causes a problem that it takes time.

On the other hand, a wet etching method is known as another method for processing the surface of the sapphire substrate. In the wet etching method, first a chemical vapor deposition on the sapphire substrate surface: by (CVD Chemical Vapor Deposition) to form a SiO ₂ layer, then to form a photoresist pattern on the SiO ₂ layer, by etching the SiO ₂ Pattern formation is performed. Next, using this SiO ₂ pattern as a mask, the surface of the sapphire is processed by dipping in a chemical solution corrosive to sapphire such as acid. However, the wet etching method has a problem that the process becomes complicated because the SiO ₂ pattern is formed by etching as described above. Moreover, since it is necessary to immerse in sapphire which is corrosive to sapphire, such as an acid, it has an effort in handling the chemical from the viewpoint of safety.

Japanese Patent No. 3595277

As a method of simplifying the complicated process as described above, by forming a convex pattern of SiO ₂ on the sapphire substrate by a photolithography method, and further forming a GaN layer on the convex pattern of SiO ₂ , A method of obtaining a GaN layer with reduced dislocation defects is conceivable. With this method, since the total reflection of light is suppressed by the convex pattern of SiO ₂ , the light extraction efficiency can be improved.

The present invention is a positive photosensitive resin composition suitable for obtaining the above-mentioned convex pattern of SiO ₂ , that is, having good development adhesiveness during development and maintaining a fine pattern without reflow after firing. The present invention provides a positive photosensitive resin composition that can be used.

  Moreover, the manufacturing method of the hardening pattern using the said positive photosensitive resin composition, the convex pattern board | substrate obtained from it, and the light emitting element obtained from it are provided.

  In order to solve the above problems, the present invention has the following configuration. That is, (a) a polysiloxane synthesized by hydrolyzing and condensing an organosilane containing a silane compound represented by the following general formula (1) and a silane compound represented by the following general formula (2), (b A positive photosensitive resin composition comprising a naphthoquinonediazide compound and (c) a solvent.

In general formula (1), R ¹ represents a condensed polycyclic aromatic hydrocarbon group. R ² represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms. n represents an integer of 0 to 3. When n is 2, 3, the plurality of R ¹ may be the same or different, and when n is 1, 2, the plurality of R ² may be the same or different.

In General Formula (2), R ³ represents an alkyl group having 1 to 10 carbon atoms. R ⁴ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms. m represents an integer of 0 to 3. When m is 2 or 3, the plurality of R ³ may be the same or different, and when m is 1 or 2, the plurality of R ⁴ may be the same or different.

According to the positive photosensitive resin composition of the present invention, a high-resolution cured pattern can be formed through photolithography, and a SiO ₂ pattern excellent in resolution can be obtained even after firing. Further, when the positive photosensitive resin composition of the present invention is used, etching is not required for pattern formation, so that the work process can be simplified, and it is suitably used as an etching material for semiconductor materials such as sapphire and GaN. Further, according to the present invention, since a transparent SiO ₂ film and pattern can be formed, it is suitably used as a planarization insulating film for semiconductor elements and a protective film for displays.

  The positive photosensitive resin composition of the present invention is synthesized by hydrolyzing and condensing (a) a silane compound represented by the following general formula (1) and a silane compound represented by the following general formula (2). A positive photosensitive resin composition comprising (b) a naphthoquinonediazide compound and (c) a solvent.

In general formula (1), R ¹ represents a condensed polycyclic aromatic hydrocarbon group. R ² represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms. n represents an integer of 1 to 3. When n is 2, 3, the plurality of R ¹ may be the same or different, and when n is 1, 2, the plurality of R ² may be the same or different.

In General Formula (2), R ³ represents an alkyl group having 1 to 10 carbon atoms. R ⁴ represents hydrogen or an alkyl group having 1 to 6 carbon atoms. m represents an integer of 1 to 3. When m is 2 or 3, the plurality of R ³ may be the same or different, and when m is 1 or 2, the plurality of R ⁴ may be the same or different.

In the silane compound represented by the general formula (1), R ¹ represents a condensed polycyclic aromatic hydrocarbon group, and the hydrogen atom is a hydroxy group, an alkyl group, an alkenyl group, an alkoxy group, an alkoxysilyl group, an alkyl group. It may be substituted with a siloxy group, a carboxyl group, a dicarboxylic anhydride group, an amino group, or the like. When two or more R ¹ are present, they may be the same or different.

  The condensed polycyclic aromatic hydrocarbon group is a group having a hydrocarbon group in which two or more aromatic rings are condensed. Preferred examples include naphthalene, anthracene, phenanthrene, tetracene, benz (a) anthracene, Examples include benzo (c) phenanthrene, pentacene, pyrene, fluorene, fluorenone, indene, azulene, acenaphthene, acenaphthylene, carbazole, and the like. From the viewpoint of heat resistance of the cured film, naphthalene, phenanthrene, pyrene, fluorene, fluorenone, indene, acenaphthene. Acenaphthylene is preferred. Moreover, the silane compound substituted by Si atom in one substitutable position of the said condensed polycyclic aromatic is preferable.

In the silane compound represented by the general formula (1), R ² represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms, and R ² represents When two or more are present, they may be the same or different, and can be selected according to the characteristics of the positive photosensitive resin composition.

  Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, and n-butyl group. Specific examples of the acyl group having 2 to 6 carbon atoms include an acetyl group. Specific examples of the aryl group having 6 to 16 carbon atoms include a phenyl group.

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

  Preferred specific examples of the silane compound represented by the general formula (1) include 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, di (1-naphthyl) dimethoxysilane, di (1-naphthyl) dimethoxysilane, 2-naphthyltrimethoxysilane, 1-anthracenyltrimethoxysilane, 9-anthracenyltrimethoxysilane, 9-phenanthrenyltrimethoxysilane, 9-fluorenyltrimethoxysilane, 2 -Fluorenyltrimethoxysilane, 2-fluorenoneyltrimethoxysilane, 1-pyrenyltrimethoxysilane, 2-indenyltrimethoxysilane, 5-acenaphthenyltrimethoxysilane and the like. These organosilanes may be used alone or in combination of two or more.

  By using the silane compound represented by the general formula (1), a positive photosensitive resin composition excellent in development adhesiveness can be obtained.

  (A) The content ratio of the silane compound represented by the general formula (1) in the organosilane used for the synthesis of polysiloxane is 5% or more and 90% or less with respect to the number of moles of Si atoms in the whole organosilane. It is preferably 10% or more and 80% or less. By being 5% or more and 90% or less, the contribution to development adhesiveness becomes more sufficient, and the occurrence of development peeling of a fine pattern at the optimum exposure amount can be further suppressed. In addition, the pattern is less likely to reflow during curing, and the post-curing resolution is improved.

In the silane compound represented by the general formula (2), R ³ may be the same or different when two or more exist, and represents an alkyl group having 1 to 10 carbon atoms. Preferably it is a C1-C6 alkyl group, More preferably, it is 1 or more groups chosen from a methyl group, an ethyl group, n-propyl group, isopropyl group, and n-butyl group, Most preferably, it is a methyl group or An ethyl group.

In the silane compound represented by the general formula (2), R ⁴ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms, and R ⁴ represents When two or more are present, they may be the same or different, and can be selected according to the characteristics of the positive photosensitive resin composition. Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Specific examples of the acyl group having 2 to 6 carbon atoms include an acetyl group. Specific examples of the aryl group having 6 to 16 carbon atoms include a phenyl group.

  M in the general formula (2) represents an integer of 1 to 3. When m = 1, trifunctional silane, when m = 2, bifunctional silane, and when m = 3, monofunctional silane.

  Preferred specific examples of the silane compound represented by the general formula (2) include 2-methoxyphenyltrimethoxysilane, 2-methoxyphenyltriethoxysilane, 2-methoxyphenyltri-n-propoxysilane, and di (2-methoxyphenyl). ) Dimethoxysilane, di (2-methoxyphenyl) diethoxysilane, 2-ethoxyphenyltrimethoxysilane, 2-ethoxyphenyltriethoxysilane, 2-n-propoxyphenyltrimethoxysilane, 2-isopropoxyphenyltrimethoxysilane, 3-methoxyphenyltrimethoxysilane, 3-methoxyphenyltriethoxysilane, 3-methoxyphenyltri-n-propoxysilane, di (3-methoxyphenyl) dimethoxysilane, di (3-methoxyphenyl) diethoxysilane, 3- Toxiphenyltrimethoxysilane, 3-ethoxyphenyltriethoxysilane, 3-n-propoxyphenyltrimethoxysilane, 3-isopropoxyphenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane, 4-methoxyphenyltriethoxysilane, 4 -Methoxyphenyltri-n-propoxysilane, di (4-methoxyphenyl) dimethoxysilane, di (4-methoxyphenyl) diethoxysilane, 4-ethoxyphenyltrimethoxysilane, 4-ethoxyphenyltriethoxysilane, 4-n -Propoxyphenyltrimethoxysilane, 4-isopropoxyphenyltrimethoxysilane, etc. are mentioned. These organosilanes may be used alone or in combination of two or more.

  The silane compound represented by the general formula (2) contributes to alkali solubility because electrons are localized, and a positive photosensitive resin composition that can be patterned without residue even in a fine pattern of 4 μm or less is obtained. .

  (A) The content ratio of the silane compound represented by the general formula (2) in the organosilane used for synthesizing the polysiloxane is 5% or more and 80% or less with respect to the number of moles of Si atoms in the whole organosilane. Preferably, it is 5% or more and 50% or less. When the content is 5% or more and 80% or less, the generation of residues between patterns is reduced, and the resolution of the fine pattern is facilitated. Further, the alkali solubility becomes more moderate, and the peeling with a fine pattern becomes less during development.

  The positive photosensitive resin composition of the present invention is a polysiloxane synthesized by hydrolyzing and condensing organosilane containing a silane compound represented by the following general formula (3): (a) polysiloxane It is preferable that

In general formula (3), R ⁵ represents a group in which a hydrogen atom of an alkyl group, an oxyalkyl group, an alkenyl group or a monocyclic aryl group is substituted with a carboxyl group or a dicarboxylic anhydride group. R ⁶ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms. l represents an integer of 1 to 3. When l is 2, 3, the plurality of R ⁵ may be the same or different, and when l is 1, 2, the plurality of R ⁶ may be the same or different.

  In the silane compound represented by the general formula (3), the carboxylic acid of the carboxyl group or dicarboxylic anhydride group contributes to alkali solubility, and is effective in further improving the resolution in a fine pattern.

In the silane compound represented by the general formula (3), R ⁵ represents a group in which a hydrogen atom of an alkyl group, an oxyalkyl group, an alkenyl group or a monocyclic aryl group is substituted with a carboxyl group or a dicarboxylic anhydride group. Represent. The dicarboxylic acid anhydride group is preferably a succinic acid anhydride group. In the alkyl group, oxyalkyl group, alkenyl group or monocyclic aryl group, a hydrogen atom is substituted with a carboxyl group or a dicarboxylic anhydride group, but the other hydrogen atoms are a hydroxy group, an alkoxy group, an alkoxy group. It may be substituted with a group such as a silyl group, an alkylsiloxy group or an amino group.

  Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 2, 2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 3-aminopropyl group, 3-mercaptopropyl group, 3-isocyanatopropyl group, methyl group, ethyl group, n-propyl Group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group and n-decyl group are more preferred.

  Specific examples of the oxyalkyl group include n-butoxy-n-propyl group, isopropoxymethyl group, ethoxyethyl group and the like.

  Specific examples of the alkenyl group include a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group.

  Specific examples of the monocyclic aryl group include phenyl group, tolyl group, p-hydroxyphenyl group, 1- (p-hydroxyphenyl) ethyl group, 2- (p-hydroxyphenyl) ethyl group, 4-hydroxy-5. A-(p-hydroxyphenylcarbonyloxy) pentyl group may be mentioned.

In the silane compound represented by the general formula (3), R ⁶ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having ⁶ to 16 carbon atoms, and R ⁶ represents When two or more are present, they may be the same or different, and can be selected according to the characteristics of the positive photosensitive resin composition. Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Specific examples of the acyl group having 2 to 6 carbon atoms include an acetyl group. Specific examples of the aryl group having 6 to 16 carbon atoms include a phenyl group.

  In the general formula (3), l represents an integer of 1 to 3. A trifunctional silane when l = 1, a bifunctional silane when l = 2, and a monofunctional silane when l = 3.

  Specific examples of the compound represented by the general formula (3) include silane compounds substituted with a carboxyl group, such as 3-trimethoxysilylpropionic acid, 3-triethoxysilylpropionic acid, 3-dimethylmethoxysilylpropion. Acid, 3-dimethylethoxysilylpropionic acid, 4-trimethoxysilylbutyric acid, 4-triethoxysilyl entangling acid, 4-dimethylmethoxysilyl entangling acid, 4-dimethylethoxysilyl entangling acid, 5-trimethoxysilylvaleric acid, 5 -Triethoxysilylvaleric acid, 5-dimethylmethoxysilylvaleric acid, 5-dimethylethoxysilylvaleric acid, 6-trimethoxysilylcaproic acid, 6-triethoxysilylcaproic acid, 6-dimethylmethoxysilylcaproic acid, 6-dimethyl Linear aliphatic cals such as ethoxysilylcaproic acid Acid, 4- (3-trimethoxysilylpropoxy) cyclohexanecarboxylic acid, 4- (3-triethoxysilylpropoxy) cyclohexanecarboxylic acid, 4- (3-dimethylmethoxysilylpropoxy) cyclohexanecarboxylic acid, 4- (3 -Dimethylethoxysilylpropoxy) cycloaliphatic carboxylic acid such as cyclohexanecarboxylic acid and 4- (3-trichlorosilylpropoxy) benzoic acid, 4- (3-trimethoxysilylpropoxy) benzoic acid, 4- (3- Examples include those containing aromatic carboxylic acids such as triethoxysilylpropoxy) benzoic acid, 4- (3-dimethylmethoxysilylpropoxy) benzoic acid, and 4- (3-dimethylethoxysilylpropoxy) benzoic acid.

  Examples of the silane compound substituted with a dicarboxylic anhydride group include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylsilylpropyl succinic anhydride, 3-dimethylmethoxysilylpropyl succinic anhydride, 3 -Dimethylethoxysilylpropyl succinic anhydride, 4- (2-trimethoxysilylethyl) cyclohexyl-1,2-dicarboxylic anhydride, 4- (2-triethoxysilylethyl) cyclohexyl-1,2-dicarboxylic anhydride 4- (2-dimethylmethoxysilylethyl) cyclohexyl-1,2-dicarboxylic anhydride, 4- (2-dimethylethoxysilylethyl) cyclohexyl-1,2-dicarboxylic anhydride, 3- (3-tri Methoxysilylpropyl) cyclohexyl-1,2-dicarboxylic anhydride, -(3-triethoxysilylpropyl) cyclohexyl-1,2-dicarboxylic anhydride, 3- (3-dimethylmethoxysilylpropyl) cyclohexyl-1,2-dicarboxylic anhydride, 3- (3-dimethylethoxysilylpropyl) ) Cyclohexyl-1,2-dicarboxylic anhydride, 4- (2-trimethoxysilylethyl) phthalic anhydride, 4- (2-triethoxysilylethyl) phthalic anhydride, 4- (2-dimethylmethoxysilyl) Ethyl) phthalic anhydride, 4- (2-dimethylethoxysilylethyl) phthalic anhydride, 3- (3-trimethoxysilylpropyl) phthalic anhydride, 3- (3-triethoxysilylpropyl) phthalic anhydride , 3- (3-dimethylmethoxysilylpropyl) phthalic anhydride, 3- (3-dimethylethoxysilyl) Propyl) and the like phthalic anhydride. In addition, these compounds may be used individually or may be used in combination of 2 or more types.

  When copolymerizing the silane compound represented by the general formula (3), when using a silane compound having a succinic anhydride group, the succinic anhydride group needs to be opened to form a succinic acid group. By opening the succinic anhydride group, a highly hydrophilic succinic acid group is generated, and the resulting polysiloxane has improved solubility in a dilute alkaline developer. In order to sufficiently open the succinic anhydride group, it is desirable that the polymerization temperature is 100 ° C. or higher and the reaction is performed for 30 minutes or longer.

  The positive photosensitive resin composition of the present invention is a polysiloxane synthesized by hydrolyzing and condensing organosilane containing (a) polysiloxane and a silane compound represented by the following general formula (4): It is preferable that Two or more silane compounds represented by the general formula (4) may be used.

In the general formula (4), R ⁷ represents a hydrogen atom, an alkyl group, an alkenyl group or a phenyl group. In the case of an alkyl group, the alkyl group having 1 to 20 carbon atoms is used. In the case of an alkenyl group, R ⁷ has 1 to 20 carbon atoms. An alkenyl group is preferred. When two or more R ⁷ are present, they may be the same or different, and can be selected according to the characteristics of the positive photosensitive resin composition.

  Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, and an n-decyl group, and the alkenyl group. Specific examples of these include vinyl groups.

In the silane compound represented by the general formula (4), R ⁸ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms, and R ⁸ represents When two or more are present, they may be the same or different, and can be selected according to the characteristics of the positive photosensitive resin composition. Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Specific examples of the acyl group having 2 to 6 carbon atoms include an acetyl group. Specific examples of the aryl group having 6 to 16 carbon atoms include a phenyl group.

  K in the general formula (4) represents an integer of 0 to 3. A tetrafunctional silane when k = 0, a trifunctional silane when k = 1, a bifunctional silane when k = 2, and a monofunctional silane when k = 3.

  In addition to the silane compounds represented by the general formulas (1) to (4), a trifluoromethyl group, a 3,3,3-trifluoropropyl group, a 3-glycidoxypropyl group, 2- (3, 4-epoxycyclohexyl) ethyl group, [(3-ethyl-3-oxetanyl) methoxy] propyl group, 3-aminopropyl group, 3-mercaptopropyl group, 3-isocyanatopropyl group and other alkyl group substitution products, 3-acrylic Substituted alkenyl groups such as loxypropyl group and 3-methacryloxypropyl group, tolyl group, p-hydroxyphenyl group, 1- (p-hydroxyphenyl) ethyl group, 2- (p-hydroxyphenyl) ethyl group, 4- Aromatic substituents such as hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl group may be used.

  As an embodiment of the polysiloxane (a), the (a) polysiloxane is preferably synthesized by hydrolysis and condensation in the presence of (d) inorganic particles. The presence of inorganic particles in the positive photosensitive polysiloxane composition improves the post-curing resolution of the pattern. This is presumably because the positive photosensitive polysiloxane composition contains inorganic particles, so that the glass transition temperature of the film is increased and the pattern dripping at the time of thermosetting is suppressed.

  The number average particle diameter of the inorganic particles is preferably 1 nm to 200 nm, and more preferably 5 nm to 70 nm. When the thickness is 1 nm to 200 nm, the effect of improving the pattern resolution becomes more sufficient. Moreover, the generation of cracks during the formation of the thick film can be further suppressed. Moreover, since it can suppress that a particle | grain aggregates and a polymer aggregates, the storage stability of a polymer improves more.

  The inorganic particles are preferably silica particles or titanium oxide particles.

Specific examples of the silica particles include IPA-ST having a particle diameter of 12 nm using isopropanol as a dispersion medium, MIBK-ST having a particle diameter of 12 nm using methyl isobutyl ketone as a dispersion medium, and IPA-ST having a particle diameter of 45 nm using isopropanol as a dispersion medium. ST-L, IPA-ST-ZL having a particle diameter of 100 nm using isopropanol as a dispersion medium, PGM-ST having a particle diameter of 15 nm using propylene glycol monomethyl ether as a dispersion medium (trade name, manufactured by Nissan Chemical Industries, Ltd.), “Oscal” 101 with a particle diameter of 12 nm using γ-butyrolactone as a dispersion medium, “Oscal” 105 with a particle diameter of 60 nm using γ-butyrolactone as a dispersion medium, and “Oscal” 106 with a particle diameter of 120 nm using diacetone alcohol as a dispersion medium. "Cataloid" having a particle size of 5 to 80 nm, whose dispersion solution is water- S (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.), “Quortron” PL-2L-PGME having a particle diameter of 16 nm using propylene glycol monomethyl ether as a dispersion medium, “Quatron” having a particle diameter of 16 nm using isopropyl alcohol as a dispersion medium "PL-2L-IPA, 17-nm particle" Quatron "PL-2L-BL using γ-butyrolactone as a dispersion medium, 17-nm particle" Quatron "PL-2L-DAA, dispersion using diacetone alcohol as a dispersion medium, dispersion "Quartron" PL-2L particle size 18~20nm solution is water, GP-2L (trade names, manufactured by Fuso chemical Co.), silica particle size is _{100nm (SiO 2) SG-SO100} ( Product name, manufactured by Kyoritsu Material Co., Ltd., Leolosil (product name, Co., Ltd.) with a particle size of 5 to 50 nm Tokuyama).

  Further, the number average particle diameter of the silica particles can be obtained from the specific surface area method conversion value. The specific surface area conversion value is obtained by drying and firing the particles, measuring the specific surface area of the obtained particles, then determining the particle diameter from the specific surface area assuming that the particles are spheres, and determining the average particle diameter as a number average. . Although the apparatus to be used is not specifically limited, Asap 2020 (trade name, manufactured by Micromeritics) or the like can be used.

  Specific examples of the titanium oxide particles include commercially available “OPTRAIK TR-505”, “OPTRAIK TR-513”, and “OPTRAIK TR-527” (above, trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.). ) And the like.

  The number average particle size of the titanium oxide particles can be measured by a gas adsorption method, a dynamic light scattering method, an X-ray small angle scattering method, a method of directly measuring the particle size by a transmission electron microscope or a scanning electron microscope. .

  The content of the inorganic particles is preferably 1 part by weight to 200 parts by weight, and more preferably 5 parts by weight to 90 parts by weight with respect to 100 parts by weight of the (a) polysiloxane. By being 1 part by weight to 200 parts by weight, the compatibility between the (a) polysiloxane and the naphthoquinonediazide compound is further improved. In addition, generation of minute residue between patterns after development can be further reduced. Further, the post-curing resolution of the pattern can be further improved by suppressing the reflow property. Moreover, these inorganic particles may be used alone or in combination of two or more.

  The weight average molecular weight (Mw) of the (a) polysiloxane used in the present invention is not particularly limited, but is preferably 1000 to 100,000, more preferably 1000 to 100000 in terms of polystyrene measured by GPC (gel permeation chromatography). 50000. When Mw is less than 1000, the coating properties are deteriorated, and when it is greater than 100,000, the solubility in a developer during pattern formation is deteriorated.

  The polysiloxane (a) in the present invention is synthesized by hydrolysis and partial condensation of a monomer such as an organosilane represented by the general formula (1). Alternatively, (a) polysiloxane is preferably synthesized by hydrolyzing and partially condensing a monomer such as organosilane represented by the general formula (1) in the presence of (d) inorganic particles. A general method can be used for hydrolysis and partial condensation. For example, a solvent, water, and a catalyst as required are added to the mixture, and the mixture is heated and stirred at 50 to 150 ° C. for about 0.5 to 100 hours. During stirring, if necessary, hydrolysis by-products (alcohols such as methanol) and condensation by-products (water) may be distilled off by distillation.

  Although there is no restriction | limiting in particular as said reaction solvent, Usually, the thing similar to the below-mentioned (c) solvent is used. The addition amount of the solvent is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the monomer such as organosilane. The amount of water used for the hydrolysis reaction is preferably 0.5 to 2 mol with respect to 1 mol of the hydrolyzable group.

  Although there is no restriction | limiting in particular in the catalyst added as needed, An acid catalyst and a base catalyst are used preferably. Specific examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyvalent carboxylic acid or anhydride thereof, and ion exchange resin. Specific examples of the base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, amino Examples include alkoxysilanes having groups and ion exchange resins. The addition amount of the catalyst is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer such as organosilane.

  Further, from the viewpoint of the storage stability of the composition, the polysiloxane solution after hydrolysis and partial condensation preferably does not contain the catalyst, and the catalyst can be removed as necessary. The removal method is not particularly limited, but water washing and / or ion exchange resin treatment is preferable from the viewpoint of easy operation and removability. Water washing is a method of concentrating an organic layer obtained by diluting a polysiloxane solution with an appropriate hydrophobic solvent and then washing several times with water with an evaporator or the like. The treatment with an ion exchange resin is a method of bringing a polysiloxane solution into contact with an appropriate ion exchange resin.

  The positive photosensitive resin composition of the present invention contains (b) a naphthoquinonediazide compound. The photosensitive composition containing a naphthoquinone diazide compound forms a positive type in which the exposed portion is removed with a developer. The naphthoquinonediazide compound to be used is not particularly limited, but is preferably a compound in which naphthoquinonediazidesulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group, and the ortho position and para position of the phenolic hydroxyl group of the compound are independently hydrogenated. Or the compound which is a substituent represented by General formula (5) is used preferably.

^{Wherein, R 9, R 10, R} 11 each independently represents an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, or a substituted phenyl group. Further, R ⁹ , R ¹⁰ and R ¹¹ may form a ring. The alkyl group may be either unsubstituted or substituted, and can be selected according to the characteristics of the composition. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n- Examples include an octyl group, a trifluoromethyl group, and a 2-carboxyethyl group. Examples of the substituent on the phenyl group include a hydroxyl group and a methoxy group. Specific examples of the ring formed by R ⁹ , R ¹⁰ , and R ¹¹ include a cyclopentane ring, a cyclohexane ring, an adamantane ring, and a fluorene ring.

Since the ortho-position and para-position of the phenolic hydroxyl group of the compound are hydrogen or a substituent represented by the general formula (5), oxidative decomposition due to thermal curing hardly occurs, and a cured film is obtained. The colorless transparency in the case can be further improved.

  In addition, these naphthoquinone diazide compounds can be synthesized by a known esterification reaction between a compound having a phenolic hydroxyl group and naphthoquinone diazide sulfonic acid chloride.

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

  As the naphthoquinone diazide sulfonic acid chloride as a raw material, 4-naphthoquinone diazide sulfonic acid chloride or 5-naphthoquinone diazide sulfonic acid chloride can be used. Since 4-naphthoquinonediazide sulfonic acid ester compound has absorption in the i-line (wavelength 365 nm) region, it is suitable for i-line exposure. Moreover, since 5-naphthoquinone diazide sulfonic acid ester compound has absorption in a wide range of wavelengths, it is suitable for exposure in a wide range of wavelengths. It is preferable to select a 4-naphthoquinone diazide sulfonic acid ester compound or a 5-naphthoquinone diazide sulfonic acid ester compound depending on the wavelength to be exposed. A 4-naphthoquinone diazide sulfonic acid ester compound and a 5-naphthoquinone diazide sulfonic acid ester compound may be mixed and used.

  The addition amount of the naphthoquinone diazide compound is not particularly limited, but is preferably 2 to 30 parts by weight, more preferably 4 to 20 parts by weight with respect to 100 parts by weight of (a) polysiloxane. When the addition amount of the naphthoquinone diazide compound is 2 to 30 parts by weight relative to 100 parts by weight of the polysiloxane (a), the dissolution contrast between the exposed part and the unexposed part becomes more sufficient, and more sufficient photosensitivity is exhibited. be able to. Further, (a) the compatibility between the polysiloxane and the naphthoquinonediazide compound becomes more sufficient, and the coating film is less likely to be whitened.

  The positive photosensitive resin composition of the present invention contains (c) a solvent. Although there is no restriction | limiting in particular in the solvent to be used, Preferably the compound which has alcoholic hydroxyl group is used. When these solvents are used, (a) the polysiloxane and the quinonediazide compound are uniformly dissolved, and when the composition is applied, a film can be formed without becoming cloudy.

  The compound having an alcoholic hydroxyl group is not particularly limited, but is preferably a compound having a boiling point of 110 to 250 ° C. under atmospheric pressure. When the boiling point is higher than 250 ° C., the amount of residual solvent in the film increases and film shrinkage during curing increases, and good flatness cannot be obtained. On the other hand, if the boiling point is lower than 110 ° C., the coating properties deteriorate, such as drying at the time of coating is too fast and the film surface becomes rough.

  Specific examples of the compound having an alcoholic hydroxyl group include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy- 4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, propylene glycol mono t- Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 3-methoxy-1- Pentanol, 3-methyl-3-methoxy-1-butanol. In addition, you may use the compound which has these alcoholic hydroxyl groups individually or in combination of 2 or more types.

  Solvents other than compounds having an alcoholic hydroxyl group include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl Esters such as 3-methoxy-1-butyl acetate and ethyl acetoacetate, ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone and acetylacetone, diethyl ether, diisopropyl ether, di n-butyl ether, diphenyl ether, diethylene glycol ethyl methyl Ethers, ethers such as diethylene glycol dimethyl ether, γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methyl Pyrrolidone, cyclopentanone, cyclohexanone, etc. cycloheptanone and the like.

  (C) Although there is no restriction | limiting in particular in the addition amount of a solvent, Preferably it is the range of 100-2000 weight part with respect to 100 weight part of (a) polysiloxane.

  The positive photosensitive resin composition of the present invention may contain a silane coupling agent as necessary. By containing the silane coupling agent, it is possible to improve the adhesion to the base material during development.

  Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p -Styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, 1-anthracenyltrimethoxysilane, 4-hydroxyphenyltrimethoxysilane 4-methoxyphenyl silane, a silane coupling agent such as 4-ethoxyphenyl trimethoxysilane. Two or more of these may be contained.

  As for content of a silane coupling agent, 0.1-10 weight part is preferable with respect to 100 weight part of (a) polysiloxane.

  The positive photosensitive resin composition of the present invention may contain a thermal acid generator, if necessary. The thermal acid generator is a compound that decomposes to generate an acid upon thermal curing. Since the condensation of unreacted silanol groups is promoted by the generated acid, the degree of crosslinking of the cured film is increased. Thereby, the surface hardness, chemical resistance, and pattern resolution of the cured film are improved. It is preferable that no acid is generated or only a small amount is generated by pre-baking after application of the composition. That is, it is preferably a compound that generates an acid at a pre-bake temperature or higher, for example, 100 ° C. or higher. When an acid is generated at a temperature lower than the pre-baking temperature, the polysiloxane is likely to be crosslinked during pre-baking, resulting in a decrease in sensitivity or a residue during development.

  Specific examples of the thermal acid generator include “Sun-Aid” SI-60, SI-80, SI-100, SI-200, SI-110, SI-145, SI-150, SI-60L, SI-80L, SI -100L, SI-110L, SI-145L, SI-150L, SI-160L, SI-180L (above trade name, manufactured by Sanshin Chemical Industry Co., Ltd.), 4-hydroxyphenyldimethylsulfonium trifluoromethanesulfonate, benzyl- 4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenyldimethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenylbenzylmethylsulfonium Trifluoromethane sulfonate, 4-methoxycarbonyloxy-phenyl dimethyl sulfonium trifluoromethanesulfonate, benzyl-4-methoxycarbonyloxy-phenyl methyl sulfonium trifluoromethanesulfonate (manufactured by Sanshin Chemical Industry Co.), and the like. Two or more of these may be contained.

  Although there is no restriction | limiting in particular in the addition amount of a thermal acid generator, Preferably it is the range of 0.01-5 weight part with respect to 100 weight both parts of (a) polysiloxane.

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

  Specific examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl. Hexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1 , 1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2 , 8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N- [3- (Perful Looctanesulfonamido) propyl] -N, N′-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salt, perfluoroalkyl-N-ethylsulfonylglycine salt, bis (N-par) phosphate Fluorosurfactant comprising a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain, such as fluorooctylsulfonyl-N-ethylaminoethyl) and monoperfluoroalkylethyl phosphate ester An agent can be mentioned. Commercially available products include MegaFuck F142D, F172, F173, F183, F183, F475 (above, manufactured by Dainippon Ink & Chemicals, Inc.), Ftop EF301, 303, 352 (Shinakita Kasei ( ), Florard FC-430, FC-431 (Sumitomo 3M)), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC -104, SC-105, SC-106 (Asahi Glass Co., Ltd.), BM-1000, BM-1100 (manufactured by Yusho Co., Ltd.), NBX-15, FTX-218, DFX-218 ((Co., Ltd.) ) Fluorosurfactants such as Neos).

  Examples of commercially available silicone surfactants include SH28PA, SH7PA, SH21PA, SH30PA, ST94PA (all manufactured by Toray Dow Corning Silicone Co., Ltd.), BYK-333 (manufactured by Big Chemie Japan Co., Ltd.), and the like. It is done.

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

  The manufacturing method of the hardening pattern using the positive photosensitive resin composition of this invention is demonstrated.

The curing pattern using the positive photosensitive resin composition of the present invention is obtained by changing the positive photosensitive resin composition of the present invention to silicon (Si), sapphire (Al ₂ O ₃ ), gallium nitride (GaN), silicon carbide. It can be manufactured by patterning on a substrate of (SiC), gallium arsenide (GaAs) or aluminum nitride (AlN) and baking. Moreover, it is preferable to perform a baking process at 600-1700 degreeC.

First, the positive photosensitive resin composition of the present invention is patterned on a substrate. It is applied onto a base substrate by a known method such as a spinner or a slit, and prebaked with a heating device such as a hot plate or oven. As described above, a silicon (Si), sapphire (Al ₂ O ₃ ), gallium nitride (GaN), silicon carbide (SiC), gallium arsenide (GaAs), or aluminum nitride (AlN) substrate is used as described above. Pre-baking is performed in the range of 50 to 150 ° C. for 30 seconds to 30 minutes, and the film thickness after pre-baking is preferably 0.05 to 15 μm.

After pre-baking, using a UV-visible exposure machine such as a stepper, mirror projection mask aligner (MPA), parallel light mask aligner (PLA), i-line stepper, etc., about 10 to 4000 J / m ² (wavelength 365 nm exposure dose conversion) is desired Pattern exposure is performed through a mask.

  After exposure, the exposed portion is dissolved by development, and a positive pattern can be obtained. As a developing method, it is preferable to immerse in a developing solution for 5 seconds to 10 minutes by a method such as shower, dipping or paddle. As the developer, a known alkali developer can be used. Specific examples include alkali metal hydroxides, carbonates, phosphates, silicates, borates, and other inorganic alkalis, amines such as 2-diethylaminoethanol, monoethanolamine, diethanolamine, and tetramethyl hydroxide. Examples include aqueous solutions containing one or more quaternary ammonium salts such as ammonium and choline. Moreover, it is preferable to rinse with water after development, and if necessary, dehydration drying baking can be performed in a range of 50 to 150 ° C. with a heating device such as a hot plate or an oven.

  After that, if necessary, after performing soft baking in a heating device such as a hot plate or oven at a temperature of 50 to 250 ° C. for 30 seconds to 30 minutes, a heating device such as a hot plate or an oven is used in a range of 150 to 450 ° C. A cured pattern is formed by baking for about 2 to 2 hours.

Furthermore, it is preferable to perform this baking pattern at 600-1700 degreeC with high temperature baking apparatuses, such as a baking furnace. Further, the treatment time is preferably 0.5 to 24 hours. As a result, an SiO ₂ pattern containing no organic component is obtained. The resolution after firing is preferably 8 μm or less, and more preferably 4 μm or less.

  Moreover, the convex pattern board | substrate of this invention can be obtained by etching the hardening pattern obtained by the manufacturing method of the said hardening pattern. In particular, the substrate is preferably etched using a chemical solution such as nitric acid or phosphoric acid using the cured pattern as a mask.

  The light emitting device of the present invention is formed by forming one or more layers selected from a GaN layer, an AlN layer, and an InN layer on the cured pattern obtained by the method for producing a cured pattern or the convex pattern substrate. Can be obtained.

  For example, the cured pattern or the convex pattern substrate is mounted on a MOVPE apparatus, and thermal cleaning is performed at a high temperature of 1000 ° C. or higher in a nitrogen gas main atmosphere, and a GaN low temperature buffer layer, an n-GaN layer, an InGaN light emitting layer, By forming a p-AlGaN layer, a p-GaN layer, and the like, an LED epitaxial substrate can be manufactured. An LED light emitting element can be obtained by subjecting this substrate to etching, electrode formation, and element separation.

The positive photosensitive resin composition of the present invention, the sensitivity at patterning exposure by the parallel light mask aligner (PLA) is preferably not more than 1000 J / ^{m 2,} and more preferably 600 J / ^{m 2} or less. If the sensitivity is required to be 1000 J / m ² or more, the radiation exposure time at the time of pattern formation becomes long, and the productivity is lowered.

  The sensitivity in patterning exposure using the PLA is determined by the following method. The composition is spin-coated on a silicon wafer at an arbitrary rotation number using a spin coater, and prebaked at 110 ° C. for 2 minutes using a hot plate to produce a film having a thickness of 1 μm. The prepared film was exposed to an ultra-high pressure mercury lamp through a gray scale mask for sensitivity measurement using PLA (PLA-501F manufactured by Canon Inc.), and then an automatic developing device (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.). ) For 60 seconds with 2.38 wt% TMAH aqueous solution and then rinse with water for 30 seconds. In the formed pattern, an exposure amount for resolving a 10 μm line-and-space pattern with a one-to-one width is obtained as sensitivity.

The cured pattern formed by the positive photosensitive resin composition of the present invention is suitably used for an element such as a semiconductor element, a display element, or an optical waveguide material. Specific examples include semiconductor interlayer planarization insulating films that perform insulation and planarization between semiconductor layers, condensing microlenses and optical waveguides formed on solid-state imaging devices, flattening materials for display TFT substrates, liquid crystals Examples include protective films for displays and color filters. In addition, the positive photosensitive polysiloxane composition of the present invention can form a fine cured pattern by a photosensitive process, and further, this cured pattern can be baked to form SiO ₂ , so that silicon, sapphire, GaN, It is suitably used as a fine SiO ₂ pattern when forming a hard mask for etching a semiconductor material such as SiC or a semiconductor element such as an LED or a photodiode.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to these Examples. In addition, it shows below about what used the abbreviation among the used compounds.
PGMEA: propylene glycol monomethyl ether acetate DAA: diacetone alcohol IPA: isopropyl alcohol The solid content concentration of the polysiloxane solution was determined as follows.

  1.5 g of the polysiloxane solution was weighed in an aluminum cup and heated at 250 ° C. for 30 minutes using a hot plate to evaporate the liquid. The solid content remaining in the heated aluminum cup was weighed to determine the solid content concentration of the polysiloxane solution.

Synthesis Example 1 Synthesis of Polysiloxane Solution (PS-01) 61.32 g (0.25 mol) of 1-naphthyltrimethoxysilane and 56.31 g (0.25 mol) of 4-methoxyphenyltrimethoxysilane in a 500 ml three-necked flask , 155.17 g of DAA (initial monomer concentration = 35 wt%) was charged, and an aqueous phosphoric acid solution prepared by dissolving 0.529 g of phosphoric acid (0.45 wt% with respect to the charged monomer) in 26.67 g of water while stirring at room temperature. Added over 10 minutes. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (PS-01). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 47.6 g of methanol and water as by-products were distilled out. The resulting polysiloxane solution (PS-01) had a solid content concentration of 33% by weight.

Synthesis Example 2 Synthesis of Polysiloxane Solution (PS-02) In a 500 ml three-necked flask, 74.26 g (0.30 mol) of 1-naphthyltrimethoxysilane and 13.62 (0.06 mol) of 4-methoxyphenyltrimethoxysilane In addition, 32.53 g (0.24 mol) of methyltrimethoxysilane and 146.9 g of DAA (initial monomer concentration = 35 wt%) were charged, and 0.541 g of phosphoric acid (based on the charged monomers) was added to 32.25 g of water while stirring at room temperature. The phosphoric acid aqueous solution in which 0.45% by weight) was dissolved was added over 10 minutes. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (PS-02). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 58.9 g of methanol and water as by-products were distilled out. The resulting polysiloxane solution (PS-02) had a solid content concentration of 35% by weight.

Synthesis Example 3 Synthesis of Polysiloxane Solution (PS-03) 44.67 g (0.180 mol) of 1-naphthyltrimethoxysilane and 8.20 g (0.036 mol) of 4-methoxyphenyltrimethoxysilane in a 500 ml three-necked flask , 19.66 g (0.144 mol) of methyltrimethoxysilane, 81.36 g of “Quartron” PL-2L-IPA (manufactured by Fuso Chemical Industry Co., Ltd., dispersion medium: IPA, silica particle content 25.1 wt%), A solution of phosphoric acid in which 0.326 g of phosphoric acid (0.45 wt% with respect to the charged monomer) was dissolved in 19.43 g of water while stirring at room temperature was charged with 126.42 g of DAA (initial monomer concentration = 35 wt%). Added over minutes. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (PS-03). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 84.1 g of methanol and water as by-products were distilled. The resulting polysiloxane solution (PS-03) had a solid content concentration of 34% by weight.

Synthesis Example 4 Synthesis of polysiloxane solution (PS-04) 42.69 g (0.172 mol) of 1-naphthyltrimethoxysilane and 7.84 g (0.034 mol) of 4-methoxyphenyltrimethoxysilane in a 500 ml three-necked flask , 4.51 g (0.017 mol) of 3-trimethoxysilylpropyl succinic anhydride, 16.39 g (0.120 mol) of methyltrimethoxysilane, “Quartrone” PL-2L-IPA (manufactured by Fuso Chemical Industries, Ltd.) , Dispersion medium: IPA, silica particle content 25.1 wt%) 81.99 g, DAA 127.39 g (initial monomer concentration = 35 wt%) were charged and stirred at room temperature with water 18.87 g phosphoric acid 0.321 g Add phosphoric acid aqueous solution (0.45% by weight to charged monomer) over 10 minutes It was. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (PS-04). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 83.2 g of methanol and water as by-products were distilled. The resulting polysiloxane solution (PS-04) had a solid content concentration of 34% by weight.

Synthesis Example 5 Synthesis of polysiloxane solution (PS-05) 37.67 g (0.152 mol) of 1-naphthyltrimethoxysilane and 6.92 g (0.030 mol) of 4-methoxyphenyltrimethoxysilane in a 500 ml three-necked flask , 3.98 g (0.015 mol) of 3-trimethoxysilylpropyl succinic anhydride, 21.06 g (0.106 mol) of phenyltrimethoxysilane, “Quartrone” PL-2L-IPA (manufactured by Fuso Chemical Industries, Ltd.) , Dispersion medium: IPA, silica particle content 25.1 wt%) 83.60 g, DAA 129.90 g (initial monomer concentration = 35 wt%) were charged and stirred at room temperature with water 16.65 g phosphoric acid 0.219 g Add the phosphoric acid aqueous solution (0.45% by weight with respect to the charged monomer) over 10 minutes. The pressure was. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (PS-05). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 78.9 g of methanol and water as by-products were distilled out. The resulting polysiloxane solution (PS-05) had a solid content concentration of 33% by weight.

Synthesis Example 6 Synthesis of Polysiloxane Solution (PS-06) 6.19 g (0.025 mol) of 1-naphthyltrimethoxysilane and 11.37 g (0.050 mol) of 4-methoxyphenyltrimethoxysilane in a 500 ml three-necked flask 6.54-g (0.025 mol) of 3-trimethoxysilylpropyl succinic anhydride, 54.31 g (0.400 mol) of methyltrimethoxysilane, “Quartrone” PL-2L-IPA (manufactured by Fuso Chemical Industries, Ltd.) , Dispersion medium: IPA, silica particle content 25.1 wt%) 75.92 g, DAA 117.96 g (initial monomer concentration = 35 wt%) were charged and stirred at room temperature with 27.37 g water 0.353 g phosphoric acid Add phosphoric acid aqueous solution (0.45% by weight to charged monomer) over 10 minutes It was. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (PS-06). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 93.3 g of methanol and water as by-products were distilled out. The resulting polysiloxane solution (PS-06) had a solid content concentration of 34% by weight.

Synthesis Example 7 Synthesis of polysiloxane solution (PS-07) 29.71 g (0.12 mol) of 1-naphthyltrimethoxysilane and 9.09 g (0.04 mol) of 4-methoxyphenyltrimethoxysilane in a 500 ml three-necked flask , 3-trimethoxysilylpropyl succinic anhydride 5.23 g (0.02 mol), methyltrimethoxysilane 29.87 g (0.22 mol), “Quartrone” PL-2L-IPA (manufactured by Fuso Chemical Industries, Ltd.) , Dispersing medium: IPA, silica particle content 25.1 wt%) 79.83 g, DAA 124.04 g (initial monomer concentration = 35 wt%) were charged and stirred at room temperature 21.89 g of water 0.333 g of phosphoric acid An aqueous phosphoric acid solution in which (0.45% by weight with respect to the charged monomer) was dissolved was added over 10 minutes. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (PS-07). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 86.5 g of methanol and water as by-products were distilled out. The resulting polysiloxane solution (PS-07) had a solid content concentration of 33% by weight.

Synthesis Example 8 Synthesis of polysiloxane solution (PS-08) In a 500 ml three-necked flask, 52.52 g (0.211 mol) of 1-naphthyltrimethoxysilane and 6.89 g (0.030 mol) of 4-methoxyphenyltrimethoxysilane , 3.96 g (0.015 mol) of 3-trimethoxysilylpropyl succinic anhydride, 6.17 g (0.045 mol) of methyltrimethoxysilane, “Quartrone” PL-2L-IPA (manufactured by Fuso Chemical Industries, Ltd.) , Dispersion medium: IPA, silica particle content 25.1 wt%) 83.62 g, DAA 129.93 g (initial monomer concentration = 35 wt%) were charged and stirred at room temperature with water 16.59 g and phosphoric acid 0.313 g Add phosphoric acid solution (0.45% by weight with respect to charged monomer) over 10 minutes It was. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (PS-08). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 79.7 g of methanol and water as by-products were distilled out. The resulting polysiloxane solution (PS-08) had a solid content concentration of 35% by weight.

Synthesis Example 9 Synthesis of Polysiloxane Solution (PS-09) 43.30 g (0.174 mol) of 1-naphthyltrimethoxysilane and 5.96 g (0.026 mol) of 4-methoxyphenyltrimethoxysilane in a 500 ml three-necked flask , 4.57 g (0.017 mol) of 3-trimethoxysilylpropyl succinic anhydride, 17.81 g (0.131 mol) of methyltrimethoxysilane, “Quartrone” PL-2L-IPA (manufactured by Fuso Chemical Industries, Ltd.) , Dispersion medium: IPA, silica particle content 25.1 wt%) 81.79 g, DAA 127.09 g (initial monomer concentration = 35 wt%) were charged and stirred at room temperature with 19.14 g water 0.322 g phosphoric acid Add phosphoric acid aqueous solution (0.45% by weight to charged monomer) over 10 minutes It was. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (PS-09). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 83.4 g of methanol and water as by-products were distilled out. The solid content concentration of the obtained polysiloxane solution (PS-09) was 36% by weight.

Synthesis Example 10 Synthesis of Polysiloxane Solution (PS-10) In a 500 ml three-necked flask, 42.52 g (0.167 mol) of 1-naphthyltrimethoxysilane and 11.44 g (0.050 mol) of 4-methoxyphenyltrimethoxysilane 4.39 g (0.017 mol) of 3-trimethoxysilylpropyl succinic anhydride, 13.66 g (0.100 mol) of methyltrimethoxysilane, “Quartrone” PL-2L-IPA (manufactured by Fuso Chemical Industries, Ltd.) , Dispersion medium: IPA, silica particle content 25.1 wt%) 82.71 g, DAA 127.97 g (initial monomer concentration = 35 wt%) were charged and stirred at room temperature with water 18.36 g phosphoric acid 0.320 g Add 10% aqueous phosphoric acid solution (0.45% by weight of charged monomer) It was added. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (PS-10). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 83.2 g of methanol and water as by-products were distilled. The solid content concentration of the obtained polysiloxane solution (PS-10) was 36% by weight.

Synthesis Example 11 Synthesis of Polysiloxane Solution (PS-11) 40.41 g (0.163 mol) of 1-naphthyltrimethoxysilane and 14.84 g (0.065 mol) of 4-methoxyphenyltrimethoxysilane in a 500 ml three-necked flask , 3.27 g (0.016 mol) of 3-trimethoxysilylpropyl succinic anhydride, 11.08 g (0.081 mol) of methyltrimethoxysilane, “Quartrone” PL-2L-IPA (manufactured by Fuso Chemical Industries, Ltd.) , Dispersion medium: IPA, silica particle content 25.1 wt%) 82.71 g, DAA 128.51 g (initial monomer concentration = 35 wt%) were charged and stirred at room temperature with water 17.87 g phosphoric acid 0.318 g Add 10% aqueous phosphoric acid solution (0.45% by weight of charged monomer) It was added. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (PS-11). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 81.7 g of methanol and water as by-products were distilled out. The solid content concentration of the obtained polysiloxane solution (PS-11) was 37% by weight.

Synthesis Example 12 Synthesis of Polysiloxane Solution (PS-12) 38.71 g (0.156 mol) of 1-naphthyltrimethoxysilane and 7.11 g (0.031 mol) of 4-methoxyphenyltrimethoxysilane in a 500 ml three-necked flask , 4.09 g (0.016 mol) of 3-trimethoxysilylpropyl succinic anhydride, 14.86 g (0.109 mol) of methyltrimethoxysilane, “Quatron” PL-2L-IPA (manufactured by Fuso Chemical Industries, Ltd.) , Dispersion medium: IPA, silica particle content 25.1 wt%) was charged 93.41 g, DAA 124.41 g (initial monomer concentration = 35 wt%), and stirred at room temperature with 17.12 g water 0.291 g phosphoric acid Add the phosphoric acid aqueous solution (0.45% by weight with respect to the charged monomer) over 10 minutes. The pressure was. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (PS-12). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 85.7 g of methanol and water as by-products were distilled out. The solid content concentration of the obtained polysiloxane solution (PS-12) was 34% by weight.

Synthesis Example 13 Synthesis of Polysiloxane Solution (PS-13) 51.25 g (0.206 mol) of 1-naphthyltrimethoxysilane and 9.41 g (0.041 mol) of 4-methoxyphenyltrimethoxysilane in a 500 ml three-necked flask 5.41 g (0.021 mol) of 3-trimethoxysilylpropyl succinic anhydride, 19.67 g (0.144 mol) of methyltrimethoxysilane, “Quatron” PL-2L-IPA (manufactured by Fuso Chemical Industries, Ltd.) , Dispersion medium: IPA, silica particle content 25.1 wt%) 57.41 g, DAA 133.80 g (initial monomer concentration = 35 wt%) were charged and stirred at room temperature with water 22.66 g phosphoric acid 0.386 g Add the phosphoric acid aqueous solution (0.45% by weight with respect to the charged monomer) over 10 minutes. The pressure was. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (PS-13). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 74.5 g of methanol and water as by-products were distilled out. The resulting polysiloxane solution (PS-13) had a solid content concentration of 34% by weight.

Synthesis Example 14 Synthesis of Polysiloxane Solution (PS-14) 65.83 g (0.256 mol) of 1-naphthyltrimethoxysilane and 12.09 g (0.053 mol) of 4-methoxyphenyltrimethoxysilane in a 500 ml three-necked flask 6.95 g (0.027 mol) of 3-trimethoxysilylpropyl succinic anhydride, 25.27 g (0.186 mol) of methyltrimethoxysilane, “Quartrone” PL-2L-IPA (manufactured by Fuso Chemical Industries, Ltd.) , Dispersion medium: IPA, silica particle content 25.1 wt%) 15.52 g, DAA 144.74 g (initial monomer concentration = 35 wt%) were charged and stirred at room temperature with 29.10 g water 0.496 g phosphoric acid Add 10% aqueous phosphoric acid solution (0.45% by weight of charged monomer) It was added. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (PS-14). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 61.0 g of methanol and water as by-products were distilled. The solid content concentration of the obtained polysiloxane solution (PS-14) was 34% by weight.

Synthesis Example 15 Synthesis of Polysiloxane Solution (PS-15) In a 500 ml three-necked flask, 33.22 g (0.244 mol) of methyltrimethoxysilane, 89.81 g (0.453 mol) of phenyltrimethoxysilane, and 139.DAA were added. 19 g (initial monomer concentration = 35 wt%) was charged, and an aqueous phosphoric acid solution in which 0.149 g of phosphoric acid (0.45 wt% with respect to the charged monomer) was dissolved in 37.64 g of water was added over 10 minutes while stirring at room temperature. did. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (PS-15). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 92.6 g of methanol and water as by-products were distilled. The resulting polysiloxane solution (PS-15) had a solid content concentration of 36% by weight.

Synthesis Example 16 Synthesis of Polysiloxane Solution (PS-16) In a 500 ml three-necked flask, 20.44 g (0.15 mol) of methyltrimethoxysilane, 55.26 g (0.279 mol) of phenyltrimethoxysilane, “Quatron” PL-2L-IPA (manufactured by Fuso Chemical Co., Ltd., dispersion medium: IPA, silica particle content 25.1 wt%) was charged with 78.73 g, DAA 122.34 g (initial monomer concentration = 35 wt%), and stirred at room temperature. Then, an aqueous phosphoric acid solution in which 0.092 g of phosphoric acid (0.45% by weight based on the charged monomers) was dissolved in 23.15 g of water was added over 10 minutes. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (PS-16). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 110.2 g of methanol and water as by-products were distilled. The solid content concentration of the obtained polysiloxane solution (PS-16) was 35% by weight.

Synthesis Example 17 Synthesis of Polysiloxane Solution (PS-17) In a 500 ml three-necked flask, 5.45 g (0.021 mol) of 3-trimethoxysilylpropyl succinic anhydride and 19.81 g (0.145 mol) of methyltrimethoxysilane were added. ), 40.45 g (0.249 mol) of phenyltrimethoxysilane, 79.24 g of “Quartron” PL-2L-IPA (manufactured by Fuso Chemical Industries, Ltd., dispersion medium: IPA, silica particle content 25.1 wt%) A solution of phosphoric acid prepared by dissolving 123.12 g of DAA (initial monomer concentration = 35 wt%) and dissolving 0.114 g of phosphoric acid (0.45 wt% with respect to the charged monomer) in 22.82 g of water while stirring at room temperature. Added over 10 minutes. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (PS-17). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 105.2 g of methanol and water as by-products were distilled out. The resulting polysiloxane solution (PS-17) had a solid content concentration of 34% by weight.

Synthesis Example 18 Synthesis of Polysiloxane Solution (PS-18) In a 500 ml three-necked flask, 9.27 g (0.041 mol) of 4-methoxyphenyltrimethoxysilane and 5.33 g of 3-trimethoxysilylpropyl succinic anhydride ( 0.020 mol), 19.38 g (0.142 mol) of methyltrimethoxysilane, 40.31 g (0.203 mol) of phenyltrimethoxysilane, “Quatron” PL-2L-IPA (manufactured by Fuso Chemical Industries, Ltd., dispersion) Medium: 79.58 g of IPA, silica particle content 25.1 wt%) and 123.65 g DAA (initial monomer concentration = 35 wt%) were charged, and 0.153 g phosphoric acid (charged) was added to 22.32 g of water while stirring at room temperature. Add phosphoric acid aqueous solution dissolved in 0.45% by weight to monomer over 10 minutes It was. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (PS-18). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 100.9 g of methanol and water as by-products were distilled. The resulting polysiloxane solution (PS-18) had a solid content concentration of 36% by weight.

Synthesis Example 19 Synthesis of Polysiloxane Solution (PS-19) In a 500 ml three-necked flask, 43.49 g (0.175 mol) of 1-naphthyltrimethoxysilane and 4.59 g of 3-trimethoxysilylpropyl succinic anhydride (0 .018 mol), 16.70 g (0.123 mol) of methyltrimethoxysilane, 6.95 g (0.035 mol) of phenyltrimethoxysilane, “Quatron” PL-2L-IPA (manufactured by Fuso Chemical Industries, Ltd., dispersion medium : 81.74 g of IPA, silica particle content 25.1 wt%) and 127.01 g DAA (initial monomer concentration = 35 wt%) were charged, and 0.292 g phosphoric acid (charged monomer) was added to 19.23 g of water while stirring at room temperature. The phosphoric acid aqueous solution in which 0.45% by weight) was dissolved was added over 10 minutes. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (PS-19). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 84.6 g of methanol and water as by-products were distilled out. The resulting polysiloxane solution (PS-19) had a solid content concentration of 34% by weight.

Synthesis Example 20 Synthesis of quinonediazide compound (QD-1) Under dry nitrogen stream, Ph-cc-AP-MF (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 15.32 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl 37.62 g (0.14 mol) of acid chloride was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (QD-1) having the following structure.

Example 1
22.32 g of the polysiloxane solution (PS-01) obtained in Synthesis Example 1, 2.68 g of the quinonediazide compound (QD-1) obtained in Synthesis Example 20, 52.50 g of DAA as a solvent, and 22.5 g of PGMEA under a yellow light The mixture was mixed and stirred to obtain a uniform solution, and then filtered through a 0.20 μm filter to prepare Composition 1.

  After spin-coating the composition 1 on a 2-inch sapphire substrate using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) at an arbitrary rotation number, a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) is used. And prebaked at 100 ° C. for 2 minutes to prepare a film having a thickness of 1.0 μm. Using the parallel light mask aligner (hereinafter abbreviated as PLA) (PLA-501F manufactured by Canon Inc.), the ultra-high pressure mercury lamp was converted into a gray scale mask and a dot pattern mask for sensitivity measurement (dot pattern mask). The diameter of the dot pattern is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20 μm), and then an automatic developing device (manufactured by Takizawa Sangyo Co., Ltd.). AD-2000) was used for paddle development with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds, followed by rinsing with water for 30 seconds. Then, it cured at 230 degreeC for 30 minute (s) in air atmosphere using oven, and also baked at 1000 degreeC for 1 hour under air atmosphere using the baking furnace, and produced the hardening pattern.

  Table 2 shows the evaluation results of photosensitive characteristics and cured film characteristics (resolution after development, resolution after baking). Evaluation in the table was performed by the following method. The following (1) was evaluated using a gray scale mask for sensitivity measurement, and (2) to (3) were evaluated using a dot pattern mask.

(1) Calculation of photosensitivity After exposure and development, an exposure amount (hereinafter referred to as a 10 μm line-and-space remaining pattern (line pattern) and a blank pattern (space pattern) can be formed in a one-to-one width. This is called the optimum exposure amount).

(2) Calculation of post-development resolution The minimum post-development resolution is the minimum pattern dimension that can form a dot pattern without peeling after development at the optimum exposure amount.

(3) Calculation of post-baking resolution In the optimum exposure amount, the minimum pattern size that can maintain the dot pattern independently after baking was defined as the post-baking resolution.

Examples 2-14, Comparative Examples 1-5
Compositions 2 to 19 were prepared in the same manner as in Example 1 except that PS-02 to PS-19 were used instead of PS-01. The composition is shown in Table 1. Each composition was evaluated in the same manner as in Example 1 using each obtained composition. The results are shown in Table 2.

Claims (12)

(A) a polysiloxane synthesized by hydrolyzing and condensing an organosilane containing a silane compound represented by the following general formula (1) and a silane compound represented by the following general formula (2), (b) A positive photosensitive resin composition comprising a naphthoquinonediazide compound and (c) a solvent.

(In General Formula (1), R ¹ represents a condensed polycyclic aromatic hydrocarbon group. R ² represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or 6 carbon atoms. Represents an aryl group of ˜16, n represents an integer of 1 to 3. When n is 2 or 3, a plurality of R ^{1 s} may be the same or different from each other. ² may be the same or different.

(In General Formula (2), R ³ represents an alkyl group having 1 to 10 carbon atoms. R ⁴ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or 6 to 16 carbon atoms. M represents an integer of 1 to 3. When m is 2 or 3, the plurality of R ³ may be the same or different, and when m is 1 or 2, the plurality of R ⁴ are Each may be the same or different.) 2. The positive photosensitive resin composition according to claim 1, wherein the polysiloxane (a) is a polysiloxane synthesized by hydrolysis and condensation in the presence of (d) inorganic fine particles. The polysiloxane (a) is a polysiloxane synthesized by further hydrolyzing and condensing an organosilane containing a silane compound represented by the following general formula (3). The positive photosensitive resin composition as described.

(In general formula (3), R ⁵ represents a group in which a hydrogen atom of an alkyl group, oxyalkyl group, alkenyl group or monocyclic aryl group is substituted with a carboxyl group or a dicarboxylic anhydride group. R ⁶ represents Represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms, l represents an integer of 1 to 3. And R ⁵ may be the same or different, and when l is 1 or 2, the plurality of R ⁶ may be the same or different.) (A) The content ratio of the silane compound represented by the general formula (1) in the organosilane used for the synthesis of the polysiloxane is 5% or more and 90% or less with respect to the number of moles of Si atoms in the whole organosilane. The positive photosensitive resin composition according to any one of claims 1 to 3. (A) The content ratio of the silane compound represented by the general formula (2) in the organosilane used for the synthesis of polysiloxane is 5% or more and 80% or less with respect to the number of moles of Si atoms in the whole organosilane. The positive photosensitive resin composition as claimed in claim 1, wherein the positive photosensitive resin composition is a resin composition. The positive photosensitive resin composition according to claim 1, wherein R ³ in the general formula (2) in (a) polysiloxane is a methyl group or an ethyl group. (D) The positive photosensitive resin composition according to any one of claims 2 to 6, wherein the inorganic particles are silica particles or titanium oxide particles, and the number average particle diameter thereof is 1 to 200 nm. The positive photosensitive composition according to any one of claims 2 to 7, wherein the content of (d) inorganic fine particles is 1 part by weight or more and 200 parts by weight or less with respect to 100 parts by weight of (a) polysiloxane. Resin composition. The positive photosensitive resin composition according to claim 1, wherein silicon (Si), sapphire (Al ₂ O ₃ ), gallium nitride (GaN), silicon carbide (SiC), gallium arsenide (GaAs) ) Or aluminum nitride (AlN) substrate and patterning, followed by baking. The method for producing a cured pattern according to claim 9, wherein the baking treatment is performed at 600 to 1700 ° C. A convex pattern substrate obtained by etching a cured pattern obtained by the method for producing a cured pattern according to claim 9. One or more layers selected from a GaN layer, an AlN layer, and an InN layer were formed on the cured pattern obtained by the method for producing a cured pattern according to claim 9 or 10 or the convex pattern substrate according to claim 11. Light emitting element.