JP2008202033A - Siloxane-based resin composition, optical device using the same and method for preparing siloxane-based resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a siloxane-based resin composition capable of formimg a cured film high in refractive index and in visible light transmission, and excellent in crack resistance after a thermal load. <P>SOLUTION: The resin composition contains a condensation product and a thermally crosslinkable compound represented by general formula (1) or (3), wherein, the former is prepared by acid catalyzed hydrolysis of an alkoxysilane compound in the presence of particles of a compound of at least one sort of metal selected from aluminium, tin, titanium, and zirconium in a solvent, and by successive condensation reaction. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a siloxane-based resin composition and an optical device. The siloxane-based resin composition of the present invention is suitably used for optical devices such as solid-state imaging devices, antireflection films, antireflection plates, optical filters, and displays.

  In recent years, with the rapid development of digital cameras, camera-equipped mobile phones, and the like, there has been a demand for downsizing and increasing the number of pixels of solid-state imaging devices. Since downsizing of the solid-state imaging device causes a decrease in sensitivity, a condensing lens is disposed between the light receiving unit and the color filter or above the color filter to efficiently collect light and prevent a decrease in sensitivity. As a general manufacturing method of this condensing lens, there are a method of processing an inorganic film formed by a CVD method or the like by dry etching, and a method of applying and processing a resin. The former method is currently attracting attention because it is difficult to obtain a refractive index of 1.70 to 1.90 optimum for a lens.

  For example, a curable composition containing a hydroxyl group-containing resin such as polyvinyl butyral resin, titanium oxide particles, a curable compound, and a curing catalyst is disclosed (for example, see Patent Document 1). In this method, although a cured film having a high refractive index can be obtained, it is difficult to obtain a film thickness of 1 μm or more optimum for a lens because the viscosity is not sufficiently high. Further, when the viscosity is increased, there is a problem that when the dispersibility between the particles and the resin is not sufficient, the particles are aggregated to become a foreign substance, and the transmittance is reduced when the film thickness is 1 μm or more.

  Further, a positive photosensitive resin composition containing an alkali-soluble polymer, a compound having a phenolic hydroxyl group, an esterified quinonediazide compound, and metal particles is disclosed (for example, see Patent Document 2). In this method, particularly when the film thickness exceeds 1 μm, the transmittance is lowered, and a sufficient film for use in an optical element cannot be obtained. Furthermore, if the film thickness of the coating film is increased in order to increase the lens height, it is difficult to obtain a coating film with a uniform film thickness, and there is a problem that the film is likely to crack due to heat shrinkage during curing. there were.

In addition, a coating agent used for an antireflection film or the like needs to arbitrarily control a refractive index and a film thickness while maintaining a high transmittance, but obtains a desired refractive index and film properties while maintaining the transmittance. It is difficult. For example, Patent Document 3 discloses a photosensitive siloxane composition having a high heat resistance and a high chemical resistance, comprising a polysiloxane, a quinonediazide compound, a solvent, and a thermally crosslinkable compound, but has a high refractive index of about 1.7. It is difficult to obtain a cured film having. Further, Patent Document 4 discloses a coating material containing organosilane, siloxane oligomer, and metal oxide fine particles, but it is inevitable that the viscosity increases due to the aggregation of the metal oxide fine particles and an increase in fine foreign matters. In addition, depending on the structure of the siloxane oligomer, the cured film may become cloudy and the visible light transmittance may be greatly reduced, so that the above-mentioned characteristics are not obtained.
JP 2004-169018 A JP 2003-75997 A JP 2006-293337 A JP 2001-81404 A

  In particular, in a vehicle-mounted application that requires high reliability, a solid-state imaging device having high resistance to a heat load such as a heat cycle is required. For this reason, an antireflection film and a lens forming material excellent in crack resistance after thermal load are demanded.

  An object of the present invention is to provide a siloxane-based resin composition capable of forming a cured film having a high refractive index, a high visible light transmittance, and excellent crack resistance after thermal load.

  In the present invention, an alkoxysilane compound is hydrolyzed with an acid catalyst in a solvent in the presence of at least one metal compound particle selected from the group consisting of aluminum compound particles, tin compound particles, titanium compound particles, and zirconium compound particles. A reaction product obtained by condensation reaction of the hydrolyzate, a thermally crosslinkable compound having a heat crosslinkable group represented by the following general formula (1), or a heat crosslinkable compound represented by the following general formula (3) It is a siloxane-type resin composition characterized by containing.

In general formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In General Formula (3), R ⁸ and R ⁹ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a substituted product thereof. However, at least one of p R ⁸ and R ⁹ is a phenyl group or a substituted product thereof. p represents an integer of 4 or more and 20 or less.

  Moreover, this invention is an optical device which has a cured film formed by hardening | curing the said siloxane resin composition.

  In the present invention, an alkoxysilane compound is hydrolyzed with an acid catalyst in a solvent in the presence of at least one metal compound particle selected from the group consisting of aluminum compound particles, tin compound particles, titanium compound particles, and zirconium compound particles. After decomposing and subjecting the hydrolyzate to a condensation reaction, a thermally crosslinkable compound having a heat crosslinkable group represented by the general formula (1) or a heat crosslinkable compound represented by the general formula (3) is obtained. It is the manufacturing method of the siloxane type resin composition characterized by adding.

  According to the siloxane-based resin composition of the present invention, a cured film having a high refractive index, a high visible light transmittance, and excellent crack resistance after repeated thermal load can be formed. The obtained cured film can be suitably used particularly for a hard coat layer such as an antireflection film or an antireflection plate, a microlens of a solid-state imaging device, or the like.

  The present invention will be specifically described below.

  The siloxane-based resin composition of the present invention contains an alkoxysilane compound in a solvent in the presence of at least one metal compound particle selected from the group consisting of aluminum compound particles, tin compound particles, titanium compound particles, and zirconium compound particles. Hydrolysis by an acid catalyst and condensation reaction of the hydrolyzate, and a thermally crosslinkable compound having a thermally crosslinkable group represented by the following general formula (1) or the following general formula (3) The heat-crosslinkable compound is contained. By containing such a thermally crosslinkable compound, when the siloxane-based resin composition of the present invention is cured, the hydrolysis / condensation reaction product (siloxane compound) of the alkoxysilane compound as the matrix material and the metal compound particles are formed. Bonded firmly, high heat cycle properties can be obtained, and a cured film excellent in crack resistance and mechanical strength after repeated thermal load can be formed. Both of the above-mentioned heat crosslinkable compounds may be contained, or any one of the heat crosslinkable compounds may be contained.

In general formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In General Formula (3), R ⁸ and R ⁹ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a substituted product thereof. However, at least one of p R ⁸ and R ⁹ is a phenyl group or a substituted product thereof. p represents an integer of 4 or more and 20 or less.

  The heat-crosslinkable compound having the heat-crosslinkable group represented by the general formula (1) (hereinafter sometimes referred to as the heat-crosslinkable compound (1)) is not particularly limited, but the transmittance is further improved. The thing which has a heat crosslinkable group represented by following General formula (2) by the point which can be made to be preferable.

In general formula (2), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Specific examples of R ¹ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, and a butyl group. From the viewpoint of the temporal stability of the resin composition and the reactivity of the thermally crosslinkable compound, a methyl group, an ethyl group, and the like. Is preferred.

  Moreover, the said heat crosslinkable compound (1) has a preferable thing which does not contain a phenolic hydroxyl group from a viewpoint of the transmittance | permeability of a cured film. This effect is particularly prominent when the resin composition is cured by heat treatment at a high temperature of 280 ° C. or higher.

  Specific examples of the thermally crosslinkable compound (1) in the present invention are shown below.

  Among these, “NIKALAC” (registered trademark) MX-290, “NIKALAC” (registered trademark) MX-280, “NIKACALAC” (registered trademark) MX- having a thermally crosslinkable group represented by the general formula (2) 270 (above, trade name, manufactured by Sanwa Chemical Co., Ltd.) is preferable because it can further improve the transmittance.

  The heat-crosslinkable compound represented by the following general formula (3) (hereinafter sometimes referred to as the heat-crosslinkable compound (3)) may further improve the transmittance in addition to the crack resistance after repeated thermal loads. This is preferable because it is possible. Since the thermally crosslinkable compound (3) has a phenyl group, the transmittance can be further improved while keeping the refractive index of the resulting composition high. Further, by containing the thermally crosslinkable compound (3), unlike the case of containing a reaction product obtained by condensation reaction of the compound, the thermally crosslinkable compound (3) undergoes a curing reaction during the heat treatment of the composition. Further, the crack resistance after repeated heat load can be improved.

In General Formula (3), R ⁸ and R ⁹ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a substituted product thereof. However, at least one of p R ⁸ and R ⁹ is a phenyl group or a substituted product thereof. p represents an integer of 4 or more and 20 or less. Examples of the substituent of the alkyl group or phenyl group include CF ₃ group, CH ₂ CF ₃ group, C ₂ H ₄ CF ₃ group, C ₆ H ₄ CH ₃ group, C ₆ H ₄ t-Bu group and the like. Can be mentioned. From the viewpoint of improving the refractive index and further improving the crack resistance, R ⁸ and R ⁹ are preferably a methyl group or a phenyl group. Specific examples of the thermally crosslinkable compound (3) in the present invention are shown below.

Among the thermally crosslinkable compounds represented by the general formula (3), when the molar ratio of the alkyl group to the phenyl group in R ⁸ and R ⁹ (alkyl group / phenyl group) is 0 to 1, the transmittance and crack resistance It is preferable because the properties can be further improved. Specifically, S-3, S-4, S-11, S-12, S-13, S-14, and S-15 are preferable.

  The thermally crosslinkable compound (1) is an organic compound having no silicon atom, and the effect of improving crack resistance appears remarkably even if the content is small. In the present invention, the content of the thermally crosslinkable compound (1) is preferably 0.1% by weight or more, and more preferably 0.5% by weight or more, based on the total solid content in the siloxane-based resin composition. Moreover, 20 weight% or less is preferable and 10 weight% or less is more preferable. If it is this range, the oxidative degradation of the heat crosslinkable compound by heat processing can be suppressed, and the transmittance | permeability and refractive index can be maintained at a higher level. On the other hand, the thermally crosslinkable compound (3) is a compound having a silicon atom, and is preferably contained in a larger amount than the thermally crosslinkable compound (1). Specifically, it is preferably 10% by weight or more, more preferably 20% by weight or more, based on the total amount of solid content in the siloxane-based resin composition. By containing 10% by weight or more, crack resistance can be further improved. Moreover, 50 weight% or less is preferable and 40 weight% or less is more preferable.

  When the thermally crosslinkable compound (1) and the thermally crosslinkable compound (3) are used in combination, the total content thereof is preferably 10% by weight or more with respect to the total solid content in the siloxane-based resin composition, and is 20% by weight. The above is more preferable. Moreover, 40 weight% or less is more preferable. In this case, the content of the thermally crosslinkable compound (1) is preferably 0.1% by weight or more, and more preferably 0.5% by weight or more with respect to the total solid content in the siloxane-based resin composition. Moreover, 20 weight% or less is preferable and 10 weight% or less is more preferable.

  The metal compound particles used in the present invention are at least one selected from the group consisting of aluminum compound particles, tin compound particles, titanium compound particles, and zirconium compound particles. Examples of the metal compound particles include aluminum, tin, titanium or zirconium oxides, sulfides and hydroxides. Of these, zirconium oxide particles and / or titanium oxide particles are preferably used from the viewpoint of adjusting the refractive index of the coating film and the cured film. Moreover, in order to make it easy to react with the hydrolysis / condensation reaction product of the alkoxysilane compound forming the matrix, the metal compound particle having a reactive group capable of reacting with the hydrolysis / condensation reaction product of the alkoxysilane compound such as a hydroxyl group on the surface. Is preferred.

  As an example of the metal compound particles, commercially available inorganic particles include tin oxide-titanium oxide composite particles “OPTRAIK” (registered trademark) TR-502, “OPTRAIK” (registered trademark) TR-504, oxidation Silicon-titanium oxide composite particles “OPTRAIK” (registered trademark) TR-503, “OPTRAIK” (registered trademark) TR-513, “OPTRAIK” (registered trademark) TR-520, “OPTRAIK” (registered trademark) ) TR-527, “Optlake” (registered trademark) TR-528, “Optlake” (registered trademark) TR-529, “Optlake” (registered trademark) TR-505 of titanium oxide particles (above, trade name, Catalyst Chemical Industry Co., Ltd.), zirconium oxide particles (manufactured by High Purity Chemical Laboratory Co., Ltd.), tin oxide-zirconium oxide composite particles (catalyst chemical industry Co., Ltd.), acid Tin particles (Co. Kojundo Chemical Laboratory), and the like. These inorganic particles have a hydroxyl group on the surface and have good reactivity with the hydrolysis / condensation reaction product of the alkoxysilane compound forming the matrix.

  The number average particle diameter of the metal compound particles is preferably 1 nm to 200 nm. By setting the number average particle diameter to 1 nm or more, cracks are less likely to occur during thick film formation. Moreover, a film | membrane more transparent with respect to visible light is obtained by setting it as a number average particle diameter of 200 nm or less. In order to achieve both of these, the number average particle diameter is more preferably 1 nm to 70 nm. Here, the number average particle size of the metal compound particles is 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 using a transmission electron microscope or a scanning electron microscope, and the like. be able to.

  The content of the metal compound particles in the siloxane-based resin composition of the present invention is preferably 5% by weight or more, and more preferably 20% by weight or more based on the total solid content excluding the solvent. Moreover, 80 weight% or less is preferable and 70 weight% or less is more preferable. Within this range, a film having better transmittance and crack resistance after repeated thermal loading can be obtained.

  The siloxane-based resin composition of the present invention is formed by hydrolyzing an alkoxysilane compound in a solvent with an acid catalyst in the presence of the metal compound particles to form a silanol compound and then subjecting the silanol compound to a condensation reaction. Contains the reaction product that can be obtained. As the alkoxysilane compound, one or more alkoxysilane compounds selected from the alkoxysilane compounds represented by the following general formulas (4) to (6) are preferable.

R ² Si (OR ⁵ ) ₃ (4)
R ² represents hydrogen, an alkyl group, an alkenyl group, an aryl group, or a substituted product thereof. From the viewpoint of crack resistance at the time of thick film formation, it is preferable to use an alkoxysilane compound having a phenyl group as R ^2. R ⁵ represents a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group, and may be the same or different. R ⁵ is more preferably a methyl group or an ethyl group.

R ³ R ⁴ Si (OR ⁶ ) ₂ (5)
R ³ and R ⁴ each represent hydrogen, an alkyl group, an alkenyl group, an aryl group, or a substituted product thereof. R ⁶ represents a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and may be the same or different. R ⁶ is more preferably a methyl group or an ethyl group.

Si (OR ⁷ ) ₄ (6)
R ⁷ represents a methyl group or an ethyl group, and may be the same or different.

  Specific examples of the alkoxysilane compound represented by any one of the general formulas (4) to (6) are shown below.

  Examples of the trifunctional alkoxysilane compound represented by the general formula (4) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, and ethyltrimethoxysilane. , Ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, 3-aminopropyltriethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, 3-glycidoxysilane Rutrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- β- (aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α- Glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane , Β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxy Silane, γ-glycidoxypropyl triisopropoxy silane, γ-glycidoxypropyl tributoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyl Trimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyl Triethoxysilane, (3,4-epoxy Cyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltripropoxysilane, 2- (3,4-epoxycyclohexyl) ethyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrie Xysilane, 4- (3,4-epoxycyclohexyl) butyltrimethoxysilane, 4- (3,4-epoxycyclohexyl) butyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltri Methoxysilane, trifluoropropyltriethoxysilane, perfluoropropylethyltrimethoxysilane, perfluoropropylethyltriethoxysilane, perfluoropentylethyltrimethoxysilane, perfluoropentylethyltriethoxysilane, tridecafluorooctyltrimethoxysilane, Tridecafluorooctyltriethoxysilane, tridecafluorooctyltripropoxysilane, tridecafluorooctyltripropoxysilane, Examples include butadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane. Of these, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane are preferred from the viewpoint of crack resistance of the resulting coating film.

  Examples of the bifunctional alkoxysilane compound represented by the general formula (5) include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, and methylvinyl. Diethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, γ- Methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycid Cyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α- Glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane Γ-glycidoxypropylmethyldipropoxysilane, β-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropioxy Vinyldimethoxysilane, γ-glycidoxypropyl vinyldiethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, trifluoropropylvinyldimethoxy Examples include silane, trifluoropropylvinyldiethoxysilane, heptadecafluorodecylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, and octadecylmethyldimethoxysilane. Among these, dimethyl dialkoxysilane is preferably used for the purpose of imparting flexibility to the resulting coating film.

  Examples of the tetrafunctional alkoxysilane compound represented by the general formula (6) include tetramethoxysilane and tetraethoxysilane.

  The alkoxysilane compound represented by any one of these general formulas (4) to (6) may be used alone or in combination of two or more.

  The content of the component derived from the hydrolysis / condensation reaction product (siloxane compound) of the alkoxysilane compound in the siloxane-based resin composition is preferably 10% by weight or more, more preferably 20% by weight or more based on the total solid content excluding the solvent. Is more preferable. Moreover, 80 weight% or less is more preferable. By containing the siloxane compound within this range, the transmittance and crack resistance of the coating film can be further increased.

  The hydrolysis reaction is preferably performed at room temperature to 110 ° C. for 1 to 180 minutes after an acid catalyst and water are added to the above alkoxysilane compound in a solvent over 1 to 180 minutes. By performing the hydrolysis reaction under such conditions, a rapid reaction can be suppressed. The reaction temperature is more preferably 40 to 105 ° C.

  Moreover, after obtaining a silanol compound by a hydrolysis reaction, it is preferable to heat the reaction liquid at 50 ° C. or higher and below the boiling point of the solvent for 1 to 100 hours to perform a condensation reaction. In order to increase the degree of polymerization of the siloxane compound obtained by the condensation reaction, reheating or addition of a base catalyst can be performed.

  Various conditions in the hydrolysis can be obtained by considering the reaction scale, reaction vessel size, shape, etc., for example, by setting the acid concentration, reaction temperature, reaction time, etc., and obtaining physical properties suitable for the intended application. Can do.

  Examples of the acid catalyst used in the hydrolysis reaction include acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid or anhydrides thereof, and ion exchange resins. In particular, an acidic aqueous solution using formic acid, acetic acid or phosphoric acid is preferred.

  The preferred content of these acid catalysts is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, with respect to 100 parts by weight of the total alkoxysilane compound used during the hydrolysis reaction. Further, it is preferably 10 parts by weight or less, more preferably 5 parts by weight or less. Here, the total amount of the alkoxysilane compound means an amount including all of the alkoxysilane compound, its hydrolyzate and its condensate, and the same shall apply hereinafter. When the amount of the acid catalyst is 0.05 parts by weight or more, hydrolysis proceeds smoothly, and when the amount is 10 parts by weight or less, the hydrolysis reaction is easily controlled.

  The solvent is not particularly limited, but is appropriately selected in consideration of the stability, wettability, volatility, etc. of the siloxane-based resin composition. Not only one type of solvent but also two or more types can be used. Specific examples of the solvent include, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl- Alcohols such as 3-methoxy-1-butanol and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, Ethers such as lenglycol diethyl ether, ethylene glycol dibutyl ether and diethyl ether; ketones such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone and 2-heptanone; dimethylformamide Amides such as dimethylacetamide; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, lactic acid Acetates such as methyl, ethyl lactate and butyl lactate; toluene, xylene, hexane, In addition to the aromatic or aliphatic hydrocarbons such as cyclohexane, .gamma.-butyrolactone, N- methyl-2-pyrrolidone, dimethyl sulfoxide and the like. Of these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t in terms of the transmittance of the cured film, crack resistance, etc. -Butyl ether, γ-butyrolactone and the like are preferably used. Moreover, it is also preferable to adjust to a suitable density | concentration as a resin composition by adding a solvent after completion | finish of a hydrolysis reaction. It is also possible to distill and remove all or part of the product alcohol etc. by heating and / or under reduced pressure after hydrolysis and then adding a suitable solvent.

  The amount of the solvent used in the hydrolysis reaction is preferably 50 parts by weight or more, more preferably 80 parts by weight or more, and preferably 500 parts by weight or less, based on 100 parts by weight of the total alkoxysilane compound. Preferably, it is 200 parts by weight or less. The production | generation of a gel can be suppressed by making the quantity of a solvent into 50 weight part or more. Moreover, a hydrolysis reaction advances rapidly by setting it as 500 parts weight or less.

  Moreover, as water used for a hydrolysis reaction, ion-exchange water is preferable. The amount of water can be arbitrarily selected, but it is preferably used in the range of 1.0 to 4.0 mol with respect to 1 mol of the alkoxysilane compound.

  In the siloxane-based resin composition of the present invention, a crosslinking agent or a curing agent other than the thermally-crosslinkable compound (1) and the thermally-crosslinkable compound (3) that accelerates the curing of the siloxane-based resin composition or facilitates the curing. An agent may be contained. Specific examples include silicone resin curing agents, various metal alcoholates, various metal chelate compounds, isocyanate compounds and polymers thereof, polyfunctional acrylic resins, and the like, and these may be used alone or in combination of two or more.

  In the siloxane-based resin composition of the present invention, a solvent can be used so that the solid content has an appropriate concentration. Specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, Ethers such as ethylene glycol diethyl ether and ethylene glycol dibutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl Acetate, methyl lactate, lactate , Acetates such as butyl lactate, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, ketones such as 2-heptanone, methanol, ethanol, propanol, butanol, isobutyl alcohol, pentanol, 4 Alcohols such as methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, diacetone alcohol, aromatic hydrocarbons such as toluene and xylene, γ-butyrolactone , N-methylpyrrolidinone and the like. These may be used alone or in combination. Among these, examples of particularly preferred solvents are propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, diacetone alcohol. , Γ-butyrolactone and the like. These may be used alone or in combination of two or more.

  The content of the total solvent in the siloxane-based resin composition of the present invention is preferably in the range of 100 parts by weight to 9900 parts by weight, more preferably 100 parts by weight to 5000 parts with respect to 100 parts by weight of the total alkoxysilane compound content. The range is parts by weight.

  The siloxane-based resin composition of the present invention may contain various surfactants in order to improve flow properties and film thickness uniformity during coating. There is no restriction | limiting in particular in the kind of surfactant, For example, a fluorine-type surfactant, a silicone type surfactant, a polyalkylene oxide type surfactant, a poly (meth) acrylate type surfactant etc. can be used. Of these, fluorine surfactants are particularly preferably used from the viewpoints of flowability and film thickness uniformity.

  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 “Megafac” (registered trademark) F142D, F172, F173, F183 (manufactured by Dainippon Ink and Chemicals), “Ftop” (registered trademark) EF301, 303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.), "Florard" FC-430, FC-431 (manufactured by Sumitomo 3M), "Asahi Guard" (registered trademark) AG710, "Surflon" (registered trademark) ) S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), "BM-1000", "BM" -1100 "(manufactured by Yusho Co., Ltd.)," NBX-15 ", and" FTX-218 "(manufactured by Neos Co., Ltd.). Among these, the above-mentioned “Megafuck” (registered trademark) F172, “BM-1000”, “BM-1100”, “NBX-15”, “FTX-218” are particularly preferable from the viewpoint of flowability and film thickness uniformity. preferable.

  Commercially available silicone surfactants include “SH28PA”, “SH7PA”, “SH21PA”, “SH30PA”, “ST94PA” (all manufactured by Toray Dow Corning Silicone Co., Ltd.), “BYK-333”. (Bic Chemie Japan Co., Ltd.). Examples of other surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene distearate and the like.

  The content of the surfactant is usually 0.001 to 10 parts by weight with respect to 100 parts by weight of the total alkoxysilane compound content in the siloxane-based resin composition. These may be used alone or in combination of two or more.

  The siloxane-based resin composition of the present invention can contain a viscosity modifier, a stabilizer, a colorant, a vitreous forming agent, and the like as necessary.

  Moreover, in order to provide photosensitivity to the siloxane-type resin composition of this invention, you may contain various photosensitive agents. For example, when a quinonediazide photosensitizer is contained, a positive relief pattern can be obtained by dissolving the exposed portion with an alkaline aqueous solution such as an aqueous tetramethylammonium hydroxide solution. Moreover, negative photosensitivity can be provided by containing a photocrosslinking agent or a photoacid generator.

  As the quinonediazide-based photosensitizer, a compound in which a sulfonic acid of naphthoquinonediazide is bonded with an ester to a compound having a phenolic hydroxyl group is preferable. Examples of the compound having a phenolic hydroxyl group used here include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ. BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (Tetrakis P-DO-BPA), TrisP -HAP, TrisP-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOC P-OC, Bis236T-OCHP, Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR -PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), 4,4'-sulfonyldiphenol (Manufactured by Wako Pure Chemical Industries, Ltd.) and BPFL (trade name, manufactured by JFE Chemical Co., Ltd.).

  Among these, preferable compounds having a phenolic hydroxyl group include, for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR- BIPC-F, 4,4′-sulfonyldiphenol, BPFL. Preferred examples of the quinonediazide-based photosensitizer include those in which 4-naphthoquinonediazidesulfonic acid or 5-naphthoquinonediazidesulfonic acid is introduced into the compound having a phenolic hydroxyl group by an ester bond, but other compounds are used. You can also.

  The content of the quinonediazide photosensitizer is preferably 1 part by weight or more and more preferably 2 parts by weight or more with respect to 100 parts by weight of the siloxane compound. Moreover, 50 weight part or less is preferable and 10 weight part or less is more preferable. By setting the content of the quinonediazide photosensitizer to 1 part by weight or more, pattern formation can be performed with practical sensitivity. Moreover, the resin composition excellent in the transmittance | permeability and pattern resolution is obtained by setting it as 50 weight part or less.

  The molecular weight of the preferred quinonediazide photosensitizer is 300 or more, more preferably 350 or more, and 1000 or less, more preferably 800 or less. When the molecular weight is 300 or more, an effect of inhibiting dissolution of unexposed portions is obtained, and when the molecular weight is 1000 or less, a good relief pattern free from scum or the like is obtained.

  When a quinonediazide photosensitizer is contained, an unreacted photosensitizer remains in the unexposed area, and the film may be colored after heat curing. In order to obtain a transparent cured film, it is preferable to irradiate the entire surface of the developed film with ultraviolet rays to decompose the quinonediazide-based photosensitizer, followed by heat curing.

  Examples of photoacid generators include onium salt compounds, halogen-containing compounds, diazoketone compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and sulfonimide compounds.

  Specific examples of the onium salt compounds include diazonium salts, ammonium salts, iodonium salts, sulfonium salts, phosphonium salts, oxonium salts and the like. Preferred onium salts include diphenyliodonium triflate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, (hydroxyphenyl) benzylmethylsulfonium toluenesulfonate Etc.

  Specific examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Preferred halogen-containing compounds include 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, and 2-naphthyl-4,6. -Bis (trichloromethyl) -s-triazine and the like can be mentioned.

  Specific examples of the diazoketone compound include 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and the like. Preferred diazo ketone compounds are esters of 1,2-naphthoquinonediazido-4-sulfonic acid and 2,2,3,4,4′-tetrahydroxybenzophenone, 1,2-naphthoquinonediazide-4-sulfonic acid and 1,1, Examples thereof include esters with 1-tris (4-hydroxyphenyl) ethane.

  Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, and bis (2,4-xylyl). Sulfonyl) diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl ( And benzoyl) diazomethane.

  Specific examples of the sulfone compound include β-ketosulfone compounds and β-sulfonylsulfone compounds. Preferred compounds include 4-trisphenacyl sulfone, mesityl phenacyl sulfone, bis (phenylsulfonyl) methane, and the like.

  Examples of the sulfonate compound include alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, imino sulfonate, and the like. Specific examples of the sulfonic acid compound include benzoin tosylate, pyrogallol trimesylate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, and the like.

  Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethyl). Sulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5 Ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (trifluoromethylsulfonyl) Oxy) naphthyl dicarboxylimide, N- (camphorsulfur Nyloxy) succinimide, N- (camphorsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyl Imido, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] Heptane-5,6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) naphthyl dicarboxylimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) Phthalimide, N- (4-methylpheny Sulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) -7 -Oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy- 2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide N- (2-trifluoromethylphenylsulfonyloxy) diphe Nilmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy)- 7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6 -Oxy-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (2-fluorophenylsulfonyloxy) Phthalimide, N- (4-fluorophenylsulfonyloxy) diphenylmale N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3- Examples thereof include dicarboxylimide and N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide.

  In addition, 5-norbornene-2,3-dicarboxyimidyl triflate (trade name “NDI-105” manufactured by Midori Chemical Co., Ltd.), 5-norbornene-2,3-dicarboxyimidyl tosylate (trade name “NDI”) -101 "Midori Chemical Co., Ltd.), 4-methylphenylsulfonyloxyimino-α- (4-methoxyphenyl) acetonitrile (trade name" PAI-101 "Midori Chemical Co., Ltd.), trifluoromethylsulfonyloxyimino -Α- (4-Methoxyphenyl) acetonitrile (trade name “PAI-105” manufactured by Midori Chemical Co., Ltd.), 9-camphorsulfonyloxyimino α-4-methoxyphenylacetonitrile (trade name “PAI-106” Midori Chemical ( 1,8-naphthalimidyl butane sulfonate (trade) Product name “NAI-1004” Midori Chemical Co., Ltd.), 1,8-Naphthalimidyl tosylate (trade name “NAI-101” Midori Chemical Co., Ltd.), 1,8-Naphthalimidyl triflate (Product name “NAI-105”) “Midori Chemical Co., Ltd.”, 1,8-naphthalimidyl nonafluorobutane sulfonate (trade name “NAI-109” Midori Chemical Co., Ltd.) and the like can also be mentioned as examples.

  These photoacid generators can be used alone or in combination of two or more. The content of the photoacid generator is generally 0.01 to 20 parts by weight with respect to 100 parts by weight of the siloxane compound.

  The siloxane-based resin composition of the present invention can be obtained by mixing the siloxane compound and the thermally crosslinkable compound. At this time, it may be diluted with an arbitrary solvent. Although there is no restriction | limiting in particular in mixing temperature, The range of 5-50 degreeC is preferable from the simplicity of operation.

  The siloxane-based resin composition of the present invention can be applied on a substrate to obtain a coating film, which can be dried and cured by heating to form a cured film.

  As a method for applying the siloxane-based resin composition in the present invention, microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, flow coating, and the like can be preferably used.

  The heat drying and curing conditions are appropriately selected according to the substrate to be applied and the resin composition, but are usually treated at a temperature of room temperature to 400 ° C. for 0.5 minutes to 240 minutes. It is preferable. A particularly preferable curing temperature is preferably 100 to 400 ° C, and more preferably 150 to 400 ° C.

  Although there is no restriction | limiting in particular in the film thickness of a coating film and a cured film, Generally it is in the range of 0.001-100 micrometers.

  The coating film and cured film formed from the siloxane-based resin composition of the present invention are suitably used for optical devices such as solid-state imaging devices, antireflection films, antireflection plates, optical filters, and displays. Specific examples of use include condensing microlenses formed on solid-state imaging devices, hard coat layers used for antireflection films and antireflection plates, flattening materials for display TFT substrates, liquid crystal displays and colors. Examples include a protective film for a filter, an optical waveguide, and a phase shifter. Since both high transparency and a relatively high refractive index can be achieved, it is particularly preferably used as a hard coat layer used for a microlens or an antireflection film formed on a solid-state imaging device. Further, it can be used as a buffer coat, an interlayer insulating film, and various protective films of a semiconductor device.

  Hereinafter, the present invention will be described with reference to examples and techniques, but the present invention is not limited to these examples. In addition, evaluation of the non-photosensitive resin composition in an Example was performed with the following method.

Preparation of cured film A siloxane-based resin composition is applied on a 6-inch silicon wafer or a 40 mm square glass substrate, and then a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) is used in an air atmosphere. By prebaking at 120 ° C. for 3 minutes, a coating film was obtained. This coating film was heated at 250 ° C. for 5 minutes on a hot plate in an air atmosphere, and then heated at 300 ° C. for 5 minutes to obtain a cured film.

Measurement of refractive index and film thickness A cured film prepared on a 6-inch silicon wafer or a 40 mm square glass substrate is 633 nm (using a He-Ne laser) at 22 ° C. using a prism coupler MODEL2010 (manufactured by Metricon). The refractive index (TE) and film thickness in the direction perpendicular to the film surface were measured.

Measurement of transmittance A transmittance of 400 nm was measured using a UV-visible spectrophotometer UV-260 (manufactured by Shimadzu Corporation) for a cured film having a thickness of 1.0 μm prepared on a 40 mm square glass substrate. .

Evaluation of crack resistance after heat load A cured film prepared on a 6-inch silicon wafer was subjected to a heat cycle test with the following temperature history, and the temperature at which cracks occurred was confirmed with an optical microscope. Heating was performed on a hot plate in an air atmosphere.
Temperature history of heat cycle test 250 ° C. 5 minutes → room temperature (23 ° C.) 5 minutes → 280 ° C. 5 minutes → room temperature (23 ° C.) 5 minutes → 300 ° C. 5 minutes → room temperature (23 ° C.) 5 minutes → 320 ° C. 5 minutes → Room temperature (23 ° C.) 5 minutes → 340 ° C. 5 minutes → Room temperature (23 ° C.) 5 minutes → 360 ° C. 5 minutes → Room temperature (23 ° C.) 5 minutes → 380 ° C. 5 minutes → Room temperature (23 ° C.) 5 minutes → 400 ° C. 5 Minutes → room temperature (23 ° C.) 5 minutes → 420 ° C. 5 minutes → room temperature (23 ° C.) 5 minutes → 430 ° C. 5 minutes → room temperature (23 ° C.) 5 minutes.

Synthesis Example 1 Synthesis of quinonediazide compound Under a dry nitrogen stream, TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 21.22 g (0.05 mol) and 5-naphthoquinonediazidesulfonic acid chloride (Toyo Gosei Co., Ltd.) ), NAC-5) 26.8 g (0.1 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 12.65 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° C. or higher. It stirred at 40 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 and further washed with 1 L of 1% aqueous hydrochloric acid. Thereafter, it was further washed twice with 2 L of water. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound represented by the following formula.

Example 1
Methyltrimethoxysilane 20.4 g (0.15 mol), phenyltrimethoxysilane 69.4 g (0.35 mol), “OPTRAIK” TR-520 (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) having a number average particle diameter of 15 nm Composition: 30% by weight of titanium oxide particles, 70% by weight of γ-butyrolactone) 70.6 g and 44.1 g of γ-butyrolactone were placed in a reaction vessel, and 30.6 g of water and 0.48 g of phosphoric acid were stirred into this solution. However, it was added dropwise so that the reaction temperature did not exceed 40 ° C. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 130 ° C. for 2 hours, and then cooled to room temperature to obtain a polymer solution A (solid content 55% by weight).

  To 10 g of the obtained polymer solution A, 10 g of γ-butyrolactone and 0.5 g of thermally crosslinkable compound “Nikalac” MX-280 (manufactured by Sanwa Chemical) were added and dissolved to obtain a siloxane-based resin composition 1. .

  Using the obtained siloxane-based resin composition 1, a cured film was prepared on a glass substrate and a silicon wafer as described above, and evaluation was performed regarding refractive index, transmittance, and crack resistance after thermal load.

Example 2
“OPTRAIK” TR- with 8.2 g (0.06 mol) of methyltrimethoxysilane, 55.5 g (0.28 mol) of phenyltrimethoxysilane, 7.2 g (0.06 mol) of dimethyldimethoxysilane, and a number average particle diameter of 15 nm 521 (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd., composition: titanium oxide particles 30% by weight, diacetone alcohol 70% by weight) 71.1 g and γ-butyrolactone 23.9 g were placed in a reaction vessel. 0.5 g and 1.0 g of phosphoric acid were added dropwise with stirring so that the reaction temperature did not exceed 40 ° C. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 130 ° C. for 2 hours and then cooled to room temperature to obtain a polymer solution B (solid content: 48% by weight).

  To 10 g of the obtained polymer solution B, 10 g of γ-butyrolactone and 0.1 g of a heat-crosslinkable compound “Nicarac” MX-270 (manufactured by Sanwa Chemical) were added and dissolved to obtain a siloxane-based resin composition 2.

  A cured film was prepared using the obtained siloxane-based resin composition 2 and evaluated for refractive index, transmittance, and crack resistance after thermal load.

Example 3
Instead of “OPTRAIK” TR-521, 70.0 g of propylene glycol monomethyl ether acetate dispersion (zirconium oxide 30% by weight, propylene glycol monomethyl ether acetate 70% by weight) of zirconium oxide particles (number average particle diameter 30 nm) is used. Except for the above, the same operation as in Example 2 was performed to obtain a polymer solution C (solid content: 46% by weight).

  To 10 g of the resulting polymer solution C, 15 g of propylene glycol monomethyl ether acetate and 0.7 g of thermally crosslinkable compound TriML-P were added and dissolved to obtain siloxane-based resin composition 3.

  A cured film was prepared using the resulting siloxane-based resin composition 3 and evaluated for refractive index, transmittance, and crack resistance after thermal load.

Example 4
Except for using 45.0 g of propylene glycol monomethyl ether acetate dispersion (30% by weight of aluminum oxide, 70% by weight of propylene glycol monomethyl ether acetate) of aluminum oxide particles (number average particle size 30 nm) instead of “OPTRAIK” TR-521 Performed the same operation as in Example 2 to obtain a polymer solution D (solid content: 40% by weight).

  To 10 g of the obtained polymer solution D, 20 g of 3-methyl-3-methoxybutyl acetate and 1.3 g of a heat-crosslinkable compound “Nicarac” MX-290 (manufactured by Sanwa Chemical Co., Ltd.) are added and dissolved to obtain a siloxane-based resin composition 4. Obtained.

  A cured film was prepared using the resulting siloxane-based resin composition 4 and evaluated for refractive index, transmittance, and crack resistance after thermal load.

Example 5
“OPTRAIK” TR- with 8.2 g (0.06 mol) of methyltrimethoxysilane, 55.5 g (0.28 mol) of phenyltrimethoxysilane, 5.4 g (0.026 mol) of tetraethoxysilane, and a number average particle diameter of 15 nm 521 (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd., composition: titanium oxide particles 30% by weight, diacetone alcohol 70% by weight) 52.4 g and γ-butyrolactone 20.5 g were put in a reaction vessel. 0.5 g and 1.0 g of phosphoric acid were added dropwise with stirring so that the reaction temperature did not exceed 40 ° C. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol and ethanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 130 ° C. for 2 hours and then cooled to room temperature to obtain a polymer solution E (solid content: 60% by weight).

  To 20 g of the obtained polymer solution E, 40 g of γ-butyrolactone and 2 g of the heat-crosslinkable compound “Nicalac” MX-270 (manufactured by Sanwa Chemical) were added and dissolved to obtain a siloxane-based resin composition 5.

  A cured film was prepared using the resulting siloxane-based resin composition 5 and evaluated for refractive index, transmittance, and crack resistance after thermal load.

Example 6
Methyltrimethoxysilane 12.3 g (0.15 mol), phenyltrimethoxysilane 41.6 g (0.35 mol), “OPTRAIK” TR-527 (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) having a number average particle diameter of 15 nm Composition: 193 g of titanium oxide particles 20 wt%, methanol 80 wt%) and 94.0 g of propylene glycol monomethyl ether acetate were put in a reaction vessel, and 16.2 g of water and 0.27 g of phosphoric acid were added to this solution while stirring. The reaction was dropwise added so that the reaction temperature did not exceed 40 ° C. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 115 ° C. for 2 hours and then cooled to room temperature to obtain a polymer solution F (solid content: 44% by weight).

  20 g of the obtained polymer solution F was taken, 0.70 g of the quinonediazide compound obtained in Synthesis Example 1, 2 g of heat-crosslinkable compound “Nicalac” MX-270 (manufactured by Sanwa Chemical), and 20 g of propylene glycol monomethyl ether acetate were added. It melt | dissolved and the siloxane type resin composition 6 was obtained.

Next, the positive photosensitive characteristics of the siloxane-based resin composition 6 were evaluated by the following procedure. The siloxane resin composition was spin-coated on a 6-inch silicon wafer and then baked for 2 minutes on a hot plate (Mark-7) at 120 ° C. to prepare a pre-baked film having a thickness of 1 μm. The film was exposed at 20 mJ / cm ² steps by the exposure amount of 0~200mJ / cm ² using an i-line stepper (GCA manufactured DSW-8000), 2.38% of tetramethylammonium (TMAH) aqueous solution (Mitsubishi Development was performed with Gas Chemical Co., Ltd. (ELM-D) for 60 seconds, followed by rinsing with pure water. When observed with an optical microscope, a positive pattern with a width of 5 μm was resolved at an exposure amount of 80 mJ / cm ² .

The obtained siloxane-based resin composition 6 is applied onto a 6-inch silicon wafer and a 40 mm square glass substrate, and then using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) under an air atmosphere. By prebaking at 120 ° C. for 3 minutes, a coating film was obtained. This coating film was exposed to an ultraviolet full-wavelength entire surface for 3 minutes (bleaching exposure main wavelength: 365 nm) with an ultraviolet intensity of about 5 mW / cm ² (wavelength 365 nm conversion) using an exposure machine (Contact Aligner PLA501F manufactured by Canon Inc.). 405 nm, 436 nm) to decompose the unreacted quinonediazide photosensitizer, and then heated at 300 ° C. for 5 minutes on a hot plate in an air atmosphere to obtain a cured film. The cured film obtained was evaluated for refractive index, transmittance, and crack resistance after heat load.

Example 7
To 20 g of the polymer solution F used in Example 6, 25 g of propylene glycol monomethyl ether acetate and 0.4 g of thermally crosslinkable compound “Nicalac” MX-270 (manufactured by Sanwa Chemical) were added and dissolved, and a siloxane-based resin composition 7 was obtained. Obtained.

  A cured film was prepared using the resulting siloxane-based resin composition 7 and evaluated for refractive index, transmittance, and crack resistance after thermal load.

Example 8
To 20 g of the polymer solution F used in Example 6, 25 g of propylene glycol monomethyl ether acetate and 2.2 g of thermally crosslinkable compound S-3 were added and dissolved to obtain a siloxane-based resin composition 8.

  A cured film was prepared using the resulting siloxane-based resin composition 8 and evaluated for refractive index, transmittance, and crack resistance.

Example 9
25 g of propylene glycol monomethyl ether acetate and 3.5 g of thermally crosslinkable compound S-11 (trade name: PDS-9931 (manufactured by Gerest)) were added to and dissolved in 20 g of the polymer solution F used in Example 6 to obtain a siloxane resin. Composition 9 was obtained.

  A cured film was prepared using the resulting siloxane-based resin composition 9 and evaluated for refractive index, transmittance, and crack resistance.

Comparative Example 1
24.5 g (0.18 mol) of methyltrimethoxysilane, 83.3 g (0.42 mol) of phenyltrimethoxysilane and 124.0 g of γ-butyrolactone were placed in a reaction vessel, and while stirring, 38 g of water and 0.57 g of phosphoric acid Was added dropwise so that the reaction temperature did not exceed 30 ° C. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 130 ° C. for 2 hours and then cooled to room temperature to obtain a polymer solution A1 (solid content: 32% by weight).

  10.0 g of the obtained polymer solution A1 was added, and 13.3 g of “OPTRAIK” TR-520 having a number average particle diameter of 15 nm and propylene glycol monomethyl ether acetate were added and stirred to obtain a siloxane-based resin composition A1. Obtained.

  A cured film was prepared using the obtained siloxane-based resin composition A1 in the same manner as in Example 1, and evaluated for refractive index, transmittance, and crack resistance after thermal load.

Comparative Example 2
25 g of propylene glycol monomethyl ether acetate was added to and dissolved in 20 g of the polymer solution F used in Example 6 to obtain a siloxane-based resin composition A2.

  A cured film was prepared using the obtained siloxane-based resin composition A2, and evaluation was performed on the refractive index, transmittance, and crack resistance after thermal load.

Comparative Example 3
25 g of propylene glycol monomethyl ether acetate and 3.1 g of silanol-terminated polydimethylsiloxane (trade name: DMS-S12 (manufactured by Gerest)) were added to and dissolved in the polymer solution F20 g used in Example 6 to obtain a siloxane-based resin composition A3. Got.

  A cured film was prepared using the obtained siloxane-based resin composition A3, and evaluation was performed on the refractive index, transmittance, and crack resistance after thermal load.

Comparative Example 4
Methyltrimethoxysilane 12.3 g (0.15 mol), phenyltrimethoxysilane 41.6 g (0.35 mol), thermally crosslinkable compound S-11 (trade name: PDS-9931 (manufactured by Gelest)) 20 g (0.025 mol) ), “OPTRAIK” TR-527 (trade name, manufactured by Catalyst Chemical Industry Co., Ltd., composition: titanium oxide particles 20% by weight, methanol 80% by weight) 193 g, propylene glycol monomethyl ether acetate 94.0 g Into this solution, 16.2 g of water and 0.27 g of phosphoric acid were added dropwise with stirring so that the reaction temperature did not exceed 40 ° C. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 115 ° C. for 2 hours, then cooled to room temperature, and propylene glycol monomethyl ether acetate was added to obtain a polymer solution A4 (solid content 30% by weight).

  29.3 g of the obtained polymer solution A4 was taken and 15.7 g of propylene glycol monomethyl ether acetate was added and dissolved to obtain a siloxane-based resin composition A4.

  A cured film was prepared in the same manner as in Example 1 using the obtained siloxane-based resin composition A4, and evaluated for refractive index, transmittance, and crack resistance after thermal load.

  The results of Examples 1 to 9 and Comparative Examples 1 to 4 are shown in Table 1.

  The cured film formed with the siloxane-based resin composition of the present invention is suitably used for optical devices such as solid-state imaging devices, antireflection films, antireflection plates, optical filters, and displays. Further, it can be used as a buffer coat, an interlayer insulating film, and various protective films.

Claims (11)

In the presence of at least one metal compound particle selected from the group consisting of aluminum compound particles, tin compound particles, titanium compound particles and zirconium compound particles, an alkoxysilane compound is hydrolyzed with an acid catalyst in a solvent. A siloxane-based resin composition comprising a reaction product obtained by subjecting a product to a condensation reaction and a thermally crosslinkable compound having a thermally crosslinkable group represented by the following general formula (1).

(In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) The siloxane-based resin composition according to claim 1, wherein the thermally crosslinkable compound has a thermally crosslinkable group represented by the following general formula (2).

(In General Formula (2), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) In the presence of at least one metal compound particle selected from the group consisting of aluminum compound particles, tin compound particles, titanium compound particles and zirconium compound particles, an alkoxysilane compound is hydrolyzed with an acid catalyst in a solvent. A siloxane-based resin composition comprising a reaction product obtained by subjecting a product to a condensation reaction and a thermally crosslinkable compound represented by the following general formula (3).

(In General Formula (3), R ⁸ and R ⁹ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a substituted product thereof, provided that p R ⁸ and R ^(At least one of ⁹ is a phenyl group or a substituted product thereof. P represents an integer of 4 or more and 20 or less.) The siloxane-based resin composition according to any one of claims 1 to 3, wherein the alkoxysilane compound is at least one selected from the following general formulas (4) to (6).
R ² Si (OR ⁵ ) ₃ (4)
(R ² represents hydrogen, an alkyl group, an alkenyl group, an aryl group, or a substituted product thereof. R ⁵ represents a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, which may be the same or different. .)
R ³ R ⁴ Si (OR ⁶ ) ₂ (5)
(R ³ and R ⁴ each represent hydrogen, an alkyl group, an alkenyl group, an aryl group, or a substituent thereof. R ⁶ represents a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, May be different.)
Si (OR ⁷ ) ₄ (6)
(R ⁷ represents a methyl group or an ethyl group, and each may be the same or different.) The siloxane-based resin composition according to claim 1, wherein the number average particle diameter of the metal compound particles is 1 nm to 200 nm. The siloxane-based resin composition according to claim 1, wherein the metal compound particles contain zirconium oxide particles and / or titanium oxide particles. The siloxane-based resin composition according to claim 1, further comprising a quinonediazide-based photosensitive agent. A cured film obtained by curing the siloxane-based resin composition according to claim 1. An optical device having the cured film according to claim 8. In the presence of at least one metal compound particle selected from the group consisting of aluminum compound particles, tin compound particles, titanium compound particles and zirconium compound particles, an alkoxysilane compound is hydrolyzed with an acid catalyst in a solvent. A method for producing a siloxane-based resin composition, comprising subjecting a product to a condensation reaction and then adding a thermally crosslinkable compound having a thermally crosslinkable group represented by the following general formula (1).

(In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) In the presence of at least one metal compound particle selected from the group consisting of aluminum compound particles, tin compound particles, titanium compound particles and zirconium compound particles, an alkoxysilane compound is hydrolyzed with an acid catalyst in a solvent. A method for producing a siloxane-based resin composition, comprising subjecting a product to a condensation reaction and then adding a heat-crosslinkable compound represented by the following general formula (3).

(In General Formula (3), R ⁸ and R ⁹ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a substituted product thereof, provided that p R ⁸ and R ^(At least one of ⁹ is a phenyl group or a substituted product thereof. P represents an integer of 4 or more and 20 or less.)