JP2009263507A - Siloxane resin composition and production method of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a siloxane resin composition, from which a cured film excellent in crack resistance after subjected to thermal load such as a high-temperature heat treatment or repeated heat cycles can be formed. <P>SOLUTION: The siloxane resin composition comprises: (a) a siloxane resin obtained by hydrolyzing an alkoxysilane compound in the presence of at least one of metal compound particles selected from a group consisting of aluminum compound particles, tin compound particles, titanium compound particles and zirconium compound particles, and condensing the hydrolysate; and (b) an organosilane compound expressed by general formula (1), wherein m represents 0 to 5 and n represents 2 or 3. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a siloxane-based resin composition and a method for producing the same. The cured film formed by the siloxane-based resin composition of the present invention is a solid-state imaging device, an on-vehicle camera, a projector, an optical integrated circuit or other micro optical device, an antireflection film, an antireflection plate, an optical filter, an optical display or the like. It is suitably used for a device.

  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.

  As a siloxane resin composition containing metal compound particles, for example, a metal oxide formed by mixing a metal oxide fine particle dispersion obtained by mixing metal oxide fine particles and polyfunctional polysiloxane and a silicone having a polydimethylsiloxane structure. A fine particle-containing polysiloxane composition is disclosed (see, for example, Patent Document 1). Although a cured film having a high refractive index can be obtained by this method, there is a problem that the film quality including the metal oxide fine particles becomes hard and cracks are likely to occur due to heat treatment at a high temperature. Moreover, the cured film containing metal oxide fine particles whitened, and there existed a subject that the transmittance | permeability fell. On the other hand, a siloxane resin composition obtained by subjecting an alkoxysilane compound to a condensation reaction in the presence of a metal oxide has been proposed (see, for example, Patent Document 2). By this method, a cured film having high visible light transmittance and improved crack resistance can be obtained. Moreover, the photosensitive siloxane composition containing polysiloxane, a quinonediazide compound, a solvent, and an organosilane compound is proposed (for example, refer patent document 3).

In recent years, a technique for efficiently condensing light by using a lens material having a high refractive index and a high transparency in a portion close to a solid-state imaging element that is an inorganic material has been developed. There is also a need for materials that require repeated heat cycle resistance, such as in-vehicle camera applications. When polysiloxane compositions containing conventionally known metal compound particles are used for these applications, there is a problem that cracks are generated by heat treatment at a high temperature of the inorganic material and repeated heat cycles.
JP 2007-270054 A JP 2007-246877 A JP 2007-163720 A

  In view of the said subject, it aims at providing the siloxane-type resin composition which can form the cured film excellent in the crack tolerance after heat loads, such as high temperature heat processing and a repeated heat cycle.

  The present invention includes (a) hydrolyzing an alkoxysilane compound 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 siloxane-based resin composition comprising a siloxane-based resin obtained by subjecting a product to a condensation reaction, and (b) an organosilane compound represented by the following general formula (1).

R ¹ may be the same or different and represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. R ² may be the same or different and each 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 15 carbon atoms. m represents an integer of 0 to 5, and n represents 2 or 3.

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

  The present invention also includes (1) hydrolyzing an alkoxysilane compound 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) a step of obtaining a siloxane-based resin by subjecting the hydrolyzate to a condensation reaction; and (2) mixing the (a) siloxane-based resin with (b) the organosilane compound represented by the general formula (1). It is a manufacturing method of the siloxane-type resin composition characterized by having a process in this order.

  According to the siloxane-based resin composition of the present invention, a cured film excellent in crack resistance after a thermal load such as high-temperature heat treatment or repeated heat cycle can be formed. The obtained cured film is particularly suitably used for a micro optical device such as a solid-state imaging device, a micro lens material for an in-vehicle camera, a color filter protective film for a projector, and the like.

  The present invention will be specifically described below.

  The siloxane-based resin composition of the present invention hydrolyzes an alkoxysilane compound in the presence of at least one metal compound particle selected from the group consisting of (a) aluminum compound particles, tin compound particles, titanium compound particles, and zirconium compound particles. It contains a siloxane-based resin obtained by decomposing and subjecting the hydrolyzate to a condensation reaction, and (b) an organosilane compound represented by the following general formula (1). (B) By containing the organosilane compound represented by the general formula (1), a bulky phenyl group is introduced into the terminal of the siloxane resin by thermosetting. In the siloxane-based resin having a phenyl group introduced therein, cross-linking between terminals is suppressed by a bulky phenyl group. For this reason, the progress of crosslinking in the siloxane-based resin composition of the present invention is suppressed, and as a result, film stress after curing is reduced, and crack resistance after thermal load is improved.

R ¹ may be the same or different and represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. R ² may be the same or different and each 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 15 carbon atoms. m represents an integer of 0 to 5, and n represents 2 or 3.

  The siloxane-based resin composition of the present invention includes (b) an organosilane compound represented by the general formula (1). By containing the organosilane represented by the general formula (1), high heat cycle resistance can be obtained, and a cured film having excellent crack resistance after repeated thermal load can be formed.

R ¹ in the general formula (1) is an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group or a tert-butyl group, an alkenyl group such as a vinyl group, a phenyl group, a tolyl group or a naphthyl group. Of the aryl group. Among these, an ethyl group and a tert-butyl group are preferable because coloring due to oxidation during curing can be reduced. R ² includes hydrogen, alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group, acyl group such as acetyl group, aryl group such as phenyl group, tolyl group and naphthyl group. Can be mentioned. Among them, a methyl group and an ethyl group are particularly preferable because the alkoxy group is highly hydrolyzable.

  Specific examples of the organosilane compound represented by the general formula (1) include diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, diphenyldin-butoxysilane, diphenylsilanediol, and bis (4-methylphenyl). ) Dimethoxysilane, bis (4-methylphenyl) diethoxysilane, bis (4-methylphenyl) diisopropoxysilane, bis (4-methylphenyl) silanediol, bis (4-biphenyl) dimethoxysilane, bis (4- Biphenyl) diethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylsilanol and the like. Two or more of these may be contained. Of these, triphenylmethoxysilane, triphenylethoxysilane, triphenylsilanol, diphenyldimethoxysilane, diphenyldiethoxysilane, and diphenylsilanediol are particularly preferable.

  (B) As for content of the organosilane compound represented by General formula (1), 5-50 weight part is preferable with respect to 100 weight part of (a) siloxane-type resin. If it is 5 weight part or more, the crack tolerance after a heat load will improve more. On the other hand, if it is 50 parts by weight or less, the viscosity of the resulting siloxane-based resin composition can be increased moderately, and a thick film with high film thickness uniformity can be easily formed. More preferably, it is 30 parts by weight or less.

  Next, (a) siloxane-based resin will be described.

  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.

  Examples of metal compound particles include titanium oxide fine powders HT331B, HT431B, HT631B, HT731B, HT830X (trade name: manufactured by Toho Titanium Co., Ltd.), ultrafine titanium oxide TTO-F, TTO-D, TTO-55. , TTO-A-1, TTO-S, TTO-V (trade name: manufactured by Ishihara Sangyo Co., Ltd.), zirconia sol "Nanouse (registered trademark)" ZR-30BL, "Nanouse" ZR-30BS, "Nanouse" ZR-30BH, “Nano Youth” ZR-30AL, “Nano Youth” ZR-30AH, “Nano Youth” OZ-30M (above trade name: manufactured by Nissan Chemical Industries, Ltd.), ZSL-M20, ZSL-10T, ZSL-10A, ZSL-20N (above trade name: Daiichi Rare Element Chemical Industry Co., Ltd.), “Optore” of tin oxide-titanium oxide composite particles (Registered trademark) “TR-502”, “Optlake” TR-504, “Oplake” TR-503 of silicon oxide-titanium oxide composite particles, “Optlake” TR-513, “Optlake” TR-520, “OPTRAIK” TR-527, “OPTRAIK” TR-528, “OPTRAIK” TR-529, “OPTRAIK” TR-505 of titanium oxide particles (above, trade name, manufactured by Catalyst Chemical Industries, Ltd.) Zirconium oxide particles (manufactured by Kojundo Chemical Laboratory Co., Ltd.), tin oxide-zirconium oxide composite particles (manufactured by Catalyst Chemical Industry Co., Ltd.), tin oxide particles (manufactured by Kojundo Chemical Laboratory Co., Ltd.), etc. .

  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. More preferably, it is 70 nm or less. 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. In the present invention, it refers to a value measured by a dynamic light scattering method. Although the apparatus to be used is not specifically limited, Dynamic light scattering altimeter DLS-8000 (made by Otsuka Electronics Co., Ltd.) etc. can be mentioned.

  The content of the metal compound particles in the siloxane-based resin composition of the present invention is preferably 5% by weight or more, more preferably 20% by weight or more in the siloxane-based resin. Moreover, 80 weight% or less is preferable and 70 weight% or less is more preferable. Within this range, it is possible to obtain a cured film having both high transmittance and crack resistance after thermal load. Here, the total weight of the siloxane-based resin including the metal compound particles is 100%.

  The (a) siloxane resin used in the siloxane-based resin composition of the present invention is formed by hydrolyzing an alkoxysilane compound to form a silanol compound in the presence of the metal compound particles, and then subjecting the silanol compound to a condensation reaction. Can be obtained by: As an alkoxysilane compound, 1 or more types chosen from the alkoxysilane compound represented by the following general formula (2)-(4) are preferable.

R ³ Si (OR ⁴ ) ₃ (2)
R ³ represents hydrogen, an alkyl group, an alkenyl group, an aryl group, or a substituted product thereof. Examples of the substituent include an epoxy group, an oxetanyl group, an acrylic group, a methacryl group, and a fluoroalkyl group. From the viewpoint of crack resistance when forming a thick film, R ³ is preferably a phenyl group. R ⁴ 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 ⁴ is more preferably a methyl group or an ethyl group.

R ⁵ R ⁶ Si (OR ⁷ ) ₂ (3)
R ⁵ and R ⁶ each represent hydrogen, an alkyl group, an alkenyl group, an aryl group, or a substituted product thereof. Examples of the substituent include an epoxy group, an oxetanyl group, an acrylic group, a methacryl group, and a fluoroalkyl group. R ⁷ 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 ⁷ is more preferably a methyl group or an ethyl group.

Si (OR ⁸ ) ₄ (4)
R ⁸ represents a methyl group or an ethyl group, and may be the same or different.

  As the trifunctional alkoxysilane compound represented by the general formula (2), for example, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane are preferable. As the bifunctional alkoxysilane compound represented by the general formula (3), for example, dimethyl dialkoxysilane is preferable. Examples of the tetrafunctional alkoxysilane compound represented by the general formula (4) include tetramethoxysilane and tetraethoxysilane. The alkoxysilane compounds represented by any one of these general formulas (2) to (4) may be used in combination of two or more.

  The hydrolysis reaction of the alkoxysilane compound is preferably carried out at room temperature to 110 ° C. for 1 to 180 minutes after adding an acid catalyst and water to the above-described 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-based resin, it is possible to reheat or add a base catalyst.

  Various conditions in the hydrolysis are obtained in consideration of the reaction scale, the size and shape of the reaction vessel, for example, by setting the acid concentration, reaction temperature, reaction time, etc., and obtaining physical properties suitable for the intended application. be able to.

  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, 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 used in the hydrolysis reaction is not particularly limited, but is appropriately selected in consideration of the stability, wettability, volatility, etc. of the siloxane-based resin composition. Two or more solvents may 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. Among these, in terms of transmittance of the cured film, 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, γ -Butyrolactone is 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. The amount is preferably 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.

  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 photosensitive agent such as a quinonediazide compound 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. In this invention, it is preferable to contain (c) quinonediazide compound.

  (C) As the quinonediazide compound, 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, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR-BIPC-F, 4,4′-sulfonyldiphenol BPFL is preferred.

  (C) As the quinonediazide compound, those obtained by introducing 4-naphthoquinonediazidesulfonic acid or 5-naphthoquinonediazidesulfonic acid into the compound having a phenolic hydroxyl group by an ester bond are preferable, but other compounds can also be used. .

  (C) 1 part weight or more is preferable with respect to 100 weight part of siloxane resin compounds, and, as for content of a quinonediazide compound, 2 weight part or more is more preferable. Moreover, 50 weight part or less is preferable and 10 weight part or less is more preferable. (C) By setting the content of the quinonediazide compound 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 siloxane-based resin composition of the present invention may contain a thermally crosslinkable compound. The thermally crosslinkable compound is a compound that crosslinks (a) the siloxane-based resin during thermosetting, and is a compound that is incorporated into the (a) siloxane-based resin skeleton by crosslinking. When the siloxane-based resin composition containing a heat-crosslinkable compound is cured by heat, the polysiloxane compound that is the matrix material and the metal compound particles are firmly bonded, and crack resistance after thermal load is further improved.

  The heat-crosslinkable compound is not particularly limited as long as it is a compound that crosslinks the siloxane-based resin at the time of thermosetting and is incorporated into the siloxane-based resin skeleton, but a compound having two or more groups represented by the general formula (5) Preferably used.

In the general formula (5), R ⁹ represents hydrogen or an alkyl group having 1 to 10 carbon atoms. A plurality of R ⁹ in the compound may be the same or different. 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, and n-decyl group. Moreover, you may use in combination of 2 or more types of compounds which have 2 or more groups represented by General formula (5).

  Specific examples of the compound having two or more groups represented by the general formula (5) include the following melamine derivatives and urea derivatives (trade names, manufactured by Sanwa Chemical Co., Ltd.), and phenolic compounds (commodities). Name, manufactured by Honshu Chemical Industry Co., Ltd.).

  The content of the thermally crosslinkable compound is not particularly limited, but is preferably in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of (a) siloxane-based resin. By containing 0.1 part by weight or more, crack resistance after heat load can be further improved, and 3 parts by weight or more is more preferable. Moreover, a highly transparent cured film can be obtained by containing 30 weight part or less, and 20 weight part or less is more preferable.

  The siloxane-based resin composition of the present invention may contain a curing agent that accelerates the curing of the siloxane-based resin composition or facilitates the curing. For example, there are a silicone resin curing agent, various metal alcoholates, various metal chelate compounds, an isocyanate compound and a polymer thereof, and two or more of these may be contained.

  The siloxane-based resin composition of the present invention can contain a solvent so that the solid content has an appropriate concentration. Specific examples include ethers, acetates, ketones, alcohols, aromatic hydrocarbons, γ-butyrolactone, N-methylpyrrolidinone and the like exemplified as the solvent for hydrolysis. Two or more of these may be contained. 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-butyl ether, diacetone alcohol, γ-butyrolactone and the like are preferable. .

  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 mentioned. Two or more of these may be contained. Of these, fluorine surfactants are particularly preferably used from the viewpoints of flowability and film thickness uniformity.

  Specific examples of the fluorosurfactant include “Megafac (registered trademark)” F172 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), BM-1000, BM-1100 (above, trade name, Yusho) NBX-15, FTX-218 (trade name, manufactured by Neos Co., Ltd.) are particularly preferable from the viewpoints of flowability and film thickness uniformity. Specific examples of the silicone surfactant include SH28PA, SH7PA, SH21PA, SH30PA, ST94PA (above, trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.), BYK-333 (trade name, Big Chemie Japan Co., Ltd.) ))). Specific 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.

  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.

  Next, the manufacturing method of the siloxane resin composition of this invention is demonstrated. First, by the above method (1) alkoxysilane is hydrolyzed in the presence of metal compound particles, and the hydrolyzate is subjected to a condensation reaction to obtain (a) a siloxane-based resin. Next, (2) the obtained siloxane-based resin and the (b) organosilane compound are mixed. The (a) siloxane resin composition may be added to the (a) siloxane resin solution, or the (a) siloxane resin composition may be added to the (b) organosilane compound solution. Moreover, you may add and mix other components, such as (c) quinonediazide compound, as needed. Mixing may be performed under heating, for example, heating and mixing at 40 to 100 ° C. Examples of the apparatus used for mixing include a rotary shaker, a mechanical stirrer, and a mechanical stirrer.

  The cured film of the present invention can be obtained by curing the siloxane-based resin composition of the present invention. For example, the siloxane-based resin composition of the present invention is applied onto a substrate to obtain a coating film, which is dried and cured by heating.

  Examples of the application method of the siloxane-based resin composition include microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, and flow coating.

  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. The curing temperature is preferably from 100 to 400 ° C, more preferably from 150 to 400 ° C.

When the siloxane-based resin composition of the present invention has photosensitivity, after obtaining a coating film by the above method, a cured film patterned by the following method can be obtained, for example. The coating film produced on the substrate is pre-baked with a heating device such as a hot plate or oven. The pre-baking is generally performed in the range of 50 to 150 ° C. for 30 seconds to 30 minutes. After pre-baking, using a UV-visible exposure machine such as a stepper, mirror projection mask aligner (MPA), parallel light mask aligner (PLA), etc., about 10 to 6000 J / m ² (wavelength 365 nm exposure amount conversion) is passed through the desired mask. Pattern exposure is performed. After patterning 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 developer for 5 seconds to 10 minutes by a method such as showering, dipping or paddle. As the developer, a known alkali developer can be used. Specific examples include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, and tetramethylammonium hydroxide. And aqueous solutions containing one or more quaternary ammonium salts such as choline. After development, it is preferable to rinse with water, followed by drying and baking in the range of 50 to 150 ° C.

Thereafter, it is preferable to perform bleaching exposure. By performing bleaching exposure, the unreacted quinonediazide compound remaining in the film is photodegraded, and the light transparency of the film is further improved. Examples of the bleaching exposure method include a method in which an entire surface is exposed to about 100 to 4000 J / m ² (wavelength 365 nm exposure amount conversion) using an ultraviolet-visible exposure machine such as PLA.

  Then, the cured film in which the pattern was formed can be obtained by making it heat-dry and harden | cure by the said method.

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

  Coating films and cured films formed from the siloxane-based resin composition of the present invention are used for solid-state imaging devices, in-vehicle cameras, projectors, micro integrated devices such as optical integrated circuits, antireflection films, antireflection plates, optical filters, It is suitably used for optical device applications such as displays, buffer coatings for semiconductor devices, interlayer insulating films, and various protective films. Specifically, as a micro-optical device application, a condensing microlens formed in a solid-state imaging device, a vehicle-mounted camera, a color filter protective film used in a projector, an optical waveguide used in an optical integrated circuit, A phase shifter is mentioned. Examples of optical device applications include hard coat layers used for antireflection films and antireflection plates, flattening materials for display TFT substrates, and protective films for liquid crystal displays and color filters. In particular, microlenses formed on solid-state image sensors that require high-temperature processing in the manufacturing process, microlenses for in-vehicle cameras that require durability under high-temperature conditions, and micro-optics such as color filter protective films for projectors It is suitably used as a 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 on a hot plate in an air atmosphere at 220 ° C. for 5 minutes to produce 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. In addition, about what generate | occur | produced the crack at the time of cured film preparation, it was 220 degreeC.
Temperature history of heat cycle test 240 ° C. 5 minutes → room temperature (23 ° C.) → 260 ° C. 5 minutes → room temperature (23 ° C.) → 280 ° C. 5 minutes → room temperature (23 ° C.) → 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.

Film thickness uniformity test A siloxane-based resin composition was applied onto a 6-inch silicon wafer at an arbitrary rotation speed using a spin coater, and then baked on a hot plate at 120 ° C. for 2 minutes to obtain an average thickness of 1.5 μm. A pre-baked film was prepared. The film thickness was measured at all 13 points at the center, left and right upper and lower 10, 30, and 60 mm positions with an optical interference type film thickness meter Lambda Ace (trade name: Dainippon Screen Mfg. Co., Ltd.). The film thickness uniformity at all 13 points was determined from the following equation.
Film thickness uniformity (%) = 100 − {(film thickness maximum value−film thickness minimum value) × 100 / (film thickness maximum value + film thickness minimum value)}.

Synthesis Example 1 Synthesis of quinonediazide compound A TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 21.22 g (0.05 mol) and 5-naphthoquinonediazidesulfonic acid chloride (Toyosei Co., Ltd.) under a dry nitrogen stream 26.8 g (0.1 mol) manufactured by NAC-5, Inc. 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. After dropping, the mixture was stirred at 40 ° C. 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 A represented by the following formula.

Synthesis Example 2 Synthesis of Siloxane Resin A 20.4 g (0.15 mol) of methyltrimethoxysilane, 69.4 g (0.35 mol) of phenyltrimethoxysilane, “OPTRAIK” TR-520 (product) Name: Catalyst Chemical Industries, Ltd. Composition: Titanium oxide particles 30 wt%, γ-butyrolactone 70 wt%) 70.6 g, γ-butyrolactone 44.1 g were placed in a reaction vessel, and 30.6 g water and 0.48 g of phosphoric acid was added dropwise with stirring so that the reaction temperature did not exceed 40 ° C. After the dropping, a distillation apparatus was attached to the flask, and the resulting solution was heated and mixed 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 mixed at a bath temperature of 130 ° C. for 2 hours, and then cooled to room temperature. After measuring the solid content concentration of the obtained solution, it was diluted with propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) to 40% by weight to obtain a solution of siloxane-based resin A.

The solid content concentration was measured by the following method. The solution was weighed in an aluminum cup, placed on a 120 ° C. hot plate, heated to 250 ° C. and heated for 30 minutes to evaporate volatile components. Thereafter, the weight of the nonvolatile content was measured, and the solid content concentration was determined from the following formula.
(Weight of non-volatile content) × 100 / (weight of solution before measurement)%

Synthesis Example 3 Synthesis of Siloxane Resin B 8.2 g (0.06 mol) of methyltrimethoxysilane, 55.5 g (0.28 mol) of phenyltrimethoxysilane, 7.2 g (0.06 mol) of dimethyldimethoxysilane, number average particles A reaction vessel containing 71.1 g of “Optlake” TR-521 (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd., composition: titanium oxide particles 30 wt%, diacetone alcohol 70 wt%) and γ-butyrolactone 23.9 g Into this solution, 34.5 g of water and 1.0 g of phosphoric acid were added dropwise with stirring so that the reaction temperature did not exceed 40 ° C. After the dropping, a distillation apparatus was attached to the flask, and the resulting solution was heated and mixed 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 mixed at a bath temperature of 130 ° C. for 2 hours, and then cooled to room temperature. The resulting solution was diluted with PGMEA to 40% by weight to obtain a solution of siloxane resin B.

Synthesis Example 4 Synthesis of Siloxane Resin C 8.2 g (0.06 mol) of methyltrimethoxysilane, 55.5 g (0.28 mol) of phenyltrimethoxysilane, 7.2 g (0.06 mol) of dimethyldimethoxysilane, zirconia sol “ Nano-use “OZ-30M (trade name: Nissan Chemical Industries, Ltd.) (zirconium oxide 30 wt%, methanol 70 wt%) 70.0 g and PGMEA 47 g were put in a reaction vessel, and 34.5 g of water and phosphoric acid were added to this solution. While stirring, 1.0 g was added dropwise so that the reaction temperature did not exceed 40 ° C. After the dropping, a vacuum distillation apparatus was attached to the flask, and the resulting solution was heated and mixed at a bath temperature of 75 ° C. for 4.5 hours under reduced pressure, and reacted while distilling off the methanol produced by hydrolysis. Then it was cooled to room temperature. The resulting solution was diluted with PGMEA to 40% by weight to obtain a solution of siloxane-based resin C.

Synthesis Example 5 Synthesis of Siloxane Resin D Except for using 45.0 g of PGMEA dispersion (aluminum oxide 30% by weight, PGMEA 70% by weight) of aluminum oxide particles (number average particle diameter 30 nm) instead of “OPTRAIK” TR-520 Performed the same operation as in Synthesis Example 2 to obtain a solution of siloxane-based resin D (solid content: 40% by weight).

Synthesis Example 6 Synthesis of Siloxane Resin E 8.2 g (0.06 mol) of methyltrimethoxysilane, 55.5 g (0.28 mol) of phenyltrimethoxysilane, 5.4 g (0.026 mol) of tetraethoxysilane, number average particle A reaction container containing 52.4 g of “Optlake” TR-521 (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd., composition: titanium oxide particles 30% by weight, diacetone alcohol 70% by weight) and γ-butyrolactone 20.5 g Into this solution, 34.5 g of water 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 mixed 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 mixed at a bath temperature of 130 ° C. for 2 hours, and then cooled to room temperature. The resulting solution was diluted with PGMEA to 40 wt% to obtain a siloxane resin E.

Synthetic Example 7 Synthesis of Siloxane Resin F 12.3 g (0.15 mol) of methyltrimethoxysilane, 41.6 g (0.35 mol) of phenyltrimethoxysilane, “OPTRAIK TR-527” having a number average particle diameter of 15 nm (product) Name, manufactured by Catalyst Chemical Industry Co., Ltd. Composition: 193 g of titanium oxide particles 20 wt%, methanol 80 wt%) and 94.0 g of PGMEA 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, it was added dropwise so that the reaction temperature did not exceed 40 ° C. After the dropping, a distillation apparatus was attached to the flask, and the resulting solution was heated and mixed 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 mixed at a bath temperature of 115 ° C. for 2 hours, and then cooled to room temperature. The resulting solution was diluted with PGMEA to 40 wt% to obtain a solution of siloxane resin F.

Synthesis Example 8 Synthesis of Siloxane Resin G Methyltrimethoxysilane 24.5 g (0.18 mol), phenyltrimethoxysilane 83.3 g (0.42 mol), and γ-butyrolactone 124.0 g were placed in a reaction vessel while stirring. Then, 38 g of water and 0.57 g of phosphoric acid were added dropwise so that the reaction temperature did not exceed 30 ° C. After the dropping, a distillation apparatus was attached to the flask, and the resulting solution was heated and mixed 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 mixed at a bath temperature of 130 ° C. for 2 hours and then cooled to room temperature to obtain a siloxane-based resin G (solid content: 32% by weight).

Example 1
0.2 g of KBM-202SS (product name: manufactured by Shin-Etsu Chemical Co., Ltd.) having the following structure may be added to 25 g of the siloxane-based resin A solution (2 parts by weight with respect to 100 parts by weight of the siloxane-based resin). Stir. The solid content concentration of the obtained composition was measured, and diluted with PGMEA so that the solid content concentration was 22% by weight. Thereafter, filtration was performed with a polypropylene syringe filter to obtain a siloxane-based resin composition 1. Using the composition 1 thus obtained, a cured film was prepared on a glass substrate and a silicon wafer as described above, and the refractive index, transmittance, and crack resistance after thermal load were evaluated. The results are shown in Table 3. .

  Further, a siloxane-based resin composition 1a was obtained by performing the same operation except that the solid content concentration was changed to 22% by weight so as to be 30% by weight. Table 5 shows the result of the film thickness uniformity test performed by the above method using the obtained composition 1a.

Example 2
A composition 2 was obtained in the same manner as in Example 1 except that the siloxane resin B was used instead of the siloxane resin A. The same evaluation as in Example 1 was performed, and the results are shown in Table 3.

  Further, a siloxane-based resin composition 2a was obtained by performing the same operation except that the solid content concentration was changed to 22% by weight so as to be 30% by weight. Table 5 shows the results of a film thickness uniformity test performed by the above method using the obtained composition 2a.

Example 3
Composition 3 was obtained in the same manner as in Example 2 except that the amount of KBM-202SS was changed from 0.2 g to 0.5 g (5 parts by weight with respect to 100 parts by weight of the siloxane resin). The same evaluation as in Example 1 was performed, and the results are shown in Table 3.

  A siloxane-based resin composition 3a was obtained in the same manner except that the solid content concentration was changed to 22% by weight so as to be 30% by weight. Table 5 shows the result of the film thickness uniformity test performed by the above method using the obtained composition 3a.

Example 4
Composition 4 was obtained in the same manner as in Example 2 except that the amount of KBM-202SS was changed from 0.2 g to 5 g (50 parts by weight with respect to 100 parts by weight of the siloxane resin). The same evaluation as in Example 1 was performed, and the results are shown in Table 3.

  Further, a siloxane-based resin composition 4a was obtained by performing the same operation except that the solid content concentration of 22% by weight was changed to 30% by weight. Table 5 shows the results of the film thickness uniformity test performed by the above method using the obtained composition 4a.

Example 5
Composition 5 was obtained in the same manner as in Example 2 except that the amount of KBM-202SS was changed from 0.2 g to 6 g (60 parts by weight with respect to 100 parts by weight of the siloxane-based resin). The same evaluation as in Example 1 was performed, and the results are shown in Table 3.

  Further, a siloxane-based resin composition 5a was obtained by performing the same operation except that the solid content concentration was changed to 22% by weight so as to be 30% by weight. Table 5 shows the results of the film thickness uniformity test performed by the above method using the obtained composition 5a.

Example 6
0.5 g of LS-4320 (product name: manufactured by Shin-Etsu Chemical Co., Ltd.) having the following structure in 25 g of a solution of siloxane-based resin C (5 parts by weight with respect to 100 parts by weight of siloxane-based resin), thermal crosslinking 2 g (20 parts by weight with respect to 100 parts by weight of siloxane resin) of “Nicarak (registered trademark)” MX-270 (trade name: manufactured by Sanwa Chemical Co., Ltd.) having the structure shown below as a functional compound was added and stirred well. The solid content concentration of the obtained composition was measured, and diluted with PGMEA so that the solid content concentration was 22% by weight. Filtration was performed with a polypropylene syringe filter to obtain Composition 6. Using the obtained siloxane-based resin composition 6, the same evaluation as in Example 1 was performed, and the results are shown in Table 3.

Example 7
1 g of TrisML-P (product name: manufactured by Honshu Chemical Co., Ltd.) having the following structure as a thermally crosslinkable compound is dissolved in 5 g of PGMEA (10 parts by weight with respect to 100 parts by weight of siloxane-based resin) to obtain a siloxane-based resin. 25 g of the solution of B, 0.5 g of LS-6400 (product name: manufactured by Shin-Etsu Chemical Co., Ltd.) having the structure shown below (5 parts by weight with respect to 100 parts by weight of the siloxane resin), as a surfactant 5 mg of “Megafuck” F-172 (product name: manufactured by Dainippon Ink, Inc.) was added and stirred well. The solid content concentration of the obtained composition was measured, and diluted with PGMEA so that the solid content concentration was 22% by weight. Filtration was performed with a polypropylene syringe filter to obtain a composition 7. Using the obtained siloxane-based resin composition 7, the same evaluation as in Example 1 was performed, and the results are shown in Table 3.

Example 8
A solution of siloxane-based resin E by dissolving 0.7 g (7 parts by weight of 100 parts by weight of siloxane-based resin) of “Nicarac” MX-270 (trade name: manufactured by Sanwa Chemical Co., Ltd.) as a thermally crosslinkable compound in 5 g of PGMEA 25 g, 0.5 g of bis (4-methylphenyl) dimethoxysilane (5 parts by weight with respect to 100 parts by weight of siloxane resin), and BM-1000 (product name: manufactured by Yusho Co., Ltd.) as a surfactant. 2 mg was added and stirred well. The solid content concentration of the obtained composition was measured, and diluted with PGMEA so that the solid content concentration was 22% by weight. Filtration was performed with a polypropylene syringe filter to obtain a composition 8. Using the obtained siloxane-based resin composition 8, the same evaluation as in Example 1 was performed, and the results are shown in Table 3.

Example 9
In a mixed solution of 5 g of PGMEA and 5 g of γ-butyrolactone, 2.0 g (20 parts by weight with respect to 100 parts by weight of siloxane resin) of “Nicarac” MX-270 (trade name: manufactured by Sanwa Chemical Co., Ltd.) is dissolved as a thermally crosslinkable compound. Then, 25 g of a solution of siloxane-based resin C and 0.7 g of LS-6690 (product name: manufactured by Shin-Etsu Chemical Co., Ltd.) having the following structure (7 parts by weight with respect to 100 parts by weight of siloxane-based resin) were added. Stir well. The solid content concentration of the obtained composition was measured, and diluted with PGMEA so that the solid content concentration was 22% by weight. Filtration was performed with a polypropylene syringe filter to obtain a composition 9. Using the obtained siloxane-based resin composition 9, the same evaluation as in Example 1 was performed, and the results are shown in Table 3.

Example 10
Except for using siloxane-based resin D in place of siloxane-based resin C, and using TM-BIP-A (product name: manufactured by Honshu Chemical Co., Ltd.) having the following structure in place of “Nicalac” MX-270. The same operation as in Example 9 was performed to obtain a composition 10. Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 3.

Example 11
25 g of a solution of siloxane-based resin F was taken, 0.7 g of KBM-202SS (7 parts by weight with respect to 100 parts by weight of siloxane-based resin), 0.7 g of quinonediazide compound obtained in Synthesis Example 1 (100 parts by weight of siloxane-based resin) 7 parts by weight), 2 g of thermally crosslinkable compound “Nicalac” MX-270 (20 parts by weight with respect to 100 parts by weight of siloxane-based resin) and 20 g of PGMEA are added and dissolved to obtain siloxane-based resin composition 11. Obtained.

Next, the positive photosensitive characteristics of the siloxane-based resin composition 11 were evaluated by the following procedure. The siloxane-based resin composition was spin-coated on a 6-inch silicon wafer, and then baked on a 120 ° C. hot plate (Mark-7) for 2 minutes 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, and then rinsed 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.), in an air atmosphere. The coating film was obtained by pre-baking at 120 ° C. for 3 minutes. 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 compound, and then heated at 300 ° C. for 5 minutes on a hot plate in an air atmosphere to obtain a cured film. The obtained cured film was evaluated for refractive index, transmittance, and crack resistance after thermal load, and are shown in Table 3.

Example 12
A composition 12 was obtained in the same manner as in Example 3 except that 1 part by weight of “Nicalac” MX-270 (trade name: manufactured by Sanwa Chemical Co., Ltd.) was used with respect to 100 parts by weight of the siloxane resin. Evaluation similar to Example 1 was performed using the composition 12, and the results are shown in Table 4.

Example 13
A composition 13 was obtained in the same manner as in Example 3 except that 3 parts by weight of “Nicalac” MX-270 (trade name: manufactured by Sanwa Chemical Co., Ltd.) was used with respect to 100 parts by weight of the siloxane resin. Evaluation similar to Example 1 was performed using the composition 13, and the results are shown in Table 4.

Example 14
A composition 14 was obtained in the same manner as in Example 3 except that 20 parts by weight of “Nicalac” MX-270 (trade name: manufactured by Sanwa Chemical Co., Ltd.) was used with respect to 100 parts by weight of the siloxane resin. The same evaluation as in Example 1 was performed using the composition 14, and the results are shown in Table 4.

Example 15
A composition 15 was obtained in the same manner as in Example 3 except that 30 parts by weight of “Nicalac” MX-270 (trade name: manufactured by Sanwa Chemical Co., Ltd.) was used with respect to 100 parts by weight of the siloxane resin. Evaluation similar to Example 1 was performed using the composition 15, and the results are shown in Table 4.

Example 16
A composition 16 was obtained in the same manner as in Example 3 except that 10 parts by weight of TrisML-P (product name: manufactured by Honshu Chemical Co., Ltd.) was used with respect to 100 parts by weight of the siloxane resin. Evaluation similar to Example 1 was performed using the composition 16, and the results are shown in Table 4.

Comparative Example 1
A composition 17 was obtained in the same manner as in Example 2 except that KBM-202SS was not used. Evaluation similar to Example 1 was performed using the composition 17, and the results are shown in Table 4.

Comparative Example 2
A composition 18 was obtained in the same manner as in Example 9 except that LS-6690 was not used. Evaluation similar to Example 1 was performed using the composition 18, and the results are shown in Table 4.

Comparative Example 3
A composition 19 was obtained in the same manner as in Example 10 except that LS-6690 was not used. Evaluation similar to Example 1 was performed using the composition 19, and the results are shown in Table 4.

Comparative Example 4
10.0 g of a solution of the siloxane-based resin G was taken, and “Optlake” TR-52013.3 g (titanium oxide particles 30 w%) having a number average particle diameter of 15 nm was added thereto and stirred. The solid content concentration of the obtained composition was measured, and diluted with PGMEA so that the solid content concentration was 22% by weight. Thereafter, filtration was carried out with a polypropylene syringe filter to obtain a composition 20. Using the obtained siloxane-based resin composition 20, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 4.

Comparative Example 5
A composition 21 was obtained in the same manner as in Example 3 except that KBE-04 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of KBM-202SS. Evaluation similar to Example 1 was performed using the composition 21, and the results are shown in Table 4.

Comparative Example 6
A composition 22 was obtained in the same manner as in Example 7, except that LS-6690 was not used. Evaluation similar to Example 1 was performed using the composition 22, and the results are shown in Table 4.

Comparative Example 7
A composition 23 was obtained in the same manner as in Example 8, except that bis (4-methylphenyl) dimethoxysilane was not used. The same evaluation as in Example 1 was performed using the composition 23, and the results are shown in Table 4.

  The compositions of Examples 1 to 16 and Comparative Examples 1 to 7 are shown in Tables 1 and 2, and the evaluation results are shown in Tables 3 to 5.

  The cured film formed by the siloxane-based resin composition of the present invention is a solid-state imaging device, an on-vehicle camera, a projector, an optical integrated circuit or other micro optical device, an antireflection film, an antireflection plate, an optical filter, an optical display or the like. It is suitably used for a device.

Claims (6)

(A) The alkoxysilane compound is hydrolyzed 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, and the hydrolyzate is subjected to a condensation reaction. A siloxane-based resin composition comprising: a siloxane-based resin obtained by heating, and (b) an organosilane compound represented by the following general formula (1).

(R ¹ may be the same or different and represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. R ² may be the same or different. Well, it 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 15 carbon atoms, m is an integer of 0 to 5, and n is 2 or 3. The siloxane-based resin composition according to claim 1, wherein 5 to 50 parts by weight of the (b) organosilane compound is contained with respect to 100 parts by weight of the (a) siloxane-based resin. The siloxane-based resin composition according to claim 1 or 2, further comprising (c) a quinonediazide compound. A cured film obtained by curing the siloxane-based resin composition according to claim 1. A micro optical device having the cured film according to claim 4. (1) The alkoxysilane compound is hydrolyzed 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, and the hydrolyzate is subjected to a condensation reaction. (A) a step of obtaining a siloxane-based resin, and (2) a step of mixing the (a) siloxane-based resin and (b) an organosilane compound represented by the following general formula (1) in this order. A process for producing a siloxane-based resin composition characterized by the above.

(R ¹ may be the same or different and represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. R ² may be the same or different. Well, it 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 15 carbon atoms, m is an integer of 0 to 5, and n is 2 or 3.