JP2012214772A - Siloxane-based resin composition, process for producing the same, cured film made by curing the same, and optical product and solid image-pickup element having the cured film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a siloxane-based resin composition containing a low-refractive index microparticle, the composition being capable of being coated with no coating unevenness on a multilevel substrate, and being excellent in coatability and coating liquid stability.SOLUTION: The siloxane-based resin composition contains (A) a siloxane-based resin made by hydrolyzing and thereafter condensation-reacting (a-3) a specific silane compound in the presence of (a-1) a silica microparticle and (a-2) a solvent, (B) a polyalkylene glycol, and (C) a solvent, wherein the boiling point at 1 atm of (C) the solvent is 130 to 180°C, and the surface tension of (C) the solvent is ≤28 mN/m.

Description

  The present invention relates to a siloxane-based resin composition and a method for producing the same, a cured film obtained by curing the composition, an optical article having the cured film, and a solid-state imaging device. The siloxane-based resin composition and optical article of the present invention include an optical lens including a microlens array for a solid-state imaging device, a flattening film for a thin film transistor (TFT) of a liquid crystal or organic EL (electroluminescence) display, and an antireflection film. It is suitably used for antireflection films, antireflection plates, optical filters and the like.

Charge coupled devices: CCD (charge coupled devices) and complementary metal oxide semiconductors: CMOS (Complementary Metal-Oxide Semiconductor) Image sensors and other solid-state image sensors, display substrates, various anti-reflection films, and other lens materials Various coating materials such as a flattening film and the like are used. These coating materials are required to have many properties such as heat resistance and low-temperature workability in addition to optical properties such as transparency and an appropriate refractive index. It is known that a resin composition containing a siloxane compound is suitable for such a demand (for example, see Patent Document 1). It is also known to make a porous structure a resin composition or a cured film containing siloxane having fluorine atoms and low refractive index fine particles for the purpose of reducing the reflectance. (For example, see Patent Documents 2, 3, and 4)
In many cases, the coating material used for such applications is applied on a base or a substrate having various steps. For this reason, in addition to the above-mentioned characteristics, a performance that completely covers the base step and does not cause uneven coating is required, and a resin composition containing a conventional siloxane compound, particularly with a substrate in a coating method using a spinner. It is also known to improve applicability such as coating unevenness such as improvement in wettability failure and uneven coating thickness. (For example, see Patent Documents 5 and 6)
In particular, the planarization film of a microlens for a solid-state imaging device has a characteristic of planarizing a microlens with large irregularities, and further lowering the refractive index is strongly desired for improving the light collection efficiency of the microlens. . However, a good planarization film that satisfies both of these characteristics is not known.

  In recent years, various siloxane compounds have been used in various applications, but it is necessary to ensure the stability of the coating solution in a clean environment. In particular, it is important that no foreign matter is generated and the coating property does not change even during long-term use under normal temperature (room temperature) conditions. On the other hand, conventional siloxane-based coating materials have problems such as generation of foreign matters and changes in optical properties of films due to long-term storage at room temperature.

JP 2001-81404 A JP 2001-329096 A JP 2008-297550 A JP 2001-166490 A WO2007 / 049440 JP 2008-248239 A

  The present invention provides a siloxane-based resin composition having excellent coating properties and coating liquid stability, which can be applied onto a stepped substrate without uneven coating, in a siloxane-based resin composition containing low refractive index fine particles. With the goal.

In the present invention, (A) (a-1) two or more silane compounds selected from general formulas (1) to (3) are hydrolyzed in the presence of (a-1) silica fine particles and (a-2) solvent. A siloxane-based resin composition comprising a siloxane-based resin subjected to a condensation reaction after decomposition, (B) polyalkylene glycol and (C) a solvent, wherein (C) the solvent has a boiling point of 130 to 180 ° C. under 1 atm. And (C) a siloxane-based resin composition, wherein the solvent has a surface tension of 28 mN / m or less.
(R ¹ ) _a Si (OR ⁶ ) _4-a (1)
(R ¹ represents hydrogen and a hydrocarbon group having 1 to 20 carbon atoms. R ⁶ represents a hydrocarbon group having 1 to 4 carbon atoms, and a plurality of R ¹ and R ⁶ may be the same or different. , A is 0, 1 or 2.)
R ² Si (R ³ ) _b (OR ⁷ ) _3-b (2)
(R ² represents a fluoroalkyl group having ³ to 13 fluorine atoms, R ³ represents a hydrocarbon group having 1 to 5 carbon atoms, R ⁷ represents a hydrocarbon group having 1 to 4 carbon atoms, A plurality of R ² , R ³ and R ⁷ may be the same or different, and b is 0 or 1.)
R ⁴ Si (R ⁵ ) _c (OR ⁸ ) _3-c (3)
(R ⁴ represents a vinyl group, an allyl group, a (meth) acryl group, a mercapto group, an epoxy group, and a hydrocarbon group having 1 to 20 carbon atoms, and R ⁵ represents 1 to 5 carbon atoms. R ⁸ represents a hydrocarbon group having 1 to 4 carbon atoms, and a plurality of R ⁴ , R ⁵ , and R ⁸ may be the same or different, and c is 0 or 1. .)
Moreover, this invention is an optical article which has a cured film formed by hardening | curing the said siloxane resin composition.

  Further, the present invention provides (a-1) silica fine particles, (a-2) solvent, and (a-3) two or more silane compounds selected from general formulas (1) to (3) at 20 to 110 ° C. Mix for 1 to 180 minutes to hydrolyze (a-3) two or more silane compounds selected from general formulas (1) to (3), then 50 ° C. or higher and (a-2) below the boiling point of the solvent. (A-3) is mixed for 1 to 100 hours to condense a hydrolyzate of two or more silane compounds selected from general formulas (1) to (3) to obtain (A) a siloxane-based resin; A method for producing a siloxane-based resin composition, comprising mixing the obtained (A) siloxane-based resin, (B) polyalkylene glycol, and (C) a solvent, wherein (C) the solvent is under 1 atm. The boiling point is 130 to 180 ° C., and (C) the surface tension of the solvent is 28 mN / m or less. A method for producing a siloxane-based resin composition characterized Rukoto.

  According to the present invention, it is possible to provide a siloxane-based resin composition excellent in coating properties and coating liquid stability that can be coated on a stepped substrate without uneven coating. It can be suitably used for an optical lens, a flattening film for TFT of a liquid crystal or an organic EL display.

It is substrate sectional drawing which showed the outline | summary of the level | step difference coverage evaluation of a coating film.

  The present invention will be specifically described below.

  The siloxane-based resin composition of the present invention comprises two types selected from (a-3) general formulas (1) to (3) in the presence of (A) (a-1) silica fine particles and (a-2) a solvent. A siloxane-based resin composition comprising a siloxane-based resin obtained by condensation reaction after hydrolysis of the above silane compound, (B) a polyalkylene glycol, and (C) a solvent, wherein (C) the solvent has a boiling point under 1 atm. It is 130-180 degreeC, and the surface tension of the (C) solvent is 28 mN / m or less, It is a siloxane type resin composition characterized by the above-mentioned. As a result, a cured film having good coating liquid stability and low refractive index can be obtained. Further, the flatness without coating unevenness is also good.

  The number average particle diameter of the (a-1) silica fine particles used in the present invention is preferably 1 to 200 nm. In order to obtain a cured film having a high visible light transmittance, the number average particle diameter is more preferably 1 to 120 nm. Among these, in the case of silica fine particles having a hollow, the number average particle diameter is more preferably 30 to 100 nm. If it is 1 nm or more, the low refractive index is sufficient, and if it is 200 nm or less, reflection is sufficiently suppressed and the hardness of the film is sufficiently high. The number average particle size of the silica fine particles can be measured by a gas adsorption method, a dynamic light scattering method, an X-ray small angle scattering method, a method of directly measuring the particle size using a transmission electron microscope or a scanning electron microscope, and the like. The number average particle diameter in the present invention refers to a value measured by a dynamic light scattering method.

  Examples of the (a-1) silica fine particles used in the present invention include silica fine particles having a porous and / or hollow inside, and silica fine particles having a non-porous inside and having no hollow. Among these silica fine particles, silica fine particles having a porous and / or hollow interior are preferable for reducing the refractive index of the coating film. Silica fine particles which are not porous inside and do not have a hollow have a refractive index of 1.45 to 1.5, so that the expected effect of lowering the refractive index is small. On the other hand, silica fine particles having a porous and / or hollow interior have a large refractive index reduction effect because the refractive index of the particles themselves is 1.2 to 1.4. That is, silica fine particles having a porous and / or hollow interior are preferably used in that they can impart excellent hardness and low refractive index properties.

  The silica fine particle having a hollow inside used in the present invention refers to a silica fine particle having a hollow portion surrounded by an outer shell. Further, the silica fine particles having a porous interior used in the present invention are silica fine particles having a large number of cavities on the surface or inside of the particles. Among these, when the hardness of the transparent coating is taken into consideration, silica fine particles having hollow with high strength of the particles themselves are preferable. The refractive index of the silica fine particle itself is preferably 1.2 to 1.4, and more preferably 1.2 to 1.35. These silica fine particles can be produced by the methods disclosed in Japanese Patent No. 3272111 and Japanese Patent Application Laid-Open No. 2001-233611. Examples of such silica fine particles include those disclosed in Japanese Patent Application Laid-Open No. 2001-233611, and those generally commercially available as disclosed in Japanese Patent No. 3272111.

  The refractive index of silica fine particles can be measured by the following method. A mixed solution sample of a matrix resin and a silica fine particle having a solid content concentration of 10% prepared so that the content of the silica fine particle is 0% by mass, 20% by mass, 30% by mass, 40% by mass, and 50% by mass is prepared. On the wafer, coating is performed using a spin coater so as to have a thickness of 0.3 to 1.0 μm, followed by heating and drying on a hot plate at 200 ° C. for 5 minutes to obtain a coating film. Next, for example, the refractive index at a wavelength of 633 nm can be obtained using an ellipsometer (manufactured by Otsuka Electronics Co., Ltd.), and the value of 100% by mass of silica fine particles can be extrapolated.

  Introducing silica fine particles having a porous and / or hollow interior into the coating material not only can optimize the refractive index of the film obtained from the coating material, but also increase the hardness of the film. preferable.

  Silica fine particles that are not porous inside and have no hollow are, for example, IPA-ST using 12-nm-diameter isopropanol as a dispersant, MIBK-ST using 12-nm methyl isobutyl ketone as a dispersant, particles IPA-ST-L using isopropanol having a diameter of 45 nm as a dispersant, IPA-ST-ZL using isopropanol having a particle diameter of 100 nm as a dispersant (trade name, manufactured by Nissan Chemical Industries, Ltd.), γ having a particle diameter of 12 nm -Oscar 101 using butyrolactone as a dispersant, Oscar 105 using γ-butyrolactone having a particle diameter of 60 nm as a dispersant, Oscar 106 using diacetone alcohol having a particle diameter of 120 nm as a dispersant (trade name, JGC Catalysts & Chemicals ( Co., Ltd.). In addition, the presence or absence of a hollow can be confirmed by a particle cross-sectional image by a TEM (scanning electron microscope) photograph.

  Examples of commercially available silica fine particles include organosilica sol “OSCAL” (manufactured by JGC Catalysts & Chemicals Co., Ltd.), colloidal silica “Snowtex”, organosilica sol (manufactured by Nissan Chemical Industries, Ltd.), high purity colloidal Silica, high-purity organosol “Quartron” (Fuso Chemical Co., Ltd.) and the like can be mentioned.

  In order to obtain a cured film having a low refractive index, it is preferable to contain hollow silica fine particles. The presence or absence of a hollow can be confirmed by a particle cross-sectional image by a TEM (scanning electron microscope) photograph. There is no restriction | limiting in particular in content of a silica fine particle, Although it can be set as a suitable quantity by a use, It is common to set it as about 1-70 weight% of the total solid of a siloxane type resin composition.

  The solvent (a-2) of the present invention is not limited by the hydrolysis reaction of two or more silane compounds selected from (a-3) general formulas (1) to (3) and the condensation reaction of the hydrolyzate. The siloxane-based resin composition is preferably selected in consideration of stability, wettability, volatility, and the like. It is more preferable to use a solvent having good dispersibility of silica fine particles. Two or more kinds of solvents 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, 1-t-butoxy-2-propanol, diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono Propyl ether, ethylene glycol-n-butyl ether, ethylene glycol-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Recall monopropyl ether, propylene glycol-n-butyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethyl ether, and other ethers; methyl ethyl ketone, acetyl acetone, methyl propyl ketone, methyl Ketones such as butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone and 2-heptanone; Amides such as dimethylformamide and dimethylacetamide; Ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate , Propylene glycol monomethyl ether acetate Acetates such as 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, butyl lactate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, cyclohexane, and γ- Examples include butyrolactone, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. In the present invention, propylene glycol-t-butyl ether, ethylene glycol-t-butyl ether, propylene glycol-n-butyl ether, propylene glycol monoethyl ether or ethylene glycol-n-butyl ether is used as a solvent for hydrolysis reaction and condensation reaction. Is more preferable. Moreover, you may use a mixed solvent with solvents other than these.

  The amount of the solvent used during the hydrolysis reaction is preferably 50 parts by weight or more, and more preferably 80 parts by weight or more with respect to 100 parts by weight of the total siloxane compound in the siloxane-based resin composition. On the other hand, the upper limit is preferably 1000 parts by weight or less, and more preferably 500 parts by weight or less. By controlling the amount of the solvent within the above range, the reaction can be easily controlled, and a solvent-soluble resin can be easily obtained.

  Here, the total amount of the siloxane compound means an amount including all of the alkoxysilane compound, its hydrolyzate and its condensate. Specifically, the siloxane-based resin composition is weighed into an aluminum dish, and 200 This refers to the weight of the residual component after being heated in an oven at 2 ° C. for 2 hours.

  Moreover, it is preferable to use a solvent having a high flash point as the solvent (a-2) because the flash point of the siloxane-based resin composition is increased and workability is improved. As a solvent for increasing the flash point, it is preferable to use propylene glycol-n-butyl ether or propylene glycol monoethyl ether.

  After completion of the reaction, it is also preferable to adjust the concentration to an appropriate level as a siloxane-based resin by adding a solvent. In addition, after hydrolysis, a suitable amount of the produced alcohol may be removed by distillation under heating and / or reduced pressure, and then a suitable solvent may be added.

  The hydrolysis reaction is preferably carried out at 20 to 110 ° C. for 1 to 180 minutes after adding an acid catalyst and water 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. As a solvent for the hydrolysis reaction, a solvent having a boiling point of 130 to 180 ° C. and a surface tension of 28 mN / m or less may be used.

  The hydrolysis reaction is preferably performed in the presence of an acid catalyst. Examples of the acid catalyst include hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid or anhydride thereof, ion exchange resin, and the like, particularly formic acid, acetic acid or An acidic aqueous solution containing phosphoric acid is preferred. The content of these acid catalysts is preferably 0.05 with respect to 100 parts by weight of two or more silane compounds selected from (a-3) general formulas (1) to (3) used during the hydrolysis reaction. Part by weight or more, more preferably 0.1 part by weight or more, and preferably 10 parts by weight or less, more preferably 5 parts by weight or less. By performing the hydrolysis reaction using an acid catalyst within the above range, the reaction can be easily controlled.

  Various conditions in the hydrolysis may be set 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, and the like within appropriate ranges, physical properties suitable for the intended application can be obtained.

  The water used for the hydrolysis reaction is preferably ion exchange water. 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.

  (A-3) After obtaining a silanol compound that is a hydrolyzate by hydrolysis reaction of two or more silane compounds selected from the general formulas (1) to (3), the reaction solution is prepared without taking out the silanol compound. The siloxane-based resin can be obtained by mixing at 50 ° C. or higher and (a-2) the boiling point (° C.) or lower of the solvent for 1 to 100 hours and performing 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.

The two or more silane compounds selected from (a-3) general formulas (1) to (3) used in the siloxane-based resin composition of the present invention will be described.
(R ¹ ) _a Si (OR ⁶ ) _4-a (1)
R ¹ represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. R ¹ can be selected appropriately depending on the use of the cured film. For example, in order to improve the hardness of the cured film, the range of 1 to 3 carbon atoms is preferable. R ⁶ represents a hydrocarbon group having 1 to 4 carbon atoms, and is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, an n-butyl group, or a sec-butyl group. A plurality of R ¹ and R ⁶ may be the same or different. R ⁶ is more preferably a methyl group or an ethyl group from the viewpoint of easy hydrolysis reaction and availability of raw materials. A is 0, 1 or 2.
R ² Si (R ³ ) _b (OR ⁷ ) _3-b (2)
R ² represents a fluoroalkyl group having 3 to 13 fluorine atoms. R ² can be selected appropriately depending on the use of the cured film. For example, in order to make the refractive index of the cured film smaller, the number of fluorines can be selected in the range of 9-13. In order to reduce the refractive index while maintaining the hardness of the cured film, the number of fluorine is preferably in the range of 3-5. R ³ represents a hydrocarbon group having 1 to 5 carbon atoms. For example, in order to improve the cured film, the range of 1 to 3 carbon atoms is preferable. R ⁷ represents a hydrocarbon group having 1 to 4 carbon atoms, and is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, an n-butyl group, or a sec-butyl group. A plurality of R ² , R ³ and R ⁷ may be the same or different. R ⁷ is preferably a methyl group or an ethyl group from the viewpoint of ease of hydrolysis reaction and availability of raw materials. B is 0 or 1.
R ⁴ Si (R ⁵ ) _c (OR ⁸ ) _3-c (3)
R ⁴ represents a vinyl group, an allyl group, (meth) acryl group, a mercapto group, a hydrocarbon group having 1 to 20 carbon atoms containing an epoxy group and substituents thereof. An appropriate one can be selected according to the use of the cured film. R ⁵ represents a hydrocarbon group having 1 to 5 carbon atoms. For example, in order to improve the cured film, the range of 1 to 3 carbon atoms is preferable. R ⁸ represents a hydrocarbon group having 1 to 4 carbon atoms, and is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, an n-butyl group, or a sec-butyl group. A plurality of R ⁴ , R ⁵ and R ⁸ may be the same or different. R ⁸ is preferably a methyl group or an ethyl group from the viewpoint of easy hydrolysis reaction and availability of raw materials. C is 0 or 1.

  Specific examples of the alkoxysilane compound represented by the general formulas (1) to (3) are shown below.

  Examples of the trifunctional silane compound represented by the general formula (1) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, and methyltri-t. -Butoxysilane, methyltri-sec-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxy Examples thereof include silane, 1-naphthyltrimethoxysilane, and 2-naphthyltrimethoxysilane. In particular, an alkyl group having 1 to 10 hydrocarbons is preferable from the viewpoint of refractive index. Specifically, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, methyltri-t-butoxysilane, methyltri-sec-butoxysilane, ethyltrimethoxy Silane, ethyltriethoxysilane, and hexyltrimethoxysilane are preferred.

  Examples of the bifunctional silane compound represented by the general formula (1) include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, methylvinyldi Examples thereof include ethoxysilane and cyclohexylmethyldimethoxysilane. Of these, dimethyl dialkoxysilane is preferably used for the purpose of imparting flexibility to the resulting coating film.

  Examples of the tetrafunctional silane compound represented by the general formula (1) include tetramethoxysilane and tetraethoxysilane.

  Examples of the trifunctional silane compound represented by the general formula (2) include trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, and perfluoropropyl. Trimethoxysilane, perfluoropropyltriethoxysilane, perfluoropentyltrimethoxysilane, perfluoropentyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyltripropoxysilane, tri Examples include decafluorooctyltriisopropoxysilane.

  Examples of the bifunctional silane compound represented by the general formula (2) include trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylmethyldipropoxysilane, and trifluoropropylmethyldiisopropoxysilane. , Trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, trifluoropropylvinyldimethoxysilane, trifluoropropylvinyldiethoxysilane, heptadecafluorodecylmethyldimethoxysilane, tridecafluorooctylmethyldimethoxysilane, tridecafluoro Octylmethyldiethoxysilane, tridecafluorooctylmethyldipropoxysilane, tridecafluorooctylmethyldiisopropoxysilane Etc., and the like.

  Examples of the trifunctional silane compound represented by the general formula (3) include 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, and γ. -Methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxytrimethoxysilane, γ-acryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, Glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-n -Butoxysilane, γ-glycidoxypropyltri-t-butoxysilane, γ-glycidoxypropyltri-sec-butoxysilane, γ-glycidoxypropyltrimethoxysilane, α-glycidoxybutyltrimethoxysilane, α-Glycidoxy-t-butyltrie Toxisilane, α-glycidoxy-t-butyltriethoxysilane, α-glycidoxy-t-butyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyl Trimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3, 4-epoxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyl tripropoxysila 2- (3,4-epoxycyclohexyl) ethyltri-t-butoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri-n-butoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri-sec- Butoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 4- (3,4-epoxycyclohexyl) butyltrimethoxysilane, 4- (3,4-epoxycyclohexyl) butyltriethoxysilane and the like.

  Examples of the bifunctional silane compound represented by the general formula (3) include γ-glycidoxypropylmethyldimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropylmethyldiethoxysilane, and γ-methacrylic. Oxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane , Α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidyl Sidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, β-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyl Examples include diethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, 3-methacryloxypropyldimethoxysilane, and octadecylmethyldimethoxysilane.

  As a preferable example of the silane compound represented by the general formula (3), an alkoxysilane compound containing an epoxy group is preferable from the viewpoint of coatability. Specifically, 3-glycidoxypropyltrimethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltriisopropoxysilane Γ-glycidoxy Ropiltri-n-butoxysilane, γ-glycidoxypropyltri-t-butoxysilane, γ-glycidoxypropyltri-sec-butoxysilane, γ-glycidoxypropyltrimethoxysilane, α-glycidoxybutyltri Methoxysilane, α-glycidoxy-t-butyltriethoxysilane, α-glycidoxy-t-butyltriethoxysilane, α-glycidoxy-t-butyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycid Xylbutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4 -Epoxycyclohexyl) methyltrimethoxysila , (3,4-epoxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltripropoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri-t-butoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri-n-butoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltri-sec-butoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 4- (3,4-epoxycyclohexyl) Butyltrimethoxysilane 4- (3,4-epoxycyclohexyl) butyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane , Α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyl Diethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycid Xylpropylmethyldipropoxysilane, β-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane and γ-glycidoxypropylvinyldiethoxysilane are exemplified.

  The alkoxysilane compound represented by any one of these general formulas (1) to (3) is used in a combination of two or more depending on the use of the cured film.

  When lowering the refractive index of the cured film obtained from the siloxane-based resin composition of the present invention or imparting water repellency, (a-3) two or more selected from general formulas (1) to (3) One of the silane compounds is preferably a silane compound represented by the general formula (2). Since the silane compound represented by the general formula (2) has an organic group containing a fluorine atom, the refractive index of the cured film obtained from the siloxane-based resin composition can be lowered and water repellency can be imparted. Examples of the organic group containing a fluorine atom include a trifluoromethyl group, a trifluoropropyl group, a perfluoropropyl group, a perfluoropentyl group, and a tridecafluorooctyl group. Since a film having a low refractive index can be obtained by increasing the fluorine atom content, it is 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, based on the total solid content of the siloxane-based resin composition. More preferably, it contains 10% by weight or more, more preferably 15% by weight or more of fluorine atoms. For the flattening film of the on-chip microlens pattern for the solid-state imaging device, it is preferable to use a material having a low refractive index from the viewpoint of improving the light collection efficiency of the microlens. For this reason, it is preferable to use the alkoxysilane compound which contains the organic group containing a fluorine atom, and does not contain an aromatic ring for this use.

  Moreover, in order to improve the hardness of a cured film, (a-3) 1 type of silane compounds of 2 or more types of silane compounds chosen from General formula (1)-(3) are represented by General formula (1). It is preferable to contain a trifunctional alkoxysilane compound. For example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane and the like are preferably used.

  Furthermore, it is preferable to contain a trifunctional alkoxysilane compound represented by the general formula (3) for the purpose of improving coating properties and adhesion with a (step) substrate. For example, γ-glycidoxypropyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, vinyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane are preferable.

  Since the siloxane-based resin composition of the present invention forms a siloxane cured film, the content of the (A) siloxane-based resin in the total solid content is preferably 10 to 90% by mass. More preferably, it is 20-70 mass%. By being in this range, it is possible to obtain a siloxane-based resin composition having more excellent coating properties and coating stability.

  The siloxane-based resin composition of the present invention contains (B) polyalkylene glycol as a stabilizer for improving coatability. (B) By containing polyalkylene glycol, the condensation reaction of silanol can be suppressed, and generation | occurrence | production reduction | decrease of foreign materials and storage stability can be lengthened.

  The (B) polyalkylene glycol of the present invention is used in terms of improving the stability of the siloxane-based resin composition. Examples thereof include polyethylene oxide, polypropylene oxide, polytetramethylene oxide, and those having a polybutylene oxide structure. Specific examples include polyethylene glycol, polypropylene glycol, polybutylene glycol, and block ether compositions thereof. Of these, diol-type polyalkylene glycols such as polyethylene glycol and polypropylene glycol are preferable. The weight average molecular weight should be selected according to the type of silane compound, the coating method, the curing conditions, etc., but those having a weight average molecular weight of 200 to 20000 are preferred. A weight average molecular weight of 200 or more and 2000 or less is more preferable from the viewpoint of flatness of the cured film, and a weight average molecular weight of 200 or more and 600 or less is more preferable from the viewpoint of low temperature curability and workability. A weight average molecular weight is represented by the weight average molecular weight calculated | required from a hydroxyl value.

  (B) As a commercial item of polyalkylene glycol, for example, Sanyo Kasei Kogyo Co., Ltd. (trade name: New Pole PP, New Pole GP, PEG-200, 300, 400, 600, 1000, 1500, 1540, 2000, 4000N) , 4000S, 6000P, 6000S, 10000, 13000, 20000, 20000P), manufactured by NOF Corporation (trade names: UNIOR D-250, 400, 700, 1000, 1200, 2000, 4000, UNIOR TG-330, 1000, 2000, 3000, 4000, Uniol PB-500, 700, 1000, 2000). The molecular weight and addition amount can be adjusted according to the type of siloxane-based resin composition. The amount of (B) polyalkylene glycol used is preferably from 0.05 to 50 parts by weight, more preferably from 2 to 30 parts by weight, based on 100 parts by weight of the (A) siloxane resin. It is more preferable to adjust appropriately according to the kind of (C) solvent used for a siloxane-type resin composition, and solid content concentration. (B) By making polyalkylene glycol amount into the said range, it becomes easy to control surface smoothness and it is easy to obtain the siloxane-type resin composition which improved stability.

  Further, depending on (a-1) silica fine particles and (a-3) two or more silane compounds selected from the general formulas (1) to (3), (B) condensation of silanol which is an effect of polyalkylene glycol Tetraethylene glycol or triethylene glycol is also preferably used in order to suppress the reaction and further enhance the effects of reducing the generation of foreign matter and increasing the storage stability.

  The concentration of the siloxane-based resin composition of the present invention is adjusted using a solvent (C) so that the solid content has an appropriate concentration. The concentration is not particularly limited, but for example, when film formation is performed by spin coating, the solid content concentration is generally 5 to 85% by weight. The solvent (C) used in the siloxane-based resin composition of the present invention has a boiling point of 130 to 180 ° C. under 1 atm and a surface tension of 28 mN / m or less, but contains one or more other solvents. It doesn't matter. In this case, the content of the solvent (C) is preferably 20% by weight or more in the total solvent, more preferably 50% by weight, and further preferably 80% by weight or more.

  By increasing the content of the solvent having a boiling point under 1 atm of 130 to 180 ° C. and a surface tension of 28 mN / m or less, the flatness without coating unevenness and the (step) coverage are improved.

  Examples of the solvent having a boiling point of 130 to 180 ° C. and a surface tension of 28 mN / m or less include ethylene glycol-t-butyl ether (boiling point: 153 ° C., surface tension: 26 mN / m), propylene glycol -T-butyl ether (boiling point: 151 ° C, surface tension: 24 mN / m), ethylene glycol monoethyl ether (boiling point: 135 ° C, surface tension: 28 mN / m), ethylene glycol-n-butyl ether (boiling point: 171 ° C, surface) Tension: 27 mN / m), propylene glycol monopropyl ether (boiling point: 150 ° C., surface tension: 27 mN / m), propylene glycol-n-butyl ether (boiling point: 170 ° C., surface tension: 27.5 mN / m), etc. . Propylene glycol-t-butyl ether, ethylene glycol-t-butyl ether, propylene glycol-n-butyl ether, and ethylene glycol-n-butyl ether can be exemplified as those having better flatness without coating unevenness.

  Specific examples of other solvents include triethylene glycol, tetraethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol-n-butyl ether, ethylene Ethers such as glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol diethyl ether, 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-methoxybuty Acetates such as acetate, methyl lactate, ethyl lactate, butyl lactate, ketones such as acetylacetone, methylpropylketone, methylbutylketone, methylisobutylketone, cyclopentanone, 2-heptanone, methanol, ethanol, propanol, butanol, isobutyl Alcohols such as alcohol, pentaanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, diacetone alcohol, and aromatics such as toluene and xylene Examples include hydrocarbons, γ-butyrolactone, N-methylpyrrolidinone and the like. 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, dipropylene glycol-n-butyl ether, diacetone alcohol. , Γ-butyrolactone and the like.

  The content of the solvent (C) in the siloxane-based resin composition of the present invention is preferably 30 parts by weight or more and more preferably 50 parts by weight or more with respect to 100 parts by weight of the (A) siloxane-based resin. On the other hand, it is preferably 9900 parts by weight or less, and more preferably 5000 parts by weight or less.

  The siloxane-based resin composition of the present invention may contain a (D) (meth) acrylic surfactant for improving flowability during coating. In particular, when the siloxane compound represented by the general formula (2) is used as one of two or more silane compounds selected from the general formulas (1) to (3), the flowability at the time of coating Will be improved.

  Examples of (D) (meth) acrylic surfactants include polymers containing one or more structures selected from structures represented by the following general formulas (4) to (7).

(In the general formulas (4) to (7), R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be the same or different, and each represents hydrogen or a methyl group. R ¹⁴ represents an alkyl group, R ^15. Represents a polyester group, R ¹⁶ represents a polyether group, and R ¹⁷ represents an amine salt.)
When used in the siloxane-based resin composition of the present invention, the coating property is further improved, and the “striation” unevenness that can be formed in a streak shape from the center to the outside of the wafer and the “chuck trace” unevenness that can be formed on the vacuum chuck portion of the spin coater. This reduces the “wire traces” caused by the lack of a hot plate portion for the transfer wire.

R ¹⁴ is preferably an alkyl group having 1 to 40 carbon atoms, R ¹⁵ is preferably a polyester group having 1 to 40 carbon atoms, and R ¹⁶ is a polyether group having 1 to 40 carbon atoms. Is preferred. If it is these ranges, the repellency of a coating film will be suppressed more. Moreover, it is preferable that the weight average molecular weights of (D) (meth) acrylic-type surfactant are 500-10 million. More preferably, it is 1000-100000. Within this range, the repellency of the coating film is further suppressed. In addition, a weight average molecular weight can be calculated | required in polystyrene conversion by GPC (gel permeation chromatography).

  (D) Examples of commercially available (meth) acrylic surfactants include BYK-350, 352, 356, 361N, 380N, 381, 392, 394, 154 (manufactured by Big Chemie Japan Co., Ltd.), Disroll AQ- 3, Disoll DE12-T, Texnol RS-811 (manufactured by Nippon Emulsifier Co., Ltd.), Polyflow No. 7, Polyflow No. 50E, Polyflow No. 50EHF, Polyflow No. 54N, Polyflow No. 75, Polyflow No. 77, Polyflow No. 85, Polyflow No. 85HF, Polyflow No. 90, polyflow no. 90D-50, Polyflow No. 95, Polyflow No. PW-95, Polyflow No. 99C (Kyoeisha Chemical Co., Ltd.). Preferably, it is a nonionic surfactant (o = 0 in the general formula (5)), BYK-350, 352, 356, 361N, 380N, 381, 392, 394 (manufactured by Big Chemie Japan Co., Ltd.), Polyflow No. 7, Polyflow No. 50E, Polyflow No. 50EHF, Polyflow No. 75, Polyflow No. 77, Polyflow No. 85, Polyflow No. 85HF, Polyflow No. 90, polyflow no. 90D-50, Polyflow No. 95, Polyflow No. PW-95, Polyflow No. 99C (Kyoeisha Chemical Co., Ltd.) is preferred.

  When applying the siloxane-based resin composition of the present invention with a spin coater, BYK-350, 352, 356, 361N is preferably used in order to suppress the generation of foreign substances and coating unevenness.

  Moreover, you may add another surfactant to the siloxane-type resin composition of this invention. There is no restriction | limiting in particular in the kind of other surfactant, For example, a fluorine-type surfactant, a silicone type surfactant, a polyalkylene oxide type surfactant etc. can be used.

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

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

  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 generally 0.0001 to 1% by mass in the siloxane-based resin composition. These may be used alone or in combination of two or more. Regarding the coatability of the siloxane-based resin composition of the present invention, it is preferable to use a (meth) acrylic surfactant.

  The siloxane-based resin composition of the present invention may contain various curing agents that accelerate the curing of the resin composition or facilitate the curing. Specific examples of the curing agent include nitrogen-containing organic substances, silicone resin curing agents, various metal alcoholates, various metal chelate compounds, isocyanate compounds and polymers thereof, melamine resins, polyfunctional acrylic resins, urea resins, and the like. You may contain 1 type or 2 or more types. Of these, metal chelate compounds are preferably used in view of the stability of the curing agent and the processability of the obtained coating film.

  Examples of the metal chelate compound include a titanium chelate compound, a zirconium chelate compound, an aluminum chelate compound, and a magnesium chelate compound. These metal chelate compounds can be easily obtained by reacting a metal alkoxide with a chelating agent. Examples of chelating agents include β-diketones such as acetylacetone, benzoylacetone, and dibenzoylmethane; β-keto acid esters such as ethyl acetoacetate and ethyl benzoylacetate. Preferable specific examples of metal chelate compounds include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate (aluminum chelate M (manufactured by Kawaken Fine Chemical Co., Ltd.)) Aluminum chelate compounds such as aluminum monoacetyl acetate bis (ethyl acetoacetate) and aluminum tris (acetylacetonate), ethyl acetoacetate magnesium monoisopropylate, magnesium bis (ethyl acetoacetate), alkyl acetoacetate magnesium monosopropylate, magnesium Examples include magnesium chelate compounds such as bis (acetylacetonate).

  The content of the curing agent is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, with respect to 100 parts by weight of the total siloxane compound in the siloxane-based resin composition. It is 6 parts by weight or less, more preferably 6 parts by weight or less. Here, the total amount of the siloxane compound means an amount including all of the alkoxysilane compound, its hydrolyzate and its condensate. Specifically, the siloxane-based resin composition is weighed into an aluminum dish, and 200 This refers to the weight of the residual component after being heated in an oven at 2 ° C. for 2 hours.

  Further, since curing of the siloxane compound is accelerated by an acid, it is also preferable to contain a curing catalyst such as a thermal acid generator. Examples of the thermal acid generator include various onium salt compounds such as sulfonium salts, aromatic diazonium salts, diaryliodonium salts, triarylsulfonium salts, and triarylselenium salts, sulfonate esters, and halogen-containing compounds.

  Specific examples of sulfonium salts include 4-hydroxyphenyldimethylsulfonium triflate (prototype “W” manufactured by Sanshin Chemical Industry Co., Ltd.) and benzyl-4-hydroxyphenylmethylsulfonium triflate (prototype). “O” manufactured by Sanshin Chemical Industry Co., Ltd.), 2-methylbenzyl-4-hydroxyphenylmethylsulfonium triflate (prototype “N” manufactured by Sanshin Chemical Industry Co., Ltd.), 4-methylbenzyl-4 -Hydroxyphenylmethylsulfonium triflate, 4-hydroxyphenylmethyl-1-naphthylmethylsulfonium triflate, 4-methoxycarbonyloxyphenyldimethylsulfonium triflate (prototype "J" Sanshin Chemical Industry Co., Ltd. ), Benzyl-4-methoxycarbonyloxypheny Methylsulfonium triflate (prototype “T” manufactured by Sanshin Chemical Industry Co., Ltd.), 4-acetoxyphenylbenzylmethylsulfonium triflate (prototype “U” manufactured by Sanshin Chemical Industry Co., Ltd.), 4 -Acetoxyphenylmethyl-4-methylbenzylsulfonium triflate, 4-acetoxyphenyldimethylsulfonium triflate (prototype "V" manufactured by Sanshin Chemical Industry Co., Ltd.), 4-hydroxyphenyldimethylsulfonium hexa Fluorophosphate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-methylbenzyl-4-hydroxyphenylmethylsulfoniumXafluorophosphate, 4-hydroxyphenylmethyl-1-naphthylmethylsulfonium hexafluorophosphate, 4-methoxycarbonyloxyphenyldimethylsulfonium hexafluorophosphate, benzyl-4-methoxycarbonyloxyphenylmethylsulfonium Hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluorophosphate (prototype “A”, manufactured by Sanshin Chemical Industry Co., Ltd.), 4-acetoxyphenylmethyl-4-methylbenzylsulfonium hexafluorophos Fate, 4-acetoxyphenyldimethylsulfonium hexafluorophosphate (trade name “SI-150” manufactured by Sanshin Chemical Industry Co., Ltd.), “SI-180L” (three Chemical Industry Co., Ltd.), 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium hexa Fluoroantimonate, 4-methylbenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-hydroxyphenylmethyl-1-naphthylmethylsulfonium hexafluoroantimonate, 4-methoxycarbonyloxyphenyldimethylsulfonium Hexafluoroantimonate, benzyl-4-methoxycarbonyloxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxypheny Benzylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylmethyl-4-methylbenzylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexa Examples include fluoroantimonate and benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate.

  Examples of the aromatic diazonium salt include chlorobenzene diazonium hexafluorophosphate, dimethylaminobenzenediazonium hexafluoroantimonate, naphthyldiazonium hexafluorophosphate, dimethylaminonaphthyldiazonium tetrafluoroborate and the like.

  Diaryliodonium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium triflate, 4,4′-di-t-butyl-diphenyliodonium triflate, 4 4,4′-di-t-butyl-diphenyliodonium tetrafluoroborate, 4,4′-di-t-butyl-diphenyliodonium hexafluorophosphate, and the like.

  Examples of triarylsulfonium salts include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, tri (p-chlorophenyl) sulfonium tetrafluoroborate, triphenylsulfone. (P-chlorophenyl) sulfonium hexafluorophosphate, tri (p-chlorophenyl) sulfonium hexafluoroantimonate, 4-t-butyltriphenylsulfonium hexafluorophosphate and the like.

  Triaryl selenium salts include triphenyl selenium tetrafluoroborate, triphenyl selenium hexafluorophosphate, triphenyl selenium hexafluoroantimonate, di (chlorophenyl) phenyl selenium tetrafluoroborate, di (chlorophenyl) phenyl selenium hexafluoro Examples thereof include phosphate, di (chlorophenyl) phenyl selenium hexafluoroantimonate, and the like.

  Examples of the sulfonic acid ester compounds include benzoin tosylate, p-nitrobenzyl-9,10-ethoxyanthracene-2-sulfonate, 2-nitrobenzyl tosylate, 2,6-dinitrobenzyl tosylate, 2,4-dinitrobenzyl tosylate. Rate and the like.

  Examples of halogen-containing compounds include 2-chloro-2-phenylacetophenone, 2,2 ′, 4′-trichloroacetophenone, 2,4,6-tris (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (4'-methoxy-1'-naphthyl) -4,6-bis (trichloromethyl) -s-triazine, bis-2- (4-chlorophenyl) -1,1,1- Trichloroethane, bis-1- (4-chlorophenyl) -2,2,2-trichloroethanol, bis-2- (4-methoxyphenyl) -1,1,1-trichloro Ethane and the like.

  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” manufactured by Midori Chemical Co., Ltd.), 1,8-naphthalimidyl tosylate (trade name “NAI-101” manufactured by Midori Chemical Co., Ltd.), 1,8-naphthalimidyl triflate (trade name “NAI-105”) Thermal acid generators such as “Midori Chemical Co., Ltd.” and 1,8-naphthalimidyl nonafluorobutane sulfonate (trade name “NAI-109” manufactured by Midori Chemical Co., Ltd.) can also be mentioned as examples.

  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.

  When photosensitivity is imparted to the siloxane-based resin composition of the present invention, an arbitrary pattern can be formed by photolithography. The following method is mentioned as an example of a pattern formation process. The siloxane-based resin composition of the present invention is applied and dried by heating at an arbitrary temperature of about 80 ° C to 130 ° C. Next, pattern exposure is performed using an arbitrary exposure light source. After the exposure, development is performed with an arbitrary developer to obtain a desired pattern. After the pattern formation, a cured film pattern can be obtained by heat curing. In this process, post-exposure baking may be performed as necessary after exposure. The exposure light source is not limited, and ultraviolet rays such as i-line, g-line, and h-line, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like can be used.

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

  The siloxane-based resin composition of the present invention includes, for example, (a-1) silica fine particles, (a-2) solvent, and (a-3) two or more silane compounds selected from general formulas (1) to (3) Are mixed at 20 to 110 ° C. for 1 to 180 minutes to hydrolyze (a-3) two or more silane compounds selected from the general formulas (1) to (3), and then 50 ° C. or higher (a-2 ) Mixing for 1 to 100 hours below the boiling point of the solvent, and (a-3) condensing a hydrolyzate of two or more silane compounds selected from the general formulas (1) to (3). And then the obtained (A) siloxane-based resin, (B) polyalkylene glycol and (C) solvent are mixed. In addition, (C) the boiling point of the solvent under 1 atm is 130 to 180 ° C., and (C) the surface tension of the solvent is 28 mN / m or less.

  The refractive index of the cured film obtained from the coating material of the present invention is preferably 1.25 to 1.45. More preferably, it is 1.28-1.38. In this range, in the case where the high refractive index layer having a refractive index of 1.5 to 2.0 is the lower layer, incident light and reflected light at the layer surface and the layer interface effectively interfere with each other, Reflected light entering the field of view can be reduced. The thickness of the cured film is usually 50 to 200 nm, more preferably 70 to 150 nm. In the case of a step film, it is preferable that the film is covered with the film thickness described above.

  In the present invention, (a-1) silica fine particles are preferably contained in 30% by mass to 70% by mass in (A) siloxane-based resin. If it is 30% by mass or more, the effect of lowering the refractive index due to the hollowness of the particles becomes larger, and if it is 70% by mass or less, aggregation of the particles hardly occurs, and the resulting cured film surface becomes sufficiently uniform and the cured film becomes sufficiently uniform. It is less likely to cause a decrease in hardness, a decrease in transmittance due to whitening, and a nonuniformity in refractive index.

  In order to set the refractive index of the cured film after curing to 1.25 to 1.45, (a-1) the amount of silica fine particles having an internal porous and / or hollow structure is set to the total amount in the siloxane-based resin composition. By adjusting each amount of two or more silane compounds selected from (a-3) general formulas (1) to (3) to 30% by mass to 70% by mass with respect to the amount of siloxane compound, A refractive index can be obtained. If it is 1.25 to 1.45, the refractive index difference from the high refractive index layer becomes an appropriate value, and better antireflection properties can be obtained.

  The total amount of the siloxane compound means an amount including all of the alkoxysilane compound, its hydrolyzate and its condensate. Specifically, the siloxane-based resin composition is weighed on an aluminum dish and heated at 200 ° C. This refers to the weight of the residual component after heating in an oven for 2 hours.

  A cured film can be formed by applying the siloxane-based resin composition of the present invention on a substrate to prepare a coating film, and heating and drying and curing the coating film.

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

The heating and drying conditions should be determined depending on the substrate to be applied and the resin composition, but it is usually preferable to perform the treatment at a temperature of room temperature to 400 ° C. for 0.5 to 240 minutes. The curing temperature is more preferably 100 to 400 ° C., further preferably 150 to 400.
° C. Moreover, you may heat and dry under reduced pressure. Depending on the type of solvent used, the first stage heating is performed at a temperature of 70 ° C. or more and less than 200 ° C. for 1 to 30 minutes, and then the second stage heating is performed at 150 ° C. or more and 400 ° C. or less. It can also be preferably used in terms of improving the heat resistance and refractive index stability of the obtained cured film.

Although there is no restriction | limiting in particular in the coating film and the film thickness after hardening, Both the range of 0.001-100 micrometers is common.

  The cured film formed from the siloxane-based resin composition of the present invention includes an on-chip microlens formed on a solid-state imaging device, a hard coat layer used for an antireflection film, a buffer coat of a semiconductor device, a planarizing material, a liquid crystal In addition to the protective film of the display, it can be used as various optical articles such as an interlayer insulating film, a waveguide forming material, a phase shifter material, and various protective films. When it contains a fluorine atom, it exhibits high transparency and a low refractive index, and is therefore preferably used as a planarizing film or various antireflection films formed on the on-chip microlens of the solid-state imaging device. In such applications, the refractive index of the cured film is preferably 1.50 or less, and more preferably 1.45 or less. For example, in a semiconductor device described in Japanese Patent Application Laid-Open No. 2003-86778, the siloxane-based resin composition of the present invention is applied on an inner lens and cured to form a planarizing film, and a color filter, a protective film, A solid-state imaging device with high light collection efficiency can be formed by sequentially forming external microlenses and the like. In any application, the transmittance at a wavelength of 400 nm of a cured film having a thickness of 1 μm is preferably 95% or more, and more preferably 98% or more.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition, the characteristic evaluation in each Example was performed with the following method.

1. Coating stability (defect density)
The siloxane-based resin composition was applied on a 4-inch silicone wafer to obtain a substrate for evaluating surface foreign matter. The presence or absence of surface foreign matter was observed using a surface foreign matter measuring apparatus (manufactured by Hitachi Electronics Engineering Co., Ltd .: trade name: LS-5000), and foreign matters having a size of 0.27 μm or more were counted and represented by defect density (pieces / cm ² ). A defect density of 0 to 0.2 (pieces / cm ² ) was considered good.

  The value when the above evaluation was performed immediately after obtaining the siloxane-based resin composition was defined as the defect density (initial). The value obtained when the obtained siloxane-based resin composition was stored at 23 ° C. for 1 month was defined as the defect density (after 1 month).

2. Film thickness of coating film and cured film Using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., the film thickness of the coating film and the cured film was measured.

3. Step coverage of coating film As shown in FIG. 1, the film thickness of the coating film at the measurement points a, b, c in the vicinity of the step of 0.3 μm in height due to the polyimide pattern and the measurement point d of the flat portion without the step. Was measured. Here, as shown in FIG. 1, the measurement point a is a point having a distance of 10 μm from the end of the polyimide pattern 1, the measurement point b is a point having a distance of 100 μm, the measurement point c is a point having a distance of 500 μm, and the measurement point d is a distance of 5 mm. The above is a portion without a step. The step coverage was evaluated based on a value of ((maximum value of a to c) −d) / d × 100 (%). The smaller this value, the smaller the variation in film thickness due to the step, and the better the step coverage.

4). Refractive index About the obtained cured film on the 4-inch silicone wafer, the refractive index in wavelength 632.8nm in 23 degreeC room temperature was measured using the ellipsometer (made by Otsuka Electronics Co., Ltd.).

5. Heat resistance The cured film on the obtained 4-inch silicone wafer was further heat-treated for 3 minutes on a hot plate at 265 ° C., and the refractive index after the heat treatment was measured. The refractive index difference before and after the heat treatment was determined, and it was determined that the refractive index difference was 0.01 or less.

6). Transmittance The transmittance of 400 nm was measured for the obtained cured film on the 5 cm square glass substrate using an ultraviolet-visible spectrophotometer UV-260 (manufactured by Shimadzu Corporation).

7). Weight average molecular weight (Mw)
The weight average molecular weight (Mw) was determined by polystyrene conversion with GPC (HLC-8220 GPC manufactured by Tosoh Corporation, RI detector, fluidized bed: tetrahydrofuran, column: TSK-GEL SUPPER HM-H). The number average molecular weight (Mn) was calculated at the same time.

Example 1
(I) Silica fine particles (manufactured by JGC Catalysts & Chemicals Co., Ltd., Thruria 4110, silica solid content 20.5% by weight, hollow silica fine particles, number average particle size 80 nm) 200.0 g, methyltrimethoxysilane 34.9 g (0 .26 mol), 3,3,3-trifluoropropyltrimethoxysilane, 37.3 g (0.17 mol), 3,4-epoxycyclohexylethyltrimethoxysilane, 5.5 g (0.02 mol), propylene glycol-t-butyl ether (Kuraray Co., Ltd.), Arcosolve PTB, boiling point under 1 atm: 151 ° C., surface tension: 24 mN / m) 350 g was placed in a reaction vessel, and 49.4 g of water and 0.78 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 stirred at a bath temperature of 80 ° C. for 1.0 hour, and reacted while distilling off the methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 120 ° C. for 2 hours and then cooled to room temperature to obtain a polymer solution 1 (solid content: 23% by weight).

  In addition, since it is 20.5 weight% of silica solid content in the silica fine particle which is (a-1) component, the silica solid content derived from the (a-1) component is 200 g × 20.5 / 100 = 41 g. The total amount of the component (a-3) is 34.9 g + 37.3 g + 5.5 g = 77.7 g, but water and the like are lost due to dehydration condensation after hydrolysis, etc. The minute was 46 g. Therefore, the weight ratio of the solid content derived from the component (a-1) and the solid content derived from the component (a-3) is 47:53.

  (Ii) 20 g of the obtained polymer solution 1 was taken, 0.33 g of polypropylene glycol (Uniol D-400 manufactured by NOF Corporation), propylene glycol-t-butyl ether (Kuraray Co., Ltd.), ARCOSOLVE PTB, Boiling point under 1 atm: 151 ° C., surface tension: 24 mN / m) 15.0 g, (meth) acrylic surfactant BYK-352 (by Big Chemie, Mw = 37300, Mn = 11300), 0.05 g, cured As an agent, 0.05 g of alkyl acetoacetate aluminum diisopropylate was added and stirred, and finally an appropriate amount of propylene glycol-t-butyl ether was added so that the weight ratio of polypropylene glycol to propylene glycol-t-butyl ether was 1:99, A siloxane-based resin composition 1 was obtained. Using the resulting siloxane-based resin composition 1, the coating solution stability (defect density) was evaluated. The results are shown in Table 3. Moreover, the flash point of the obtained siloxane-based resin composition 1 was 19 ° C.

  (Iii) The obtained siloxane-based resin composition 1 was applied on a 6-inch silicon substrate 3 having a step of 0.3 μm height by the polyimide pattern 1 shown in FIG. The coating film 1 was obtained by prebaking at 120 ° C. for 3 minutes using SCW-636 manufactured by Manufacturing Co., Ltd. Using the obtained coating film 1, the step coverage of the coating film was evaluated. The results are shown in Table 3.

  (Iv) Appropriate amount of the obtained siloxane-based resin composition 1 is applied onto a 4-inch silicone wafer, prebaked at 120 ° C. for 3 minutes on a hot plate in an air atmosphere, and then heated at 230 ° C. for 5 minutes. A cured film 1 having a thickness of 0.5 μm was obtained. The obtained cured film 1 was used to evaluate the refractive index and heat resistance. Table 3 shows the measurement results.

  (V) An appropriate amount of the obtained siloxane-based resin composition 1 is applied on a 5 cm square glass substrate, heated on a hot plate in an air atmosphere at 230 ° C. for 5 minutes, and a cured film 1 ′ having a thickness of 1.0 μm. Got. The transmittance was evaluated using the obtained cured film 1 ′. Table 3 shows the measurement results.

Example 2
(A-1) 150 g of silica fine particles, 34.9 g of methyltrimethoxysilane, 3,3,3-tri such that the weight ratio of the silica fine particles and (a-3) silane compound in the solid is 40:60. 37.3 g of fluoropropyltrimethoxysilane, 5.5 g of 3,4-epoxycyclohexylethyltrimethoxysilane, and 308 g of propylene glycol-t-butyl ether were placed in a reaction vessel, and 49.4 g of water and 0.78 g of phosphoric acid were added to this solution. A polymer solution 2, a siloxane-based resin composition 2, a coating film 2, a cured film 2 and a cured film 2 ′ were obtained in the same manner as in Example 1 except that was used. The obtained results are shown in Table 3.

Example 3
(A-1) 97 g of silica fine particles, 34.9 g of methyltrimethoxysilane, 3,3,3-tri such that the weight ratio of the silica fine particles and (a-3) silane compound in the solid is 30:70. 37.3 g of fluoropropyltrimethoxysilane, 5.5 g of 3,4-epoxycyclohexylethyltrimethoxysilane, and 264 g of propylene glycol-t-butyl ether were placed in a reaction vessel, and 49.4 g of water and 0.78 g of phosphoric acid were added to this solution. A polymer solution 3, a siloxane-based resin composition 3, a coating film 3, a cured film 3 and a cured film 3 ′ were obtained in the same manner as in Example 1 except that was used. The obtained results are shown in Table 3.

Example 4
(I) Silica fine particles 200 g, methyltrimethoxysilane 34.9 g, 3, 3, so that the weight ratio of (a-1) silica fine particles and (a-3) silane compound in the solid is 48:52. 37.3 g of 3-trifluoropropyltrimethoxysilane, 2.54 g of 3-mercaptopropyltrimethoxysilane, and 264 g of propylene glycol-t-butyl ether were placed in a reaction vessel, and 49.4 g of water and 0.78 g of phosphoric acid were added to this solution. A polymer solution 4 (solid content: 23% by weight) was obtained in the same manner as in Example 1 (i) except that was used.

  (Ii) 20 g of the obtained polymer solution 4 was taken, 0.33 g of polypropylene glycol (Uniol D-400, manufactured by NOF Corporation), Procoglycol-t-butyl ether (Kuraray Co., Ltd.), Arcosolv PTB, Boiling point under 1 atm: 151 ° C., surface tension: 24 mN / m 15.0 g, (meth) acrylic surfactant BYK-352 (manufactured by Big Chemie) 0.05 g, aluminum tris (acetylacetonate) as a curing agent ) 0.05 g was added and stirred. Finally, an appropriate amount of propylene glycol-t-butyl ether was added so that the weight ratio of polypropylene glycol to propylene glycol-t-butyl ether was 1:99, to obtain a siloxane-based resin composition 4. It was. Using the resulting siloxane-based resin composition 4, the coating solution stability (defect density) was evaluated. The results are shown in Table 3.

  Also, the coating film 4, the cured film 4 and the cured film 4 were the same as in Examples 1 (iii) to (v) except that the obtained siloxane-based resin composition 4 was used instead of the siloxane-based resin composition 1. 'I got. The obtained results are shown in Table 3.

Example 5
(A-1) Silica fine particles and (a-3) The weight ratio of the silane compound in the solid was 47:53, and 2.54 g of 3-mercaptopropyltrimethoxysilane was added to 3-methacryloxypropyltri Except having changed into 3.58 g of methoxysilane, it carried out similarly to Example 4, and obtained the polymer solution 5, the siloxane resin composition 5, the coating film 5, the cured film 5, and cured film 5 '. The obtained results are shown in Table 3.

Example 6
The same procedure as in Example 4 was conducted except that 2.54 g of 3-mercaptopropyltrimethoxysilane was changed to 1.67 g of 3-glycidoxypropyltrimethoxysilane, and polymer solution 6, siloxane-based resin composition 6, coating film 6. A cured film 6 and a cured film 6 ′ were obtained. The obtained results are shown in Table 3.

Example 7
Except not adding (meth) acrylic-type surfactant BYK-352 (made by Big Chemie), it carries out similarly to Example 1, and performs the polymer solution 7, the siloxane-type resin composition 7, the coating film 7, the cured film 7, and A cured film 7 ′ was obtained. The obtained results are shown in Table 3.

Example 8
Polymer solution 8, except that polypropylene glycol (Uniol D-400, manufactured by NOF Corporation) was changed to polypropylene glycol (Uniol D-2000, manufactured by NOF Corporation). A siloxane-based resin composition 8, a coating film 8, a cured film 8, and a cured film 8 ′ were obtained. The obtained results are shown in Table 3.

Example 9
Polymer solution 9, except that polypropylene glycol (Uniol D-400, manufactured by NOF Corporation) was changed to polypropylene glycol (Uniol D-4000, manufactured by NOF Corporation), A siloxane-based resin composition 9, a coating film 9, a cured film 9, and a cured film 9 ′ were obtained. The obtained results are shown in Table 3.

Example 10
Example (Example) except that (meth) acrylic surfactant BYK-352 (manufactured by Big Chemie) was changed to (meth) acrylic surfactant BYK-361N (manufactured by Big Chemie, Mw = 7600, Mn = 2600). 1 was performed to obtain a polymer solution 10, a siloxane-based resin composition 10, a coating film 10, a cured film 10, and a cured film 10 ′. The obtained results are shown in Table 3.

Comparative Example 1
(I) Polymer solution 11 in the same manner as in Example 1 (i) except that propylene glycol monoethyl ether (boiling point: 133 ° C., surface tension: 29.7 mN / m) was used instead of propylene glycol-t-butyl ether. Got.

  (Ii) 20 g of the obtained polymer solution 11 was taken and 15.0 g of propylene glycol-n-butyl ether (boiling point: 170 ° C., surface tension: 27.5 mN / m), (meth) acrylic surfactant BYK-352 ( A siloxane-based resin composition 4 was obtained by adding 0.05 g of Big Chemie) and 0.05 g of alkyl acetoacetate aluminum diisopropylate as a curing agent and stirring. Using the resulting siloxane-based resin composition 11, the coating solution stability (defect density) was evaluated. The results are shown in Table 3. The resulting siloxane-based resin composition 11 had a flash point of 30 ° C.

  Further, in the same manner as in Examples 1 (iii) to (v) except that the siloxane-based resin composition 11 was used instead of the siloxane-based resin composition 1, the step coverage evaluation, refractive index, and heat resistance of the coating film were evaluated. Evaluation and transmittance were evaluated. The results are shown in Table 3.

  In addition, it showed to Tables 1-2 about the structure of each siloxane-type resin composition obtained in Examples 1-10 and the comparative example 1. FIG.

  The siloxane-based resin composition of the present invention can be applied even on a substrate having a level difference without application unevenness, and the coverage of the base level difference is good. The cured film obtained by curing the obtained coating film is an optical lens including a microlens array for a solid-state imaging device, a planarization film for TFTs of liquid crystal and organic EL displays, an antireflection film, an antireflection film, It can be suitably used as an antireflection plate, an optical filter or the like.

1: Polyimide pattern (height 0.3 μm)
2: Coating film 3: Silicon substrate a: Measurement point at a distance of 10 μm from the end of the polyimide pattern b: Measurement point at a distance of 100 μm from the end of the polyimide pattern c: Measurement point at a distance of 500 μm from the end of the polyimide pattern d: End of the polyimide pattern Measuring point of the part with no step, 5mm or more from

Claims (11)

(A) Condensation reaction after hydrolysis of two or more silane compounds selected from (a-3) general formulas (1) to (3) in the presence of (a-1) silica fine particles and (a-2) solvent A siloxane-based resin composition containing a siloxane-based resin, (B) polyalkylene glycol, and (C) a solvent, wherein (C) the solvent has a boiling point of 130 to 180 ° C. under 1 atm, and (C ) A siloxane-based resin composition having a solvent surface tension of 28 mN / m or less.
(R ¹ ) _a Si (OR ⁶ ) _4-a (1)
(R ¹ represents hydrogen and a hydrocarbon group having 1 to 20 carbon atoms. R ⁶ represents a hydrocarbon group having 1 to 4 carbon atoms, and a plurality of R ¹ and R ⁶ may be the same or different. , A is 0, 1 or 2.)
R ² Si (R ³ ) _b (OR ⁷ ) _3-b (2)
(R ² represents a fluoroalkyl group having ³ to 13 fluorine atoms, R ³ represents a hydrocarbon group having 1 to 5 carbon atoms, R ⁷ represents a hydrocarbon group having 1 to 4 carbon atoms, A plurality of R ² , R ³ and R ⁷ may be the same or different, and b is 0 or 1.)
R ⁴ Si (R ⁵ ) _c (OR ⁸ ) _3-c (3)
(R ⁴ represents a vinyl group, an allyl group, a (meth) acryl group, a mercapto group, an epoxy group, and a hydrocarbon group having 1 to 20 carbon atoms, and R ⁵ represents 1 to 5 carbon atoms. R ⁸ represents a hydrocarbon group having 1 to 4 carbon atoms, and a plurality of R ⁴ , R ⁵ , and R ⁸ may be the same or different, and c is 0 or 1. .) (C) The solvent is one or more selected from propylene glycol-t-butyl ether, ethylene glycol-t-butyl ether, propylene glycol-n-butyl ether, and ethylene glycol-n-butyl ether. The siloxane-based resin composition described. The number average particle diameter of (a-1) silica fine particles is 30 to 100 nm, and (a-1) the inside of the silica fine particles is porous and / or hollow. A siloxane-based resin composition. (A-3) One of two or more silane compounds selected from the general formulas (1) to (3) is a silane compound represented by the general formula (2). 4. The siloxane-based resin composition according to any one of 3. Furthermore, (D) (meth) acrylic-type surfactant is contained, The siloxane-type resin composition in any one of Claims 1-4 characterized by the above-mentioned. (B) Polyalkylene glycol is 1 or more types chosen from polypropylene glycol and polyethyleneglycol, The siloxane-type resin composition in any one of Claims 1-5 characterized by the above-mentioned. A cured film obtained by curing the siloxane-based resin composition according to claim 1. The cured film according to claim 7, wherein a refractive index after curing is 1.25 to 1.45. An optical article having the cured film according to claim 7. A solid-state imaging device having the cured film according to claim 7 on a microlens. (A-1) Silica fine particles, (a-2) solvent, and (a-3) two or more silane compounds selected from general formulas (1) to (3) are mixed at 20 to 110 ° C. for 1 to 180 minutes. (A-3) two or more silane compounds selected from the general formulas (1) to (3) are hydrolyzed and then mixed at 50 ° C. or higher and (a-2) below the boiling point of the solvent for 1 to 100 hours. (A-3) by condensing a hydrolyzate of two or more silane compounds selected from general formulas (1) to (3) to obtain (A) a siloxane-based resin, and then obtaining (A) A method for producing a siloxane-based resin composition comprising mixing a siloxane-based resin, (B) polyalkylene glycol, and (C) a solvent, wherein (C) the solvent has a boiling point of 130 to 180 ° C. under 1 atm. And (C) the surface tension of the solvent is 28 mN / m or less. Method of manufacturing that the siloxane-based resin composition.
(R ¹ ) _a Si (OR ⁶ ) _4-a (1)
(R ¹ represents hydrogen and a hydrocarbon group having 1 to 20 carbon atoms. R ⁶ represents a hydrocarbon group having 1 to 4 carbon atoms, and a plurality of R ¹ and R ⁶ may be the same or different. , A is 0, 1 or 2.)
R ² Si (R ³ ) _b (OR ⁷ ) _3-b (2)
(R ² represents a fluoroalkyl group having ³ to 13 fluorine atoms, R ³ represents a hydrocarbon group having 1 to 5 carbon atoms, R ⁷ represents a hydrocarbon group having 1 to 4 carbon atoms, A plurality of R ² , R ³ and R ⁷ may be the same or different, and b is 0 or 1.)
R ⁴ Si (R ⁵ ) _c (OR ⁸ ) _3-c (3)
(R ⁴ represents a vinyl group, an allyl group, a (meth) acryl group, a mercapto group, an epoxy group, and a hydrocarbon group having 1 to 20 carbon atoms, and R ⁵ represents 1 to 5 carbon atoms. R ⁸ represents a hydrocarbon group having 1 to 4 carbon atoms, and a plurality of R ⁴ , R ⁵ , and R ⁸ may be the same or different, and c is 0 or 1. .)

Images