JP5830978B2 - Siloxane resin composition and method for producing the same, cured film obtained by curing the same, optical article having the same, and solid-state imaging device - Google Patents

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 of the present invention is a flattening film for optical lenses including microlens arrays for solid-state imaging devices, solar cells, liquid crystals, organic EL (electroluminescence), plasma displays, and LED (Light emitting diode) lighting devices. It is suitably used for insulating films, protective films, antireflection films, 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 coating properties 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

  An object of the present invention is to provide a siloxane-based resin composition containing a specific solvent, which can be applied without application unevenness and has excellent coating solution stability.

(A) (a-1) A siloxane system obtained by subjecting a silane compound of the general formula (1) and the general formula (2) and / or the general formula (3) to a condensation reaction after hydrolysis in the presence of a solvent. Resin, (B) A siloxane-based resin composition containing a solvent, wherein the (B) solvent in the siloxane-based resin composition is a compound represented by (B-1) general formula (4) and has 1 atm. A solvent having a boiling point of 130 to 180 ° C. and (B-2) a compound represented by the general formula (4) having a boiling point of 190 to 300 ° C., and (B-1) and ( A siloxane-based resin composition, wherein the weight percentage ratio of the solvent of B-2) is (B-1) / (B-2) = 99/1 to 40/60 .
(R ¹ ) Si (R ² ) _a (OR ⁶ ) _3-a (1)
(R ¹ represents a fluoroalkyl group having 3 to 13 fluorine atoms, R ² represents hydrogen or a hydrocarbon group having 1 to 12 carbon atoms, and R ⁶ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. And a plurality of R ¹ , R ² and R ⁶ may be the same or different, and a is 0 or 1.)
(R ³ ) _b Si (OR ⁷ ) _4-b (2)
(R ³ represents hydrogen or a hydrocarbon group having 1 to 12 carbon atoms. R ⁷ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and a plurality of R ³ and R ⁷ are the same or different. And b is 0, 1 or 2.)
R ⁴ Si (R ⁵ ) _c (OR ⁸ ) _3-c (3)
(R ⁴ is a (meth) acryl group, mercapto group, epoxy group, glycidoxy group, carboxylic anhydride group, amino group, isocyanate group, urea group or a monovalent group having 1 to 10 carbon atoms having these substituents. Represents an organic group, R ⁵ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, R ⁸ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and a plurality of R ⁴ , R ⁵ , R ⁸ may be the same or different, and c is 0 or 1.)

(R ⁹ and R ¹⁰ represent hydrogen, an alkyl group having 1 to 12 carbon atoms, an acetyl group, or an aromatic group. R ¹¹ represents hydrogen or a methyl group. E is 0, 1 or 2, and d is 1. An integer from 1 to 3.)
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) (a-1) a solvent, (a-2) a silane compound of the general formula (1) and the general formula (2) and / or the general formula (3) at 20 to 110 ° C. ˜180 minutes to mix (a-2) to hydrolyze the silane compound of general formula (1) and general formula (2) and / or general formula (3), then 50 ° C. or higher (a-1) of the solvent (A-2) by condensing the hydrolyzate of the silane compound of the general formula (1) and the general formula (2) and / or the general formula (3) by mixing at a boiling point (° C.) or lower for 1 to 100 hours (A ) Obtaining a siloxane-based resin, and then mixing the obtained (A) siloxane-based resin and (B) solvent, wherein (B) the solvent is ( B-1) A compound represented by the general formula (4) having a boiling point of 130 to 180 ° C. at 1 atm. A solvent and (B-2) a compound represented by the general formula (4) contain a solvent having a boiling point of 190-300 ° C., the weight% ratio of solvent (B-1) and (B-2) There is a method for producing a sheet Rokisan resin composition, which is a (B-1) / (B -2) = 99 / 1~40 / 60.

  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 applied without uneven application. For example, an optical system including a microlens for a solid-state imaging device It can be suitably used for a lens, a solar cell, a liquid crystal, an organic EL, a plasma display, a flattening film, an antireflection film, etc. of an LED illumination element.

It is a photograph which shows the applicability | paintability after forming a coating film in a 4-inch silicon wafer with the siloxane type resin composition of this invention.

  The present invention will be specifically described below.

  The siloxane-based resin composition of the present invention comprises (A) (a-1) a silane compound represented by (a-2) general formula (1) and general formula (2) and / or general formula (3) in the presence of a solvent. A siloxane-based resin obtained by condensation reaction after hydrolysis, (B) a siloxane-based resin composition containing a solvent, wherein (B) the solvent is a compound represented by (B-1) general formula (4) And a solvent having a boiling point of 130 to 180 ° C. at 1 atm and a compound represented by (B-2) general formula (4) and having a boiling point of 190 to 300 ° C. This is a siloxane-based resin composition. 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 (a-1) solvent of the present invention is not limited by the silane compound of (a-2) general formula (1) and general formula (2) and / or general formula (3), and the stability of the siloxane-based resin composition It is preferable to select in consideration of property, wettability, volatility and the like. Further, it is more preferable to use a solvent having good dispersibility of (E) silica fine particles described later. 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 mono-n-butyl ether, ethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Pyrene glycol monopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol di-n-butyl ether, ethylene glycol di-t -Butyl ether, diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol di-t-butyl ether, dipropylene glycol monomethyl ether, dipropylene Glycol monoethyl ether, dipropylene glycol Nopropyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, Diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol di-n-butyl ether, diethylene glycol di-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono-n-butyl ether, Ethers such as triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol mono-n-butyl ether; methyl ethyl ketone, acetyl acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl Ketones such as ketone, cyclopentanone and 2-heptanone; Amides such as dimethylformamide and dimethylacetamide; Ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene Glycol mono-n-butyl ether acetate, propylene glycol Rumonomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, butyl lactate, propylene glycol diacetate, dipropylene glycol methyl ether acetate, 1 , 3-butylene glycol acetate, cyclohexanol acetate, 1,6-hexanediol acetate, acetates such as triacetin; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, cyclohexane, γ-butyrolactone, N- Examples thereof include methyl-2-pyrrolidone and dimethyl sulfoxide. In the present invention, (a-1) the solvent is a compound represented by the general formula (4), and the boiling point at 1 atm is preferably 130 to 180 ° C. This is because water and alcohol by-produced during the condensation reaction can be easily removed using the difference in boiling points. Specifically, propylene glycol mono-t-butyl ether, ethylene glycol mono-t-butyl ether, propylene glycol mono-n-butyl ether, propylene glycol monopropyl ether, propylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene Glycol monopropyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol di-t-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol Monoethyl ether, dipropylene glycol monopropyl ether, dipropylene Glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, it is more preferable to use tripropylene glycol mono -n- butyl ether. More preferably, a solvent containing a hydroxyl group structure is preferable from the viewpoints of the stability of the coating solution, the coating properties of the coating film prepared from the coating solution (no coating unevenness), and the flash point (safety of the chemical solution). . Specifically, propylene glycol mono-n-butyl ether, propylene glycol monopropyl ether, propylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl Examples include ether, dipropylene glycol monopropyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, and tripropylene glycol mono-n-butyl ether. Moreover, you may use a mixed solvent with solvents other than these.

  The amount of the solvent (a-1) 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-1) because the flash point of the siloxane-based resin composition is increased and workability is improved. Solvents for increasing the flash point include propylene glycol mono-n-butyl ether, propylene glycol monopropyl ether, propylene glycol monoethyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol monopropyl ether, dipropylene glycol The use of monoethyl ether is preferred.

  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. The use of a solvent having a boiling point of 130 to 180 ° C. and a surface tension of 28 mN / m or less, more preferably 26.6 mN / m or less, as a solvent for the hydrolysis reaction is a coating property produced from a coating solution (coating This is preferable from the viewpoint of no unevenness.

  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 relative to 100 parts by weight of the silane compound of the general formula (1) and the general formula (2) and / or the general formula (3) used during the hydrolysis reaction. Is 0.05 parts by weight or more, more preferably 0.1 parts 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-2) After obtaining the silanol compound which is a hydrolyzate by the hydrolysis reaction of the silane compound of General formula (1) and General formula (2) and / or General formula (3), without taking out a silanol compound A siloxane-based resin can be obtained by mixing the reaction liquid at 50 ° C. or more and (a-1) the boiling point (° C.) 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 silane compound represented by (a-2) general formula (1) and general formula (2) and / or general formula (3) used in the siloxane-based resin composition of the present invention will be described.
(R ¹ ) Si (R ² ) _a (OR ⁶ ) _3-a (1)
R ¹ represents a fluoroalkyl group having 3 to 13 fluorine atoms. R ¹ 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 ² represents hydrogen or a hydrocarbon group having 1 to 12 carbon atoms. For example, methyl, ethyl, propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, phenyl, p-styryl, vinyl, and allyl are preferred. R ⁶ represents hydrogen or a hydrocarbon group having 1 to 10 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. 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 plurality of R ¹ , R ² and R ⁶ may be the same or different. A is 0 or 1.
(R ³ ) _b Si (OR ⁷ ) _4-b (2)
R ³ represents hydrogen or a hydrocarbon group having 1 to 12 carbon atoms. For example, methyl, ethyl, propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, phenyl, p-styryl, vinyl, and allyl are preferred. R ³ can be selected appropriately depending on the use of the cured film. For example, the hardness of the cured film is preferably in the range of 1 to 8 carbon atoms, more preferably 1 to 3 carbon atoms. R ⁷ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and may be hydrogen, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, n-butyl group or sec-butyl group. preferable. R ⁷ is preferably a methyl group or an ethyl group from the viewpoint of ease of hydrolysis reaction and availability of raw materials. A plurality of R ³ and R ⁷ may be the same or different. B is 0, 1 or 2.
R ⁴ Si (R ⁵ ) _c (OR ⁸ ) _3-c (3)
R ⁴ is a (meth) acryl group, mercapto group, epoxy group, glycidoxy group, carboxylic anhydride group, amino group, isocyanate group, urea group or a monovalent organic having 1 to 10 carbon atoms having these substituents. Represents a group. An appropriate one can be selected according to the use of the cured film. R ⁵ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. For example, in order to improve the cured film, the range of 1 to 3 carbon atoms is preferable. R ⁸ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and may be hydrogen, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, n-butyl group or sec-butyl group. preferable. R ⁸ is preferably a methyl group or an ethyl group from the viewpoint of easy hydrolysis reaction and availability of raw materials. A plurality of R ⁴ , R ⁵ and R ⁸ may be the same or different. 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 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 (1) 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 (2) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, and methyltri-t. -Butoxysilane, methyltri-sec-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, cyclopentyltrimethoxysilane, hexyltrimethoxysilane, cyclohexyltrimethoxysilane , Octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, 1-naphthi Trimethoxysilane, 2-naphthyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, allyltrimethoxysilane, etc. Can be mentioned.

  Examples of the bifunctional silane compound represented by the general formula (2) 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 (2) include tetramethoxysilane and tetraethoxysilane.

  Examples of the trifunctional silane compound represented by the general formula (3) include 3-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, and γ-acrylic. Oxytrimethoxysilane, γ-acryloxypropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxy Propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycid Xylpropyltri-n-butoxysilane, γ-glycidoxypropyltri-t-butoxysilane, γ-glycidoxypropyltri-sec-butoxysilane, γ-glycidoxypropyltrimethoxysilane, α-glycidoxy Butyltrimethoxysilane, α-glycidoxy-t-butyltriethoxysilane, α-glycidoxy-t-butyltriethoxysilane, α-glycidoxy-t-butyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β- Glycidoxybutyl triethoxy , Γ-glycidoxybutyltrimethoxysilane, 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) ethyltripropoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri-t-butoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri-n-butoxysilane, 2- ( 3,4-epoxycyclohexyl) eth Rutri-sec-butoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 4- (3,4-epoxycyclohexyl) butyltrimethoxy Silane, 4- (3,4-epoxycyclohexyl) butyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, Examples include 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropyl succinic anhydride, and 3-ureidopropyltriethoxysilane.

  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, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldi Ethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-g Sidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, β-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyl Examples include dimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, and 3-methacryloxypropyldimethoxysilane.

  In the present invention, the alkoxysilane compound represented by the general formula (1) and the alkoxysilane compound represented by any one or more of the general formulas (2) to (3) Both general formulas (2) and (3) may be combined, or other alkoxysilane compounds may be used in combination. A preferred ratio of the alkoxysilane compound represented by the general formula (1) and the siloxane resin derived from the alkoxysilane compound represented by any one or more of the general formulas (2) to (3) is a siloxane-based resin. The Si atom derived from the alkoxysilane compound represented by the general formula (1) is 1 to 70 mol%, preferably 5 to 60 mol%, more preferably 10 to 50 mol%, based on 100 mol% of the Si atom. It is. The Si atom derived from the alkoxysilane compound represented by the general formula (2) is 5 to 90 mol%, preferably 20 to 80 mol%, and more preferably 30 to 70 mol%. The Si atom derived from the alkoxysilane compound represented by the general formula (3) is 1 to 50 mol%, preferably 2 to 30 mol%, and more preferably 3 to 20 mol%.

  Since the silane compound represented by the general formula (1) of the present invention 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 2% by weight or more, more preferably 3% by weight or more, further preferably 4% by weight, based on the total solid content of the siloxane-based resin composition. It is preferable to contain the above 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. However, when a large amount of fluorine atoms are introduced into the siloxane-based resin composition, coating unevenness generally occurs during the formation of a coating film because of its water repellency. Therefore, the amount of fluorine atoms introduced is preferably 40% by weight or less, more preferably 30% by weight or less, and still more preferably 20% by weight or less.

  Moreover, in order to improve the hardness of a cured film, it is preferable that the silane compound represented by General formula (2) is a trifunctional alkoxysilane compound. For example, in the general formula (2), methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane and the like are preferably used.

  Furthermore, it is preferable that the silane compound represented by the general formula (2) or (3) is a trifunctional alkoxysilane compound for the purpose of improving coating properties and adhesion to the substrate. For example, γ-glycidoxypropyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, p-styrylsilane, 3-aminopropyltrimethoxy Silane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride are preferred.

  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 100% by mass. More preferably, it is 30-99 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 (B) solvent of the siloxane-based resin composition of the present invention is (B-1) a compound represented by the general formula (4), a solvent having a boiling point of 130 to 180 ° C. at 1 atm and (B -2) It is a compound represented by General formula (4), Comprising: Two types of solvents whose boiling point is 190 to 300 degreeC are contained. The concentration is adjusted using the solvent (B) 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. In addition to the solvent (B) used in the siloxane-based resin composition of the present invention, one or more other solvents may be contained. In this case, the content of the solvent (B) is preferably 20% by weight or more in the total solvent, more preferably 50% by weight or more, and further preferably 80% by weight or more. (B) The solvent may be the same as or different from the solvent of (a-1).

(B-1) A compound represented by the general formula (4), a solvent having a boiling point of 130 to 180 ° C. at 1 atm, and (B-2) a compound represented by the general formula (4). In addition, the coating unevenness is improved by containing two kinds of solvents having a boiling point of 190 ° C. to 300 ° C. Preferably, the solvent (B-2) has a boiling point of 200 ° C. to 280 ° C., more preferably 210 ° C. to 260 ° C.
The weight percent ratio of the solvent of (B-1) to (B-2) is (B-1) / (B-2) = 99/1 to 40/60, preferably 97/3 to 55/45, More preferably, it is 95/5 to 65/35, and more preferably 95/5 to 75/25. If the solvent (B-1) is 99% by weight or more, or the solvent (B-2) is 60% by weight or more, coating unevenness may occur.

  (B-1) A compound represented by the general formula (4), and specific examples of the solvent having a boiling point of 130 to 180 ° C. at 1 atmosphere include ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, 3- Methoxybutyl acetate, 3-methoxybutanol, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene Glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether , Dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol mono-t-butyl ether, ethylene glycol mono-t-butyl ether, propylene glycol mono-n-butyl ether, ethylene glycol mono-n-butyl ether, One or more selected from propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol monoethyl ether, dipropylene glycol dimethyl ether and ethylene glycol monoethyl ether are preferred. More preferably, ethylene glycol mono-t-butyl ether, propylene glycol mono-n-butyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol monoethyl ether, dipropylene glycol dimethyl ether And ethylene glycol monoethyl ether.

(B-2) Specific examples of the solvent represented by the general formula (4) and having a boiling point of 190 ° C. to 300 ° C. include the following solvents. Ethylene glycol diethyl ether, ethylene glycol di-n-butyl ether, ethylene glycol di-t-butyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol di-t- Butyl ether, dipropylene glycol propyl methyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether , Tripropylene glycol monopropyl ether, tripropylene glycol Cole mono-n-butyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol di-n-butyl ether, diethylene glycol di-t-butyl ether, diethylene glycol butyl methyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol Mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol mono-n-butyl ether, triethylene glycol butyl methyl ether, 1,3-butylene glycol, diethylene Glycol monobutyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, 1,3-butylene glycol diacetate, propylene glycol diacetate, triethylene Glycol.
More preferably, R ⁹ or R ¹⁰ in the general formula (4) is preferably an alkyl group having 3 or more carbon atoms, specifically, ethylene glycol di-n-butyl ether, ethylene glycol di-t-butyl ether. , Dipropylene glycol dipropyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol di-t-butyl ether, dipropylene glycol propyl methyl ether, dipropylene glycol monopropyl ether, dipropylene glycol mono-n-butyl ether, tri Propylene glycol monopropyl ether, tripropylene glycol mono-n-butyl ether, diethylene glycol dipropyl ether, diethylene glycol di-n-butyl ether, diethylene glycol di- -Butyl ether, diethylene glycol butyl methyl ether, diethylene glycol monopropyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monopropyl ether, triethylene glycol mono-n-butyl ether, triethylene glycol butyl methyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol mono Examples thereof include propyl ether acetate, ethylene glycol monobutyl ether acetate, and 1,3-butylene glycol diacetate.

  (B-1) A compound represented by the general formula (4) having a boiling point of 130 to 180 ° C. at 1 atm, and a solvent having a surface tension of 28 mN / m or less is a coating property. It is preferable from the viewpoint. For example, ethylene glycol mono-t-butyl ether (boiling point: 153 ° C., surface tension: 26 mN / m), propylene glycol mono-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 mono-n-butyl ether (boiling point: 171 ° C., surface tension: 27 mN / m), propylene glycol monopropyl ether (boiling point: 150 ° C., surface tension: 25. 9 mN / m), propylene glycol mono-n-butyl ether (boiling point: 170 ° C., surface tension: 26.3 mN / m), dipropylene glycol dimethyl ether (boiling point: 175 ° C., surface tension: 26.3 mN / m), etc. . More excellent flatness without coating unevenness include propylene glycol mono-t-butyl ether, ethylene glycol mono-t-butyl ether, propylene glycol mono-n-butyl ether, ethylene glycol mono-n-butyl ether, and dipropylene glycol dimethyl ether. Can be mentioned. You may combine with other solvents other than (B-1) and (B-2).

  The surface tension can be measured by a platinum plate method with an automatic surface tension meter K11 manufactured by KRUSS. The measurement conditions are as follows. Measuring speed (measurement speed): 3 mm / min, Immersion depth (depth at which the plate is immersed): 10 mm, Sensitivity (sensitivity at which the plate detects the liquid level): 0.0015 g.

  The content of the (B) solvent 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 (C) (meth) acrylic surfactant for improving coating properties. (C) As a (meth) acrylic-type surfactant, the polymer containing the following general formula (6) structure is mentioned.

(R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ are hydrogen or a methyl group, R ¹⁹ is an alkyl group, R ²⁰ is a polyester group, R ²¹ is a polyether group, R ²² is an amine salt, , N, o are integers from 0 to 100,000, and l, m, n, o are not 0 at the same time.)
(A-2) When used in combination with the silane compound of the general formula (1) and the general formula (2) and / or the general formula (3), the coating property is further improved, and the streaks from the wafer center to the outside, which will be described later. The unevenness of “striation” that can be formed, the unevenness of “chuck trace” that can be formed in the vacuum chuck portion of the spin coater, and the “wire trace” that occurs because there is no hot plate portion for the transfer wire are reduced.

(C) 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, a nonionic surfactant (o = 0 in the general formula (5)) is good, and 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 good.
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 polyalkylene oxide surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene distearate and the like.

  The content of the surfactant is preferably 0.0001 to 1% by weight in the siloxane-based resin composition, more preferably 0.003 to 0.5% by weight, and still more preferably 0.01 to 0.2% by weight. It is. These may be used alone or in combination of two or more. Regarding the coating properties 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 preferably contains (D) a compound represented by the general formula (5) as a stabilizer for improving coating properties. (D) By containing the compound represented by the general formula (5), the condensation reaction of silanol can be suppressed, and the generation of foreign matter and the storage stability can be improved.

(R ¹² and R ¹³ represent hydrogen, an alkyl group having 1 to 12 carbon atoms, an acetyl group, or an aromatic group. R ¹⁴ represents hydrogen or a methyl group. F is 0, 1 or 2, and g is An integer from 4 to 100.)
(D) Polyalkylene glycol 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.

  (D) As a commercial item of polyalkylene glycol, for example, polypropylene glycol (PPG-400 (molecular weight: 400), PPG-1000 (molecular weight: 1000), PPG-2000 (molecular weight: 2000) manufactured by Wako Pure Chemical Industries, Ltd. , PPG-4000 (molecular weight: 4000)), manufactured by Sanyo Chemical Industries Co., Ltd. (trade names: 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) , UNIOR PB- 00,700,1000,2000), and the like. The molecular weight and addition amount can be adjusted according to the type of siloxane-based resin composition. The amount of (D) polyalkylene glycol used is preferably 0.05 to 50 parts by weight, preferably 1 to 30 parts by weight, more preferably 1 to 100 parts by weight of (A) siloxane-based resin. More preferred is 10 parts by weight or more. It is more preferable to adjust appropriately according to the kind of (B) solvent used for a siloxane-type resin composition, and solid content concentration. (D) By controlling the amount of polyalkylene glycol within the above range, the surface smoothness can be easily controlled, and a siloxane-based resin composition with improved stability can be easily obtained.

  In the present invention, it is preferable to contain (E) silica fine particles from the viewpoint of adjusting the refractive index. (E) Silica fine particles can also be added to the siloxane-based resin composition of the present invention. (E) In the presence of silica fine particles and (a-1) solvent, (a-2) general formula (1) and general From the viewpoint of compatibility, it is preferable to use a composite siloxane-based resin with (E) silica fine particles obtained by subjecting the silane compound of the formula (2) and / or the general formula (3) to a condensation reaction after hydrolysis. (E) The silica fine particles preferably have a number average particle diameter of 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. (E) The number average particle diameter of the silica fine particles should 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 with a transmission electron microscope or a scanning electron microscope, and the like. Can do. The number average particle diameter in the present invention refers to a value measured by a dynamic light scattering method.

  Examples of the (E) 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 (E) silica fine particles, silica fine particles having a porous and / or hollow interior are preferred 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 preferably 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. (E) The refractive index of the silica fine particle itself is preferably from 1.2 to 1.4, more preferably from 1.2 to 1.35. These (E) 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 (E) silica fine particles include those disclosed in JP-A No. 2001-233611 and those generally commercially available as disclosed in Japanese Patent No. 3272111.

  (E) The refractive index of silica fine particles can be measured by the following method. (E) A mixed solution sample of a matrix resin having a solid content concentration of 10% and (E) silica fine particles prepared so that the content of silica fine particles is 0% by mass, 20% by mass, 30% by mass, 40% by mass, and 50% by mass. Each was prepared and applied onto a silicon wafer using a spin coater so that the thickness was 0.3 to 1.0 μm, and then heated and dried on a hot plate at 200 ° C. for 5 minutes to form a coating film. Get. 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 (E) 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 (E) silica fine particles include “OSCAL” of organosilica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd.), colloidal silica “Snowtex”, organosilica sol (manufactured by Nissan Chemical Industries, Ltd.), Examples include high-purity colloidal silica and high-purity organosol “Quartron” (Fuso Chemical Co., Ltd.).

  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. (E) There is no restriction | limiting in particular in content of a silica fine particle, Although it can be made into a suitable quantity with a use, it is common to set it as about 1 to 70 weight% of the total solid of a siloxane-type resin composition. .

  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 the metal chelate compound include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetate bis (ethyl acetoacetate), aluminum tris Examples include aluminum chelate compounds such as acetylacetonate), and magnesium chelate compounds such as ethyl acetoacetate magnesium monoisopropylate, magnesium bis (ethylacetoacetate), alkyl acetoacetate magnesium monosopropylate, and magnesium 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) (a-1) solvent, (a-2) general formula (1), and silane compounds represented by general formula (2) and / or general formula (3). (A-2) Hydrolysis of the silane compound of the general formula (1) and the general formula (2) and / or the general formula (3) by mixing at 20 to 110 ° C. for 1 to 180 minutes, and then 50 ° C. or more ( a-1) Mixing for 1 to 100 hours below the boiling point (° C.) of the solvent (a-2) Hydrolyzate of silane compound of general formula (1) and general formula (2) and / or general formula (3) Can be produced by mixing (A) a siloxane-based resin and then mixing the obtained (A) siloxane-based resin and (B) solvent, and (B) the solvent is (B-1 ) A compound represented by the general formula (4) having a boiling point of 130 to 180 ° C. at 1 atm. Agent and (B-2) boiling a compound represented by the general formula (4) requires that a solvent is from 190 to 300 ° C..

  The refractive index of the cured film obtained from the coating material of the present invention is preferably 1.20 to 1.45. More preferably, it is 1.28 to 1.42. 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.

  It is preferable that (E) silica fine particle used by this invention is contained in 10 mass%-70 mass% in (A) siloxane type resin. If it is 10% 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, the aggregation of the particles hardly occurs, and the resulting cured film surface becomes sufficiently uniform and the cured film 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 1.20 to 1.45, the addition amount of silica fine particles having a porous and / or hollow interior with respect to the total amount of siloxane compounds in the siloxane-based resin composition By adjusting each amount of the silane compound of (a-2) general formula (1) and general formula (2) and / or general formula (3) to 10 mass% to 70 mass%, the desired refraction Rate can be obtained. If it is 1.20 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 for 0.5 to 240 minutes at a temperature of room temperature to 800 ° C. The curing temperature is more preferably from 100 to 800 ° C, still more preferably from 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 higher and lower than 200 ° C. for 1 to 30 minutes, and then the second stage heating is performed at 150 ° C. or higher and 800 ° C. or lower. 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. Preparation of cured film A 4-inch wafer was coated with a siloxane-based resin composition at 700 rpm (10 seconds), followed by 1100 rpm (30 seconds) with a spine coater (1H-360S (Mikasa Co., Ltd.)). Using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.), it was prebaked at 120 ° C. for 3 minutes to obtain a coating film. This coating film was heated on a hot plate in an air atmosphere at 230 ° C. for 5 minutes to obtain a cured film having a thickness of 0.5 μm.

2. Coating liquid stability (defect density)
In a class 1000 clean room, the siloxane-based resin composition was filtered using a 0.2 μmφ polypropylene syringe filter and bottled in a clean bottle. 1 mL of this solution was applied onto a 4-inch silicone wafer, and then applied with a spine coater (1H-360S (Mikasa Co., Ltd.)) at 700 rpm (10 seconds), followed by 1100 rpm (30 seconds), and then a hot plate. Was used for pre-baking at 120 ° C. for 3 minutes to obtain a coating film 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 0.4 (pieces / cm ² ) is satisfactory.

  The value when the above evaluation was performed immediately after obtaining the siloxane-based resin composition was defined as the defect density (initial). Moreover, the value at the time of performing after filtering the above-mentioned filtered siloxane-type resin composition at 23 degreeC for 1 week and 1 month was made into the defect density (1 week later, 1 month later).

3. 1. About coating properties The film produced on the silicon wafer used in the coating liquid stability test was visually observed under a sodium lamp to examine the coating properties. Items include "streaks" irregularities that can be streaked from the center of the wafer to the outside, "chuck traces" irregularities that can be formed on the vacuum chuck of the spin coater, and the "wire" that occurs because there is no hot plate for the transfer wire. The unevenness of the “trace” was observed. The evaluation criteria are as follows.
◎: No unevenness ○: Slight unevenness can be confirmed Δ: Unevenness can be partially confirmed ×: Can be confirmed over the entire surface

4). Refractive index, film thickness Using the ellipsometer (manufactured by Otsuka Electronics Co., Ltd.), the refractive index at a wavelength of 632.8 nm at a room temperature of 23 ° C. was measured. At this time, the film thickness was also measured.

5. Measurement of transmittance 1. On a 5 cm square glass substrate. A cured film was prepared in the same manner as described above (however, the spin coating conditions were adjusted so that the film thickness was 1 μm). For the cured film, an ultraviolet-visible spectrophotometer UV-260 (manufactured by Shimadzu Corporation) was used. Used to measure the transmittance at 400 nm.

6). Measurement of flash point Using the obtained siloxane-based resin composition, the flash point was measured in a JIS K 2265-1 tag sealing method.

7). Adhesion test In the cured film on a 4-inch silicone wafer obtained in step 10, cut with a cutter into 10 grids vertically at 1 mm intervals, 10 so as to be perpendicular to it, and 100 squares of 1 × 1 mm squares. Thereafter, a tape peeling test was performed using a scotch tape. When the film peeling area is 0%: 5B, when the film peeling area is larger than 0 and less than 5%: 4B, when the film peeling is 5% or more and less than 20%: 3B, peeling is 20% or more and less than 50% Case: 2B, when peeling is 50 or more: 1B.

Example 1
Methyltrimethoxysilane 81.7 g (0.60 mol), 3,3,3-trifluoropropyltrimethoxysilane 65.5 g (0.30 mol), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 24. 60.8 g (0.10 mol), 150.8 g of propylene glycol mono-n-butyl ether (PNB, boiling point at 1 atm: 170 ° C., surface tension: 26.3 mN / m) were placed in a reaction vessel, 0.8 g and phosphoric acid 0.86 g 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 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: 40% by weight).

  2.91 g of the obtained polymer solution 1 was taken, 5.81 g of PNB and 0.89 g of dipropylene glycol mono-n-butyl ether (DPNB) were added, and PNB and DPNB were added so as to be 90/10. Further, 0.05 g of alkyl acetoacetate aluminum diisopropylate (AL-D) was added as a curing agent and stirred, and the siloxane-based resin composition was filtered using a 0.2 μmφ polypropylene syringe filter in a class 1000 clean room. Then, it was bottled in a clean bottle to obtain a siloxane-based resin composition 1.

  Using the obtained siloxane-based resin composition 1, the coating liquid stability (defect density), coating properties, refractive index, transmittance, flash point, and adhesion test were measured as described above. The results are shown in Table 3.

  In addition, the compounds used other than Example 1 are shown below.

<Solvent>
Ethylene glycol mono-t-butyl ether (ETB, boiling point: 153 ° C., surface tension: 26 mN / m), propylene glycol mono-t-butyl ether (PTB, boiling point: 151 ° C., surface tension: 24 mN / m), tripropylene glycol monomethyl Ether (TPNB, boiling point: 274 ° C), dipropylene glycol mono-n-butyl ether (DPNB, boiling point: 229 ° C), dipropylene glycol monopropyl ether (DPNP, boiling point: 212 ° C)
<(Meth) acrylic surfactant>
BYK-352, 356 (manufactured by Big Chemie), Polyflow 77 (Kyoeisha Chemical Co., Ltd.)
<Other surfactants>
BYK-333 (siloxane-based surfactant, manufactured by Big Chemie), FTX-218 (fluorine-based surfactant, manufactured by Neos)
<Alkylene glycol>
Polypropylene glycol 400 (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 400 (PPG-400)), polypropylene glycol 1000 (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 1000 (PPG-1000)), polypropylene glycol 2000 (Wako Pure Chemical Industries, Ltd. ( Co., Ltd., molecular weight 2000 (PPG-2000)), polypropylene glycol 4000 (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 4000 (PPG-4000))
<Curing agent>
Aluminum tris (acetylacetonate) (Al-A)
Examples 2-24, Comparative Examples 1-5
(A-1) Solvents, siloxane compounds, solvents ((B-1), (B-2), other solvents), surfactants, (D) alkylene glycol, (E) silica fine particles, curing agents are shown in Table 1. A siloxane-based resin composition was obtained in the same manner as in Example 1 except that the procedure was as described in 2. Tables 3 and 4 show the results obtained by measuring in the same manner as in Example 1 using the obtained siloxane-based resin compositions.

Example 25
Silica fine particles (manufactured by JGC Catalysts & Chemicals Co., Ltd., Surria 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) and PNB 350 g were put in a reaction vessel. While stirring, 49.4 g of water and 0.78 g of phosphoric acid were added dropwise to the solution 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 to distill off by-produced water and then cooled to room temperature to obtain a polymer solution 25 (solid content: 23% by weight).

  Since the silica solid content in the silica fine particles is 20.5% by weight, the silica fine particle solid content is 200 g × 20.5 / 100 = 41 g. The total amount of the siloxane resin component is 34.9 g + 37.3 g + 5.5 g = 77.7 g. However, water and the like are lost due to dehydration condensation after hydrolysis, and the solid content derived from the siloxane resin component is 46 g. It was. Therefore, the weight ratio of the solid content derived from the silica fine particle component and the solid content derived from the siloxane resin component is 47:53 (silica weight ratio (47 wt%)).

  10.07 g of polymer solution 25 was added so that 8.09 g of PNB and 1.76 g of dipropylene glycol mono-n-butyl ether (DPNB) were added, and PNB and DPNB were 90/10. Further, 0.069 g of alkyl acetoacetate aluminum diisopropylate (AL-D) and 0.014 g of BYK-352 were added as a curing agent and stirred. Thereafter, the siloxane-based resin composition was filtered using a 0.2 μmφ polypropylene syringe filter in a class 1000 clean room, and bottled in a clean bottle to obtain a siloxane-based resin composition 25.

  Table 4 shows the results of measurement using the siloxane-based resin composition 25 in the same manner as in Example 1.

Examples 26-31, Comparative Example 6
Table 2 shows (a-1) solvent, siloxane compound, solvent ((B-1), (B-2), other solvents), surfactant, (D) alkylene glycol, (E) silica fine particles, and curing agent. A siloxane-based resin composition was obtained in the same manner as in Example 1 except that the procedure was as described above. Table 4 shows the results of measurement performed in the same manner as in Example 1 using the obtained siloxane-based resin compositions.

  In addition, it showed to Table 1, 2 about the structure of each siloxane-type resin composition obtained by the Example and the comparative example.

  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.

Claims (11)

(A) (a-1) A siloxane system obtained by subjecting a silane compound of the general formula (1) and the general formula (2) and / or the general formula (3) to a condensation reaction after hydrolysis in the presence of a solvent. Resin, (B) A siloxane-based resin composition containing a solvent, wherein the (B) solvent in the siloxane-based resin composition is a compound represented by (B-1) general formula (4) and has 1 atm. A solvent having a boiling point of 130 to 180 ° C. and (B-2) a compound represented by the general formula (4) having a boiling point of 190 to 300 ° C., and (B-1) and ( A siloxane-based resin composition, wherein the weight percentage ratio of the solvent of B-2) is (B-1) / (B-2) = 99/1 to 40/60 .
(R ¹ ) Si (R ² ) _a (OR ⁶ ) _3-a (1)
(R ¹ represents a fluoroalkyl group having 3 to 13 fluorine atoms, R ² represents hydrogen or a hydrocarbon group having 1 to 12 carbon atoms, and R ⁶ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. And a plurality of R ¹ , R ² and R ⁶ may be the same or different, and a is 0 or 1.)
(R ³ ) _b Si (OR ⁷ ) _4-b (2)
(R ³ represents hydrogen or a hydrocarbon group having 1 to 12 carbon atoms. R ⁷ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and a plurality of R ³ and R ⁷ are the same or different. And b is 0, 1 or 2.)
R ⁴ Si (R ⁵ ) _c (OR ⁸ ) _3-c (3)
(R ⁴ is a (meth) acryl group, mercapto group, epoxy group, glycidoxy group, carboxylic anhydride group, amino group, isocyanate group, urea group or a monovalent group having 1 to 10 carbon atoms having these substituents. Represents an organic group, R ⁵ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, R ⁸ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and a plurality of R ⁴ , R ⁵ , R ⁸ may be the same or different, and c is 0 or 1.)
(R ⁹ and R ¹⁰ represent hydrogen, an alkyl group having 1 to 12 carbon atoms, an acetyl group, or an aromatic group. R ¹¹ represents hydrogen or a methyl group. E is 0, 1 or 2, and d is 1. An integer from 1 to 3.) (B-1) The siloxane-based resin composition according to claim 1, wherein the solvent has a surface tension of 28 mN / m or less. (B-1) Solvent is propylene glycol mono-t-butyl ether, ethylene glycol mono-t-butyl ether, propylene glycol mono-n-butyl ether, ethylene glycol-n-butyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether The siloxane-based resin composition according to claim 1, wherein the siloxane-based resin composition is one or more selected from propylene glycol monoethyl ether, dipropylene glycol dimethyl ether, and ethylene glycol monoethyl ether. Furthermore, the siloxane-type resin composition in any one of Claims 1-3 containing (C) (meth) acrylic-type surfactant. Furthermore, (D) the compound represented by General formula (5) is contained, The siloxane-type resin composition in any one of Claims 1-4 characterized by the above-mentioned.
(R ¹² and R ¹³ represent hydrogen, an alkyl group having 1 to 12 carbon atoms, an acetyl group or an aromatic group. R ¹⁴ represents hydrogen or a methyl group. F represents 0, 1 or 2, and g represents 4) Integer from 1 to 100.) Furthermore, (E) Silica fine particle is contained, 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, which has a refractive index of 1.20 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) (a-1) solvent, (a-2) silane compound of general formula (1) and general formula (2) and / or general formula (3) is mixed at 20 to 110 ° C. for 1 to 180 minutes. (A-2) Hydrolyzing the silane compound of the general formula (1) and the general formula (2) and / or the general formula (3), and then at 50 ° C. or higher and (a-1) the boiling point (° C.) or lower of the solvent. (A-2) Mixing for 1 to 100 hours to condense the hydrolyzate of the silane compound of general formula (1) and general formula (2) and / or general formula (3) to obtain (A) siloxane-based resin Next, a method for producing a siloxane-based resin composition, which comprises mixing the obtained (A) siloxane-based resin and (B) solvent, wherein (B) the solvent is represented by the general formula (B-1) (4) a solvent having a boiling point of 130 to 180 ° C. at 1 atm and (B 2) boiling a compound represented by the general formula (4) is a solvent which is 190-300 ° C., a weight% ratio of solvent (B-1) and (B-2), (B- 1) / (B-2) = 99 / 1~40 / 60 method of manufacturing a sheet Rokisan resin composition which is a.
(R ¹ ) Si (R ² ) _a (OR ⁶ ) _3-a (1)
(R ¹ represents a fluoroalkyl group having 3 to 13 fluorine atoms, R ² represents hydrogen or a hydrocarbon group having 1 to 12 carbon atoms, and R ⁶ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. And a plurality of R ¹ , R ² and R ⁶ may be the same or different, and a is 0 or 1.)
(R ³ ) _b Si (OR ⁷ ) _4-b (2)
(R ³ represents hydrogen or a hydrocarbon group having 1 to 12 carbon atoms. R ⁷ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and a plurality of R ³ and R ⁷ are the same or different. And b is 0, 1 or 2.)
R ⁴ Si (R ⁵ ) _c (OR ⁸ ) _3-c (3)
(R ⁴ is a (meth) acryl group, mercapto group, epoxy group, glycidoxy group, carboxylic acid anhydride group, amino group, isocyanate group, urea group, and monovalent monovalent carbon atoms having 1 to 10 carbon atoms having these substituents. Represents an organic group, R ⁵ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, R ⁸ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and a plurality of R ⁴ , R ⁵ , R ⁸ may be the same or different, and c is 0 or 1.)
(R ⁹ and R ¹⁰ represent hydrogen, an alkyl group having 1 to 12 carbon atoms, an acetyl group, or an aromatic group. R ¹¹ represents hydrogen or a methyl group. E is 0, 1 or 2, and d is 1. An integer from 1 to 3.)