JP2015017195A - Composition for forming reflow-type high refractive index film for solid-state imaging device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film satisfying a high refractive index, high transparency, high heat resistance, high flatness and high light resistance.SOLUTION: A composition for forming the film for solid-state imaging devices contains phenyl silsesquioxane (A), zirconia particles (B) having a 1-100 nm average particle diameter, a curing catalyst (C) and a solvent (D). The phenyl silsesquioxane is a hydrolysis condensate of the hydrolyzable silane shown by the following formula (1): (in the formula, Ris an alkoxy group, an acyloxy group or a halogen group; R's are each independently a 1-10C alkyl group, an alkoxy group or a phenyl group; m is an integer of 0-5). A refractive index of the zirconia particles (B) is 1.50-2.20. An average particle diameter of the zirconia particles (B), which is measured by a dynamic light scattering method, is 1-100 nm. A cured film is obtained by applying the composition for forming the film for solid-state imaging devices onto a substrate and firing the same.

Description

  The present invention relates to a film-forming composition for a solid-state imaging device, and more particularly to a film-forming composition containing polyphenylsilsesquioquinsan, a curing catalyst and zirconia fine particles.

Photodiode embedding materials and microlens materials used for solid-state imaging devices are required to have heat resistance and light resistance to a device manufacturing process and high transparency for use as a device.
Recently, there is a trend to increase the number of pixels in order to achieve higher definition of devices. However, as the number of pixels increases, the amount of light incident on the photodiode decreases due to the reduction in area per pixel. Therefore, in order to increase the light capturing efficiency, the microlens material and the embedding material for the photodiode are required to have a high refractive index in addition to the above characteristics.
For example, a technique for increasing the refractive index using a hybrid material obtained by mixing a siloxane polymer and a fine particle dispersion material in which zirconia or titania is dispersed has been reported (Patent Document 1).

  Furthermore, a method of introducing a condensed cyclic skeleton having a high refractive index into a part of the siloxane polymer has also been reported (Patent Document 2).

  High-refractive index materials are required to have high heat resistance and high light resistance. In particular, high-refractive index materials having good characteristics with respect to light resistance have not been studied.

  In addition, flatness is required for a planarization film for a solid-state imaging device, and there is no study of a high refractive index material that can achieve both flatness and light resistance.

JP 2007-246877 A JP 2008-24832 A

  The present invention has been made in view of such circumstances, and has a high refractive index and is suitable for producing a film for an electronic device that can achieve high transparency, high heat resistance, high light resistance, and high flatness. An object of the present invention is to provide a film-forming composition.

The present invention as a first aspect,
A film-forming composition for a solid-state imaging device comprising phenylsilsesquioxane (A), zirconia particles (B) having an average particle diameter of 1 to 100 nm, a curing catalyst (C), and a solvent (D);
As a second aspect, phenylsilsesquioxane is represented by the following formula (1):

(In the formula, R ¹ is an alkoxy group, an acyloxy group, or a halogen group. R ² is an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a phenyl group. M is an integer of 0 to 5. The film-forming composition according to the first aspect, which is a hydrolysis-condensation product of a hydrolyzable silane represented by
As a third aspect, phenylsilsesquioxane is represented by the following formula (2):

[In Formula (2), R < ² > is a C1-C10 alkyl group, an alkoxy group, or a phenyl group, respectively. m is an integer of 0-5. n is an integer of 3-5. R ³ is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an acyloxy group, a halogen group, an alkoxyalkyleneoxy group,
Chemical group represented by formula (3):

(In Formula (3), R ⁴ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a phenyl group. M is an integer of 0 to 5. n is an integer of 3 to 5.) ,
Chemical group represented by formula (4):

(In the formula (4), ^{R 5} are each an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a phenyl group .m is an integer from 0 to 5.), Or combinations thereof groups. A film-forming composition according to the first aspect, which is a compound represented by:
As a fourth aspect, phenylsilsesquioxane is represented by the above formula (2) and the above formula (5):

(In formula, R < ⁶ > is a C1-C10 alkyl group, an alkoxy group, or a phenyl group, respectively, m is an integer of 0-5.) The film formation composition as described in a 1st viewpoint which is a mixture. object,
As a fifth aspect, the film-forming composition according to any one of the first to fourth aspects, wherein the phenylsilsesquioxane has a weight average molecular weight of 500 to 10,000.
As 6th viewpoint, when the solid content of (B) component is 100 mass parts, the solid as described in any one of 1st viewpoint thru | or 5th viewpoint which contains 5 thru | or 100 mass parts of said (A) component. Film-forming composition for image sensor,
As a seventh aspect, the film forming composition according to any one of the first to sixth aspects, wherein the zirconia particles (B) have a refractive index of 1.50 to 2.20,
As an eighth aspect, the film forming composition according to any one of the first aspect to the seventh aspect, in which the zirconia particles (B) have an average particle diameter of 1 to 100 nm by a dynamic light scattering method,
As a ninth aspect, the film-forming composition according to any one of the first to eighth aspects, wherein the curing catalyst (C) is an ammonium salt, a phosphine, a phosphonium salt, a sulfonium salt, or a metal chelate compound,
As a tenth aspect, a cured film obtained by coating the film-forming composition according to any one of the first aspect to the ninth aspect on a substrate and firing, and as an eleventh aspect, a cured film according to the tenth aspect It is a solid-state image sensor provided with as a planarizing film.

The reflow-type film forming composition for a solid-state imaging device of the present invention has high refractivity because the phenylsilsesquioxane (A) component contained in the composition has a high refractive index and high transparency. Flatness can be achieved.
When the dispersed particle diameter of the zirconia particles (B) by the dynamic light scattering method is 1 to 100 nm, the filterability is good and the high transmittance of the film-forming composition can be achieved. Since the component (B) is zirconia particles, it does not absorb light in the vicinity of 400 nm like titania particles, and the transmittance is increased.
When the solid content of the component (B) is 100 parts by mass, a low refractive index component other than zirconia particles can be reduced by using a composition containing 5 to 100 parts by mass of the component (A). Thus, a film excellent in heat resistance and light resistance can be obtained while having high flatness.
Since (C) component contains a curing catalyst, it promotes the condensation reaction between the hydroxyl groups of phenylsilsesquioxane (A) component and zirconia particles (B) during curing, and has sufficient solvent resistance for solid-state imaging device applications. And the reliability as a permanent film is enhanced.
The film obtained by the present invention can satisfy high refractive index, high transparency, high heat resistance, high flatness, and high light resistance at a time, and particularly high flatness and high light resistance are required. It can be suitably used as a planarizing film of a solid-state imaging device.

Sectional drawing of the board | substrate with a structure which evaluated planarization property.

The present invention relates to a film-forming composition for a solid-state imaging device comprising phenylsilsesquioxane (A), zirconia particles (B) having an average particle diameter of 1 to 100 nm, a curing catalyst (C), and a solvent (D). It is a thing.

  The solid content concentration of the film-forming composition only needs to be adjusted so as to obtain the film thickness of the target film, and is 0.1 to 50% by mass, or 1 to 30% by mass, or 5 to 20% by mass. Concentration range. The solid content is the remaining ratio after the solvent is removed from the film-forming composition.

The content of phenylsilsesquioxane (A), zirconia particles (B), and curing catalyst (C) in the solid content is 50 to 100% by mass, or 70 to 100% by mass, or 70 to 99% by mass. Can do.
The silsesquioxane used in the present invention has a ring-like structure, a cage-like structure, or a ladder structure, and a random structure may be added thereto.

  The above phenylsilsesquioxane can be used as a hydrolysis condensate (polysiloxane) of a hydrolyzable silane represented by the formula (1).

In the formula (1), R ¹ is an alkoxy group, an acyloxy group, or a halogen group. R ² is an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a phenyl group. m is an integer of 0-5.
Examples of the alkoxy group include an alkoxy group having a linear, branched or cyclic alkyl moiety having 1 to 10 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i- Butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl -N-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group 2-methyl-n-pentyloxy group, 3-methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n -Butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group Group, 1-ethyl-2-methyl-n-propoxy group and the like, and cyclic alkoxy groups include cyclopropoxy group, cyclobutoxy group, 1-methyl-cyclopropoxy group, 2-methyl-cyclopropoxy group, cyclopentyl Loxy group, 1-methyl-cyclobutoxy group, 2-methyl-cyclobutoxy group, 3-methyl-cyclobutoxy group, 1,2-dimethyl-cyclopropoxy group, 2,3-dimethyl-cyclopro Xy group, 1-ethyl-cyclopropoxy group, 2-ethyl-cyclopropoxy group, cyclohexyloxy group, 1-methyl-cyclopentyloxy group, 2-methyl-cyclopentyloxy group, 3-methyl-cyclopentyloxy group, 1-ethyl-cyclobutoxy group, 2-ethyl-cyclobutoxy group, 3-ethyl-cyclobutoxy group, 1,2-dimethyl-cyclobutoxy group, 1,3-dimethyl-cyclobutoxy group, 2,2-dimethyl- Cyclobutoxy group, 2,3-dimethyl-cyclobutoxy group, 2,4-dimethyl-cyclobutoxy group, 3,3-dimethyl-cyclobutoxy group, 1-n-propyl-cyclopropoxy group, 2-n-propyl- Cyclopropoxy group, 1-i-propyl-cyclopropoxy group, 2-i-propyl-cyclopropoxy group, 1,2,2-trimethyl- Chloropropoxy group, 1,2,3-trimethyl-cyclopropoxy group, 2,2,3-trimethyl-cyclopropoxy group, 1-ethyl-2-methyl-cyclopropoxy group, 2-ethyl-1-methyl-cyclopropoxy group Group, 2-ethyl-2-methyl-cyclopropoxy group, 2-ethyl-3-methyl-cyclopropoxy group and the like.
Examples of the acyloxy group include an acyloxy group having 1 to 10 carbon atoms, such as methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, i-propylcarbonyloxy group, n-butylcarbonyloxy group, i- Butylcarbonyloxy group, s-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, 1-methyl-n-butylcarbonyloxy group, 2-methyl-n-butylcarbonyloxy group, 3- Methyl-n-butylcarbonyloxy group, 1,1-dimethyl-n-propylcarbonyloxy group, 1,2-dimethyl-n-propylcarbonyloxy group, 2,2-dimethyl-n-propylcarbonyloxy group, 1- Ethyl-n-propylcarbonyloxy group, n-hexylcarbo Nyloxy group, 1-methyl-n-pentylcarbonyloxy group, 2-methyl-n-pentylcarbonyloxy group, 3-methyl-n-pentylcarbonyloxy group, 4-methyl-n-pentylcarbonyloxy group, 1,1 -Dimethyl-n-butylcarbonyloxy group, 1,2-dimethyl-n-butylcarbonyloxy group, 1,3-dimethyl-n-butylcarbonyloxy group, 2,2-dimethyl-n-butylcarbonyloxy group, 2 1,3-dimethyl-n-butylcarbonyloxy group, 3,3-dimethyl-n-butylcarbonyloxy group, 1-ethyl-n-butylcarbonyloxy group, 2-ethyl-n-butylcarbonyloxy group, 1,1 1,2-trimethyl-n-propylcarbonyloxy group, 1,2,2-trimethyl-n-propylcarbonyloxy group, Examples thereof include a til-1-methyl-n-propylcarbonyloxy group, a 1-ethyl-2-methyl-n-propylcarbonyloxy group, a phenylcarbonyloxy group, and a tosylcarbonyloxy group.

  Examples of the halogen group include fluorine, chlorine, bromine and iodine.

R ² is a substituent to the phenyl group, and examples thereof include an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a phenyl group.
The alkyl group is a linear or branched alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n- Propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2- Methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3 -Dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-di Til-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1 2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, and the like.

A cyclic alkyl group can also be used. For example, as a cyclic alkyl group having 1 to 10 carbon atoms, a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2 -Ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl Group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl Group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2- n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl The groups 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl and Examples include 2-ethyl-3-methyl-cyclopropyl group.

Alkoxy group for R ² can be exemplified an alkoxy group as described above.

The phenylsilsesquioxane obtained by hydrolyzing the silane of formula (1) can exemplify the structure of formula (2).
^{R 2} can be exemplified by the same and ^{R 2} of formula (1) in equation (2). m is an integer of 0-5. n can exemplify 3-5. When n is 3, a 6-membered ring composed of silicon and oxygen is formed. When n is 4, an 8-membered ring composed of silicon and oxygen is formed. When n is 5, a 10-membered ring composed of silicon and oxygen is formed. It is formed.

R ³ bonded to silicon forming a ring is represented by a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an acyloxy group, a halogen group, an alkoxyalkyleneoxy group, a chemical group represented by formula (3), and formula (4), respectively. Or a combination of these groups.

  Examples of the alkoxy group, acyloxy group, and halogen group can include the above-mentioned examples.

Formula (3) is cyclic silsesquioxane, and R ⁴ in formula (3) may be the same as R ² in formula (2). m is an integer of 0-5.

Formula (4) is a random silsesquioxane structure. R ⁵ in formula (4) may be the same as R ² in formula (2). m is an integer of 0-5.

Therefore, the silsesquioxane of the formula (2) has a ring structure, a cage structure, or a ladder structure, and a random structure may be added thereto. In the formula (2), when R ³ is a hydroxyl group, an alkoxy group, an acyloxy group, a halogen group, or an alkoxyalkyleneoxy group, it has a ring structure. In the formula (2), when R ³ is the formula (3), it is a cage structure and a ladder structure. In the formula (2), when R ³ is the formula (4), it is a structure in which a random structure portion is added to the ring-shaped structure, the cage-shaped structure, and the ladder structure.

  The structure of Formula (4) can be made into the silsesquioxane structure whose repeating unit is 1-70, 1-50, or 1-5, for example.

R ^{3 in the} formula (2) is a compound in which when an alcohol such as propylene glycol monomethyl ether or propylene glycol monoethyl ether is used as a solvent for hydrolysis and condensation, the hydrolyzate of the silane reacts with the above-mentioned solvent. Formula (6-1), Formula (6-2):

An alkoxyalkyleneoxy group having the following structure can be taken. Examples of the alkoxy group can include the above-described examples, and examples of the alkylene group include alkylene groups corresponding to the above-described alkyl groups.
As the phenylsilsesquioxane, a mixture of the formulas (2) and (5) may be used.
In the formula (5), R ⁶ may be the same as R ² in the formula (2). m is an integer of 0-5.
The polysiloxane obtained by hydrolyzing at least one hydrolyzable silane represented by the formula (1) and condensing the hydrolyzate has a weight average molecular weight of, for example, 500 to 10,000. These molecular weights are average molecular weights obtained in terms of standard polystyrene by gel permeation chromatography (hereinafter abbreviated as GPC) analysis.
Examples of the hydrolysis catalyst for synthesizing the silsesquioxane (polysiloxane) include organic acids, inorganic acids, organic bases, and inorganic bases.

Examples of organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid (succinic acid), maleic acid, methylmalonic acid, adipic acid, sebacic acid, Gallic acid, butyric acid, merit acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, Examples include monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.
Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and the like.

Examples of organic bases include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazine Examples include xabicycloundecene, tetramethylammonium hydroxide, 1,8-diazabicyclo [5,4,0] -7-undecene.
Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like. Of these catalysts, organic acids and inorganic acids are preferable, and one or more catalysts may be used simultaneously.
For hydrolysis of an alkoxy group bonded to a silicon atom of a hydrolyzable silane (hereinafter referred to as a hydrolyzable group), 0.1 to 100 mol, or 0.1 to 10 mol, per mol of these hydrolyzable groups, Or 1 to 5 mol, or 2 to 3.5 mol of water is used. Further, 0.0001 to 10 mol, preferably 0.001 to 2 mol, of a hydrolysis catalyst can be used per mol of hydrolyzing group.

The reaction temperature for carrying out the hydrolysis and condensation is usually 23 ° C. (room temperature) or higher and the reflux temperature at normal pressure of the organic solvent used for the hydrolysis.
Hydrolysis may be carried out completely (converting all hydrolyzable groups to silanol groups) or partially hydrolyzed (unreacted hydrolyzable groups remain). Moreover, the hydrolyzate may remain after the hydrolysis and condensation reaction.
Although it does not specifically limit as a method to obtain polysiloxane, For example, the method of heating the mixture of the silane compound, the organic solvent, water, and the oxalic acid which is a catalyst for hydrolysis is mentioned. Specifically, after adding oxalic acid and water to alcohol in advance to obtain a solution of oxalic acid, the solution and the silane compound are mixed and heated. In that case, the amount of succinic acid is generally 0.2 to 2 mol relative to 1 mol of all hydrolyzable groups (alkoxy group and the like) of the silane compound. The heating in this method can be performed at a liquid temperature of 50 to 180 ° C., and is preferably performed, for example, for 10 minutes to 12 hours under reflux in a sealed container so that the liquid does not evaporate or volatilize. The synthesis of polysiloxane may be in the order of adding a mixture of an organic solvent, water and oxalic acid to the silane compound and reacting them, or in the order of adding the silane compound to the mixture of organic solvent, water and oxalic acid and reacting. The reaction temperature at the time of synthesizing the polysiloxane may be reacted at a reaction temperature of 0 to 50 ° C. for 24 to 2000 hours for the purpose of stably synthesizing a uniform polymer.

Examples of the organic solvent used for hydrolysis include toluene, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, diacetone alcohol, methyl ethyl ketone, methyl-isobutyl ketone, and cyclohexanone. , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl lactate, N-methylpyrrolidone and the like. These solvents can be used alone or in combination of two or more.
Since alcohol is produced by the hydrolysis reaction, alcohols and organic solvents having good compatibility with alcohols are generally used as the organic solvent. Specific examples of such organic solvents include methanol, ethanol, propanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, n-propyl acetate, and lactic acid. Preferred examples include ethyl, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether, and cyclohexanone.

Hydrolyzable silane is hydrolyzed in an organic solvent, and the hydrolyzate is subjected to a condensation reaction to obtain a condensate (polysiloxane), which is obtained as a polysiloxane varnish dissolved in the organic solvent. It is done.
The polysiloxane varnish obtained may be solvent-substituted. Specifically, when ethanol is selected as the organic solvent for the hydrolysis and condensation reaction (solvent for synthesis), after the polysiloxane is obtained in ethanol, a replacement solvent is added, and the ethanol is azeotroped with an evaporator or the like. It may be distilled off. At the time of solvent replacement, since the solvent during synthesis is distilled off azeotropically, it is preferable that the boiling point is lower than that of the replacement solvent. For example, the synthesis solvent includes methanol, ethanol, isopropanol and the like, and the substitution solvent includes propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone and the like.

In addition, the obtained polysiloxane varnish can be made to have a solid concentration of 100% by distilling off the organic solvent if the storage stability is not bad.
The organic solvent used for the dilution of the polysiloxane varnish may be the same as or different from the organic solvent used for the hydrolysis and condensation reaction of the hydrolyzable silane.
Specific examples of such organic solvents include toluene, p-xylene, o-xylene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, ethylene glycol monoethyl. Ether, ethylene glycol monoisopropyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl Ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol, 1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol, 1-methoxy- 2-butanol, cyclohexanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyl Lactone, acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, methyl Isobutyl ketone, methyl normal butyl ketone, cyclohexanone, ethyl acetate, isopropyl acetate, normal propyl acetate, isobutyl acetate, normal butyl acetate, methanol, ethanol, isopropanol, tert-butanol, allyl alcohol, normal propanol, 2-methyl-2- Butanol, isobutanol, normal butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol, 1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol, 1-methoxy-2-butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol, isop Pyrether, 1,4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, N-cyclohexyl-2-pyrrolidinone Is mentioned. Polysiloxane varnish, more preferably methanol, ethanol, isopropanol, butanol, diacetone alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol, propylene glycol, hexylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, Examples include butyl carbitol, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monobutyl ether, cyclohexanone, acetic acid methyl ester, acetic acid ethyl ester, and lactate ethyl ester.
The component (B) used in the present invention is zirconia particles (B) having an average particle diameter of 1 to 100 nm, and the refractive index of the zirconia particles (B) is 1.50 to 2.20, or 1.50. A range of 1.70, or 1.60 to 2.00, or 1.90 to 2.20, or 2.20 to 2.70 can be selected.

The zirconia particles may be used alone or in combination of two or more.
As the component (B) used in the present invention, zirconia particles having an average particle diameter of 1 to 100 nm, 5 to 50 nm, or 10 nm or less by a dynamic light scattering method can be used.
Regarding the above particle diameter, zirconia particles having different average particle diameters may be mixed and used.

  In addition, when using the zirconia particles, the particles may be used as they are, and those in a colloidal state in which the particles are previously dispersed in water or an organic solvent (in which colloidal particles are dispersed in a dispersion medium, ie, sol). It may be used. The concentration of zirconia particles in the sol can be used in the range of 0.1 to 60% by mass.

Furthermore, particles obtained by treating zirconia particles with silicon oxide, an organosilicon compound, an organometallic compound, or the like may be used.
The treatment with silicon oxide is to grow silicon oxide particles on the particle surface in a dispersion containing zirconia particles by a known method. The treatment with an organosilicon compound or an organometallic compound means that these compounds are added to a dispersion containing zirconia particles, and these compounds or reaction products of these compounds are adsorbed or bonded to the surface of the zirconia particles. Is.

Examples of the organosilicon compound include silane coupling agents and silanes. Specific examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and 2- (3,4-epoxycyclohexyl). ) Ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethylditriethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyl Dimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (A Noethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyltriethoxysilane, 3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-chloropropyltri Examples include methoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, and 3-isocyanatopropyltriethoxysilane.

Specific examples of silane include methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, methyltriethoxysilane, dimethyldisilane. Ethoxysilane phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, hexamethyldisilazane, etc. It is done.

  Examples of the organometallic compound include titanate coupling agents and aluminum coupling agents, and specific examples of titanate coupling agents include Preneact KR TTS, KR 46B, KR 38B, KR 138S, KR238S, 338X, Specific examples of KR 44, KR 9SA, KR ET5, KR ET (manufactured by Ajinomoto Fine Techno Co., Ltd.) and aluminum coupling agents include Plenact AL-M (manufactured by Ajinomoto Fine Techno Co., Ltd.) and the like.

  The amount of these organosilicon compounds and organometallic compounds used is preferably 2 to 100 parts by mass with respect to 100 parts by mass of the zirconia particles.

  The metal oxide colloidal particles used for the zirconia particles can be produced by a known method such as an ion exchange method, a peptization method, a hydrolysis method, or a reaction method.

  Examples of the ion exchange method include a method in which particles of the above-mentioned zirconium salt are treated with an ion exchange resin to remove counter ions and generate particles.

Peptide is obtained by neutralizing the zirconium salt with an acid or base, hydrolyzing the zirconium alkoxide, or hydrolyzing the basic salt of zirconium under heating, Examples thereof include a method of removing unnecessary electrolyte from the gel or adding ions necessary for dispersion. Examples of reaction methods include a method of reacting the zirconium powder with an acid.
As the curing catalyst for component (C), ammonium salts, phosphines, phosphonium salts, sulfonium salts, and metal chelate compounds can be used.
As an ammonium salt, the formula (7):

(Wherein p represents an integer of 2 to 11, q represents an integer of 2 to 3, R ⁴ represents an alkyl group, an aryl group, or a combination thereof, and Y − represents an anion.) (8):

(However, R ⁵ , R ⁶ , R ⁷ and R ⁸ represent an alkyl group, an aryl group, or a combination thereof, N represents a nitrogen atom, Y ⁻ represents an anion, and R ⁵ , R ⁶ , R ^7. And R ⁸ are each bonded to a nitrogen atom by a C—N bond), a quaternary ammonium salt having the structure represented by formula (9):

A quaternary ammonium salt having the structure (wherein R ⁹ and R ¹⁰ represent an alkyl group, an aryl group, or a combination thereof, Y ⁻ represents an anion), formula (10):

A quaternary ammonium salt having the structure (wherein R ¹¹ represents an alkyl group, an aryl group, or a combination thereof, Y ⁻ represents an anion), formula (11):

A quaternary ammonium salt having the structure (wherein R ¹² and R ¹³ represent an alkyl group, an aryl group, or a combination thereof, and Y ⁻ represents an anion), formula (12):

A tertiary ammonium salt having a structure (wherein p represents an integer of 2 to 11, q represents an integer of 2 to 3, H represents a hydrogen atom, and Y ⁻ represents an anion).
Moreover, as a phosphonium salt, Formula (13):

(However, R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ represent an alkyl group, an aryl group, or a combination thereof, P represents a phosphorus atom, Y ⁻ represents an anion, and R ¹⁴ , R ¹⁵ , R) ¹⁶ and R ¹⁷ are each bonded to a phosphorus atom by a C—P bond).
Moreover, as a sulfonium salt, Formula (14):

(However, R ¹⁸ , R ¹⁹ , and R ²⁰ represent an alkyl group, an aryl group, or a combination thereof, S represents a sulfur atom, Y ⁻ represents an anion, and R ¹⁸ , R ¹⁹ , and R ²⁰ represent Each of which is bonded to a sulfur atom by a C—S bond).

The compound of the above formula (7) is a quaternary ammonium salt derived from an amine, p is an integer of 2 to 11, and q is an integer of 2 to 3. R ⁴ of this quaternary ammonium salt represents an alkyl group having 1 to 18 carbon atoms, preferably 2 to 10 carbon atoms, an aryl group, or a combination thereof. For example, linear alkyl such as ethyl group, propyl group, and butyl group Group, benzyl group, cyclohexyl group, cyclohexylmethyl group, dicyclopentadienyl group and the like. Anions (Y ⁻ ) are halogen ions such as chlorine ions (Cl ⁻ ), bromine ions (Br ⁻ ) and iodine ions (I ⁻ ), carboxylates (—COO ⁻ ), sulfonates (—SO ₃ ⁻ ). And acid groups such as alcoholate (—O ⁻ ).

The compound of the above formula (8) is a quaternary ammonium salt represented by R ⁵ R ⁶ R ⁷ R ⁸ N ⁺ Y ⁻ . In this quaternary ammonium salt, R ⁵ , R ⁶ , R ⁷ and R ⁸ are silane bonded to a silicon atom by an alkyl group having 1 to 18 carbon atoms, an aryl group, or a combination thereof, or a Si—C bond. A compound. The anion (Y ⁻ ) is a halogen ion such as chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), iodine ion (I ⁻ ), carboxylate (—COO ⁻ ), sulfonate (—SO ₃ ⁻ ), An acid group such as alcoholate (—O ⁻ ) can be mentioned. This quaternary ammonium salt can be obtained commercially, for example, tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzyl chloride. Examples include ammonium and trimethylbenzylammonium chloride. These can be added as ammonium compounds.

The compound of the above formula (9) is a quaternary ammonium salt derived from 1-substituted imidazole, R ⁹ and R ⁷ have 1 to 18 carbon atoms, and the total number of carbon atoms of R ⁹ and R ¹⁰ Is preferably 7 or more. For example, R ⁹ represents a methyl group, an ethyl group, a propyl group, a phenyl group, a benzyl group, a silane compound bonded to a silicon atom through a Si—C bond, or a combination thereof. R ¹⁰ can be exemplified by a benzyl group, an octyl group, and an octadecyl group. The anion (Y ⁻ ) is a halogen ion such as chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), iodine ion (I ⁻ ), carboxylate (—COO ⁻ ), sulfonate (—SO ₃ ⁻ ), An acid group such as alcoholate (—O ⁻ ) can be mentioned. This compound can be obtained as a commercial product. For example, imidazole compounds such as 1-methylimidazole and 1-benzylimidazole are reacted with alkyl halides and aryl halides such as benzyl bromide and methyl bromide. Can be manufactured. Further, the compound of the formula (9) can be used as a 4,5-dihydroimidazole compound in which the 4-position and the 5-position are hydrogenated. These can be added as cyclic ammonium compounds.

The compound of the above formula (10) is a quaternary ammonium salt derived from pyridine, and R ¹¹ is an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, an aryl group, or a combination thereof. For example, a butyl group, an octyl group, a benzyl group, and a lauryl group can be exemplified. The anion (Y ⁻ ) is a halogen ion such as chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), iodine ion (I ⁻ ), carboxylate (—COO ⁻ ), sulfonate (—SO ₃ ⁻ ), An acid group such as alcoholate (—O ⁻ ) can be mentioned. Although this compound can be obtained as a commercial product, it is produced, for example, by reacting pyridine with an alkyl halide such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, octyl bromide, or an aryl halide. I can do it. Examples of this compound include N-laurylpyridinium chloride and N-benzylpyridinium bromide.

The compound of the above formula (11) is a quaternary ammonium salt derived from a substituted pyridine represented by picoline or the like, and R ¹² is an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, or an aryl group. Or a combination thereof, and examples thereof include a methyl group, an octyl group, a lauryl group, and a benzyl group. R ¹³ is an alkyl group having 1 to 18 carbon atoms, an aryl group, or a combination thereof. For example, in the case of quaternary ammonium derived from picoline, R ¹³ is a methyl group. The anion (Y ⁻ ) is a halogen ion such as chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), iodine ion (I ⁻ ), carboxylate (—COO ⁻ ), sulfonate (—SO ₃ ⁻ ), An acid group such as alcoholate (—O ⁻ ) can be mentioned. This compound can also be obtained as a commercial product. For example, a substituted pyridine such as picoline is reacted with an alkyl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride or benzyl bromide, or an aryl halide. Can be manufactured. Examples of this compound include N-benzylpicolinium chloride, N-benzylpicolinium bromide, N-laurylpicolinium chloride and the like.

The compound of the above formula (12) is a tertiary ammonium salt derived from an amine, p is an integer of 2 to 11, and q is an integer of 2 to 3. Anions (Y ⁻ ) are halogen ions such as chlorine ions (Cl ⁻ ), bromine ions (Br ⁻ ) and iodine ions (I ⁻ ), carboxylates (—COO ⁻ ), sulfonates (—SO ₃ ⁻ ). And acid groups such as alcoholate (—O ⁻ ). It can be produced by reacting an amine with a weak acid such as carboxylic acid or phenol. Examples of the carboxylic acid include formic acid and acetic acid. When formic acid is used, the anion (Y ⁻ ) is (HCOO ⁻ ), and when acetic acid is used, the anion (Y ⁻ ) is (CH ₃ COO). ^- ). When phenol is used, the anion (Y ⁻ ) is (C ₆ H ₅ O ⁻ ).

The compound of the above formula (13) is a quaternary phosphonium salt having a structure of R ¹⁴ R ¹⁵ R ¹⁶ R ¹⁷ P ⁺ Y ⁻ . R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are alkyl groups having 1 to 18 carbon atoms, aryl groups, or a combination thereof, or a silane compound bonded to a silicon atom through a Si—C bond, preferably Is a phenyl group or a substituted phenyl group among the four substituents of R ^{14 to} R ^17. For example, a phenyl group or a tolyl group can be exemplified, and the remaining one has a carbon number of 1 to 1. It is a silane compound bonded to a silicon atom by 18 alkyl groups, an aryl group, or a Si-C bond. Anions (Y ⁻ ) are halogen ions such as chlorine ions (Cl ⁻ ), bromine ions (Br ⁻ ) and iodine ions (I ⁻ ), carboxylates (—COO ⁻ ), sulfonates (—SO ₃ ⁻ ). And acid groups such as alcoholate (—O ⁻ ). This compound can be obtained as a commercial product, for example, halogenated tetraalkylphosphonium such as halogenated tetra n-butylphosphonium, halogenated tetra n-propyl phosphonium, or halogenated triethylbenzyl phosphor. Halogenated trialkylbenzylphosphonium, triphenylmethylphosphonium halide, triphenylmonoalkylphosphonium halide such as triphenylethylphosphonium halide, triphenylbenzylphosphonium halide, Examples include halogenated tetraphenylphosphonium, halogenated tolylyl monoarylphosphonium, or halogenated tolylyl monoalkylphosphonium (the halogen atom is a chlorine atom or a bromine atom). In particular, halogenated triphenylmonoalkylphosphonium such as triphenylmethylphosphonium halide, triphenylethylphosphonium halide, triphenylmonoarylphosphonium halide such as triphenylbenzylphosphonium halide , Tritolyl monoaryl phosphonium halides such as tritolyl monophenyl phosphonium halide, and tolyl monoalkyl phosphonium halides such as tolyl monomethyl phosphonium halide (halogen atom is chlorine or bromine atom) preferable.

The phosphines include methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, phenylphosphine and other first phosphine, dimethylphosphine, diethylphosphine, diisopropylphosphine, diisoamylphosphine, diphenylphosphine and other second phosphine. And tertiary phosphines such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine and dimethylphenylphosphine.
The compound of the above formula (14) is a tertiary sulfonium salt having a structure of R ¹⁸ R ¹⁹ R ²⁰ S ⁺ Y ⁻ . R ¹⁸ , R ¹⁹ , and R ²⁰ are an alkyl group having 1 to 18 carbon atoms, an aryl group, or a combination thereof, or a silane compound that is bonded to a silicon atom through a Si—C bond, and preferably R ^18. three among four substituents to R ²⁰ is a phenyl group or substituted phenyl group, for example, it is possible to illustrate the phenyl group or tolyl group, and the remaining one substituent having 1 to 18 carbon atoms Or an alkyl group, an aryl group, or a combination thereof. Anions (Y ⁻ ) are halogen ions such as chlorine ions (Cl ⁻ ), bromine ions (Br ⁻ ) and iodine ions (I ⁻ ), carboxylates (—COO ⁻ ), sulfonates (—SO ₃ ⁻ ). And acid groups such as alcoholate (—O ⁻ ). This compound can be obtained as a commercial product. For example, a halogenated tetraalkylphosphonium such as tri-n-butylsulfonium halide and tri-n-propylsulfonium halide, and a trihalogenated halogen such as diethylbenzylsulfonium halide. Alkylbenzylsulfonium, halogenated diphenylmethylsulfonium, halogenated diphenylmonoalkylsulfonium, such as halogenated diphenylethylsulfonium, halogenated triphenylsulfonium, (halogen atom is chlorine atom or bromine atom), tri n-butylsulfonium carboxylate, tri Tetraalkylphosphonium carboxylates such as n-propylsulfonium carboxylate and trialkylbennes such as diethylbenzylsulfonium carboxylate Le sulfonium carboxylate, diphenylmethyl sulfonium carboxylate, diphenyl monoalkyl sulfonium carboxylates such as diphenylethyl sulfonium carboxylate, triphenylsulfonium carboxylate, triphenylsulfonium trifluoromethane sulfonate, and the like. Particularly, triphenylsulfonium halide and triphenylsulfonium carboxylate are preferable. These can be added as sulfonium compounds.

Examples of the metal chelate compound include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri-n-butoxy. Mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di-n -Propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetonate) ) Titanium, di-t-butoxy bis Acetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n-butoxy Tris (acetylacetonato) titanium, mono-sec-butoxytris (acetylacetonato) titanium, mono-t-butoxytris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy mono (ethyl) Acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri-sec Butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, di- i-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t-butoxy bis (ethyl acetoacetate) Acetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tris (Ethyl acetoacetate Tate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris (ethyl aceto) Acetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium, and other titanium chelate compounds; triethoxy mono (acetylacetonato) zirconium, tri- n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonato) zirconium, tri-s c-butoxy mono (acetylacetonato) zirconium, tri-t-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetonato) zirconium, Di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) zirconium, di-t-butoxy bis ( Acetylacetonato) zirconium, monoethoxy-tris (acetylacetonato) zirconium, mono-n-propoxy-tris (acetylacetonato) zirconium, mono-i-propoxy-tris (acetylacetonato) zirconi Mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t-butoxy-tris (acetylacetonato) zirconium, tetrakis (acetylacetonate) Zirconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl aceto) Acetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethylacetoa Cetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di-sec- Butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, mono -I-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirco , Mono-t-butoxy-tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) Zirconium chelate compounds such as zirconium and tris (acetylacetonato) mono (ethylacetoacetate) zirconium; Aluminum chelate compounds such as tris (acetylacetonato) aluminum and tris (ethylacetoacetate) aluminum;

The addition amount of the curing catalyst (C) component is 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass, or 0.01 to 3 parts by mass with respect to 100 parts by mass of the phenylsilsesquioxane (A) component. Part.
The method for preparing the reflow-type film forming composition for a solid-state imaging device of the present invention is not particularly limited. It suffices if the (A) component, (B) component, (C) component, and (D) component are uniformly mixed. The order of mixing components (A) to (D) is not particularly limited as long as a uniform varnish can be obtained.

The content of the phenyl silsesquioxane in the film-forming composition for a solid-state imaging device of the present invention is preferably 5 to 100 parts by mass, when the solid content of the component (B) is 100 parts by mass, Is 20 to 50 parts by mass. If the phenylsilsesquioxane content is higher than 100 parts by mass, the refractive index may be lowered. On the other hand, when the content of the phenylsilsesquioxane is lower than 5 parts by mass, the reflow property is lowered and the flatness may be insufficient.
The addition amount of the curing catalyst (C) component is 0.01 to 10 parts by mass with respect to 100 parts by mass of the phenylsilsesquioxane (A) component. If the content of the curing catalyst is lower than 0.01 parts by mass, curing may be insufficient and solvent resistance may be insufficient. Moreover, when content of a curing catalyst is higher than 10 mass parts, storage stability may be impaired.

Specific examples of the solvent (D) include toluene, p-xylene, o-xylene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, ethylene glycol monoethyl. Ether, ethylene glycol monoisopropyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether Diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol, 1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol, 1-methoxy-2 -Butanol, cyclohexanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyllactone , Acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, methyl iso Butyl ketone, methyl normal butyl ketone, cyclohexanone, ethyl acetate, isopropyl ketone, normal propyl acetate, isobutyl acetate, normal butyl acetate, methanol, ethanol, isopropanol, tert-butanol, allyl alcohol, normal propanol, 2-methyl-2-butanol , Isobutanol, normal butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol, 1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol, 1 -Methoxy-2-butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol, isopropyl Ether, 1,4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, N-cyclohexyl-2-pyrrolidinone Can be mentioned.

The component (D) of the present invention is a solvent. The solvent is preferably the same solvent as the solvent from which component (A) was obtained, but is not particularly limited as long as the storage stability of the film-forming composition of the present invention is not significantly impaired. The general organic solvent mentioned above can be used.
From the viewpoint of compatibility between phenylsilsesquioquinsan (A), zirconia particles (B) having an average particle diameter of 1 to 100 nm, and a curing catalyst (C), the solvent (D) is more preferably diacetone alcohol, Examples include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monobutyl ether, cyclohexanone, acetic acid methyl ester, acetic acid ethyl ester, and lactate ethyl ester.
The solid content of the film-forming composition contains phenylsilsesquioxane (A) and zirconia particles (B), a curing catalyst (C) and a solvent (D), but may contain other components.
In the present invention, in addition to the component (A), the component (B), the component (C), and the component (D), other components such as a leveling agent and a surfactant, as long as the effects of the present invention are not impaired. May be included.

Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene, and the like. Polyoxyethylene alkyl allyl ethers such as nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan trioleate Sorbitan fatty acid esters such as stearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as bitane monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, trade name EFTOP EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), trade names MegaFuck F171, F173, F-553, F-554, R-08, R-30, R-30-N (manufactured by Dainippon Ink & Chemicals, Inc.) ), Fluorads FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), trade names Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) Activator, and organosiloxane polymer-KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378 (manufactured by Big Chemie Japan Co., Ltd.) and the like can be mentioned. These surfactants may be used alone or in combination of two or more. When a surfactant is used, the proportion thereof is 0.0001-5 parts by mass, or 0.001-1 parts by mass, or 0.01-0.5 with respect to 100 parts by mass of the silicon compound (A). Part by mass.
The method of mixing the other components, the solvent, the leveling agent, or the surfactant may be performed simultaneously with the addition of the zirconia particles (B), the curing catalyst (C), and the solvent (D) to the phenylsilsesquioxane (A). It may be after mixing of component (A) to component (D), and is not particularly limited.

<Formation of coating>
The film-forming composition of the present invention can be applied to a substrate and thermally cured to obtain a desired film. A known or well-known method can be adopted as the coating method. For example, spin coating method, dip method, flow coating method, ink jet method, spray method, bar coating method, gravure coating method, slit coating method, roll coating method, transfer printing method, brush coating, blade coating method, air knife coating method Etc. can be adopted. The base materials used in this case are silicon, indium tin oxide (ITO), indium zinc oxide (IZO), polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene (PE), ionomer (IO), polyimide (PI), polyamide (PA), polyvinyl chloride (PVC), polycycloolefin (PCO), polyvinylidene chloride (PVDC), polyvinyl alcohol (PVA), polypropylene (PP), polycarbonate (PC), polystyrene (PS) , Polyacrylonitrile (PAN), ethylene vinyl acetate copolymer (EVA), ethylene vinyl alcohol copolymer (EVOH), ethylene methacrylic acid copolymer (EMMA), polymethacrylic acid (PMMA), nylon, plastic, glass, S Dia, quartz, diamond, ceramics, aluminum gallium arsenide (AlGaAs), gallium arsenide phosphorus (GaAsP), indium gallium nitride (InGaN), gallium nitride (GaN), aluminum gallium nitride (AlGaN), gallium phosphide (GaP), selenium Examples thereof include a base material made of zinc halide (ZnSe), aluminum indium gallium phosphide (AlGaInP), zinc oxide (ZnO), or the like.
The baking equipment is not particularly limited, and may be fired in an appropriate atmosphere, that is, in an inert gas such as air or nitrogen, in a vacuum, or the like, using a hot plate, an oven, or a furnace, for example. Thereby, it is possible to obtain a film having a uniform film forming surface.

  Although a calcination temperature is not specifically limited in order to evaporate a solvent, For example, it can carry out at 40-200 degreeC. In these cases, the temperature may be changed in two or more steps for the purpose of expressing a higher uniform film forming property or allowing the reaction to proceed on the substrate.

The firing temperature and firing time may be selected in accordance with the process steps of the target electronic device, and the firing conditions can be selected in which the physical properties of the film are adapted to the required characteristics of the electronic device.
The film-forming composition comprising phenylsilsesquioxane (A), zirconia particles (B), curing catalyst (C) and solvent (D) according to the present invention has a uniform dispersion of a varnish obtained by hybridizing these components. It is preferable that

  Here, in a broad sense, hybridization means mixing solutes having different properties and mixing them in a solution state. Even if different solutes have chemical or physical interaction, they are present. The dispersibility may be maintained as long as it is not necessary.

  Hybridization is not particularly limited as long as the final varnish stability can be obtained.

  For example, (1) phenylsilsesquioxane (A) is mixed with a dispersion (zirconia sol) of zirconia particles in a solution state (varnish), and (2) phenylsilsesquioxane (A) is added in solution (varnish). Various methods such as dispersing the zirconia particles in the middle) can be mentioned. From the viewpoint of handling properties, the dispersion of zirconia particles (A) of the phenylsilsesquioxane copolymer (A) in a solution (varnish) state ( A method of mixing with zirconia sol) is preferred.

  The stability of the final hybridized varnish is due to precipitation due to reduced dispersibility, drastic changes in primary particle size or secondary particle size, poor applicability, coloring (whitening, yellowing), and poor film quality. Don't cause it.

  The content of the zirconia particles in the composition may be in a range that does not impair the dispersibility of the final varnish obtained, and is controlled in accordance with the intended refractive index, transmittance, and heat resistance of the coating film to be produced. It is possible.

The film-forming composition (coating solution) containing phenylsilsesquioxane (A), zirconia particles (B), curing catalyst (C), and solvent (D) according to the present invention is precipitated by a decrease in dispersibility. The storage conditions are not particularly limited as long as they do not cause a significant change in the particle diameter or secondary particle diameter, deterioration in applicability, coloring (whitening, yellowing), and deterioration in film quality. For example, it may be stored at 23 ° C. (room temperature storage), 5 ° C. (refrigerated storage) and −20 ° C. (frozen storage), and −20 ° C. (freezer storage) to prevent hydroxyl groups from reacting in the varnish state. It is preferable to store in
The film made of the composition of the present invention thus obtained can satisfy high refractive index, high transparency, high heat resistance, high flatness and high light resistance at a time, and particularly high flatness. In addition, it can be suitably used as a planarizing film for a solid-state imaging device that requires high light resistance.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. In addition, each measuring apparatus used in the Example is as follows.
[GPC]
Equipment: HLC-8200 GPC manufactured by Tosoh Corporation
Column: Shodex KF-804L + KF-805L
Column temperature: 40 ° C
Solvent: Tetrahydrofuran (hereinafter THF)
Detector: UV (254 nm)
Calibration curve: Standard polystyrene [UV-visible spectrophotometer]
Apparatus: SHIMADSU UV-3600 manufactured by Shimadzu Corporation
[Refractive index of coating / Ellipsometer]
Apparatus: Multi-angle-of-incidence spectroscopic ellipsometer VASE manufactured by JA Woollam Japan.
Measured at a wavelength of 450 nm.

[Refractive index of particles]
Apparatus: Multi-angle-of-incidence spectroscopic ellipsometer VASE manufactured by JA Woollam Japan.
Measured at a wavelength of 450 nm.
A film obtained by diluting zirconia particles with propylene glycol monomethyl ether so as to have a film thickness of 100 nm, spin-coating on a silicon substrate, firing on a hot plate at 100 ° C. for 1 minute, and then firing on a hot plate at 200 ° C. for 5 minutes. The refractive index of was measured.
[Average particle size]
Device: N5 made by Beckman Coulter
The zirconia particle dispersion was diluted with the same solvent as the dispersion medium, and the particle size (Unimodal mode, intensity average particle size) of the dynamic light scattering method was measured.
[Evaluation of flatness]
Device: Kosaka Laboratories Co., Ltd. High-precision fine shape measuring instrument SUREFCORDER ET4000A
The structure substrate used for the flatness evaluation was a substrate in which the material was SiO ₂ , the line having a depth of 600 nm was patterned to 10 μm, and the space was patterned to 20 μm.

[Synthesis Example 1]
35.14 g of tetraethoxysilane and 52.71 g of ethanol were placed in a 300 ml flask, and 12.16 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixed solution while stirring the mixed solution with a magnetic stirrer. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C., and reacted for 240 minutes under heating and reflux. Thereafter, the reaction solution is cooled to room temperature, 70.00 g of PGMEA is added to the reaction solution, ethanol as a solvent, ethanol, water and hydrochloric acid as reaction by-products are distilled off under reduced pressure, and concentrated to a hydrolysis-condensation product ( Polymer) PGMEA solution was obtained. Further, PGMEA was added and adjusted to 20 mass percent in terms of solid residue at 140 ° C. The obtained polymer is a polyteos (pTEOS) varnish (abbreviated as P1) obtained from a tetrafunctional monomer. The weight average molecular weight of the obtained P1 by GPC was Mw 4000 in terms of polystyrene.
[Reference Example 1]
Zirconia dispersion: Propylene glycol monomethyl ether dispersion (abbreviated as D1) containing 30.5% by mass of zirconia particles surface-treated with alkoxysilane (manufactured by Nissan Chemical Industries, Ltd.)
Table 1 shows each physical property value of the zirconia particles obtained in Reference Example 1.

[Table 1]
Table 1 Physical properties of zirconia particles ―――――――――――――――――――――――――
Abbreviation D1
Particle type Zirconia
Average particle size (nm) 14
Particle refractive index 1.66
Solid content (mass%) 30.5
B-type viscosity (BL adapter) 4.3
(MPa · s, 20 ° C)
―――――――――――――――――――――――――

<Production of Film Forming Composition and Film>
[Example 1]
9.0000 g of D1 obtained in Reference Example 1 was weighed into a 20 mL eggplant-shaped flask, then 4.3270 g of PGME was added, and phenylsilsesquioxane SR-23 manufactured by Konishi Chemical Industry Co., Ltd. was added with 20 PGME. 3.4313 g of a solution diluted to mass% (the solid content of phenylsilsesquioxane is 25 mass% with respect to the solid content of D1) was added, and benzyltriethylammonium chloride (abbreviated as BTEAC) as a curing catalyst with 10 PGME. 0.2745 g of a solution diluted to mass% (the solid content of BTEAC is 1 mass% with respect to the solid content of D1) is added, and R-30-N manufactured by Dainippon Ink & Chemicals, Inc. is used as a surfactant. Add 0.2745 g of a solution diluted to 1% by mass with PGME and mix until completely uniform at room temperature. The total mass of solids is 20.0% by mass. A varnish (abbreviated as V1) was obtained.

The obtained V1 was spin-coated on a silicon substrate and a quartz substrate using a spin coater so as to have a film thickness of 400 nm, and baked using a hot plate at 100 ° C. for 1 minute and then at 200 ° C. for 5 minutes. And a film was obtained. The film on the silicon substrate measures the refractive index of light having a wavelength of 450 nm using an ellipsometer, the film on the quartz substrate measures the transmittance, calculates the average transmittance from 400 nm to 800 nm, and the results are shown in Table 2. . The coating on the silicon substrate was subjected to a solvent resistance test. A solvent tolerance test is a test which shows that the film after this baking is insolubilized with respect to the contact with a solvent. Solvent resistance is a characteristic that is required when a post-process for patterning is performed by recoating a resist or the like on the film. If there is no solvent resistance, the film dissolves in the resist solvent when recoating, and the film And the resist may be mixed and the original characteristics may not be exhibited.
The film thickness after firing of the V1 film was 400.3 nm, which was defined as the initial film thickness. The coating was completely immersed in PGME and left for 5 minutes. Next, after drying with air and baking on a hot plate at 200 ° C. for 1 minute to completely evaporate the residual solvent, the film thickness was measured and compared with an initial film thickness of 100%. Show.

  Further, V1 was similarly formed on the substrate with structure shown in FIG. 1, and the flatness was evaluated. The flatness was measured by a palpation method after a film was formed on a substrate patterned with a depth of 10 nm for a line having a depth of 600 nm and a space of 20 μm, and the measured step X μm was determined (FIG. 1). The flatness was substituted into the following formula ((0.6 μm−X μm) /0.6 μm) × 100 and calculated as a flattening rate (%). The results are shown in Table 2.

[Example 2]
9.0000 g of D1 obtained in Reference Example 1 was weighed into a 20 mL eggplant-shaped flask, then 4.3270 g of PGME was added, and phenylsilsesquioxane SR-23 manufactured by Konishi Chemical Industry Co., Ltd. was added with 20 PGME. 5.4900 g of a solution diluted to mass% (the solid content of phenylsilsesquioxane is 40 mass% with respect to the solid content of D1), and 0.2745 g of a solution obtained by diluting the curing catalyst BTEAC to 10 mass% with PGME (The solid content of BTEAC is 1% by mass with respect to the solid content of D1), and R-30-N manufactured by Dainippon Ink & Chemicals, Inc. as a surfactant is diluted with PGME to 1% by mass. 0.2745 g of the solution was added and mixed until it became completely uniform at room temperature to obtain a varnish (abbreviated as V2) having a total solid content of 20.0% by mass.
A film was obtained by firing in the same manner as in Example 1. Table 2 shows the results of measurement of refractive index, average transmittance, solvent resistance, and flattening rate.
[Example 3]
A varnish (abbreviated as V3) was obtained in the same manner as in Example 1 except that BTEAC in Example 1 was replaced with benzyltrimethylammonium chloride (abbreviated as BTMAC). A film was obtained by firing in the same manner as in Example 1. Table 2 shows the results of measurement of refractive index, average transmittance, solvent resistance, and flattening rate.
[Example 4]
A varnish (abbreviated as V4) was obtained in the same manner as in Example 1 except that BTEAC in Example 1 was replaced with N-laurylpyridinium chloride (abbreviated as NLPC). A film was obtained by firing in the same manner as in Example 1. Table 2 shows the results of measurement of refractive index, average transmittance, solvent resistance, and flattening rate.

[Example 5]
A varnish (abbreviated as V5) was obtained in the same manner as in Example 1 except that BTEAC in Example 1 was replaced with triethylbenzylphosphonium chloride (abbreviated as TEBPC). A film was obtained by firing in the same manner as in Example 1. Table 2 shows the results of measurement of refractive index, average transmittance, solvent resistance, and flattening rate.
[Example 6]
A varnish (abbreviated as V6) was obtained in the same manner as in Example 1 except that BTEAC in Example 1 was replaced with triphenylsulfonium chloride (abbreviated as TPSC). A film was obtained by firing in the same manner as in Example 1. Table 2 shows the results of measurement of refractive index, average transmittance, solvent resistance, and flattening rate.

[Comparative Example 1]
A varnish (abbreviated as RV1) was obtained in the same manner as in Example 1 except that SR-23 in Example 1 was replaced with P1 obtained in Synthesis Example 1. A film was obtained by firing in the same manner as in Example 1. Table 2 shows the results of measurement of refractive index, average transmittance, solvent resistance, and flattening rate.
[Comparative Example 2]
A varnish (abbreviated as RV2) was obtained in the same manner as in Example 1 except that SR-23 in Example 1 was replaced with methyl silsesquioxane (SR-13) manufactured by Konishi Chemical Industry Co., Ltd. A film was obtained by firing in the same manner as in Example 1. Table 2 shows the results of measurement of refractive index, average transmittance, solvent resistance, and flattening rate.
[Comparative Example 3]
A varnish (abbreviated as RV3) was obtained in the same manner as in Example 1 except that SR-23 in Example 1 was replaced with polydimethylsiloxane (KR-400) manufactured by Shin-Etsu Chemical Co., Ltd. A film was obtained by firing in the same manner as in Example 1. Table 2 shows the results of measurement of refractive index, average transmittance, solvent resistance, and flattening rate.
[Comparative Example 4]
In a 20 mL eggplant-shaped flask, weighed 12.0000 g of D1 obtained in Reference Example 1, and then added 0.3-23 g of a solution obtained by diluting the curing catalyst BTEAC to 10% by mass with PGME without adding SR-23 (solid of D1 0.366 g of a solution prepared by adding RTE-30-N manufactured by Dainippon Ink & Chemicals, Inc. as a surfactant to 1% by mass with PGME. Was added until the mixture became completely uniform at room temperature to obtain a varnish (abbreviated as RV4) having a total solid content of 20.0% by mass.
A film was obtained by firing in the same manner as in Example 1. Table 2 shows the results of measurement of refractive index, average transmittance, solvent resistance, and flattening rate.

[Comparative Example 5]
In a 20 mL eggplant type flask, 12.0000 g of SR-23 diluted to 30.5% by mass with PGME was weighed, then 5.7893 g of PGME was added, and without adding D1, the curing catalyst BTEAC was 10% by mass with PGME. 0.3660 g of the diluted solution (the solid content of BTEAC is 1% by mass with respect to the solid content of SR-23), and R-30-N manufactured by Dainippon Ink & Chemicals, Inc. as a surfactant. 0.3660 g of a solution diluted to 1% by mass with PGME was added and mixed until it was completely uniform at room temperature to obtain a varnish (abbreviated as RV5) having a total solid content of 20.0% by mass.
A film was obtained by firing in the same manner as in Example 1. Table 2 shows the results of measurement of refractive index, average transmittance, solvent resistance, and flattening rate.
[Comparative Example 6]
9.0000 g of D1 obtained in Reference Example 1 was weighed into a 20 mL eggplant-shaped flask, and then 4.4642 g of PGME was added. Phenylsilsesquioxane SR-23 manufactured by Konishi Chemical Industry Co., Ltd. was added with 20 PGME. Dainippon Ink & Chemicals, Inc. as a surfactant without adding a curing catalyst, adding 3.4314 g of a solution diluted to mass% (the solid content of phenylsilsesquioxane is 25 mass% with respect to the solid content of D1) 0.2745 g of a solution made by diluting R-30-N made by Co., Ltd. with PGME to 1% by mass was added and mixed until it was completely uniform at room temperature, and the total mass of solids was 20.0% by mass. A varnish (abbreviated as RV6) was obtained.
A film was obtained by firing in the same manner as in Example 1. Table 2 shows the results of measurement of refractive index, average transmittance, solvent resistance, and flattening rate.

[Comparative Example 7]
In a 20 mL eggplant-shaped flask, 12.0000 g of D1 obtained in Reference Example 1 was weighed, then 5.793 g of PGME was added, and phenylsilsesquioxane SR-23 manufactured by Konishi Chemical Industry Co., Ltd. was added with 20 PGME. 0.1830 g of a solution diluted to mass% (the solid content of phenylsilsesquioxane is 1 mass% with respect to the solid content of D1) is added, and 0.3660 g of a solution obtained by diluting the curing catalyst BTEAC to 10 mass% with PGME (The solid content of BTEAC is 1 part by mass with respect to the solid content of D1), and R-30-N manufactured by Dainippon Ink & Chemicals, Inc. as a surfactant is diluted with PGME to 1 mass%. 0.3660 g of the solution was added and mixed until it was completely uniform at room temperature to obtain a varnish (abbreviated as RV7) having a total solid content of 20.0% by mass.
A film was obtained by firing in the same manner as in Example 1. Table 2 shows the results of measurement of refractive index, average transmittance, solvent resistance, and flattening rate.
[Comparative Example 8]
5.0000 g of D1 obtained in Reference Example 1 was weighed into a 20 mL eggplant-shaped flask, then 2.4039 g of PGME was added, and phenylsilsesquioxane SR-23 manufactured by Konishi Chemical Industry Co., Ltd. was added with 20 PGME. 11.4375 g of a solution diluted to mass% (the solid content of phenylsilsesquioxane is 150 mass% with respect to the solid content of D1), and 0.1525 g of a solution obtained by diluting the curing catalyst BTEAC to 10 mass% with PGME (The solid content of BTEAC is 1 part by mass with respect to the solid content of D1), and R-30-N manufactured by Dainippon Ink & Chemicals, Inc. as a surfactant is diluted with PGME to 1 mass%. 0.1525 g of the solution was added and mixed until it was completely uniform at room temperature to obtain a varnish (abbreviated as RV8) having a total solid content of 20.0% by mass.
A film was obtained by firing in the same manner as in Example 1. Table 2 shows the results of measurement of refractive index, average transmittance, solvent resistance, and flattening rate.

[Table 2]
Table 2 Refractive index, average transmittance, solvent resistance and flattening rate at 450 nm wavelength of the coating ――――――――――――――――――――――――――――― ――――――――――
Refractive index Average transmittance Solvent resistance Flattening rate
[Wavelength 450nm] [%] [%] [%]
Example 1 1.6239 99.5 100 98
Example 2 1.6013 99.6 100 99
Example 3 1.6236 99.5 100 98
Example 4 1.6235 99.5 100 98
Example 5 1.6240 99.5 100 98
Example 6 1.6237 99.5 100 98
Comparative Example 1 1.6228 99.5 100 43
Comparative Example 2 1.6232 99.5 100 86
Comparative Example 3 1.59992 99.5 0 98
Comparative Example 4 1.6712 98.6 100 21
Comparative Example 5 1.5637 99.6 100 99
Comparative Example 6 1.6238 99.5 42 98
Comparative Example 7 1.6662 98.7 100 80
Comparative Example 8 1.5661 99.6 98 99
――――――――――――――――――――――――――――――――――――――――

  For the results in Table 2, Examples 1 to 6 and Comparative Examples 1 to 8 are compared. It turned out that Example 1 and Example 2 have high refractive index, high transmittance, high solvent resistance, and high flatness. On the other hand, the flatness of Comparative Example 1 and Comparative Example 2 deteriorated to 43% and 86%. This result shows that the reflow property of polytheos and methylsilsesquioxane is lower than that of phenyl silsesquioxane, and it is difficult to contribute to the flattening rate. Further, in Comparative Example 3, phenylsilsesquioxane was changed to polydimethylsiloxane, so that despite the same composition as in Example 1, the solvent resistance was 0% and a good cured film could not be obtained. Solvent resistance is a characteristic that is required when a post-process for patterning is performed by recoating a resist or the like on the film. If there is no solvent resistance, the film dissolves in the resist solvent when recoating, and the film And the resist may be mixed and the original characteristics may not be exhibited. Therefore, solvent resistance is essential for a film-forming composition for a solid-state imaging device. Comparative Example 4 was a system excluding phenylsilsesquioxane, but the flattening rate was extremely deteriorated to 21% because it did not have reflowability. Comparative Example 5 was a system excluding D1, but since no zirconia particles were added, a high refractive index did not appear and a low refractive index of 1.5637 was obtained. Comparative Example 6 was a system excluding the curing catalyst, but by removing BTEAC, the solvent resistance was remarkably lowered to 42%. Comparative Examples 7 and 8 are systems in which the amount of phenylsilsesquioxane added is 1% by mass and 150% by mass with respect to the solid content of D1. In Comparative Example 7, the addition amount was too low, no reflow property was exhibited, and the flattening rate was 80%. In Comparative Example 8, the addition amount was too high, and the refractive index was not high, but was 1.5661, which was a low refractive index.

From these results, it was clarified that phenylsilsesquioxane is an essential component and has an optimum addition amount. In addition, it has been clarified that a zirconia particle is necessary for developing a high refractive index, and a curing catalyst is an essential component for developing solvent resistance.
<Light resistance test>
In the light resistance test, light irradiation was performed at the Japan Weathering Test Center, and a xenon arc lamp having an illuminance of 38.7 W / m ² and an exposure wavelength of 320 nm to 400 nm was used as a light source. The testing machine used was SX75-AP type manufactured by Suga Test Instruments Co., Ltd. The test environment was a temperature of 42 ± 3 ° C. and a relative humidity of 50 ± 5% RH.
[Example 6]
The light resistance test of the V1 film produced in Example 1 was conducted. The light irradiation time was 62.5 hours, and the film thickness, refractive index, and average transmittance before and after light irradiation were measured. The results are shown in Table 3.
[Example 7]
The light resistance test of the V2 film produced in Example 2 was conducted in the same manner as in Example 6. The results are shown in Table 3.

[Table 3]
Table 3 Results of light resistance test of coatings ―――――――――――――――――――――――――――――――――――――
Film thickness Refractive index Average transmittance
[Nm] [wavelength 450nm] [%]
Example 6 Before test 400.3 1.6239 99.5
After the test 400.0 1.6434 99.5
Example 7 Before test 400.1 1.6013 99.6
After the test 400.0 1.6012 99.6
―――――――――――――――――――――――――――――――――――――

  Regarding the results shown in Table 3, in Examples 6 and 7, there was no change in film thickness, refractive index, and average transmittance after 62.5 hours of light irradiation. Light irradiation for 62.5 hours under the present light resistance test conditions means 5 million Lux equivalent, and it can be said that the film-forming composition for a solid-state imaging device has very good light resistance. Generally, the light resistance of a film used in a solid-state imaging device is 1 million Lux or less.

The film obtained from the composition of the present invention can satisfy high refractive index, high transparency, high heat resistance, high flatness, and high light resistance at a time, and particularly requires high flatness and high light resistance. It can be suitably used as a planarizing film for a solid-state imaging device.

Claims (11)

A film-forming composition for a solid-state imaging device comprising phenylsilsesquioxane (A), zirconia particles (B) having an average particle diameter of 1 to 100 nm, a curing catalyst (C), and a solvent (D). Phenylsilsesquioxane is represented by the following formula (1):

(In the formula, R ¹ is an alkoxy group, an acyloxy group, or a halogen group. R ² is an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a phenyl group. M is an integer of 0 to 5. The film-forming composition according to claim 1, which is a hydrolyzed condensate of a hydrolyzable silane represented by Phenylsilsesquioxane is represented by the following formula (2):

[In Formula (2), R < ² > is a C1-C10 alkyl group, an alkoxy group, or a phenyl group, respectively. m is an integer of 0-5. n is an integer of 3-5. R ³ is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an acyloxy group, a halogen group, an alkoxyalkyleneoxy group,
Chemical group represented by formula (3):

(In Formula (3), R ⁴ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a phenyl group. M is an integer of 0 to 5. n is an integer of 3 to 5.) ,
Chemical group represented by formula (4):

(In the formula (4), ^{R 5} are each an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a phenyl group .m is an integer from 0 to 5.), Or combinations thereof groups. The film-forming composition according to claim 1, which is a compound represented by the formula: Phenylsilsesquioxane is the above formula (2) and the above formula (5):

The film forming composition according to claim 1, wherein R ⁶ is a mixture of each of R ⁶ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a phenyl group, and m is an integer of 0 to 5. object.   The film-forming composition according to any one of claims 1 to 4, wherein the phenylsilsesquioxane has a weight average molecular weight of 500 to 10,000. The film formation for a solid-state imaging device according to any one of claims 1 to 5, comprising 5 to 100 parts by mass of the component (A) when the solid content of the component (B) is 100 parts by mass. Composition. The film-forming composition according to any one of claims 1 to 6, wherein the zirconia particles (B) have a refractive index of 1.50 to 2.20. The film-forming composition according to any one of claims 1 to 7, wherein the zirconia particles (B) have an average particle diameter of 1 to 100 nm by a dynamic light scattering method. The film-forming composition according to any one of claims 1 to 8, wherein the curing catalyst (C) is an ammonium salt, a phosphine, a phosphonium salt, a sulfonium salt, or a metal chelate compound.   A cured film obtained by coating the film-forming composition according to claim 1 on a substrate and baking the composition. A solid-state imaging device comprising the cured film according to claim 10 as a planarizing film.

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