JP2017052812A - Composition for forming alkali-soluble developable high refractive index film and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film-forming composition and a pattern forming method suitable for producing a film having a high refractive index, high transparency, high heat resistance, high light fastness and high hardness, for increasing light extraction efficiency to achieve a longer service life and low power consumption of a light-emitting diode (LED).SOLUTION: The film-forming composition comprises: a silicon compound (A) having a weight average molecular weight of 700 to 4000, which is a hydrolysis condensate of a hydrolyzable silane comprising hydrolyzable silane compounds respectively represented by formula (a1) and formula (a2); inorganic particles (B) having an average particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70; and a solvent (C). In the formulae, Rand Reach represent an alkoxy group, an acyloxy group or a halogen group; and L represents a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a film forming composition, and further relates to a film forming composition containing polysiloxane and inorganic fine particles and a pattern forming method.

Light emitting diodes (LEDs) are used as backlight light sources for various displays, traffic lights, lighting, lasers, biosensors, and the like, and are widely used for consumer use.

  In order to achieve a longer life and lower power consumption, LEDs have been developed mainly for device development that enhances light extraction efficiency. In these currents, element structures and materials for improving light extraction efficiency are being developed.

  In order to increase the light extraction efficiency, there is a method of controlling the optical refractive index, and studies have been reported to increase the refractive index of the sealing material.

For example, fine particles of at least one metal oxide selected from the group consisting of zirconium oxide, titanium oxide and composites thereof, and an alkoxy group-containing siloxane polymer having a weight average molecular weight in the range of 1,000 to 100,000 ( b1), a hydroxyl group-containing polysiloxane (b2) having a weight average molecular weight of 500 to 100,000, a β-diketone, a ketoester, a dicarboxylic acid and a derivative thereof, a hydroxycarboxylic acid and a derivative thereof, a ketoalcohol, a dihydroxy compound, an oxy A composition for forming a high refractive material containing an aldehyde compound and at least one chelating agent selected from the group consisting of an amine compound and a derivative thereof (see Patent Document 1);
An optical device sealing resin composition containing an organopolysiloxane containing an alkyl group, aryl group, hydroxyl group, etc., a condensation catalyst, and inorganic particles (see Patent Document 2),
A trialkoxysilane (A) having a phenyl group which may have an alkyl group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms, and a substituent containing a reactive cyclic ether group For a B-staged optical device comprising a ladder-type or random-type silsesquioxane derivative obtained by co-hydrolysis and co-condensation with trialkoxysilane (B), and inorganic fine particles as main components A sealing resin composition is disclosed (see Patent Document 3).

  The target high refractive index material is required to have high transparency, high heat resistance, high light resistance, and high hardness, and it is difficult to satisfy the material at once.

  When inorganic particles are added, the film hardness may decrease. Polysiloxane has a high film hardness but does not exhibit a high refractive index. From these backgrounds, a method of combining inorganic particles and polysiloxane to obtain a high refractive index material is known as a known technique.

  The high refractive index film for LED is required to have alkali developability, and in order to produce a pattern of 10 μm or less, dissolution developability is required for alkali. Therefore, it is conceivable that the high refractive index composition itself is imparted with photosensitivity to obtain a pattern. However, since it contains a photosensitizer, it is difficult to satisfy long-term light resistance and reliability as a member of an LED element.

  A high refractive index composition containing polysiloxane and inorganic particles has not been studied for patterning using a photosensitive material recoated thereon, and 10 μm or less is considered in consideration of a process for manufacturing an LED. There are no known studies on patterning.

JP 2006-316264 A JP 2006-328315 A JP2008-202008

  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 a display device that can achieve high transparency, high heat resistance, high light resistance, and high hardness. An object is to provide a film forming composition and a pattern forming method.

As a first aspect of the present invention, hydrolyzable silane (a1) and hydrolyzable silane (a2):

(Wherein R ¹ and R ² each represents an alkoxy group, an acyloxy group, or a halogen group, and L represents a linear, branched, or cyclic alkyl group having 3 to 6 carbon atoms). A silicon compound (A) having a weight average molecular weight of 700 to 4000, an inorganic particle (B) having an average particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70, and a solvent ( A film-forming composition comprising C),
As a second aspect, the silicon compound (A) has a hydrolyzable silane (a1) and hydrolyzable silane (a2) ratio of 90 to 50 mol% hydrolyzable silane (a1). The film-forming composition according to the first aspect, which is a polymer obtained by hydrolyzing and condensing hydrolyzable silane containing 10 mol% to 50 mol% of decomposable silane (a2),
As a third aspect, the film forming composition according to the first aspect or the second aspect, wherein the inorganic particles (B) are zirconia,
As a fourth aspect, a hydrolyzable silane containing hydrolyzable silane (a1) and hydrolyzable silane (a2) is hydrolyzed in a solvent (c1) to obtain a silicon compound (A) having a weight average molecular weight of 700 to 4000. Obtaining a varnish of
A step of obtaining a sol in which inorganic particles (B) having an average particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70 are dispersed in a dispersion medium (c2) by a dynamic light scattering method;
A step of mixing a varnish of a silicon compound (A) and a sol of inorganic particles (B) to obtain a film-forming composition containing the silicon compound (A), inorganic particles (B), and a solvent (C). A method for producing the film-forming composition according to any one of the viewpoints to the third aspect,
As a fifth aspect, a photosensitive resist is applied on a film obtained from the film-forming composition according to any one of the first to third aspects, and drying, light irradiation, development, and resist peeling are performed. Pattern formation method,
As a sixth aspect, the film-forming composition according to any one of the first to third aspects is coated on a substrate and heated, and has a refractive index of 1.50 to 1.90 at a wavelength of 633 nm. A membrane having,
As a seventh aspect, the film according to the sixth aspect, wherein the contact angle of water on the film surface is 60 ° to 80 °,
As an eighth aspect, the film according to the sixth aspect or the seventh aspect used as a light extraction film or a protective film,
As a ninth aspect, an apparatus having an electronic device having the film according to any one of the sixth aspect to the eighth aspect, and as a tenth aspect, an apparatus according to the ninth aspect, in which the electronic device is an LED. .

  Members such as light extraction films and protective films for LEDs are required to have a high refractive index and alkali developability, and it is necessary to produce a pattern of 10 μm or less. In order to produce a pattern of 10 μm or less, alkali developability is required for a film produced from a composition comprising a silicon compound (A), inorganic particles (B), and a solvent (C). Alkali developability is distinguished between dissolution development and release development. Dissolution development is development in which an alkaline solution dissolves a film, and pattern development is performed. Release development is development in which an alkaline solution hardly dissolves a film, and pattern formation is performed while causing swelling and cracking of the film. It is. Here, in order to form a pattern of 10 μm or less, dissolution developability is indispensable, and it is difficult to perform peeling development. In peeling development, the size at which cracks occur cannot be suppressed to 10 μm or less, and a uniform pattern of 10 μm or less cannot be obtained.

  The film-forming composition of the present invention comprises a silicon compound (A) having a weight average molecular weight of 700 to 4000, inorganic particles (B) having an average particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70, a solvent A film-forming composition containing (C).

  The silicon compound (A) has a weight average molecular weight of 700 to 4000, and further, by copolymerizing the hydrolyzable silane (a1) with a very specific type of hydrolyzable silane (a2) at a specified ratio, The film produced from the composition comprising the inorganic particles (B) exhibits dissolution and developability with respect to the alkaline solution, and a high refractive index film having a pattern of 10 μm or less is obtained.

Also, by specifying the type of hydrolyzable silane (a2), sublimation of the ring-shaped low molecular weight compound during the main heating can be suppressed, and the refractive index drop and the film density during heating or reliability test can be suppressed. Decline can be prevented.
When the inorganic particles (B) have an average particle diameter of 1 to 100 nm according to the dynamic light scattering method, the filterability is good and high transmittance of the film-forming composition can be achieved.
The silicon compound (A) is polysiloxane, and the inorganic particles (B) are zirconia having a high refractive index. However, since the composition is composed of an inorganic compound, the light resistance is good.
The hydroxyl groups present on the surfaces of the silicon compound (A) and the inorganic particles (B) start polycondensation when heated as an external stimulus and can form a strong and high hardness film.
Since the composition comprising the polysiloxane of the present invention and inorganic particles having an average particle diameter of 1 to 100 nm or less has dissolution developability in an alkaline solution, patterning of 10 μm or less is possible using a photosensitive resist. It is. Since a process such as dry etching is not performed, the process is simplified and the production cost can be reduced.
The film obtained by the present invention can satisfy high refractive index, high transparency, high heat resistance, high light resistance, and high hardness at a time, and can be patterned, so that it can be used for liquid crystal displays and plasma displays. , Cathode ray tubes, organic light-emitting displays, electronic paper, LEDs, solid-state imaging devices, solar cells, organic thin film transistors, and other electronic devices. In particular, it can be suitably used as an LED member that requires high light resistance.

Pattern observation when TT73 is used for the polymer of Example 1 Pattern observation when TI73 is used for the polymer of Example 2 Pattern observation when TH73 is used as the polymer of Example 3 Pattern observation when TI73M1 is used for the polymer of Example 8 Pattern observation when pTEOS is used for the polymer of Comparative Example 1 Pattern observation when TI73M4 is used for the polymer of Comparative Example 5

The present invention is a hydrolyzable condensate of hydrolyzable silane containing hydrolyzable silane (a1) and hydrolyzable silane (a2), and a silicon compound (A) having a weight average molecular weight of 700 to 4000 and having a thickness of 1 to 100 nm A film-forming composition comprising inorganic particles (B) having an average particle diameter and a refractive index of 1.50 to 2.70, and a solvent (C). Formula (1) In formula (2), R1 and R2 each represent an alkoxy group, an acyloxy group, or a halogen group, and L represents a linear, branched, or cyclic alkyl group having 3 to 6 carbon atoms.
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-forming film, and is 0.1 to 50% by mass, or 1 to 30% by mass, or 5 to 5%. The concentration range can be 20% by mass. The solid content is the remaining ratio after the solvent is removed from the film-forming composition.
Content of the silicon compound (A) and inorganic particle (B) in solid content can be 50-100 mass%, 70-100 mass%, or 70-99 mass%.
When the inorganic particles (B) are 100 parts by mass in terms of solid content, the silicon compound (A) can be added in the range of 0.1 to 200 parts by mass, preferably 0.1 to 100 parts by mass. In order to maintain film quality and storage stability, the amount is more preferably 0.1 to 50 parts by mass.
The silicon compound (A) used in the present invention is a hydrolysis condensate obtained by hydrolyzing and copolymerizing a hydrolyzable silane represented by the formula (a1) and a hydrolyzable silane represented by the formula (a2). This hydrolysis-condensation product may contain a hydrolysis product.

The silicon compound (A) has a hydrolyzable silane (a1) and hydrolyzable silane (a2) ratio of 90 mol% to 50 mol%, or 80 mol% to 60 mol%. Or hydrolyzable silane (a2) containing 10 mol% to 50 mol%, or 20 mol% to 40 mol%, or 30 mol% of the hydrolyzable silane. It is a polymer.
The silicon compound (A) produced by containing 95 mol% or more of the hydrolyzable silane (a1) has a developability of an alkaline solution as a peel development, and does not exhibit the melt developability which is an important object of the present invention. Further, the silicon compound produced by containing (a2) in an amount of 55 mol% or more has increased hydrophobicity, repels an alkaline solution, and loses developability itself.
The hydrolyzate is a product in which the hydrolyzable group of the silane monomer is hydrolyzed to produce a silanol group. The hydrolyzed condensate is a hydrolyzed condensate in which silanol groups in the hydrolyzed product undergo dehydration condensation and forms a polysiloxane, and the terminal of the condensate usually has a silanol group. . The silicon compound (A) is a hydrolyzed condensate (polysiloxane), but may have a hydrolyzate that is a precursor thereof.
R ¹ and R ^{2 in} formula (a1) and formula (a2) represent an alkoxy group, an acyloxy group, or a halogen group.

Examples of the alkoxy group include an alkoxy group having 1 to 20 carbon atoms, and examples thereof include an alkoxy group having a linear, branched or cyclic alkyl moiety, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, n -Butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, n-pentoxy 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- Examples include an n-propoxy group, a 1-ethyl-1-methyl-n-propoxy group, and a 1-ethyl-2-methyl-n-propoxy group.

Examples of the acyloxy group include an acyloxy group having 2 to 20 carbon atoms, such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, and an isobutylcarbonyloxy 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-hexylca Bonyloxy 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 include, but are not limited to, ethyl-1-methyl-n-propylcarbonyloxy group, 1-ethyl-2-methyl-n-propylcarbonyloxy group, phenylcarbonyloxy group, and tosylcarbonyloxy group. is not.
Examples of the halogen group as the hydrolyzable group include fluorine, chlorine, bromine and iodine.
Said hydrolysable silane (a1) is illustrated below, for example.

Examples include tetramethoxysilane, tetraacetoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraacetoxysilane, tetrachlorosilane, and the like. The siloxane monomer having a functional group is not limited to these. Among these, tetramethoxysilane and tetraethoxysilane can be preferably used. A commercially available product can be used as the hydrolyzable silane.

L in the hydrolyzable silane (a2) represents a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms.
n-propyl group, isopropyl group, n-butyl group, isobutyl 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-dimethyl-n-butyl group, 3,3- Dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl -N-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2, -trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl Examples include, but are not limited to, a 2-methyl-n-propyl group, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl group and the like.

The hydrolyzable silane (a2) is exemplified below. For example, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltriethoxysilane, cyclopropyltriethoxysilane, n-butyltriethoxysilane, sec-butyltriethoxysilane, t-butyltriethoxysilane, isobutyltri Ethoxysilane, cyclobutyltriethoxysilane, n-pentyltriethoxysilane, t-pentyltriethoxysilane, triethoxy (pentan-2-yl) silane, triethoxy (pentan-3-yl) silane, cyclopentyltrimethoxysilane, n- Hexyltrimethoxysilane, n-hexyltriethoxysilane, triethoxy (hexane-2-yl) silane, triethoxy (hexane-3-yl) silane, triethoxy (4-methylpentan-2-yl Silane, triethoxy (2-methyl-2-yl) silane, triethoxy (3-methyl-3-yl) silane, cyclohexyl trimethoxy silane, but and the like, but is not limited thereto.
Among these, n-propyltrimethoxysilane, n-propyltriethoxysilane, isobutyltriethoxysilane, and n-hexyltrimethoxysilane can be preferably used. A commercially available product can be used as the hydrolyzable silane.

A silicon compound (A), which is a copolymer containing a hydrolysis condensate obtained by hydrolyzing and condensing a hydrolyzable silane containing the hydrolyzable silane of the formula (a1) and the hydrolyzable silane of the formula (a2), , And a condensate having a weight average molecular weight of 700 to 4000 or 1000 to 2000. These molecular weights are molecular weights obtained in terms of polystyrene by GPC analysis. When the weight average molecular weight is less than 700, the polymer is too low in molecular weight and a uniform film cannot be obtained. On the other hand, when the weight average molecular weight is more than 4000, the polymer becomes too high in molecular weight, resulting in peeling development with respect to the alkaline solution.
Organic acids as hydrolysis catalysts are, for example, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacin 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, benzenesulfone Examples include acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like.
Examples of the inorganic acid as the hydrolysis catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

Organic bases as hydrolysis catalysts include, for example, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazine. Examples thereof include zabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, 1,8-diazabicyclo [5,4,0] -7-undecene and the like.
Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like. Of these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferred, and these may be used alone or in combination of two or more.
As the hydrolysis catalyst, a volatile inorganic acid such as hydrochloric acid can be preferably used. For hydrolysis of an alkoxysilyl group, an acyloxysilyl group, or a halogenated silyl group, 0.1 to 100 mol, or 0.1 to 10 mol, or 1 to 5 mol, or 1 mol per mol of the hydrolyzable group, or Use 2 to 3.5 moles of water.
The reaction temperature for carrying out the hydrolysis and condensation is usually in the range of 20 ° C. (room temperature) to the reflux temperature under normal pressure of the solvent used for the hydrolysis. Moreover, it can carry out under pressure, for example, can heat up to about 200 degreeC of liquid temperature.

Examples of the method for obtaining the silicon compound (A) containing the hydrolysis condensate (polysiloxane) include a method of heating a mixture of a hydrolyzable silane, a solvent, pure water and an acid catalyst. Specifically, the hydrolyzable silane is dissolved in a solvent in advance, and hydrochloric acid and pure water are added to form an aqueous hydrochloric acid solution, which is then dropped into the hydrolyzable silane solution and heated. In that case, it is common that the quantity of hydrochloric acid shall be 0.0001-0.5 mol with respect to 1 mol of all the hydrolysis groups (all alkoxy groups) which hydrolyzable silane has. The heating in this method can be performed at a liquid temperature of 50 to 180 ° C., and is preferably performed, for example, for several tens of minutes to several tens of hours under reflux in a sealed container so that the liquid does not evaporate or volatilize. Is called.

Examples of the solvent (c1) used for hydrolysis and condensation include n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, Aliphatic hydrocarbon solvents such as methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, isopropyl benzene, diethyl benzene, isobutyl benzene, triethyl benzene, di-isopropyl benzene, trimethyl benzene, etc. Aromatic hydrocarbon solvents; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-pentyl , Ketone solvents such as ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-isobutyl ketone, cyclohexanone, methylcyclohexanone; ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, Ethers such as tetrahydrofuran and 2-methyltetrahydrofuran, 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, Pyrene 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 Lucol, 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 isobutyl 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- Butanol, 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, etc. Can be mentioned. These solvents can be used alone or in combination of two or more.
Hydrolyzable silane is hydrolyzed in a solvent (c1), and the hydrolyzate is subjected to a condensation reaction to obtain a hydrolyzed condensate (polysiloxane), which is dissolved in the hydrolyzing solvent. Obtained as a polysiloxane varnish.

The solvent (C) used for diluting or replacing the varnish of the silicon compound (A) containing the hydrolysis condensate (polysiloxane) is the same as the solvent (c1) used for hydrolysis and condensation polymerization of the hydrolyzable silane. However, another solvent may be used. And the solvent in the varnish of the silicon compound (A) containing a hydrolysis-condensation product (polysiloxane) can be said solvent (C).
When used as a varnish of the silicon compound (A), the concentration of the silicon compound (A) in the varnish can be used in the range of 0.1 to 60% by mass.
The component (C) 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 coating solution of the present invention is not significantly impaired. The general organic solvent mentioned above can be used.

From the viewpoint of compatibility between the silicon compound (A) containing the hydrolysis condensate (polysiloxane) and the inorganic particles (B) having an average particle diameter of 1 to 100 nm, the solvent (C) is more preferably butanol, di- Acetone alcohol, methyl ethyl ketone, methyl isobutyl ketone, hexylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, Examples include propylene glycol monobutyl ether, cyclohexanone, acetic acid methyl ester, acetic acid ethyl ester, and lactate ethyl ester.

The silicon compound (A), which is a hydrolyzable condensate of hydrolyzable silane containing the hydrolyzable silane (a1) and (a2) of the present invention, is a straight, branched or cyclic (a2) having 3 to 6 carbon atoms. A hydrolyzable silane having three alkyl groups, (a1) is 90 to 50 mol%, and (a2) is 10 to 50 mol%. In addition, the mass average molecular weight can be set to 700 to 4000. As a result, a film obtained from the composition containing the silicon compound (A), the inorganic particles (B), and the solvent (C) has a dissolution developability with respect to an alkaline solution, and therefore a photosensitive resist is used. Therefore, patterning of 10 μm or less is possible, and high refractive index, high light resistance, and prevention of intermixing of a photosensitive resist can be satisfied at the same time.

By specifying the mass average molecular weight of the silicon compound (A) and the copolymerization ratio in the hydrolysis condensate of hydrolyzable silanes (a1) and (a2), fully automatic made by Kyowa Interface Science Co., Ltd. Using a contact angle meter, product name Drop Master series DM700, a droplet of pure water was prepared from a needle having a size of 22G, and the droplet deposited on the coating surface was calculated by the droplet method (θ / 2 method). The contact angle of water is 60 ° to 80 °, and dissolution development is performed with respect to an alkaline solution.
The water contact angle is an important film physical property that is directly related to dissolution and developability in an alkaline solution. When the water contact angle of the coating is less than 60 °, peeling development occurs, and when it exceeds 80 °, the alkaline solution is repelled. It will not develop developability. When the water contact angle is less than 60 °, the amount of silanol is large and the hydrophilicity is relatively high, so that the alkaline solution easily penetrates into the film. When the alkali solution permeates, polycondensation starts before the silanol of the silicon compound existing in the coating comes into direct contact with the base and dissolves, and the molecular weight increases. As the increase in the molecular weight proceeds, peeling development occurs instead of dissolution development. On the other hand, when the water contact angle is more than 80 °, the hydrophobicity of the coating surface increases, so that the alkaline solution is repelled, development itself cannot be performed, and a pattern cannot be formed.

Optimum dissolution and development in an alkaline solution by controlling the weight average molecular weight, copolymerization ratio, mixing ratio with particles (B), and preheating temperature conditions so that the water contact angle of the coating is 60 ° to 80 °. It becomes possible for the first time to express sex.
The inorganic particle (B) component used in the present invention is an inorganic particle (B) having an average particle diameter of 1 to 100 nm, and the refractive index of the inorganic particle (B) is 1.50 to 2.70, or 1. A range of 50 to 1.70, or 1.60 to 2.00, or 1.90 to 2.20, or 2.20 to 2.70 can be selected.
Zirconia is mentioned as a kind of inorganic particle (B) which comprises the composition of this invention with the polysiloxane mentioned above.
The inorganic particles may be used alone or in combination of two or more.

Specific examples of the metal oxide include composite oxides containing SiO ₂ and HfO ₂ . The composite oxide is a mixture of two or more inorganic oxides in the particle production stage.

Furthermore, these compounds can be used alone or in admixture of two or more, and may be used in admixture with the above oxides.
As the inorganic particle (B) component used in the present invention, inorganic particles having an average particle diameter of 1 to 100 nm, 5 to 50 nm, or 1 to 10 nm by a dynamic light scattering method can be used.
As for the particle size, particles having different average particle sizes may be mixed and used.

Moreover, when using the said inorganic particle (B), you may use particle | grains as it is, the thing of the colloid state (The colloid particle was disperse | distributed to the dispersion medium) which dispersed the particle | grains beforehand in water or the organic solvent. Sol) may be used. The density | concentration of the inorganic particle in sol can be used in 0.1-60 mass%.
An organic solvent sol in which a dispersion medium of a water sol in which inorganic particles are dispersed in an aqueous medium is substituted from water to an organic solvent can be used. This dispersion medium (c2) is combined with the solvent (C) used in the present invention in combination with the solvent (C) used for diluting or replacing the varnish of the silicon compound (A) containing the hydrolysis condensate (polysiloxane). can do.

Therefore, the same dispersion medium (c2) as the solvent (C) can be used.
Furthermore, particles obtained by treating the inorganic particles (B) 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 inorganic particles (B) by a known method. Treatment with an organosilicon compound or an organometallic compound means that these compounds are added to a dispersion containing inorganic particles (B), and these compounds or reaction products of these compounds are adsorbed on the surfaces of the inorganic particles. Or they are to be combined.

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.
As for the usage-amount of these organosilicon compounds and organometallic compounds, 2-100 mass parts is preferable with respect to 100 mass parts of said inorganic particles (B).
The metal oxide colloidal particles used for the inorganic particles (B) 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 the metal salt is treated with an ion exchange resin to remove counter ions and generate particles.

Peptides include a precipitate obtained by neutralizing the metal salt with an acid or base, hydrolyzing the metal alkoxide, or hydrolyzing the metal basic salt under heating, or Examples thereof include a method of removing unnecessary electrolyte from the gel or adding ions necessary for dispersion. Examples of the reaction method include a method of reacting the metal powder with an acid.
The method for preparing the film forming composition of the present invention is not particularly limited. It suffices if the (A) component, (B) component, and (C) component are uniformly mixed. The order of mixing components (A) to (C) is not particularly limited as long as a uniform varnish can be obtained.
For example, a hydrolyzable silane containing hydrolyzable silane (a1) and hydrolyzable silane (a2) is hydrolyzed in a solvent (c1), and a varnish of a silicon compound (A) having a weight average molecular weight of 700 to 4000 is obtained. Obtaining step,
A step of obtaining a sol in which inorganic particles (B) having an average particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70 are dispersed in a dispersion medium (c2) by a dynamic light scattering method;
Forming a film comprising: mixing a varnish of a silicon compound (A) and a sol of inorganic particles (B) to obtain a film-forming composition containing the silicon compound (A), inorganic particles (B), and a solvent (C) The manufacturing method of a composition is mentioned.

The solid content of the film-forming composition contains the silicon compound (A) and inorganic particles (B), but may contain other components.
In the present invention, in addition to the component (A), the component (B), and the component (C), other components such as a leveling agent and a surfactant are included as long as the effects of the present invention are not impaired. May be.
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 described above may be performed simultaneously with the addition of the inorganic particles (B) and the solvent (C) to the silicon compound (A). ) It may be after mixing 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 heating device is not particularly limited, and may be heated in an appropriate atmosphere, that is, in an inert gas such as air or nitrogen, in a vacuum, or the like using, for example, a hot plate, an oven, or a furnace. Thereby, it is possible to obtain a film having a uniform film forming surface.
The heating temperature is not particularly limited for the purpose of evaporating the solvent, but can be performed at 40 to 200 ° C., for example. 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 heating temperature and the heating time may be selected in accordance with the process steps of the target electronic device, and the heating conditions in which the physical property value of the polysiloxane film is compatible with the required characteristics of the electronic device can be selected.
The film-forming composition comprising the silicon compound (A) containing the hydrolysis condensate (polysiloxane), the inorganic particles (B) and the solvent (C) of the present invention is a film-forming composition obtained by hybridizing these components. (Varnish) is preferably a uniform dispersion.
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.

  The method for preparing the hybrid is not particularly limited as long as the stability of the final film-forming composition (varnish) can be obtained.

For example, (1) a silicon compound (A) containing a hydrolysis condensate (polysiloxane) is mixed with a dispersion (sol) of inorganic particles (B) in a solution state (varnish), (2) a hydrolysis condensate There are various methods such as dispersing the inorganic particles (B) in the solution (in the varnish) of the silicon compound (A) containing (polysiloxane). From the viewpoint of handling properties, hydrolysis condensate (polysiloxane) ) Containing a silicon compound (A) is preferably mixed with a dispersion (sol) of inorganic particles (B) in a solution (varnish) state.
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 inorganic 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 liquid) containing the silicon compound (A) containing the hydrolysis condensate (polysiloxane) of the present invention, the inorganic particles (B), and the solvent (C) is deposited due to a decrease in dispersibility. The storage conditions are not particularly limited as long as the storage conditions do not cause a significant change in the secondary particle size or secondary particle size, 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
In the present invention, the film-forming composition is coated on a substrate and heated, and is 1.50 to 1.90, 1.50 to 1.70, or 1.70 to 1.90 at a wavelength of 633 nm. The film has a refractive index and a hardness of H-9H, H-5H, or H-3H, as determined by JIS standard K5600.

<Pattern patterning method>
The film-forming composition itself of the present invention itself is not photosensitive, but has a pattern of 10 μm or less by using a photosensitive resist because it has solubility and developability in an alkaline solution. The reason for not imparting photosensitivity to the film-forming composition is that the photosensitizer added when the photosensitive material is used causes deterioration in light resistance.
The patterning method is completed by obtaining the following steps 1 to 9.
Step 1: A film-forming composition is applied to a substrate.
Step 2: The film on the substrate is temporarily dried.
Step 3: A photosensitive resist is applied on the film-forming composition.
Step 4: The photosensitive resist is dried.
Step 5: Light is irradiated from above the photosensitive resist through a mask.
Step 6: Alkali development.
Step 7: Rinse with pure water.
Step 8: Strip the resist.
Step 9: Mainly heat the patterned film-forming composition.

  Step 2 is a step of pre-drying the film-forming composition and is not particularly limited as long as it is heated until it is not dissolved in the main solvent of the photosensitive resist of Step 3, but 40 ° C to 200 ° C, or 80 ° C to 150 ° C, Alternatively, heating may be performed at 90 ° C. to 120 ° C., and the heating time may be 30 seconds to 300 seconds, or 60 seconds to 120 seconds, or 180 seconds to 240 seconds.

  Step 3 is a step of applying a photosensitive resist, and a commercially available general positive photosensitive resist or negative photosensitive resist may be used. For example, as the positive photoresist, THMR-iP1800 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), AZ3100, AZ1500 (manufactured by AZ ELECTRONIC MATERIALS) or the like may be used.

Step 5 is a step of irradiating light through a mask, and a general exposure machine may be used. For example, aligner PLA-600FA (manufactured by Canon Inc.), i-line stepper NSR-2205i12D (manufactured by Nikon Corporation), or the like may be used.
Step 6 is a step of alkali development, and a common tetramethylammonium hydride (TMAH) aqueous solution may be used as the alkali developer. The concentration of TMAH may be 0.1% to 2.38%, 0.5% to 1.0%, or 1.0% to 2.0% by weight, and the development time is 10%. Second to 180 seconds, 20 seconds to 60 seconds, or 90 seconds to 120 seconds may be sufficient. The alkaline developer may be an inorganic base such as sodium carbonate, sodium hydroxide, or potassium hydroxide aqueous solution.

Step 8 is a step of stripping the resist, and any common resist solvent may be used. Examples thereof include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and ethyl pyruvate.
Step 9 is a step of subjecting the film-forming composition to main heating, which may be performed at 80 ° C. to 300 ° C., 100 ° C. to 150 ° C., 180 ° C. to 230 ° C., or 250 ° C. to 300 ° C.

Through the patterning method as described above, it is possible to perform patterning by having alkali developability even though the film forming composition is a non-photosensitive material.
The film made of the composition of the present invention thus obtained can satisfy a high refractive index, high transparency, high heat resistance, high light resistance, and high hardness at the same time. , Cathode ray tubes, organic light-emitting displays, electronic paper, LEDs, solid-state imaging devices, solar cells, organic thin film transistors, and other electronic devices. In particular, it can be suitably used as an LED member that requires high light resistance.

  More specifically, it can be suitably used as a backlight light source for various displays, traffic lights, illumination, lasers, biosensors, and the like.

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 [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.
The inorganic particles (B) are diluted with propylene glycol monomethyl ether so as to have a film thickness of 100 nm, spin-coated on a silicon substrate, heated on a hot plate at 100 ° C. for 1 minute, and then heated at 200 ° C. for 5 minutes. The refractive index of the heated film was measured.
[Average particle size]
Device: N5 made by Beckman Coulter
The dispersion of the inorganic particles (B) 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.

[Spin coat]
Equipment: Clean Electron ACT8 manufactured by Tokyo Electron Ltd.
〔exposure〕
Device: Nikon i-line stepper NSR-2205i12D
[Water contact angle]
Using a fully automatic contact angle meter Drop Master series DM700 manufactured by Kyowa Interface Science Co., Ltd., droplets were made from pure water using a 22G size needle, and the droplets deposited on the coating surface were subjected to the droplet method (θ / 2 Method) to calculate the water contact angle.
(Optical microscope)
Equipment: ECLIPSE E600 POL made by Nikon
The optical microscope was observed at a magnification of 50 times.
〔electronic microscope〕
Apparatus: S-4800 manufactured by Hitachi High-Technologies Corporation

[Synthesis Example 1]
29.17 g of tetraethoxysilane and 116.66 g of propylene glycol monomethyl ether (abbreviated as PGME) were placed in a 300 ml flask, and the mixed solution was stirred with a magnetic stirrer and 0.019 g of 0.01 mol / L hydrochloric acid. Was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C., and reacted for 240 minutes under heating and reflux. Thereafter, the reaction solution is cooled to room temperature, 116.66 g of PGME is added to the reaction solution, and ethanol, water, and hydrochloric acid as reaction byproducts are distilled off under reduced pressure, and concentrated to a PGME solution of hydrolysis condensate (polymer). Got. Subsequently, PGME was added and adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer is a varnish of polysiloxane (abbreviated as pTEOS) composed only of the component (a1). The weight average molecular weight by GPC of the obtained pTEOS was Mw1800 in terms of polystyrene.

[Synthesis Example 2]
29.17 g of tetraethoxysilane, 10.70 g of methyltriethoxysilane, and 159.46 g of PGME were placed in a 300 ml flask, and 0.01 mol / L hydrochloric acid 13. 33 g was added dropwise to the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C., and reacted for 240 minutes under heating and reflux. Then, it operated similarly to the synthesis example 1, and adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer was hydrolyzed with 70 mol% of (a1) and 30 mol% of a silane monomer having a methyl group having 1 carbon atom and three hydrolyzable groups instead of (a2). It is a varnish of polymerized polysiloxane (abbreviated as TM73). The weight average molecular weight of the obtained TM73 by GPC was Mw1155 in terms of polystyrene.

[Synthesis Example 3]
29.17 g of tetraethoxysilane, 11.54 g of ethyltriethoxysilane and 162.82 g of PGME were placed in a 300 ml flask, and the mixed solution was stirred with a magnetic stirrer and 0.01 mol / L hydrochloric acid 13. 33 g was added dropwise to the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C., and reacted for 240 minutes under heating and reflux. Then, it operated similarly to the synthesis example 1, and adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer was copolymerized by hydrolyzing 70 mol% of (a1) and 30 mol% of a silane monomer having an ethyl group having 2 carbon atoms and three hydrolyzable groups instead of (a2). A varnish of polysiloxane (abbreviated as TE73). The weight average molecular weight of the obtained TE73 by GPC was Mw1310 in terms of polystyrene.

[Synthesis Example 4]
29.17 g of tetraethoxysilane, 9.86 g of propyltrimethoxysilane and 156.09 g of PGME were placed in a 300 ml flask, and the mixed solution was stirred with a magnetic stirrer to 0.01 mol / L hydrochloric acid. 33 g was added dropwise to the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C., and reacted for 240 minutes under heating and reflux. Then, it operated similarly to the synthesis example 1, and adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer was copolymerized by hydrolyzing 70 mol% of (a1) and a silane monomer having 3 propyl groups and 3 hydrolyzable groups as (a2) at a ratio of 30 mol%. It is a varnish of polysiloxane (abbreviated as TT73). The weight average molecular weight of the obtained TT73 by GPC was Mw1041 in terms of polystyrene.

[Synthesis Example 5]
29.17 g of tetraethoxysilane, 13.22 g of isobutyltriethoxysilane, and 169.56 g of PGME were placed in a 300 ml flask, and the mixed solution was stirred with a magnetic stirrer to 0.01 mol / L hydrochloric acid. 33 g was added dropwise to the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C., and reacted for 240 minutes under heating and reflux. Then, it operated similarly to the synthesis example 1, and adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer was copolymerized by hydrolyzing 70 mol% of (a1) and 30 mol% of a silane monomer having 4 isobutyl groups and three hydrolyzable groups as (a2). It is a varnish of polysiloxane (abbreviated as TI73). The weight average molecular weight of the obtained TI73 by GPC was Mw1087 in terms of polystyrene.

[Synthesis Example 6]
29.17 g of tetraethoxysilane, 12.38 g of n-hexyltrimethoxysilane, 166.19 g of PGME were placed in a 300 ml flask, and the mixed solution was stirred with a magnetic stirrer and 0.01 mol / L hydrochloric acid. 13.33 g was dripped at the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C., and reacted for 240 minutes under heating and reflux. Then, it operated similarly to the synthesis example 1, and adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer was hydrolyzed at a ratio of 30 mol% of 70 mol% of (a1) and, as (a2), an n-hexyl group having 6 carbon atoms and a silane monomer having three hydrolyzable groups. It is a varnish of polymerized polysiloxane (abbreviated as TH73). The weight average molecular weight of the obtained TH73 by GPC was Mw 1060 in terms of polystyrene.

[Synthesis Example 7]
29.17 g of tetraethoxysilane, 3.43 g of isobutyltriethoxysilane, and 130.38 g of PGME were placed in a 300 ml flask, and the mixed solution was stirred with a magnetic stirrer to 0.01 mol / L hydrochloric acid. 93 g was added dropwise to the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C., and reacted for 240 minutes under heating and reflux. Then, it operated similarly to the synthesis example 1, and adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer was copolymerized by hydrolyzing 90 mol% of (a1) and a silane monomer having 4 isobutyl groups and 3 hydrolyzable groups as (a2) at a ratio of 10 mol%. It is a varnish of polysiloxane (abbreviated as TI91). The weight average molecular weight of the obtained TI91 by GPC was Mw1237 in terms of polystyrene.

[Synthesis Example 8]
29.17 g of tetraethoxysilane, 7.71 g of isobutyltriethoxysilane, and 147.52 g of PGME were placed in a 300 ml flask, and the mixed solution was stirred with a magnetic stirrer to 0.01 mol / L hydrochloric acid. 98 g was added dropwise to the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C., and reacted for 240 minutes under heating and reflux. Then, it operated similarly to the synthesis example 1, and adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer was copolymerized by hydrolyzing 80 mol% of (a1) and (a2) 20 mol% of a silane monomer having an isobutyl group having 4 carbon atoms and three hydrolyzable groups. It is a varnish of polysiloxane (abbreviated as TI82). The weight average molecular weight of the obtained TI82 by GPC was Mw1235 in terms of polystyrene.

[Synthesis Example 9]
20.83 g of tetraethoxysilane, 14.69 g of isobutyltriethoxysilane, and 140.10 g of PGME were placed in a 300 ml flask, and the mixed solution was stirred with a magnetic stirrer to 0.01 mol / L hydrochloric acid. 81 g was added dropwise to the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C., and reacted for 240 minutes under heating and reflux. Then, it operated similarly to the synthesis example 1, and adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The polymer obtained was copolymerized by hydrolyzing 60 mol% of (a1) and (a2) 40 mol% of a silane monomer having 4 isobutyl groups and 3 hydrolyzable groups. It is a varnish of polysiloxane (abbreviated as TI64). The weight average molecular weight of the obtained TI64 by GPC was Mw1051 in terms of polystyrene.

[Synthesis Example 10]
20.83 g of tetraethoxysilane, 22.04 g of isobutyltriethoxysilane, and 171.48 g of PGME were placed in a 300 ml flask, and the mixed solution was stirred with a magnetic stirrer and 0.01 mol / L hydrochloric acid 12. 61 g was added dropwise to the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C., and reacted for 240 minutes under heating and reflux. Then, it operated similarly to the synthesis example 1, and adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The polymer obtained was copolymerized by hydrolyzing 50 mol% of (a1) and 50 mol% of a silane monomer having 4 isobutyl groups and three hydrolyzable groups as (a2). It is a varnish of polysiloxane (abbreviated as TI55). The weight average molecular weight of the obtained TI55 by GPC was Mw 1025 in terms of polystyrene.

[Synthesis Example 11]
16.67 g of tetraethoxysilane, 26.45 g of isobutyltriethoxysilane, and 172.45 g of PGME were placed in a 300 ml flask, and the mixed solution was stirred with a magnetic stirrer and 12.25 g of 0.01 mol / L hydrochloric acid. Was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C., and reacted for 240 minutes under heating and reflux. Then, it operated similarly to the synthesis example 1, and adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer was copolymerized by hydrolyzing 40 mol% of (a1) and 60 mol% of a silane monomer having 4 isobutyl groups and three hydrolyzable groups as (a2). It is a varnish of polysiloxane (abbreviated as TI46). The weight average molecular weight of the obtained TI46 by GPC was Mw1015 in terms of polystyrene.

[Synthesis Example 12]
TI73 obtained in Synthesis Example 5 was heated and stirred in an oil bath at 100 ° C. for 9 hours to confirm that it became Mw2097 in terms of polystyrene, and a varnish of polysiloxane (abbreviated as TI73M1) was obtained.
[Synthesis Example 13]
TI73 obtained in Synthesis Example 5 was heated and stirred in an oil bath at 100 ° C. for 20 hours to confirm that it became Mw3014 in terms of polystyrene, and a varnish of polysiloxane (abbreviated as TI73M2) was obtained.
[Synthesis Example 14]
TI73 obtained in Synthesis Example 5 was heated and stirred for 32 hours in an oil bath at 100 ° C., and it was confirmed that it became Mw4235 in terms of polystyrene to obtain a varnish of polysiloxane (abbreviated as TI73M3).
[Synthesis Example 15]
TI73 obtained in Synthesis Example 5 was heated and stirred in an oil bath at 100 ° C. for 62 hours to confirm that it became Mw6357 in terms of polystyrene, and a varnish of polysiloxane (abbreviated as TI73M4) was obtained.

[Synthesis Example 16]
10.42 g of tetraethoxysilane, 4.72 g of isobutyltriethoxysilane, and 136.25 g of PGME were placed in a 300 ml flask, and the mixed solution was stirred with a magnetic stirrer to 0.01 mol / L hydrochloric acid. 76 g was added dropwise to the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C., and reacted for 240 minutes under heating and reflux. Then, it operated similarly to the synthesis example 1, and adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer was copolymerized by hydrolyzing 70 mol% of (a1) and 30 mol% of a silane monomer having 4 isobutyl groups and three hydrolyzable groups as (a2). It is a varnish of polysiloxane (abbreviated as TI73L1). The weight average molecular weight by GPC of the obtained TI73L1 was Mw 760 in terms of polystyrene.

[Synthesis Example 17]
5.21 g of tetraethoxysilane, 2.36 g of isobutyltriethoxysilane, and 143.82 g of PGME were placed in a 300 ml flask, and the mixed solution was stirred with a magnetic stirrer and 0.01 mol / L hydrochloric acid. 38 g was added dropwise to the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C., and reacted for 240 minutes under heating and reflux. Then, it operated similarly to the synthesis example 1, and adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer was copolymerized by hydrolyzing 70 mol% of (a1) and 30 mol% of a silane monomer having 4 isobutyl groups and three hydrolyzable groups as (a2). It is a varnish of polysiloxane (abbreviated as TI73L2). The weight average molecular weight by GPC of the obtained TI73L2 was Mw652 in terms of polystyrene.

[Synthesis Example 18]
20.83 g of tetraethoxysilane, 9.62 g of n-octyltrimethoxysilane and 121.80 g of PGME were placed in a 300 ml flask, and the mixed solution was stirred with a magnetic stirrer and 0.01 mol / L hydrochloric acid. 9.52 g was added dropwise to the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C., and reacted for 240 minutes under heating and reflux. Then, it operated similarly to the synthesis example 1, and adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer hydrolyzed 70 mol% of (a1) and 30 mol% of a silane monomer having 8 n-octyl groups and three hydrolyzable groups instead of (a2). And varnish of polysiloxane (abbreviated as TO73). The weight average molecular weight of the obtained TO73 by GPC was Mw998 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 inorganic particle sol obtained in Reference Example 1.

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

<Production of film-forming composition and film>
[Example 1]
6.5000 g of D1 obtained in Reference Example 1 was weighed into a 50 mL eggplant-shaped flask, then 23.8851 g of PGME was added, and 4.9563 g of TT73 obtained in Synthesis Example 4 (based on the solid content of D1). The solid content of polysiloxane was 35% by mass), and 0.3965 g of a solution obtained by diluting R-30-N manufactured by Dainippon Ink & Chemicals, Inc. with PGME as a surfactant to 1% by mass, The mixture was mixed until it became completely uniform at room temperature to obtain a varnish (abbreviated as V1) having a total solid content of 7.5% by mass.

Obtained V1 evaluated the patterning characteristic. V1 is spin-coated on a 8 inch silicon substrate treated with hexamethyldisilazane (HMDS) using a clean track ACT8 manufactured by Tokyo Electron Co., Ltd. so as to have a film thickness of 100 nm. Heating was performed in minutes. Next, AZ3100 (manufactured by AZ ELECTRONIC MATERIALS) was spin-coated on the obtained V1 film so as to have a film thickness of 1.5 μm, and heated at 100 ° C. for 1 minute using a hot plate. . Thereafter, an exposure amount of 300 mJ / cm ² was irradiated through a mask using an i-line stepper NSR-2205i12D manufactured by Nikon Corporation. After light irradiation, development was performed for 30 seconds using 2.38 mass% tetramethylammonium hydride (abbreviated as TMAH), and after 1 minute of pure water rinse, the film was dried with air. Furthermore, the photosensitive resist was immersed in PGME for 2 minutes, the resist was peeled off, and the 5 μm portion where Line: Space was 1: 1 was observed with an optical microscope. As a result of observation with an optical microscope, an example in which Line: Space is close to 5 μm of 1: 1 is evaluated as ○, an example in which Line: Space is 1: 1 from 5 μm, or an example in which the remaining film is left is evaluated as ×. did. The results observed with an optical microscope are shown in FIG.

  In addition, at the 5 μm portion where Line: Space is 1: 1, the Space portion was measured from the top direction of the pattern using an electron microscope. As a result of the measurement, the width of the Space portion was 5.15 μm. Here, the space portion is a portion that dissolves in the alkaline developer, and the closer to 5 μm, the better the pattern can be formed.

  Obtained V1 evaluated the heat-resistant refractive index. It spin-coated so that the film thickness of V1 might be set to 100 nm on a silicon substrate, and it heated at 150 degreeC for 1 minute using the hotplate. After heating, the refractive index at 450 nm was measured. Next, heating was performed at 300 ° C. for 1 hour using a hot plate, and after measuring the refractive index at 450 nm, the refractive indexes before and after heating at 300 ° C. were compared. The results of the refractive index comparison are shown in Table 2.

Obtained V1 measured the water contact angle. It spin-coated so that the film thickness of V1 might be set to 100 nm on a silicon substrate, and it heated at 150 degreeC 1 minute using the hotplate, and then heated at 100 degreeC 1 minute. The two-step heating in this hot plate is a heating condition that reproduces the thermal history before alkali development in consideration of applying a photosensitive resist and drying.
The obtained film was made from Kyowa Interface Science Co., Ltd. fully automatic contact angle meter Drop Master series DM700. The water contact angle was calculated by the method (θ / 2 method). The results are shown in Table 2.

[Example 2]
The alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example 1 except that TT73 in Example 1 was replaced with TI73 obtained in Synthesis Example 5. The results are shown in Table 2. The result of the optical microscope observation of the pattern is shown in FIG.
In addition, at the 5 μm portion where Line: Space is 1: 1, the Space portion was measured from the top direction of the pattern using an electron microscope. As a result of measurement, the width of the space portion was 5.12 μm.
[Example 3]
The alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example 1 except that TT73 in Example 1 was replaced with TH73 obtained in Synthesis Example 6. The results are shown in Table 2. The result of optical microscope observation of the pattern is shown in FIG.
In addition, at the 5 μm portion where Line: Space is 1: 1, the Space portion was measured from the top direction of the pattern using an electron microscope. As a result of measurement, the width of the space portion was 5.12 μm.

[Example 4]
The alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example 1 except that TT73 in Example 1 was replaced with TI91 obtained in Synthesis Example 7. The results are shown in Table 2.
[Example 5]
The same procedure as in Example 1 was conducted except that TT73 in Example 1 was replaced with TI82 obtained in Synthesis Example 8, and alkali developability, heat resistance, and water contact angle were measured. The results are shown in Table 2.
[Example 6]
The alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example 1 except that TT73 in Example 1 was replaced with TI64 obtained in Synthesis Example 9. The results are shown in Table 2.
[Example 7]
The alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example 1 except that TT73 in Example 1 was replaced with TI55 obtained in Synthesis Example 10. The results are shown in Table 2.
[Example 8]
The alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example 1 except that TT73 in Example 1 was replaced with TI73M1 obtained in Synthesis Example 12. The results are shown in Table 2. The result of observing the pattern with an optical microscope is shown in FIG.
In addition, at the 5 μm portion where Line: Space is 1: 1, the Space portion was measured from the top direction of the pattern using an electron microscope. As a result of the measurement, the width of the Space portion was 5.15 μm.

[Example 9]
The alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example 1 except that TT73 in Example 1 was replaced with TI73M2 obtained in Synthesis Example 13. The results are shown in Table 2.
[Example 10]
The alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example 1 except that TT73 in Example 1 was replaced with TI73L1 obtained in Synthesis Example 16. The results are shown in Table 2.
[Example 11]
The alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example 1 except that TT73 in Example 1 was replaced with TI46 obtained in Synthesis Example 11. The results are shown in Table 2.

[Comparative Example 1]
The alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example 1 except that TT73 in Example 1 was replaced with pTEOS obtained in Synthesis Example 1. The results are shown in Table 2. The result of the optical microscope observation of the pattern is shown in FIG.
[Comparative Example 2]
The alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example 1 except that TT73 in Example 1 was replaced with TM73 obtained in Synthesis Example 2. The results are shown in Table 2.
[Comparative Example 3]
The alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example 1 except that TT73 in Example 1 was replaced with TE73 obtained in Synthesis Example 3. The results are shown in Table 2.

[Comparative Example 4]
The alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example 1 except that TT73 in Example 1 was replaced with TI73M3 obtained in Synthesis Example 14. The results are shown in Table 2.
[Comparative Example 5]
The alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example 1 except that TT73 in Example 1 was replaced with TI73M4 obtained in Synthesis Example 15. The results are shown in Table 2. The result of the optical microscope observation of the pattern is shown in FIG.
[Comparative Example 6]
The alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example 1 except that TT73 in Example 1 was replaced with TI73L2 obtained in Synthesis Example 17. The results are shown in Table 2. It was found that the spin coat film obtained using TI73L2 was remarkably developed so that radial coating unevenness could be visually confirmed, and the film forming property was poor.
[Comparative Example 7]
The alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example 1 except that TT73 in Example 1 was replaced with TO73 obtained in Synthesis Example 18. The results are shown in Table 2.

[Table 2]
Table 2
――――――――――――――――――――――――――――――――――――――
Alkali refractive index of [a2] [wavelength 450 nm] water contact angle
Carbon number of L Developability Before test → After test Result [°]
Example 1 3 ○ 1.612 → 1.612 ○ 66.4
Example 2 4 ○ 1.608 → 1.608 ○ 76.7
Example 3 6 ○ 1.601 → 1.601 ○ 78.5
Example 4 4 ○ 1.609 → 1.609 ○ 75.5
Example 5 4 ○ 1.608 → 1.608 ○ 76.1
Example 6 4 ○ 1.604 → 1.604 ○ 76.8
Example 7 4 ○ 1.603 → 1.603 ○ 79.9
Example 8 4 ○ 1.608 → 1.608 ○ 76.0
Example 9 4 ○ 1.609 → 1.609 ○ 76.6
Example 10 4 ○ 1.608 → 1.608 ○ 76.6
Example 11 4 ○ 1.602 → 1.602 ○ 83.0
Comparative Example 1 0 × 1.622 → 1.622 ○ 52.5
Comparative Example 2 1 ○ 1.618 → 1.585 × 65.4
Comparative Example 3 2 ○ 1.615 → 1.591 × 66.3
Comparative Example 4 4 × 1.608 → 1.608 ○ 71.3
Comparative Example 5 4 × 1.609 → 1.609 ○ 70.2
Comparative Example 7 8 × 1.600 → 1.600 ○ 88.7
――――――――――――――――――――――――――――――――――――――

With respect to the results in Table 2, Examples 1 to 11 and Comparative Examples 1 to 7 are compared.
Examples 1 to 11 and Comparative Examples 2 to 3 have better alkali developability as compared with Comparative Examples 4 to 5 and 7 in view of patterning of 5 μm which is 10 μm or less. I understood.
Although Example 11 has a mass average molecular weight in the range of 700 to 4000, the composition (a1) constituting the silicon compound (A) was copolymerized at 40 mol% and (a2) at 60 mol%, Although the contact angle is slightly outside the preferred range, it can be used depending on the application.
Although Comparative Example 4 and Comparative Example 5 are compositions having a polymerization ratio within the range of 70 mol% (a1) constituting the silicon compound (A) and 30 mol% (a2), the mass average molecular weight is 700. Or out of the range of 4000.
Comparative Example 7 has a mass average molecular weight in the range of 700 to 4000, and a polymerization ratio of 70 mol% (a1) and 30 mol% (a2) constituting the silicon compound (A) is within the range. However, L in (a2) is an alkyl group having 8 carbon atoms, and is outside the range of a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms.

In Examples 1 to 11, Comparative Example 1, Comparative Examples 4 to 5, and Comparative Example 7, it was found that the change in refractive index during heating was better than that of Comparative Example 2 and Comparative Example 3.
In Comparative Examples 2 and 3, L in (a2) is an alkyl group having 1 and 2 carbon atoms, and is outside the range of a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms. The phenomenon that the refractive index decreases when heated is that when L is a silicon compound (A) having 1 and 2 carbon atoms, the low molecular weight compound that has become a ring in the polymer sublimes when heated and forms an air layer. It is thought to be caused. Since air has a refractive index of 1.0, it is known that the refractive index of a film decreases when an air layer is mixed in the film.
The water contact angles of Examples 1 to 11 and Comparative Examples 1 to 7 are compared. Examples 1 to 10 are droplets in which pure water was made from a 22 G size needle using a fully automatic contact angle meter Drop Master series DM700 manufactured by Kyowa Interface Science Co., Ltd., and landed on the coating surface The contact angle of water calculated by the droplet method (θ / 2 method) is in the range of 60 ° to 80 °. In Comparative Example 2, Comparative Example 3, Comparative Example 4 and Comparative Example 5, the contact angle of water is 60 ° to 80 °, which is within the range, but the change in refractive index with heat is poor or less than 10 μm. When the alkali developability is poor when a certain pattern of 5 μm is seen, the performance as a target film is insufficient.

In the film-forming composition of the present invention, the silicon compound (A) has a mass average molecular weight in the range of 700 to 4000, constituting (a1) is 90 mol% to 50 mol%, and (a2) is 10 mol% to 50 mol%. It is a copolymerized range, L in (a2) is a range of a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, and the water contact angle is in the range of 60 ° to 80 °. By using such a composition, a permanent film having a good alkali developability and a good change in refractive index when heated is obtained without undergoing a process such as a dry process. be able to.
Since the film obtained by the present invention can satisfy high refractive index, high transparency, high heat resistance, high light resistance and patterning characteristics of 10 μm or less at a time, liquid crystal display, plasma display, cathode ray tube It can be suitably used as an electronic device such as an organic light emitting display, electronic paper, LED, solid-state imaging device, solar cell, or organic thin film transistor. In particular, it can be suitably used as an LED member that requires high light resistance.

Claims (10)

Hydrolyzable silane (a1) and hydrolyzable silane (a2):

(Wherein R ¹ and R ² each represents an alkoxy group, an acyloxy group, or a halogen group, and L represents a linear, branched, or cyclic alkyl group having 3 to 6 carbon atoms). A silicon compound (A) having a weight average molecular weight of 700 to 4000, an inorganic particle (B) having an average particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70, and a solvent ( A film-forming composition comprising C). When the silicon compound (A) is hydrolyzable silane (a1) and hydrolyzable silane (a2), the hydrolyzable silane (a1) is 90 mol% to 50 mol%. 2. The film-forming composition according to claim 1, which is a polymer obtained by hydrolyzing and condensing a hydrolyzable silane containing 10 mol% to 50 mol%. The film-forming composition according to claim 1 or 2, wherein the inorganic particles (B) are zirconia. A step of hydrolyzing a hydrolyzable silane containing hydrolyzable silane (a1) and hydrolyzable silane (a2) in a solvent (c1) to obtain a varnish of a silicon compound (A) having a weight average molecular weight of 700 to 4000. ,
A step of obtaining a sol in which inorganic particles (B) having an average particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70 are dispersed in a dispersion medium (c2) by a dynamic light scattering method;
A step of mixing a varnish of a silicon compound (A) and a sol of inorganic particles (B) to obtain a film-forming composition containing the silicon compound (A), inorganic particles (B) and a solvent (C). The manufacturing method of the film forming composition of any one of Claim 1 thru | or 3. The pattern formation method which apply | coats a photosensitive resist on the film | membrane obtained from the film forming composition of any one of Claims 1 thru | or 3, a drying, light irradiation, image development, and resist peeling. A film having a refractive index of 1.50 to 1.90 at a wavelength of 633 nm, obtained by coating the film-forming composition according to any one of claims 1 to 3 on a substrate and heating. 7. The membrane according to claim 6, wherein the contact angle of water on the membrane surface is 60 ° to 80 °. The film according to claim 6 or 7, which is used as a light extraction film or a protective film. The apparatus which has an electronic device which has a film | membrane of any one of Claim 6 thru | or 8. The apparatus of claim 9, wherein the electronic device is an LED.