WO2015111717A1

WO2015111717A1 - Composition for forming alkali dissolution-developable high-refractive-index film and pattern forming method

Info

Publication number: WO2015111717A1
Application number: PCT/JP2015/051893
Authority: WO
Inventors: 加藤　拓; 中島　誠; 淳平小林; 雅規永井; 正睦鈴木
Original assignee: 日産化学工業株式会社
Priority date: 2014-01-27
Filing date: 2015-01-23
Publication date: 2015-07-30
Also published as: TW201542694A

Abstract

[Problem] To provide: a film forming composition which is suitable for the production of a film having high refractive index, high transparency, high heat resistance, high light resistance and high hardness; and a pattern forming method. [Solution] A film forming composition which contains: a silicon compound (A) that is a hydrolysis-condensation product of a hydrolyzable silane containing a hydrolyzable silane (a1) represented by formula (a1) and a hydrolyzable silane (a2) represented by formula (a2) and has a weight average molecular weight of 700-4,000; inorganic particles (B) having an average particle diameter of 1-100 nm and a refractive index of 1.50-2.70; and a solvent (C). The silicon compound (A) is a polymer that is obtained by hydrolyzing and condensing a hydrolyzable silane which contains the hydrolyzable silane (a1) and the hydrolyzable silane (a2) respectively in an amount of 90-50% by mole and in an amount of 10-50% by mole. Si(R¹)₄ Formula (a1) L-Si(R²)₃ Formula (a2) (In the formulae, each of R¹ and R² represents an alkoxy group having 1-20 carbon atoms, an acyloxy group having 2-20 carbon atoms or a halogen group; and L represents a linear, branched or cyclic alkyl group having 3-6 carbon atoms.)

Description

Alkali-dissolvable and developable high refractive index film forming composition and pattern forming method

The present invention 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, etc., and are widely used for consumer use.

In order to achieve further long life and low power consumption, LEDs have been mainly developed for devices that increase the 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, zinc oxide, tantalum oxide, indium oxide, hafnium oxide, tin oxide, niobium oxide, and a composite thereof, and a weight average molecular weight Is an alkoxy group-containing siloxane polymer (b1) in the range of 1,000 to 100,000, a hydroxy group-containing polysiloxane (b2) having a weight average molecular weight of 500 to 100,000, β-diketone, ketoester, dicarboxylic acid For forming a high refractive material containing at least one chelating agent selected from the group consisting of acids and derivatives thereof, hydroxycarboxylic acids and derivatives thereof, keto alcohols, dihydroxy compounds, oxyaldehyde compounds, and amine compounds and derivatives thereof Composition (patent Document reference 1),
Organopolysiloxane containing alkyl group, aryl group, hydroxy group, etc., resin composition for optical device sealing containing condensation catalyst and inorganic fine particles (see Patent Document 2), and alkyl group having 1 to 20 carbon atoms Or a trialkoxysilane (A) having a phenyl group which may have a hydrocarbon group having 1 to 8 carbon atoms, and a trialkoxysilane (B) having a substituent containing a reactive cyclic ether group, A B-stage encapsulating resin composition for optical elements, which mainly comprises a silsesquioxane derivative having a ladder type structure or a random type structure obtained by cohydrolysis and cocondensation, and inorganic fine particles (patent) Reference 3) is disclosed.

The target high refractive index material is required to have high transparency, high heat resistance, high light resistance, and high hardness, but no sufficiently satisfactory material that satisfies all of these required performances has been obtained so far.

When adding inorganic particles, 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 is a film-forming composition suitable for producing a film for a display device that can achieve high refractive index, high transparency, high heat resistance, high light resistance, and high hardness. It is an object of the present invention to provide an object, a pattern forming method using the same, and a method for preventing film roughness when the resist film is peeled off.

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

(In the formula, R ¹ and R ² are each an alkoxy group having 1 to 20 carbon atoms, show an acyloxy group, or a halogen group having a carbon number of 2 to 20 L is a straight chain of 3 to 6 carbon atoms, branched Or a hydrolyzable condensate of hydrolyzable silane containing a silicon compound (A) having a weight average molecular weight of 700 to 4000 and an average particle diameter of 1 to 100 nm and 1.50 to 2 A film-forming composition (1) comprising inorganic particles (B) having a refractive index of .70 and a solvent (C),
As a second aspect, the silicon compound (A) has a hydrolyzable silane (a1) and hydrolyzable silane (a2) ratio of 90 mol% to 50 mol%, The film-forming composition (1) according to the first aspect, which is a polymer obtained by hydrolyzing and condensing hydrolyzable silanes each containing 10 to 50 mol% of the decomposable silane (a2),
As a third aspect, the film-forming composition (1) according to the first aspect, wherein the silicon compound (A) is obtained by hydrolyzing and condensing a hydrolyzable silane in a non-alcohol solvent,
As a fourth aspect, the film-forming composition (1) according to the third aspect, in which the non-alcohol solvent is a ketone or ether,
As a fifth aspect, the film-forming composition (1) according to the third aspect, wherein the non-alcohol solvent is acetone or tetrahydrofuran,
As a sixth aspect, the solvent (C) is used for solvent replacement to remove the non-alcohol solvent used in the hydrolysis of the hydrolyzable silane and the subsequent condensation, and the reactant generated by the hydrolysis of the hydrolyzable silane. A film-forming composition (1) according to the third aspect, comprising a solvent to be used;
As a seventh aspect, the film-forming composition (1) according to the first aspect, wherein the inorganic particles (B) are zirconia,
As an eighth aspect, the film-forming composition (2) according to the third aspect, further comprising a curing catalyst (D) selected from ammonium salts, phosphines, phosphonium salts, sulfonium salts, or chelate compounds,
As a ninth aspect, the film-forming composition (3) according to the third aspect, further comprising a diketone compound (E) selected from 1,2-diketone and / or 1,3-diketone,
As a tenth aspect, the diketone compound (E) is represented by the following formula (3) and / or the following formula (4):

(Wherein W represents a carbon atom or an oxygen atom) The film-forming composition (3) according to the ninth aspect, which is a compound containing a skeleton represented by:
As an eleventh aspect, the film-forming composition (3) according to the ninth aspect, wherein the diketone compound (E) is diacetyl, methyl pyruvate, ethyl pyruvate, or acetylacetone.
As a twelfth aspect, the film-forming composition (4) according to the eighth aspect, further comprising water (F) and an acid (G),
As a thirteenth 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) in measurement 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 (1) according to the aspect,
As a fourteenth aspect, a hydrolyzable silane containing hydrolyzable silane (a1) and hydrolyzable silane (a2) is hydrolyzed in a non-alcohol solvent (c1) to obtain a silicon compound having a weight average molecular weight of 700 to 4000 ( A step of obtaining the varnish of A),
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) in measurement by a dynamic light scattering method;
The varnish of the silicon compound (A), the sol of the inorganic particles (B), and the curing catalyst (D) are mixed, and the silicon compound (A), the inorganic particles (B), the curing catalyst (D), and the solvent (C) are mixed. A method for producing the film-forming composition (2) according to the eighth aspect, including a step of obtaining a film-forming composition comprising,
As a fifteenth aspect, a hydrolyzable silane containing hydrolyzable silane (a1) and hydrolyzable silane (a2) is hydrolyzed in a non-alcohol solvent (c1), and a silicon compound having a weight average molecular weight of 700 to 4000 ( A step of obtaining the varnish of A),
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) in measurement by a dynamic light scattering method;
The varnish of the silicon compound (A), the sol of the inorganic particles (B), and the diketone compound (E) are mixed, and the silicon compound (A), the inorganic particles (B), the diketone compound (E), and the solvent (C) are mixed. A method for producing a film-forming composition (3) according to the ninth aspect, including a step of obtaining a film-forming composition comprising:
As a sixteenth aspect, a hydrolyzable silane containing hydrolyzable silane (a1) and hydrolyzable silane (a2) is hydrolyzed in a non-alcohol solvent (c1), and a silicon compound having a weight average molecular weight of 700 to 4000 ( A step of obtaining the varnish of A),
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) in measurement by a dynamic light scattering method;
The varnish of the silicon compound (A), the sol of the inorganic particles (B), the curing catalyst (D), water (F), and the acid (G) are mixed, and the silicon compound (A), the inorganic particles (B), and the curing catalyst ( A process for producing a film-forming composition (4) according to the twelfth aspect, including a step of obtaining a film-forming composition comprising D), water (F), an acid (G), and a solvent (C),
As a seventeenth aspect, a photosensitive resist is applied on a film obtained from the film-forming composition according to any one of the first to twelfth aspects, dried, and light is applied to the photosensitive resist film. A pattern forming method comprising irradiating, subsequently developing, and then removing the resist film;
As an eighteenth aspect, the film forming composition according to any one of the first to twelfth 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 nineteenth aspect, the film according to the eighteenth aspect, wherein the contact angle of water on the film surface is 60 ° to 80 °,
As a twentieth aspect, the light extraction film or the film according to the eighteenth aspect used as a protective film,
As a twenty-first aspect, an apparatus having an electronic device having the film described in the eighteenth aspect, and as a twenty-second aspect, an apparatus according to the twenty-first aspect, in which the electronic device is an LED.

For members such as light extraction films and protective films for LEDs, a high refractive index and alkali developability are required, 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 development is classified into 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, it is essential to be able to perform dissolution development, but it is difficult to form the pattern by 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 is obtained by copolymerizing a very specific type of hydrolyzable silane (a2) at a specified ratio with the hydrolyzable silane (a1). The resulting hydrolyzed condensate has a high refractive index in which a film formed from the composition comprising the inorganic particles (B) exhibits dissolution and developability with respect to an alkaline solution and has a pattern of 10 μm or less. A coating 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. Decrease can be prevented.

Since the average particle diameter of the inorganic 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.

Further, when the silicon compound (A) is polysiloxane and the inorganic particles (B) are zirconia having a high refractive index, the composition is composed of an inorganic compound, so that the light resistance is good.

The hydroxy group present on the surface of the silicon compound (A) and the inorganic particles (B) can start polycondensation when heat is applied 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 size 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.

Further, a comparison between a composition using a fully hydrolyzed polysiloxane and a partially hydrolyzed polysiloxane has the following characteristics.

Partially hydrolyzed polysiloxane refers to a polymer obtained by using an alcohol containing a functional group such as a hydroxy group as a solvent during hydrolysis or polycondensation. The partially hydrolyzed polysiloxane is hydrolyzed and in the stage of polycondensation, the alcohol produced from the solvent alcohol or the monomer silane alkoxide reacts with the silanol groups produced by the hydrolysis and remains in the form of silane alkoxide. Further, since the silanol group and the silane alkoxide in the polymer in a solution state are chemically equilibrium reactions, polysiloxane having a large residual ratio of silane alkoxide is obtained when alcohol is selected as a solvent for hydrolysis and condensation.

On the other hand, fully hydrolyzed polysiloxane refers to a polymer obtained by using a non-alcohol containing no hydroxy group as a solvent for hydrolysis and condensation. In the fully hydrolyzed polysiloxane, the non-alcohol solvent, which is a solvent for hydrolysis and polycondensation, does not have hydroxy groups that end-block the polymer silanol, so the resulting polymer has a high residual ratio of silanol. It becomes polysiloxane. That is, since the fully hydrolyzed polysiloxane contains almost no silane alkoxide as an organic component, it becomes a polymer containing almost no carbon element which is disadvantageous in the light resistance test.

Since the partially hydrolyzed polysiloxane contains a large amount of silane alkoxide, when it reacts with the silanols of fine particles, it must pass through hydrolysis once, and an additional additive or the like is required. Additives include silanol formation accelerators and silane alkoxide decomposition accelerators, but these additives contain organic groups and metals and deteriorate the light resistance, so they are not suitable for the composition of the present invention. is there.

Compared with the partially hydrolyzed polysiloxane, the fully hydrolyzed polysiloxane has more silanol at the end, so that a highly reliable film can be obtained after thermosetting. The solubility becomes too high, and it is difficult to form a pattern of 10 μm or less using the photosensitive resist of the present invention. However, after spin coating the coating film by adding a curing catalyst (D) Alkali solution resistance can be improved or controlled at the stage of temporary drying, and a pattern of 10 μm or less can be efficiently formed under conditions suitable for practical processes.

In addition, a composition comprising the polysiloxane of the present invention, inorganic particles having an average particle diameter of 1 to 100 nm or less and a hydrogen bonding film roughening prevention material (for example, diketone compound) can be patterned using a photosensitive resist, Further, film roughness does not occur when the photosensitive resist is recoated or the resist film is peeled off.

In addition, by stabilizing the hydroxy group, which is a reactive group, including water (F) and acid (G), no change in quality occurs in a varnish with a storage temperature of 23 ° C. or 5 ° C., and a good 10 μm A film capable of forming the following pattern can be obtained over a long period of time.

The film obtained by the present invention can satisfy all the conditions of high refractive index, high transparency, high heat resistance, high light resistance, and high hardness, and can be patterned, so that it can be patterned. , 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.

The pattern observation figure at the time of using the composition of Example (1-1) containing polymer TT73. The pattern observation figure at the time of using the composition of Example (1-2) containing polymer TI73. The pattern observation figure at the time of using the composition of Example (1-3) containing polymer TH73. The pattern observation figure at the time of using the composition of Example (1-8) containing polymer TI73M1. The pattern observation figure at the time of using the composition of the comparative example (1-1) containing polymer pTEOS. The pattern observation figure at the time of using the composition of the comparative example (1-5) containing polymer TI73M4. The pattern observation figure at the time of using the composition of Example (2-10) containing varnish V (2-1). The pattern observation figure at the time of using the composition of Example (2-11) containing varnish V (2-2). The pattern observation figure at the time of using the composition of Example (2-12) containing varnish V (2-3). The pattern observation figure at the time of using the composition of the reference example (2-14) containing varnish RV (2-1). The pattern observation figure at the time of using the composition of the reference example (2-15) containing varnish RV (2-2). The pattern observation figure at the time of using the composition of the reference example (2-16) containing varnish RV (2-3). FIG. 11 is a view of the film forming surface after the resist film is peeled off when varnish V (3-1) is used in Example (3-10). FIG. 14 is a view of the film forming surface after the resist film is peeled off when varnish RV (3-1) is used in Reference Example (3-14). The pattern observation figure at the time of using the composition of Example (4-1) containing varnish V (4-1). The pattern observation figure at the time of using the composition of Example (4-2) containing varnish V (4-2). The pattern observation figure at the time of using the composition of Example (4-3) containing varnish V (4-3). The pattern observation figure at the time of using the composition of Example (4-10) containing varnish V (4-10). The pattern observation figure at the time of using the composition of Example (4-14) containing varnish V (4-14). The pattern observation figure at the time of using the composition of Example (4-15) containing varnish V (4-15). The pattern observation figure at the time of using the composition of Example (4-16) containing varnish V (4-16). The pattern observation figure at the time of using the composition of Example (4-17) containing varnish V (4-17). FIG. 5 is a film formation surface observation view after patterning using varnish RV (4-1) in Reference Example (4-1). The film formation surface observation figure after patterning which used varnish RV (4-2) in reference example (4-2). The film formation surface observation figure after patterning which used varnish RV (4-3) in the reference example (4-3).

The present invention is a hydrolyzable condensate of hydrolyzable silane containing hydrolyzable silane (a1) and hydrolyzable silane (a2) and having a weight average molecular weight of 700 to 4000, silicon compound (A), 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). R ¹ and R ^{2 in the} formula (1) and the formula (2) each represent an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, or a halogen group, and L represents 3 carbon atoms. Represents 6 to 6 linear, branched or cyclic alkyl groups;

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

The content of the silicon compound (A) and the inorganic particles (B) in the solid content can be 50 to 100% by mass, 70 to 100% by mass, or 70 to 99% by 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 obtained by hydrolyzing and copolymerizing a hydrolyzable silane (a1) represented by the formula (a1) and a hydrolyzable silane (a2) represented by the formula (a2). It is a condensate. This hydrolysis-condensation product may contain a hydrolysis product.

In the silicon compound (A), the ratio of hydrolyzable silane (a1) to hydrolyzable silane (a2) is 90 mol% to 50 mol%, 80 mol% to 60 mol%. Alternatively, hydrolyzable silane (a2) contained in 10 mol% to 50 mol%, 20 mol% to 40 mol%, or 30 mol%, respectively, is hydrolyzed and condensed at 70 mol%. It is a polymer.

The silicon compound (A) produced by containing 95 mol% or more of the hydrolyzable silane (a1) has the developability of an alkaline solution as a peel development, and does not exhibit the dissolution developability which is an important object of the present invention. Further, a silicon compound produced by containing 55 mol% or more of hydrolyzable silane (a2) 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 a linear, branched or cyclic alkyl portion having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group. Group, sec-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 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 Group, 1-ethyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n-propoxy group and the like.

Examples of the acyloxy group include acyloxy groups having 2 to 20 carbon atoms, such as methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group, isobutylcarbonyloxy group. Group, sec-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-hexylcarbonyloxy 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-butylcarbonyl Oxy group, 2,3-dimethyl-n-butylcarbonyloxy group, 3,3-dimethyl-n-butylcarbonyloxy group, 1-ethyl-n-butylcarbonyloxy group, 2-ethyl-n-butylcarbonyloxy group 1,1,2-trimethyl-n-propylcarbonyloxy group, 1,2,2-trimethyl-n- Examples include propylcarbonyloxy group, 1-ethyl-1-methyl-n-propylcarbonyloxy group, 1-ethyl-2-methyl-n-propylcarbonyloxy group, phenylcarbonyloxy group, and tosylcarbonyloxy group. However, it is not limited to these.

Also, examples of the halogen group as the hydrolyzing group include fluorine, chlorine, bromine, iodine and the like.

Examples of the hydrolyzable silane (a1) include tetramethoxysilane, tetraacetoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraacetoxysilane, and tetrachlorosilane. Examples thereof include, but are not limited to, tetrafunctional (having four hydrolyzable groups) siloxane monomers. 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. For example, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-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 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 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, and Examples thereof include, but are not limited to, 1-ethyl-2-methyl-n-propyl group, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl group and the like.

Examples of the hydrolyzable silane (a2) include n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltriethoxysilane, cyclopropyltriethoxysilane, n-butyltriethoxysilane, sec-butyltriethoxysilane, t-butyltriethoxysilane, isobutyltriethoxysilane, 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-methylpentan-2-yl) silane, triethoxy (3-methylpentan-3-yl) silane, cyclohexyltrimethoxysilane and the like can be mentioned. It is not limited.

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 hydrolyzable silane containing a hydrolyzable silane (a1) of the formula (a1) and a hydrolyzable silane (a2) of the formula (a2) is hydrolyzed and condensed to form a copolymer containing the hydrolyzed condensate. The silicon compound (A) can be 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, phosphoric acid and the like.

Organic bases as hydrolysis catalysts include, for example, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazine. And 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 suitably used. For hydrolysis of an alkoxysilyl group, an acyloxysilyl group, or a halogenated silyl group, 0.1 to 100 mol, 0.1 to 10 mol, 1 to 5 mol, or 2 to 2 mol per mol of the above hydrolyzable group. Use 3.5 moles of water.

The reaction temperature during 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 hydrolyzable silane, solvent, pure water and 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. At that time, the amount of hydrochloric acid is generally 0.0001 to 0.5 mol with respect to 1 mol of all hydrolyzable groups (total alkoxy groups) of the hydrolyzable silane. The heating in this method can be performed at a liquid temperature of 50 to 180 ° C., and preferably performed 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; aromatics such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, isopropyl benzene, diethyl benzene, isobutyl benzene, triethyl benzene, diisopropyl benzene and trimethyl benzene Hydrocarbon solvents: acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentylke Ketone solvents such as ethyl, n-butyl ketone, methyl-n-hexyl ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone; ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, tetrahydrofuran, Ethers such as 2-methyltetrahydrofuran, 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 monomethyl ether acetate, propylene glycol Cole monomethyl ether acetate, ethylene glycol monoethyl 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, 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 n-butyl ketone, cyclohexanone, ethyl acetate, isopropyl ketone, n-propyl acetate, isobutyl acetate, n-butyl acetate, methanol, ethanol, isopropanol, tert-butanol, allyl alcohol, n-propanol, 2-methyl-2-butanol, isobutanol, n-butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol, isopro 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 the 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.

In the present invention, the silicon compound (A) obtained by hydrolyzing and condensing a hydrolyzable silane in a non-alcohol solvent can be used.

The silicon compound (A) containing the hydrolyzed condensate (polysiloxane) of the present invention is obtained by using a non-alcohol containing no hydroxy group as a solvent for hydrolysis and polycondensation. This is a polysiloxane having a high hydrolysis rate. On the other hand, a polymer obtained by using an alcohol containing a hydroxy group as a solvent for hydrolysis or polycondensation is called a partially hydrolyzed polysiloxane to be distinguished. The major difference between the fully hydrolyzed type and the partially hydrolyzed type is that the abundance of silanol (Si—OH) at the end of the polymer is different. The fully hydrolyzed polysiloxane has a partially hydrolyzed type of polysiloxane. There are more than polysiloxanes. The abundance of Si—OH may be quantified by ¹ H-NMR with the same solid content using a varnish substituted with a non-alcohol solvent. The quantification can be determined by comparing the number of protons obtained by integrating the Si-OH peak of polysiloxane and calculating the peak area with the number of protons obtained by integrating the peak of the internal standard or the solvent and calculating the peak area.

When the proton number calculated from the internal standard or the peak of the solvent is 1.00, the calculated proton number of the fully hydrolyzed polysiloxane Si—OH is 0.1 or more, preferably 0.2 or more. . On the other hand, the partially hydrolyzed polysiloxane is defined as the number of protons calculated by the Si—OH of the polysiloxane being less than 0.1 when the number of protons calculated from the internal standard or the peak of the solvent is 1.00. .

Examples of the non-alcohol solvent (c1) used for hydrolysis and condensation include n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, Aliphatic hydrocarbon solvents such as cyclohexane and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, trimethylbenzene, etc. Aromatic hydrocarbon solvents; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl-n Ketone solvents such as pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone; ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, tetrahydrofuran And ether solvents such as 2-methyltetrahydrofuran. These solvents can be used alone or in combination of two or more. Of these, ketone solvents such as acetone and ether solvents such as tetrahydrofuran are preferable, and acetone can be particularly preferably used.

Hydrolyzable silane is hydrolyzed in a non-alcohol solvent (c1), and the hydrolyzate is subjected to a condensation reaction to obtain a hydrolyzate condensate (polysiloxane), which is dissolved in the hydrolyzate. It is obtained as a polysiloxane varnish.

The solvent of the silicon compound (A) containing the obtained hydrolysis condensate (polysiloxane) may be substituted. Specifically, when acetone is selected as the solvent used during hydrolysis and subsequent condensation (solvent during synthesis), after the polysiloxane is obtained in acetone, the same amount of substitution as the solvent used in the synthesis is performed. When the solvent is added and replaced with another solvent, acetone may be distilled off by azeotropic distillation with an evaporator or the like. At that time, reactants (for example, methanol, ethanol) generated by hydrolysis of the hydrolyzable silane can be distilled off simultaneously. Further, when a volatile acid catalyst is used, it can be removed at the same time.

This replacement solvent becomes a solvent component (C) when the silicon compound (A) containing the hydrolysis condensate (polysiloxane) is used as a varnish.

Since the solvent during synthesis at the time of solvent substitution is azeotropically distilled off, the boiling point is preferably lower than that of the substitution solvent. For example, examples of the solvent used for hydrolysis and subsequent condensation include acetone and tetrahydrofuran, and examples of the solvent for substitution include propylene glycol monomethyl ether acetate.

The solvent (C) used for diluting or replacing the varnish of the silicon compound (A) containing the hydrolysis condensate (polysiloxane) may be the same as the non-alcohol solvent used for hydrolysis and condensation polymerization of the hydrolyzable silane. Good or 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).

Specific examples of the solvent (C) at this time 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 monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol Nomethyl 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, 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 T-methyl-n-butyl ketone, cyclohexanone, ethyl acetate, isopropyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate, methanol, ethanol, isopropanol, tert-butanol, allyl alcohol, n-propanol, 2-methyl -2-butanol, isobutanol, n-butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol, isopropyl ether, 1,4-dioxane, N, Examples thereof include N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide and N-cyclohexyl-2-pyrrolidinone.

The component (C) of the present invention is a solvent. The solvent is preferably a non-alcohol solvent similar to the solvent from which component (A) was obtained, but is not particularly limited as long as the storage stability of the coating solution for film formation of the present invention is not significantly impaired. The general organic solvent mentioned above can be used.

The silicon compound (A) which is a hydrolysis condensate of a hydrolyzable silane containing the hydrolyzable silane (a1) and the hydrolyzable silane (a2) of the present invention has a hydrolyzable silane (a2) having the number of carbon atoms. A hydrolyzable silane having 3 to 6 linear, branched or cyclic alkyl groups and having three hydrolyzable groups, the hydrolyzable silane (a1) being 90 to 50 mol%, The condensate can be produced at a ratio of 10 mol% to 50 mol% of the hydrolyzable silane (a2), and the weight average molecular weight can be 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 defining the weight average molecular weight of the silicon compound (A) and the copolymerization ratio in the hydrolyzable condensate of hydrolyzable silane (a1) and hydrolyzable silane (a2), Kyowa Interface Science Co., Ltd. ) Using a fully automatic contact angle meter manufactured by Seikan Co., Ltd., a product name “Drop” Master series “DM700”, droplets were made from pure water with a 22G size needle, and the droplets deposited on the coating surface were subjected to the droplet method (θ / 2). The contact angle of water calculated by (Method) is 60 ° to 80 °, and dissolution development is performed with respect to the 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 alkali 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, 1.50. A range from 1 to 1.70, 1.60 to 2.00, 1.90 to 2.20, or 2.20 to 2.70 can be selected.

As the kind of inorganic particles (B) constituting the composition of the present invention together with the polysiloxane described above, metal oxides such as zirconia can be mentioned. The inorganic particles may be zirconia alone or in combination of two or more.

Specific examples of the metal oxide include composite oxides containing SiO ₂ and HfO ₂ in zirconia in addition to zirconia. 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 concentration of the inorganic particles in the sol can be used in the range of 0.1 to 60% by 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 replaced with an organic solvent from water 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, 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- ( Minoethyl) -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, dimethyldiethoxysilane phenyltriethoxy. Examples thereof include silane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, and hexamethyldisilazane.

Examples of the organometallic compound include titanate coupling agents and aluminum coupling agents, and specific examples of titanate coupling agents include trade names of Plenact KR TTS, KR46B, KR38B, KR138S, KR238S, KR338X, and KR44. , KR9SA, KR ET5, KR ET (manufactured by Ajinomoto Fine Techno Co., Ltd.), and specific examples of aluminum coupling agents include Plenact AL-M (manufactured by Ajinomoto Fine Techno Co., Ltd.) and the like.

These organic silicon compounds and organometallic compounds are preferably used in an amount of 2 to 100 parts by mass with respect to 100 parts by mass of the inorganic particles (B).

The metal oxide colloidal particles used for the inorganic particles (B) can be produced by a known method, for example, 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 method of neutralizing the metal salt with an acid or base, a method of hydrolyzing the metal alkoxide, a precipitate obtained by hydrolyzing the metal basic salt under heating, or Examples thereof include a method of removing unnecessary electrolyte from the gel or a method of 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 (1) 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) in measurement 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 (1) is mentioned.

The method for preparing the film forming composition (2) 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.

For example, a hydrolyzable silane containing a hydrolyzable silane (a1) and a hydrolyzable silane (a2) is hydrolyzed in a non-alcohol solvent (c1) to obtain a silicon compound (A) having a weight average molecular weight of 700 to 4000. Obtaining a varnish,
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) in measurement by a dynamic light scattering method;
The varnish of the silicon compound (A), the sol of the inorganic particles (B), and the curing catalyst (D) are mixed, and the silicon compound (A), the inorganic particles (B), the curing catalyst (D), and the solvent (C) are mixed. The manufacturing method of the film forming composition (2) including the process of obtaining the film forming composition containing is mentioned.

The method for preparing the film forming composition (3) of the present invention is not particularly limited. The component (A), the component (B), the component (C), and the component (E) may be in a uniformly mixed state. The order of mixing the component (A), the component (B), the component (C), and the component (E) is not particularly limited as long as a uniform varnish can be obtained.

For example, a hydrolyzable silane containing a hydrolyzable silane (a1) and a hydrolyzable silane (a2) is hydrolyzed in a non-alcohol solvent (c1) to obtain a silicon compound (A) having a weight average molecular weight of 700 to 4000. Obtaining a varnish,
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) in measurement by a dynamic light scattering method;
The varnish of the silicon compound (A), the sol of the inorganic particles (B), and the diketone compound (E) are mixed, and the silicon compound (A), the inorganic particles (B), the diketone compound (E), and the solvent (C) are mixed. The manufacturing method of the film formation composition (3) including the process of obtaining the film formation composition containing is mentioned.

The method for preparing the film forming composition (4) of the present invention is not particularly limited. The component (A), the component (B), the component (C), the component (D), the component (F), and the component (G) may be in a uniformly mixed state. The order of mixing component (A), component (B), component (C), component (D), component (F), and component (G) is not particularly limited as long as a uniform varnish can be obtained.

For example, a hydrolyzable silane containing a hydrolyzable silane (a1) and a hydrolyzable silane (a2) is hydrolyzed in a non-alcohol solvent (c1) to obtain a silicon compound (A) having a weight average molecular weight of 700 to 4000. Obtaining a varnish,
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) in measurement by a dynamic light scattering method;
The varnish of the silicon compound (A), the sol of the inorganic particles (B), the curing catalyst (D), water (F), and the acid (G) are mixed, and the silicon compound (A), the inorganic particles (B), and the curing catalyst ( A method for producing a film-forming composition (4) including a step of obtaining a film-forming composition containing D), water (F), an acid (G), and a solvent (C).

As the curing catalyst for component (D), ammonium salts, phosphines, phosphonium salts, sulfonium salts, or metal chelate compounds can be used.

As an ammonium salt, the formula (5):

(Wherein p represents an integer of 2 to 11, q represents an integer of 2 to 3, R ¹¹ represents an alkyl group, an aryl group, or a combination thereof, and Y ⁻ represents an anion.) Having formula (6):

(Wherein R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ represent an alkyl group, an aryl group, or a combination thereof, N represents a nitrogen atom, Y ⁻ represents an anion, and R ¹² , R ¹³⁾ , R ¹⁴ and R ¹⁵ are each bonded to a nitrogen atom by a C—N bond.) A quaternary ammonium salt having the structure represented by formula (7):

A quaternary ammonium salt having the structure (wherein R ¹⁶ and R ¹⁷ represent an alkyl group, an aryl group, or a combination thereof, and Y ⁻ represents an anion):

A quaternary ammonium salt having the structure (wherein R ¹⁸ represents an alkyl group, an aryl group, or a combination thereof; Y ⁻ represents an anion):

^{(Wherein, R 19} and ^{R 20} an alkyl group, an aryl group, or a combination thereof,, Y ^- represents an anion.) A quaternary ammonium salt of formula (10) having the structure:

And tertiary ammonium salts having the 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 (11):

(Wherein R ²¹ , R ²² , R ²³ , and R ²⁴ represent an alkyl group, an aryl group, or a combination thereof, P represents a phosphorus atom, Y ⁻ represents an anion, and R ²¹ , R ²² , R ²³ , and R ²⁴ are each bonded to a phosphorus atom by a CP bond.).

Further, as the sulfonium salt, the formula (12):

(Wherein R ²⁵ , R ²⁶ , and R ²⁷ represent an alkyl group, an aryl group, or a combination thereof, S represents a sulfur atom, Y ⁻ represents an anion, and R ²⁵ , R ²⁶ , and R ²⁷ is each bonded to a sulfur atom by a C—S bond)).

The compound of the above formula (5) 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 ¹¹ of the quaternary ammonium salt represents an alkyl group having 1 to 18, preferably 2 to 10 carbon atoms, an aryl group, or a combination thereof, and includes, for example, an ethyl group, a propyl group, a butyl group, and the like. Examples thereof include a chain alkyl group, a benzyl group, a cyclohexyl group, a cyclohexylmethyl group, and a dicyclopentadienyl group. Anions (Y ⁻ ) include halogen ions such as chlorine ions (Cl ⁻ ), bromine ions (Br ⁻ ), iodine ions (I ⁻ ), carboxylates (—COO ⁻ ), sulfonates (—SO ₃ ⁻ ). And acid groups such as alcoholate (—O ⁻ ).

The compound of the above formula (6) is a quaternary ammonium salt represented by R ¹² R ¹³ R ¹⁴ R ¹⁵ N ⁺ Y ⁻ . R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ of this quaternary ammonium salt are each 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. It is a silane compound. Anion (Y ^-), chlorine ion (Cl ^-), bromine ion (Br ^-) ^- or a halogen ion such as, carboxylate (-COO ^-), iodide ion (I), sulfonato _(-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 (7) is a quaternary ammonium salt derived from 1-substituted imidazole, R ¹⁶ and R ¹⁷ have 1 to 18 carbon atoms, and the number of carbon atoms of R ¹⁶ and R ¹⁷ Is preferably 7 or more. For example, R ¹⁶ 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 ¹⁷ can be exemplified by a benzyl group, an octyl group, and an octadecyl group. Anion (Y ^-), chlorine ion (Cl ^-), bromine ion (Br ^-) ^- or a halogen ion such as, carboxylate (-COO ^-), iodide ion (I), sulfonato _(-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 (7) can be used as a 4,5-dihydroimidazole compound in which the 4-position and 5-position are hydrogenated. These can be added as cyclic ammonium compounds.

The compound of the above formula (8) is a quaternary ammonium salt derived from pyridine, and R ¹⁸ is an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, an aryl group, or For example, a butyl group, an octyl group, a benzyl group, and a lauryl group can be exemplified. Anion (Y ^-), chlorine ion (Cl ^-), bromine ion (Br ^-) ^- or a halogen ion such as, carboxylate (-COO ^-), iodide ion (I), sulfonato _(-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 (9) is a quaternary ammonium salt derived from a substituted pyridine represented by picoline and the like, and R ¹⁹ is an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, An aryl group or a combination thereof, and examples thereof include a methyl group, an octyl group, a lauryl group, and a benzyl group. Each R ²⁰ is an alkyl group having 1 to 18 carbon atoms, an aryl group, or a combination thereof. For example, when R ²⁰ is quaternary ammonium derived from picoline, R 19 is a methyl group. Anion (Y ^-), chlorine ion (Cl ^-), bromine ion (Br ^-) ^- or a halogen ion such as, carboxylate (-COO ^-), iodide ion (I), sulfonato _(-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 (10) 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 ⁻ ) include halogen ions such as chlorine ions (Cl ⁻ ), bromine ions (Br ⁻ ), 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 (11) is a quaternary phosphonium salt having a structure of R ²¹ R ²² R ²³ R ²⁴ P ⁺ Y ^— . R ²¹ , R ²² , R ²³ , and R ²⁴ are each an alkyl group having 1 to 18 carbon atoms, an aryl group, or a combination thereof, or a silane compound bonded to a silicon atom through a Si—C bond. Preferably, three of the four substituents of R ²¹ to R ²⁴ are a phenyl group or a substituted phenyl group. For example, a phenyl group or a tolyl group can be exemplified, and the remaining one is a carbon group. A silane compound bonded to a silicon atom by an alkyl group having 1 to 18 atoms, an aryl group, or a Si—C bond. Anions (Y ⁻ ) include halogen ions such as chlorine ions (Cl ⁻ ), bromine ions (Br ⁻ ), 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 tetra-n-butylphosphonium halide, tetra-n-propylphosphonium halide, or a trialkylbenzyl halide such as triethylbenzylphosphonium halide. Triphenylmonoalkylphosphonium halides such as phosphonium, triphenylmethylphosphonium halide, triphenylethylphosphonium halide, triphenylbenzylphosphonium halide, tetraphenylphosphonium halide, tritolylmonoarylphosphonium halide, or tritolyl monohalogenate Examples thereof include alkylphosphonium (the halogen atom is a chlorine atom or a bromine atom). In particular, halogens such as triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide, triphenylethylphosphonium halide, triphenylmonoarylphosphonium halides such as triphenylbenzylphosphonium halide, and halogens such as tritolylmonophenylphosphonium halide. Preferred is a tolylyl monoarylphosphonium halide, or a tolyl monoalkylphosphonium halide such as a tolyl monomethylphosphonium halide (the halogen atom is a chlorine atom or a bromine atom).

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.

Compounds of formula (12) described ^{^{^{^{above, R 25 R 26 R 27 S}}}} + Y - is a tertiary sulfonium salt having a structure. R ²⁵ , R ²⁶ , and R ²⁷ are each an alkyl group having 1 to 18 carbon atoms, an aryl group, or a combination thereof, or a silane compound bonded to a silicon atom through a Si—C bond, Of the three substituents of R ²⁵ to R ²⁷ , three are phenyl groups or substituted phenyl groups. For example, a phenyl group or a tolyl group can be exemplified, and the remaining ones each have 1 carbon atom. 18 to 18 optionally substituted alkyl groups, aryl groups, or combinations thereof. Anions (Y ⁻ ) include halogen ions such as chlorine ions (Cl ⁻ ), bromine ions (Br ⁻ ), 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 tri-n-butylsulfonium halide, tri-n-propylsulfonium halide, and trialkylbenzyl halide such as diethylbenzylsulfonium halide. Halogenated diphenylmonoalkylsulfonium, such as sulfonium, halogenated diphenylmethylsulfonium, halogenated diphenylethylsulfonium, halogenated triphenylsulfonium, (halogen atom is chlorine or bromine atom), tri-n-butylsulfonium carboxylate, tri-n- Tetraalkylphosphonium carboxylates such as propylsulfonium carboxylate and trialkylbenzyls such as diethylbenzylsulfonium carboxylate Sulfo 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 compounds include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, triisopropoxy mono (acetylacetonato) titanium, tri-n-butoxy mono (Acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxy bis (acetylacetonato) titanium, di-n-propoxy Bis (acetylacetonato) titanium, diisopropoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetonato) titanium, di -T-Butoxy bis ( Cetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, monoisopropoxy-tris (acetylacetonato) titanium, mono-n-butoxy-tris (Acetylacetonato) titanium, mono-sec-butoxy tris (acetylacetonato) titanium, mono-t-butoxy tris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy mono (ethylacetoacetate) ) Titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, triisopropoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri-sec-but Si mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, diiso 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) Titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, monoisopropoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tris (ethyl acetoacetate) ) Tan, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris (ethyl acetoacetate) Titanium chelate compounds such as titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium; triethoxy mono (acetylacetonato) zirconium, tri-n- Propoxy mono (acetylacetonato) zirconium, triisopropoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonato) zirconium, tri-sec-butoxy・ Mono (acetylacetonato) zirconium, tri-t-butoxy ・ mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetonato) zirconium, diisopropoxy・ Bis (acetylacetonato) zirconium, di-n-butoxy ・ bis (acetylacetonato) zirconium, di-sec-butoxybis (acetylacetonato) zirconium, di-t-butoxybis (acetylacetonato) zirconium , Monoethoxytris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, monoisopropoxytris (acetylacetonato) zirconium, mono-n- Toxitris (acetylacetonato) zirconium, mono-sec-butoxytris (acetylacetonato) zirconium, mono-t-butoxytris (acetylacetonato) zirconium, tetrakis (acetylacetonato) zirconium, triethoxymono ( Ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, triisopropoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium, tri-sec- Butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconi , Di-n-propoxy bis (ethyl acetoacetate) zirconium, diisopropoxy 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, monoisopropoxy tris (Ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirconium, mono-t-but Si-tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) zirconium, tris (acetylacetate) Zirconium chelate compounds such as nato) mono (ethylacetoacetate) zirconium; Aluminum chelate compounds such as tris (acetylacetonato) aluminum and tris (ethylacetoacetate) aluminum;

The addition amount of the curing catalyst (D) component is 0.01 to 10 parts by mass, 0.01 to 5 parts by mass, or 0.01 to 3 parts by mass with respect to 100 parts by mass of the silicon compound (A) component. The curing catalyst (D) is added for the purpose of controlling the alkali developability of the silicon compound (A), which is a fully hydrolyzed polysiloxane, and is added for the purpose of control. In some cases, all of them are dissolved with an alkali developer, and when the amount is more than 10 parts by mass, the curing may proceed too much to form a pattern.

The component (E) of the present invention is a diketone compound that functions as a hydrogen bonding film roughening prevention material. The diketone compound that functions as a hydrogen bonding film roughening preventing agent refers to a compound that forms a hydrogen bond with the hydroxy group present in the silicon compound (A) and the inorganic particles (B) in the varnish or during temporary drying. In the case where hydrogen bonds are formed, film roughness during recoating of the photosensitive resist and peeling of the resist film can be suppressed.

Examples of the diketone compound (E) include 1,2-diketone and / or 1,3-diketone. The diketone compound (E) has a partial structure represented by the formula (3) and / or the formula (4). In formula (3), W represents a carbon atom or an oxygen atom.

The diketone compound (E) functioning as a hydrogen bonding film roughening prevention material is preferably a liquid at 23 ° C. and atmospheric pressure from the viewpoint of handling properties, and is a compound having the basic skeleton shown in the above compound (3). is there.

Specific examples of the component (E) include acetylacetone, 3-ethyl-2,4-pentanedione, 3-ethyl-2,4-pentanedione, dipivaloylmethane, 2,6-dimethyl-3,5. -Heptanedione, 6-methyl-2,4-heptanedione, methyl pyruvate, ethyl pyruvate, diacetyl, 3,4-hexanedione, 2,3-pentanedione, 2,3-heptanedione, 5-methyl- Examples include 2,3-hexanedione. The component (E) has a partial structure having an O═C—C═O bond in the case of the formula (3) and an O═C—C—C═O bond in the case of the formula (4). Well, not specific. These partial structures can suppress film roughness when the photosensitive resist is peeled off by hydrogen bonding with the hydroxy groups present in the silicon compound (A) and the inorganic particles (B).

Preferred examples of the diketone compound (E) include diacetyl, methyl pyruvate, ethyl pyruvate, and acetylacetone.

The addition amount of the diketone compound (E) component is 1 to 10000 parts by mass, 100 to 5000 parts by mass, or 500 to 2000 parts by mass, preferably 100 to 5000 parts by mass with respect to 100 parts by mass of the silicon compound (A) component. Part, more preferably 500 to 2000 parts by weight.

The water (F) component is preferably ion-exchanged water. When general tap water is used, sodium ions, potassium ions, chlorine ions, etc. contained in tap water are brought into the varnish, which deteriorates the storage stability of the polysiloxane or impairs the uniform varnish quality. There is. The ratio of the water (F) component in the total solvent including water (F) and the solvent (C) needs to be 6% by mass to 18% by mass.

When the ratio of the component (F) in the total solvent is less than 6% by mass, the storage stability may be impaired, and when it exceeds 18% by mass, the coating property may be deteriorated. A preferable amount of the water (F) component is 8% by mass to 16% by mass in the total solvent, and more preferably 10% by mass to 14% by mass.

The acid (G) component is an acid that contains 1 to 2 carboxyl groups in the molecule, and the final film-forming composition (varnish) can have a pH of 3 to 5.

The amount of acid (G) added can be added to the film-forming composition (varnish) to adjust the film-forming composition (varnish) to pH 3 to 5.

Specific examples of component (G) include 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, sebacic acid , Gallic acid, butyric acid, meritic 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 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. By setting the final film-forming composition (varnish) to pH 3 to 5, the stability of silanol present at the terminal of the fully hydrolyzed polysiloxane can be improved. The final varnish has a pH of 3 to 5, preferably around pH 4. It is known that the stability of silanol is best achieved by adjusting the pH of the film-forming composition (varnish) to 4. In view of setting the pH of the final film-forming composition (varnish) to 4, component (G) is particularly preferably formic acid, acetic acid, propionic acid, oxalic acid, and maleic acid.

By adding the component (F) and the component (G) described above to the varnish, the storage stability of the film-forming composition (varnish) at 5 ° C. to 23 ° C. is drastically improved, and a good coating is obtained over a long period of time. Can be provided.

The solid content of the film-forming composition contains silicon compound (A), inorganic particles (B), curing catalyst (D), diketone compound (E), and acid (G), but contains other components. Also good.

In the present invention, as long as the effects of the present invention are not impaired, the component (A), the component (B), the component (C), the component (D), the component (E), the component (F), and the component (G). In addition, other components such as leveling agents and surfactants may be contained.

Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol. Polyoxyethylene alkyl allyl ethers such as ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as rubitan 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 (Dainippon Ink Chemical Industries, Ltd.) Fluorine, FC430, FC431 (Sumitomo 3M Co., Ltd.), trade names Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) Surface activity , 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. These surfactants may be used alone or in combination of two or more. When a surfactant is used, the proportion thereof is 0.0001 to 5 parts by mass, 0.001 to 1 part by mass, or 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the silicon compound (A). Part.

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 for example, it may be heated in a suitable 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. 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 heating time may be selected in accordance with the process steps of the target electronic device, and the heating conditions in which the physical properties of the polysiloxane film are compatible with the required characteristics of the electronic device can be selected.

Silicon compound (A) containing the hydrolysis condensate (polysiloxane) of the present invention, inorganic particles (B), solvent (C), further component (D), component (E), component (F), component (G) It is preferable that the film forming composition (varnish) formed by hybridizing these components is 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.

Hybridization is not particularly limited in its preparation method as long as the stability of the final film-forming composition (varnish) can be obtained.

For example, Method (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). Method (2): Various methods such as dispersing the inorganic particles (B) in the solution (in the varnish) of the silicon compound (A) containing the hydrolyzed condensate (polysiloxane) can be mentioned, but from the viewpoint of handling properties, hydrolysis condensation A method in which a silicon compound (A) containing a product (polysiloxane) is mixed with a dispersion (sol) of inorganic particles (B) in a solution (varnish) state is preferable.

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. (refrigerated storage). In order to prevent hydroxy groups from reacting with each other in the varnish state, −20 ° C. (freezer storage) ) Is preferably stored.

In the present invention, the film-forming composition is coated on a substrate and heated to obtain a refraction of 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 ratio and a hardness with a pencil hardness defined by JIS standard K5600 of H to 9H, H to 5H, or H to 3H.

<Pattern patterning method>
Although the film-forming composition itself of the present invention has no photosensitivity, patterning of 10 μm or less is possible by using a photosensitive resist because it has dissolution 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 temporarily 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., 80 ° C. to 150 ° C., or Heating may be performed at 90 ° C. to 120 ° C., and the heating time may be 30 seconds to 300 seconds, 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, an 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 seconds. Or 180 seconds, 20 seconds to 60 seconds, or 90 seconds to 120 seconds. 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 may be a general resist solvent. Examples thereof include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and ethyl pyruvate.

Step 9 is a step of heating the film-forming composition, and it may be heated 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, a comparative example, etc. 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 [ ¹ H-NMR]
Device: ECP300 manufactured by JEOL Ltd.
Solvent: heavy acetone [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.
[Ultraviolet visible spectrophotometer]
Apparatus: SHIMADSU UV-3600 manufactured by Shimadzu Corporation
[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: Beckman Coulter, device name N5
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: Tokyo Electron Co., Ltd., clean truck, equipment name ACT8
〔exposure〕
Equipment: Nikon Corporation, i-line stepper, equipment name NSR-2205i12D
[Water contact angle]
Using a fully automatic contact angle meter Drop Master series, device name DM700, manufactured by Kyowa Interface Science Co., Ltd., droplets were made from pure water using a 22G size needle, and then dropped onto the coating surface. The water contact angle was calculated by the method (θ / 2 method).
(Optical microscope)
Device: Nikon, device name ECLIPSE E600 POL
The optical microscope was observed at a magnification of 50 times.
〔electronic microscope〕
Apparatus: Hitachi High-Technologies Corporation, apparatus name S-4800

[Synthesis Example (1-1)]
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 hydrolyzable silane (a1) component. The weight average molecular weight by GPC of the obtained pTEOS was Mw1800 in terms of polystyrene.

[Synthesis Example (1-2)]
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. Thereafter, the operation was performed in the same manner as in Synthesis Example (1-1), and the mixture was adjusted to 14 mass percent in terms of solid residue at 140 ° C. The obtained polymer comprises 30 mol% hydrolyzable silane (a1) and 30 silane monomers having a methyl group having 1 carbon atom and three hydrolyzable groups instead of hydrolyzable silane (a2). It is a varnish of polysiloxane (abbreviated as TM73) which is hydrolyzed and copolymerized at a mole percent. The weight average molecular weight of the obtained TM73 by GPC was Mw1155 in terms of polystyrene.

[Synthesis Example (1-3)]
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. Thereafter, the operation was performed in the same manner as in Synthesis Example (1-1), and the mixture was adjusted to 14 mass percent in terms of solid residue at 140 ° C. The obtained polymer comprises 30 mol% of hydrolyzable silane (a1) and 30 silane monomers having an ethyl group having 2 carbon atoms and three hydrolyzable groups instead of hydrolyzable silane (a2). It is a varnish of polysiloxane (abbreviated as TE73) hydrolyzed and copolymerized at a mole percentage. The weight average molecular weight of the obtained TE73 by GPC was Mw1310 in terms of polystyrene.

[Synthesis Example (1-4)]
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. Thereafter, the operation was performed in the same manner as in Synthesis Example (1-1), and the mixture was adjusted to 14 mass percent in terms of solid residue at 140 ° C. The polymer obtained was 30 mol% of 70 mol% hydrolyzable silane (a1) and 30 mol% of a silane monomer having a propyl group having 3 carbon atoms and three hydrolyzable groups as the hydrolyzable silane (a2). Is a varnish of polysiloxane (abbreviated as TT73) hydrolyzed and copolymerized at a ratio of The weight average molecular weight of the obtained TT73 by GPC was Mw1041 in terms of polystyrene.

[Synthesis Example (1-5)]
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. Thereafter, the operation was performed in the same manner as in Synthesis Example (1-1), and the mixture was adjusted to 14 mass percent in terms of solid residue at 140 ° C. The polymer obtained was 30 mol% of 70 mol% hydrolyzable silane (a1) and a silane monomer having 4 hydrolyzable isobutyl groups and 3 hydrolyzable groups as hydrolyzable silane (a2). Is a varnish of polysiloxane (abbreviated as TI73) hydrolyzed and copolymerized at a ratio of The weight average molecular weight of the obtained TI73 by GPC was Mw1087 in terms of polystyrene.

[Synthesis Example (1-6)]
29.17 g of tetraethoxysilane, 12.38 g of n-hexyltrimethoxysilane, and 166.19 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. 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. Thereafter, the operation was performed in the same manner as in Synthesis Example (1-1), and the mixture was adjusted to 14 mass percent in terms of solid residue at 140 ° C. The obtained polymer was composed of 30 mol% of hydrolyzable silane (a1) and 30 hydrolyzable silane (a2), an n-hexyl group having 6 carbon atoms and a silane monomer having three hydrolyzable groups. It is a varnish of polysiloxane (abbreviated as TH73) hydrolyzed and copolymerized at a mole percentage. The weight average molecular weight of the obtained TH73 by GPC was Mw 1060 in terms of polystyrene.

[Synthesis Example (1-7)]
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. Thereafter, the operation was performed in the same manner as in Synthesis Example (1-1), and the mixture was adjusted to 14 mass percent in terms of solid residue at 140 ° C. The polymer obtained was 90 mol% hydrolyzable silane (a1) and 10 mol% of a hydrolyzable silane (a2) having a silane monomer having an isobutyl group having 4 carbon atoms and three hydrolyzable groups. Is a varnish of polysiloxane (abbreviated as TI91) hydrolyzed and copolymerized at a ratio of The weight average molecular weight of the obtained TI91 by GPC was Mw1237 in terms of polystyrene.

[Synthesis Example (1-8)]
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. Thereafter, the operation was performed in the same manner as in Synthesis Example (1-1), and the mixture was adjusted to 14 mass percent in terms of solid residue at 140 ° C. The obtained polymer was composed of 80 mol% hydrolyzable silane (a1) and 20 mol% of a hydrolyzable silane (a2) having a silane monomer having an isobutyl group having 4 carbon atoms and three hydrolyzable groups. Is a varnish of polysiloxane (abbreviated as TI82) hydrolyzed and copolymerized at a ratio of The weight average molecular weight of the obtained TI82 by GPC was Mw1235 in terms of polystyrene.

[Synthesis Example (1-9)]
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. Thereafter, the operation was performed in the same manner as in Synthesis Example (1-1), and the mixture was adjusted to 14 mass percent in terms of solid residue at 140 ° C. The obtained polymer was composed of 60 mol% hydrolyzable silane (a1) and 40 mol% hydrolyzable silane (a2), a silane monomer having 4 isobutyl groups and 3 hydrolyzable groups. It is a varnish of polysiloxane (abbreviated as TI64) hydrolyzed and copolymerized at a ratio of The weight average molecular weight of the obtained TI64 by GPC was Mw1051 in terms of polystyrene.

[Synthesis Example (1-10)]
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. Thereafter, the operation was performed in the same manner as in Synthesis Example (1-1), and the mixture was adjusted to 14 mass percent in terms of solid residue at 140 ° C. The obtained polymer was 50 mol% hydrolyzable silane (a1) and 50 mol% of a hydrolyzable silane (a2) silane monomer having an isobutyl group having 4 carbon atoms and three hydrolyzable groups. It is a varnish of polysiloxane (abbreviated as TI55) hydrolyzed and copolymerized at a ratio of The weight average molecular weight of the obtained TI55 by GPC was Mw 1025 in terms of polystyrene.

[Synthesis Example (1-11)]
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 to 0.01 mol / L hydrochloric acid. 25 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. Thereafter, the operation was performed in the same manner as in Synthesis Example (1-1), and the mixture was adjusted to 14 mass percent in terms of solid residue at 140 ° C. The obtained polymer was composed of 40 mol% hydrolyzable silane (a1) and 60 mol% hydrolyzable silane (a2), a silane monomer having an isobutyl group having 4 carbon atoms and three hydrolyzable groups. Is a varnish of polysiloxane (abbreviated as TI46) hydrolyzed and copolymerized at a ratio of The weight average molecular weight of the obtained TI46 by GPC was Mw1015 in terms of polystyrene.

[Synthesis Example (1-12)]
TI73 obtained in Synthesis Example (1-5) 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 (1-13)]
The TI73 obtained in Synthesis Example (1-5) 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 (1-14)]
The TI73 obtained in Synthesis Example (1-5) was heated and stirred for 32 hours in an oil bath at 100 ° C., and was confirmed to be Mw4235 in terms of polystyrene to obtain a varnish of polysiloxane (abbreviated as TI73M3). .

[Synthesis Example (1-15)]
The TI73 obtained in Synthesis Example (1-5) 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 (1-16)]
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. Thereafter, the operation was performed in the same manner as in Synthesis Example (1-1), and the mixture was adjusted to 14 mass percent in terms of solid residue at 140 ° C. The polymer obtained was 30 mol% of 70 mol% hydrolyzable silane (a1) and a silane monomer having 4 hydrolyzable isobutyl groups and 3 hydrolyzable groups as hydrolyzable silane (a2). Is a varnish of polysiloxane (abbreviated as TI73L1) hydrolyzed and copolymerized at a ratio of The weight average molecular weight by GPC of the obtained TI73L1 was Mw 760 in terms of polystyrene.

[Synthesis Example (1-17)]
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. Thereafter, the operation was performed in the same manner as in Synthesis Example (1-1), and the mixture was adjusted to 14 mass percent in terms of solid residue at 140 ° C. The polymer obtained was 30 mol% of 70 mol% hydrolyzable silane (a1) and a silane monomer having 4 hydrolyzable isobutyl groups and 3 hydrolyzable groups as hydrolyzable silane (a2). Is a varnish of polysiloxane (abbreviated as TI73L2) hydrolyzed and copolymerized at a ratio of The weight average molecular weight by GPC of the obtained TI73L2 was Mw652 in terms of polystyrene.

[Synthesis Example (1-18)]
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. Thereafter, the operation was performed in the same manner as in Synthesis Example (1-1), and the mixture was adjusted to 14 mass percent in terms of solid residue at 140 ° C. The obtained polymer was composed of 70 mol% hydrolyzable silane (a1), a silane monomer having an n-octyl group having 8 carbon atoms and three hydrolyzable groups instead of hydrolyzable silane (a2). Is a varnish of polysiloxane (abbreviated as TO73) which is hydrolyzed and copolymerized at a ratio of 30 mol%. The weight average molecular weight of the obtained TO73 by GPC was Mw998 in terms of polystyrene.

[Synthesis Example (2-1)]
20.83 g of tetraethoxysilane, 7.04 g of n-propyltrimethoxysilane and 111.49 g of acetone 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 85 ° C., and reacted for 240 minutes under heating and reflux. Thereafter, the reaction solution was cooled to room temperature, 111.49 g of propylene glycol monomethyl ether acetate (abbreviated as PGMEA) was added to the reaction solution, and ethanol, methanol, water, hydrochloric acid and acetone as reaction by-products were distilled off under reduced pressure. Concentration gave a PGMEA solution of hydrolysis condensate (polymer). Furthermore, PGMEA was added, and it adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer is a varnish of a silicon compound (A) containing a hydrolyzed condensate (polysiloxane) and a varnish of a completely hydrolyzed polysiloxane (abbreviated as P1). The weight average molecular weight of the obtained P1 by GPC was Mw1541 in terms of polystyrene.
PGMEA was added so that the PGMEA varnish of P1 was 6 mass percent in terms of solid residue at 140 ° C., and 1H-NMR was measured. ^From the result of ¹ H-NMR, when the peak of 5.1 ppm attributed to the proton of PGMEA as a solvent is set to 1.00, the peak around 6.0 ppm attributed to silanol (Si—OH) of the polysiloxane is observed. The peak was 0.32, confirming that a large amount of Si—OH remained. Table 1 shows the weight average molecular weight and the proton number ratio by ¹ H-NMR.

[Synthesis Example (2-2)]
20.83 g of tetraethoxysilane, 9.44 g of isobutyltriethoxysilane, and 121.11 g of acetone were put into a 300 ml flask, and the mixed solution was stirred with a magnetic stirrer to 0.01 mol / L hydrochloric acid. 52 g was added dropwise to the mixed solution. 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, 121.11 g of PGMEA is added to the reaction solution, and ethanol, water, hydrochloric acid, and acetone as reaction by-products are distilled off under reduced pressure and concentrated to obtain a hydrolysis-condensation product (polymer). A PGMEA solution was obtained. Furthermore, PGMEA was added, and it adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer is a varnish of a silicon compound (A) containing a hydrolyzed condensate (polysiloxane), and a varnish of a completely hydrolyzed polysiloxane (abbreviated as P2). Table 1 shows the weight average molecular weight of P2 and the proton number ratio by ¹ H-NMR.

[Synthesis Example (2-3)]
20.83 g of tetraethoxysilane, 8.84 g of n-hexyltrimethoxysilane and 118.71 g of acetone 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 85 ° C., and reacted for 240 minutes under heating and reflux. Thereafter, the reaction solution is cooled to room temperature, 118.71 g of PGMEA is added to the reaction solution, and ethanol, methanol, water, hydrochloric acid, and acetone as reaction by-products are distilled off under reduced pressure, and concentrated to hydrolyzed condensate (polymer). ) PGMEA solution was obtained. Furthermore, PGMEA was added, and it adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer is a varnish of a silicon compound (A) containing a hydrolysis condensate (polysiloxane), and a varnish of a completely hydrolyzed polysiloxane (abbreviated as P3). Table 1 shows the weight average molecular weight of P3 and the proton number ratio by ¹ H-NMR.

[Synthesis Example (2-4)]
20.83 g of tetraethoxysilane, 2.45 g of isobutyltriethoxysilane, and 93.13 g of acetone were put into a 300 ml flask, and the mixed solution was stirred with a magnetic stirrer to 0.01 mol / L hydrochloric acid. 80 g was added dropwise to the mixed solution. 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, 93.13 g of PGMEA is added to the reaction solution, and ethanol, water, hydrochloric acid, and acetone as reaction by-products are distilled off under reduced pressure and concentrated to obtain a hydrolysis-condensation product (polymer). A PGMEA solution was obtained. Furthermore, PGMEA was added, and it adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer is a varnish of a silicon compound (A) containing a hydrolyzed condensate (polysiloxane), and a varnish of a completely hydrolyzed polysiloxane (abbreviated as P4). Table 1 shows the weight average molecular weight of P4 and the proton number ratio by ¹ H-NMR.

[Synthesis Example (2-5)]
12.50 g of tetraethoxysilane, 13.22 g of isobutyltriethoxysilane and 102.89 g of acetone were placed in a 300 ml flask, and the mixed solution was stirred with a magnetic stirrer to 0.01 mol / L hydrochloric acid. 56 g was dripped at the mixed solution. 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, 102.89 g of PGMEA is added to the reaction solution, and ethanol, water, hydrochloric acid, and acetone as reaction by-products are distilled off under reduced pressure and concentrated to obtain a hydrolysis-condensation product (polymer). A PGMEA solution was obtained. Furthermore, PGMEA was added, and it adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer is a varnish of a silicon compound (A) containing a hydrolysis condensate (polysiloxane), and a varnish of a completely hydrolyzed polysiloxane (abbreviated as P5). Table 1 shows the weight average molecular weight of P5 and the proton number ratio by ¹ H-NMR.

[Synthesis Example (2-6)]
5.21 g of tetraethoxysilane, 2.36 g of isobutyltriethoxysilane and 118.59 g of acetone were placed in a 300 ml flask, and the mixed solution was stirred with a magnetic stirrer and 0.01 mol / L hydrochloric acid was added. 38 g was added dropwise to the mixed solution. 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, 118.59 g of PGMEA is added to the reaction solution, and ethanol, water, hydrochloric acid, and acetone as reaction by-products are distilled off under reduced pressure and concentrated to obtain a hydrolysis-condensation product (polymer). A PGMEA solution was obtained. Furthermore, PGMEA was added, and it adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer is a varnish of a silicon compound (A) containing a hydrolyzed condensate (polysiloxane) and a varnish of a completely hydrolyzed polysiloxane (abbreviated as P6). Table 1 shows the weight average molecular weight of P6 and the proton number ratio by ¹ H-NMR.

[Synthesis Example (2-7)]
20.83 g of tetraethoxysilane and 83.33 g of acetone were placed in a 300 ml flask, and 7.20 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, 83.33 g of PGMEA is added to the reaction solution, and ethanol, water, hydrochloric acid and acetone as reaction by-products are distilled off under reduced pressure, and concentrated to obtain a hydrolysis-condensation product (polymer). A PGMEA solution was obtained. Furthermore, PGMEA was added, and it adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer is a varnish of a silicon compound (A) containing a hydrolyzed condensate (polysiloxane) and a varnish of a completely hydrolyzed polysiloxane (abbreviated as P7). Table 1 shows the weight average molecular weight of P7 and the proton number ratio by ¹ H-NMR.

[Synthesis Example (2-8)]
10.42 g of tetraethoxysilane, 16.53 g of isobutyltriethoxysilane, and 107.78 g of acetone were placed in a 300 ml flask, and the mixed solution was stirred with a magnetic stirrer to 0.01 mol / L hydrochloric acid. 65 g was added dropwise to the mixed solution. 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, 107.78 g of PGMEA is added to the reaction solution, and ethanol, water, hydrochloric acid, and acetone as reaction by-products are distilled off under reduced pressure and concentrated to obtain a hydrolysis-condensation product (polymer) A PGMEA solution was obtained. Furthermore, PGMEA was added, and it adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer is a varnish of a silicon compound (A) containing a hydrolyzed condensate (polysiloxane) and a varnish of a completely hydrolyzed polysiloxane (abbreviated as P8). Table 1 shows the weight average molecular weight of P8 and the proton number ratio by ¹ H-NMR.

[Synthesis Example (2-9)]
P2 obtained in Synthesis Example 2 was heated and stirred in an oil bath at 100 ° C. for 22 hours to confirm that it became Mw 3401 in terms of polystyrene, and a varnish of polysiloxane (abbreviated as P9) was obtained. Table 1 shows the weight average molecular weight of P9 and the proton number ratio by ¹ H-NMR.

[Synthesis Example (2-10)]
P2 obtained in Synthesis Example 2 was heated and stirred in an oil bath at 100 ° C. for 35 hours to confirm that it became Mw4545 in terms of polystyrene, and a polysiloxane (abbreviated as P10) varnish was obtained. Table 1 shows the weight average molecular weight of P10 and the proton number ratio by ¹ H-NMR.

[Synthesis Example (2-11)]
20.83 g of tetraethoxysilane, 7.64 g of methyltriethoxysilane, and 113.90 g of acetone were placed in a 300 ml flask, and the mixed solution was stirred with a magnetic stirrer to 0.01 mol / L hydrochloric acid. 52 g was added dropwise to the mixed solution. 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, 113.90 g of PGMEA is added to the reaction solution, and ethanol, water, hydrochloric acid and acetone as reaction by-products are distilled off under reduced pressure, and concentrated to obtain a hydrolysis-condensation product (polymer). A PGMEA solution was obtained. Furthermore, PGMEA was added, and it adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer is a varnish of a silicon compound (A) containing a hydrolyzed condensate (polysiloxane) and a varnish of a completely hydrolyzed polysiloxane (abbreviated as P11). Table 1 shows the weight average molecular weight of P11 and the proton number ratio by ¹ H-NMR.

[Synthesis Example (2-12)]
20.83 g of tetraethoxysilane, 8.24 g of ethyltriethoxysilane, and 116.30 g of acetone were placed in a 300 ml flask, and the mixed solution was stirred with a magnetic stirrer to 0.01 mol / L hydrochloric acid. 52 g was added dropwise to the mixed solution. 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, 116.30 g of PGMEA is added to the reaction solution, and ethanol, water, hydrochloric acid, and acetone as reaction by-products are distilled off under reduced pressure and concentrated to obtain a hydrolysis-condensation product (polymer). A PGMEA solution was obtained. Furthermore, PGMEA was added, and it adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer is a varnish of a silicon compound (A) containing a hydrolysis condensate (polysiloxane) and a varnish of a completely hydrolyzed polysiloxane (abbreviated as P12). Table 1 shows the weight average molecular weight of P12 and the proton number ratio by ¹ H-NMR.

[Synthesis Example (2-13)]
20.83 g of tetraethoxysilane, 8.24 g of n-octyltrimethoxysilane and 123.47 g of acetone 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 85 ° C., and reacted for 240 minutes under heating and reflux. Thereafter, the reaction solution is cooled to room temperature, 123.47 g of PGMEA is added to the reaction solution, and ethanol, methanol, water, hydrochloric acid, and acetone as reaction byproducts are distilled off under reduced pressure, and concentrated to hydrolyzed condensate (polymer). ) PGMEA solution was obtained. Furthermore, PGMEA was added, and it adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer is a varnish of a silicon compound (A) containing a hydrolyzed condensate (polysiloxane) and a varnish of a completely hydrolyzed polysiloxane (abbreviated as P13). Table 1 shows the weight average molecular weight of P13 and the proton number ratio by 1H-NMR.

[Synthesis Example (2-14)]
20.83 g of tetraethoxysilane and 7.04 g of n-propyltrimethoxysilane 111.49 g of ethanol 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 85 ° C., and reacted for 240 minutes under heating and reflux. Thereafter, the reaction solution is cooled to room temperature, 111.49 g of PGMEA is added to the reaction solution, ethanol as a solvent, ethanol, methanol, water and hydrochloric acid as reaction by-products are distilled off under reduced pressure, and concentrated to hydrolytic condensation. A PGMEA solution of the product (polymer) was obtained. Furthermore, PGMEA was added, and it adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer is a varnish of a silicon compound containing a hydrolysis condensate (polysiloxane) and a varnish of a partially hydrolyzed polysiloxane (abbreviated as P14). The weight average molecular weight of the obtained P14 by GPC was Mw1520 in terms of polystyrene.
PGMEA was added to PGMEA varnish of P14 at 6 mass percent in terms of solid residue at 140 ° C., and 1H-NMR was measured.
From the result of 1H-NMR, when the peak of 5.1 ppm attributed to the proton of PGMEA as a solvent is taken as 1.00, the peak around 6.0 ppm attributed to silanol (Si—OH) of polysiloxane Was 0.06, and it was confirmed that Si—OH was very small.

[Synthesis Example (2-15)]
20.83 g of tetraethoxysilane and 9.44 g of isobutyltrimethoxysilane 121.11 g of ethanol were placed in a 300 ml flask, and the mixed solution was stirred with a magnetic stirrer and 9.52 g of 0.01 mol / L hydrochloric acid was stirred. Was dropped into the mixed solution. 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, 121.11 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. Furthermore, PGMEA was added, and it adjusted so that it might become 14 mass% in conversion of the solid residue in 140 degreeC. The obtained polymer is a varnish of a silicon compound containing a hydrolysis condensate (polysiloxane), and a varnish of a partially hydrolyzed polysiloxane (abbreviated as P15). Table 1 shows the weight average molecular weight of P15 and the proton number ratio by ¹ H-NMR.

[Production Example 1]
Zirconia dispersion; Propylene glycol monomethyl ether dispersion (abbreviated as B1) containing 30.5% by mass of zirconia particles surface-treated with alkoxysilane (manufactured by Nissan Chemical Industries, Ltd.)
Table 2 shows physical property values of the inorganic particle sol obtained in Production Example 1.

<Production of Film-Forming Composition (1) and Film>
[Example (1-1)]
6.5000 g of B1 obtained in Production 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 (B1 solid matter obtained in Synthesis Example (1-4)) was added. A solid solution of polysiloxane of 35% by mass) was added, and R-30-N manufactured by Dainippon Ink & Chemicals, Inc. as a surfactant was diluted with PGME to obtain 1% by mass. 3965 g was added and mixed until it became completely uniform at room temperature to obtain a varnish (abbreviated as V (1-1)) having a total solid content of 7.5% by mass.
The obtained V (1-1) was evaluated for patterning characteristics. V (1-1) was spin-coated on a 8 inch silicon substrate treated with hexamethyldisilazane (HMDS) to a thickness of 100 nm using a clean track ACT8 manufactured by Tokyo Electron Ltd., and a hot plate was used. Then, heating was performed at 150 ° C. for 1 minute. Next, AZ3100 (manufactured by AZ ELECTRONIC MATERIALS) was spin-coated on the obtained V (1-1) film so as to have a film thickness of 1.5 μm, and using a hot plate at 100 ° C. for 1 minute. Heating was performed. Thereafter, using an i-line stepper NSR-2205i12D manufactured by Nikon Corporation, an exposure dose of 300 mJ / cm ² was irradiated through the mask. 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.
The obtained V (1-1) was evaluated for heat resistant refractive index. A silicon substrate was spin-coated so that the film thickness of V (1-1) was 100 nm, and heated at 150 ° C. for 1 minute using a hot plate. 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. Table 3 shows the results of the refractive index comparison.
The obtained V (1-1) was measured for water contact angle. A silicon substrate was spin-coated so that the film thickness of V (1-1) was 100 nm, and heated using a hot plate at 150 ° C. for 1 minute, and then heated at 100 ° C. for 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.
Using the fully automatic contact angle meter Drop Master series DM700 manufactured by Kyowa Interface Science Co., Ltd., the resulting coating was made from pure water using a 22G size needle, and the droplet deposited on the coating surface was removed. The water contact angle was calculated by the drop method (θ / 2 method). The results are shown in Table 3.

[Example (1-2)]
The same procedure as in Example (1-1) was conducted except that TT73 in Example (1-1) was replaced with TI73 obtained in Synthesis Example (1-5), and the alkali developability, heat resistance, and water contact angle were adjusted. It was measured. The results are shown in Table 3. 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 (1-3)]
The same procedure as in Example (1-1) was performed except that TT73 in Example (1-1) was replaced with TH73 obtained in Synthesis Example (1-6). It was measured. The results are shown in Table 3. 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 (1-4)]
The same procedure as in Example (1-1) was performed except that TT73 in Example (1-1) was replaced with TI91 obtained in Synthesis Example (1-7), and the alkali developability, heat resistance, and water contact angle were adjusted. It was measured. The results are shown in Table 3.

[Example (1-5)]
The same procedure as in Example (1-1) was conducted except that TT73 in Example (1-1) was replaced with TI82 obtained in Synthesis Example (1-8), and the alkali developability, heat resistance, and water contact angle were adjusted. It was measured. The results are shown in Table 3.

[Example (1-6)]
The same procedure as in Example (1-1) was performed except that TT73 in Example (1-1) was replaced with TI64 obtained in Synthesis Example (1-9), and the alkali developability, heat resistance, and water contact angle were adjusted. It was measured. The results are shown in Table 3.

[Example (1-7)]
The same procedure as in Example (1-1) was performed except that TT73 in Example (1-1) was replaced with TI55 obtained in Synthesis Example (1-10), and the alkali developability, heat resistance and water contact angle were It was measured. The results are shown in Table 3.

[Example (1-8)]
The same procedure as in Example (1-1) was performed except that TT73 in Example (1-1) was replaced with TI73M1 obtained in Synthesis Example (1-12), and the alkali developability, heat resistance, and water contact angle were adjusted. It was measured. The results are shown in Table 3. 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 (1-9)]
The same procedure as in Example (1-1) was conducted except that TT73 in Example (1-1) was replaced with TI73M2 obtained in Synthesis Example (1-13), and the alkali developability, heat resistance, and water contact angle were It was measured. The results are shown in Table 3.

[Example (1-10)]
The same procedure as in Example (1-1) was performed except that TT73 in Example (1-1) was replaced with TI73L1 obtained in Synthesis Example (1-16), and the alkali developability, heat resistance, and water contact angle were It was measured. The results are shown in Table 3.

[Example (1-11)]
The same procedure as in Example (1-1) was performed except that TT73 in Example (1-1) was replaced with TI46 obtained in Synthesis Example (1-11), and the alkali developability, heat resistance, and water contact angle were adjusted. It was measured. The results are shown in Table 3.

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

[Comparative Example (1-2)]
The same procedure as in Example (1-1) was performed except that TT73 in Example (1-1) was replaced with TM73 obtained in Synthesis Example (1-2), and the alkali developability, heat resistance, and water contact angle were adjusted. It was measured. The results are shown in Table 3.

[Comparative Example (1-3)]
The same procedure as in Example (1-1) was performed except that TT73 in Example (1-1) was replaced with TE73 obtained in Synthesis Example (1-3), and the alkali developability, heat resistance, and water contact angle were adjusted. It was measured. The results are shown in Table 3.

[Comparative Example (1-4)]
The same procedure as in Example (1-1) was conducted except that TT73 in Example (1-1) was replaced with TI73M3 obtained in Synthesis Example (1-14), and the alkali developability, heat resistance, and water contact angle were adjusted. It was measured. The results are shown in Table 3.

[Comparative Example (1-5)]
The same procedure as in Example (1-1) was performed except that TT73 in Example (1-1) was replaced with TI73M4 obtained in Synthesis Example (1-15). The alkali developability, heat resistance, and water contact angle were It was measured. The results are shown in Table 3. The result of the optical microscope observation of the pattern is shown in FIG.

[Comparative Example (1-6)]
The same procedure as in Example (1-1) was performed except that TT73 in Example (1-1) was replaced with TI73L2 obtained in Synthesis Example (1-17), and the alkali developability, heat resistance, and water contact angle were adjusted. It was measured. 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 (1-7)]
The same procedure as in Example (1-1) was performed except that TT73 in Example (1-1) was replaced with TO73 obtained in Synthesis Example (1-18). It was measured. The results are shown in Table 3.

The results of Table 3 are compared between Example (1-1) to Example (1-11) and Comparative Example (1-1) to Comparative Example (1-7).

Examples (1-1) through (1-11) and Comparative Examples (1-2) through (1-3) are compared with Comparative Examples (1-4) through (1-5) and Comparative Examples. Compared to Example (1-7), it was found that the alkali developability was better when patterning of 5 μm which was 10 μm or less was observed.

In Example (1-11), although the weight average molecular weight is in the range of 700 to 4000, the hydrolyzable silane (a1) constituting the silicon compound (A) is 40 mol%, and the hydrolyzable silane (a2) is Although the composition is copolymerized at 60 mol%, the water contact angle is slightly outside the preferred range, but it can be used depending on the application.

Comparative Example (1-4) and Comparative Example (1-5) were copolymerized with 70 mol% of hydrolyzable silane (a1) constituting the silicon compound (A) and 30 mol% of hydrolyzable silane (a2). The polymerization rate is within the range, but the weight average molecular weight is outside the range of 700 to 4000.

Comparative Example (1-7) has a weight average molecular weight in the range of 700 to 4000, 70 mol% of hydrolyzable silane (a1) constituting silicon compound (A), and hydrolyzable silane (a2). Although the polymerization ratio copolymerized at 30 mol% is within the range, L of the hydrolyzable silane (a2) is an alkyl group having 8 carbon atoms and is a straight, branched or cyclic group having 3 to 6 carbon atoms Is outside the range of the alkyl group.

Examples (1-1) to (1-11), Comparative Example (1-1), Comparative Examples (1-4) to (1-5) and Comparative Example (1-7) are comparative examples ( Compared with 1-2) and Comparative Example (1-3), it was found that the refractive index change during heating was good.

In Comparative Example (1-2) and Comparative Example (1-3), L of the hydrolyzable silane (a2) is an alkyl group having 1 and 2 carbon atoms, and is a straight chain, branched or branched group having 3 to 6 carbon atoms. It is outside the range of the cyclic alkyl group. 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 forms a ring in the polymer sublimes when heated and forms an air layer. It is thought to be caused by 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 Example (1-1) to Example (1-11) and Comparative Example (1-1) to Comparative Example (1-7) are compared. In Examples (1-1) to (1-10), droplets were made from pure water using a 22 G size needle using a fully automatic contact angle meter Drop Master series DM700 manufactured by Kyowa Interface Science Co., Ltd. Then, the contact angle of water calculated by the droplet method (θ / 2 method) for the droplets deposited on the surface of the coating is in the range of 60 ° to 80 °. In Comparative Example (1-2), Comparative Example (1-3), Comparative Example (1-4) and Comparative Example (1-5), the contact angle of water is 60 ° to 80 °, which is within the range. When the refractive index changes with heat or when the alkali developability is poor when the patterning of 5 μm which is 10 μm or less is seen, the performance as a target film is insufficient.

In the present invention, the results shown in Table 3 according to <Production of film-forming composition (1) and coating film> have a high refractive index and can achieve high transparency, high heat resistance, high light resistance, and high hardness. Although it can be a film forming composition and pattern forming method suitable for device film preparation, depending on the application to be used, higher level patterning characteristics, film roughening prevention characteristics after resist film peeling, and aging characteristics are required. There are uses to do. For example, [1] silicon compound (A) obtained by hydrolyzing and condensing hydrolyzable silane in a non-alcohol solvent, [2] using curing catalyst (D), [3] diketone compound ( E), [4] By using water (F) and acid (G), <Preparation of film-forming composition (2) and film>, <Preparation of film-forming composition (3) and film> The results shown in <Film-forming composition (4) and production of coating film> have shown below that it can be applied to the above applications.

<Production of Film-Forming Composition (2) and Film>
[Example (2-1)]
In a 20 mL eggplant-shaped flask, 3.0000 g of B1 obtained in Production Example 1 was weighed, and then 10.9446 g of propylene glycol monoethyl ether (abbreviated as PGEE) was added to obtain Synthesis Example (2-1). 2.2875 g of P1 (the solid content of polysiloxane is 35% by mass with respect to the solid content of B1), and benzyltriethylammonium chloride (abbreviated as BTEAC) as a curing catalyst (D) was diluted with PGEE to 1% by mass. 0.0915 g of the solution was added, and 0.1830 g of a solution prepared by diluting R-30-N manufactured by Dainippon Ink & Chemicals, Inc. with PGEE as a surfactant to 1% by mass was added, and the solution became completely uniform at room temperature. To obtain a varnish (abbreviated as V (2-1)) having a total solid content of 7.5% by mass.

[Example (2-2)]
The same operation as in Example (2-1) was conducted except that P1 in Example (2-1) was replaced with P2 obtained in Synthesis Example (2-2), and the total mass of the solid content was 7.5% by mass. Varnish (abbreviated as V (2-2)) was obtained.

[Example (2-3)]
The same operation as in Example (2-1) was performed except that P1 in Example (2-1) was replaced with P3 obtained in Synthesis Example (2-3), and the total mass of the solid content was 7.5% by mass. Varnish (abbreviated as V (2-3)) was obtained.

[Example (2-4)]
The same operation as in Example (2-1) was conducted except that P1 in Example (2-1) was replaced with P4 obtained in Synthesis Example (2-4), and the total mass of the solid content was 7.5% by mass. Varnish (abbreviated as V (2-4)) was obtained.

[Example (2-5)]
The same operation as in Example (2-1) was conducted except that P1 in Example (2-1) was replaced with P5 obtained in Synthesis Example (2-5), and the total mass of the solid content was 7.5% by mass. Varnish (abbreviated as V (2-5)) was obtained.

[Example (2-6)]
The same operation as in Example (2-1) was performed except that P1 in Example (2-1) was replaced with P6 obtained in Synthesis Example (2-6), so that the total mass of the solid content was 7.5% by mass. Of varnish (abbreviated as V (2-6)).

[Example (2-7)]
The same operation as in Example (2-1) was performed except that P1 in Example (2-1) was replaced with P9 obtained in Synthesis Example (2-9), so that the total mass of the solid content was 7.5% by mass. Varnish (abbreviated as V (2-7)) was obtained.

[Example (2-8)]
Weighing 3.0000 g of B1 obtained in Production Example 1 into a 20 mL eggplant-shaped flask, then adding 9.4379 g of PGEE, and adding 2.2875 g of P2 (B1 solid matter obtained in Synthesis Example (2-2)). The solid content of the polysiloxane was 35% by mass), and 1.8300 g of a BTEAC diluted with PGEE as a curing catalyst (D) to 1% by mass was added, and Dainippon Ink & Chemicals, Ltd. as a surfactant ( 0.1830 g of R-30-N manufactured by Co., Ltd. diluted to 1% by mass with PGEE was added and mixed until complete homogeneity at room temperature, and varnish with a total solid content of 7.5% by mass (Abbreviated as V (2-8)).

[Example (2-9)]
In a 20 mL eggplant-shaped flask, 3.0000 g of B1 obtained in Production Example 1 was weighed, and then 10.94446 g of PGEE was added, and 2.2875 g of P2 (solid of B1 obtained in Synthesis Example (2-2) was added. The polysiloxane solid content was 35% by mass), 0.0915 g of benzyl trimethylammonium chloride (abbreviated as BTMAC) as a curing catalyst (D) was diluted with PGEE to 1% by mass, and the surface activity was added. Add 0.1830g of R-30-N manufactured by Dainippon Ink & Chemicals, Inc. as a solubilizer and dilute with PGEE to make 1% by mass. Of varnish (abbreviated as V (2-9)) was obtained.

[Reference Example (2-1)]
In a 20 mL eggplant-shaped flask, 3.0000 g of B1 obtained in Production Example 1 was weighed, and then 11.0239 g of PGEE was added. 0.1830 g of a polysiloxane having a solid content of 35% by mass) and R-30-N manufactured by Dainippon Ink & Chemicals, Inc. as a surfactant diluted to 1% by mass with PGEE. In addition, the mixture was mixed until it became completely uniform at room temperature to obtain a varnish (abbreviated as RV (2-1)) having a total mass of 7.5% by mass with no added curing catalyst.

[Reference Example (2-2)]
The same operation as in Reference Example (2-1) was performed except that P1 in Reference Example (2-1) was replaced with P2 obtained in Synthesis Example (2-2), and the total solid content was 7.5% by mass. Of varnish (abbreviated as RV (2-2)).

[Reference Example (2-3)]
The same operation as in Reference Example (2-1) was carried out except that P1 in Reference Example (2-1) was replaced with P3 obtained in Synthesis Example (2-3). Varnish (abbreviated as RV (2-3)) was obtained.

[Reference Example (2-4)]
The same operation as in Reference Example (2-1) was conducted except that P1 in Reference Example (2-1) was replaced with P4 obtained in Synthesis Example (2-4), and the total mass of the solid content was 7.5% by mass. Varnish (abbreviated as RV (2-4)) was obtained.

[Reference Example (2-5)]
The same operation as in Reference Example (2-1) was conducted except that P1 in Reference Example (2-1) was replaced with P5 obtained in Synthesis Example (2-5), so that the total mass of the solid content was 7.5% by mass. Varnish (abbreviated as RV (2-5)) was obtained.

[Reference Example (2-6)]
The same operation as in Reference Example (2-1) was conducted except that P1 in Reference Example (2-1) was replaced with P7 obtained in Synthesis Example (2-7), and the total mass of the solid content was 7.5% by mass. Varnish (abbreviated as RV2-6)).

[Reference Example (2-7)]
The same operation as in Reference Example (2-1) was conducted except that P1 in Reference Example (2-1) was replaced with P8 obtained in Synthesis Example (2-8), so that the total mass of the solid content was 7.5% by mass. Of varnish (abbreviated as RV (2-7)).

[Reference Example (2-8)]
The same operation as in Reference Example (2-1) was carried out except that P1 in Reference Example (2-1) was replaced with P10 obtained in Synthesis Example (2-10). Of varnish (abbreviated as RV (2-8)).

[Reference Example (2-9)]
The same operation as in Reference Example (2-1) was conducted except that P1 in Reference Example (2-1) was replaced with P11 obtained in Synthesis Example (2-11), and the total mass of the solid content was 7.5% by mass. Varnish (abbreviated as RV (2-9)) was obtained.

[Reference Example (2-10)]
The same operation as in Reference Example (2-1) was conducted except that P1 in Reference Example (2-1) was replaced with P12 obtained in Synthesis Example (2-12), and the total mass of the solid content was 7.5% by mass. Varnish (abbreviated as RV (2-10)) was obtained.

[Reference Example (2-11)]
The same operation as in Reference Example (2-1) was carried out except that P1 in Reference Example (2-1) was replaced with P13 obtained in Synthesis Example (2-13). Varnish (abbreviated as RV (2-11)) was obtained.

[Reference Example (2-12)]
The same operation as in Reference Example (2-1) was carried out except that P1 in Reference Example (2-1) was replaced with P14 obtained in Synthesis Example (2-14). Of varnish (abbreviated as RV (2-12)).

[Reference Example (2-13)]
The same operation as in Reference Example (2-1) was conducted except that P1 in Reference Example (2-1) was replaced with P15 obtained in Synthesis Example (2-15), and the total mass of the solid content was 7.5% by mass. Varnish (abbreviated as RV (2-13)) was obtained.

<Preparation of coating>
[Example (2-10) to Example (2-18) and Reference Example (2-14) to Reference Example (2-26)]
[Patterning characteristics (tests with more stringent evaluation than alkali developability tests in Table 3)]
The obtained V (2-1) to V (2-9) and RV (2-1) to RV (2-13) were evaluated for patterning characteristics. Each varnish was spin-coated on a 8 inch silicon substrate treated with hexamethyldisilazane (HMDS) to a thickness of 100 nm using a clean track ACT8 manufactured by Tokyo Electron Co., Ltd., and 150 ° C. using a hot plate. Heating was performed for 1 minute. Next, AZ3100 (manufactured by AZ ELECTRONIC MATERIALS) was spin-coated on the obtained coating so as to have a film thickness of 1.5 μm, and heated at 100 ° C. for 1 minute using a hot plate. Thereafter, using an i-line stepper NSR-2205i12D manufactured by Nikon Corporation, an exposure dose of 300 mJ / cm ² was irradiated through the mask. After light irradiation, development was performed for 30 seconds using 2.38% 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.
Table 4 shows the results of V (2-1) to V (2-9) and RV (2-1) to RV (2-13). In addition, observation results of V (2-1) to V (2-3) and RV (2-1) to RV (2-3) are shown in FIGS.
Further, in FIGS. 7 to 9, the space portion was measured from the top direction of the pattern using an electron microscope at a 5 μm portion where Line: Space was 1: 1. As a result of the measurement, the width of the Space portion in FIG. 7 was 5.10 μm, the width of the Space portion in FIG. 8 was 5.07 μm, and the width of the Space portion in FIG. 9 was 5.07 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.

[Heat-resistant refractive index]
The obtained V (2-1) to V (2-9) and RV (2-1) to RV (2-13) were evaluated for heat resistant refractive index. Each varnish was spin-coated on a silicon substrate so as to have a film thickness of 100 nm, and heated at 150 ° C. for 1 minute using a hot plate. 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. Table 4 shows the results of the comparison of refractive indexes.

[Water contact angle]
Each varnish measured the water contact angle. A silicon substrate was spin-coated so as to have a film thickness of 100 nm, and heated at 150 ° C. for 1 minute using a hot plate, and then heated at 100 ° C. for 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.
Using the fully automatic contact angle meter Drop Master series DM700 manufactured by Kyowa Interface Science Co., Ltd., the resulting coating was made from pure water using a 22G size needle, and the droplet deposited on the coating surface was removed. The water contact angle was calculated by the drop method (θ / 2 method). The results are shown in Table 4.

Note) In the alkali developability test of Table 3, even when the width of the portion where Line: Space is 1: 1 is ○ 12 to 5.15 μm, the patterning characteristic test is a test that requires a level higher than that. The case where it did not reach around 5 μm was marked as x.

When V (2-1) to V (2-9) and RV (2-1) to RV (2-13) are used as coatings and the patterning characteristics of the coatings are compared, Examples (2-10) to Examples Patterning characteristics were good in (2-18), Reference Example (2-25) and Reference Example (2-26).

In Examples (2-10) to (2-18), the silicon compound (A) of the present invention has a weight average molecular weight in the range of 700 to 4000, and the hydrolyzable silane constituting the silicon compound (A) (A1) is 90 to 50 mol%, hydrolyzable silane (a2) is copolymerized at 10 to 50 mol%, and L of hydrolyzable silane (a2) is 3 carbon atoms An inorganic particle (B) having a mean particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70, a curing catalyst (C), The water contact angle of the coating obtained from the composition comprising the solvent (D) is in the range of 60 ° to 80 °.

From the viewpoint of the necessity of the curing catalyst, Examples (2-10) to (2-14) are compared with Reference Examples (2-14) to (2-18). Examples (2-10) to (2-14) contain BTEAC as a curing catalyst, and Reference Examples (2-14) to (2-18) are compositions not containing BTEAC. . By containing a curing catalyst, curing during heating progressed, resist film resistance, alkali developer and resist film stripping solution resistance were imparted to the film, and a pattern of 10 μm or less could be formed. On the other hand, Reference Example (2-14) to Reference Example (2-18) which do not contain a curing catalyst are not provided with resist solvent resistance, alkali developer and resist film stripping solution resistance, and patterning due to insufficient alkali resistance. Before the film was formed, all the film portions were dissolved in the alkaline developer, and a pattern could not be obtained.

Example (2-11), Example (2-15), Example (2-16) and Reference Example (2-21) are compared from the viewpoint of weight average molecular weight. The weight average molecular weight of the polymer is 1500 in Example (2-11), 735 in Example (2-15), 3401 in Example (2-16), and 4545 in Reference Example (2-21). Here, using a polymer having a weight average molecular weight in the range of 700 to 4,000, the composition and the coating film had good patterning characteristics. It is considered that the patterning characteristics of the composition and coating film using the polymer having a weight average molecular weight of more than 4000 in Reference Example (2-21) are the residual film, and the solubility of the high molecular weight material is lowered.

From the viewpoint of the copolymerization ratio of the hydrolyzable silane (a1) and the hydrolyzable silane (a2) constituting the silicon compound (A), Example (2-11), Example (2-13), and Example (2-14) and Reference Example (2-20) are compared. The copolymerization ratio of the polymer in Example (2-11) was (a1) / (a2) = 70 mol% / 30 mol%, and Example (2-13) was (a1) / (a2) = 90 mol% / 10 mol%, Example (2-14) is (a1) / (a2) = 50 mol% / 50 mol%, Reference Example (2-20) is (a1) / (a2) = 40 mol% / 60 mol %. Here, the polymer in which the hydrolyzable silane (a1) constituting the silicon compound (A) is 90 to 50 mol% and the hydrolyzable silane (a2) is 10 to 50 mol% is copolymerized. The patterning characteristics of the composition and coating film were good. The patterning characteristics of the composition and film obtained using the polymer of the reference example (2-20) having a copolymerization ratio of (a1) / (a2) = 40 mol% / 60 mol% resulted in a pattern not being obtained. This is considered to be due to the loss of solubility in an alkaline developer because the hydrophobicity is too high.

From the viewpoint of the number of carbon atoms of L in the hydrolyzable silane (a2) constituting the silicon compound (A), Examples (2-10) to (2-12) and Reference Example (2-19), Reference examples (2-22) to (2-24) are compared. The number of carbon atoms of L in the hydrolyzable silane (a2) is 3 in Example (2-10), 4 in Example (2-11), 6 in Example (2-12), and Reference Example (2- 19) is 0, Reference Example (2-22) is 1, Reference Example (2-23) is 2, and Reference Example (2-24) is 8. Here, the composition and the film of the hydrolyzable silane (a2) having an L of 3 to 6 carbon atoms were used, and the patterning characteristics and the heat resistant refractive index were good. The polysiloxane having 0 carbon atoms in Reference Example (2-19), the polymer having 1 carbon atom in Reference Example (2-22), and the polymer having 2 carbon atoms in Reference Example (2-23) are patterned. The characteristic was release development, and a uniform 5 μm pattern could not be formed. When a polymer having 0 to 2 carbon atoms was copolymerized, the condensation of the film progressed, and dissolution developability in an alkaline developer was not obtained.

The polymer obtained by copolymerizing the monomer having 8 carbon atoms in Reference Example (2-24) did not dissolve in the alkaline developer and had poor patterning characteristics. This result can be explained from the hydrophilicity / hydrophobicity of the film surface during alkali development. The alkaline developer is generally an aqueous solution, and examples thereof include dilute TMAH aqueous solution or potassium hydroxide aqueous solution. Since these developers are aqueous solutions, if the hydrophobicity of the film is high, the film does not penetrate into the film and bounces, so that developability is lost in the first place. The coating may dissolve when immersed in an alkaline developer for a long time, but considering the process throughput, it is preferable to finish the alkali developing step within at least 120 seconds, so that it is hydrophobic enough to repel the alkaline developer. Is not preferable as a film characteristic.

From these results, in order to achieve both patterning characteristics and heat-resistant refractive index, it is important to copolymerize a specific monomer at a specific ratio, and particularly to the number of carbon atoms of L in the hydrolyzable silane (a2). Found that there was an optimal value.

Regarding the alkali developability, the hydrophilicity / hydrophobicity of the film surface at the time of alkali development has already been described above. However, Examples (2-10) to (2-18) and Reference Examples (2-14) to From the result of (2-26), the parameter of the film having a wide margin for alkali developability and dissolving developability and capable of forming a pattern of 10 μm or less is that the contact angle of water is in the range of 60 ° to 80 °. Proven.

[Light resistance test]
[Example (2-19) to Example (2-20) and Reference Example (2-27) to Reference Example (2-28)]
The obtained V (2-1) to V (2-2) and RV (2-12) to RV (2-13) were evaluated for light resistance.
V (2-1) to V (2-2) and RV (2-12) to RV (2-13) are spin-coated on a silicon substrate to a film thickness of 100 nm, and using a hot plate, Heating was performed at 150 ° C. for 60 minutes. After heating, the film thickness, the refractive index of 450 nm, and the average transmittance were measured. Next, a light resistance test was performed, and the film thickness, refractive index, and average transmittance of the film after the light resistance test were measured. The results are shown in Table 5.
The film thickness and refractive index of 450 nm were measured on the film on the silicon substrate, and the average transmittance was measured on the film on the quartz substrate. As the average transmittance, an average transmittance of 400 nm to 800 nm was calculated.
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. SX75-AP type manufactured by Suga Test Instruments Co., Ltd. was used as the test machine. The test environment was a temperature of 42 ± 3 ° C. and a relative humidity of 50 ± 5% RH.

The light resistance of Example (2-19) to Example (2-20) and Reference Example (2-27) to Reference Example (2-28) are compared. In Examples (2-19) to (2-20) and Reference Examples (2-27) to (2-28), the heat-resistant refractive index and the patterning characteristics were good, respectively. In 2-27) to Reference Example (2-28), it was found that the film thickness after light resistance test decreased, the refractive index increased, and the average transmittance decreased. On the other hand, in Example (2-19) to Example (2-20), the film thickness, refractive index, and average transmittance after the light resistance test did not change.

As a result of the light resistance test, polymers of V (2-1) to V (2-2) are completely hydrolyzed, and polymers of RV (2-12) to RV (2-13) are partially hydrolyzed. Only the difference is that the copolymerization ratio of the monomers is the same and the weight average molecular weight is the same level of the polymer, indicating that the difference in predominance was expressed by the difference in the polymerization method of the polymer. That is, it was found that the completely hydrolyzed polymer had a good light resistance test. In the fully hydrolyzed polymer, the thermosetting reaction of the film is terminated in the heating process, whereas in the partially hydrolyzed polymer, the thermosetting reaction is not completely terminated in the heating process, and the alkoxy group remains. Therefore, it is considered that the reaction progressed during the light resistance test.

Summing up the above results, the weight average molecular weight of the silicon compound (A) of the present invention is within the range of 700 to 4000 in order to achieve all of the heat resistant refractive index, patterning characteristics, and light resistance required for the LED material. The hydrolyzable silane (a1) constituting the silicon compound (A) is 90 to 50 mol%, the hydrolyzable silane (a2) is copolymerized at 10 to 50 mol%, and L of the hydrolyzable silane (a2) is composed of a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, and has an average particle diameter of 1 to 100 nm and a refraction of 1.50 to 2.70. Achieved by satisfying the requirement that the water contact angle of the film obtained from the composition comprising the inorganic particles (B) having a rate, the curing catalyst (D), and the solvent (C) is in the range of 60 ° to 80 °. Was shown to be .

<Production of Film-Forming Composition (3) and Film>
[Example (3-1)]
In a 20 mL eggplant-shaped flask, 3.0000 g of B1 obtained in Production Example 1 was weighed, and then 7.9724 g of propylene glycol monoethyl ether (abbreviated as PGEE) was added to obtain Synthesis Example (2-1). 2.875 g of P1 (solid content of polysiloxane is 35% by mass with respect to the solid content of B1), 3 ethyl pyruvate (abbreviated as PE) as diketone compound (E) which is a hydrogen bonding film roughening prevention material Add 0,515 g, add 0.1830 g of R-30-N manufactured by Dainippon Ink & Chemicals, Inc. as a surfactant to 1% by weight with PGEE, and mix until uniform at room temperature. A varnish (abbreviated as V (3-1)) having a total solid content of 7.5% by mass was obtained.
The obtained V (3-1) was evaluated for refractive index. A silicon substrate was spin-coated so that the film thickness of V (3-1) was 100 nm, and heated at 150 ° C. for 1 minute using a hot plate. Subsequently, it heated at 300 degreeC with the hotplate for 1 hour, and as a result of measuring the refractive index of 450 nm, it was 1.613.

[Example (3-2)]
The same operation as in Example (3-1) was performed except that P1 in Example (3-1) was replaced with P2 obtained in Synthesis Example (2-2), and the total mass of the solid content was 7.5% by mass. Of varnish (abbreviated as V (3-2)).
V (3-2) obtained was 1.610 as a result of measuring the refractive index in the same manner as in Example (3-1).

[Example (3-3)]
The same operation as in Example (3-1) was conducted except that P1 in Example (3-1) was replaced with P3 obtained in Synthesis Example (2-3), and the total mass of the solid content was 7.5% by mass. Varnish (abbreviated as V (3-3)) was obtained.
The obtained V (3-3) was 1.603 as a result of measuring the refractive index in the same manner as in Example (3-1).

[Example (3-4)]
The same operation as in Example (3-1) was performed except that P1 in Example (3-1) was replaced with P4 obtained in Synthesis Example (2-4), so that the total mass of the solid content was 7.5% by mass. Varnish (abbreviated as V (3-4)) was obtained.

[Example (3-5)]
The same operation as in Example (3-1) was conducted except that P1 in Example (3-1) was replaced with P5 obtained in Synthesis Example (2-5), so that the total mass of the solid content was 7.5% by mass. Of varnish (abbreviated as V (3-5)).

[Example (3-6)]
The procedure was the same as in Example (3-1) except that P1 in Example (3-1) was replaced with P6 obtained in Synthesis Example (2-6), so that the total mass of the solid content was 7.5% by mass. Varnish (abbreviated as V (3-6)) was obtained.

[Example (3-7)]
The same operation as in Example (3-1) was conducted except that P1 in Example (3-1) was replaced with P8 obtained in Synthesis Example (2-8), and the total mass of the solid content was 7.5% by mass. Varnish (abbreviated as V (3-7)) was obtained.

[Example (3-8)]
The procedure of Example (3-1) was repeated except that PE in Example (3-1) was replaced with methyl pyruvate (abbreviated as PM). V (3-8)) was obtained.

[Example (3-9)]
The procedure of Example (3-1) was repeated except that PE in Example (3-1) was replaced with acetylacetone (abbreviated as ACA), and a varnish (V ( Abbreviated as 3-9).

[Reference Example (3-1)]
In a 20 mL eggplant-shaped flask, 3.0000 g of B1 obtained in Production Example 1 was weighed, and then 11.0239 g of PGEE was added, and 2.2875 g of P1 (solid of B1 obtained in Synthesis Example (2-1) was added. 0.1830 g of a polysiloxane having a solid content of 35% by mass) and R-30-N manufactured by Dainippon Ink & Chemicals, Inc. as a surfactant diluted to 1% by mass with PGEE. In addition, the mixture was mixed until it became completely uniform at room temperature, and a varnish (RV (3-1) having a total solid content not containing the diketone compound (E), which is a hydrogen bonding film roughening preventing material, was added. )).

[Reference Example (3-2)]
The same operation as in Reference Example (3-1) was performed except that P1 in Reference Example (3-1) was replaced with P2 obtained in Synthesis Example (2-2), and the total mass of the solid content was 7.5% by mass. Of varnish (abbreviated as RV (3-2)).

[Reference Example (3-3)]
The same operation as in Reference Example (3-1) was carried out except that P1 in Reference Example (3-1) was replaced with P3 obtained in Synthesis Example (2-3). Varnish (abbreviated as RV (3-3)) was obtained.

[Reference Example (3-4)]
The same operation as in Reference Example (3-1) was carried out except that P1 in Reference Example (3-1) was replaced with P4 obtained in Synthesis Example (2-4). Of varnish (abbreviated as RV (3-4)).

[Reference Example (3-5)]
The same operation as in Reference Example (3-1) was conducted except that P1 in Reference Example (3-1) was replaced with P5 obtained in Synthesis Example (2-5), and the total mass of the solid content was 7.5% by mass. Varnish (abbreviated as RV (3-5)) was obtained.

[Reference Example (3-6)]
The same operation as in Reference Example (3-1) was carried out except that P1 in Reference Example (3-1) was replaced with P7 obtained in Synthesis Example (2-7). Varnish (abbreviated as RV (3-6)) was obtained.

<Preparation of coating>
[Example (3-10) to Example (3-18) and Reference Example (3-7) to Reference Example (3-12)]
[Alkali solubility and film roughening characteristics after resist film peeling]
The obtained V (3-1) to V (3-9) and RV (3-1) to RV (3-6) were evaluated for alkali solubility. Each varnish was spin-coated on a 8 inch silicon substrate treated with hexamethyldisilazane (HMDS) to a thickness of 100 nm using a clean track ACT8 manufactured by Tokyo Electron Co., Ltd., and 150 ° C. using a hot plate. Heating was performed for 1 minute. Next, AZ3100 (manufactured by AZ ELECTRONIC MATERIALS) was spin-coated on the obtained coating so as to have a film thickness of 1.5 μm, and heated at 100 ° C. for 1 minute using a hot plate. Thereafter, using an i-line stepper NSR-2205i12D manufactured by Nikon Corporation, an exposure dose of 300 mJ / cm ² was irradiated through the mask. 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. Table 6 shows an example in which dissolution development was performed with respect to an alkaline developer at this time, and an example in which peeling development or dissolution did not occur, and x.
Further, the photosensitive resist was immersed in PGME for 2 minutes, the resist was peeled off, and a portion having no pattern (a portion after the photosensitive resist was laminated and peeled) was observed with an optical microscope. As a result of observation with an optical microscope, an example in which film roughness did not occur was evaluated as ○, and an example in which film roughness occurred was evaluated as ×, and V (3-1) to V (3-9) and RV (3-1) The results of RV (3-6) are shown in Table 6. In addition, observation results of V (3-1) to RV (3-1) are shown in FIGS.

When V (3-1) to V (3-9) and RV (3-1) to RV (3-6) are used as coatings and the alkali solubility of the coatings is compared, Examples (3-10) to Examples (3-18) and Reference Examples (3-7) to Reference Examples (3-11) had good alkali solubility. On the other hand, the example in which the number of carbon atoms of L in the hydrolyzable silane (a2) in Reference Example (3-12) is 0 is peeled off from the alkaline developer, and the target solution developability cannot be obtained. I understood.

When V (3-1) to V (3-9) and RV (3-1) to RV (3-6) are used as coatings, and the film roughness characteristics after the resist film peeling of the coatings are compared, the example (3 It was found that the film roughness after the resist film peeling did not occur in −10) to Example (3-18), and the film roughness occurred in Reference Examples (3-7) to Reference Example (3-12). These differences are only differences in the presence or absence of the diketone compound (E), which is a hydrogen bonding film roughening inhibitor.

From the results of Table 6, it is important to copolymerize a specific monomer at a specific ratio in order to better achieve both alkali solubility and film roughness characteristics after resist film peeling, and in particular, hydrolyzable silane (a2 It has been found that there is an optimum value for the number of carbon atoms in L.

In summary of the above results, the weight average molecular weight of the silicon compound (A) of the present invention is in the range of 700 to 4000 in order to achieve both the alkali solubility required for the LED material and the film roughness characteristics after the resist film is peeled off. Preferably, the hydrolyzable silane (a1) constituting the silicon compound (A) is 90 to 50 mol%, and the hydrolyzable silane (a2) is 10 to 50 mol%. L of the hydrolyzable silane (a2) is composed of a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, and has an average particle diameter of 1 to 100 nm and 1.50 to 2. It was shown that this can be achieved by satisfying the requirements of a composition comprising inorganic particles (B) having a refractive index of 70, a hydrogen bonding film roughening inhibitor (E), and a solvent (C).

<Production of Film-Forming Composition (4) and Film>
[Example (4-1)]
In a 20 mL eggplant-shaped flask, 3.0000 g of B1 obtained in Production Example 1 was weighed, and then 8.3058 g of propylene glycol monoethyl ether (abbreviated as PGEE) was added to obtain Synthesis Example (2-1). 2.2875 g of P1 (the solid content of polysiloxane is 35% by mass with respect to the solid content of B1), and benzyltriethylammonium chloride (abbreviated as BTEAC) as a curing catalyst (D) was diluted with PGEE to 1% by mass. Add 0.0915 g of the solution, add 0.9150 g of acetic acid diluted with PGEE to 1 mass%, dilute R-30-N made by Dainippon Ink & Chemicals, Ltd. with PGEE as the surfactant. 0.1830 g of a mass solution was added, and 1.8458 g of ion-exchanged water (the ratio in the total solvent was 12 mass%) was added at room temperature. It was mixed until uniform, to obtain a total mass of the solid content of 7.5 wt% of varnish (abbreviated as V (4-1)).
The obtained V (4-1) was evaluated for refractive index. Spin coating was performed on a silicon substrate so that the film thickness of V (4-1) was 100 nm, and heating was performed at 150 ° C. for 1 minute using a hot plate. Subsequently, it heated at 300 degreeC with the hotplate for 1 hour, and as a result of measuring the refractive index of 450 nm, it was 1.616.

[Example (4-2)]
The same operation as in Example (4-1) was performed except that P1 in Example (4-1) was replaced with P2 obtained in Synthesis Example (2-2), and the total mass of the solid content was 7.5% by mass. Of varnish (abbreviated as V (4-2)).
The obtained V (4-2) was 1.612 as a result of measuring the refractive index in the same manner as in Example (4-1).

[Example (4-3)]
The same operation as in Example (4-1) was carried out except that P1 in Example (4-1) was replaced with P3 obtained in Synthesis Example (2-3), and the total mass of the solid content was 7.5% by mass. Varnish (abbreviated as V (4-3)).
V (4-3) obtained was 1.608 as a result of measuring the refractive index in the same manner as in Example (4-1).

[Example (4-4)]
The same operation as in Example (4-1) was conducted except that P1 in Example (4-1) was replaced with P4 obtained in Synthesis Example (2-4), and the total mass of the solid content was 7.5% by mass. Of varnish (abbreviated as V (4-4)).

[Example (4-5)]
The same operation as in Example (4-1) was conducted except that P1 in Example (4-1) was replaced with P5 obtained in Synthesis Example (2-5), and the total mass of the solid content was 7.5% by mass. Varnish (V (abbreviated as 4-5)) was obtained.

[Example (4-6)]
The procedure was the same as in Example (4-1) except that P1 in Example (4-1) was replaced with P6 obtained in Synthesis Example (2-6). Varnish (abbreviated as V (4-6)) was obtained.

[Example (4-7)]
The same operation as in Example (4-1) was conducted except that P1 in Example (4-1) was replaced with P9 obtained in Synthesis Example (2-9), so that the total mass of the solid content was 7.5% by mass. Of varnish (abbreviated as V (4-7)).

[Example (4-8)]
In a 20 mL eggplant-shaped flask, weighed 3.0000 g of B1 obtained in Production Example 1, then added 7.9932 g of PGEE, and added 2.2875 g of P2 (solid of B1) obtained in Synthesis Example (2-2). The solid content of the polysiloxane is 35% by mass), and 0.4575 g of a solution of BTEAC diluted with PGEE to 1% by mass is added as a curing catalyst (D), and acetic acid is diluted with PGEE to 1% by mass. 0.9150 g of the solution was added, 0.1830 g of a solution made by diluting R-30-N manufactured by Dainippon Ink & Chemicals, Ltd. with PGEE as a surfactant to 1% by mass, and 1. Add 8512 g (the ratio in the total solvent is 12% by mass) and mix it at room temperature until it is completely uniform, and add varnish (abbreviated as V (4-8)) whose total mass is 7.5% by mass. Obtained.

[Example (4-9)]
A varnish having a total solid content of 7.5% by mass was operated in the same manner as in Example (4-1) except that BTEAC of Example (4-1) was changed to benzyltrimethylammonium chloride (abbreviated as BTMAC). (Abbreviated as V (4-9)).

[Example (4-10)]
Weighing 3.0000 g of B1 obtained in Production Example 1 into a 20 mL eggplant-shaped flask, then adding 8.2252 g of PGEE, and adding 2.2875 g of P2 (B1 solid matter obtained in Synthesis Example (2-2)). 0.1830 g of a polysiloxane having a solid content of 35% by mass), a curing catalyst (D) diluted with BTEAC with PGEE to make 1% by mass, and acetic acid with 1% by mass diluted with PGEE. 0.9150 g of the solution was added, 0.1830 g of a solution made by diluting R-30-N manufactured by Dainippon Ink & Chemicals, Ltd. with PGEE as a surfactant to 1% by mass, and 1. 8471 g (the ratio in the total solvent is 12% by mass) is added until it is completely uniform at room temperature, and a varnish (abbreviated as V (4-10)) having a total solid content of 7.5% by mass is added. Obtained.

[Example (4-11)]
Weighing 3.0000 g of B1 obtained in Production Example 1 into a 20 mL eggplant-shaped flask, then adding 8.8409 g of PGEE, and adding 2.2875 g of P2 (B1 solid matter obtained in Synthesis Example (2-2)) 0.1830 g of a polysiloxane having a solid content of 35% by mass), a curing catalyst (D) diluted with BTEAC with PGEE to make 1% by mass, and acetic acid with 1% by mass diluted with PGEE. 0.9150 g of the solution was added, 0.1830 g of a solution made by diluting R-30-N manufactured by Dainippon Ink & Chemicals, Ltd. with PGEE as a surfactant to 1% by mass, and 1. 2314 g (the ratio in the total solvent is 8% by mass) is added to the mixture until it is completely uniform at room temperature, and a varnish having a total solid content of 7.5% by mass (abbreviated as V (4-11)) is added. Obtained.

[Example (4-12)]
In a 20 mL eggplant-shaped flask, weighed 3.0000 g of B1 obtained in Production Example 1, and then added 7.6095 g of PGEE to obtain 2.2875 g of P2 (solid of B1) obtained in Synthesis Example (2-2). 0.1830 g of a polysiloxane having a solid content of 35% by mass), a curing catalyst (D) diluted with BTEAC with PGEE to make 1% by mass, and acetic acid with 1% by mass diluted with PGEE. 0.9830 g of the prepared solution was added, 0.1830 g of a solution prepared by diluting R-30-N manufactured by Dainippon Ink & Chemicals, Ltd. with PGEE as a surfactant to 1% by mass, and ion-exchanged water 2. 4628 g (the ratio in the total solvent is 16% by mass) is added and mixed until it is completely uniform at room temperature, and a varnish (abbreviated as V (4-12)) having a total solid content of 7.5% by mass is added. Obtained.

[Example (4-13)]
In a 20 mL eggplant-shaped flask, weighed 3.0000 g of B1 obtained in Production Example 1, then added 6.6121 g of PGEE, and added 2.2875 g of P2 (solid of B1) obtained in Synthesis Example (2-2). 0.1830 g of a polysiloxane having a solid content of 35% by mass), a curing catalyst (D) diluted with BTEAC with PGEE to make 1% by mass, and acetic acid with 1% by mass diluted with PGEE. 2.7450 g of the solution was added, 0.1830 g of a solution made by diluting R-30-N manufactured by Dainippon Ink & Chemicals, Inc. with PGEE as a surfactant to 1% by mass, and 1. 8742 g (the ratio in the total solvent is 12% by mass) is added until it is completely uniform at room temperature, and a varnish (abbreviated as V (4-13)) having a total solid content of 7.5% by mass is added. Obtained.

[Example (4-14)]
Weigh 3.0000 g of B1 obtained in Production Example 1 into a 20 mL eggplant-shaped flask, then add 7.4186 g of PGEE, and add 2.2875 g of P2 (B1 solid matter obtained in Synthesis Example (2-2)). 0.1830 g of a polysiloxane having a solid content of 35% by mass), a curing catalyst (D) diluted with BTEAC to 1% by mass with PGEE, and formic acid diluted with PGEE to 1% by mass. 1.8300 g of the prepared solution was added, 0.1830 g of a solution prepared by diluting R-30-N manufactured by Dainippon Ink & Chemicals, Inc. with PGEE as a surfactant to 1% by mass, and 1. 8607 g (the ratio in the total solvent is 12% by mass) is added and mixed until it is completely uniform at room temperature, and a varnish (abbreviated as V (4-14)) having a total solid content of 7.5% by mass is added. Obtained.

[Example (4-15)]
Weighing 3.0000 g of B1 obtained in Production Example 1 into a 20 mL eggplant-shaped flask, then adding 4.9990 g of PGEE, and adding 2.2875 g of P2 (solid of B1) obtained in Synthesis Example (2-2) The solid content of polysiloxane is 35% by mass with respect to the component, 0.1830 g of BTEAC diluted to 1% by mass with PGEE as a curing catalyst (D) is added, and propionic acid is diluted with PGEE to 1% by mass 4.5750 g of the above solution was added, 0.1830 g of R-30-N manufactured by Dainippon Ink & Chemicals, Inc. diluted with PGEE as a surfactant was added to 1% by mass, and ion-exchanged water 1 9013 g (the ratio in the total solvent is 12% by mass) and mixed until it is completely uniform at room temperature, and the varnish having a total solid content of 7.5% by mass (abbreviated as V (4-15)) Got

[Example (4-16)]
A varnish (V (4-16)) having a total mass of 7.5% by mass was operated in the same manner as in Example (4-10) except that acetic acid in Example (4-10) was replaced with oxalic acid. Abbreviated).

[Example (4-17)]
The same procedure as in Example (4-10) was conducted except that acetic acid in Example (4-10) was replaced by maleic acid, and a varnish (V (4-17) having a total solid content of 7.5% by mass was obtained. Abbreviated).

[Example (4-18)]
To a 20 mL eggplant-shaped flask, 3.0000 g of B1 obtained in Production Example 1 was weighed, and then 5.2295 g of PGEE and 3.0763 g of ethyl pyruvate (abbreviated as PE. Diketone compound) were added. 2.2875 g of P2 obtained in (2-2) (solid content of polysiloxane was 35% by mass with respect to the solid content of B1), and BTEAC was diluted with PGEE as a curing catalyst (D) to 1% by mass 0.0915 g was added, 0.9150 g of acetic acid diluted to 1% by mass with PGEE was added, and R-30-N manufactured by Dainippon Ink & Chemicals, Ltd. as a surfactant was diluted with PGEE to 1%. 0.1830 g of a solution, and 1.8458 g of ion-exchanged water (the ratio in the total solvent is 12% by mass), and mixed until it is completely uniform at room temperature. The amount was obtained 7.5 mass% of varnish (abbreviated as V (4-18)).

[Example (4-19)]
In a 20 mL eggplant-shaped flask, 3.0000 g of B1 obtained in Production Example 1 was weighed, then 5.1466 g of PGEE and 3.0785 g of PE were added, and 2.2875 g obtained in Synthesis Example (2-2). P2 (solid content of polysiloxane is 35% by mass with respect to the solid content of B1), 0.1830 g of BTEAC diluted with PGEE as a curing catalyst (D) to 1% by mass was added, and acetic acid was added with PGEE. 0.90.9 g of a solution diluted to 1% by mass was added, and 0.1830 g of a solution made by diluting R-30-N manufactured by Dainippon Ink & Chemicals, Inc. with PGEE as a surfactant was added. Further, 1.8471 g of ion-exchanged water (the ratio in the total solvent is 12% by mass) is mixed until it is completely uniform at room temperature, and the varnish (V (4- ( 19) Abbreviated) was obtained.

[Example (4-20)]
In a 20 mL eggplant-shaped flask, weighed 3.0000 g of B1 obtained in Production Example 1, then added 2.8737 g of PGEE and 3.1237 g of PE, and added 2.2875 g obtained in Synthesis Example (2-2). P2 (solid content of polysiloxane is 35% by mass with respect to the solid content of B1), 0.1830 g of BTEAC diluted with PGEE as a curing catalyst (D) to 1% by mass was added, and acetic acid was added with PGEE. 2.7450 g of a solution diluted to 1% by mass was added, and 0.1830 g of a solution made by diluting R-30-N manufactured by Dainippon Ink & Chemicals, Inc. with PGEE as a surfactant was added, Further, 2.4990 g of ion-exchanged water (the ratio in the total solvent is 16% by mass) is mixed until it is completely uniform at room temperature, and a varnish (V (4- ( 20) Abbreviated) was obtained.

[Reference Example (4-1)]
Weighing 3.0000 g of B1 obtained in Production Example 1 into a 20 mL eggplant-shaped flask, then adding 8.3865 g of PGEE, and adding 2.2875 g of P1 (solid B1 obtained in Synthesis Example (2-1)). The solid content of polysiloxane was 35% by mass, and 0.9150 g of a solution obtained by diluting acetic acid with PGEE to 1% by mass was added as a surfactant. R-manufactured by Dainippon Ink & Chemicals, Inc. Add 0.1830 g of 30-N diluted with PGEE to 1% by mass, add 1.8444 g of ion-exchanged water (12% by mass in all solvents), and mix until completely uniform at room temperature. As an example in which the curing catalyst (D) of Example (4-1) was not added, a varnish (abbreviated as RV (4-1)) having a total solid content of 7.5% by mass was obtained.

[Reference Example (4-2)]
The curing catalyst of Example (4-2) was treated in the same manner as Reference Example (4-1) except that P1 of Reference Example (4-1) was replaced with P2 obtained in Synthesis Example (2-2). As an example not added, a varnish (abbreviated as RV (4-2)) having a total solid content of 7.5% by mass was obtained.

[Reference Example (4-3)]
The curing catalyst of Example (4-3) was prepared in the same manner as in Reference Example (4-1) except that P1 of Reference Example (4-1) was replaced with P3 obtained in Synthesis Example (2-3). As an example that was not added, varnish (abbreviated as RV (4-3)) having a total solid content of 7.5% by mass was obtained.

[Reference Example (4-4)]
The curing catalyst of Example (4-4) was prepared in the same manner as Reference Example (4-1) except that P1 of Reference Example (4-1) was replaced with P4 obtained in Synthesis Example (2-4). As an example not added, a varnish (abbreviated as RV (4-4)) having a total solid content of 7.5% by mass was obtained.

[Reference Example (4-5)]
The curing catalyst of Example (4-5) was prepared in the same manner as in Reference Example (4-1) except that P1 of Reference Example (4-1) was replaced with P5 obtained in Synthesis Example (2-5). As an example not added, a varnish (abbreviated as RV (4-5)) having a total solid content of 7.5% by mass was obtained.

[Reference Example (4-6)]
In a 20 mL eggplant-shaped flask, 3.0000 g of B1 obtained in Production Example 1 was weighed, then 10.1516 g of PGEE was added, and 2.2875 g of P1 (solid of B1 obtained in Synthesis Example (2-1) was added. 0.095 g of a polysiloxane solid content of 35% by mass), benzyl triethylammonium chloride (abbreviated as BTEAC) as a curing catalyst (D) diluted to 1% by mass with PGEE, and acetic acid 0.9150 g of a solution diluted to 1% by mass with PGEE was added, and 0.1830 g of R-30-N manufactured by Dainippon Ink & Chemicals, Inc. as a surfactant was diluted to 1% by mass with PGEE. In addition, as an example in which the ion exchange water of Example (4-1) was not added until it was completely uniform at room temperature, a varnish (RV (RV ( -6) abbreviated) was obtained.

[Reference Example (4-7)]
The same procedure as in Reference Example (4-6) was performed except that P1 in Reference Example (4-6) was replaced with P2 obtained in Synthesis Example (2-2), and ion-exchanged water of Example (4-2) As an example in which varnish was not added, a varnish (abbreviated as RV (4-7)) having a total solid content of 7.5% by mass was obtained.

[Reference Example (4-8)]
The same procedure as in Reference Example (4-6) was conducted except that P1 in Reference Example (4-6) was replaced with P3 obtained in Synthesis Example (2-3), and ion-exchanged water of Example (4-3) As an example in which varnish was not added, a varnish (abbreviated as RV (4-8)) having a total solid content of 7.5% by mass was obtained.

[Reference Example (4-9)]
The same procedure as in Reference Example (4-6) was carried out except that P1 in Reference Example (4-6) was replaced with P4 obtained in Synthesis Example (2-4), and ion-exchanged water of Example (4-4) As an example in which varnish was not added, a varnish (abbreviated as RV (4-9)) having a total solid content of 7.5% by mass was obtained.

[Reference Example (4-10)]
The same procedure as in Reference Example (4-6) was performed except that P1 in Reference Example (4-6) was replaced with P5 obtained in Synthesis Example (2-5), and ion-exchanged water of Example (4-5) As an example in which varnish was not added, a varnish (abbreviated as RV (4-10)) having a total solid content of 7.5% by mass was obtained.

[Reference Example (4-11)]
Weighing 3.0000 g of B1 obtained in Production Example 1 into a 20 mL eggplant-shaped flask, then adding 9.1124 g of PGEE, and adding 2.2875 g of P1 (solid of B1) obtained in Synthesis Example (2-1) The solid content of the polysiloxane is 35% by mass), 0.0915 g of BTEAC diluted with PGEE as a curing catalyst (D) to 1% by mass is added, and Dainippon Ink & Chemicals, Ltd. as a surfactant ( 0.1830 g of R-30-N manufactured by Co., Ltd. diluted to 1% by mass with PGEE was added, and 1.8322 g of ion-exchanged water (the ratio in the total solvent was 12% by mass) was completely added at room temperature. As an example in which the acid of Example (4-1) was not added, a varnish (abbreviated as RV (4-11)) having a total solid content of 7.5% by mass was obtained. .

[Reference Example (4-12)]
The procedure of Reference Example (4-11) was repeated, except that P1 of Reference Example (4-11) was replaced by P2 obtained in Synthesis Example (2-2), and the acid of Example (4-2) was added. As an example, there was obtained a varnish (abbreviated as RV (4-12)) having a total solid content of 7.5% by mass.

[Reference Example (4-13)]
The procedure of Reference Example (4-11) was repeated, except that P1 of Reference Example (4-11) was replaced with P3 obtained in Synthesis Example (2-3), and the acid of Example (4-3) was added. As an example, there was obtained a varnish (abbreviated as RV (4-13)) having a total solid content of 7.5% by mass.

[Reference Example (4-14)]
The procedure of Reference Example (4-11) was repeated, except that P1 of Reference Example (4-11) was replaced by P4 obtained in Synthesis Example (2-4), and the acid of Example (4-4) was added. As an example, there was obtained a varnish (abbreviated as RV (4-14)) having a total solid content of 7.5% by mass.

[Reference Example (4-15)]
The procedure of Reference Example (4-11) was repeated, except that P1 of Reference Example (4-11) was replaced by P5 obtained in Synthesis Example (2-5), and the acid of Example (4-5) was added. As an example, there was obtained a varnish (abbreviated as RV (4-15)) having a total solid content of 7.5% by mass.

[Reference Example (4-16)]
The same operation as in Example (4-1) was conducted except that P1 in Example (4-1) was replaced with P7 obtained in Synthesis Example (2-7), and the total mass of the solid content was 7.5% by mass. Varnish (abbreviated as RV (4-16)) was obtained.

[Reference Example (4-17)]
The same operation as in Example (4-1) was conducted except that P1 in Example (4-1) was replaced with P8 obtained in Synthesis Example (2-8), and the total mass of the solid content was 7.5% by mass. Of varnish (abbreviated as RV (4-17)).

[Reference Example (4-18)]
The same operation as in Example (4-1) was conducted except that P1 in Example (4-1) was replaced with P10 obtained in Synthesis Example (2-10), and the total mass of the solid content was 7.5% by mass. Of varnish (abbreviated as RV (4-18)).

[Reference Example (4-19)]
The same operation as in Example (4-1) was conducted except that P1 in Example (4-1) was replaced with P11 obtained in Synthesis Example (2-11), and the total mass of the solid content was 7.5% by mass. Varnish (abbreviated as RV (4-19)) was obtained.

[Reference Example (4-20)]
The procedure of Example (4-1) was repeated except that P1 of Example (4-1) was replaced with P12 obtained in Synthesis Example (2-12), so that the total mass of the solid content was 7.5% by mass. Varnish (abbreviated as RV (4-20)) was obtained.

[Reference Example (4-21)]
The same operation as in Example (4-1) was conducted except that P1 in Example (4-1) was replaced with P13 obtained in Synthesis Example (2-13), and the total mass of the solid content was 7.5% by mass. Of varnish (abbreviated as RV (4-21)).

[Reference Example (4-22)]
The same operation as in Example (4-1) was conducted except that P1 in Example (4-1) was replaced with P14 obtained in Synthesis Example (2-14), and the total mass of the solid content was 7.5% by mass. Of varnish (abbreviated as RV (4-22)).

[Reference Example (4-23)]
The same operation as in Example (4-1) was performed except that P1 in Example (4-1) was replaced with P15 obtained in Synthesis Example (2-15), and the total mass of the solid content was 7.5% by mass. Varnish (abbreviated as RV (4-23)).

[Reference Example (4-24)]
In a 20 mL eggplant-shaped flask, weighed 3.0000 g of B1 obtained in Production Example 1, then added 6.6927 g of PGEE, and added 2.2875 g of P2 (solid B1) obtained in Synthesis Example (2-2). The solid content of the polysiloxane is 35% by mass), 0.0915 g of BTEAC diluted with PGEE to 1% by mass is added as a curing catalyst (D), and nitric acid is diluted with PGEE to 1% by mass. 2.7450 g of the solution was added, 0.1830 g of a solution made by diluting R-30-N manufactured by Dainippon Ink & Chemicals, Inc. with PGEE as a surfactant to 1% by mass, and 1. 8729 g (the ratio in the total solvent is 12% by mass) is added until it is completely uniform at room temperature, and a varnish (abbreviated as RV (4-24)) having a total solid content of 7.5% by mass is added. Obtained.

[Reference Example (4-25)]
The procedure of Reference Example (4-24) was followed except that nitric acid in Reference Example (4-24) was replaced with sulfuric acid, and a varnish (RV (4-25) with a total solid content of 7.5% by mass was used. Abbreviated).

[Reference Example (4-26)]
In a 20 mL eggplant-shaped flask, weighed 3.0000 g of B1 obtained in Production Example 1, then added 9.1043 g of PGEE, and added 2.2875 g of P2 (B1 solid matter obtained in Synthesis Example (2-2)). The solid content of the polysiloxane is 35% by mass) and 0.0915 g of a solution of BTEAC diluted with PGEE to 1% by mass is added as a curing catalyst (D), and acetic acid is diluted with PGEE to 1% by mass. 0.0092 g of the prepared solution was added, 0.1830 g of a solution prepared by diluting R-30-N manufactured by Dainippon Ink & Chemicals, Ltd. with PGEE as a surfactant to 1% by mass, and ion-exchanged water 1. Add 8324 g (the ratio in the total solvent is 12% by mass), mix until it is completely uniform at room temperature, and add varnish (abbreviated as RV (4-26)) whose total mass is 7.5% by mass. Obtained.

[Reference Example (4-27)]
In a 20 mL eggplant-shaped flask, weighed 3.0000 g of B1 obtained in Production Example 1, then added 9.5363 g of PGEE, and added 2.2875 g of P2 (solid B1) obtained in Synthesis Example (2-2). The solid content of the polysiloxane is 35% by mass) and 0.0915 g of a solution of BTEAC diluted with PGEE to 1% by mass is added as a curing catalyst (D), and acetic acid is diluted with PGEE to 1% by mass. 0.9150 g of the prepared solution was added, 0.1830 g of a solution prepared by diluting R-30-N manufactured by Dainippon Ink and Chemicals, Ltd. with PGEE as a surfactant to 1% by mass, Add 6153 g (the ratio in the total solvent is 4% by mass) and mix it at room temperature until it is completely uniform, and add a varnish (abbreviated as RV (4-27)) whose total mass is 7.5% by mass. Obtained.

[Reference Example (4-28)]
In a 20 mL eggplant-shaped flask, weighed 3.0000 g of B1 obtained in Production Example 1, then added 7.0753 g of PGEE, and added 2.2875 g of P2 (solid of B1) obtained in Synthesis Example (2-2). The solid content of the polysiloxane is 35% by mass) and 0.0915 g of a solution of BTEAC diluted with PGEE to 1% by mass is added as a curing catalyst (D), and acetic acid is diluted with PGEE to 1% by mass. 0.9830 g of the prepared solution, 0.1830 g of a solution made by diluting R-30-N manufactured by Dainippon Ink & Chemicals, Inc. with PGEE as a surfactant to 1% by mass, and ion-exchanged water 3. Add 0763 g (the ratio in the total solvent is 20% by mass) and mix it at room temperature until it is completely uniform, and add a varnish (abbreviated as RV (4-28)) whose total mass is 7.5% by mass. Obtained.

V (4-1) to V (4-20) and RV obtained in Examples (4-1) to (4-20) and Reference Examples (4-1) to (4-28) The compositions of (4-1) to RV (4-28) are summarized in Tables 7 to 10. Each varnish was measured for pH with a digital pH meter, and the results are shown in Table 7.

Tables 7 to 10 are parameters relating to the present invention, weight average molecular weight, copolymerization ratio of hydrolyzable silane (a1) and hydrolyzable silane (a2) constituting the silicon compound (A), and hydrolyzability. The number of carbon atoms of L in silane (a2), the presence / absence and type of addition of a curing catalyst, the presence / absence and type of acid addition, the presence / absence of water addition and the ratio of water to the total solvent (% by weight) are shown.

In Tables 7 to 10, the types of acids are abbreviated as G1 for acetic acid, G2 for formic acid, G3 for propionic acid, G4 for oxalic acid, G5 for maleic acid, G6 for nitric acid, and G7 for sulfuric acid.

<Storage stability test of varnish>
[Aging test]
V (4-1) to V (4-20) and RV obtained in Examples (4-1) to (4-20) and Reference Examples (4-1) to (4-28) After preparing the varnishes (4-1) to RV (4-28), an aging test was performed in an oven at a temperature of 40 ° C. and a relative humidity of 50%. The time for the aging test was 336 hours.
Before and after the aging test, each varnish produced a film, and it was confirmed whether foreign matter was generated on the surface of the film. Each varnish was spin-coated on a 8 inch silicon substrate using a clean track ACT8 manufactured by Tokyo Electron Co., Ltd. and fired at 150 ° C. for 1 minute using a hot plate.
As for the coating film, the surface of the coating film is observed using an optical microscope, ○ is an example in which a foreign film is not generated and a uniform film is obtained, and x is an example in which a foreign material is generated and a storage stability test is defective. It shows in Table 11 thru | or Table 12.
<Preparation of coating>

[Patterning characteristics]
The obtained V (4-1) to V (4-20) and RV (4-1) to RV (4-28) were evaluated for patterning characteristics. Each varnish was spin-coated on a 8 inch silicon substrate treated with hexamethyldisilazane (HMDS) to a thickness of 100 nm using a clean track ACT8 manufactured by Tokyo Electron Co., Ltd., and 150 ° C. using a hot plate. Firing was performed for 1 minute. Next, AZ3100 (manufactured by AZ ELECTRONIC MATERIALS) was spin-coated on the obtained coating so as to have a film thickness of 1.5 μm, and baked at 100 ° C. for 1 minute using a hot plate. Thereafter, using an i-line stepper NSR-2205i12D manufactured by Nikon Corporation, an exposure dose of 300 mJ / cm ² was irradiated through the mask. After light irradiation, development was performed for 30 seconds using 2.38% 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 ×. Tables 11 to 12 show the results of V (4-1) to V (4-20) and RV (4-1) to RV (4-28). Also, V (4-1) to V (4-3), V (4-10), V (4-14) to V (4-17) and RV (4-1) to RV (4-3) The observation results are shown in FIGS.
Further, in FIGS. 15 to 22, the space portion was measured from the top direction of the pattern using an electron microscope at a 5 μm portion where Line: Space was 1: 1. As a result of the measurement, the width of the space portion of FIG. 15 is 5.04 μm, the width of the space portion of FIG. 16 is 5.02 μm, the width of the space portion of FIG. 17 is 5.02 μm, and the width of the space portion of FIG. .01 μm, the width of the Space portion of FIG. 19 is 5.01 μm, the width of the Space portion of FIG. 20 is 5.01 μm, the width of the Space portion of FIG. 21 is 5.01 μm, and the width of the Space portion of FIG. It became. 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.

[Water contact angle]
The obtained V (4-1) to V (4-20) and RV (4-1) to RV (4-28) were measured for water contact angle. A silicon substrate was spin-coated so as to have a film thickness of 100 nm, and baked using a hot plate at 150 ° C. for 1 minute, and then baked at 100 ° C. for 1 minute. The two-step baking in this hot plate is a baking condition that reproduces the heat history before alkali development based on applying a photosensitive resist and drying.
Using the fully automatic contact angle meter Drop Master series DM700 manufactured by Kyowa Interface Science Co., Ltd., the resulting coating was made from pure water using a 22G size needle, and the droplet deposited on the coating surface was removed. The water contact angle was calculated by the drop method (θ / 2 method). The results are shown in Tables 11 to 12.

Tables 7 to 12 compare the patterning characteristics of varnish foreign matter and its coating before and after aging of V (4-1) to V (4-20) and RV (4-1) and RV (4-28). .

The varnishes V (4-1) to V (4-20) have a weight average molecular weight in the range of 700 to 4000, and the hydrolyzable silane (a1) constituting the silicon compound (A) is 90 mol% to 50%. Linear, branched or cyclic, in which hydrolyzable silane (a2) is copolymerized at 10 to 50 mol%, and L of hydrolyzable silane (a2) has 3 to 6 carbon atoms Inorganic particles (B) having an average particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70, a curing catalyst (D), water (F), and an acid (G) In the varnish composed of the solvent (C), the ratio of water (F) in the total solvent is 6 to 18% by weight, and the pH of the varnish is controlled to 3 to 5 in the varnish before and after aging. Foreign matter does not occur and foreign matter appears on the resulting coating It was found not.

On the other hand, Reference Example (4-1) to Reference Example (4-5) are examples in which the curing catalyst (D) was omitted. However, when the patterning characteristics were evaluated, the film was too dissolved in the alkaline developer, and the pattern was changed. Couldn't get. From this result, it became clear that the curing catalyst (D) is an essential component.

Reference Example (4-6) to Reference Example (4-10) are examples in which water (F) was removed, but when the patterning characteristics were evaluated, the film was not dissolved in the alkaline developer, and a pattern could not be obtained. It was. Water (F) is an essential component for expressing silanol of the silicon compound (A) in the varnish, enhancing and stabilizing the curability when heated, and appropriately expressing the hydrogen ion concentration of the acid (G). It became clear that there was.

Reference examples (4-11) to (4-15) are examples in which the acid (G) was removed, but there was a problem that foreign matter was generated after aging. This is because the pH of the varnish is 6.8, and condensation is promoted more than the stabilization of silanol, and it is considered that foreign matters are generated in the varnish. This result revealed that acid (G) is an essential component.

Reference Example (4-16), Reference Example (4-19) and Reference Example (4-20) are examples in which L of the hydrolyzable silane (a2) is an alkyl group having 0 to 2 carbon atoms. When the patterning characteristics were evaluated, the film was peeled and developed with respect to the alkaline developer, and a pattern could not be obtained. This is presumably because the condensation progressed too much and did not exhibit dissolution developability with respect to the alkaline developer. Reference Example (4-21) is an example in which L of the hydrolyzable silane (a2) is an alkyl group having 8 carbon atoms. When the patterning characteristics are evaluated, the coating does not dissolve in the alkaline developer, The pattern could not be obtained. From these results, it became clear that L of the hydrolyzable silane (a2) must be composed of a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms. Further, when the hydrolyzable silane (a2) L is composed of a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, the water contact angle of the resulting film is in the range of 60 ° to 80 °. Inside. It was clarified that the hydrophilicity / hydrophobicity of the film is very important in order to obtain the solution developability with respect to the alkaline developer, and it was found that the optimum hydrophilicity / hydrophobicity was expressed from the structure of the silicon compound.

In Reference Example (4-17), the hydrolyzable silane (a1) constituting the silicon compound (A) is 90 mol% to 50 mol%, and the hydrolyzable silane (a2) is 10 mol% to 50 mol%. It is an example using a polymer in which the hydrolyzable silane (a1) is 40 mol% and the hydrolyzable silane (a2) is 60 mol%, not a copolymerized polymer. The film did not dissolve in the alkaline developer, and a pattern could not be obtained. From this result, the copolymerization ratio of the hydrolyzable silane (a1) and the hydrolyzable silane (a2) is important, the hydrolyzable silane (a1) of Example (4-5) is 50 mol%, In an example in which a polymer in which 50 mol% of the reactive silane (a2) is copolymerized is used, alkali solubility is expressed, so the copolymerization ratio of the hydrolyzable silane (a1) and the hydrolyzable silane (a2) It became clear that there was an optimal value.

Reference Example (4-18) is an example using a polymer having a weight average molecular weight of 4545. When the patterning characteristics were evaluated, the film was peeled and developed with an alkaline developer, and a pattern could not be obtained. From this result, it was revealed that when the weight average molecular weight of the silicon compound (A) is too high, peeling development occurs and there is an optimum value for the weight average molecular weight.

Reference Example (4-22) and Reference Example (4-23) are both examples using a partially hydrolyzed silicon compound (A). In both cases, the patterning characteristics, no foreign matter was generated before and after aging, and good results were obtained. The results of the light resistance test will be described later.

Reference Example (4-24) and Reference Example (4-25) are examples in which the acid type is changed to strong acid and the pH of the varnish is 1.2. In the varnishes of Reference Example (4-24) and Reference Example (4-25), a gel insoluble in the solvent (C) was generated after aging. From this result, it became clear that there is an optimum value for the pH of the varnish.

Reference Example (4-26) is an example in which the addition amount of acetic acid was decreased, 0.01 phr was added, and the pH of the varnish was 5.6. In Reference Example (4-26), foreign matter was generated after aging. This result also revealed that the pH of the varnish has an optimum value.

Reference Example (4-27) and Reference Example (4-28) are examples in which the amount of water (F) added is 4% and 20%. In Reference Example (4-27), foreign matter was generated after aging, and in Reference Example (4-28), striation occurred when the varnish was applied to the substrate, and a uniform film could not be obtained. From this result, it became clear that there is an optimum value for the amount of water (F) added.

[Light resistance test]
[Example (4-21) to Example (4-22) and Reference Example (4-29) to Reference Example (4-30)]
The obtained V (4-1) to V (4-2) and RV (4-22) to RV (4-23) were evaluated for light resistance.
V (4-1) to V (4-2) and RV (4-22) to RV (4-23) are spin-coated on a silicon substrate to a film thickness of 100 nm, and using a hot plate, Firing was performed at 150 ° C. for 60 minutes. After firing, the film thickness, the refractive index of 450 nm, and the average transmittance were measured. Next, a light resistance test was performed, and the film thickness, refractive index, and average transmittance of the film after the light resistance test were measured. The results are shown in Table 13.
The film thickness and refractive index of 450 nm were measured on the film on the silicon substrate, and the average transmittance was measured on the film on the quartz substrate. As the average transmittance, an average transmittance of 400 nm to 800 nm was calculated.
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. SX75-AP type manufactured by Suga Test Instruments Co., Ltd. was used as the test machine. The test environment was a temperature of 42 ± 3 ° C. and a relative humidity of 50 ± 5% RH.

The light resistance of Example (4-21) to Example (4-22) and Reference Example (4-29) to Reference Example (4-30) are compared. In Examples (4-21) to (4-22) and Reference Examples (4-29) to (4-30), the patterning characteristics and the generation of foreign matter after the aging were good. In (4-29) to Reference Example (4-30), it was found that the film thickness after light resistance test decreased, the refractive index increased, and the average transmittance decreased. On the other hand, in Examples (4-21) to (4-22), the film thickness, refractive index, and average transmittance after the light resistance test did not change.

As a result of the light resistance test, the polymers V (4-1) to V (4-2) are completely hydrolyzed, and the polymers RV (4-22) to RV (4-23) are partially hydrolyzed. Only the difference is that the copolymerization ratio of the monomers is the same and the weight average molecular weight is the same level of the polymer, indicating that the difference in predominance was expressed by the difference in the polymerization method of the polymer. That is, it was found that the completely hydrolyzed polymer had a good light resistance test. In the fully hydrolyzed polymer, the thermosetting reaction of the film is terminated in the baking process, whereas in the partially hydrolyzed polymer, the thermosetting reaction is not completely terminated in the baking process, and the alkoxy group remains. Therefore, it is considered that the reaction progressed during the light resistance test.

Summing up the above results, in order to achieve all of the high refractive index, heat-resistant refractive index, advanced patterning characteristics, light resistance, and sufficient varnish stability after aging required for LED materials, A silicon compound (A) having a weight average molecular weight of 700 to 4000 obtained by hydrolyzing and condensing degradable silane in a non-alcohol solvent, an average particle diameter of 1 to 100 nm, and a refractive index of 1.50 to 2.70. It was shown that this can be achieved by forming a film-forming composition containing the inorganic particles (B), the curing catalyst (D), water (F), acid (G), and solvent (C).

In the film-forming composition of the present invention, the weight average molecular weight of the silicon compound (A) is in the range of 700 to 4000, the hydrolyzable silane (a1) is 90 mol% to 50 mol%, and the hydrolyzable silane (A2) is a range copolymerized at 10 mol% to 50 mol%, and L of the hydrolyzable silane (a2) is a range of a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms. By using a very characteristic composition in which the water contact angle is in the range of 60 ° to 80 °, the alkali developability is good when the patterning of 10 μm or less which is useful as a coating for LED is observed, and the heat of refractive index. A permanent film with good temporal change can be obtained without going through a process such as a dry process.

The film obtained by the present invention can satisfy the patterning characteristics of high refractive index, high transparency, high heat resistance, high light resistance and 10 μm or less at a time, so that it can be used for liquid crystal displays, plasma displays, cathode ray tubes. 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

Hydrolyzable silane (a1) represented by formula (a1) and hydrolyzable silane (a2) represented by formula (a2):

(Wherein R 1 and R 2 each represent an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, or a halogen group, and L represents a straight-chain or branched group having 3 to 6 carbon atoms. Or a hydrolyzable condensate of hydrolyzable silane containing a silicon compound (A) having a weight average molecular weight of 700 to 4000 and an average particle diameter of 1 to 100 nm and 1.50 to 2 A film-forming composition (1) comprising inorganic particles (B) having a refractive index of .70 and a solvent (C).
The silicon compound (A) has a hydrolyzable silane (a1) and hydrolyzable silane (a2) ratio of 90 to 50 mol% hydrolyzable silane (a2). Is a polymer obtained by hydrolyzing and condensing hydrolyzable silanes respectively contained in 10 mol% to 50 mol%.
The film-forming composition (1) according to claim 1, wherein the silicon compound (A) is obtained by hydrolyzing and condensing a hydrolyzable silane in a non-alcohol solvent.
The film-forming composition (1) according to claim 3, wherein the non-alcohol solvent is ketone or ether.
The film-forming composition (1) according to claim 3, wherein the non-alcohol solvent is acetone or tetrahydrofuran.
The solvent (C) contains a non-alcohol solvent used for the hydrolysis of the hydrolyzable silane and the subsequent condensation, and a solvent used for solvent replacement for removing a reaction product generated by hydrolysis of the hydrolyzable silane. The film-forming composition (1) according to claim 3, wherein
The film-forming composition (1) according to claim 1, wherein the inorganic particles (B) are zirconia.
The film-forming composition (2) according to claim 3, further comprising a curing catalyst (D) selected from ammonium salts, phosphines, phosphonium salts, sulfonium salts, or chelate compounds.
The film-forming composition (3) according to claim 3, further comprising a diketone compound (E) selected from 1,2-diketone and / or 1,3-diketone.
The diketone compound (E) is represented by the following formula (3) and / or the following formula (4):

The film forming composition (3) according to claim 9, which is a compound containing a skeleton represented by the formula (W represents a carbon atom or an oxygen atom).
The film-forming composition (3) according to claim 9, wherein the diketone compound (E) is diacetyl, methyl pyruvate, ethyl pyruvate, or acetylacetone.
The film-forming composition (4) according to claim 8, further comprising water (F) and an acid (G).
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) in measurement 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 (1) according to 1.
A hydrolyzable silane containing hydrolyzable silane (a1) and hydrolyzable silane (a2) is hydrolyzed in a non-alcohol solvent (c1) to obtain a varnish of a silicon compound (A) having a weight average molecular weight of 700 to 4000. 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) in measurement by a dynamic light scattering method;
The varnish of the silicon compound (A), the sol of the inorganic particles (B), and the curing catalyst (D) are mixed, and the silicon compound (A), the inorganic particles (B), the curing catalyst (D), and the solvent (C) are mixed. The manufacturing method of the film forming composition (2) of Claim 8 including the process of obtaining the film forming composition containing.
A hydrolyzable silane containing hydrolyzable silane (a1) and hydrolyzable silane (a2) is hydrolyzed in a non-alcohol solvent (c1) to obtain a varnish of a silicon compound (A) having a weight average molecular weight of 700 to 4000. 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) in measurement by a dynamic light scattering method;
The varnish of the silicon compound (A), the sol of the inorganic particles (B), and the diketone compound (E) are mixed, and the silicon compound (A), the inorganic particles (B), the diketone compound (E), and the solvent (C) are mixed. The manufacturing method of the film forming composition (3) of Claim 9 including the process of obtaining the film forming composition containing.
A hydrolyzable silane containing hydrolyzable silane (a1) and hydrolyzable silane (a2) is hydrolyzed in a non-alcohol solvent (c1) to obtain a varnish of a silicon compound (A) having a weight average molecular weight of 700 to 4000. 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) in measurement by a dynamic light scattering method;
The varnish of the silicon compound (A), the sol of the inorganic particles (B), the curing catalyst (D), water (F), and the acid (G) are mixed, and the silicon compound (A), the inorganic particles (B), and the curing catalyst ( The process for producing a film-forming composition (4) according to claim 12, comprising a step of obtaining a film-forming composition comprising D), water (F), acid (G) and solvent (C).
A photosensitive resist is applied on a film obtained from the film-forming composition according to any one of claims 1 to 12, dried, and then irradiated to the photosensitive resist film. A pattern forming method comprising developing and then removing the resist film.
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 12 on a substrate and heating.
The film according to claim 18, wherein a contact angle of water on the film surface is 60 ° to 80 °.
The film according to claim 18, which is used as a light extraction film or a protective film.
An apparatus having an electronic device having the film according to claim 18.
The apparatus according to claim 21, wherein the electronic device is an LED.