JP2017052815A - Composition having high storage stability for forming alkali-soluble developable high refractive index film and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film-forming composition having high (long-term) storage stability for forming a film having a high refractive index, high transparency, high heat resistance, high light fastness and high hardness.SOLUTION: The film-forming composition comprises: a silicon compound (A) having a weight average molecular weight of 700 to 4000 obtained by hydrolyzing and condensing a hydrolyzable silane comprising compounds of formula (a1) and formula (a2) in a non-alcohol solvent; 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 (C); water (D); an acid (E); and a solvent (F). The water (D) is included by 6 to 18 wt.% in the whole solvent comprising the water (D) and the solvent (F). The acid (E) is added so as to adjust a pH of the film-forming composition to the range from 3 to 5.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a film-forming composition. More specifically, the present invention relates to a film-forming composition containing polysiloxane, inorganic particles, a curing catalyst, water and an acid, a pattern-forming method, and a storage method.

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

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

In order to increase the light extraction efficiency, there is a method of controlling the optical refractive index, and studies have been reported to increase the refractive index of the sealing material.
For example, fine particles of at least one metal oxide selected from the group consisting of zirconium oxide, titanium oxide and composites thereof, and an alkoxy group-containing siloxane polymer having a weight average molecular weight in the range of 1,000 to 100,000 ( b1), a hydroxyl group-containing polysiloxane (b2) having a weight average molecular weight of 500 to 100,000, a β-diketone, a ketoester, a dicarboxylic acid and a derivative thereof, a hydroxycarboxylic acid and a derivative thereof, a ketoalcohol, a dihydroxy compound, an oxy A composition for forming a high refractive material containing an aldehyde compound and at least one chelating agent selected from the group consisting of an amine compound and a derivative thereof (see Patent Document 1);

An optical device sealing resin composition containing an organopolysiloxane containing an alkyl group, aryl group, hydroxyl group, etc., a condensation catalyst, and inorganic particles (see Patent Document 2),
A trialkoxysilane (A) having a phenyl group which may have an alkyl group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms, and a substituent containing a reactive cyclic ether group For a B-staged optical device comprising a ladder-type or random-type silsesquioxane derivative obtained by co-hydrolysis and co-condensation with trialkoxysilane (B), and inorganic fine particles as main components A sealing resin composition is disclosed (see Patent Document 3).
The target high refractive index material is required to have high transparency, high heat resistance, high light resistance, and high hardness, and it is difficult to satisfy the material at once.

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

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

  A high refractive index composition containing a fully hydrolyzed polysiloxane, inorganic particles, a curing catalyst, water and an acid is not known to be patterned using a photosensitive material recoated thereon. In consideration of the process for fabricating the film, there is no known study of patterning of 10 μm or less. Furthermore, the high refractive index film for LED is used in the actual process in the state of varnish, but the high refractive index varnish containing polysiloxane, inorganic particles, curing catalyst, water and acid does not change over time by the storage method, It is necessary to develop performance for a long time. There are no known studies on these storage methods.

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

  The present invention has been made in view of such circumstances, and a display capable of achieving high (long-term) storage stability, high refractive index, high transparency, high heat resistance, high light resistance, and high hardness. It aims at providing the film formation composition and pattern formation method suitable for film preparation for a device.

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

(Wherein R ¹ and R ² each represents an alkoxy group, an acyloxy group, or a halogen group, and L represents a linear, branched, or cyclic alkyl group having 3 to 6 carbon atoms). A silicon compound (A) having a weight average molecular weight of 700 to 4000 obtained by hydrolysis and condensation in a non-alcohol solvent, an inorganic particle having an average particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70 ( B), a film-forming composition comprising a curing catalyst (C), water (D), acid (E), and solvent (F),
When the silicon compound (A) is hydrolyzable silane (a1) and hydrolyzable silane (a2), the hydrolyzable silane (a1) is 90 mol% to 50 mol%. ) Is a polymer obtained by hydrolyzing and condensing a hydrolyzable silane containing 10 mol% to 50 mol%,
Water (D) is contained in a ratio of 6 to 18% by weight in the total solvent including water (D) and solvent (F),
The film wherein the acid (E) has 1 to 2 carboxyl groups in the molecule, and the acid is added so that the pH of the film-forming composition is adjusted in the range of 3 to 5. Forming composition,
As a second aspect, the film-forming composition according to the first aspect, wherein the non-alcohol solvent is a ketone or an ether,
As a third aspect, the film-forming composition according to the first aspect, wherein the non-alcohol solvent is acetone or tetrahydrofuran,
As a fourth aspect, the solvent (D) includes a non-alcohol solvent used at the time of hydrolysis and condensation of the silane and a reaction product obtained by hydrolysis of the hydrolyzable silane, and includes a solvent by solvent substitution. Thru | or the film formation composition as described in any one of 3rd viewpoints,
As a fifth aspect, the film-forming composition according to any one of the first to fourth aspects, wherein the inorganic particles (B) are zirconia,
As a sixth aspect, the film-forming composition according to any one of the first to fifth aspects, wherein the curing catalyst (C) is an ammonium salt, a phosphine, a phosphonium salt, a sulfonium salt, or a chelate compound,
As a seventh aspect, the film-forming composition according to any one of the first to sixth aspects, wherein the acid (E) is formic acid, acetic acid, propionic acid, oxalic acid, or maleic acid,
As an eighth aspect, a hydrolyzable silane containing hydrolyzable silane (a1) and hydrolyzable silane (a2) is hydrolyzed in a non-alcohol solvent (f1), 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 (f2) by a dynamic light scattering method;
The varnish of the silicon compound (A), the sol of the inorganic particles (B), the curing catalyst (C), water (D), and the acid (E) are mixed, and the silicon compound (A), the inorganic particles (B), and the curing catalyst ( C), water (D), acid (E), and the process of obtaining the film formation composition containing a solvent (F), The film formation composition as described in any one of the 1st viewpoint thru | or 7th viewpoint including Production method,
As a ninth aspect, a photosensitive resist is applied on a film obtained from the film-forming composition described in any one of the first to seventh aspects, and drying, light irradiation, development, and resist peeling are performed. Pattern formation method,
As a tenth aspect, a cured film obtained by coating and heating the film forming composition according to any one of the first aspect to the seventh aspect on a substrate,
The film according to the tenth aspect, characterized in that, as an eleventh aspect, the contact angle of water on the film surface is 60 ° to 80 °,
As a twelfth aspect, the film according to the tenth aspect or the eleventh aspect used as a light extraction film or a protective film,
A thirteenth aspect is an apparatus having an electronic device having the film according to any one of the tenth aspect to the twelfth aspect, and a fourteenth aspect is an apparatus according to the thirteenth aspect, in which the electronic device is an LED. .

A comparison of compositions using fully hydrolyzed polysiloxane and partially hydrolyzed polysiloxane has the following characteristics.
The partially hydrolyzed polysiloxane refers to a polymer obtained by using an alcohol containing a functional group such as a hydroxyl 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. Moreover, since silanol groups and silane alkoxides in the polymer are chemically balanced in a solution state, polysiloxane having a large residual ratio of silane alkoxides is obtained when alcohol is selected as a solvent for hydrolysis and condensation.
On the other hand, the fully hydrolyzed polysiloxane refers to a polymer obtained by using a non-alcohol containing no hydroxyl group as a solvent for hydrolysis and condensation. In a fully hydrolyzed polysiloxane, the non-alcohol solvent, which is a solvent for hydrolysis and polycondensation, does not have a hydroxyl group that clogs the silanol of the polymer, so that the polymer obtained has a high residual ratio of silanol. It becomes siloxane. That is, since the completely hydrolyzed polyteos contains almost no silane alkoxide as an organic component, it is a polymer containing almost no carbon element which is disadvantageous in the light resistance test.

When the inorganic particles (B) have an average particle diameter of 1 to 100 nm according to the dynamic light scattering method, the filterability is good and high transmittance of the film-forming composition can be achieved.
The silicon compound (A) is polysiloxane, and the inorganic particles (B) are zirconia having a high refractive index. However, since the composition is composed of an inorganic compound, the light resistance is good.
The hydroxyl groups present on the surfaces of the silicon compound (A) and the inorganic particles (B) start polycondensation when heated as an external stimulus and can form a strong and high hardness film.
The composition comprising the polysiloxane of the present invention, inorganic particles having an average particle size of 1 to 100 nm or less, and a curing catalyst has a dissolution developability with respect to an alkaline solution. Patterning is possible. Since a process such as dry etching is not performed, the process is simplified and the production cost can be reduced.

Since the partially hydrolyzed polysiloxane contains a large amount of silane alkoxide, when it reacts with the silanols of the fine particles, it must pass through hydrolysis once, and it is necessary to add an additive or the like separately. Additives include silanol formation accelerators and silane alkoxide decomposition accelerators, but these additives contain organic groups and metals and deteriorate light resistance, so they are not suitable for the composition of the present invention. .
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 targeted by the present invention. However, the coating film is added after spin coating by adding a curing catalyst (C). 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 the process.

Compared with the partially hydrolyzed polysiloxane, the fully hydrolyzed polysiloxane has more silanol at the end, so the varnish containing this has high reactivity and the storage temperature at 23 ° C. or 5 ° C. In this case, molecular weight and viscosity increase, and gelation may occur in the varnish state and patterning characteristics may deteriorate in the coating state. Thus, when the completely hydrolyzed polysiloxane changes during storage, it becomes difficult to form a pattern of 10 μm or less, which is a feature of the present invention, but it contains water (D) and acid (E) and is reactive. By stabilizing the hydroxyl group as a group, a quality change in a varnish state having a storage temperature of 23 ° C. or 5 ° C. does not occur, and a film capable of forming a good pattern of 10 μm or less can be obtained over a long period of time.
The varnish obtained by the present invention has good storage stability, and the obtained coating film can form a pattern of 10 μm or less, so that both storage stability and patterning characteristics can be achieved.
The film obtained by the present invention can satisfy high refractive index, high transparency, high heat resistance, high light resistance, and high hardness at a time, and can be patterned, so that it can be used for liquid crystal displays and plasma displays. , Cathode ray tubes, organic light-emitting displays, electronic paper, LEDs, solid-state imaging devices, solar cells, organic thin film transistors, and other electronic devices. In particular, it can be suitably used as an LED member that requires high light resistance.

Patterning characteristics when V1 is used in Example 1 Patterning characteristics when V2 is used in Example 2 Patterning characteristics when V3 is used in Example 3 Patterning characteristics when V10 is used in Example 10 Patterning characteristics when V14 is used in Example 14 Patterning characteristics when V15 is used in Example 15 Patterning characteristics when V16 is used in Example 16 Patterning characteristics when V17 is used in Example 17 Patterning characteristics when using RV1 in Comparative Example 1 Patterning characteristics when using RV2 in Comparative Example 2 Patterning characteristics when using RV3 in Comparative Example 3

The present invention relates to a silicon compound (A ) 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 (C), water (D), an acid (E), and a solvent (F). A film-forming composition comprising:
When the silicon compound (A) is hydrolyzable silane (a1) and hydrolyzable silane (a2), the hydrolyzable silane (a1) is 90 mol% to 50 mol%. ) Is a polymer obtained by hydrolyzing and condensing a hydrolyzable silane containing 10 mol% to 50 mol%,
Water (D) is contained in a ratio of 6 to 18% by weight in the total solvent including water (D) and solvent (F),
The film wherein the acid (E) has 1 to 2 carboxyl groups in the molecule, and the acid is added so that the pH of the film-forming composition is adjusted in the range of 3 to 5. A forming composition.

In formulas (a1) and (a2), R ¹ and R ² each represent an alkoxy group, an acyloxy group, or a halogen group, and L represents a linear, branched, or cyclic alkyl group having 3 to 6 carbon atoms.
The solid content concentration of the film-forming composition only needs to be adjusted so as to obtain the film thickness of the target film-forming film, and is 0.1 to 50% by mass, or 1 to 30% by mass, or 5 to 5%. The concentration range can be 20% by mass. Solid content is the remaining ratio which removed the solvent (F) and water (D) from the film formation composition.
The content of the silicon compound (A), the inorganic particles (B), the curing catalyst (C), and the acid (E) in the solid content is 50 to 100% by mass, or 70 to 100% by mass, or 70 to 99% by mass. can do.
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 addition amount of the curing catalyst (C) 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 silicon compound (A) used in the present invention is a hydrolysis condensate obtained by hydrolyzing and copolymerizing a hydrolyzable silane represented by the formula (a1) and a hydrolyzable silane represented by the formula (a2). This hydrolysis-condensation product may contain a hydrolysis product.
The silicon compound (A) has a hydrolyzable silane (a1) and hydrolyzable silane (a2) ratio of 90 mol% to 50 mol%, or 80 mol% to 60 mol%. Or hydrolyzable silane (a2) containing 10 mol% to 50 mol%, or 20 mol% to 40 mol%, or 30 mol% of the hydrolyzable silane. It is a polymer.

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

Examples of the alkoxy group include an alkoxy group having 1 to 20 carbon atoms, and examples thereof include an alkoxy group having a linear, branched or cyclic alkyl moiety, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, n -Butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, n-pentoxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1 , 1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl -N-pentyloxy group, 2-methyl-n-pentyloxy group, 3-methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3 , 3-Dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2, -trimethyl- Examples include an n-propoxy group, a 1-ethyl-1-methyl-n-propoxy group, and a 1-ethyl-2-methyl-n-propoxy group.

Examples of the acyloxy group include an acyloxy group having 2 to 20 carbon atoms, such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, and an isobutylcarbonyloxy group. , S-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, 1-methyl-n-butylcarbonyloxy group, 2-methyl-n-butylcarbonyloxy group, 3-methyl-n- Butylcarbonyloxy group, 1,1-dimethyl-n-propylcarbonyloxy group, 1,2-dimethyl-n-propylcarbonyloxy group, 2,2-dimethyl-n-propylcarbonyloxy group, 1-ethyl-n- Propylcarbonyloxy group, n-hexylca Bonyloxy group, 1-methyl-n-pentylcarbonyloxy group, 2-methyl-n-pentylcarbonyloxy group, 3-methyl-n-pentylcarbonyloxy group, 4-methyl-n-pentylcarbonyloxy group, 1,1 -Dimethyl-n-butylcarbonyloxy group, 1,2-dimethyl-n-butylcarbonyloxy group, 1,3-dimethyl-n-butylcarbonyloxy group, 2,2-dimethyl-n-butylcarbonyloxy group, 2 1,3-dimethyl-n-butylcarbonyloxy group, 3,3-dimethyl-n-butylcarbonyloxy group, 1-ethyl-n-butylcarbonyloxy group, 2-ethyl-n-butylcarbonyloxy group, 1,1 1,2-trimethyl-n-propylcarbonyloxy group, 1,2,2-trimethyl-n-propylcarbonyloxy group, Examples include, but are not limited to, ethyl-1-methyl-n-propylcarbonyloxy group, 1-ethyl-2-methyl-n-propylcarbonyloxy group, phenylcarbonyloxy group, and tosylcarbonyloxy group. is not.
Examples of the halogen group as the hydrolyzable group include fluorine, chlorine, bromine and iodine.

Said hydrolysable silane (a1) is illustrated below, for example.
Examples include tetramethoxysilane, tetraacetoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraacetoxysilane, tetrachlorosilane, and the like. The siloxane monomer having a functional group is not limited to these. Among these, tetramethoxysilane and tetraethoxysilane can be preferably used.

A commercially available product can be used as the hydrolyzable silane.
L in the hydrolyzable silane (a2) represents a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms.
n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3 -Methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl Group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3- Dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl -N-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2, -trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl Examples include, but are not limited to, a 2-methyl-n-propyl group, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl group and the like.

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

A silicon compound (A), which is a copolymer containing a hydrolysis condensate obtained by hydrolyzing and condensing a hydrolyzable silane containing the hydrolyzable silane of the formula (a1) and the hydrolyzable silane of the formula (a2), , And a condensate having a weight average molecular weight of 700 to 4000 or 1000 to 2000. These molecular weights are molecular weights obtained in terms of polystyrene by GPC analysis. When the weight average molecular weight is less than 700, the polymer is too low in molecular weight and a uniform film cannot be obtained. On the other hand, when the weight average molecular weight is more than 4000, the polymer becomes too high in molecular weight, resulting in peeling development with respect to the alkaline solution.

Organic acids as hydrolysis catalysts are, for example, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacin Acid, gallic acid, butyric acid, merit acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfone Examples include acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like.
Examples of the inorganic acid as the hydrolysis catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

Organic bases as hydrolysis catalysts include, for example, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazine. Examples thereof include zabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, 1,8-diazabicyclo [5,4,0] -7-undecene and the like.
Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like. Of these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferred, and these may be used alone or in combination of two or more.

As the hydrolysis catalyst, a volatile inorganic acid such as hydrochloric acid can be preferably used. For hydrolysis of an alkoxysilyl group, an acyloxysilyl group, or a halogenated silyl group, 0.1 to 100 mol, or 0.1 to 10 mol, or 1 to 5 mol, or 1 mol per mol of the hydrolyzable group, or Use 2 to 3.5 moles of water.
The reaction temperature for carrying out the hydrolysis and condensation is usually in the range of 20 ° C. (room temperature) to the reflux temperature under normal pressure of the solvent used for the hydrolysis. Moreover, it can carry out under pressure, for example, can heat up to about 200 degreeC of liquid temperature.

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

Examples of the non-alcohol solvent (f1) 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, di-isopropylbenzene, trimethylbenzene Aromatic hydrocarbon solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl- -Ketone solvents such as pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-isobutyl ketone, cyclohexanone, methylcyclohexanone; ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl Examples thereof include ether solvents such as ether, tetrahydrofuran and 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 (f1), 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.
You may substitute the solvent of the silicon compound (A) containing the obtained hydrolysis-condensation product (polysiloxane). Specifically, when acetone is selected as a solvent for hydrolysis and condensation (solvent for synthesis), after the polysiloxane is obtained in acetone, the same amount of substitution solvent as that for the synthesis is added. When replacing with another solvent, the acetone may be distilled off azeotropically 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 substitution solvent becomes the solvent component (F) when the silicon compound (A) containing the hydrolysis condensate (polysiloxane) is used as a varnish.

The solvent at the time of synthesis at the time of solvent substitution is preferably azeotropically distilled off, and therefore has a lower boiling point than the solvent for substitution. For example, the solvent for hydrolysis and condensation includes acetone, tetrahydrofuran and the like, and the substitution solvent includes propylene glycol monomethyl ether acetate and the like.
The solvent (F) 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 (F).
When used as a varnish of the silicon compound (A), the concentration of the silicon compound (A) in the varnish can be used in the range of 0.1 to 60% by mass.

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

The component (F) 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.

A silicon compound (A) containing a hydrolysis condensate (polysiloxane) and an average particle diameter of 1 to
From the viewpoint of compatibility with 100 nm inorganic particles (B), the solvent (F) is more preferably butanol, diacetone alcohol, methyl ethyl ketone, methyl isobutyl ketone, hexylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethylcarby. Thor, butyl carbitol, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monobutyl ether, cyclohexanone, acetic acid methyl ester, acetic acid ethyl ester, lactate ethyl ester and the like.

The silicon compound (A), which is a hydrolyzable condensate of hydrolyzable silane containing the hydrolyzable silane (a1) and (a2) of the present invention, is a straight, branched or cyclic (a2) having 3 to 6 carbon atoms. A hydrolyzable silane having three alkyl groups, (a1) is 90 to 50 mol%, and (a2) is 10 to 50 mol%. In addition, the mass average molecular weight can be set to 700 to 4000. Thereby, the film | membrane obtained from the composition containing a silicon compound (A), an inorganic particle (B), a curing catalyst (C), water (D), an acid (E), and a solvent (F) is In addition, since it has dissolution developability, patterning of 10 μm or less using a photosensitive resist is possible, and high refractive index and high light resistance can be satisfied at the same time.

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

The mass average molecular weight, the copolymerization ratio, the mixing ratio with the particles (B), the addition amount of the curing catalyst (C), and the preheating temperature condition are controlled so that the water contact angle of the coating is 60 ° to 80 °. This makes it possible for the first time to exhibit optimum dissolution developability in an alkaline solution.
The silicon compound (A) containing the hydrolysis-condensation product (polysiloxane) of the present invention is obtained by using a non-alcohol containing no hydroxyl group as a solvent for hydrolysis and polycondensation. This polysiloxane is called polysiloxane and has a high hydrolysis rate. On the other hand, a polymer obtained by using an alcohol containing a hydroxyl group as a solvent for hydrolysis or polycondensation is referred to as a partially hydrolyzed polysiloxane for distinction. 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, and the fully hydrolyzed polysiloxane has a partially hydrolyzed Si-OH. 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 peak of the internal standard or the solvent is 1.00, the calculated proton number of Si-OH of the fully hydrolyzed polysiloxane 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. .
The inorganic particle (B) component used in the present invention is an inorganic particle (B) having an average particle diameter of 1 to 100 nm, and the refractive index of the inorganic particle (B) is 1.50 to 2.70, or 1. A range of 50 to 1.70, or 1.60 to 2.00, or 1.90 to 2.20, or 2.20 to 2.70 can be selected.
The kind of inorganic particles constituting the composition of the present invention together with the above fully hydrolyzed polysiloxane is zirconia.
The inorganic particles may be used alone or in combination of two or more.

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

Furthermore, these compounds can be used alone or in admixture of two or more, and may be used in admixture with the above oxides.
As the inorganic particle (B) component used in the present invention, inorganic particles having an average particle diameter of 1 to 100 nm, 5 to 50 nm, or 1 to 10 nm by a dynamic light scattering method can be used.
As for the particle size, particles having different average particle sizes may be mixed and used.
Moreover, when using the said inorganic particle (B), you may use particle | grains as it is, the thing of the colloid state (The colloid particle was disperse | distributed to the dispersion medium) which dispersed the particle | grains beforehand in water or the organic solvent. Sol) may be used. The density | concentration of the inorganic particle in sol can be used in 0.1-60 mass%.
An organic solvent sol in which a dispersion medium of a water sol in which inorganic particles are dispersed in an aqueous medium is substituted from water to an organic solvent can be used. This dispersion medium (f2) is combined with the solvent (F) used in the present invention in combination with the solvent (F) used for diluting or replacing the varnish of the silicon compound (A) containing the hydrolysis condensate (polysiloxane). can do.

Therefore, the same dispersion medium (f2) as the solvent (F) can be used.
Furthermore, particles obtained by treating the inorganic particles (B) with silicon oxide, an organosilicon compound, an organometallic compound, or the like may be used.
The treatment with silicon oxide is to grow silicon oxide particles on the particle surface in a dispersion containing inorganic particles (B) by a known method. Treatment with an organosilicon compound or an organometallic compound means that these compounds are added to a dispersion containing inorganic particles (B), and these compounds or reaction products of these compounds are adsorbed on the surfaces of the inorganic particles. Or they are to be combined.

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

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

Examples of the organometallic compound include titanate coupling agents and aluminum coupling agents, and specific examples of titanate coupling agents include Preneact KR TTS, KR 46B, KR 38B, KR 138S, KR238S, 338X, Specific examples of KR 44, KR 9SA, KR ET5, KR ET (manufactured by Ajinomoto Fine Techno Co., Ltd.) and aluminum coupling agents include Plenact AL-M (manufactured by Ajinomoto Fine Techno Co., Ltd.) and the like.
As for the usage-amount of these organosilicon compounds and organometallic compounds, 2-100 mass parts is preferable with respect to 100 mass parts of said inorganic particles (B).

The metal oxide colloidal particles used for the inorganic particles (B) can be produced by a known method such as an ion exchange method, a peptization method, a hydrolysis method, or a reaction method.
Examples of the ion exchange method include a method in which the metal salt is treated with an ion exchange resin to remove counter ions and generate particles.
Peptides include a precipitate obtained by neutralizing the metal salt with an acid or base, hydrolyzing the metal alkoxide, or hydrolyzing the metal basic salt under heating, or Examples thereof include a method of removing unnecessary electrolyte from the gel or adding ions necessary for dispersion. Examples of the reaction method include a method of reacting the metal powder with an acid.
The method for preparing the film forming composition of the present invention is not particularly limited. The component (A), the component (B), the component (C), the component (D), the component (E), and the component (F) may be mixed uniformly. The order of mixing the components (A) to (F) 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 non-alcohol solvent (f1), and a silicon compound (A) having a weight average molecular weight of 700 to 4000 is obtained. 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 (f2) by a dynamic light scattering method;
The varnish of the silicon compound (A), the sol of the inorganic particles (B), the curing catalyst (C), water (D), and the acid (E) are mixed, and the silicon compound (A), the inorganic particles (B), and the curing catalyst ( C), water (D), acid (E), and the process of obtaining the film forming composition containing a solvent (F), The manufacturing method of the film forming composition is mentioned.
As the curing catalyst for component (C), ammonium salts, phosphines, phosphonium salts, sulfonium salts, or metal chelate compounds can be used.
As the ammonium salt, the formula (3):

(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.) (4):

(However, 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 (5):

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), formula (6):

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), formula (7):

A quaternary ammonium salt having the structure (wherein R ¹⁹ and R ²⁰ represent an alkyl group, an aryl group, or a combination thereof, Y ⁻ represents an anion), formula (8):

A tertiary ammonium salt having a structure (wherein p represents an integer of 2 to 11, q represents an integer of 2 to 3, H represents a hydrogen atom, and Y ⁻ represents an anion).
Moreover, as a phosphonium salt, Formula (9):

(However, 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 the quaternary phosphonium salts represented by the a) being coupled with the phosphorus atom by C-P bond, respectively.
As the sulfonium salt, the formula (10):

(However, 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 represent Each of which is bonded to a sulfur atom by a C—S bond).

The compound of the above formula (3) 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 carbon atoms, preferably 2 to 10 carbon atoms, an aryl group, or a combination thereof. For example, linear alkyl such as ethyl group, propyl group, and butyl group Group, benzyl group, cyclohexyl group, cyclohexylmethyl group, dicyclopentadienyl group and the like. Anions (Y ⁻ ) are halogen ions such as chlorine ions (Cl ⁻ ), bromine ions (Br ⁻ ) and iodine ions (I ⁻ ), carboxylates (—COO ⁻ ), sulfonates (—SO ₃ ⁻ ). And acid groups such as alcoholate (—O ⁻ ).

Compounds of formula (4) ^{above, R 12 R 13 R 14 R} 15 N + Y - is a quaternary ammonium salt represented by. In this quaternary ammonium salt, R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are silanes bonded to a silicon atom by an alkyl group having 1 to 18 carbon atoms, an aryl group, or a combination thereof, or a Si—C bond. A compound. The anion (Y ⁻ ) is a halogen ion such as chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), iodine ion (I ⁻ ), carboxylate (—COO ⁻ ), sulfonate (—SO ₃ ⁻ ), An acid group such as alcoholate (—O ⁻ ) can be mentioned. This quaternary ammonium salt can be obtained commercially, for example, tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzyl chloride. Examples include ammonium and trimethylbenzylammonium chloride. These can be added as ammonium compounds.

The compound of the above formula (5) is a quaternary ammonium salt derived from 1-substituted imidazole, R ¹⁶ and R ¹⁷ have 1 to 18 carbon atoms, and the total 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. The anion (Y ⁻ ) is a halogen ion such as chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), iodine ion (I ⁻ ), carboxylate (—COO ⁻ ), sulfonate (—SO ₃ ⁻ ), An acid group such as alcoholate (—O ⁻ ) can be mentioned. This compound can be obtained as a commercial product. For example, imidazole compounds such as 1-methylimidazole and 1-benzylimidazole are reacted with alkyl halides and aryl halides such as benzyl bromide and methyl bromide. Can be manufactured. Further, the compound of the formula (5) can be used as a 4,5-dihydroimidazole compound in which the 4-position and the 5-position are hydrogenated. These can be added as cyclic ammonium compounds.

The compound of the above formula (6) 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 a combination thereof. For example, a butyl group, an octyl group, a benzyl group, and a lauryl group can be exemplified. The anion (Y ⁻ ) is a halogen ion such as chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), iodine ion (I ⁻ ), carboxylate (—COO ⁻ ), sulfonate (—SO ₃ ⁻ ), An acid group such as alcoholate (—O ⁻ ) can be mentioned. This compound can be obtained as a commercial product. For example, it is produced 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 (7) is a quaternary ammonium salt derived from a substituted pyridine represented by picoline or the like, and R ¹⁹ is an alkyl group or aryl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms. Or a combination thereof, and examples thereof include a methyl group, an octyl group, a lauryl group, and a benzyl group. R ²⁰ is an alkyl group having 1 to 18 carbon atoms, an aryl group, or a combination thereof. For example, in the case of quaternary ammonium derived from picoline, R ¹⁹ is a methyl group. The anion (Y ⁻ ) is a halogen ion such as chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), iodine ion (I ⁻ ), carboxylate (—COO ⁻ ), sulfonate (—SO ₃ ⁻ ), An acid group such as alcoholate (—O ⁻ ) can be mentioned. This compound can also be obtained as a commercial product. For example, a substituted pyridine such as picoline is reacted with an alkyl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride or benzyl bromide, or an aryl halide. Can be manufactured. Examples of this compound include N-benzylpicolinium chloride, N-benzylpicolinium bromide, N-laurylpicolinium chloride and the like.

The compound of the above formula (8) is a tertiary ammonium salt derived from an amine, p is an integer of 2 to 11, and q is an integer of 2 to 3. Anions (Y ⁻ ) are halogen ions such as chlorine ions (Cl ⁻ ), bromine ions (Br ⁻ ) and iodine ions (I ⁻ ), carboxylates (—COO ⁻ ), sulfonates (—SO ₃ ⁻ ). And acid groups such as alcoholate (—O ⁻ ). It can be produced by reacting an amine with a weak acid such as carboxylic acid or phenol. Examples of the carboxylic acid include formic acid and acetic acid. When formic acid is used, the anion (Y ⁻ ) is (HCOO ⁻ ), and when acetic acid is used, the anion (Y ⁻ ) is (CH ₃ COO). ^- ). When phenol is used, the anion (Y ⁻ ) is (C ₆ H ₅ O ⁻ ).

Compounds of formula ^{(9), R 21 R 22 R 23 R} 24 P + Y - is a quaternary phosphonium salt having the structure. R ²¹ , R ²² , R ²³ , and R ²⁴ are preferably a silane compound 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. Is a phenyl group or a substituted phenyl group among the four substituents of R ^{21 to} R ²⁴ , and examples thereof include a phenyl group and a tolyl group, and the remaining one has a carbon number of 1 to It is a silane compound bonded to a silicon atom by 18 alkyl groups, an aryl group, or a Si-C bond. Anions (Y ⁻ ) are halogen ions such as chlorine ions (Cl ⁻ ), bromine ions (Br ⁻ ) and iodine ions (I ⁻ ), carboxylates (—COO ⁻ ), sulfonates (—SO ₃ ⁻ ). And acid groups such as alcoholate (—O ⁻ ). This compound can be obtained as a commercial product, for example, halogenated tetraalkylphosphonium such as halogenated tetra n-butylphosphonium, halogenated tetra n-propyl phosphonium, or halogenated triethylbenzyl phosphor. Halogenated trialkylbenzylphosphonium, triphenylmethylphosphonium halide, triphenylmonoalkylphosphonium halide such as triphenylethylphosphonium halide, triphenylbenzylphosphonium halide, Examples include halogenated tetraphenylphosphonium, halogenated tolylyl monoarylphosphonium, or halogenated tolylyl monoalkylphosphonium (the halogen atom is a chlorine atom or a bromine atom). In particular, halogenated triphenylmonoalkylphosphonium such as triphenylmethylphosphonium halide, triphenylethylphosphonium halide, triphenylmonoarylphosphonium halide such as triphenylbenzylphosphonium halide , Tritolyl monoaryl phosphonium halides such as tritolyl monophenyl phosphonium halide, and tolyl monoalkyl phosphonium halides such as tolyl monomethyl phosphonium halide (halogen atom is chlorine or bromine atom) preferable.

The phosphines include methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, phenylphosphine and other first phosphine, dimethylphosphine, diethylphosphine, diisopropylphosphine, diisoamylphosphine, diphenylphosphine and other second phosphine. And tertiary phosphines such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine and dimethylphenylphosphine.
Compounds of formula (10) 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 alkyl groups having 1 to 18 carbon atoms, aryl groups, or a combination thereof, or a silane compound that is bonded to a silicon atom through a Si—C bond, and preferably R ^25. three of the three substituents to R ²⁷ is a phenyl group or substituted phenyl group, for example, it is possible to illustrate the phenyl group or tolyl group, and the remaining one substituent having 1 to 18 carbon atoms Or an alkyl group, an aryl group, or a combination thereof. Anions (Y ⁻ ) are halogen ions such as chlorine ions (Cl ⁻ ), bromine ions (Br ⁻ ) and iodine ions (I ⁻ ), carboxylates (—COO ⁻ ), sulfonates (—SO ₃ ⁻ ). And acid groups such as alcoholate (—O ⁻ ). This compound can be obtained as a commercial product. For example, a halogenated tetraalkylphosphonium such as tri-n-butylsulfonium halide and tri-n-propylsulfonium halide, and a trihalogenated halogen such as diethylbenzylsulfonium halide. Alkylbenzylsulfonium, halogenated diphenylmethylsulfonium, halogenated diphenylmonoalkylsulfonium such as diphenylethylsulfonium, halogenated triphenylsulfonium, (halogen atom is chlorine or bromine atom), tri-n-butylsulfonium carboxylate, tri Tetraalkylphosphonium carboxylates such as n-propylsulfonium carboxylate and trialkylbennes such as diethylbenzylsulfonium carboxylate Le sulfonium carboxylate, diphenylmethyl sulfonium carboxylate, diphenyl monoalkyl sulfonium carboxylates such as diphenylethyl sulfonium carboxylate, triphenylsulfonium carboxylate, triphenylsulfonium trifluoromethane sulfonate, and the like. Particularly, triphenylsulfonium halide and triphenylsulfonium carboxylate are preferable. These can be added as sulfonium compounds.

Examples of the metal chelate compound include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri-n-butoxy. Mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di-n -Propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetonate) ) Titanium, di-t-butoxy bis Acetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n-butoxy Tris (acetylacetonato) titanium, mono-sec-butoxytris (acetylacetonato) titanium, mono-t-butoxytris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy mono (ethyl) Acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri-sec Butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, di- i-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t-butoxy bis (ethyl acetoacetate) Acetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tris (Ethyl acetoacetate Tate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris (ethyl aceto) Acetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium, and other titanium chelate compounds; triethoxy mono (acetylacetonato) zirconium, tri- n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonato) zirconium, tri-s c-butoxy mono (acetylacetonato) zirconium, tri-t-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetonato) zirconium, Di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) zirconium, di-t-butoxy bis ( Acetylacetonato) zirconium, monoethoxy-tris (acetylacetonato) zirconium, mono-n-propoxy-tris (acetylacetonato) zirconium, mono-i-propoxy-tris (acetylacetonato) zirconi Mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t-butoxy-tris (acetylacetonato) zirconium, tetrakis (acetylacetonate) Zirconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl aceto) Acetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethylacetoa Cetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di-sec- Butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, mono -I-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirco , Mono-t-butoxy-tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) Zirconium chelate compounds such as zirconium and tris (acetylacetonato) mono (ethylacetoacetate) zirconium; Aluminum chelate compounds such as tris (acetylacetonato) aluminum and tris (ethylacetoacetate) aluminum;
Of these curing catalyst (C) components, benzyltrimethylammonium chloride or benzyltriethylammonium chloride is particularly preferable. These curing catalysts are selected because they are readily available, inexpensive, exhibit an effect when added in small amounts, and dissolve well in alcohol-based resist solvents.

The addition amount of the curing catalyst (C) 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 (C) is added for the purpose of controlling the alkali developability of the silicon compound (A), which is a completely 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 water (D) component is preferably ion exchange water. When general tap water is used, sodium ions, potassium ions, chlorine ions, etc. contained in tap water may be brought into the varnish, degrading the storage stability of the polysiloxane or impairing the uniform varnish quality. There is. The ratio of the water (D) component in the total solvent including water (D) and the solvent (F) needs to be 6% by mass to 18% by mass.

When the ratio of the component (D) in the total solvent is less than 6% by mass, storage stability may be impaired, and when it exceeds 18% by mass, applicability may be deteriorated. A preferred amount of the water (D) 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 (E) component is an acid that contains 1 to 2 carboxyl groups in the molecule, and can make the final film-forming composition (varnish) have a pH of 3 to 5.
The acid (E) can be added to the film-forming composition (varnish) in such an amount that the film-forming composition (varnish) is adjusted to pH 3 to 5.

Specific examples of component (E) 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 (E) is particularly preferably formic acid, acetic acid, propionic acid, oxalic acid, and maleic acid.

By adding the above component (D) and component (E) to the varnish, the storage stability of the film-forming composition (varnish) at 5 ° C. to 23 ° C. is drastically improved, and a good film is formed over a long period of time. Can be provided.
The film-forming composition contains a silicon compound (A), inorganic particles (B), a curing catalyst (C), water (D), an acid (E), and a solvent (F), but contains other components. May be.
In the present invention, as long as the effect of the present invention is not impaired, the component (A), the component (B), the component (C), the component (D), the component (E) and the component (F) other components, For example, components such as a leveling agent and a surfactant 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 octyl phenol ether, polyoxyethylene, and the like. Polyoxyethylene alkyl allyl ethers such as nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan trioleate Sorbitan fatty acid esters such as stearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as bitane monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, trade name EFTOP EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), trade names MegaFuck F171, F173, F-553, F-554, R-08, R-30, R-30-N (manufactured by Dainippon Ink & Chemicals, Inc.) ), Fluorads FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), trade names Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) Activator, and organosiloxane polymer-KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378 (manufactured by Big Chemie Japan Co., Ltd.) and the like can be mentioned. These surfactants may be used alone or in combination of two or more. When a surfactant is used, the proportion thereof is 0.0001-5 parts by mass, or 0.001-1 parts by mass, or 0.01-0.5 with respect to 100 parts by mass of the silicon compound (A). Part by mass.
In the method of mixing the other components, solvent, leveling agent or surfactant, the inorganic particles (B) and the curing catalyst (C), water (D), and acid (E) are added to the silicon compound (A). It may be simultaneous or after mixing of component (A) to component (E), and is not particularly limited.

<Formation of coating>
The film-forming composition of the present invention can be applied to a substrate and thermally cured to obtain a desired film. A known or well-known method can be adopted as the coating method. For example, spin coating method, dip method, flow coating method, ink jet method, spray method, bar coating method, gravure coating method, slit coating method, roll coating method, transfer printing method, brush coating, blade coating method, air knife coating method Etc. can be adopted. The base materials used in this case are silicon, indium tin oxide (ITO), indium zinc oxide (IZO), polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene (PE), ionomer (IO), polyimide (PI), polyamide (PA), polyvinyl chloride (PVC), polycycloolefin (PCO), polyvinylidene chloride (PVDC), polyvinyl alcohol (PVA), polypropylene (PP), polycarbonate (PC), polystyrene (PS) , Polyacrylonitrile (PAN), ethylene vinyl acetate copolymer (EVA), ethylene vinyl alcohol copolymer (EVOH), ethylene methacrylic acid copolymer (EMMA), polymethacrylic acid (PMMA), nylon, plastic, glass, S Dia, quartz, diamond, ceramics, aluminum gallium arsenide (AlGaAs), gallium arsenide phosphorus (GaAsP), indium gallium nitride (InGaN), gallium nitride (GaN), aluminum gallium nitride (AlGaN), gallium phosphide (GaP), selenium Examples thereof include a base material made of zinc halide (ZnSe), aluminum indium gallium phosphide (AlGaInP), zinc oxide (ZnO), or the like.

The heating device is not particularly limited, and may be heated in an appropriate atmosphere, that is, in an inert gas such as air or nitrogen, in a vacuum, or the like using, for example, a hot plate, an oven, or a furnace. Thereby, it is possible to obtain a film having a uniform film forming surface.
The heating temperature is not particularly limited for the purpose of evaporating the solvent, but can be performed at 40 to 200 ° C., for example. In these cases, the temperature may be changed in two or more steps for the purpose of expressing a higher uniform film forming property or allowing the reaction to proceed on the substrate.
The heating temperature and the heating time may be selected in accordance with the process steps of the target electronic device, and the heating conditions in which the physical property value of the polysiloxane film is compatible with the required characteristics of the electronic device can be selected.
Film formation including silicon compound (A) containing hydrolysis condensate (polysiloxane) of the present invention, inorganic particles (B), curing catalyst (C), water (D), acid (E) and solvent (F) In the composition, a film-forming composition (varnish) obtained by hybridizing these components is preferably a uniform dispersion.

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

The method for preparing the hybrid is not particularly limited as long as the stability of the final film-forming composition (varnish) can be obtained.
For example, (1) a silicon compound (A) containing a hydrolysis condensate (polysiloxane) is mixed with a dispersion (sol) of inorganic particles (B), a curing catalyst, water, and an acid in a solution state (varnish). (2) Various methods such as dispersion of inorganic particles (B) in a solution (in varnish) of a silicon compound (A) containing a hydrolysis condensate (polysiloxane), a curing catalyst, water, and an acid can be mentioned. From the viewpoint of handling properties, a silicon compound (A) containing a hydrolytic condensate (polysiloxane) is mixed with a dispersion catalyst (sol) of inorganic particles in a solution (varnish) and a curing catalyst, water, and acid. The method of making it preferable is.
The stability of the hybridized final film-forming composition (varnish) is a precipitation due to a decrease in dispersibility at a storage temperature of 5 ° C. or 23 ° C., and a significant change in the primary particle size or secondary particle size. It does not have to cause deterioration of properties, coloring (whitening, yellowing), deterioration of film quality, and deterioration of patterning characteristics.

The content of the inorganic particles in the composition may be within the range in which the dispersibility of the final film-forming composition (varnish) to be obtained is not impaired, and the intended refractive index, transmittance and heat resistance of the coating film to be produced It is possible to control according to sex.
Film formation containing silicon compound (A) containing hydrolysis condensate (polysiloxane) of the present invention, inorganic particles (B), curing catalyst (C), water (D), acid (E) and solvent (F) Composition (coating liquid) is stored under conditions that do not cause precipitation due to a decrease in dispersibility, significant change in primary particle size or secondary particle size, deterioration in coating properties, coloring (whitening, yellowing), and deterioration in film quality. If it is, it will not specifically limit. For example, it may be stored at 23 ° C. (room temperature storage), 5 ° C. (refrigerated storage) and −20 ° C. (refrigerated storage), and may be stored at −20 ° C. to 23 ° C.
In the present invention, the film-forming composition is coated on a substrate and heated, and is 1.50 to 1.90, 1.50 to 1.70, or 1.70 to 1.90 at a wavelength of 633 nm. The film has a refractive index and a hardness of H-9H, H-5H, or H-3H, as determined by JIS standard K5600.
<Pattern patterning method>
The film-forming composition itself of the present invention itself is not photosensitive, but has a pattern of 10 μm or less by using a photosensitive resist because it has solubility and developability in an alkaline solution. The reason for not imparting photosensitivity to the film-forming composition is that the photosensitizer added when the photosensitive material is used causes deterioration in light resistance.

The patterning method is completed by obtaining the following steps 1 to 9.
Step 1: Applying the film-forming composition to the substrate Step 2: Temporarily drying the film on the substrate Step 3: Applying the photosensitive resist onto the film-forming composition Step 4: Drying the photosensitive resist Step 5: Light irradiation through a mask from the top of the photosensitive resist 6: Alkali development step 7: Rinsing with pure water 8: Stripping the resist 9: Book the patterned film-forming composition The heating step 2 is a step of temporarily drying the film-forming composition, and is not particularly limited as long as heating is performed until the film-forming composition is not dissolved in the main solvent of the photosensitive resist in step 3, but it is 40 ° C. to 200 ° C. The heating may be performed at a temperature of 90 ° C. or 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. Etc. may be used.

Step 5 is a step of irradiating light through a mask, and a general exposure machine may be used. For example, aligner PLA-600FA (manufactured by Canon Inc.), i-line stepper NSR-2205i12D (manufactured by Nikon Corporation), or the like may be used.
Step 6 is a step of alkali development, and a common tetramethylammonium hydride (TMAH) aqueous solution may be used as the alkali developer. The concentration of TMAH may be 0.1% to 2.38%, 0.5% to 1.0%, or 1.0% to 2.0% by weight, and the development time is 10%. Second to 180 seconds, 20 seconds to 60 seconds, or 90 seconds to 120 seconds may be sufficient. The alkaline developer may be an inorganic base such as sodium carbonate, sodium hydroxide, or potassium hydroxide aqueous solution.
Step 8 is a step of stripping the resist, and any common resist solvent may be used. Examples thereof include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and ethyl pyruvate.
Step 9 is a step of subjecting the film-forming composition to main heating, which may be performed at 80 ° C. to 300 ° C., 100 ° C. to 150 ° C., 180 ° C. to 230 ° C., or 250 ° C. to 300 ° C.

Through the patterning method as described above, it is possible to perform patterning by having alkali developability even though the film forming composition is a non-photosensitive material.
The film made of the composition of the present invention thus obtained can satisfy a high refractive index, high transparency, high heat resistance, high light resistance, high hardness, and storage stability of varnish at a time. , Liquid crystal displays, 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.

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

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. In addition, each measuring apparatus used in the Example is as follows.
[GPC]
Equipment: HLC-8200 GPC manufactured by Tosoh Corporation
Column: Shodex KF-804L + KF-805L
Column temperature: 40 ° C
Solvent: Tetrahydrofuran (hereinafter THF)
Detector: UV (254 nm)
Calibration curve: Standard polystyrene [ 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, baked on a hot plate at 100 ° C. for 1 minute, and then heated at 200 ° C. for 5 minutes. The refractive index of the fired film was measured.
[Average particle size]
Device: N5 made by Beckman Coulter
The dispersion of the inorganic particles (B) was diluted with the same solvent as the dispersion medium, and the particle size (Unimodal mode, intensity average particle size) of the dynamic light scattering method was measured.

[Spin coat]
Equipment: Clean Electron ACT8 manufactured by Tokyo Electron Ltd.
〔exposure〕
Device: Nikon i-line stepper NSR-2205i12D
[Water contact angle]
Using the Drop Master series DM700 made by Kyowa Interface Science Co., Ltd., Droplet method (θ / 2) Method) to calculate the water contact angle.
(Optical microscope)
Equipment: ECLIPSE E600 POL made by Nikon
The optical microscope was observed at a magnification of 50 times.
〔electronic microscope〕
Apparatus: S-4800 manufactured by Hitachi High-Technologies Corporation

[Synthesis Example 1]
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 might be 6 mass percent in terms of solid residue at 140 ° C., and ¹ H-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 polysiloxane is obtained. The peak was 0.32, confirming that a large amount of Si—OH remained. Table 1 shows the mass average molecular weight and the proton number ratio according to ¹ H-NMR.

[Synthesis Example 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 mass average molecular weight of P2 and the proton number ratio according to ¹ H-NMR.

[Synthesis Example 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 mass average molecular weight of P3 and the proton number ratio by ¹ H-NMR.

[Synthesis Example 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 mass average molecular weight of P4 and the proton number ratio by ¹ H-NMR.

[Synthesis Example 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 mass average molecular weight of P5 and the proton number ratio by ¹ H-NMR.

[Synthesis Example 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 mass average molecular weight of P6 and the proton number ratio by ¹ H-NMR.

[Synthesis Example 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 mass average molecular weight of P7 and the proton number ratio by ¹ H-NMR.

[Synthesis Example 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 mass average molecular weight of P8 and the proton number ratio by ¹ H-NMR.
[Synthesis Example 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 mass average molecular weight of P9 and the proton number ratio by ¹ H-NMR.
[Synthesis Example 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 mass average molecular weight of P10 and the proton number ratio by ¹ H-NMR.

[Synthesis Example 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 mass average molecular weight of P11 and the proton number ratio by ¹ H-NMR.

[Synthesis Example 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 mass average molecular weight of P12 and the proton number ratio by ¹ H-NMR.

[Synthesis Example 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 mass average molecular weight of P13 and the proton number ratio by ¹ H-NMR.

[Synthesis Example 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 ¹ H-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 polysiloxane is obtained. The peak was 0.06, and it was confirmed that there was very little Si-OH.

[Synthesis Example 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 mass average molecular weight of P15 and the proton number ratio according to ¹ H-NMR.

[Table 1]
Table 1 Weight average molecular weight and proton number ratio by ¹ H-NMR ―――――――――――――――――――――――――――――――――――― ――――
Mass average molecular weight PGMEA proton ratio Silanol proton ratio
[Mw] [5.1 ppm] [6.0 ppm]
Synthesis Example 1 1541 1.00 0.32
Synthesis Example 2 1500 1.00 0.31
Synthesis Example 3 1537 1.00 0.30
Synthesis Example 4 1761 1.00 0.35
Synthesis Example 5 1520 1.00 0.31
Synthesis Example 6 735 1.00 0.31
Synthesis Example 7 3401 1.00 0.31
Synthesis Example 8 1531 1.00 0.30
Synthesis Example 9 1541 1.00 0.31
Synthesis Example 10 4545 1.00 0.33
Synthesis Example 11 1283 1.00 0.32
Synthesis Example 12 1585 1.00 0.31
Synthesis Example 13 1002 1.00 0.33
Synthesis Example 14 1520 1.00 0.06
Synthesis Example 15 1488 1.00 0.05
――――――――――――――――――――――――――――――――――――――――

[Reference Example 1]
Zirconia dispersion: Propylene glycol monomethyl ether dispersion (abbreviated as D1) containing 30.5% by mass of zirconia particles surface-treated with alkoxysilane (manufactured by Nissan Chemical Industries, Ltd.)
Table 2 shows each physical property value of the inorganic particle sol obtained in Reference Example 1.

[Table 2]
Table 2 Properties of inorganic particle sols ――――――――――――――――――――――――
Abbreviation D1
Particle type Zirconia
Average particle size (nm) 14
Particle refractive index 1.66
Solid content (wt%) 30.5
B-type viscosity (BL adapter) 4.3
(MPa · s, 20 ° C)
――――――――――――――――――――――――

<Production of film-forming composition and film>
[Example 1]
In a 20 mL eggplant-shaped flask, 3.0000 g of D1 obtained in Reference Example 1 was weighed, then 8.3058 g of propylene glycol monoethyl ether (abbreviated as PGEE) was added, and 2.2875 g of Synthesis Example 1 was obtained. P1 (solid content of polysiloxane is 35% by mass with respect to the solid content of D1), 0.0915 g of a solution prepared by diluting benzyl triethylammonium chloride (abbreviated as BTEAC) with PGEE as a curing catalyst (C) to 1% by mass 0.950 g of acetic acid diluted with PGEE to 1% by mass was added, and R-30-N manufactured by Dainippon Ink & Chemicals, Inc. as a surfactant was diluted with PGEE to 1% by mass. 0.1830 g of the solution was added, and 1.8458 g of ion-exchanged water (the ratio in the total solvent was 12% by mass) was added. Mixed until the total weight of solids to obtain a 7.5 wt% of varnish (abbreviated as V1).

Obtained V1 evaluated the refractive index. It spin-coated so that the film thickness of V1 might be set to 100 nm on a silicon substrate, and it heated at 150 degreeC for 1 minute using the hotplate. 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 2]
A varnish (abbreviated as V2) having a total solid content of 7.5 mass% was obtained in the same manner as in Example 1, except that P1 in Example 1 was replaced with P2 obtained in Synthesis Example 2.
The obtained V2 was 1.612 as a result of measuring the refractive index in the same manner as in Example 1.
[Example 3]
A varnish (abbreviated as V3) having a total solid content of 7.5% by mass was obtained in the same manner as in Example 1 except that P1 in Example 1 was replaced with P3 obtained in Synthesis Example 3.
V3 obtained was 1.608 as a result of measuring the refractive index in the same manner as in Example 1.
[Example 4]
A varnish (abbreviated as V4) having a total solid content of 7.5 mass% was obtained in the same manner as in Example 1 except that P1 in Example 1 was replaced with P4 obtained in Synthesis Example 4.

[Example 5]
A varnish (abbreviated as V5) having a total solid content of 7.5% by mass was obtained in the same manner as in Example 1 except that P1 in Example 1 was replaced with P5 obtained in Synthesis Example 5.
[Example 6]
A varnish (abbreviated as V6) having a total solid content of 7.5% by mass was obtained in the same manner as in Example 1 except that P1 in Example 1 was replaced with P6 obtained in Synthesis Example 6.
[Example 7]
A varnish (abbreviated as V7) having a total solid content of 7.5 mass% was obtained in the same manner as in Example 1 except that P1 in Example 1 was replaced with P9 obtained in Synthesis Example 9.

[Example 8]
In a 20 mL eggplant-shaped flask, weighed 3.0000 g of D1 obtained in Reference Example 1, then added 7.9932 g of PGEE, and 2.2875 g of P2 obtained in Synthesis Example 2 (based on the solid content of D1) 0.475 g of a solution of BTEAC diluted with PGEE to 1 mass% as a curing catalyst (C) was added as a curing catalyst (C), and 0.4575 g of acetic acid was diluted with PGEE to obtain 1 mass%. 9150 g 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 to 1% by mass was added, and 1.8512 g of ion-exchanged water (all solvents) The mixture was mixed until it was completely uniform at room temperature to obtain a varnish (abbreviated as V8) having a total solid content of 7.5% by mass.
[Example 9]
A varnish (abbreviated as V9) having a total solid content of 7.5% by mass was obtained in the same manner as in Example 1 except that BTEAC in Example 1 was changed to benzyltrimethylammonium chloride (abbreviated as BTMAC). .

[Example 10]
Weighing 3.0000 g of D1 obtained in Reference Example 1 into a 20 mL eggplant-shaped flask, then adding 8.2252 g of PGEE, and adding 2.2875 g of P2 obtained in Synthesis Example 2 (based on the solid content of D1) 0.130 g of a solution of BTEAC diluted with PGEE to 1 mass% as a curing catalyst (C) was added to 0.1830 g, and acetic acid was diluted with PGEE to obtain 1 mass%. 9150 g 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 1.8471 g of ion-exchanged water (all solvents) The mixture was mixed until it was completely uniform at room temperature to obtain a varnish (abbreviated as V10) having a total solid content of 7.5% by mass.

[Example 11]
In a 20 mL eggplant-shaped flask, weighed 3.0000 g of D1 obtained in Reference Example 1, then added 8.8409 g of PGEE, and 2.2875 g of P2 obtained in Synthesis Example 2 (based on the solid content of D1) 0.130 g of a solution of BTEAC diluted with PGEE to 1 mass% as a curing catalyst (C) was added to 0.1830 g, and acetic acid was diluted with PGEE to obtain 1 mass%. 9150 g 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 1.2314 g of ion-exchanged water (all solvents) The mixture was mixed until it was completely uniform at room temperature to obtain a varnish (abbreviated as V11) having a total solid content of 7.5% by mass.

[Example 12]
In a 20 mL eggplant-shaped flask, weighed 3.0000 g of D1 obtained in Reference Example 1, then added 7.6095 g of PGEE, and 2.2875 g of P2 obtained in Synthesis Example 2 (based on the solid content of D1) 0.130 g of a solution of BTEAC diluted with PGEE to 1 mass% as a curing catalyst (C) was added to 0.1830 g, and acetic acid was diluted with PGEE to obtain 1 mass%. 9150 g 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 2.4628 g of ion-exchanged water (all solvents) Was added until the mixture was completely uniform at room temperature to obtain a varnish (abbreviated as V12) having a total solid content of 7.5% by mass.

[Example 13]
In a 20 mL eggplant-shaped flask, weighed 3.0000 g of D1 obtained in Reference Example 1, then added 6.6121 g of PGEE, and obtained 2.2875 g of P2 obtained in Synthesis Example 2 (based on the solid content of D1). 1. A solid solution of polysiloxane of 35% by mass), 0.1830 g of BTEAC diluted to 1% by mass with PGEE as a curing catalyst (C) was added, and acetic acid was diluted to 1% by mass with PGEE. 7450 g 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 1.8742 g of ion-exchanged water (all solvents) The mixture was mixed until it was completely uniform at room temperature to obtain a varnish (abbreviated as V13) having a total solid content of 7.5% by mass.

[Example 14]
Weigh out 3.0000 g of D1 obtained in Reference Example 1 in a 20 mL eggplant-shaped flask, then add 7.4186 g of PGEE, and add 2.2875 g of P2 obtained in Synthesis Example 2 (based on the solid content of D1). And 0.1830 g of a solution of BTEAC diluted to 1% by mass with PGEE as a curing catalyst (C) and 0.183 g of formic acid diluted to 1% by mass with PGEE. 8300 g 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 1.8607 g of ion-exchanged water (all solvents) The mixture was mixed until it was completely uniform at room temperature to obtain a varnish (abbreviated as V14) having a total solid content of 7.5% by mass.

[Example 15]
In a 20 mL eggplant-shaped flask, weighed 3.0000 g of D1 obtained in Reference Example 1, and then added 4.9990 g of PGEE to obtain 2.2875 g of P2 obtained in Synthesis Example 2 (based on the solid content of D1). (Solid content of polysiloxane was 35% by mass), 0.1830 g of BTEAC diluted with PGEE to 1% by mass was added as a curing catalyst (C), and propionic acid was diluted with PGEE to 1% by mass. Solution 4 0.1830 g of a solution prepared by diluting R-30-N manufactured by Dainippon Ink & Chemicals, Inc. with PGEE to make 1% by mass as a surfactant, and further adding 1.90313 g of ion-exchanged water (total The proportion in the solvent was 12% by mass) and mixed until it was completely uniform at room temperature to obtain a varnish (abbreviated as V15) having a total solid content of 7.5% by mass.
[Example 16]
A varnish (abbreviated as V16) having a total solid content of 7.5% by mass was obtained in the same manner as in Example 10 except that acetic acid in Example 10 was replaced with oxalic acid.
[Example 17]
A varnish (abbreviated as V17) having a total solid content of 7.5% by mass was obtained in the same manner as in Example 10 except that the acetic acid in Example 10 was replaced with maleic acid.

[Example 18]
In a 20 mL eggplant-shaped flask, 3.0000 g of D1 obtained in Reference 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 (solid content of polysiloxane is 35% by mass with respect to the solid content of D1) obtained in the above, 0.0915 g of a solution prepared by diluting BTEAC with PGEE as a curing catalyst (C) to 1% by mass In addition, 0.9150 g of a solution of acetic acid diluted with PGEE to 1% by mass was added, and R-30-N manufactured by Dainippon Ink & Chemicals, Inc. as a surfactant was diluted to 1% by mass with PGEE. 0.1830 g is added, and further 1.8458 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. 5 wt% of varnish (abbreviated as V18) was obtained.

[Example 19]
In a 20 mL eggplant-shaped flask, 3.0000 g of D1 obtained in Reference Example 1 was weighed, then 5.1466 g of PGEE and 3.0785 g of PE were added, and 2.2875 g of P2 (D1 obtained in Synthesis Example 2) was added. The solid content of polysiloxane was 35% by mass), and 0.1830 g of BTEAC diluted with PGEE as a curing catalyst (C) to 1% by mass was added, and acetic acid was diluted with PGEE to 1 mass. 0.9150 g of a 1% by weight solution, 0.1830 g of a 1% by weight solution of R-30-N manufactured by Dainippon Ink & Chemicals, Inc. diluted with PGEE as a surfactant, and ion-exchanged water 1.8471 g (the ratio in the total solvent was 12% by mass) was added and mixed until it was completely uniform at room temperature to obtain a varnish (abbreviated as V19) having a total solid content of 7.5% by mass.

[Example 20]
In a 20 mL eggplant-shaped flask, 3.0000 g of D1 obtained in Reference Example 1 was weighed, then 2.8737 g of PGEE and 3.1237 g of PE were added, and 2.2875 g of P2 (D1 obtained in Synthesis Example 2) was added. The solid content of polysiloxane was 35% by mass), and 0.1830 g of BTEAC diluted with PGEE as a curing catalyst (C) to 1% by mass was added, and acetic acid was diluted with PGEE to 1 mass. % Solution 2.7450g was added, Dainippon Ink & Chemicals Co., Ltd. R-30-N was diluted with PGEE to add 0.1830g of 1% by mass, and ion-exchanged water. 2.4990 g (the ratio in the total solvent was 16% by mass) was added and mixed until it was completely uniform at room temperature to obtain a varnish (abbreviated as V20) having a total solid content of 7.5% by mass.

[Comparative Example 1]
In a 20 mL eggplant-shaped flask, weighed 3.0000 g of D1 obtained in Reference Example 1, then added 8.3865 g of PGEE, and obtained 2.2875 g of P1 obtained in Synthesis Example 1 (based on the solid content of D1). And a solid content of polysiloxane of 35% by mass), 0.9150 g of a solution obtained by diluting acetic acid with PGEE to 1% by mass, and adding R-30-N manufactured by Dainippon Ink & Chemicals, Inc. as a surfactant. 0.1830 g of a solution diluted to 1% by mass with PGEE was added, and 1.8444 g of ion-exchanged water (the ratio in the total solvent was 12% by mass) was added until mixing at room temperature until completely uniform. As an example in which 1 curing catalyst (C) was not added, a varnish (abbreviated as RV1) having a total solid content of 7.5% by mass was obtained.
[Comparative Example 2]
As an example in which P1 of Comparative Example 1 was replaced with P2 obtained in Synthesis Example 2 in the same manner as in Comparative Example 1 and the curing catalyst of Example 2 was not added, the total mass of solids was 7.5 mass. % Varnish (abbreviated as RV2).

[Comparative Example 3]
As an example in which P1 of Comparative Example 1 was replaced with P3 obtained in Synthesis Example 3 in the same manner as Comparative Example 1 and the curing catalyst of Example 3 was not added, the total mass of solids was 7.5 mass. % Varnish (abbreviated as RV3).
[Comparative Example 4]
As an example in which the curing catalyst of Example 4 was not added except that P1 of Comparative Example 1 was replaced with P4 obtained in Synthesis Example 4 and the curing catalyst of Example 4 was not added, the total mass of solids was 7.5 mass. % Varnish (abbreviated as RV4).
[Comparative Example 5]
As an example in which P1 of Comparative Example 1 was replaced with P5 obtained in Synthesis Example 5 in the same manner as in Comparative Example 1 and the curing catalyst of Example 5 was not added, the total mass of solids was 7.5 mass. % Varnish (abbreviated as RV5).

[Comparative Example 6]
To a 20 mL eggplant-shaped flask, weigh out 3.0000 g of D1 obtained in Reference Example 1, then add 10.1516 g of PGEE, and add 2.2875 g of P1 obtained in Synthesis Example 1 (based on the solid content of D1). 0.015 g of a polysiloxane having a solid content of 35% by mass), a benzyltriethylammonium chloride (abbreviated as BTEAC) as a curing catalyst (C) diluted to 1% by mass with PGEE was added, and acetic acid was diluted with PGEE. 0.9150 g of a 1% by mass solution was added, 0.1830 g of a 1% by mass solution of R-30-N manufactured by Dainippon Ink & Chemicals, Inc. as a surfactant was diluted with PGEE, and added at room temperature. As an example in which the ion-exchanged water of Example 1 was not added until mixing was complete, a varnish (abbreviated as RV6) having a total solid content of 7.5% by mass was obtained.
[Comparative Example 7]
As an example in which the same operation as in Comparative Example 6 was performed except that P1 in Comparative Example 6 was replaced with P2 obtained in Synthesis Example 2, and the ion exchange water of Example 2 was not added, the total mass of the solid content was 7.5. A mass% varnish (abbreviated as RV7) was obtained.
[Comparative Example 8]
As an example in which the same operation as in Comparative Example 6 was performed except that P1 in Comparative Example 6 was replaced with P3 obtained in Synthesis Example 3, and the ion exchange water of Example 3 was not added, the total mass of the solid content was 7.5. A mass% varnish (abbreviated as RV8) was obtained.

[Comparative Example 9]
As an example in which the same operation as in Comparative Example 6 was performed except that P1 in Comparative Example 6 was replaced with P4 obtained in Synthesis Example 4, and the ion exchange water of Example 4 was not added, the total mass of the solid content was 7.5. A mass% varnish (abbreviated as RV9) was obtained.
[Comparative Example 10]
As an example in which the same operation as in Comparative Example 6 was performed except that P1 of Comparative Example 6 was replaced with P5 obtained in Synthesis Example 5, and the ion exchange water of Example 5 was not added, the total mass of the solid content was 7.5. A mass% varnish (abbreviated as RV10) was obtained.
[Comparative Example 11]
In a 20 mL eggplant-shaped flask, weigh out 3.0000 g of D1 obtained in Reference Example 1, then add 9.1124 g of PGEE, and add 2.2875 g of P1 obtained in Synthesis Example 1 (based on the solid content of D1). The solid content of polysiloxane was 35% by mass), 0.0915 g of a BTEAC diluted with PGEE as a curing catalyst (C) to 1% by mass was added, and a surfactant was manufactured by Dainippon Ink & Chemicals, Inc. Add 0.1830 g of R-30-N diluted with PGEE to 1 mass%, add 1.8322 g of ion-exchanged water (the ratio in the total solvent is 12 mass%), and become completely uniform at room temperature. As an example in which the acid of Example 1 was not added, a varnish (abbreviated as RV11) having a total solid content of 7.5% by mass was obtained.

[Comparative Example 12]
As an example in which P1 of Comparative Example 11 was replaced with P2 obtained in Synthesis Example 2 in the same manner as in Comparative Example 11 and the acid of Example 2 was not added, the total solid content was 7.5% by mass. Varnish (abbreviated as RV12).
[Comparative Example 13]
As an example in which P1 of Comparative Example 11 was replaced with P3 obtained in Synthesis Example 3 in the same manner as in Comparative Example 11 and the acid of Example 3 was not added, the total solid content was 7.5% by mass. Varnish (abbreviated as RV13).
[Comparative Example 14]
As an example in which P1 of Comparative Example 11 was replaced with P4 obtained in Synthesis Example 4 in the same manner as in Comparative Example 11 and the acid of Example 4 was not added, the total solid content was 7.5% by mass. Varnish (abbreviated as RV14).
[Comparative Example 15]
As an example in which P1 of Comparative Example 11 was replaced with P5 obtained in Synthesis Example 5 in the same manner as in Comparative Example 11 and the acid of Example 5 was not added, the total solid content was 7.5% by mass. Varnish (abbreviated as RV15).

[Comparative Example 16]
A varnish (abbreviated as RV16) having a total solid mass of 7.5 mass% was obtained in the same manner as in Example 1 except that P1 in Example 1 was replaced with P7 obtained in Synthesis Example 7.
[Comparative Example 17]
A varnish (abbreviated as RV17) having a total solid content of 7.5% by mass was obtained in the same manner as in Example 1 except that P1 in Example 1 was replaced with P8 obtained in Synthesis Example 8.
[Comparative Example 18]
A varnish (abbreviated as RV18) having a total solid content of 7.5% by mass was obtained in the same manner as in Example 1 except that P1 in Example 1 was replaced with P10 obtained in Synthesis Example 10.
[Comparative Example 19]
A varnish (abbreviated as RV19) having a total solid content of 7.5% by mass was obtained in the same manner as in Example 1 except that P1 in Example 1 was replaced with P11 obtained in Synthesis Example 11.

[Comparative Example 20]
A varnish (abbreviated as RV20) having a total solid content of 7.5% by mass was obtained in the same manner as in Example 1 except that P1 in Example 1 was replaced with P12 obtained in Synthesis Example 12.
[Comparative Example 21]
A varnish (abbreviated as RV21) having a total solid content of 7.5% by mass was obtained in the same manner as in Example 1 except that P1 in Example 1 was replaced with P13 obtained in Synthesis Example 13.
[Comparative Example 22]
A varnish (abbreviated as RV22) having a total solid content of 7.5% by mass was obtained in the same manner as in Example 1 except that P1 in Example 1 was replaced with P14 obtained in Synthesis Example 14.
[Comparative Example 23]
Except that P1 of Example 1 was replaced with P15 obtained in Synthesis Example 15, the same operation as in Example 1 was performed to obtain a varnish (abbreviated as RV23) having a total solid content of 7.5% by mass.

[Comparative Example 24]
Weigh out 3.0000 g of D1 obtained in Reference Example 1 in a 20 mL eggplant-shaped flask, then add 6.6927 g of PGEE, and add 2.2875 g of P2 obtained in Synthesis Example 2 (based on the solid content of D1). 1. A solid content of polysiloxane of 35% by mass), 0.0915 g of a BTEAC diluted with PGEE to 1% by mass as a curing catalyst (C) was added, and 0.0915 g of nitric acid was diluted with PGEE to obtain 1% by mass. 7450 g 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 1.8729 g of ion-exchanged water (all solvents) The mixture was mixed until it was completely uniform at room temperature to obtain a varnish (abbreviated as RV24) having a total solid content of 7.5% by mass.
[Comparative Example 25]
Except that the nitric acid of Comparative Example 24 was replaced with sulfuric acid, the same operation as in Comparative Example 24 was performed to obtain a varnish (abbreviated as RV25) having a total solid content of 7.5% by mass.

[Comparative Example 26]
In a 20 mL eggplant-shaped flask, weighed 3.0000 g of D1 obtained in Reference Example 1, then added 9.1043 g of PGEE, and 2.2875 g of P2 obtained in Synthesis Example 2 (based on the solid content of D1) , A solid content of polysiloxane of 35% by mass), 0.0915 g of BTEAC diluted with PGEE to 1% by mass as a curing catalyst (C) was added, and acetic acid was diluted with PGEE to obtain 1% by mass. 0092 g 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 1.8324 g of ion-exchanged water (all solvents) The mixture was mixed until it was completely uniform at room temperature to obtain a varnish (abbreviated as RV26) having a total solid content of 7.5% by mass.

[Comparative Example 27]
In a 20 mL eggplant-shaped flask, weighed 3.0000 g of D1 obtained in Reference Example 1, then added 9.5363 g of PGEE, and added 2.2875 g of P2 obtained in Synthesis Example 2 (based on the solid content of D1). , A solid content of polysiloxane of 35% by mass), 0.0915 g of BTEAC diluted with PGEE to 1% by mass as a curing catalyst (C) was added, and acetic acid was diluted with PGEE to obtain 1% by mass. 9150 g 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 0.6153 g of ion-exchanged water (all solvents) Was added until the mixture was completely uniform at room temperature to obtain a varnish (abbreviated as RV27) having a total solid content of 7.5% by mass.

[Comparative Example 28]
Weigh out 3.0000 g of D1 obtained in Reference Example 1 in a 20 mL eggplant-shaped flask, then add 7.0753 g of PGEE, and add 2.2875 g of P2 obtained in Synthesis Example 2 (based on the solid content of D1). , A solid content of polysiloxane of 35% by mass), 0.0915 g of BTEAC diluted with PGEE to 1% by mass as a curing catalyst (C) was added, and acetic acid was diluted with PGEE to obtain 1% by mass. 9150 g 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 3.0763 g of ion-exchanged water (all solvents) The mixture was mixed until it was completely uniform at room temperature to obtain a varnish (abbreviated as RV28) having a total solid content of 7.5% by mass.
The compositions of V1 to V20 and RV1 to RV28 obtained in Examples 1 to 20 and Comparative Examples 1 to 28 are summarized in Tables 3 to 6. Each varnish was measured for pH with a digital pH meter, and the results are shown in Table 3.

Tables 3 to 6 are parameters relating to the present invention, weight average molecular weight, copolymerization ratio of (a1) and (a2) constituting the silicon compound (A), carbon number of L in (a2), curing catalyst The presence / absence and type of addition, the presence / absence and type of acid addition, the presence / absence of water addition, and the ratio (% by weight) of water to the total solvent.
In Tables 3 to 6, the types of acids are abbreviated as A1 for acetic acid, A2 for formic acid, A3 for propionic acid, A4 for oxalic acid, A5 for maleic acid, A6 for nitric acid, and A7 for sulfuric acid.

[Table 3]
Table 3 Compositions of V1 to V20 and RV1 to RV28 ――――――――――――――――――――――――――――――――――――――― -
Varnish Weight average (L) (a1) and (a2) Curing catalyst Curing catalyst name Copolymerization mole ratio of carbon number of molecular weight Existence type Example 1 V1 1541 3 70/30 Yes BTEAC
Example 2 V2 1500 4 70/30 Yes BTEAC
Example 3 V3 1537 6 70/30 Yes BTEAC
Example 4 V4 1761 4 90/10 Yes BTEAC
Example 5 V5 1520 4 50/50 Yes BTEAC
Example 6 V6 735 4 70/30 Yes BTEAC
Example 7 V7 1541 4 70/30 Yes BTEAC
Example 8 V8 1500 4 70/30 Yes BTEAC
Example 9 V9 1500 4 70/30 Yes BTEAC
Example 10 V10 1500 4 70/30 Yes BTEAC
Example 11 V11 1500 4 70/30 Yes BTEAC
Example 12 V12 1500 4 70/30 Yes BTEAC
Example 13 V13 1500 4 70/30 Yes BTEAC
Example 14 V14 1500 4 70/30 Yes BTEAC
Example 15 V15 1500 4 70/30 Yes BTEAC
Example 16 V16 1500 4 70/30 Yes BTEAC
Example 17 V17 1500 4 70/30 Yes BTEAC
Example 18 V18 1500 4 70/30 Yes BTEAC
Example 19 V19 1500 4 70/30 Yes BTEAC
Example 20 V20 1500 4 70/30 Yes BTEAC
――――――――――――――――――――――――――――――――――――――――

[Table 4]
Table 4 Composition of V1 to V20 and RV1 to RV28 ―――――――――――――――――――――――――――――――――
Acid addition acid water addition water ratio pH
Existence of type Existence of type (mass%) Example 1 Yes A1 Yes 12 4.2
Example 2 Yes A1 Yes 12 4.2
Example 3 Yes A1 Yes 12 4.2
Example 4 Yes A1 Yes 12 4.2
Example 5 Yes A1 Yes 12 4.2
Example 6 Yes A1 Yes 12 4.2
Example 7 Yes A1 Yes 12 4.2
Example 8 Yes A1 Yes 12 4.2
Example 9 Yes A1 Yes 12 4.2
Example 10 Yes A1 Yes 12 4.2
Example 11 present A1 present 8 4.3
Example 12 Yes A1 Yes 16 4.1
Example 13 Existence A1 Existence 12 4.0
Example 14 Existence A2 Existence 12 4.0
Example 15 Existence A3 Existence 12 4.0
Example 16 Existence A4 Existence 12 4.0
Example 17 Existence A5 Existence 12 4.0
Example 18 present A1 present 12 4.2
Example 19 Existence A1 Existence 12 4.2
Example 20 Existence A1 Existence 16 4.0
―――――――――――――――――――――――――――――――――

[Table 5]
Table 5 Composition of V1 to V20 and RV1 to RV28 ――――――――――――――――――――――――――――――――――――――― -
Varnish Weight average (L) (a1) and (a2) Curing catalyst Curing catalyst name Copolymerization molar ratio of carbon number of molecular weight Presence type comparison example 1 RV1 1541 3 70/30 None −
Comparative Example 2 RV2 1500 4 70/30 None −
Comparative Example 3 RV3 1537 6 70/30 None −
Comparative Example 4 RV4 1761 4 90/10 None −
Comparative Example 5 RV5 1520 4 50/50 None −
Comparative Example 6 RV6 1541 3 70/30 Yes BTEAC
Comparative Example 7 RV7 1500 4 70/30 Yes BTEAC
Comparative Example 8 RV8 1537 6 70/30 Yes BTEAC
Comparative Example 9 RV9 1761 4 90/10 Yes BTEAC
Comparative Example 10 RV10 1520 4 50/50 Yes BTEAC
Comparative Example 11 RV11 1541 3 70/30 Yes BTEAC
Comparative Example 12 RV12 1500 4 70/30 Yes BTEAC
Comparative Example 13 RV13 1537 6 70/30 Yes BTEAC
Comparative Example 14 RV14 1761 4 90/10 Yes BTEAC
Comparative Example 15 RV15 1520 4 50/50 Yes BTEAC
Comparative Example 16 RV16 3401 0 100/0 Yes BTEAC
Comparative Example 17 RV17 1531 4 40/60 Yes BTEAC
Comparative Example 18 RV18 4545 4 70/30 Yes BTEAC
Comparative Example 19 RV19 1283 1 70/30 Yes BTEAC
Comparative Example 20 RV20 1585 2 70/30 Yes BTEAC
Comparative Example 21 RV21 1002 8 70/30 Yes BTEAC
Comparative Example 22 RV22 1520 3 70/30 Yes BTEAC
Comparative Example 23 RV23 1488 4 70/30 Yes BTEAC
Comparative Example 24 RV24 1500 4 70/30 Yes BTEAC
Comparative Example 25 RV25 1500 4 70/30 Yes BTEAC
Comparative Example 26 RV26 1500 4 70/30 Yes BTEAC
Comparative Example 27 RV27 1500 4 70/30 Yes BTEAC
Comparative Example 28 RV28 1500 4 70/30 Yes BTEAC
――――――――――――――――――――――――――――――――――――――――

[Table 6]
Table 6 Composition of V1 to V20 and RV1 to RV28 ―――――――――――――――――――――――――――――――――
Acid addition acid water addition water ratio pH
Existence type Existence type (mass%) value comparison example 1 Yes A1 Yes 12 4.2
Comparative Example 2 Yes A1 Yes 12 4.2
Comparative Example 3 Yes A1 Yes 12 4.2
Comparative Example 4 Yes A1 Yes 12 4.2
Comparative Example 5 Yes A1 Yes 12 4.2
Comparative Example 6 Yes A1 No 0 5.5
Comparative Example 7 Yes A1 No 0 5.5
Comparative Example 8 Yes A1 No 0 5.5
Comparative Example 9 Yes A1 No 0 5.5
Comparative Example 10 Yes A1 No 0 5.5
Comparative Example 11 No-Yes 12 6.8
Comparative Example 12 No-Yes 12 6.8
Comparative Example 13 No-Yes 12 6.8
Comparative Example 14 No-Yes 12 6.8
Comparative Example 15 No-Yes 12 6.8
Comparative Example 16 Yes A1 Yes 12 4.3
Comparative Example 17 Yes A1 Yes 12 4.3
Comparative Example 18 Yes A1 Yes 12 4.3
Comparative Example 19 Yes A1 Yes 12 4.3
Comparative Example 20 Yes A1 Yes 12 4.3
Comparative Example 21 Yes A1 Yes 12 4.3
Comparative Example 22 Yes A1 Yes 12 4.3
Comparative Example 23 Yes A1 Yes 12 4.3
Comparative Example 24 Yes A6 Yes 12 1.2
Comparative Example 25 Yes A7 Yes 12 1.2
Comparative Example 26 Yes A1 Yes 12 5.6
Comparative Example 27 Yes A1 Yes 4 4.5
Comparative Example 28 Yes A1 Yes 20 4.1
―――――――――――――――――――――――――――――――――

<Storage stability test of varnish>
[Aging test]
The varnishes of V1 to V20 and RV1 to RV28 obtained in Examples 1 to 20 and Comparative Examples 1 to 28 were prepared and then subjected to an aging test in an oven having a temperature of 40 ° C. and a relative humidity of 50%. went. 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. Tables 7 to 8 show.

<Preparation of coating>
[Patterning characteristics]
The obtained V1 to V20 and RV1 to RV28 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, an exposure amount of 300 mJ / cm ² was irradiated through a mask using an i-line stepper NSR-2205i12D manufactured by Nikon Corporation. After light irradiation, development was performed for 30 seconds using 2.38% 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 7 to 8 show the results of V1 to V20 and RV1 to RV28. Moreover, the observation results of V1 to V3, V10, V14 to V17, and RV1 to RV3 are shown in FIGS.
Further, in FIGS. 1 to 8, 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. 1 is 5.04 μm, the width of the space portion of FIG. 2 is 5.02 μm, the width of the space portion of FIG. 3 is 5.02 μm, and the width of the space portion of FIG. 5 is 5.01 μm, the width of the Space portion of FIG. 6 is 5.01 μm, the width of the Space portion of FIG. 7 is 5.01 μm, and the width of the Space portion of FIG. 8 is 5.01 μm. 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 V1 to V20 and RV1 to RV28 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.
The obtained film was made from Kyowa Interface Science Co., Ltd. fully automatic contact angle meter Drop Master series DM700. The water contact angle was calculated by the method (θ / 2 method). The results are shown in Tables 7 to 8.

[Table 7]
Table 7 Aging test and patterning of V1 to V20 and RV1 to RV28
Characteristic test results and water contact angle of the coating ――――――――――――――――――――――――――――――――――――――――
Varnish aging test Patterning Water contact angle
Front / rear characteristics [°]
Example 1 V1 ○ / ○ ○ 70.5
Example 2 V2 ○ / ○ ○ 70.8
Example 3 V3 ○ / ○ ○ 71.5
Example 4 V4 ○ / ○ ○ 67.5
Example 5 V5 ○ / ○ ○ 77.7
Example 6 V6 ○ / ○ ○ 70.4
Example 7 V7 ○ / ○ ○ 70.0
Example 8 V8 ○ / ○ ○ 70.1
Example 9 V9 ○ / ○ ○ 70.2
Example 10 V10 ○ / ○ ○ 70.8
Example 11 V11 ○ / ○ ○ 70.9
Example 12 V12 ○ / ○ ○ 70.5
Example 13 V13 ○ / ○ ○ 70.3
Example 14 V14 ○ / ○ ○ 70.3
Example 15 V15 ○ / ○ ○ 70.4
Example 16 V16 ○ / ○ ○ 70.2
Example 17 V17 ○ / ○ ○ 70.2
Example 18 V18 ○ / ○ ○ 71.1
Example 19 V19 ○ / ○ ○ 71.1
Example 20 V20 ○ / ○ ○ 70.9
――――――――――――――――――――――――――――――――――――――――

[Table 8]
Table 8 Aging test and patterning of V1 to V20 and RV1 to RV28
Characteristic test results and water contact angle of the coating ――――――――――――――――――――――――――――――――――――――――
Varnish aging test Patterning Water contact angle
Front / rear characteristics [°]
Comparative Example 1 RV1 ○ / ○ × 70.1
Comparative Example 2 RV2 ○ / ○ × 70.3
Comparative Example 3 RV3 ○ / ○ × 70.9
Comparative Example 4 RV4 ○ / ○ × 69.6
Comparative Example 5 RV5 ○ / ○ × 69.9
Comparative Example 6 RV6 ○ / ○ × 70.6
Comparative Example 7 RV7 ○ / ○ × 71.1
Comparative Example 8 RV8 ○ / ○ × 71.4
Comparative Example 9 RV9 ○ / ○ × 70.4
Comparative Example 10 RV10 ○ / ○ × 70.6
Comparative Example 11 RV11 ○ / × × 70.5
Comparative Example 12 RV12 ○ / × × 71.1
Comparative Example 13 RV13 ○ / × × 71.3
Comparative Example 14 RV14 ○ / ×× 70.3
Comparative Example 15 RV15 ○ / × × 70.5
Comparative Example 16 RV16 ○ / × × 52.1
Comparative Example 17 RV17 ○ / ○ × 82.4
Comparative Example 18 RV18 ○ / ○ × 71.0
Comparative Example 19 RV19 ○ / ○ × 63.2
Comparative Example 20 RV20 ○ / ○ × 54.2
Comparative Example 21 RV21 ○ / × ○ 86.9
Comparative Example 22 RV22 ○ / ○ ○ 74.1
Comparative Example 23 RV23 ○ / ○ ○ 76.7
Comparative Example 24 RV24 ○ / × × 70.1
Comparative Example 25 RV25 ○ / ×× 70.2
Comparative Example 26 RV26 ○ / × ○ 70.3
Comparative Example 27 RV27 ○ / ○ × 70.5
Comparative Example 28 RV28 ○ / ○ × 70.5
――――――――――――――――――――――――――――――――――――――――
In Tables 3 to 8, the varnish foreign matter before and after the aging of V1 to V20 and RV1 and RV28 and the patterning characteristics of the coating are compared.

  The varnishes of V1 to V20 have a weight average molecular weight in the range of 700 to 4000, (a1) constituting the silicon compound (A) is 90 mol% to 50 mol%, and (a2) is 10 mol% to 50 mol%. And L in (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 refractive index of 1.50 to 2.70. The varnish comprising inorganic particles (B), curing catalyst (C), water (D), acid (E), and solvent (F) has a ratio of water (D) in the total solvent of 6 to 18% by weight. When the pH of the varnish was controlled to 3 to 5, no foreign matter was generated in the varnish before and after aging, and no foreign matter was expressed on the resulting film.

  On the other hand, Comparative Examples 1 to 5 are examples in which the curing catalyst (C) was omitted, but when the patterning characteristics were evaluated, the film was too dissolved in the alkaline developer, and a pattern could not be obtained. From this result, it was revealed that the curing catalyst (C) is an essential component.

  Comparative Examples 6 to 10 are examples in which water (D) was removed. However, when the patterning characteristics were evaluated, the film was not dissolved in the alkaline developer, and a pattern could not be obtained. Water (D) is an essential component for expressing silanol of the silicon compound (A) in the varnish to enhance and stabilize the curability when heated, and to appropriately express the hydrogen ion concentration of the acid (E). It became clear that there was.

  Comparative Examples 11 to 15 are examples in which the acid (E) 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 (E) is an essential component.

  Comparative Example 16, Comparative Example 19 and Comparative Example 20 are examples in which L in (a2) is an alkyl group having 0 to 2 carbon atoms. When the patterning characteristics are evaluated, the film is peeled and developed with respect to an alkaline developer. Could not get the pattern. This is presumably because the condensation progressed too much and did not exhibit dissolution developability with respect to the alkaline developer. Further, Comparative Example 21 is an example in which L in (a2) is an alkyl group having 8 carbon atoms. However, when the patterning characteristics were evaluated, the film was not dissolved in the alkaline developer, and a pattern could not be obtained. From these results, it became clear that L in (a2) is composed of a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms. Further, when L in (a2) is composed of a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, the water contact angle of the resulting coating is in the range of 60 ° to 80 °. 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 Comparative Example 17, (a1) constituting the silicon compound (A) is 90 mol% to 50 mol%, (a2) is not a polymer copolymerized at 10 mol% to 50 mol%, (a1) is 40 mol%, ( Although a2) is an example using a polymer copolymerized by 60 mol%, when the patterning characteristics were evaluated, the film was not dissolved in the alkaline developer, and a pattern could not be obtained. From this result, the copolymerization ratio of (a1) and (a2) is important, and in the example using the polymer in which (a1) of Example 5 was copolymerized by 50 mol% and (a2) was 50 mol%, alkali solubility was obtained. From the expression, it has become clear that there is an optimum value for the copolymerization ratio of (a1) and (a2).

  Comparative Example 18 is an example using a polymer having a weight average molecular weight of 4545. However, when the patterning characteristics were evaluated, the film was peeled and developed with respect to 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.

  Comparative Example 22 and Comparative Example 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.

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

  Comparative Example 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 Comparative Example 26, foreign matter was generated after aging. This result also revealed that the pH of the varnish has an optimum value.

Comparative Example 27 and Comparative Example 28 are examples in which the amount of water (D) added is 4% and 20%. In Comparative Example 27, foreign matter was generated after aging, and in Comparative Example 28, striation occurred when 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 (D) added.
[Light resistance test]
[Examples 21 to 22 and Comparative Examples 29 to 30]
The obtained V1 to V2 and RV22 to RV23 were evaluated for light resistance.
V1 to V2 and RV22 to RV23 were spin-coated on a silicon substrate to a film thickness of 100 nm, and baked at 150 ° C. for 60 minutes using a hot plate. 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 9.
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. The average transmittance was calculated from 400 nm to 800 nm.

In the light resistance test, light irradiation was performed at the Japan Weathering Test Center, and a xenon arc lamp having an illuminance of 38.7 W / m ² and an exposure wavelength of 320 nm to 400 nm was used as a light source. The testing machine used was SX75-AP type manufactured by Suga Test Instruments Co., Ltd. The test environment was a temperature of 42 ± 3 ° C. and a relative humidity of 50 ± 5% RH.

[Table 9]
Table 9 Light resistance test of fully hydrolyzed and partially hydrolyzed polymers ―――――――――――――――――――――――――――――――――― ――――――
Varnish Film thickness [nm] Refractive index [Wavelength 450nm] Average transmittance [%]
Before test → After test Before test → After test Before test → After test Example 21 V1 100 → 100 1.614 → 1.614 98 → 98
Example 22 V2 100 → 100 1.610 → 1.610 98 → 98
Comparative Example 29 RV22 100 → 91 1.609 → 1.639 98 → 93
Comparative Example 30 RV23 100 → 92 1.608 → 1.640 98 → 94
――――――――――――――――――――――――――――――――――――――――
The light resistances of Examples 21 to 22 and Comparative Examples 29 to 30 are compared. Example 21 to Example 22 and Comparative Example 29 to Comparative Example 30 were good with no patterning characteristics and no foreign matter after aging, but Comparative Examples 29 to 30 had a reduced film thickness after the light resistance test, It was found that the refractive index increased and the average transmittance decreased. On the other hand, in Example 21 to Example 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 V1 to V2 polymers are completely hydrolyzed, and the RV22 to RV23 polymers are only partially hydrolyzed. The copolymerization ratio of the monomers is the same and the weight average molecular weight is the same. Since it is a polymer, it shows that a dominant difference is 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.

In summary of the above results, the hydrolyzable silane of the present invention can be used in order to achieve all of the high refractive index, heat resistant refractive index, patterning characteristics, light resistance, and varnish stability after aging required for LED materials. A silicon compound (A) having a weight average molecular weight of 700 to 4000 obtained by hydrolysis and condensation in a non-alcohol solvent, inorganic particles having 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 B), a curing catalyst (C), water (D), an acid (E), and a solvent (F).

A silicon compound (A) having a weight average molecular weight of 700 to 4000 obtained by hydrolyzing and condensing the hydrolyzable silane of the present invention in a non-alcohol solvent, an average particle diameter of 1 to 100 nm, and 1.50 to 2.70. The film-forming composition containing inorganic particles (B) having a refractive index of, a curing catalyst (C), water (D), an acid (E), and a solvent (F) has photosensitivity because it has alkali developability. Patterning of 10 μm or less is possible using a conductive resist. Since a process such as dry etching is not performed, the process is simplified and the production cost can be reduced. Further, since the storage stability of the varnish is good, the varnish can be used stably over a long period of time.
The film obtained by the present invention can satisfy high refractive index, high transparency, high heat resistance, and high light resistance at a time, and can be patterned, so that it can be used for liquid crystal displays, plasma displays, cathode displays. It can be suitably used as an electronic device such as a tube, 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 (14)

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

(Wherein R ¹ and R ² each represents an alkoxy group, an acyloxy group, or a halogen group, and L represents a linear, branched, or cyclic alkyl group having 3 to 6 carbon atoms). A silicon compound (A) having a weight average molecular weight of 700 to 4000 obtained by hydrolysis and condensation in a non-alcohol solvent, an inorganic particle having an average particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70 ( B), a film-forming composition comprising a curing catalyst (C), water (D), acid (E), and solvent (F),
When the silicon compound (A) is hydrolyzable silane (a1) and hydrolyzable silane (a2), the hydrolyzable silane (a1) is 90 mol% to 50 mol%. ) Is a polymer obtained by hydrolyzing and condensing a hydrolyzable silane containing 10 mol% to 50 mol%,
Water (D) is contained in a ratio of 6 to 18% by weight in the total solvent including water (D) and solvent (F),
The film wherein the acid (E) has 1 to 2 carboxyl groups in the molecule, and the acid is added so that the pH of the film-forming composition is adjusted in the range of 3 to 5. Forming composition. The film-forming composition according to claim 1, wherein the non-alcohol solvent is a ketone or an ether. The film-forming composition according to claim 1, wherein the non-alcohol solvent is acetone or tetrahydrofuran. The solvent (D) contains a solvent obtained by removing the non-alcohol solvent used in the hydrolysis and condensation of the silane and a reaction product generated by hydrolysis of the hydrolyzable silane and replacing the solvent. The film-forming composition according to any one of the above. The film-forming composition according to any one of claims 1 to 4, wherein the inorganic particles (B) are zirconia. The film-forming composition according to any one of claims 1 to 5, wherein the curing catalyst (C) is an ammonium salt, a phosphine, a phosphonium salt, a sulfonium salt, or a chelate compound. The film-forming composition according to any one of claims 1 to 6, wherein the acid (E) is formic acid, acetic acid, propionic acid, oxalic acid, or maleic acid. A hydrolyzable silane containing hydrolyzable silane (a1) and hydrolyzable silane (a2) is hydrolyzed in a non-alcohol solvent (f1), 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 (f2) by a dynamic light scattering method;
The varnish of the silicon compound (A), the sol of the inorganic particles (B), the curing catalyst (C), water (D), and the acid (E) are mixed, and the silicon compound (A), the inorganic particles (B), and the curing catalyst ( A film-forming composition according to any one of claims 1 to 7, comprising a step of obtaining a film-forming composition comprising C), water (D), acid (E) and solvent (F). Production method. The pattern formation method which apply | coats a photosensitive resist on the film | membrane obtained from the film formation composition described in any one of Claims 1 thru | or 7, drys, light irradiation, image development, and resist peeling. A cured film obtained by coating the film-forming composition according to any one of claims 1 to 7 on a substrate and heating. The film according to claim 10, wherein a contact angle of water on the film surface is 60 ° to 80 °. The film according to claim 10 or 11, which is used as a light extraction film or a protective film. The apparatus which has an electronic device which has a film | membrane of any one of Claim 10 thru | or 12. The apparatus of claim 13, wherein the electronic device is an LED.