JP6044792B2 - Composition for forming low refractive index film - Google Patents

Description

  The present invention relates to a film-forming composition, and more particularly to a film-forming composition containing polysiloxane and inorganic fine particles.

  Display devices such as liquid crystal displays, plasma displays, cathode ray tubes, organic light emitting displays, and electronic paper have been developed.

  These are used as televisions, digital signage, mobile phones, personal digital assistants, notebook computers, and are widely used for consumer use.

  Scenes using various displays are diversifying, and devices that use touch-panel input methods are becoming mainstream. Of these tidal currents, devices that are used outdoors, in particular, have poor anti-glare properties due to the reflection of external light such as sunlight and indoor lighting. It has been demanded.

  There is a method of obtaining the antireflection function by controlling the optical refractive index. This can be achieved by selecting a member having a low refractive index as a member constituting the device.

  Various developments of low refractive index materials have been studied. For example, a fluorinated alkylsilane is applied to the surface of a substrate (Patent Document 1), and a polymer containing fluorine (Patent Document 2) is proposed. . These have achieved low refractive index by introducing fluorine, but it is difficult to make the refractive index 1.30 or less at a wavelength of 633 nm.

  On the other hand, a method for reducing the refractive index by putting air having a refractive index of 1.0 into the film (Patent Document 3) and a method for decreasing the refractive index by making the center of the inorganic particles hollow (Patent Document 4) are proposed. Has been.

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

When inorganic particles are added, the film hardness may decrease. Polysiloxane has a high film hardness but does not exhibit a low refractive index. From these backgrounds, a method of combining inorganic particles and polysiloxane to obtain a low refractive index material is known as a known technique.
The polymer structure of polysiloxane varies depending on the method of synthesis, but polysiloxane is known which has been completely hydrolyzed by changing the hydrolysis solvent to a specific solvent (Patent Document 5). There has been no study of using a combination of inorganic particles and fully hydrolyzed polysiloxane as a low refractive index material.
As a method for producing inorganic particles used for the low refractive index material, a method using hydrolysis of alkoxide is known (Patent Documents 6 to 8). And the method by ion exchange of water glass is known (patent documents 9 thru / or 10). A technique for controlling the particle shape by such a method is disclosed.

JP 61-40845 A JP 2005-264064 A JP 2010-1000077 A JP 2006-291077 A Japanese Patent Laid-Open No. 62-174273 JP-A-63-74911 Japanese Patent Laid-Open No. 11-60232 JP 7-48117 A JP-A-1-317115 Japanese Patent Laid-Open No. 7-118008

  The present invention has been made in view of such circumstances, and has a low refractive index and is suitable for production of a film for a display device that can achieve high transparency, high heat resistance, high light resistance, and high hardness. It aims at providing the composition for film formation.

（式中Ｒ^１はアルコキシ基、アシルオキシ基、又はハロゲン基を示す。）で表される加水分解性シランの加水分解縮合物である第１観点に記載の膜形成用組成物、
第３観点として、式（１）で表される加水分解性シランがテトラエトキシシラン、又はテトラメトキシシランである第２観点に記載の膜形成用組成物、
第４観点として、非アルコール溶剤がケトン又はエーテルである第１観点乃至第３観点のいずれか一つに記載の膜形成用組成物、
第５観点として、非アルコール溶剤がアセトン又はテトラヒドロフランである第１観点乃至第３観点のいずれか一つに記載の膜形成用組成物、
第６観点として、溶剤（Ｃ）が上記加水分解性シランの加水分解縮合の際に用いる非アルコール溶剤と、該加水分解性シランの加水分解によって生じた反応物を除去するための溶剤置換用溶剤を含むものである第１観点乃至第５観点のいずれか一つに記載の膜形成用組成物、
第７観点として、無機粒子（Ｂ）が１．１５乃至１．５０の屈折率を有する粒子である第１観点乃至第６観点のいずれか一つに記載の膜形成用組成物、
第８観点として、無機粒子（Ｂ）が、ＢＥＴ法による比表面積から計算される平均粒子径（粒子径Ａ）が５乃至６０ｎｍであり、動的光散乱法による分散粒子径（粒子径Ｂ）が５０乃至２５０ｎｍであり、そして粒子径Ｂ／粒子径Ａが１．１以上の無機粒子（Ｂ−１）である第１観点乃至第７観点のいずれか一つに記載の膜形成用組成物、
第９観点として、無機粒子（Ｂ）が、外殻と内部とを有し、該内部が多孔質又は空洞であり、平均粒子径が１５乃至１００ｎｍである無機粒子（Ｂ−２）である第１観点乃至第７観点のいずれか一つに記載の膜形成用組成物、
第１０観点として、加水分解性シランを非アルコール溶剤中で加水分解し縮合して得られた重量平均分子量１０００乃至２００００のケイ素化合物（Ａ）が、溶剤（Ｃ）に溶解したケイ素化合物（Ａ）のワニスを得る工程と、１乃至１００ｎｍの平均粒子径を有する無機粒子（Ｂ）を含む分散媒（Ｃ’）のゾルと上記ケイ素化合物（Ａ）のワニスを混合する工程とを含む第１観点乃至第９観点のいずれか一つに記載の膜形成用組成物の製造方法、
第１１観点として、無機粒子（Ｂ）がＢＥＴ法による比表面積から計算される１乃至１００ｎｍの平均粒子径と１．１５乃至１．５０の屈折率を有する無機粒子である第１０観点に記載の製造方法、
第１２観点として、第１観点乃至第９観点のいずれか一つに記載の膜形成用組成物を基板上に被覆し焼成して得られ、波長６３３ｎｍで１．１５乃至１．３０の屈折率と、ＪＩＳ規格Ｋ５６００によって定められた鉛筆硬度がＨ乃至９Ｈの硬度を有する被膜、
第１３観点として、第１観点乃至第９観点のいずれか一つに記載の膜形成用組成物を基板上に被覆し焼成する工程を含む第１２観点に記載の被膜の形成方法、
第１４観点として、第１観点乃至第９観点のいずれか一つに記載の膜形成用組成物から得られた反射防止膜、
第１５観点として、第１観点乃至第９観点のいずれか一つに記載の膜形成用組成物を用いて得られた電子デバイスを有する装置、及び
第１６観点として、電子デバイスが液晶ディスプレイ、プラズマディスプレイ、カソードレイチューブ、有機発光ディスプレイ、電子ペーパー、光半導体（ＬＥＤ）、固体撮像素子、太陽電池、又は有機薄膜トランジスタである第１５観点に記載の装置である。The present invention provides, as a first aspect, a silicon compound (A) having a weight average molecular weight of 1000 to 20000 obtained by hydrolysis and condensation of a hydrolyzable silane in a non-alcohol solvent, and an inorganic material having an average particle diameter of 1 to 100 nm. A film-forming composition comprising particles (B) and a solvent (C);
As a second aspect, the silicon compound (A) is represented by the following formula (1):

(Wherein R ¹ represents an alkoxy group, an acyloxy group, or a halogen group) The film-forming composition according to the first aspect, which is a hydrolysis condensate of a hydrolyzable silane represented by:
As a third aspect, the film-forming composition according to the second aspect, wherein the hydrolyzable silane represented by the formula (1) is tetraethoxysilane or tetramethoxysilane,
As a fourth aspect, the film-forming composition according to any one of the first to third aspects, wherein the non-alcohol solvent is a ketone or an ether,
As a fifth aspect, the film-forming composition according to any one of the first to third aspects, wherein the non-alcohol solvent is acetone or tetrahydrofuran,
As a sixth aspect, the solvent (C) is a non-alcohol solvent used when hydrolyzing and condensing the hydrolyzable silane, and a solvent replacement solvent for removing a reaction product generated by hydrolysis of the hydrolyzable silane. A film-forming composition according to any one of the first to fifth aspects,
As a seventh aspect, the film forming composition according to any one of the first aspect to the sixth aspect, wherein the inorganic particles (B) are particles having a refractive index of 1.15 to 1.50,
As an eighth aspect, the inorganic particles (B) have an average particle size (particle size A) calculated from a specific surface area by the BET method of 5 to 60 nm, and a dispersed particle size (particle size B) by the dynamic light scattering method. The film forming composition according to any one of the first to seventh aspects, wherein the inorganic particle (B-1) has a particle diameter B / particle diameter A of 1.1 or more. ,
As a ninth aspect, the inorganic particles (B) are inorganic particles (B-2) having an outer shell and an interior, the interior being porous or hollow, and an average particle diameter of 15 to 100 nm. The film forming composition according to any one of the first aspect to the seventh aspect,
As a tenth aspect, a silicon compound (A) in which a silicon compound (A) having a weight average molecular weight of 1,000 to 20,000 obtained by hydrolysis and condensation of a hydrolyzable silane in a non-alcohol solvent is dissolved in the solvent (C). A first aspect including a step of obtaining a varnish of the above and a step of mixing a sol of a dispersion medium (C ′) containing inorganic particles (B) having an average particle diameter of 1 to 100 nm and a varnish of the silicon compound (A). Thru | or the manufacturing method of the film forming composition as described in any one of 9th viewpoints,
As an eleventh aspect, the inorganic particles (B) are inorganic particles having an average particle diameter of 1 to 100 nm and a refractive index of 1.15 to 1.50 calculated from the specific surface area by the BET method. Production method,
As a twelfth aspect, a film forming composition according to any one of the first to ninth aspects is coated on a substrate and fired, and a refractive index of 1.15 to 1.30 at a wavelength of 633 nm. A film having a pencil hardness of H to 9H defined by JIS standard K5600,
As a thirteenth aspect, the method for forming a film according to the twelfth aspect, including a step of coating and baking the film forming composition according to any one of the first aspect to the ninth aspect on a substrate,
As a fourteenth aspect, an antireflection film obtained from the film forming composition according to any one of the first aspect to the ninth aspect,
As a fifteenth aspect, an apparatus having an electronic device obtained by using the film forming composition according to any one of the first to ninth aspects, and as a sixteenth aspect, an electronic device is a liquid crystal display, plasma The device according to the fifteenth aspect, which is a display, a cathode ray tube, an organic light emitting display, electronic paper, an optical semiconductor (LED), a solid-state imaging device, a solar cell, or an organic thin film transistor.

The composition comprising the fully hydrolyzed polysiloxane of the present invention and silica fine particles having a dispersed particle size of 100 nm or less is a completely hydrolyzed polysiloxane having a high silanol reaction point of silanol on the surface of the silica fine particles having a low film hardness. Since it is thermally cured with siloxane, a film having a low refractive index and a high film hardness can be obtained. That is, the present invention provides a film-forming composition suitable for producing a film for a display device that has a low refractive index and can achieve high transparency, high heat resistance, high light resistance, and high hardness.
Therefore, the film obtained by the present invention can satisfy low refractive index, high transparency, high heat resistance, high light resistance, and high hardness at one time, and can be used for liquid crystal display, plasma display, cathode ray tube, organic light emission. It can be suitably used as an electronic device such as a display, electronic paper, an optical semiconductor (LED), a solid-state imaging device, a solar cell, and an organic thin film transistor.

It shows a ¹ H-NMR spectrum of the P1 It shows a ¹ H-NMR spectrum of P2 The figure which shows the light transmittance after the 200 degreeC heat resistant test of V1 for 5 minutes The figure which shows the light transmittance after the heat resistance test of 250 degreeC for 5 minutes of V1 The figure which shows the light transmittance after 300 degreeC 5 minute heat resistance test of V1 The figure which shows the light transmittance after the 200 degreeC 5-minute heat resistance test of V2. The figure which shows the light transmittance after the heat resistance test of 250 degreeC for 5 minutes of V2. The figure which shows the light transmittance after 300 degreeC 5 minute heat resistance test of V2. The figure which shows the light transmittance before the light resistance test of V1 The figure which shows the light transmittance after the light resistance test of V1 The figure which shows the light transmittance before the light resistance test of V2 The figure which shows the light transmittance after the light resistance test of V2 The figure which shows the light transmittance before the constant temperature and humidity test of V1 The figure which shows the light transmittance after the constant temperature and humidity test of V1 The figure which shows the light transmittance before the constant temperature and humidity test of V2. The figure which shows the light transmittance after the constant temperature and humidity test of V2.

  In general, in order to develop a low refractive index of 1.30 or less at a wavelength of 633 nm, it is necessary to reduce the number of portions that exhibit a refractive index of 1.30 or more in the polysiloxane. And, it is considered that the inorganic particles to be added are deformed to contribute to the reduction of the refractive index.

Further, when the completely hydrolyzed polysiloxane and the composition using the partially hydrolyzed polysiloxane are compared, the following characteristics are obtained.
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 polycondensation stage, the alcohol produced from the solvent alcohol or the monomer silane alkoxide reacts with the silanol group 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.
The silane alkoxide contained in the partially hydrolyzed polysiloxane shows an organic group such as carbon and is a part that increases the refractive index. On the other hand, since a fully hydrolyzed polysiloxane has a very low residual ratio of silane alkoxide, it has almost no portion that increases the refractive index such as carbon.
In addition, since the fully hydrolyzed polysiloxane contains a large amount of silanol, polycondensation can be initiated when heat is applied as an external stimulus to silanol on the surface of the silica fine particles, and a strong and high hardness film can be formed. . However, in the partially hydrolyzed polytheos, a large amount of silane alkoxide remains, so when it reacts with silanol of silica fine particles, it must go through hydrolysis once, and it is necessary to add an additive or the like separately. . In this case, examples of the additive include a silanol production accelerator and a silane alkoxide decomposition accelerator, but these additives contain organic groups and metals to increase the refractive index and are not suitable for the composition of the present invention. is there.

In addition, for inorganic particles, the ratio of the average particle size (particle size A) calculated from the specific surface area by the BET method to the dispersed particle size (particle size B) by the dynamic light scattering method is determined by deforming the inorganic particles. It is considered to be one of the scales shown. By comparing the ratio of the particle diameter A calculated as being spherical with the particle diameter B in the actual liquid, the degree of irregularity of the inorganic particles is estimated. It is considered that as the ratio of (particle diameter B) / (particle diameter A) increases, the irregular shape of the inorganic particles proceeds and the voids in the resulting coating increase.
The inorganic particles (B) have an average particle size (particle size A) calculated from a specific surface area by the BET method of 5 to 60 nm, and a dispersed particle size (particle size B) by the dynamic light scattering method of 50 to 250 nm. By introducing inorganic particles having a particle diameter B / particle diameter A of 1.1 or more, a small air layer (refractive index 1.00) is introduced into the resulting film, thereby reducing the refractive index. Can be achieved.

  In view of the above points, the present invention is calculated from a silicon compound (A) having a weight average molecular weight of 1,000 to 20,000 obtained by hydrolysis and condensation of a hydrolyzable silane in a non-alcohol solvent, and a specific surface area by the BET method. A film-forming composition comprising inorganic particles (B) having an average particle diameter of 1 to 100 nm and a solvent (C).

The solid content concentration of the film-forming coating solution 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, 1 to 30% by mass, or 5 The concentration range may be 20 to 20% by mass. The solid content is the remaining ratio after the solvent is removed from the film-forming composition.
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 50 parts by mass, preferably 0.1 to 30 parts by mass. In order to maintain the film quality and obtain a stable low refractive index, the amount is more preferably 1 to 20 parts by mass.

The silicon compound (A) used in the present invention is a hydrolysis condensate of a hydrolyzable silane represented by the formula (1). This hydrolysis-condensation product may contain a hydrolysis product.
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. . Most of the silicon compound (A) is a hydrolysis condensate (polysiloxane), but may have a hydrolyzate that is a precursor thereof.

R ¹ in Formula (1) represents 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 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 -N-propoxy group, 1-ethyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n-propoxy group and the like can be mentioned.

  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-hexyl Rubonyloxy 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, 2,3-dimethyl-n-butylcarbonyloxy group, 3,3-dimethyl-n-butylcarbonyloxy group, 1-ethyl-n-butylcarbonyloxy group, 2-ethyl-n-butylcarbonyloxy group, 1, 1,2-trimethyl-n-propylcarbonyloxy group, 1,2,2-trimethyl-n-propylcarbonyloxy group, -Ethyl-1-methyl-n-propylcarbonyloxy group, 1-ethyl-2-methyl-n-propylcarbonyloxy group, phenylcarbonyloxy group, tosylcarbonyloxy group, and the like, but are not limited thereto. It is not a thing.

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

Examples of the hydrolyzable silane represented by the above formula (1) are shown below.
Examples include tetramethoxysilane, tetraacetoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraacetoxysilane, tetrachlorosilane, and the like. However, the present invention 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.

The silicon compound (A) containing the hydrolysis condensate obtained by hydrolyzing and condensing the water-decomposable silane represented by the formula (1) can be a condensate having a weight average molecular weight of 1000 to 20000, or 1000 to 5000. . These molecular weights are molecular weights obtained in terms of polystyrene by GPC analysis.

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, and 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 2 to 3.5 moles of water are used.

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, the amount of hydrochloric acid is generally 0.0001 to 0.5 mol with respect to 1 mol of all hydrolyzable groups (total alkoxy groups) of the hydrolyzable silane. The heating in this method can be performed at a liquid temperature of 50 to 180 ° C., and 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.

  Non-alcohol solvents used for hydrolysis and condensation include, for example, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, methyl Aliphatic hydrocarbon solvents such as cyclohexane; aromatics such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, isopropyl benzene, diethyl benzene, isobutyl benzene, triethyl benzene, di-isopropyl benzene, trimethyl benzene, etc. Group hydrocarbon solvents: acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-pen Ketone ketone solvents such as ethyl 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 ether, Examples thereof include ether solvents such as 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, and the hydrolyzate is subjected to a condensation reaction to obtain a hydrolyzed condensate (polysiloxane). The condensate is dissolved in the hydrolyzed solvent. Obtained as a siloxane 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 a solvent component 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 (C) used for diluting or replacing the varnish of the silicon compound (A) containing the hydrolysis condensate (polysiloxane) may be the same as the non-alcohol solvent used for hydrolysis and condensation polymerization of the hydrolyzable silane. Good or another solvent may be used. And the solvent in the varnish of the silicon compound (A) containing a hydrolysis-condensation product (polysiloxane) can be said solvent (C).
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 (C) include toluene, p-xylene, o-xylene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, ethylene glycol monoethyl. Ether, ethylene glycol monoisopropyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether Diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol, 1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol, 1-methoxy- 2-butanol, cyclohexanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyl Lactone, acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, methyl 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 solvent which is the component (C) of the present invention is preferably a non-alcohol solvent similar to the solvent from which the component (A) was obtained, but is not particularly limited as long as the storage stability of the coating liquid for film formation of the present invention is not significantly impaired. . The general organic solvent mentioned above can be used.

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

The silicon compound (A) 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 component (B) used in the present invention is inorganic particles (B) having an average particle diameter of 1 to 100 nm. The refractive index of the inorganic particles (B) is selected from the range of 1.15 to 1.50, 1.20 to 1.50, 1.30 to 1.50, or 1.30 to 1.45. Can do.

  The kind of inorganic particles constituting the composition of the present invention together with the above fully hydrolyzed polysiloxane is not particularly limited, but in the present invention, silicon oxide or a composite oxide containing silicon is particularly used. Is preferred.

  The inorganic particles may be used alone or in combination of two or more.

Specific examples of the oxide constituting the inorganic particles include SiO ₂ and composite oxides containing SiO ₂ . This composite oxide is a mixture of two or more inorganic oxides at 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 other oxides.
As the component (B) used in the present invention, inorganic particles (B-1) having an average particle diameter of 1 to 100 nm, 5 to 100 nm, or 5 to 60 nm calculated from the specific surface area by the BET method can be used.
The component (B) used in the present invention has an average particle diameter calculated from a specific surface area by the BET method of 1 to 100 nm, 5 to 100 nm, or 5 to 60 nm, and a refractive index of 1.15 to 1. .50 inorganic particles (B-1) can be used.
The inorganic particles (B) have an average particle size (particle size A) calculated from a specific surface area by the BET method of 5 to 60 nm, a dispersed particle size (particle size B) by the dynamic light scattering method of 50 to 250 nm, The inorganic particle (B-1) whose diameter B / particle diameter A is 1.1 or more can be mentioned.

As the particle size of the inorganic particles (B-1), the average particle size (particle size A) calculated from the specific surface area by the BET method is 5 to 60 nm, and the dispersed particle size (particle size B) by the dynamic light scattering method. Is preferably 50 to 250 nm.
The relationship between the particle diameter A and the particle diameter B is such that the particle diameter B / particle diameter A is 1.1 or more, for example 1.1 to 50.0, or 1.1 to 20.0, or 1.1 to 10.0. Or 1.1 to 5.0, or 1.4 to 20.0, or 1.4 to 10.0, or 1.4 to 5.0.
As for the particle diameter, fine particles having different average particle diameters or dispersed particle diameters may be mixed and used.

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

  An organic solvent sol in which a dispersion medium of a water sol in which inorganic particles are dispersed in an aqueous medium is substituted from water to an organic solvent can be used. This dispersion medium (C ′) is combined with the solvent (C) used for diluting or replacing the varnish of the silicon compound (A) containing the hydrolysis condensate (polysiloxane) and used in the present invention. It can be.

  Therefore, the same dispersion medium (C ′) as the solvent (C) can be used.

Furthermore, particles obtained by surface treatment of inorganic particles with silicon oxide, organosilicon compounds, organometallic compounds, or the like may be used.
The treatment with silicon oxide is a method in which a silicon oxide substance is grown on a particle surface in a dispersion containing inorganic particles by a known method. The treatment with an organosilicon compound or an organometallic compound means that these compounds are added to a dispersion containing inorganic particles, and these compounds or reaction products of these compounds are adsorbed or bonded to the surface of the inorganic particles. Is.
Examples of the organosilicon compound include silane coupling agents and silanes. Specific examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and 2- (3,4-epoxycyclohexyl). ) Ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethylditriethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyl Dimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (A Noethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyltriethoxysilane, 3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-chloropropyltri Examples include methoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, and 3-isocyanatopropyltriethoxysilane.
Specific examples of silane include methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, methyltriethoxysilane, dimethyldisilane. Ethoxysilane phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, hexamethyldisilazane, etc. It is done.

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

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

  The metal oxide colloidal particles used for the inorganic particles (B-1) can be produced by a known method, for example, an ion exchange method, a peptization method, a hydrolysis method, or a reaction method.

  Examples of the ion exchange method include a method in which the metal salt is treated with an ion exchange resin to remove counter ions and generate particles.

  Peptides include neutralization of the metal salt with an acid or base, hydrolysis of the metal alkoxide, or precipitation obtained by hydrolysis of 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.

  Further, in the present invention, inorganic particles (B-2) having an outer shell and an inside, the inside being porous or hollow, and an average particle diameter of 15 to 100 nm can be used. Silica particles can be used as the inorganic particles (B-2).

  When using inorganic particles (particles having a hollow structure) having an outer shell and an interior and porous or hollow inside as the inorganic particles (B-2), the production method thereof is, for example, an alkaline composite inorganic oxide or its After forming an aqueous solution of particles, elements other than silicon are removed to form cavities inside the particles, and then a silica coating layer is formed on the fine particles by adding a silicic acid solution. The refractive index of the inorganic particles (B-2) can be in the range of 1.15 to 1.50.

  The composite inorganic oxide has a molar ratio of (inorganic oxide other than silica) / (silica) in the range of 0.2 to 1.2, or 0.3 to 1.0. ) / (Silica) molar ratio can be adjusted to a range of 0.1 to 10 to form a solution of a composite inorganic oxide or particles thereof. An alkaline solution having a pH of 10.0 or more can be used. Examples of inorganic oxides other than silica include aluminum oxide, titanium oxide, boron oxide, zirconium oxide, and antimony oxide.

  Part or all of elements other than silicon are removed from the alkaline solution of the composite inorganic oxide or particles thereof. This removal includes dissolution removal by addition of an acid and cation exchange removal. The particles after removal are performed until the molar ratio of (inorganic compound other than silica) / (silica) is in the range of 0.0001 to 0.1. The silica particles formed in this way have cavities inside. The silica coating layer can also be formed by adding an alkaline aqueous solution and an acidic silicic acid solution obtained by dealkalizing an alkali metal silicate hydrolyzate or alkali metal silicate to the fine particle dispersion. As a result of observation with an electron microscope, a film (outer shell) of about 6 to 10 nm is formed on this silica coating layer. Silica particles having a hollow structure (hollow particles) have an average particle diameter of 15 to 100 nm as observed with an electron microscope and a refractive index of 1.15 to 1.50. This dispersion of hollow particles can be made into an organic solvent-dispersed sol by solvent substitution with the above-mentioned dispersion medium at a silica particle concentration of 0.1 to 60% by mass.

  The method for preparing the film forming composition for a display device and the coating liquid for forming a film of the present invention is not particularly limited. It suffices if the (A) component, (B) component, and (C) component are uniformly mixed. The order of mixing components (A) to (C) is not particularly limited as long as a uniform varnish can be obtained.

The solid content of the film-forming composition contains the silicon compound (A) and inorganic particles (B), but may contain other components.
In the present invention, in addition to the component (A), the component (B), and the component (C), other components such as a leveling agent and a surfactant are included as long as the effects of the present invention are not impaired. May be.

  Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene, and the like. Polyoxyethylene alkyl allyl ethers such as nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan trioleate Sorbitan fatty acid esters such as stearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as bitane monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, trade name EFTOP EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), trade names MegaFuck F171, F173, F-553, F-554, R-08, R-30, R-30-N (manufactured by Dainippon Ink & Chemicals, Inc.) ), Fluorads FC430, FC431 (manufactured by Sumitomo 3M Limited), trade names Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (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 ratio is 0.0001 to 5 parts by mass, or 0.001 to 1 part by mass, or 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the silicon compound (A). Part by mass.

  The method of mixing the other components, the solvent, the leveling agent or the surfactant described above may be performed simultaneously with the addition of the inorganic particles (B) and the solvent (C) to the silicon compound (A). ) It may be after mixing and is not particularly limited.

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

  The firing 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 firing temperature and firing time may be selected in accordance with the process steps of the target electronic device, and the firing conditions in which the physical property values of the polysiloxane film are adapted to the required characteristics of the electronic device can be selected.

  The film-forming composition containing the silicon compound (A) containing the hydrolysis condensate (polysiloxane) of the present invention, the inorganic particles (B) and the solvent (C) has a uniform varnish formed by hybridizing these components. A dispersion is preferred.

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

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

  For example, (1) a silicon compound (A) containing a hydrolysis condensate (polysiloxane) is mixed with a dispersion of silica particles (silica sol) in a solution state (varnish), and (2) a hydrolysis condensate (polysiloxane). Various methods such as dispersion of silica fine particles in a solution (in varnish) of the silicon compound (A) containing a hydrolytic condensate (polysiloxane) from the viewpoint of handling properties are included. A method in which A) is mixed with a dispersion of inorganic particles (silica sol) in a solution (varnish) state is preferable.

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

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

  Storage of the film-forming composition (coating liquid) containing the silicon compound (A) containing the hydrolysis condensate (polysiloxane) of the present invention, the inorganic particles (B), and the solvent (C) is due to a decrease in dispersibility. The storage conditions are not particularly limited as long as they do not cause precipitation, a significant change in the primary particle size or the secondary particle size, deterioration in applicability, coloring (whitening, yellowing), and film quality. For example, it may be stored at 23 ° C. (room temperature storage), 5 ° C. (refrigerated storage), and −20 ° C. (frozen storage). In order to prevent silanols from reacting in the varnish state, −20 ° C. (refrigerated storage). It is preferable to store in

  The film obtained from the film-forming composition (coating solution) of the present invention has a pencil hardness defined by JIS K5600 of H or higher. Pencil hardness is as high as 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, 6B, 6B or less. It is written. Pencil hardness is one of the required performances required for a coating when a device is manufactured. If the device is easily scratched by external scratches, a device defect is generated. Therefore, a film hardness of H or higher is required. There are many cases.

  In the present invention, the film-forming composition is coated on a substrate and baked. The refractive index of 1.15 to 1.30, or 1.20 to 1.30 at a wavelength of 633 nm, and JIS standard K5600 The film has a pencil hardness of H to 9H, H to 5H, or H to 3H.

  The film made of the composition of the present invention thus obtained can satisfy a low refractive index, high transparency, high heat resistance, high light resistance, and high hardness at the same time. , Cathode ray tubes, organic light emitting displays, electronic paper, optical semiconductors (LEDs), solid-state imaging devices, solar cells, organic thin film transistors, and other electronic devices.

  More specifically, it can be suitably used as an antireflective substrate and antireflective film for televisions, digital signage, mobile phones, personal digital assistants, notebook computers 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 [pencil hardness]
Apparatus: No. made by Yasuda Seiki Co., Ltd. 553-M Electric pencil scratch hardness tester Standard: JIS K 5600
[Ultraviolet visible spectrophotometer]
Apparatus: SHIMADSU UV-3600 manufactured by Shimadzu Corporation
[Refractive index of coating / Ellipsometer]
Apparatus: Multi-angle-of-incidence spectroscopic ellipsometer VASE manufactured by JA Woollam Japan.
Measured at a wavelength of 633 nm.
[Average particle size]
Device: Monochrome manufactured by Quantachrome
After drying the inorganic particles at 300 ° C., the specific surface area of the powder obtained by pulverizing the obtained gel with a mortar was measured by the BET method. The average particle diameter of the silica particles was calculated by the following formula.
Average particle diameter (nm) = 2720 / specific surface area (m ² / g)
[Refractive index of particles]
Apparatus: Abago refractometer organic solvent manufactured by Atago Co., Ltd. Organic solvent: Solvent 1 (having a lower refractive index than particles), solvent 2 (having a higher refractive index than particles)
Solvents 1 and 2 are selected so that they can be mixed with each other.
Measurement method: After the inorganic particles were dried at 150 ° C., the powder pulverized in a mortar was immersed in the solvent 1, and then the solvent 2 was added little by little until the fine particles became almost transparent. The refractive index of this liquid was measured using an Abbe refractometer. The measurement was performed at 23 ° C. and D line = wavelength 589 nm. Depending on the refractive index, the solvent 1 and the solvent 2 may be solvents such as 1,1,1,3,3,3-hexafluoro-2-propanol, 2-propanol, chloroform, carbon tetrachloride, toluene, glycerin and the like. Can be mentioned.
[Dispersed particle size]
Device: N5 made by Beckman Coulter
The inorganic particle dispersion was diluted with the same solvent as the dispersion medium, and the particle size (Unimodal mode, intensity average particle size) of the dynamic light scattering method was measured.

[Synthesis Example 1]
35.14 g of tetraethoxysilane and 52.71 g of acetone were placed in a 300 ml flask, and 12.16 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixed solution while stirring the mixed solution with a magnetic stirrer. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C., and reacted for 240 minutes under heating and reflux. Thereafter, the reaction solution is cooled to room temperature, 70.00 g of propylene glycol monomethyl ether acetate 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 hydrolyzed condensate. (Polymer) A propylene glycol monomethyl ether acetate (abbreviated as 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 P1). The weight average molecular weight of the obtained P1 by GPC was Mw2800 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. The result is shown in FIG.

  From the result of FIG. 1, when the peak of 5.1 ppm attributed to the proton of PGMEA as a solvent is set to 1.00, the peak near 6.0 ppm attributed to silanol (Si—OH) of polysiloxane is found. It was 0.32, and it was confirmed that much Si-OH remained. In addition, since the peak attributed to ethanol appearing at 3.7 ppm was extremely small, it was found that Si—OH of polytheos was stably present without being capped by ethanol as an alcohol.

[Synthesis Example 2]
35.14 g of tetraethoxysilane and 52.71 g of ethanol were placed in a 300 ml flask, and 12.16 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixed solution while stirring the mixed solution with a magnetic stirrer. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C., and reacted for 240 minutes under heating and reflux. Thereafter, the reaction solution is cooled to room temperature, 70.00 g of PGMEA is added to the reaction solution, ethanol as a solvent, ethanol, water and hydrochloric acid as reaction by-products are distilled off under reduced pressure, and concentrated to a hydrolysis-condensation product ( Polymer) PGMEA solution was obtained. 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 partially hydrolyzed polysiloxane (abbreviated as P2). The weight average molecular weight of the obtained P2 by GPC was Mw 4000 in terms of polystyrene.
PGMEA varnish of P2 was added with PGMEA so as to be 6 mass percent in terms of solid residue at 140 ° C., and ¹ H-NMR was measured. The result is shown in FIG.

  From the result of FIG. 2, when the peak of 5.1 ppm attributed to the proton of PGMEA as a solvent is set to 1.00, the peak near 6.0 ppm attributed to silanol (Si—OH) of polysiloxane is found. It was 0.09, and it was confirmed that there was very little Si-OH. In addition, a peak attributed to ethanol appearing at 3.7 ppm was confirmed sharply, suggesting that Si—OH of polytheos was capped by ethanol, which is an alcohol.

[Synthesis Example 3]
Silica sol dispersed in PGME after dehydration and solvent substitution with a rotary evaporator while adding propylene glycol monomethyl ether (abbreviated as PGME) under reduced pressure of 100 to 200 Torr to a silica-water dispersion sol by hydrolyzing methyl orthosilicate S1) was obtained.

[Synthesis Example 4]
A silica-sol (S2) dispersed in PGME was obtained by replacing the water-dispersed sol of silica particles obtained by hydrolysis of methyl orthosilicate having different average particle diameters and dispersed particle diameters in the same manner as in S1.

[Synthesis Example 5]
A silica-sol (S3) dispersed in PGME was obtained by replacing the water-dispersed sol of silica particles obtained by hydrolysis of methyl orthosilicate having different average particle diameters and dispersed particle diameters with a solvent in the same manner as in S1.
Table 1 shows each physical property value of the inorganic particles (B-1) obtained in Synthesis Examples 3 to 5.

[Table 1]

[Synthesis Example 6] 10 g of silica sol (trade name: Snowtex ST-XS, manufactured by Nissan Chemical Industries, Ltd., SiO ₂ concentration 20% by mass) having an average particle size of 5 nm of inorganic particles (B-2) and 190 g of pure water The mixture was warmed to 80 ° C. The pH of this reaction mother liquor was 10.5, and 900 g of a 1.17 mass% sodium silicate aqueous solution as SiO ₂ and 900 g of a 0.83 mass% sodium aluminate aqueous solution as Al ₂ O ₃ were simultaneously added to the mother liquor. . Meanwhile, the temperature of the reaction solution was kept at 80 ° C. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO ₂ .Al ₂ O ₃ primary particle dispersion with a solid content concentration of 20% by mass. The pH of this reaction solution was 12.9. 170 g of pure water was added to 50 g of this primary particle dispersion and heated to 98 ° C., and while maintaining this temperature, 5,040 g of sodium sulfate having a concentration of 0.5% by mass was added, and then the SiO ₂ concentration was 1. A dispersion of complex oxide fine particles was obtained by adding 300 g of a 17% by weight aqueous sodium silicate solution and 900 g of a 0.5% by weight aqueous sodium aluminate solution as Al ₂ O ₃ . Next, 311 g of pure water was added to 138 g of the dispersion of composite oxide fine particles that had been washed with an ultrafiltration membrane to a solid content concentration of 13% by mass, and concentrated hydrochloric acid (concentration 35.5% by mass) was added dropwise to adjust the pH to 1. 0.0, and dealumination was performed. Next, the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 2.76 L of a hydrochloric acid aqueous solution of pH 3 and 1.38 L of pure water to obtain an aqueous dispersion of silica-based fine particles having a solid content concentration of 20% by mass. A mixture of 45 g of this aqueous dispersion, 15 g of pure water, 52.5 g of ethanol, and 18.8 g of 28% aqueous ammonia was heated to 35 ° C., and then 3.1 g of ethyl silicate (SiO ₂ concentration 28 mass%) was added. Addition to form a silica coating. Next, the dispersion medium is replaced with water using an ultrafiltration membrane, and the mixture is aged at 200 ° C. for 1 hour. The dispersion medium is replaced with 2-propanol again using an ultrafiltration membrane, and the solid content concentration is 20% by mass. A 2-propanol dispersion of silica-based fine particles (silica sol (S4)) was prepared. Silica sol (S4) had an average particle diameter of 46 nm and a refractive index of 1.28.

Preparation of film-forming composition and film [Example 1]
In a 20 mL eggplant-shaped flask, 14.0000 g of S1 obtained in Synthesis Example 3 was weighed, then 4.1256 g of propylene glycol monomethyl ether acetate (abbreviated as PGMEA) was added, and 1.5500 g of S1 obtained in Synthesis Example 1 was added. P1 (the solid content of polysiloxane is 10 parts by mass with respect to the solid content of S1), and BYK-307 manufactured by Big Chemie Japan Co., Ltd. as a surfactant is diluted with PGMEA to 0.1 mass%. 0.2170 g of the solution was added and mixed until it was completely uniform at room temperature to obtain a varnish (abbreviated as V1) having a total solid content of 12.0% by mass.

  The obtained V1 was spin-coated on a silicon substrate using a spin coater so as to have a film thickness of 500 nm, temporarily dried using a hot plate at 100 ° C. for 1 minute, and then fired at 200 ° C. for 5 minutes. To obtain a film. The film was measured for the refractive index of light having a wavelength of 633 nm using an ellipsometer, and the pencil hardness was measured using an electric pencil scratch hardness tester. The results are shown in Table 2.

[Example 2]
In a 20 mL eggplant-shaped flask, 14.0000 g of S1 obtained in Synthesis Example 3 was weighed, and then 3.91979 g of propylene glycol monomethyl ether acetate (abbreviated as PGMEA) was added, and 0.7750 g of Synthesis Example 1 obtained. P1 (the solid content of polysiloxane is 5 parts by mass with respect to the solid content of S1), and as a surfactant, BYK-307 manufactured by Big Chemie Japan Co., Ltd. is diluted with PGMEA and 0.1% by mass. 0.2170 g of the prepared solution was added and mixed until it was completely uniform at room temperature to obtain a varnish (abbreviated as V2) having a total solid content of 12.0% by mass.

  The obtained V2 was spin-coated on a silicon substrate using a spin coater so as to have a film thickness of 500 nm, temporarily dried using a hot plate at 100 ° C. for 1 minute, and then fired at 200 ° C. for 5 minutes. To obtain a film. The film was measured for refractive index at a wavelength of 633 nm using an ellipsometer, and pencil hardness was measured using an electric pencil scratch hardness tester. The results are shown in Table 2.

[Comparative Example 1]
A varnish (RV1) was obtained in the same manner as in Example 1 except that P1 in Example 1 was replaced with P2. RV1 was spin-coated and fired on a silicon substrate in the same manner as in Example 1, and the refractive index or pencil hardness was measured. The results are shown in Table 2.

[Comparative Example 2]
A varnish (RV2) was obtained in the same manner as in Example 2 except that P1 in Example 2 was replaced with P2. RV2 was spin-coated and fired on a silicon substrate in the same manner as in Example 2, and the refractive index or pencil hardness was measured. The results are shown in Table 2.

[Example 3]
A varnish (V3) was obtained in the same manner as in Example 1 except that S1 in Example 1 was replaced with S2 obtained in Synthesis Example 4. V3 was spin-coated and fired on a silicon substrate in the same manner as in Example 1, and the refractive index or pencil hardness was measured. The results are shown in Table 2.

[Example 4]
A varnish (V4) was obtained in the same manner as in Example 2 except that S1 in Example 2 was replaced with S2 obtained in Synthesis Example 4. V4 was spin-coated and fired on a silicon substrate in the same manner as in Example 2, and the refractive index or pencil hardness was measured. The results are shown in Table 2.

[Example 5]
A varnish (V5) was obtained in the same manner as in Example 1 except that S1 in Example 1 was replaced with S3 obtained in Synthesis Example 5. V5 was spin-coated and fired on a silicon substrate in the same manner as in Example 1, and the refractive index or pencil hardness was measured. The results are shown in Table 2.

[Example 6]
A varnish (V6) was obtained in the same manner as in Example 2 except that S1 in Example 2 was replaced with S3 obtained in Synthesis Example 5. V6 was spin-coated and fired on a silicon substrate in the same manner as in Example 2, and the refractive index or pencil hardness was measured. The results are shown in Table 2.

[Example 7]
In a 20 mL eggplant-shaped flask, 7.0000 g of S1 obtained in Synthesis Example 3 was weighed, 7.0000 g of S2 obtained in Synthesis Example 4 was added, and then 4.1256 g of propylene glycol monomethyl ether acetate (PGMEA and Abbreviation), and 1.5500 g of P1 obtained in Synthesis Example 1 (the solid content of polysiloxane is 10 parts by mass with respect to the total solid content of S1 and S2), and as a surfactant, Big Chemie Japan ( Co., Ltd. BYK-307 diluted with PGMEA to add 0.2170 g of 0.1% by mass, mixed until completely uniform at room temperature, varnish with a total solid content of 12.0% by mass (Abbreviated as V7).

  The obtained V7 was spin-coated on a silicon substrate using a spin coater so as to have a film thickness of 500 nm, temporarily dried using a hot plate at 100 ° C. for 1 minute, and then fired at 200 ° C. for 5 minutes. To obtain a film. The film was measured for refractive index at a wavelength of 633 nm using an ellipsometer, and pencil hardness was measured using an electric pencil scratch hardness tester. The results are shown in Table 2.

[Example 8]
A varnish (V8) was obtained in the same manner as in Example 7 except that S1 in Example 7 was replaced with S3 obtained in Synthesis Example 5. V8 was spin-coated and baked on a silicon substrate in the same manner as in Example 7, and the refractive index or pencil hardness was measured. The results are shown in Table 2.

[Example 9]
A varnish (V9) was obtained in the same manner as in Example 7 except that S2 in Example 7 was replaced with S3 obtained in Synthesis Example 5. V9 was spin-coated and fired on a silicon substrate in the same manner as in Example 7, and the refractive index or pencil hardness was measured. The results are shown in Table 2.

[Comparative Example 3]
In a 20 mL eggplant-shaped flask, 15.0000 g of S1 obtained in Synthesis Example 3 was weighed, then 4.1444 g of propylene glycol monomethyl ether acetate (abbreviated as PGMEA) was added, and as a surfactant, Big Chemie Japan Co., Ltd. ) BYK-307 made by PGMEA was added with 0.2325 g of 0.1% by mass and mixed until it was completely uniform at room temperature. The varnish (total mass of 12.0% by mass) (Abbreviated as RV3).

  The obtained RV3 was spin-coated on a silicon substrate using a spin coater so as to have a film thickness of 500 nm, temporarily dried using a hot plate at 100 ° C. for 1 minute, and then fired at 200 ° C. for 5 minutes. To obtain a film. The film was measured for refractive index at a wavelength of 633 nm using an ellipsometer, and pencil hardness was measured using an electric pencil scratch hardness tester. The results are shown in Table 2.

[Comparative Example 4]
A varnish (RV4) was obtained in the same manner as in Comparative Example 3 except that S1 in Comparative Example 3 was replaced with S2 obtained in Synthesis Example 4. RV4 was spin-coated and fired on a silicon substrate in the same manner as in Comparative Example 3, and the refractive index or pencil hardness was measured. The results are shown in Table 2.

[Comparative Example 5]
A varnish (RV5) was obtained in the same manner as in Comparative Example 3 except that S1 in Comparative Example 3 was replaced with S3 obtained in Synthesis Example 5. In the same manner as in Comparative Example 3, RV5 was spin-coated and baked on a silicon substrate, and the refractive index or pencil hardness was measured. The results are shown in Table 2.

[Comparative Example 6]
In a 20 mL eggplant-shaped flask, 17.0000 g of P1 obtained in Synthesis Example 1 was weighed, then 2.5973 g of propylene glycol monomethyl ether acetate (abbreviated as PGMEA) was added, and as a surfactant, Big Chemie Japan Co., Ltd. ) Manufactured by BYK-307 with PGMEA and added to 0.2380 g of 0.1% by mass, mixed at room temperature until completely uniform, varnish (total mass of 12.0% by mass) Abbreviated as RV6).

  The obtained RV6 was spin-coated on a silicon substrate using a spin coater so as to have a film thickness of 500 nm, temporarily dried using a hot plate at 100 ° C. for 1 minute, and then fired at 200 ° C. for 5 minutes. To obtain a film. The obtained coating film had cracks, and a uniform film forming surface could not be obtained. The film was measured for refractive index at a wavelength of 633 nm using an ellipsometer, and pencil hardness was measured using an electric pencil scratch hardness tester. The results are shown in Table 2.

[Comparative Example 7]
A varnish (RV7) was obtained in the same manner as in Comparative Example 6 except that P1 in Comparative Example 6 was replaced with P2 obtained in Synthesis Example 2. RV7 was spin-coated and fired on a silicon substrate in the same manner as in Comparative Example 6, and the refractive index or pencil hardness was measured. The results are shown in Table 2.

[Example 10]
In a 20 mL eggplant-shaped flask, we weighed 5.4540 g of S-4 obtained in Synthesis Example 6, then added 3.6777 g of 2-propanol, and added 0.7791 g of P1 (S4 solids obtained in Synthesis Example 1). 10 parts by mass of the solid content of polysiloxane), and BYK-307 manufactured by Big Chemie Japan Co., Ltd. as a surfactant was diluted with PGMEA to give 0.1091 g of a solution of 0.1091 g. In addition, it was mixed until it became completely uniform at room temperature to obtain a varnish (abbreviated as V10) having a total solid content of 12.0% by mass.

  The obtained V10 was spin-coated on a silicon substrate using a spin coater so as to have a film thickness of 500 nm, temporarily dried using a hot plate at 100 ° C. for 1 minute, and then fired at 200 ° C. for 5 minutes. To obtain a film. The film was measured for the refractive index of light having a wavelength of 633 nm using an ellipsometer, and the pencil hardness was measured using an electric pencil scratch hardness tester. The results are shown in Table 2.

表２の結果から、Ｖ１の膜とＶ２の膜とを比較する。ポリシロキサンの含有量が多くなるにしたがって屈折率が高まり、鉛筆硬度による膜硬度が高いことが分かった。
Ｖ１乃至Ｖ２の膜とＲＶ１乃至ＲＶ２の膜とを比較する。ポリシロキサンの種類が完全加水分解型とした膜は、部分加水分解型を選択した場合の膜と比較して鉛筆硬度による膜硬度が高くなり、屈折率が低くなることがわかった。この結果は、部分加水分解型のポリシロキサンに残留するアルコキシ基の屈折率が高く発現することと、シリカ粒子表面のシラノール基と縮合しにくく、鉛筆硬度が低下することを示していると考えられる。[Table 2]

From the results in Table 2, the V1 film and the V2 film are compared. It was found that the refractive index increased as the polysiloxane content increased, and the film hardness by pencil hardness was high.
The films V1 to V2 and the films RV1 to RV2 are compared. It was found that a film in which the type of polysiloxane is a fully hydrolyzed type has a higher film hardness due to pencil hardness and a lower refractive index than a film in the case where a partially hydrolyzed type is selected. This result is considered to indicate that the refractive index of the alkoxy group remaining in the partially hydrolyzed polysiloxane is high and that it is difficult to condense with the silanol group on the surface of the silica particles and the pencil hardness decreases. .

  The films V1 to V2, the films V3 to V4, and the films V5 to V6 are compared. Although each film had a different particle shape, there was no difference in film hardness in pencil hardness, and when polysiloxane was added at 5 phr, it was H when 10 phr was added. It was found that the difference in the shape of the inorganic particles contributes to the refractive index, and the refractive index decreases as the particle diameter B / particle diameter A becomes 1.1 or more and the shape of the silica particles becomes curved and deformed. As a result, it is considered that the ratio of the air layer having a refractive index of 1.0 is mixed into the film and the refractive index is lowered as the particle shape is curved and becomes irregular.

The films of V7, V8 to V9 are compared. These are examples of adjusting the composition using two types of silica particles. Even when two types of silica particles were used, a pencil hardness of H or higher was achieved by combining with completely hydrolyzed polysiloxane, and the refractive index at a wavelength of 633 nm was 1.3 or lower. It was found that the refractive index of the film in the case of using different types of silica particles tends to be driven by the refractive index of the silica particles exhibiting a lower refractive index.
RV3, RV4 to RV5 are comparative examples in which the silica particles are formed alone. Although a single film of silica particles exhibits a very low refractive index, it has been found that the film hardness by pencil hardness is 6B or less, and the film is damaged only by touching, and is too soft as a film for device fabrication.
RV6 to RV7 are comparative examples formed by polysiloxane alone. Although the polysiloxane single film exhibited a very high pencil hardness, the refractive index at a wavelength of 633 nm was 1.4 or more, and a refractive index of 1.3 or less at a target wavelength of 633 nm could not be achieved.

  Summarizing the above results, the refractive index at a wavelength of 633 nm is 1.30 or less, and the hardness by pencil hardness is H or more. The combination of the fully hydrolyzed polysiloxane and the silica particles used in the present invention. It turns out that it becomes only.

<Heat resistance test>
The heat resistance test of Example 1 and Example 2 was performed.

[Example 11]
V1 obtained in Example 1 was spin-coated on a silicon substrate and quartz using a spin coater so that the film thickness was 500 nm, and (A) temporarily dried at 100 ° C. for 1 minute using a hot plate. Next, firing at 200 ° C. for 5 minutes, (B) Temporary drying at 100 ° C. for 1 minute, then firing at 250 ° C. for 5 minutes, (C) Temporary drying at 100 ° C. for 1 minute, then 300 ° C. for 5 minutes Each was fired to obtain a coating. The film was measured for film thickness and refractive index at a wavelength of 633 nm with an ellipsometer, pencil hardness with an electric pencil scratch hardness tester, and transmittance with an ultraviolet-visible spectrophotometer, and the results are shown in Table 3 and FIGS. . The refractive index and pencil hardness were measured on a film on a silicon substrate, and the transmittance was measured on a quartz substrate.
The background at the time of measuring the transmittance was a quartz substrate not coated with a film. The transmittance measurement wavelength was 200 to 800 nm.
[Table 3]

表３〜４及び図３〜８の結果から、各膜は焼成温度に影響されず３００℃の高温焼成まで膜厚、屈折率、鉛筆硬度、透過率が変化せず良好であることがわかった。[Example 12]
The refractive index, pencil hardness, and transmittance were measured in the same manner as in Example 11 except that V1 used in Example 11 was replaced with V2. The results are shown in Table 4 and FIGS.
[Table 4]

From the results of Tables 3 to 4 and FIGS. 3 to 8, it was found that each film was good without being affected by the baking temperature and without changing the film thickness, refractive index, pencil hardness, and transmittance until high temperature baking at 300 ° C. .

  Since the low refractive index film is required to have no significant change in physical properties depending on the baking process to be produced, it has been found that the process margin is very wide.

<Solvent resistance>
A solvent tolerance test is a test which shows that the film after this baking is insolubilized with respect to the contact with a solvent. Solvent resistance is a characteristic that is required when a post-process for patterning is performed by recoating a resist or the like on the film. If there is no solvent resistance, the film dissolves in the resist solvent when recoating, and the film And the resist may be mixed and the original characteristics may not be exhibited.

[Example 13]
In Example 1, the solvent resistance test of the V1 film produced on the silicon substrate was performed.
The film thickness after firing was 500.1 nm, which was taken as the initial film thickness. Each coating was completely immersed in propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, acetone, and ethyl lactate and allowed to stand for 5 minutes. Next, after drying with air, baking was performed on a hot plate at 200 ° C. for 1 minute to completely evaporate the residual solvent, and then the film thickness was measured and compared with the initial film thickness.
As a result, when the initial film thickness is 100%, propylene glycol monomethyl ether is 100.0%, propylene glycol monomethyl ether acetate is 100.0%, cyclohexanone is 100.0%, acetone is 100.0%, ethyl lactate It became 100.0%, and it turned out that solvent resistance is favorable with respect to various organic solvents.

[Example 14]
In Example 2, a solvent resistance test was conducted in the same manner as in Example 12 except that the V2 film produced on the silicon substrate was used. The film thickness after firing was 500.5 nm, which was taken as the initial film thickness.
When the initial film thickness is 100%, propylene glycol monomethyl ether is 100.0%, propylene glycol monomethyl ether acetate is 100.0%, cyclohexanone is 100.0%, acetone is 100.0%, and ethyl lactate is 100.%. It was found that the solvent resistance was good against various organic solvents.

  From the results of Example 13 to Example 14, it was found that the fired coating exhibited solvent resistance, and it was found that the film had sufficient recoating performance.

<Light resistance test>
In the light resistance test, light irradiation was performed at the Japan Weathering Test Center, and a xenon arc lamp having an illuminance of 180 W / m ² and an exposure wavelength of 275 nm or more was used as a light source. The testing machine used was SX75-AP type manufactured by Suga Test Instruments Co., Ltd.

[Example 15]
The light resistance test of the V1 film produced in Example 1 was conducted. The light irradiation time was 500 hours, and the film thickness, refractive index, pencil hardness, and transmittance before and after the light irradiation were measured. The results are shown in Table 5 and FIGS.
[Table 5]

表５〜表６及び図９〜図１２の結果から、本発明の被膜は非常に強い耐光性を有していることが分かった。本光照射条件はＬＣＤの耐光性試験に一般的に用いられる光照射条件であるが、膜厚、屈折率、鉛筆硬度、透過率ともに変化は見られなかった。[Example 16]
The light resistance test of the V2 film produced in Example 2 was conducted. The light irradiation time was 500 hours, and the film thickness, refractive index, pencil hardness, and transmittance before and after the light irradiation were measured. The results are shown in Table 6 and FIGS.
[Table 6]

From the results of Tables 5 to 6 and FIGS. 9 to 12, it was found that the coating of the present invention has very strong light resistance. This light irradiation condition is a light irradiation condition generally used for the light resistance test of LCD, but no change was observed in film thickness, refractive index, pencil hardness, and transmittance.

<Constant temperature and humidity test>
The conditions of the constant temperature and humidity test were 336 hours at 90 ° C. and 90% RH.
[Example 17]
The constant temperature and humidity test of the V1 film prepared in Example 1 was performed. The film after the test was baked at 200 ° C. for 1 minute using a hot plate. The film thickness, refractive index, pencil hardness, and transmittance before and after the test were measured. The results are shown in Table 7 and FIGS.
[Table 7]

表７乃至表８及び図１３乃至図１６の結果から、本発明の被膜は恒温恒湿試験後においても良好な透過率を保持し、波長６３３ｎｍにおける屈折率も著しく変化することなく良好であることがわかった。
本発明の水酸基を含まない非アルコールを加水分解又は重縮合時の溶剤に用いて得られる分子量が１０００乃至２００００の完全加水分解型のポリシロキサンと、ＢＥＴ法による比表面積から計算される平均粒子径が１００ｎｍ以下（例えば１乃至１００ｎｍ）、および屈折率が１．５以下（例えば１．１５乃至１．５０）の無機粒子とからなる膜形成用組成物を用いることで、高透明性、高耐熱性、高耐光性、高硬度の要求特性を一度に満たすことができる。得られる被膜は具体的には、屈折率が波長６３３ｎｍで１．１５乃至１．３０となり、鉛筆硬度がＨ以上（例えばＨ乃至９Ｈ、又はＨ乃至５Ｈ、又はＨ乃至３Ｈ）であり、耐熱性、耐光性、高信頼性を有する低屈折率膜を得ることができる。[Example 18]
The constant temperature and humidity test of the V2 film prepared in Example 2 was performed. The film after the test was baked at 200 ° C. for 1 minute using a hot plate. The film thickness, refractive index, pencil hardness, and transmittance before and after the test were measured. The results are shown in Table 8 and FIGS.
[Table 8]

From the results of Tables 7 to 8 and FIGS. 13 to 16, the coating of the present invention maintains good transmittance even after the constant temperature and humidity test, and the refractive index at a wavelength of 633 nm is good without any significant change. I understood.
The average particle diameter calculated from the fully hydrolyzed polysiloxane having a molecular weight of 1000 to 20000 obtained by using the non-alcohol containing no hydroxyl group of the present invention as a solvent during hydrolysis or polycondensation, and the specific surface area by the BET method Using a film-forming composition comprising inorganic particles having a refractive index of 1.5 or less (for example, 1.15 to 1.50) and 100 nm or less (for example, 1 to 100 nm) and high refractive index and high heat resistance. Can meet the required properties of high performance, high light resistance and high hardness at once. Specifically, the obtained film has a refractive index of 1.15 to 1.30 at a wavelength of 633 nm, a pencil hardness of H or higher (for example, H to 9H, H to 5H, or H to 3H), and is heat resistant. Thus, a low refractive index film having light resistance and high reliability can be obtained.

Since the film of the present invention has solvent resistance, there is no mixing when a resist or the like is recoated, and it can be stably incorporated into a device manufacturing process.
In addition, since the storage stability is good, it leads to stable manufacturing and stable supply when manufacturing the target display device, thereby reducing costs and improving device manufacturing throughput, resulting in improved yield. . As a result, it can be suitably used as an electronic device such as a liquid crystal display, a plasma display, a cathode ray tube, an organic light emitting display, electronic paper, an optical semiconductor (LED), a solid-state imaging device, a solar cell, and an organic thin film transistor.

  More specifically, it can be suitably used as an antireflective substrate and antireflective film for televisions, digital signage, mobile phones, personal digital assistants, notebook computers and the like.

Claims (13)

A silicon compound (A ), which is a hydrolysis-condensation product of a hydrolyzable silane represented by the following formula (1), having a weight average molecular weight of 1000 to 20000, obtained by hydrolyzing and condensing a hydrolyzable silane in acetone or tetrahydrofuran. ), Inorganic particles (B) having an average particle diameter of 1 to 100 nm, and a solvent (C).

(In the formula, R ¹ represents an alkoxy group, an acyloxy group, or a halogen group.) The film-forming composition according to claim 1 , wherein the hydrolyzable silane represented by the formula (1) is tetraethoxysilane or tetramethoxysilane. The solvent (C) contains acetone or tetrahydrofuran used in the hydrolytic condensation of the hydrolyzable silane and a solvent replacement solvent for removing a reaction product generated by hydrolysis of the hydrolyzable silane. The film forming composition according to claim 1 or 2 . The film-forming composition according to any one of claims 1 to 3 , wherein the inorganic particles (B) are particles having a refractive index of 1.15 to 1.50. The inorganic particles (B) have an average particle size (particle size A) calculated from a specific surface area by the BET method of 5 to 60 nm, and a dispersed particle size (particle size B) of 50 to 250 nm by the dynamic light scattering method. The film-forming composition according to any one of claims 1 to 4 , wherein the composition is inorganic particles (B-1) having a particle diameter B / particle diameter A of 1.1 or more. The inorganic particles (B) are inorganic particles (B-2) having an outer shell and an inside, the inside being porous or hollow, and an average particle diameter of 15 to 100 nm. 5. The film forming composition according to any one of 4 above. A silicon compound which is a hydrolytic condensate of hydrolyzable silane represented by the following formula (1), having a weight average molecular weight of 1000 to 20000, obtained by hydrolyzing and condensing hydrolyzable silane in acetone or tetrahydrofuran. A) is a step of obtaining a varnish of a silicon compound (A) dissolved in a solvent (C), a sol of a dispersion medium (C ′) containing inorganic particles (B) having an average particle diameter of 1 to 100 nm, and the silicon A method for producing a film-forming composition according to any one of claims 1 to 6 , comprising a step of mixing a varnish of the compound (A).

(In the formula, R ¹ represents an alkoxy group, an acyloxy group, or a halogen group.) The production method according to claim 7, wherein the inorganic particles (B) are inorganic particles having an average particle diameter of 1 to 100 nm and a refractive index of 1.15 to 1.50 calculated from a specific surface area by a BET method. A film forming composition according to any one of claims 1 to 6 is coated on a substrate and fired, and has a refractive index of 1.15 to 1.30 at a wavelength of 633 nm, and JIS standard K5600. A film having a pencil hardness of H to 9H determined by Film forming method of claim 9 including the step of firing to cover the film-forming composition according to the substrate in any one of claims 1 to 6. An antireflection film obtained from the film-forming composition according to any one of claims 1 to 6 . The apparatus which has an electronic device obtained using the composition for film formation of any one of Claims 1 thru | or 6 . The apparatus according to claim 12 , wherein the electronic device is a liquid crystal display, a plasma display, a cathode ray tube, an organic light emitting display, electronic paper, an optical semiconductor (LED), a solid-state imaging device, a solar cell, or an organic thin film transistor.

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