JP7626971B2 - Coating composition containing a polymeric silane coupling agent having an alkoxysilyl group and a mercapto group in the side chain - Google Patents

Description

The present invention relates to a coating composition and optical components that can form a cured film that is excellent in hardness, transparency, scratch resistance, adhesion, and weather resistance and is useful for optical components such as eyeglass lenses.

Plastic molded bodies are used in large quantities, taking advantage of their advantages such as light weight, ease of processing, and impact resistance. However, they have disadvantages such as insufficient hardness and being easily scratched, being easily attacked by solvents, being electrostatically charged and attracting dust, and insufficient heat resistance. Therefore, when used as eyeglass lenses, window materials, etc., plastic molded bodies have the practical disadvantages mentioned above compared to inorganic glass molded bodies. Therefore, it has been proposed to apply a protective coat (protective film) to plastic molded bodies. A large number of types of coating compositions have been proposed for use as protective coats.

A coating composition containing an organosilicon compound or its hydrolyzate as the main component (resin component or coating film-forming component) is used for eyeglass lenses to provide a hard coating similar to that of inorganic systems (Patent Document 1).

Because the scratch resistance of the above coating composition is still unsatisfactory, a coating composition containing a colloidally dispersed silicon dioxide sol has been proposed, and this has also been put to practical use for eyeglass lenses (Patent Document 2).

A polymer-grafted colloidal silica dispersion has been disclosed in which colloidal silica has methylamino groups, dimethylamino groups, and isopropylamino groups and silyl residues bonded thereto (Patent Document 3).

Japanese Unexamined Patent Publication No. 52-11261 Japanese Unexamined Patent Publication No. 53-111336 JP 2008-100894 A

The present invention provides a coating composition that provides excellent adhesion to the substrate of the resulting cured film, appearance after weather resistance testing, adhesion after weather resistance testing, scratch resistance, and transparency.

（式（１）中、Ｒ^１はアルキル基、アリール基、ハロゲン化アルキル基、ハロゲン化アリール基、アルコキシアリール基、アルケニル基、又はエポキシ基、（メタ）アクリロイル基、メルカプト基、アミノ基、ウレイド基、もしくはシアノ基を有する有機基で且つＳｉ－Ｃ結合によりケイ素原子と結合しているものであり、Ｒ^２はアルコキシ基、アシルオキシ基、又はハロゲン原子を示し、ａは０乃至３の整数を示す。）で表されるシラン化合物、及び（Ｓ２－２）：

（式（２）中、Ｒ^３はアルキル基で且つＳｉ－Ｃ結合によりケイ素原子と結合しているものであり、Ｒ^４はアルコキシ基、アシルオキシ基、又はハロゲン原子を示し、Ｙはアルキレン基、アリーレン基、ＮＨ基、又は酸素原子を示し、ｂは０乃至３の整数を示し、ｃは０又は１の整数である。）で表されるシラン化合物からなる群より選ばれた少なくとも１種のシラン化合物を含む第１観点又は第２観点に記載のコーティング組成物に関する。
第４観点として、（Ｓ２）成分が（Ｓ２－１－１）成分として式（１）中、ａが０であるシラン化合物、式（１）中、ａが１でありＲ^１がメチル基であるシランカップリング剤、又はそれらの混合物と、（Ｓ２－１－２）として式（１）中、ａが１でありエポキシ基を含有するシランカップリング剤、式（１）中、ａが１であり（メタ）アクリロイル基を含有するシランカップリング剤、又はそれらの混合物とを含んでいて、（Ｓ２－１－１）：（Ｓ２－１－２）の質量比が１：１乃至１：２５の割合である第３観点に記載のコーティング組成物に関する。
第５観点として、（Ｓ１）：（Ｓ２）を質量比で５：９５乃至３０：７０の割合で含有する第３観点に記載のコーティング組成物に関する。
第６観点として、（Ｔ）成分が、２ｎｍ乃至６０ｎｍの平均粒子径を有する金属酸化物のコロイド粒子（Ｔ１）を核として、その表面を１ｎｍ乃至４ｎｍの平均一次粒子径を有する酸性酸化物のコロイド粒子からなる被覆物（Ｔ２）で被覆された、２ｎｍ乃至１００ｎｍの平均粒子径を有する変性金属酸化物コロイド粒子で形成されたコロイド粒子（Ｔ３）の有機溶媒分散ゾルである第１観点乃至第５観点のいずれか一つに記載のコーティング組成物に関する。
第７観点として、上記コロイド粒子（Ｔ１）が、Ｔｉ、Ｆｅ、Ｃｕ、Ｚｎ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ｉｎ、Ｓｎ、Ｓｂ、Ｔａ、Ｗ、Ｐｂ、Ｂｉ及びＣｅからなる群から選ばれる少なくとも１種の金属の酸化物である第６観点に記載のコーティング組成物に関する。
第８観点として、被覆物（Ｔ２）が、Ｓｉ、Ｚｒ、Ｓｎ、Ｍｏ、Ｓｂ及びＷからなる群
から選ばれる少なくとも１種の金属の酸化物である第６観点に記載のコーティング組成物に関する。
第９観点として、上記コロイド粒子（Ｔ１）が酸化スズ－酸化ジルコニウムからなる金属の酸化物、又は酸化チタン－酸化スズ－酸化ジルコニウムからなる金属の酸化物であり、被覆物（Ｔ２）が酸化スズ－二酸化ケイ素からなる金属の酸化物である第６観点に記載のコーティング組成物に関する。
第１０観点として、（Ｔ２）成分の表面が（メタ）アクリロイルオキシトリアルコキシシラン、ウレイドプロピルトリアルコキシシラン、又はグリシドキシプロピルトリアルコキシシランで被覆されている第６観点乃至第９観点のいずれか一つに記載のコーティング組成物に関する。
第１１観点として、（Ｔ）成分が更にアミンを含む第６観点乃至第１０観点のいずれか一つに記載のコーティング組成物に関する。
第１２観点として、更に硬化剤として金属キレート又は過塩素酸塩を含む第１観点乃至第１１観点のいずれか一つに記載のコーティング組成物に関する。
第１３観点として、更に界面活性剤を含有する第１観点乃至第１２観点のいずれか一つに記載のコーティング組成物に関する。
第１４観点として、光学基材の表面に第１観点乃至第１３観点のいずれか一つに記載のコーティング組成物により形成された硬化膜を有する光学部材に関する。
第１５観点として、第１４観点に記載の光学部材の表面に更に反射防止膜を有する光学部材に関する。
第１６観点として、（Ｓ）成分としてシラン化合物、その加水分解物、又はそれらの混合物を準備する（ａ）工程、及び
当該（ａ）工程で得られた（Ｓ）成分と（Ｔ）成分として２ｎｍ乃至１００ｎｍの平均粒子径を有するコロイド状金属酸化物粒子（Ｔ３）とを混合する（ｂ）工程を含む、コーティング組成物の製造方法に関する。 A first aspect of the present invention is a coating composition comprising the following component (S) and component (T):
the component (S) is a silane compound, a hydrolysate thereof, or a mixture thereof, the silane compound contains a polymeric silane coupling agent as a component (S1), the polymeric silane coupling agent has an alkoxysilyl group and a mercapto group as side chains on a main chain of an organic compound, the molar ratio of (mercapto group) to (alkoxysilyl group), that is, (mercapto group)/(alkoxysilyl group), is 2 to 6, and the mercapto group equivalent is in a ratio of 150 g/mol to 300 g/mol,
Component (T) is colloidal metal oxide particles (T3) having an average particle size of 2 nm to 100 nm,
The present invention relates to a coating composition comprising the component (S):component (T) in a mass ratio of 100:10 to 500.
As a second aspect, the present invention relates to the coating composition according to the first aspect, wherein the alkoxysilyl group on a side chain of the polymeric silane coupling agent of component (S1) is a trimethoxysilyl group, the molar ratio of (mercapto group) to (alkoxysilyl group), that is, (mercapto group)/(alkoxysilyl group), is 3 to 5, and the mercapto group equivalent is 200 g/mol to 250 g/mol.
As a third aspect, the silane compound of the component (S) further comprises, as the component (S2), (S2-1):

(in formula (1), R ¹ is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkoxyaryl group, an alkenyl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, and is bonded to a silicon atom via a Si-C bond; R ² is an alkoxy group, an acyloxy group, or a halogen atom; and a is an integer of 0 to 3), and (S2-2):

(in formula (2), ^R3 is an alkyl group bonded to a silicon atom via a Si-C bond; ^R4 is an alkoxy group, an acyloxy group, or a halogen atom; Y is an alkylene group, an arylene group, an NH group, or an oxygen atom; b is an integer of 0 to 3; and c is an integer of 0 or 1).
As a fourth aspect, the present invention relates to a coating composition according to the third aspect, wherein the component (S2) includes, as the component (S2-1-1), a silane compound in which a in formula (1) is 0, a silane coupling agent in which a in formula (1) is 1 and R ¹ is a methyl group, or a mixture thereof, and, as the component (S2-1-2), a silane coupling agent in which a in formula (1) is 1 and contains an epoxy group, a silane coupling agent in formula (1) is 1 and contains a (meth)acryloyl group, or a mixture thereof, and the mass ratio of (S2-1-1):(S2-1-2) is a ratio of 1:1 to 1:25.
As a fifth aspect, the present invention relates to the coating composition according to the third aspect, which contains (S1):(S2) in a mass ratio of 5:95 to 30:70.
As a sixth aspect, the present invention relates to a coating composition according to any one of the first to fifth aspects, in which the component (T) is an organic solvent dispersion sol of colloidal particles (T3) formed of modified metal oxide colloidal particles having an average particle size of 2 nm to 100 nm, the surfaces of which are coated with a coating (T2) consisting of acidic oxide colloidal particles having an average primary particle size of 1 nm to 4 nm, the core being a metal oxide colloidal particle (T1) having an average particle size of 2 nm to 60 nm.
As a seventh aspect, the present invention relates to the coating composition according to the sixth aspect, in which the colloidal particles (T1) are an oxide of at least one metal selected from the group consisting of Ti, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Ta, W, Pb, Bi, and Ce.
As an eighth aspect, the present invention relates to the coating composition according to the sixth aspect, in which the coating (T2) is an oxide of at least one metal selected from the group consisting of Si, Zr, Sn, Mo, Sb, and W.
As a ninth aspect, the present invention relates to the coating composition according to the sixth aspect, wherein the colloidal particles (T1) are a metal oxide consisting of tin oxide-zirconium oxide, or a metal oxide consisting of titanium oxide-tin oxide-zirconium oxide, and the coating (T2) is a metal oxide consisting of tin oxide-silicon dioxide.
As a tenth aspect, the present invention relates to the coating composition according to any one of the sixth to ninth aspects, in which a surface of the component (T2) is coated with (meth)acryloyloxytrialkoxysilane, ureidopropyltrialkoxysilane, or glycidoxypropyltrialkoxysilane.
As an eleventh aspect, the present invention relates to the coating composition according to any one of the sixth to tenth aspects, in which the component (T) further contains an amine.
As a twelfth aspect, the present invention relates to the coating composition according to any one of the first to eleventh aspects, further comprising a metal chelate or a perchlorate as a curing agent.
As a thirteenth aspect, the present invention relates to the coating composition according to any one of the first to twelfth aspects, further comprising a surfactant.
According to a fourteenth aspect, the present invention relates to an optical member having a cured film formed on a surface of an optical substrate from the coating composition according to any one of the first to thirteenth aspects.
As a fifteenth aspect, the present invention relates to an optical member according to the fourteenth aspect, which further comprises an antireflection film on a surface of the optical member.
As a sixteenth aspect, the present invention relates to a method for producing a coating composition, the method including: (a) a step of preparing, as a component (S), a silane compound, a hydrolysate thereof, or a mixture thereof; and (b) a step of mixing the component (S) obtained in the step (a) with colloidal metal oxide particles (T3) having an average particle size of 2 nm to 100 nm as a component (T).

The present invention is a coating composition that contains, as component (S), a silane compound, its hydrolysate, or a mixture thereof, and, as component (T), colloidal metal oxide particles having an average primary particle size of 2 nm to 100 nm.

The present invention contains a polymeric silane coupling agent as component (S). The polymeric silane coupling agent has an organic compound whose main chain has an organic structure, and whose side chain has a plurality of alkoxy groups and organic functional groups (mercapto groups). The alkoxy groups can bond with binder components (e.g., other silane coupling agents) contained in the coating composition, or with surface hydroxyl groups (e.g., silanol groups) on colloidal metal oxide particles. The mercapto groups can also react efficiently with carbon-carbon double bonds and epoxy groups in other binder components.

Polymer-type silane coupling agents have many reactive sites in one molecule, and are expected to improve adhesion. In addition, because they are large molecules, they are less volatile when heated and cured, and have high film-forming properties. By including a polymer-type silane coupling agent in the coating composition that forms the coating film, the polymer-type silane coupling agent acts as a starting point to improve the bonding with colloidal metal oxides and other binder components (glass or plastic substrates to which the binder is bonded), and high adhesion, especially improved weather-resistant adhesion, can be expected.

In addition, in recent years, plastic lenses have been made to have high refractive indexes in order to make them thinner, and sulfur atoms are involved in this high refractive index, but polymer-type silane coupling agents have many mercapto groups, and the mercapto groups and the products of their reaction are highly compatible with high refractive index lens materials, which also contributes to improving adhesion.In addition, since they contain sulfur, the refractive index of the coating film itself is high, and even if they are applied to a high refractive index substrate, the occurrence of stripes (interference fringes) caused by refractive index differences can be reduced.

The coating composition of the present invention can be applied to optical components, including eyeglass lenses, camera lenses, automobile window glass, computer displays, television displays, and mobile terminal displays.

The present invention provides a coating composition comprising the following component (S) and component (T):
The component (S) is a silane compound, a hydrolyzate thereof, or a mixture thereof, and the silane compound includes, as a component (S1), a polymer-type silane coupling agent having an alkoxysilyl group and a mercapto group as side chains on the main chain of an organic compound, and containing a molar ratio of (mercapto group)/(alkoxysilyl group)=2 to 6 and a mercapto group equivalent of 150 to 300 g/mol;
Component (T) is colloidal metal oxide particles (T3) having an average particle size of 2 to 100 nm,
The coating composition contains the component (S):component (T) in a mass ratio of 100:10 to 500.

The solid content of the coating composition of the present invention is 0.1% by mass to 60% by mass, or 1% by mass to 50% by mass, or 10% by mass to 45% by mass. Here, the solid content is the total component of the coating composition excluding the solvent component.

The polymeric silane coupling agent of the component (S1) has a structure in which an alkoxysilyl group and a mercapto group are attached to the side chain of the main chain of an organic compound. In an alkoxysilyl group, three alkoxy groups are bonded to a silicon atom, and the silicon atom is bonded to an organic compound. Examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, and butoxy, and methoxy groups are particularly preferred. The methoxy group is converted to a hydroxyl group through hydrolysis to generate a silanol group. The organic compound is a hydrocarbon having characteristics selected from saturated or unsaturated, linear or cyclic, aliphatic or aromatic, and may contain a linking group such as an ester group, an ether group, or an amino group. The molecule may have one or more ester groups, ether groups, amino groups, etc., and may have a repeating unit. A plurality of alkoxysilyl groups and mercapto groups are linked to these organic compounds.
The molar ratio of (mercapto group)/(alkoxysilyl group) is 2 to 6, or 3 to 5, typically 3 or 5. The mercapto group equivalent is 150 g/mol to 300 g/mol, or 200 g/mol to 250 g/mol, typically 240 g/mol, 210 g/mol. The mercapto group equivalent is the mass of the silane coupling agent per mole of mercapto group. The viscosity is 500 mm ² /s to 10,000 mm ² /s, or 1,000 mm ² /s to 8,000 mm ² /s, typically 1,500 mm ² /s, 5,000 ^{mm 2} /s. These polymeric silane coupling agents can be manufactured by Shin-Etsu Chemical Co., Ltd. under the trade names X-12-1154 and X-12-1156.

Shin-Etsu Chemical Co., Ltd.'s product name X-12-1154 is a polymeric silane coupling agent containing a molar ratio of (mercapto group)/(methoxysilyl group)=3, a viscosity of 1500 mm ² /s, and a mercapto group equivalent of 240 g/mol.
Shin-Etsu Chemical Co., Ltd.'s product name X-12-1156 is a polymeric silane coupling agent having a molar ratio of (mercapto group)/(methoxysilyl group)=5, a viscosity of 5000 mm ² /s, and a mercapto group equivalent of 210 g/mol.
The above-mentioned products are available in the form of products dissolved in ethanol at a concentration of about 15% by weight, for example, and can be used by diluting them with ethanol or at their original concentration.

In the present invention, as the component (S), the component (S2) can be used together with the component (S1).
The component (S2) may contain at least one silane compound selected from the group consisting of (S2-1) and (S2-2).

(S2-1) is represented by formula (1), in which R ¹ is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkoxyaryl group, an alkenyl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, and is bonded to a silicon atom via a Si-C bond, R ² is an alkoxy group, an acyloxy group, or a halogen atom, and a is an integer of 0 to 3.

(S2-2) is represented by formula (2), in which ^R3 is an alkyl group and is bonded to a silicon atom via a Si-C bond, ^R4 is an alkoxy group, an acyloxy group, or a halogen atom, Y is an alkylene group, an arylene group, an NH group, or an oxygen atom, b is an integer of 0 to 3, and c is an integer of 0 or 1.

The alkyl group is an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, a cyclopentyl group, a 1-methyl-cyclopropyl group, a cyclopentyl ... butyl group, 2-methylcyclobutyl group, 3-methylcyclobutyl group, 1,2-dimethylcyclopropyl group, 2,3-dimethylcyclopropyl group, 1-ethylcyclopropyl group, 2-ethylcyclopropyl 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 ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl Examples of the groups include cyclopropyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl groups.

Alkylene groups can also be alkylene groups derived from the alkyl groups mentioned above.

Examples of aryl groups include phenyl, naphthyl, and anthryl groups, and arylene groups are groups derived from the above aryl groups, such as phenylene, naphthylene, and anthrylene groups.

The above alkoxy groups include alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentyloxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, and n-hexyloxy.

The acyloxy group includes acyloxy groups having 2 to 10 carbon atoms, such as methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, i-propylcarbonyloxy group, n-butylcarbonyloxy group, i-butylcarbonyloxy group, s-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, 1-methyl-n-butylcarbonyloxy group, 2-methyl-n-butylcarbonyloxy group, 3-methyl-n-butylcarbonyloxy group, 1,1-dimethyl-n-propylcarbonyloxy group, 1,2-dimethyl-n-propylcarbonyloxy group, 2,2-dimethyl-n-propylcarbonyloxy group, 1-ethyl-n-propylcarbonyloxy group, n-hexylcarbonyloxy group, 1-methyl-n-pentylcarbonyloxy group, 2-methyl-n-pentylcarbonyloxy group, etc.

The above halogen atoms include fluorine, chlorine, bromine, iodine, etc.

Examples of the component (S2) include compounds represented by the following formulas (3-1) to (3-10).

The above R ¹² represents a hydrolyzable group described in R ² and R ⁴ in the formula (1) and the formula (2).

In the present invention, the component (S2) contains, as the component (S2-1-1), a silane compound in which a in formula (1) is 0, a silane coupling agent in which a in formula (1) is 1 and R ¹ is a methyl group, or a mixture thereof, and, as the component (S2-1-2), a silane coupling agent in which a in formula (1) is 1 and contains an epoxy group, a silane coupling agent in formula (1) is 1 and contains a (meth)acryloyl group, or a mixture thereof, and the mass ratio of (S2-1-1):(S2-1-2) can be in a range of 1:1 to 1:25.

As the component (S2-1-1), examples of the silane compound in which a is 0 in formula (1) include tetramethoxysilane, tetraethoxysilane, etc. Examples of the silane coupling agent in which a is 1 and ^R1 is a methyl group in formula (1) include methyltrimethoxysilane, methyltriethoxysilane, etc.

As the above (S2-1-2) component, examples of silane coupling agents in which a in formula (1) is 1 and contains an epoxy group include glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, etc. Examples of silane coupling agents in which a in formula (1) is 1 and contains a (meth)acryloyl group include methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, etc.

The hydrolysis can be carried out using a hydrolysis catalyst or without a hydrolysis catalyst. When a hydrolysis catalyst is used, 0.001 to 10 moles, preferably 0.001 to 1 mole, of the hydrolysis catalyst can be used per mole of the hydrolyzable group.
The reaction temperature in carrying out the hydrolysis is usually 20°C to 120°C.
The hydrolysis may be complete or partial. That is, in the coating composition, the silane compound exists as a monomer or a hydrolyzate, but may partially form a hydrolyzed condensate. In the coating film, the hydrolyzate forms a hydrolyzed condensate, and these silane compounds function as binders, and the hydrolyzed condensate forms a network to become a cured film.
A catalyst can be used in the hydrolysis and condensation.

The hydrolysis catalyst may include a metal chelate compound, an organic acid, an inorganic acid, an organic base, and an inorganic base.

Metal chelate compounds that can be used as hydrolysis catalysts include the chelate compounds described below.

Examples of organic acids that can be used as hydrolysis catalysts 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, mellitic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic 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 trifluoromethanesulfonic acid.

Examples of inorganic acids that can be used as hydrolysis catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

Examples of organic bases as hydrolysis catalysts include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, etc. Examples of inorganic bases include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc.

Examples of the organic solvent used in the hydrolysis include aromatic hydrocarbon solvents, monoalcohol solvents, polyhydric alcohol solvents, ketone solvents, ether solvents, ester solvents, nitrogen-containing solvents, sulfur-containing solvents, etc. These solvents can be used alone or in combination of two or more.
Among these, alcohol-based solvents are preferred, and from this viewpoint, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, etc. can be used. These organic solvents in component (S) can be used as the organic solvent in the coating composition of the present invention.

In the present invention, the above (S1):(S2) can be contained in a mass ratio of 5:95 to 30:70.

In the present invention, the component (T) is colloidal metal oxide particles (T3) having an average primary particle size of 2 nm to 100 nm.
The component (T) can be used in the form of a sol containing colloidal metal oxide particles (T3). The sol containing colloidal metal oxide particles (T3) can be an organic solvent sol obtained by replacing an aqueous sol with an organic solvent.
The sol can be used at a concentration of 0.1% to 40% by weight, 1% to 30% by weight, or 1% to 20% by weight as the metal oxide.

Examples of such organic solvents include alcohol-based organic solvents, ether-based organic solvents, ketone-based organic solvents, ester-based organic solvents, aliphatic hydrocarbon-based organic solvents, aromatic hydrocarbon-based organic solvents, and amide compound-based organic solvents.

Examples of the alcohol-based organic solvent include methyl alcohol, ethyl alcohol,
Examples of the monohydric alcohol include propyl alcohol, isopropyl alcohol, butyl alcohol, and isobutyl alcohol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, and hexanetriol; and monoethers of polyhydric alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether.

In addition to the above-mentioned polyhydric alcohol monoethers, examples of the ether-based organic solvents include polyhydric alcohol ethers in which all of the hydroxyl groups of polyhydric alcohols have been alkyl-etherified, such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; tetrahydrofuran, 1,4-dioxane, and anisole.

Examples of the ketone organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl isoamyl ketone.

Examples of the ester-based organic solvent include methyl acetate, ethyl acetate, and butyl acetate.

Examples of the aliphatic hydrocarbon organic solvent include hexane, heptane, octane, nonane, and decane.

Examples of the aromatic hydrocarbon organic solvent include benzene, toluene, and xylene.

Examples of the amide compound-based organic solvent include dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

Among the above-mentioned solvents, the following are preferred because they are easily miscible with water: methanol, ethanol, isopropanol, and butanol as the alcohol-based organic solvents; ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether as the ether-based organic solvents; acetone, methyl ethyl ketone, and methyl isobutyl ketone as the ketone-based organic solvents; and dimethylformamide, dimethylacetamide, and N-methylpyrrolidone as the amide compound-based organic solvents.
The organic solvents may be used alone or in combination of two or more.

These organic solvents in component (T) can be used as the organic solvent in the coating composition of the present invention.
When the coating composition of the present invention contains the component (S) and the component (T), if the component (T) is an organic solvent dispersion sol of colloidal metal oxide particles (T3), this organic solvent can be used as a solvent for the coating composition.

The component (T) is an organic solvent dispersion sol of colloidal particles (T3) formed of modified metal oxide colloidal particles having an average particle size of 2 nm to 100 nm, the surface of which is coated with a coating (T2) consisting of colloidal particles of an acidic oxide having an average primary particle size of 1 nm to 4 nm, with metal oxide colloidal particles (T1) having an average particle size of 2 nm to 60 nm as a nucleus.

The average particle size can be determined by dynamic light scattering using a dynamic light scattering measuring device (nm).
The average primary particle size can be determined by observation with a transmission electron microscope (nm).

The colloidal particles (T1) can be an oxide of at least one metal selected from the group consisting of Ti, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Ta, W, Pb, Bi and Ce. For example, _TiO2 , _{Fe2O3 ,} CuO, ZnO, _Y2O3 , _ZrO2 , _Nb2O5 , _NbO2 , _Nb2O3 , MoO2, _MoO3 , _In2O3 , _{SnO2 , Sb2O3} , _Sb2O5 , _Ta2O5 , _{W2O3 , WO2} , _{WO3 , PbO, Pb2O4, PbO2, Bi2O3, CeO2, Ce2O3 , etc. may be used alone . Furthermore , two or three} or more of these metal oxides may be used in combination _. For example, a combination of ZrO ₂ —SnO ₂ and a combination of TiO ₂ —SnO ₂ —ZrO ₂ can be mentioned.

The coating (T2) may be an oxide of at least one metal selected from the group consisting of Si, Zr, Sn, Mo, Sb, and W. For example, SiO ₂ , ZrO ₂ , SnO ₂ , MoO ₂ , MoO ₃ , Sb ₂ O ₃ , Sb ₂ O _5, etc. may be used alone. Furthermore, these metal oxides may be used in combination of two or three or more kinds. For example, SnO ₂ -SiO ₂ , SnO ₂ -SiO ₂ -Sb ₂ O ₅ , etc. may be used.

The colloidal particles (T1) are a metal oxide consisting of tin oxide-zirconium oxide, or a metal oxide consisting of titanium oxide-tin oxide-zirconium oxide, and the coating material (T2) is preferably, for example, a metal oxide consisting of tin oxide-silicon dioxide.

The colloidal metal oxide particles (T3) of component (T) having an average particle size of 2 nm to 100 nm can be used without coating the surface of the metal oxide particles with a surface coating agent such as a silane coupling agent, or can be used with the surface coated.

When (T1) is used alone, or when (T1) is used as a core and coated with (T2) to form a core-shell structure, each can be coated with a silane coupling agent.

When used in a core-shell structure, the surface of the outermost layer (T2) component can be coated with (meth)acryloyloxytrialkoxysilane, ureidopropyltrialkoxysilane, or glycidoxypropyltrialkoxysilane. The alkoxy group is preferably a methoxy group or an ethoxy group.

For example, when (T1) is a metal oxide consisting of tin oxide-zirconium oxide and (T2) is a metal oxide consisting of tin oxide-silicon dioxide, and the metal oxides are coated with (meth)acryloyloxytrialkoxysilane, the particle surface can be surface-treated with (meth)acryloyloxytrialkoxysilane at a ratio of 0.2 particles/nm to 1.5 particles/nm, typically at a ratio of 1.0 particles/nm.

In addition, (T1) is a metal oxide consisting of titanium oxide-tin oxide-zirconium oxide, (
When T2) is a metal oxide consisting of tin oxide-silicon dioxide and is coated with ureidopropyltrialkoxysilane, the particle surface can be surface-treated with ureidopropyltrialkoxysilane at a ratio of 0.2 particles/nm to 1.5 particles/nm, typically at a ratio of 0.5 particles/nm.

When the colloidal metal oxide particles (T3) of component (T) having an average particle size of 2 nm to 100 nm are used as a sol dispersed in an organic solvent, they can contain an amine. The inclusion of an amine improves the stability of the sol.

Examples of amines include alkylamines such as ethylamine, triethylamine, isopropylamine, and n-propylamine; aralkylamines such as benzylamine; alicyclic amines such as piperidine; and alkanolamines such as monoethanolamine and triethanolamine. Two or more of these can be mixed and contained. These can be contained in an amount of about 30% by mass or less, for example, 0.1% to 30% by mass, based on the total amount of all metal oxides.

The coating composition of the present invention may contain a metal chelate, a perchlorate, or a mixture thereof as a curing agent. These may be added at a ratio of 0.01% to 20% by mass based on the solid content. For example, metal chelate compounds may be added at a ratio of 2% to 20% by mass, and perchlorates may be added at a ratio of 0.01% to 2% by mass.

Examples of metal chelate compounds include titanium chelate compounds such as triethoxy mono(acetylacetonato)titanium, tri-n-propoxy mono(acetylacetonato)titanium, tri-i-propoxy mono(acetylacetonato)titanium, and tri-n-butoxy mono(acetylacetonato)titanium; zirconium chelate compounds such as triethoxy mono(acetylacetonato)zirconium, tri-n-propoxy mono(acetylacetonato)zirconium, tri-i-propoxy mono(acetylacetonato)zirconium, and tri-n-butoxy mono(acetylacetonato)zirconium; and aluminum chelate compounds such as tris(acetylacetonato)aluminum and tris(ethylacetoacetate)aluminum.
Perchlorates include aluminum perchlorate nonahydrate.

The coating composition of the present invention may contain a cationic, anionic, or nonionic surfactant as a surfactant. Examples of nonionic surfactants include silicone-based surfactants, acrylic-based surfactants, and fluorine-based surfactants.

Examples of fluorosurfactants include surfactants having perfluoroalkyl groups, such as perfluoroalkylsulfonic acid and perfluoroalkylcarboxylic acid.

Examples of silicone surfactants include polydimethylsiloxanes whose side chains or main chain ends are modified with various substituents such as oligomers of ethylene glycol, propylene glycol, etc., and polyether-modified silicone surfactants.

The acrylic surfactant is preferably a copolymer of an acrylic monomer. Examples of copolymerizable surfactants include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, and hexadecyl (meth)acrylate; benzyl (meth)acrylate, naphthyl (meth)acrylate, 2-hydroxy-4-methacryloyloxyethoxy-benzophenone, 3-(2H-1,2,3-benzotriazole, 1,2-dimethyl-2,3-phenylpropanediol ... Aromatic-containing (meth)acrylic acid alkyl esters such as (azol-2-yl)-4-hydroxyphenethyl-(meth)acrylate, (meth)acrylic acid alkylene oxide esters such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate, triethylene glycol monoethyl ether mono(meth)acrylate, tetraethylene glycol monoethyl ether mono(meth)acrylate, pentaethylene glycol monobutyl ether mono(meth)acrylate, and methoxytrioxypropylene (Meth)acrylic acid alkyl ether esters, which are alkyl (meth)acrylates of monools or diols with 2 to 10 moles of alkylene oxide adducts, such as tetraoxyethylene (meth)acrylate and mono(meth)acrylate of 6 moles of ethylene oxide adduct of tetrapropylene glycol; (meth)acrylic acid aminoalkyl esters, such as aminoethyl acrylate and diethylaminoethyl methacrylate; (meth)acrylamide, α-phenyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-t-octyl(meth)acrylamide; Examples of (meth)acrylic acid amide compounds include (meth)acrylic acid amide compounds such as N-n-octyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N,N'-methylenebis((meth)acrylamide), N-diacetone(meth)acrylamide, N-(n-butoxymethyl)(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, and (meth)acryloylmorpholine.

The coating composition of the present invention may further contain the organic solvent used in the above-mentioned (S) and (T) components in addition to the organic solvent derived from the (S) component and the organic solvent derived from the (T) component.

The coating composition of the present invention can be applied onto a substrate to form a cured film. By using a substrate with transparency suitable for optical applications, an optical substrate having a cured film can be obtained.

The coating composition can be cured by heat drying or by irradiation with active energy rays. The heat drying conditions are preferably 70°C to 200°C, more preferably 80°C to 150°C. A cured film is obtained after a heat curing time of 0.5 to 5 hours, or 1 to 3 hours. Heat drying is preferably performed in hot air. Examples of active energy rays include infrared rays, ultraviolet rays, and electron beams, and far infrared rays in particular can reduce damage caused by heat.

The coating composition of the present invention can be applied to a substrate by a commonly used method such as dipping, spinning, or spraying. The dipping and spinning methods are particularly preferred.

In addition, before applying the coating composition of the present invention to a substrate, the adhesion between the substrate and the cured film can be improved by chemical treatment with acid, alkali, various organic solvents or detergents, or physical treatment with plasma, ultraviolet light, etc. Furthermore, the adhesion between the substrate and the cured film can be further improved by performing a primer treatment using various resins.

In addition, the cured film formed by the coating composition of the present invention can be used as an anti-reflective film with a high refractive index, and can also be used as a multi-functional film by adding components with functions such as anti-fogging, photochromic, and anti-fouling.

Optical members having a cured film formed from the coating composition of the present invention can be used not only for eyeglass lenses, but also for camera lenses, automobile window panes, and optical filters attached to liquid crystal displays and plasma displays.

The optical member of the present invention has a cured film formed from the coating composition of the present invention on the surface of the optical substrate, and an anti-reflection film made of a vapor-deposited film of an inorganic oxide can be formed on the cured film.

〔viscosity〕
The viscosity was measured using an Ostwald viscometer (25° C.).
〔moisture〕
The value was determined by Karl Fischer titration.
[Average particle size by dynamic light scattering (dynamic light scattering particle size): unit is nm]
The sol was diluted with a dispersion solvent, and the parameters of the solvent were used to measure the dispersion using a dynamic light scattering measuring device: Zetasizer manufactured by Malvern Instruments Ltd.
[Average primary particle size measured by transmission electron microscope: Unit: nm]
The sol was dropped onto a copper mesh and dried, and observed using a transmission electron microscope (JEM-1020, manufactured by JEOL Ltd.) at an acceleration voltage of 100 kV. The average value of measurements for 100 particles was calculated as the primary particle size.
(1) Adhesion test A cured film formed on a urethane plastic lens substrate was cross-cut with 100 meshes at 1 mm intervals, and an adhesive tape (cellophane tape, product of Nichiban Co., Ltd.) was firmly attached to the cross-cut portion, and then the adhesive tape was quickly peeled off, and the presence or absence of peeling of the cured film after peeling off the adhesive tape was checked. The evaluation criteria are as follows:
A: No peeling was observed at all, or peeling was observed in less than 5 out of 100 meshes.
B: Peeling is observed at 5 to 30 of 100 meshes. C: Peeling is observed at 31 to 60 of 100 meshes. D: Peeling is observed at 61 to 90 of 100 meshes. E: Peeling is observed at 91 or more of 100 meshes. (2) Change in appearance after weather resistance test. The cured film formed on the urethane plastic lens substrate was exposed to light for 100 hours using a xenon weather meter (irradiation intensity 40 mW/ ^m2 ). The presence or absence of cracks in the cured film after exposure was visually examined.
(3) Adhesion test after weather resistance test The cured film formed on the urethane plastic lens substrate was exposed to light for 100 hours using a xenon weather meter (irradiation intensity 40 mW/ ^m2 ). The cured film after exposure was cross-cut and subjected to the same test as in (1) Adhesion test to check whether the cured film peeled off after peeling off the adhesive tape. The evaluation criteria used were the (1) Adhesion test.
(4) Scratch Resistance Test The surface of the cured film formed on the urethane plastic lens substrate was rubbed with steel wool #0000, and the cured film was visually inspected for scratches in a bright room under a fluorescent lamp. The scratch resistance test was performed once per 10 seconds with a load of 1 kg or more. The evaluation criteria were as follows:
A: No scratches were observed B: Some scratches were observed C: Significant scratches were observed (5) Transparency test In a dark room under a fluorescent lamp, the cured film formed on a urethane-based plastic substrate was visually inspected for cloudiness. The evaluation criteria were as follows:
A: Almost no clouding occurred B: Clouding occurred, but not to the extent that it was problematic as a transparent cured film C: Whitening was evident (6) Refractive Index The reflectance of the cured film formed on the glass substrate was measured using a reflectance measuring device (USPM-RU, manufactured by Olympus Corporation). The refractive index of the cured film was calculated from the measured reflectance using optical simulation.

(Reference Example 1)
Preparation of core zirconium oxide-stannic oxide composite oxide colloidal particles (T1-1) 293.7 g of tetramethylammonium hydrogen carbonate (containing 42.4% by mass in terms of tetramethylammonium hydroxide) aqueous solution was diluted with 111.5 g of pure water, and 168.4 g of zirconium oxycarbonate powder (containing 40.1% by mass in terms of _ZrO2 ) was gradually added while stirring the aqueous solution. After the addition was completed, the mixture was heated to 85°C, 9.6 g of metastannic acid (containing 86.0% by mass as _SnO2 ) was gradually added, and the mixture was aged at 105°C for 5 hours, and further hydrothermal treatment was performed at 145°C for 5 hours. Next, the sol was washed and concentrated while adding pure water in an ultrafiltration device. The obtained sol was an aqueous dispersion sol of alkaline zirconium oxide-stannic oxide composite oxide colloidal particles (T1-1), and had a pH of 9.4, a total metal oxide concentration (total of ZrO ₂ and SnO ₂ ) of 5.0 mass%, and an average particle diameter measured by dynamic light scattering (dynamic light scattering particle diameter) of 15 nm.

(Reference Example 2)
Preparation of silicon dioxide-stannic oxide composite oxide colloidal particles (T2-1) to be coated 77.2 g of JIS No. 3 sodium silicate (containing 29.8% by mass in terms of _SiO2 ) was dissolved in 668.8 g of pure water, and then _20.9 g of sodium stannate _NaSnO3.H2O (containing 55.1% by mass in terms of _SnO2 ) was dissolved. The resulting aqueous solution was passed through a column packed with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B). Next, 7.2 g of diisopropylamine was added to the resulting aqueous dispersion sol. The resulting sol was an aqueous dispersion sol of alkaline silicon dioxide-stannic oxide composite oxide colloidal particles (T2-1), had a pH of 8.0, a total metal oxide concentration ( _SnO2 and _SiO2 ) of 1.7% by mass, and an average primary particle diameter of 1 nm to 4 nm as observed by a transmission electron microscope.

(Reference Example 3)
Preparation of stannic oxide colloidal particles (T1-2) as cores 64.0 g of oxalic acid dihydrate (45.7 g in terms of oxalic acid) was dissolved in 723.3 g of pure water, and heated to 70°C while stirring, and then 290.3 g of 35% hydrogen peroxide solution and 128.1 g of metal tin powder (containing 99.7% in terms of _SnO2 ) were added. The addition of hydrogen peroxide solution and metal tin was alternately performed in 10 separate portions. First, 29.0 g of 35% hydrogen peroxide solution was added, followed by 12.8 g of metal tin. This operation was repeated after waiting for the reaction to finish (10 to 15 minutes). The time required for the addition was 2 hours, and after the addition was finished, the liquid temperature was kept at 90°C while heating for 2 hours to finish the reaction. Next, 394.5 g of 35% hydrogen peroxide solution was added, and the mixture was kept at 90°C for 5 hours. Next, 5.1 g of isopropylamine was added, and the mixture was kept at 50° C. for 3 hours, and then passed through a column packed with 500 mL of anion exchange resin (Amberlite (registered trademark) IRA-410). The obtained sol was an aqueous dispersion sol of alkaline stannic oxide composite oxide colloidal particles (T1-2), and had a pH of 11.0, an _SnO2 concentration of 4.0 mass%, and an average particle size measured by a dynamic light scattering method (dynamic light scattering particle size) of 20 nm.

(Reference Example 4)
Preparation of titanium oxide-stannic oxide composite oxide colloidal particles (T1-3) as cores 319.5 g of 25 mass% tetramethylammonium hydroxide aqueous solution was dissolved in 947.1 g of pure water, and then 14.8 g of metastannic acid (containing 12.5 g in terms of _SnO2 ), 236.6 g of titanium tetraisopropoxide (containing 66.6 g in terms of _TiO2 ), and 82.0 g of oxalic acid dihydrate (containing 58.5 g in terms of oxalic acid) were added under stirring. The mixed solution was held at 80 ° C for 2 hours, and further reduced to 580 Torr and held for 2 hours to prepare a mixed solution. The mixed solution was charged into a glass-lined autoclave vessel, hydrothermally treated at 140 ° C for 5 hours, cooled to room temperature, and then taken out. The obtained sol was an aqueous dispersion sol of acidic titanium oxide-stannic oxide composite oxide colloidal particles (T1-3), with a pH of 3.9, a total metal oxide concentration (TiO2 and SnO2) of 5.0 mass%, and an average particle size (dynamic light scattering particle size) of 16 nm as determined by dynamic light scattering. The obtained sol was dried at 110°C, and the powder was subjected to X-ray diffraction analysis, which confirmed that the powder was rutile crystals.

(Production Example 1)
Preparation of zirconium oxide-stannic oxide composite oxide colloid particles (T3-1) modified with silicon dioxide-stannic oxide composite oxide To 1411.7 g of the aqueous dispersion sol of alkaline zirconium oxide-stannic oxide composite oxide colloid particles (T1-1) obtained in Reference Example 1, 830.4 g of the aqueous dispersion sol of alkaline silicon dioxide-stannic oxide composite oxide colloid particles (T2-1) prepared in Reference Example 2 was added under stirring. Next, the mixture was heated to 95° C. and held for 2 hours, and then passed through a column packed with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B), and the aqueous dispersion sol after passing through was concentrated by ultrafiltration membrane method.
The dispersion medium of the obtained water-dispersed sol was then replaced with methanol using a rotary evaporator to obtain a methanol-dispersed sol of zirconium oxide-stannic oxide composite oxide colloidal particles (T3-1) modified with silicon dioxide-stannic oxide composite oxide. This methanol-dispersed sol had a pH of 5.0, a total metal oxide (ZrO ₂ , SnO ₂ , and SiO ₂ ) concentration of 38.5 mass%, a viscosity of 3.3 mPa·s, and an average particle size (dynamic light scattering particle size) of 20 nm as measured by dynamic light scattering (DLS).

(Production Example 2)
Preparation of zirconium oxide-stannic oxide composite oxide colloidal particles (T3-2) modified with silicon dioxide-stannic oxide composite oxide, in which an organosilicon compound having an acryloxy group is bonded to the surface 44.2 g of methanol was added to 155.8 g of the methanol dispersion sol of zirconium oxide-stannic oxide composite oxide colloidal particles (T3-1) modified with silicon dioxide-stannic oxide composite oxide obtained in Production Example 1. Next, 3.8 g of 3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM5103) was added under stirring, and reflux heating was performed at 70°C for 5 hours to obtain a methanol dispersion sol of zirconium oxide-stannic oxide composite oxide colloidal particles (T3-2) modified with silicon dioxide-stannic oxide composite oxide, in which an organosilicon compound having an acryloxy group is bonded to the surface. This methanol dispersion sol had a total metal oxide (ZrO ₂ , SnO ₂ , and SiO ₂ ) concentration of 30.5 mass %, a viscosity of 2.4 mPa·s, and an average particle size measured by dynamic light scattering (DLS) (dynamic light scattering particle size) of 25 nm.

(Production Example 3)
Preparation of zirconium oxide-stannic oxide composite oxide colloidal particles (T3-3) modified with silicon dioxide-stannic oxide composite oxide, in which an organosilicon compound having a ureido group is bonded to the surface 44.2 g of methanol was added to 155.8 g of the methanol dispersion sol of zirconium oxide-stannic oxide composite oxide colloidal particles (T3-1) modified with silicon dioxide-stannic oxide composite oxide obtained in Production Example 1. 7.3 g of a methanol solution of ureidopropyltriethoxysilane (concentration 50 mass%, Shin-Etsu Chemical Co., Ltd.: KBE585) was added under stirring, and reflux heating was performed at 70 ° C. for 5 hours, and a reduced pressure concentration process was performed using an evaporator to obtain a methanol dispersion sol of zirconium oxide-stannic oxide composite oxide colloidal particles (T3-3) modified with silicon dioxide-stannic oxide composite oxide, in which an organosilicon compound having a ureido group is bonded to the surface. This methanol dispersion sol had a total metal oxide (ZrO ₂ , SnO ₂ , and SiO ₂ ) concentration of 30.5 mass %, a viscosity of 2.3 mPa·s, and an average particle size measured by dynamic light scattering (DLS) (dynamic light scattering particle size) of 24 nm.

(Production Example 4)
Preparation of zirconium oxide-stannic oxide composite oxide colloidal particles (T3-4) modified with silicon dioxide-stannic oxide composite oxide, in which an organosilicon compound having a glycidyl group is bonded to the surface 44.2 g of methanol was added to 155.8 g of the methanol dispersion sol of zirconium oxide-stannic oxide composite oxide colloidal particles (T3-1) modified with silicon dioxide-stannic oxide composite oxide obtained in Production Example 1. 3.9 g of a methanol solution of 3-glycidoxypropyltriethoxysilane (concentration 50 mass%, Shin-Etsu Chemical Co., Ltd.: KBM403) was added under stirring, and reflux heating was performed at 70°C for 5 hours to obtain a methanol dispersion sol of zirconium oxide-stannic oxide composite oxide colloidal particles (T3-4) modified with silicon dioxide-stannic oxide composite oxide, in which an organosilicon compound having a glycidyl group is bonded to the surface. This methanol dispersion sol had a total metal oxide (ZrO ₂ , SnO ₂ , and SiO ₂ ) concentration of 30.5 mass %, a viscosity of 2.3 mPa·s, and an average particle size measured by dynamic light scattering (DLS) (dynamic light scattering particle size) of 22 nm.

(Production Example 5)
Preparation of stannic oxide colloidal particles (T3-5) modified with silicon dioxide-stannic oxide composite oxide To 1458.8 g of the aqueous dispersion sol of stannic oxide colloidal particles (T1-2) obtained in Reference Example 3, 514.9 g of the aqueous dispersion sol of alkaline silicon dioxide-stannic oxide composite oxide colloidal particles (T2-1) prepared in Reference Example 2 was added under stirring. The mixture was then heated to 95°C and held for 2 hours, after which the mixture was passed through a column packed with a hydrogen cation exchange resin (Amberlite (registered trademark) IR-120B). The aqueous dispersion sol after passing through was then concentrated by ultrafiltration membrane method.
The dispersion medium of the obtained water-dispersed sol was then replaced with methanol using a rotary evaporator to obtain a methanol-dispersed sol of stannic oxide colloidal particles (T3-5) modified with silicon dioxide-stannic oxide composite oxide. This methanol-dispersed sol had a total metal oxide (SnO ₂ and SiO ₂ ) concentration of 30.5 mass%, a viscosity of 1.3 mPa·s, and an average particle size (dynamic light scattering particle size) of 18 nm as measured by dynamic light scattering (DLS).

(Production Example 6)
Preparation of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (T3-6) modified with silicon dioxide-stannic oxide composite oxide 82.7 g of zirconium oxychloride (containing 21.2% by mass in terms of _ZrO2 ) was diluted with 501.1 g of pure water to prepare 583.8 g of an aqueous solution of zirconium oxychloride (containing 3.0% by mass in terms of _ZrO2 ), to which 1516.2 g of the aqueous dispersion sol of titanium oxide-stannic oxide composite oxide colloidal particles (T1-3) prepared in Reference Example 4 was added under stirring. Then, hydrolysis was carried out by heating to 95°C, and an aqueous dispersion sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles having a thin film layer of zirconium oxide formed on the surface was obtained. 2041.2 g of the obtained water-dispersed sol was added under stirring to 1763.3 g of the water-dispersed sol of alkaline silicon dioxide-stannic oxide composite oxide colloidal particles (T2-1) prepared in Reference Example 2, and the mixture was passed through a column packed with 500 mL of anion exchange resin (Amberlite (registered trademark) IRA-410, manufactured by Organo Corporation). The water-dispersed sol after passing through was then heated at 95° C. for 3 hours and concentrated by ultrafiltration membrane method.
The dispersion medium of the obtained water-dispersed sol was then replaced with methanol using a rotary evaporator to obtain a methanol-dispersed sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (T3-6) modified with silicon dioxide-stannic oxide composite oxide. This methanol-dispersed sol had a pH of 5.2, a total metal oxide (TiO ₂ , ZrO 2 , SnO ₂ , and SiO ₂ ) concentration of 30.5 mass%, a viscosity of 1.8 mPa·s, and an average particle size (dynamic light scattering particle size) of 20 _nm as measured by dynamic light scattering (DLS).

Example 1
(Preparation of Coating Composition)
Into a glass vessel equipped with a magnetic stirrer, 62.4 parts by mass of 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM403), 8.1 parts by mass of tetraethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.8 parts by mass of trade name X-12-1154 (manufactured by Shin-Etsu Chemical Co., Ltd.), and 26.2 parts by mass of methanol were added, and 18.6 parts by mass of 0.01N hydrochloric acid was added dropwise over 3 hours while stirring at room temperature (20°C). After completion of the dropwise addition, stirring was continued for 0.5 hours at room temperature (20°C) to obtain a partial hydrolysate of 3-glycidoxypropyltrimethoxysilane, tetraethoxysilane, and trade name X-12-1154.
Next, 25.4 parts by mass of methanol, 45.7 parts by mass of propylene glycol monomethyl ether, 96.8 parts by mass of the methanol dispersion sol (containing 38.5% by mass calculated as total metal oxides) of the zirconium oxide-stannic oxide composite oxide colloidal particles (T3-1) modified with silicon dioxide-stannic oxide composite oxide obtained in Production Example 1, and further 6.1 parts by mass of aluminum acetylacetonate as a curing agent were added to 119.0 parts by mass of the partial hydrolyzate of 3-glycidoxypropyltrimethoxysilane, tetraethoxysilane, product name X-12-1154 described above, and thoroughly stirred to prepare a coating liquid (coating composition) for hard coat. The mass ratio of (S2-1-1):(S2-1-2) was 1:7.7, and the mass ratio of (S1):(S2) was 5.1:94.9.
(Formation and Evaluation of Cured Film)
A urethane-based plastic lens (refractive index _nD = 1.60) substrate and a glass substrate were prepared, and a hard coat coating liquid (coating composition) was applied (film thickness 3 μm) to these by a dip coating method. The solvent was evaporated at 80°C for 10 minutes, and then the coating film was cured by heat treatment at 120°C for 2 hours to form an optical component having a cured film.
The tests (1) to (6) above were carried out. The evaluation results are shown in Table 1.

Example 2
Except for changing the amount of 3-glycidoxypropyltrimethoxysilane added to 59.0 parts by mass and the amount of product name X-12-1154 added to 7.5 parts by mass, preparation of a coating composition and formation and evaluation of a cured film were carried out in the same manner as in Example 1. The mass ratio of (S2-1-1):(S2-1-2) was 1:7.28, and the mass ratio of (S1):(S2) was 10.1:89.9.

Example 3
Except for changing the amount of 3-glycidoxypropyltrimethoxysilane added to 52.0 parts by mass and the amount of product name X-12-1154 added to 15.0 parts by mass in Example 1, preparation of a coating composition and formation and evaluation of a cured film were carried out in the same manner as in Example 1. The mass ratio of (S2-1-1):(S2-1-2) was 1:6.42, and the mass ratio of (S1):(S2) was 20.0:80.0.

Example 4
In Example 2, the procedure was carried out in the same manner as in Example 2 until a partial hydrolysate of 3-glycidoxypropyltrimethoxysilane, tetraethoxysilane, and product name X-12-1154 was obtained. Next, 45.7 parts by mass of propylene glycol monomethyl ether, 122.2 parts by mass of a methanol dispersion sol (containing 30.5% by mass calculated as total metal oxides) of zirconium oxide-stannic oxide composite oxide colloidal particles (T3-2) modified with silicon dioxide-stannic oxide composite oxide obtained in Production Example 2 and having an organosilicon compound having an acryloxy group bonded to the surface, and 6.1 parts by mass of aluminum acetylacetonate as a curing agent were added to 119.0 parts by mass of the partial hydrolysate of the above-mentioned 3-glycidoxypropyltrimethoxysilane, tetraethoxysilane, and product name X-12-1154, and the mixture was thoroughly stirred to prepare a coating liquid (coating composition) for hard coat. The formation and evaluation of a cured film were carried out in the same manner as in Example 1. The mass ratio of (S2-1-1):(S2-1-2) was 1:7.28, and the mass ratio of (S1):(S2) was 10.1:89.9.

Example 5
In Example 4, a coating composition was prepared and a cured film was formed and evaluated in the same manner as in Example 4, except that a methanol dispersion sol (containing 30.5% by mass calculated as total metal oxides) of zirconium oxide-stannic oxide composite oxide colloidal particles (T3-3) modified with silicon dioxide-stannic oxide composite oxide, the surface of which is bonded to an organosilicon compound having a ureido group, obtained in Production Example 3, was used instead of the colloidal particles (T3-2) obtained in Production Example 2. The mass ratio of (S2-1-1):(S2-1-2) was 1:7.28, and the mass ratio of (S1):(S2) was 10.1:89.9.

Example 6
In Example 4, a coating composition was prepared and a cured film was formed and evaluated in the same manner as in Example 4, except that a methanol dispersion sol (containing 30.5% by mass calculated as total metal oxides) of zirconium oxide-stannic oxide composite oxide colloidal particles (T3-4) modified with silicon dioxide-stannic oxide composite oxide and having an organosilicon compound having a glycidyl group bonded to the surface thereof obtained in Production Example 4 was used instead of the colloidal particles (T3-2) obtained in Production Example 2. The mass ratio of (S2-1-1):(S2-1-2) was 1:7.28, and the mass ratio of (S1):(S2) was 10.1:89.9.

Example 7
In Example 4, a coating composition was prepared and a cured film was formed and evaluated in the same manner as in Example 4, except that a methanol dispersion sol (containing 30.5% by mass calculated as total metal oxides) of stannic oxide colloidal particles (T3-5) modified with silicon dioxide-stannic oxide composite oxide obtained in Production Example 5 was used instead of the colloidal particles (T3-2) obtained in Production Example 2. The mass ratio of (S2-1-1):(S2-1-2) was 1:7.28, and the mass ratio of (S1):(S2) was 10.1:89.9.

Example 8
(Preparation of Coating Composition)
Into a glass vessel equipped with a magnetic stirrer, 49.1 parts by mass of 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM403), 6.7 parts by mass of tetraethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), 6.3 parts by mass of trade name X-12-1154 (manufactured by Shin-Etsu Chemical Co., Ltd.), and 17.9 parts by mass of methanol were added, and 14.7 parts by mass of 0.01N hydrochloric acid was added dropwise over 3 hours while stirring at room temperature (20°C). After completion of the dropwise addition, stirring was continued for 0.5 hours at room temperature (20°C), and a partial hydrolysate of 3-glycidoxypropyltrimethoxysilane, tetraethoxysilane, and trade name X-12-1154 was obtained.
Next, 45.7 parts by mass of propylene glycol monomethyl ether, 147.9 parts by mass of the methanol dispersion sol (containing 30.5% by mass calculated as total metal oxides) of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (T3-6) modified with silicon dioxide-stannic oxide composite oxide obtained in Production Example 6, and 4.8 parts by mass of aluminum acetylacetonate as a curing agent were added to 94.6 parts by mass of the partial hydrolyzate of 3-glycidoxypropyltrimethoxysilane, tetraethoxysilane, product name X-12-1154 described above, and thoroughly stirred to prepare a coating liquid (coating composition) for hard coat. The mass ratio of (S2-1-1):(S2-1-2) was 1:7.33, and the mass ratio of (S1):(S2) was 10.1:89.9.
(Formation and Evaluation of Cured Film)
A cured film was formed and evaluated in the same manner as in Example 1, except that a urethane-based plastic lens (refractive index n _D =1.67) was used.

Comparative Example 1
Preparation of a coating composition and formation and evaluation of a cured film were carried out in the same manner as in Example 1, except that the amount of 3-glycidoxypropyltrimethoxysilane added was changed to 65.9 parts by mass and trade name X-12-1154 was not added.

Comparative Example 2
Preparation of a coating composition and formation and evaluation of a cured film were carried out in the same manner as in Example 2, except that trade name KR-518 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of trade name X-12-1154 in Example 2.
The product name KR-518 was a polymeric silane coupling agent having an alkoxy group (a combination of a methoxy group and an ethoxy group) and a mercapto group as side chains on the main chain of a polysiloxane, with an alkoxy group amount of 50 mass%, a viscosity of 20 mm ² /s, and a mercapto group equivalent of 800 g/mol.

Comparative Example 3
Preparation of a coating composition and formation and evaluation of a cured film were carried out in the same manner as in Example 2, except that trade name KR-519 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of trade name X-12-1154 in Example 2.
The product name KR-519 was a polymeric silane coupling agent having an alkoxy group (methoxy group) and an organic functional group (mercapto group and methyl group) in the main chain of polysiloxane, with an alkoxy group content of 30 mass%, a viscosity of 5 mm ² /s, and a reactive functional group (mercapto group) equivalent of 450 g/mol.

なお、比較例３の屈折率測定は反射率が著しく低下したため屈折率の測定ができなかった。

In addition, in the case of Comparative Example 3, the refractive index could not be measured because the reflectance was significantly decreased.

In all of Examples 1 to 8, after preparation of the hard coat coating liquid, the liquid did not undergo gelation or phase separation, and it was confirmed that the liquid was a coating composition with excellent stability. In addition, as shown in Table 1, in all of Examples 1 to 8, the optical components having a cured film, which is a cured product of the hard coat coating liquid (coating composition), had excellent adhesion to the substrate, appearance after weather resistance testing, adhesion after weather resistance testing, scratch resistance, and transparency.

On the other hand, Comparative Example 1 was inferior to the Examples in terms of adhesion and adhesion after the weather resistance test, Comparative Example 2 was inferior to the Examples in terms of appearance change after the weather resistance test, and Comparative Example 3 was inferior to the Examples in terms of transparency.

The coating composition of the present invention provides a cured film having excellent adhesion to a substrate, appearance after a weather resistance test, adhesion after a weather resistance test, scratch resistance, and transparency, and is applicable to eyeglass lenses, camera lenses, automobile window glass, computer displays, television displays, mobile terminal displays, etc.

Claims (15)

A coating composition comprising the following components (S) and (T):
the component (S) is a silane compound, a hydrolysate thereof, or a mixture thereof, the silane compound contains a polymeric silane coupling agent as a component (S1), the polymeric silane coupling agent has an alkoxysilyl group and a mercapto group as side chains on a main chain of an organic compound, the molar ratio of (mercapto group) to (alkoxysilyl group), that is, (mercapto group)/(alkoxysilyl group), is 2 to 6, and the mercapto group equivalent is in a ratio of 150 g/mol to 300 g/mol,
The component (T) is an organic solvent dispersion sol of colloidal particles (T3) formed of modified metal oxide colloidal particles having an average particle size of 2 nm to 100 nm, the surfaces of which are coated with a coating (T2) consisting of colloidal particles of an acidic oxide having an average primary particle size of 1 nm to 4 nm, the component (T1) being a core of colloidal particles of a metal oxide having an average particle size of 2 nm to 60 nm,
A coating composition comprising the component (S):component (T) in a mass ratio of 100:10 to 500. The coating composition according to claim 1, wherein the alkoxysilyl group on the side chain of the polymeric silane coupling agent of component (S1) is a trimethoxysilyl group, the molar ratio of (mercapto group) to (alkoxysilyl group) is (mercapto group)/(alkoxysilyl group) is 3 to 5, and the mercapto group equivalent is 200 g/mol to 250 g/mol. The silane compound of the component (S) further contains, as the component (S2), (S2-1):

(in formula (1), R1 is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkoxyaryl group, an alkenyl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, and is bonded to a silicon atom via a Si-C bond; R2 is an alkoxy group, an acyloxy group, or a halogen atom; and a is an integer of 0 to 3), and (S2-2):

(in formula (2), R3 is an alkyl group and is bonded to a silicon atom through a Si-C bond; R4 is an alkoxy group, an acyloxy group, or a halogen atom; Y is an alkylene group, an arylene group, an NH group, or an oxygen atom; b is an integer of 0 to 3; and c is an integer of 0 or 1). The coating composition according to claim 3, wherein the component (S2) comprises, as the component (S2-1-1), a silane compound in which a in formula (1) is 0, a silane coupling agent in which a in formula (1) is 1 and R ¹ is a methyl group, or a mixture thereof, and, as the component (S2-1-2), a silane coupling agent in which a in formula (1) is 1 and contains an epoxy group, a silane coupling agent in which a in formula (1) is 1 and contains a (meth)acryloyl group, or a mixture thereof, and the mass ratio of (S2-1-1):(S2-1-2) is in the range of 1:1 to 1:25. The coating composition according to claim 3, containing (S1):(S2) in a mass ratio of 5:95 to 30:70. 6. The coating composition according to claim 1, wherein the colloidal particles (T1) are an oxide of at least one metal selected from the group consisting of Ti, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Ta, W, Pb, Bi and Ce. 7. The coating composition according to claim 1, wherein the coating (T2) is an oxide of at least one metal selected from the group consisting of Si, Zr, Sn, Mo, Sb and W. The coating composition according to any one of claims 1 to 7, wherein the colloidal particles (T1) are a metal oxide consisting of tin oxide-zirconium oxide, or a metal oxide consisting of titanium oxide-tin oxide-zirconium oxide, and the coating ( T2 ) is a metal oxide consisting of tin oxide-silicon dioxide. 9. The coating composition according to claim 1 , wherein the surface of the component (T2) is coated with a (meth)acryloyloxytrialkoxysilane, a ureidopropyltrialkoxysilane, or a glycidoxypropyltrialkoxysilane. The coating composition according to any one of claims 1 to 9 , wherein component (T) further comprises an amine. The coating composition according to any one of claims 1 to 10 , further comprising a metal chelate or a perchlorate as a curing agent. The coating composition according to any one of claims 1 to 11 , further comprising a surfactant. An optical member having a cured film formed on the surface of an optical substrate from the coating composition according to any one of claims 1 to 12 . The optical member according to claim 13 , further comprising an anti-reflection film on the surface thereof. A method for producing a coating composition, comprising: a step (a) of preparing a silane compound, a hydrolyzate thereof, or a mixture thereof as a component (S); and a step (b) of mixing the component (S) obtained in the step (a) with a component (T) described below ,
the silane compound includes a polymeric silane coupling agent as a component (S1), the polymeric silane coupling agent having an alkoxysilyl group and a mercapto group as side chains on a main chain of an organic compound, the molar ratio of the (mercapto group) to the (alkoxysilyl group), that is, (mercapto group)/(alkoxysilyl group), being 2 to 6, and containing a mercapto group equivalent in a ratio of 150 g/mol to 300 g/mol;
The component (T) is an organic solvent dispersion sol of colloidal particles (T3) formed of modified metal oxide colloidal particles having an average particle size of 2 nm to 100 nm, the surfaces of which are coated with a coating (T2) consisting of acidic oxide colloidal particles having an average primary particle size of 1 nm to 4 nm, said component (T1) being a core of colloidal particles of a metal oxide having an average particle size of 2 nm to 60 nm.