JP7205685B2 - Coating composition containing cycloaliphatic epoxy compound - Google Patents

Description

The present invention relates to a coating composition using an organic-inorganic composite component that can be heat-cured or photo-cured, and to an optical member using the same.

Substrates coated with the coating composition are applied to various fields such as optical members, mechanical component materials, electronic component materials, building materials, and molding materials. Refractive index, hardness, adhesion, transparency, and light resistance are required for the coated substrate depending on the application. Also, the coating liquid for coating is required to have storage stability.

For example, an organic-inorganic composite resin composition containing an organic resin component and inorganic fine particles, which contains inorganic fine particles whose pH at 25° C. ranges from an acidic range to an alkaline range when the inorganic fine particle component is dispersed in a solution. An organic-inorganic composite resin composition has been disclosed (see Patent Document 1).

A photocurable coating agent for forming a hard protective film is disclosed which contains a cyclic siloxane having an alicyclic epoxy group in its side chain, inorganic oxide fine particles having an average particle size of 1 to 500 nm, and a soluble photoacid generator. (see Patent Document 2).

JP 2008-156625 JP 2007-211249

The present invention provides a coating composition that can be heat-cured or photo-cured and has improved storage stability for forming coated substrates that require refractive index, hardness, adhesion, transparency, and light resistance. .

（式（１ａ）、式（１ｂ）中、Ｒ^１及びＲ^１１はアクリロキシ基、メタクリロキシ基、アリール基、アルキル基、グリシドキシ基、ウレイド基又はそれら官能基を含む炭素原子数１～１０のアルキレン基を含み、Ｓｉ原子にＳｉ－Ｃ結合で結合しているものであり、Ｒ^２及びＲ^１２はアルコキシ基、アシルオキシ基、又はハロゲン基からなる加水分解基であり、少なくとも１つのＲ^２の加水分解基は金属酸化物粒子表面でＭ－Ｏ－Ｓｉの結合を形成し、ＭはＴｉ、Ｓｎ、Ｚｒ、Ｓｉ、Ａｌ、Ｓｂ、Ｆｅ、Ｃｕ、Ｚｎ、Ｙ、Ｎｂ、Ｍｏ、Ｉｎ、Ｔａ、Ｐｂ、Ｂｉ、Ｈｆ、Ｇｅ、Ｃｅ、Ｗからなる群より選ばれた少なくとも１種の金属を示し、Ｙはアルキレン基、アリーレン基、ＮＨ基、又は酸素原子を示す。ａは１
～３の整数を示し、ｄは０～３の整数を示し、ｅは０又は１の整数を示す。）であり、式（２）の脂環式エポキシ化合物が：

（式（２）中、Ｒ^３はエポキシシクロアルキル基を含む炭素原子数１～１０のアルキレン基であり、Ｒ４基は水素原子又はメチル基を示し、Ｒ^３基とＲ^４基はそれぞれ同一のＳｉ原子にＳｉ－Ｃ結合又はＳｉ－Ｈ結合で結合しているものであり、ｎは３～５の整数を示す。）である上記コーティング組成物、
第２観点として、式（２）中、Ｒ^３のエポキシシクロアルキル基が、エポキシシクロヘキシル基である第１観点に記載のコーティング組成物、
第３観点として、金属酸化物粒子（Ａ）が、２～１００ｎｍの平均粒子径を有し、且つＴｉ、Ｓｎ、Ｚｒ、Ｓｉ、Ａｌ、Ｓｂ、Ｆｅ、Ｃｕ、Ｚｎ、Ｙ、Ｎｂ、Ｍｏ、Ｉｎ、Ｔａ、Ｐｂ、Ｂｉ、Ｈｆ、Ｇｅ、Ｃｅ、Ｗからなる群より選ばれた少なくとも１種の金属の酸化物又は複合酸化物（ａ１）である第１観点又は第２観点に記載のコーティング組成物、
第４観点として、金属酸化物粒子（Ａ）が、２～１００ｎｍの平均粒子径を有し、且つＴｉ、Ｓｎ、Ｚｒ、Ｓｉ、Ａｌ、Ｓｂ、Ｆｅ、Ｃｕ、Ｚｎ、Ｙ、Ｎｂ、Ｍｏ、Ｉｎ、Ｔａ、Ｐｂ、Ｂｉ、Ｈｆ、Ｇｅ、Ｃｅ、Ｗからなる群より選ばれた少なくとも１種の金属の酸化物又は複合酸化物（ａ１）を核として、その表面を１～４０ｎｍの平均一次粒子径を有し、且つＴｉ、Ｓｎ、Ｚｒ、Ｓｉ、Ａｌ、Ｓｂ、Ｆｅ、Ｃｕ、Ｚｎ、Ｙ、Ｎｂ、Ｍｏ、Ｉｎ、Ｔａ、Ｐｂ、Ｂｉ、Ｈｆ、Ｇｅ、Ｃｅ、Ｗからなる群より選ばれた少なくとも１種の金属の酸化物又は複合酸化物（ａ２）から成る少なくとも１層で被覆した金属酸化物粒子（Ａ）であって、（ａ１）からなる粒子と（ａ２）からなる層は金属成分が異なるか又は複合酸化物として異なり、最外層に被覆された（ａ２）は金属成分としてＳｉを含んでいるものである第１観点乃至第３観点の何れか一つに記載のコーティング組成物、
第５観点として、金属酸化物粒子（Ａ）が、（ａ１）からなる粒子に、（ａ２）からなる被覆層が形成されたものである第４観点に記載のコーティング組成物、
第６観点として、金属酸化物粒子（Ａ）が、（ａ１）からなる粒子に、（ａ２）からなる中間層と、（ａ２）からなる被覆層が形成されたものである第４観点に記載のコーティング組成物、
第７観点として、更に式（３）の非脂環式エポキシ化合物（Ｃ）：

（式（３）中、Ｔはｍ価の炭素原子数１～４０の有機基であって、該有機基は飽和又は不飽和であり且つ鎖式、環式、又は縮合環式の炭化水素基であり、ｍは１～１０の整数を示す。）を含み、脂環式エポキシ化合物（Ｂ）と非脂環式エポキシ化合物（Ｃ）からなるエポキシ化合物中で、脂環式エポキシ化合物（Ｂ）が１０～７５質量％、非脂環式エポキシ化合物（Ｃ）が２５～９０質量％である第１観点乃至第６観点の何れか一つに記載のコーティング組成物、
第８観点として、更に熱酸発生剤及び／又は光酸発生剤を含む第１観点乃至第７観点の何
れか一つに記載のコーティング組成物、
第９観点として、更にクエンチャーとしてアミン化合物を含有する第１観点乃至第８観点の何れか一つに記載のコーティング組成物、
第１０観点として、更に界面活性剤を含む第１観点乃至第９観点の何れか一つに記載のコーティング組成物、
第１１観点として、基板上に第１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で被覆する被覆基板の製造方法、及び
第１２観点として、第１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で被覆された基材である。 As a first aspect of the present invention, metal oxide particles having an average particle diameter of 2 nm to 100 nm and surface-coated with a hydrolyzable silane containing a hydrolyzable silane of formula (1a) and/or formula (1b) A coating composition comprising (A) and a cycloaliphatic epoxy compound (B) of formula (2), wherein the hydrolyzable silane of formula (1a) and/or formula (1b) is:

(In formulas (1a) and (1b), R ¹ and R ¹¹ are acryloxy groups, methacryloxy groups, aryl groups, alkyl groups, glycidoxy groups, ureido groups, or alkylene groups having 1 to 10 carbon atoms containing these functional groups. and is bonded to the Si atom with a Si—C bond, R ² and R ¹² are hydrolyzable groups consisting of alkoxy groups, acyloxy groups, or halogen groups, and at least one hydrolyzate of R ² The groups form MO-Si bonds on the surface of the metal oxide particles, and M is Ti, Sn, Zr, Si, Al, Sb, Fe, Cu, Zn, Y, Nb, Mo, In, Ta, Pb , Bi, Hf, Ge, Ce, and W, Y is an alkylene group, an arylene group, an NH group, or an oxygen atom, a is 1
represents an integer of ˜3, d represents an integer of 0 to 3, and e represents an integer of 0 or 1. ) and the cycloaliphatic epoxy compound of formula (2) is:

(In formula (2), R ³ is an alkylene group having 1 to 10 carbon atoms including an epoxycycloalkyl group, R 4 represents a hydrogen atom or a methyl group, and R ³ and R ⁴ are the same is bonded to the Si atom with a Si—C bond or Si—H bond, and n represents an integer of 3 to 5.),
As a second aspect, the coating composition according to the first aspect, wherein in formula (2), the epoxycycloalkyl group of R ³ is an epoxycyclohexyl group;
As a third aspect, the metal oxide particles (A) have an average particle diameter of 2 to 100 nm and are Ti, Sn, Zr, Si, Al, Sb, Fe, Cu, Zn, Y, Nb, Mo, The coating according to the first aspect or the second aspect, which is an oxide or composite oxide (a1) of at least one metal selected from the group consisting of In, Ta, Pb, Bi, Hf, Ge, Ce and W. Composition,
As a fourth aspect, the metal oxide particles (A) have an average particle diameter of 2 to 100 nm, and Ti, Sn, Zr, Si, Al, Sb, Fe, Cu, Zn, Y, Nb, Mo, With an oxide or composite oxide (a1) of at least one metal selected from the group consisting of In, Ta, Pb, Bi, Hf, Ge, Ce and W as a nucleus, the surface thereof has an average primary thickness of 1 to 40 nm. from the group consisting of Ti, Sn, Zr, Si, Al, Sb, Fe, Cu, Zn, Y, Nb, Mo, In, Ta, Pb, Bi, Hf, Ge, Ce, W Metal oxide particles (A) coated with at least one layer of at least one selected metal oxide or composite oxide (a2), wherein the particles consist of (a1) and the layer consists of (a2) The coating according to any one of the first to third aspects, wherein the metal component is different or different as a composite oxide, and (a2) coated on the outermost layer contains Si as a metal component Composition,
As a fifth aspect, the coating composition according to the fourth aspect, wherein the metal oxide particles (A) are particles of (a1) on which a coating layer of (a2) is formed;
As a sixth aspect, described in the fourth aspect, wherein the metal oxide particles (A) are particles of (a1) on which an intermediate layer of (a2) and a coating layer of (a2) are formed. a coating composition of
As a seventh aspect, further non-alicyclic epoxy compound (C) of formula (3):

(In the formula (3), T is an m-valent organic group having 1 to 40 carbon atoms, the organic group being a saturated or unsaturated chain, cyclic, or condensed cyclic hydrocarbon group and m represents an integer of 1 to 10.), Among the epoxy compounds consisting of the alicyclic epoxy compound (B) and the non-alicyclic epoxy compound (C), the alicyclic epoxy compound (B) is 10 to 75% by mass and the non-alicyclic epoxy compound (C) is 25 to 90% by mass, the coating composition according to any one of the first to sixth aspects,
As an eighth aspect, the coating composition according to any one of the first to seventh aspects, further comprising a thermal acid generator and/or a photoacid generator;
As a ninth aspect, the coating composition according to any one of the first aspect to the eighth aspect, further containing an amine compound as a quencher;
As a tenth aspect, the coating composition according to any one of the first to ninth aspects, further comprising a surfactant;
As an eleventh aspect, a method for producing a coated substrate in which a substrate is coated with the coating composition according to any one of the first to tenth aspects, and as a twelfth aspect, any one of the first to tenth aspects A substrate coated with a coating composition according to any one.

The present invention provides metal oxide particles (A) surface-coated with a hydrolyzable silane containing a hydrolyzable silane compound of formula (1a) and/or formula (1b), and an alicyclic epoxy compound of formula (2) ( B).

The metal oxide particles (A) are oxides or composite oxides composed of various metal components depending on the refractive index in order to adjust the refractive index. Sometimes. In order to improve the dispersibility in the solvent, it is possible to improve the dispersibility by introducing an organic functional group to the surface of the metal oxide particles in accordance with the hydrophilicity/hydrophobicity of the solvent. Introduction of organic functional groups can be achieved by using a hydrolyzable silane compound, such as a silane coupling agent. The hydrolyzable silane forms a MO-Si bond (M is a metal) between the silanol group generated by hydrolysis of the hydrolyzable group and the hydroxyl group on the surface of the metal particle, and coats the metal oxide particle. can do For example, in a silane coupling agent having three hydrolyzable groups, at least one hydrolyzed silanol group reacts with a hydroxyl group on the metal particle surface. All three hydrolyzable groups of the silane coupling agent may be bonded to the hydroxyl groups on the surface of the metal by hydrolysis, or may exist without reacting with the hydroxyl groups on the surface of the metal particles.

The alicyclic epoxy compound of formula (2) is an alicyclic epoxy compound having a cyclic siloxane structure. Having a cyclic siloxane structure provides high heat resistance and high compatibility with metal oxide particles. In addition, since it has an alicyclic epoxy structure, it has low viscosity and high handleability, and can impart transparency and heat resistance to the cured product. It also has high cationic curability.

A coating composition comprising metal oxide particles (A) surface-coated with a hydrolyzable silane compound of formula (1a) and/or formula (1b) and an alicyclic epoxy compound (B) of formula (2) , is highly stable and suitable for coating agents.

The present invention provides metal oxide particles (A) having an average particle size of 2 nm to 100 nm and surface-coated with a hydrolyzable silane containing a hydrolyzable silane of formula (1a) and/or formula (1b); A coating composition comprising an alicyclic epoxy compound (B) of formula (2).

The coating composition of the present invention contains a solvent in addition to the above components, and may optionally contain thermal acid generators, photoacid generators, quenchers, surfactants and the like.

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

In the hydrolyzable silane compound of formula (1a) and/or formula (1b), R ¹ and R ¹¹ are acryloxy groups, methacryloxy groups, aryl groups, alkyl groups, glycidoxy groups, ureido groups, or carbon atoms containing these functional groups. It contains 1 to ¹⁰ alkylene groups and is bonded to the Si atom via a Si ^— C bond; The hydrolyzable groups of ^two R2 form MO-Si bonds on the metal oxide particle surface, where M is Ti, Sn, Zr, Si, Al, Sb, Fe, Cu, Zn, Y, Nb, Mo , In, Ta, Pb, Bi, Hf, Ge, Ce, and W, and Y represents an alkylene group, an arylene group, an NH group, or an oxygen atom. a represents an integer of 1 to 3, d represents an integer of 0 to 3, and e represents an integer of 0 or 1.

The hydrolyzable silanes used for surface coating the metal oxide particles (A) can comprise hydrolyzable silanes of formula (1a) and/or hydrolyzable silanes of formula (1b). The hydrolyzable silane of the formula (1a) and the hydrolyzable silane of the formula (1b) can be used in combination with other hydrolyzable silanes. The weight ratio of hydrolyzable silane (1b) to other hydrolyzable silanes can be in the range of 1:0.1 to 1.0, or 1:0.5 to 1.0.

The surface coating amount of the metal oxide particles (A) is 0.1/nm ² to 3.0/nm ² or 0.3/nm as the number of silane compounds coated on the surface of the metal oxide particles. It can be used in the range of ² to 1.5/nm ² .

The above alkyl group is an alkyl group having 1 to 10 carbon atoms, such as methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group. group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3 -methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group , 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl -n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1, 2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl -cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n- propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group , 2-ethyl-2-methyl-cyclopropyl group and 2-ethyl-3-methyl-cyclopropyl group.

Further, examples of the alkylene group include alkylene groups derived from the above alkyl groups.

The aryl group includes, for example, a phenyl group, a naphthyl group, an anthryl group, and the like, and the arylene group is a group derived from the above aryl group, and includes a phenylene group, a naphthylene group, an anthrylene group, and the like.

Examples of the alkoxy group 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 group, n-pentyloxy 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 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 and 1-ethyl-2-methyl- cyclopropoxy, cyclobutoxy, 1-methyl-cyclopropoxy, 2-methyl-cyclopropoxy, cyclopentyloxy and 1-methyl-cyclobutoxy as cyclic alkoxy groups; , 2-methyl-cyclobutoxy group, 3-methyl-cyclobutoxy group, 1,2-dimethyl-cyclopropoxy group, 2,3-dimethyl-cyclopropoxy group, 1-ethyl-cyclopropoxy group, 2-ethyl-cyclo propoxy group, cyclohexyloxy group, 1-methyl-cyclopentyloxy group, 2-methyl-cyclopentyloxy group, 3-methyl-cyclopentyloxy group, 1-ethyl-cyclobutoxy group, 2-ethyl-cyclobutoxy group, 3-ethyl-cyclobutoxy group, 1,2-dimethyl-cyclobutoxy group, 1,3-dimethyl-cyclobutoxy group, 2,2-dimethyl-cyclobutoxy group, 2,3-dimethyl-cyclobutoxy group, 2, 4-dimethyl-cyclobutoxy group, 3,3-dimethyl-cyclobutoxy group, 1-n-propyl-cyclopropoxy group, 2-n-propyl-cyclopropoxy group, 1-i-propyl-cyclopropoxy group, 2- i-propyl-cyclopropoxy group, 1,2,2-trimethyl Chill-cyclopropoxy group, 1,2,3-trimethyl-cyclopropoxy group, 2,2,3-trimethyl-cyclopropoxy group, 1-ethyl-2-methyl-cyclopropoxy group, 2-ethyl-1-methyl- Cyclopropoxy group, 2-ethyl-2-methyl-cyclopropoxy group, 2-ethyl-3-methyl-cyclopropoxy group and the like.

The acyloxy group having 1 to 10 carbon atoms is, for example, a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an i-propylcarbonyloxy group, an n-butylcarbonyloxy group, i-butyl carbonyloxy 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, 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, 1-ethyl-1-methyl-n-propylcarbonyloxy group, 1-ethyl-2-methyl-n-propylcarbonyloxy group, phenylcarbonyloxy group, tosylcarbonyloxy group and the like.

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

Examples of the above hydrolyzable silanes include the following compounds.

In the above formula, ^R2 represents a hydrolyzable group consisting of an alkoxy group, an acyloxy group, or a halogen group. These are available as silane coupling agents from Shin-Etsu Chemical Co., Ltd.

The compound of formula (1b) contains a trimethylsilylating agent and includes hexamethyldisilane, hexamethyldisiloxane, hexamethyldisilazane and the like. These silylating agents are available from Tokyo Chemical Industry Co., Ltd.

In the alicyclic epoxy compound of formula (2), R ³ is an alkylene group having 1 to 10 carbon atoms including an epoxycycloalkyl group, R 4 is a hydrogen atom or a methyl group, and R ³ and R ⁴ are are bonded to the same Si atom via Si--C bonds or Si--H bonds, and n is an integer of 3-5. Examples of n include integers of 3, 4 and 5, with 4 being particularly preferred.

The ^{epoxycycloalkyl} group of R3 is a cyclic alkyl group having an epoxy ring. Cyclic alkyl groups can have monocyclic and polycyclic ring structures. Examples thereof include cyclopentyl, cyclohexyl, norbornane, adamantane, etc., but a cyclohexyl structure is preferred ^, and an epoxycyclohexyl group can be used as the epoxycycloalkyl group of R3.

The metal oxide particles (A) have an average particle diameter of 2 to 100 nm, or 3 to 50 nm, and are composed of Ti, Sn, Zr, Si, Al, Sb, Fe, Cu, Zn, Y, Nb, Mo, At least one metal oxide or composite oxide (a1) selected from the group consisting of In, Ta, Pb, Bi, Hf, Ge, Ce and W can be used. The value of the average particle size of the metal oxide or composite metal oxide includes the particle size measured by the dynamic light scattering method (DLS method).

For example, _TiO2 , _SnO2 , _ZrO2 , _SiO2 , _Al2O3 , _Sb2O5 , _{Fe2O3 , CuO} , _ZnO2 , _{Y2O3 , Nb2O5 , MoO3 , Ta2O 5} , PbO, Bi2O3, HfO2, In2O3, _GeO2 , CeO2 _{, WO3 ,} WO3 _{- Sb2O5 , WO3 - SnO2 , SnO2 - ZrO2} , _{TiO2 -} SnO ₂ , SnO ₂ -SiO ₂ , TiO ₂ -ZrO ₂ -SnO ₂ , TiO ₂ -CeO ₂ -SnO ₂ , WO ₃ -SnO ₂ -SiO ₂ and the like. Al ₂ O ₃ , Sb ₂ O ₅ , Fe ₂ O ₃ , CuO, ZnO ₂ , Y ₂ O ₃ , Nb ₂ O ₅ , MoO ₃ , Ta ₂ O ₅ , PbO, Bi ₂ O ₃ and HfO ₂ It can be contained as an impurity.

The metal oxide particles (A) have an average particle diameter of 2 to 100 nm, or 3 to 50 nm, and are Ti, Sn, Zr, Si, Al, Sb, Fe, Cu, Zn, Y, Nb, Mo, With at least one metal oxide or composite oxide (a1) selected from the group consisting of In, Ta, Pb, Bi, Hf, Ge, Ce, W as a nucleus, the surface thereof has a thickness of 1 to 40 nm, or 1 Ti, Sn, Zr, Si, Al, Sb, Fe, Cu, Zn, Y, Nb, Mo, In, Ta, Pb, Bi, Hf, Ge, Ce, Metal oxide particles (A) coated with at least one layer of at least one metal oxide or composite oxide (a2) selected from the group consisting of W, the particles consisting of (a1) and ( The layer composed of a2) has different metal components or different composite oxides, and (a2) coated on the outermost layer may contain Si as a metal component. In addition, (a2) can contain Al, Fe, Cu, Y, Nb, Mo, Ta, Pb, Bi, and Hf as impurities of metal components.

Metal oxide particles (A) may have a structure in which a coating layer of (a2) is formed on particles of (a1). The value of the average primary particle size of the metal oxide or composite oxide (a2) that is the coating includes the particle size measured by observation with a transmission electron microscope.

The metal oxide particles (A) may have a structure in which an intermediate layer of (a2) and a coating layer of (a2) are formed on particles of (a1). When the surface of the metal oxide colloidal particles (A) is coated with the particles of (a2) on the particles of (a1), the reaction at the interface between the particles causes the modified metal oxide colloidal particles (A) to be obtained. Particle size values can vary. Therefore, when the particle diameter of the modified metal oxide colloidal particles (A) is evaluated by the average particle diameter measured by observation with a transmission electron microscope, this value is the same as that of the metal oxide colloidal particles (A) and the inorganic oxide It may not necessarily match the sum of the primary particle sizes of the colloidal particles (B).

Composite metal oxide particles having these coating structures use SnO ₂ —ZrO ₂ and TiO ₂ —ZrO ₂ —SnO ₂ as core particles, and SiO ₂ and SnO ₂ —SiO as coating particles.
₂ , WO ₃ --SnO ₂ --SiO ₂ and the like can be used.

In the case of a particle consisting of a core particle and a coating layer, the weight ratio of the core particle (a1) to the coating layer particle (a2) is in the range of 1:0.01 to 1, or 1:0.1 to 0.5. can be used.

In the case of particles comprising a core particle, an intermediate layer, and a coating layer, the weight ratio of the core particle (a1), the intermediate layer particle (a2), and the coating layer particle (a2) is 1:0.01 to 1:0. .01 to 1,
Alternatively, it can be used in the range of 1:0.1-0.5:0.1-0.5.

The metal oxide particles (A) can be used as a colloidal solution of metal oxide particles. A colloidal solution (sol) of metal oxide particles can be used as an organic solvent sol by substituting an organic solvent for a solution produced as an aqueous sol. Solvents such as methanol, ethanol, propanol, methyl ethyl ketone, and propylene glycol monomethyl ether can be used as the organic solvent.

The surface treatment of the metal oxide particles (A) with a silane compound is performed, for example, by adding a hydrolyzable silane containing a hydrolyzable silane of formula (1a) and/or formula (1b) to a methanol sol of the metal oxide particles (A). Can be added for hydrolysis and surface coating.

For hydrolysis of an alkoxysilyl group, acyloxysilyl group or silyl halide group, 0.5 to 100 mol, preferably 1 to 10 mol of water is used per 1 mol of hydrolyzable group.

In addition, 0.001 to 10 mol, preferably 0.001 to 1 mol of hydrolysis catalyst can be used per 1 mol of hydrolyzable group.

The reaction temperature for hydrolysis and condensation is usually 20 to 80°C.

The hydrolysis may be a complete hydrolysis or a partial hydrolysis. That is, the hydrolyzate and the monomer may remain in the hydrolyzed condensate.

A catalyst can be used during the hydrolysis and condensation. A chelate compound, an organic acid, an inorganic acid, an organic base, or an inorganic base can be used in combination as the hydrolysis catalyst. For example, hydrochloric acid aqueous solution, acetic acid, ammonia aqueous solution, etc. can be used.

The content of the metal oxide particles (A) is 10 parts per 100 parts by mass of the total amount of the alicyclic epoxy compound (B) or the alicyclic epoxy compound (B) and the non-alicyclic epoxy compound (C). It can be contained in a ratio of up to 1000 parts by mass, or 50 to 500 parts by mass, or 50 to 300 parts by mass.

The alicyclic epoxy compound of formula (2) can be exemplified below.

These are available as silane compounds manufactured by Shin-Etsu Chemical Co., Ltd. The compound of formula (2-1) is available from Shin-Etsu Chemical Co., Ltd. under the trade name KR-470.

In the present invention, a non-alicyclic epoxy compound (C) of formula (3) can be used in combination. It is preferable to use a polyfunctional type non-alicyclic epoxy compound (C), and for example, a bifunctional epoxy compound and a trifunctional epoxy compound can be used.

In formula (3), T is an m-valent organic group having 1 to 40 carbon atoms, the organic group being a saturated or unsaturated chain, cyclic, or condensed cyclic hydrocarbon group; Yes, m is an integer from 1 to 10.

Non-alicyclic epoxy compounds (C) can be exemplified below.

These epoxy resins are available as epoxy compounds manufactured by Nagase ChemteX Corporation. The compound of formula (3-1) is a trade name EX-321L manufactured by Nagase ChemteX Co., Ltd. The compound of formula (3-2) is a trade name EX-212L manufactured by Nagase ChemteX Co., Ltd. Formula (3- The compound of 3) is available under the trade name EX-212P manufactured by Nagase ChemteX Corporation.

Moreover, it can be obtained as an epoxy compound manufactured by Japan Epoxy Resin Co., Ltd. The compound of formula (3-4) is Epicoat 828 (trade name) manufactured by Japan Epoxy Resin Co., Ltd. The compound of formula (3-5) is YX8000 (trade name) of Japan Epoxy Resin Co., Ltd., and the compound of formula (3-6) is The compound is available from Japan Epoxy Resin Co., Ltd. under the trade name of DME100.

As the epoxy compound, the alicyclic epoxy compound (B) can be used alone, but the alicyclic epoxy compound (B) and the non-alicyclic epoxy compound (C) can be used together.

In the epoxy compound consisting of the alicyclic epoxy compound (B) and the non-alicyclic epoxy compound (C), the alicyclic epoxy compound (B) is 10 to 75% by mass, and the non-alicyclic epoxy compound (C) is It can be used at a rate of 25 to 90% by mass.

An acid generator can be used in the present invention. A photoacid generator or a thermal acid generator can be used as the acid generator.

The photoacid generator or thermal acid generator is not particularly limited as long as it directly or indirectly generates an acid by light irradiation or heating.

Specific examples of photoacid generators include triazine-based compounds, acetophenone derivative compounds, disulfone-based compounds, diazomethane-based compounds, sulfonic acid derivative compounds, onium salts such as iodonium salts, sulfonium salts, phosphonium salts, and selenium salts, metallocene complexes, An iron arene complex or the like can be used.

Onium salts used as photoacid generators include iodonium salts such as diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate. diphenyliodonium hexafluoroarsenate, bis(p-tert-butylphenyl)iodonium hexafluorophosphate, bis(p-tert-butylphenyl)iodonium mesylate, bis(p-tert-butylphenyl)iodonium tosylate, bis (p-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis(p-tert-butylphenyl)iodonium tetrafluoroborate, bis(p-tert-butylphenyl)iodonium chloride, bis(p-chlorophenyl)iodonium chloride, bis( p-chlorophenyl)iodonium tetrafluoroborate, further bis(alkylphenyl)iodonium salts such as bis(4-t-butylphenyl)iodonium hexafluorophosphate, alkoxycarbonylalkoxy-trialkylaryliodonium salts (e.g. 4-[(1 -ethoxycarbonyl-ethoxy)phenyl]-(2,4,6-trimethylphenyl)-iodonium hexafluorophosphate, etc.), bis(alkoxyaryl)iodonium salts (e.g., (4-methoxyphenyl)phenyliodonium hexafluoroantimonate, etc.) bis (alkoxyphenyl) iodonium salts).

Sulfonium salts such as triphenylsulfonium chloride, triphenylsulfonium bromide, tri(p-methoxyphenyl)sulfonium tetrafluoroborate, tri(p-methoxyphenyl)sulfonium hexafluorophosphonate, tri(p-ethoxyphenyl)sulfonium tetrafluoroborate, tri Triphenylsulfonium salts such as phenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, (4-phenylthiophenyl) diphenylsulfonium hexafluoroantimonate, (4-phenylthiophenyl) diphenylsulfonium Hexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide-bis-hexafluoroantimonate, bis[4-(diphenylsulfonio)phenyl]sulfide-bis-hexafluorophosphate, (4-methoxyphenyl)diphenyl sulfonium salts such as sulfonium hexafluoroantimonate).

Phosphonium salts such as triphenylphosphonium chloride, triphenylphosphonium bromide, tri(p-methoxyphenyl)phosphonium tetrafluoroborate, tri(
Phosphonium salts such as p-methoxyphenyl)phosphonium hexafluorophosphonate, tri(p-ethoxyphenyl)phosphonium tetrafluoroborate, 4-chlorobenzenediazonium hexafluorophosphate, and benzyltriphenylphosphonium hexafluoroantimonate.

Selenium salts such as triphenylselenium hexafluorophosphate, metallocene complexes such as (η5 or η6-isopropylbenzene)(η5-cyclopentadienyl)iron(II) hexafluorophosphate.

Moreover, the following compounds can also be used as a photo-acid generator.

A sulfonium salt compound and an iodonium salt compound are preferable as the photoacid generator. Their anionic species include CF ₃ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ , C ₈ F ₁₇ SO ₃ ⁻ , camphorsulfonate anion, tosylate anion, BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ and SbF _6- ^and the like. Anion species such as phosphorus hexafluoride and antimony hexafluoride, which are particularly strongly acidic, are preferred.

The thermal acid generator includes sulfonium salts and phosphonium salts, with sulfonium salts being preferred. For example, the following compounds can be exemplified.

R includes an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 20 carbon atoms, and an alkyl group having 1 to 12 carbon atoms is particularly preferable.

Furthermore, the following thermal acid generators can be used.

The content of the thermal acid generator and/or the photoacid generator is 100 parts by mass of the total amount of the alicyclic epoxy compound (B) or the alicyclic epoxy compound (B) and the non-alicyclic epoxy compound (C). On the other hand, it can be used in the range of 0.01 to 10 parts by mass, or 0.1 to 5 parts by mass.

Thermal acid generators and photoacid generators generate acid by heat or light. Thermal acid generators can be used as photoacid generators, and photoacid generators can be used as thermal acid generators. You can also use it.

The coating composition of the present invention may contain one or more nitrogen-containing organic compounds (amine compounds) as basic compounds (quenchers).

As the nitrogen-containing organic compound, a compound capable of suppressing the diffusion speed when the acid generated by the acid generator diffuses into the film is suitable. By blending nitrogen-containing organic compounds, the diffusion rate of acid in the film is suppressed, improving resolution, suppressing changes in sensitivity after exposure, reducing dependence on substrates and environments, and improving exposure latitude and patterns. can be improved. Moreover, the storage stability of the coating composition can be improved.

Examples of such nitrogen-containing organic compounds (quenchers) include primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, and compounds containing carboxyl groups. Nitrogen compounds, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amides, imides, carbamates, ammonia, ammonium salts, sulfonium salts, etc. are mentioned.

Methylamine, ethylamine, n-propylamine as primary aliphatic amines, dimethylamine, diethylamine, di-n-propylamine as secondary aliphatic amines, tertiary aliphatic amines Specific examples of trimethylamine, triethylamine, tri-n-propylamine, aromatic amines and heterocyclic amines include aniline derivatives (eg, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N , N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitro aniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N,N-dimethyltoluidine, etc.), diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g. pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole etc.), oxazole derivatives (e.g. oxazole, isoxazole etc.), thiazole derivatives (e.g. thiazole , isothiazole etc.), imidazole derivatives (eg imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg pyrroline, 2-methyl-1-pyrroline etc.), pyrrolidine derivatives (eg pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1- Butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 4- pyrrolidinopyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (eg quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives, etc. are exemplified.

The content of the amine compound as a quencher is 0.001 with respect to 100 parts by mass of the total amount of the alicyclic epoxy compound (B) or the alicyclic epoxy compound (B) and the non-alicyclic epoxy compound (C). It can be used in the range of 1 part by mass to 1 part by mass, or 0.01 part by mass to 0.5 part by mass.

A surfactant can be used in the present invention. Surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol. Polyoxyethylene alkylallyl ethers such as ethers, polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Nonionic surfactants such as sorbitan fatty acid esters, trade names Ftop EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), trade names Megafac F171, F173, R-08, R-30, R-30N , R-40LM (manufactured by DIC Corporation), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), trade names Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass ( Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), polyether-modified silicone oil (L-7001, manufactured by Dow Corning Toray Co., Ltd.), etc. can be done. These surfactants are 0.002 to 3% by mass with respect to 100 parts by mass of the total amount of the alicyclic epoxy compound (B) or the alicyclic epoxy compound (B) and the non-alicyclic epoxy compound (C). , or can be added at a rate of 0.02 to 2% by mass.

As the solvent used in the coating composition of the present invention, any solvent capable of dissolving the solid content can be used without particular limitation. Examples of such solvents include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol mono Ether ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate , ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate , ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate , isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate , Propyl Propionate, Isopropyl Propionate, Butyl Propionate, Isobutyl Propionate, Methyl Butyrate, Ethyl Butyrate, Propyl Butyrate, Isopropyl Butyrate, Butyrate Butyl acid, isobutyl butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxy butyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N, Examples include N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone. These solvents can be used alone or in combination of two or more.

As a method for producing the coating composition, a container equipped with a stirrer is charged with a solvent, a colloidal solution of metal oxide particles (A), an alicyclic epoxy compound (B), a non-alicyclic epoxy compound (C), and if necessary It can be produced by adding a thermal acid generator and/or a photoacid generator, an amine compound as a quencher, and a surfactant, and stirring them. An amine compound as a thermal acid generator, a photoacid generator, or a quencher can be dissolved in advance in a part of the solvent and then added.

The use of the coating composition of the present invention is described below.

on substrates (such as film sheets, silicon wafer substrates, silicon/silicon dioxide coated substrates, silicon nitride substrates, glass substrates, ITO substrates, polyimide substrates, and low-k material coated substrates) The coating composition of the present invention is applied by a suitable coating method such as a spinner, a coater, etc., and then heated to form a thermally cured coating film. The heating conditions are appropriately selected from a heating temperature of 20° C. to 250° C. or 20° C. to 130° C. and a heating time of 0.3 to 120 minutes. Here, the film thickness of the coating film to be formed is, for example, 0.01 to 10 μm, 0.02 to 8 μm, 0.05 to 6 μm, or 0.1 to 5 μm. .

When the coated coating film is photocured, it is dried at 20 to 80 ° C. for a heating time of 0.3 to 60 minutes to remove the solvent. A coating film was formed by photocuring with an exposure amount of 1 to 20,000 mJ/cm ² , 10 to 15,000 mJ/cm ² , or 20 to 10,000 mJ/cm ² . The film thickness of the coating film to be formed is, for example, 0.01 to 10 μm, 0.02 to 8 μm, 0.05 to 6 μm, or 0.1 to 5 μm.

The present invention will be described in more detail below based on Production Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples.
Various physical properties of the dispersion liquid were obtained by the following measurement methods.
[Viscosity] Determined with an Ostwald viscometer (25°C).
[Moisture] Moisture content was determined by Karl Fischer titration.
[Average particle diameter by dynamic light scattering (dynamic light scattering particle diameter)] The sol was diluted with a dispersion solvent, and the parameters of the solvent were used to measure the dynamic light scattering measurement device: Zeta-Sizer manufactured by Malvern Instruments Ltd. It was measured.
[Average primary particle diameter measured by transmission electron microscope] The sol was dropped onto a copper mesh, dried, and observed at an acceleration voltage of 100 kV using a transmission electron microscope (JEM-1020 manufactured by JEOL Ltd.) to obtain 100 particles. was measured and averaged to determine the primary particle size.
Further, the physical properties of the optical members having cured films obtained in Examples and Comparative Examples were measured and evaluated by the following measuring methods.

(1) Refractive Index The reflectance of a cured film formed on a glass substrate was measured using a reflectance measuring instrument (USPM-RU manufactured by Olympus Corporation). From the measured reflectance, the refractive index of the cured film was calculated using optical simulation.

(2) Hardness Test Using a dynamic ultra-micro hardness tester (DUH-211 manufactured by Shimadzu Corporation), hardness HMs [N/mm ² ] of a cured film formed on a glass substrate was measured. Judgment criteria are as follows.
A: hardness is 250 or more B: hardness is 150 or more and less than 250 C: hardness is less than 150

(3) Adhesion test A cured film formed on a PET film (manufactured by Toyobo Co., Ltd., trade name Cosmoshine A4300) was cross-cut 100 times at intervals of 1 mm, and an adhesive tape (Nichiban Co., Ltd.) (manufactured by cellophane tape) was strongly affixed, the adhesive tape was rapidly peeled off, and the presence or absence of peeling of the cured film after peeling off the adhesive tape was examined. Evaluation criteria are as follows.
A: No peeling at all, or peeling of less than 5 out of 100 stitches can be confirmed.
B: peeling of 5 to 30 out of 100 eyes can be confirmed C: peeling of 31 to 60 out of 100 eyes can be confirmed D: peeling of 61 to 90 out of 100 eyes can be confirmed E: 91 or more out of 100 eyes peeling can be confirmed

(4) Transparency The haze value of the cured film formed on the glass substrate was measured using a haze meter (NDH7000 manufactured by Nippon Denshoku Industries Co., Ltd.). Judgment criteria are as follows.
A: Haze value is less than 0.3 B: Haze value is 0.3 or more and less than 1.0 C: Haze value is 1.0 or more and less than 3.0 D: Haze value is 3.0 or more Less than 10.0 E: Haze value is 10.0 or more

(5) Light resistance test Using a spectrophotometer (UV-3600 manufactured by Shimadzu Corporation), the transmittance of the obtained optical member (a cured film formed on a glass substrate) was measured, and the transmittance was measured according to JIS7373. Based on the YI value was calculated. After that, using a QUV accelerated weathering tester (UVA lamp irradiation intensity 890 mW/m ² ), the YI value of the optical member exposed for 120 hours was calculated. ΔYI of the optical member before and after the ultraviolet irradiation was calculated. Judgment criteria are as follows.
A: ΔYI is less than 1.0 B: ΔYI is 1.0 or more and less than 2.0 C: ΔYI is 2.0 or more

(6) Storage stability test A test similar to (2) Hardness test was performed using a coating agent stored for one month in a refrigerator set at 5°C. Judgment criteria are as follows.
A: hardness change within ±10% compared to before storage B: hardness decreased by 10 to 30% compared to before storage C: hardness decreased by 30% or more compared to before storage

Reference Example 1: Preparation of Colloidal Particles (A1) of Titanium Oxide-Stannic Oxide Composite Oxide as Cores 319.5 g of a 25% by mass tetramethylammonium hydroxide aqueous solution was dissolved in 947.1 g of pure water, and then metastannic acid 14 was dissolved. .8 g (contains 12.5 g as SnO2), 236.6 g titanium tetraisopropoxide (contains 66.6 g as _TiO2 ), and 82.0 g oxalic acid _dihydrate (58.5 g as oxalic acid) ) was 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 put into a glass-lined autoclave container, subjected to hydrothermal treatment at 140° C. for 5 hours, cooled to room temperature, and taken out. The obtained sol was a water-dispersed sol of acidic titanium oxide-stannic oxide composite oxide colloidal particles (A1), and had a pH of 3.9 and a total metal oxide concentration (TiO2 and SnO2) of 5.0% by mass. The average particle size (dynamic light scattering particle size) determined by dynamic light scattering method was 16 nm. The powder obtained by drying the obtained sol at 110° C. was subjected to X-ray diffraction analysis, and it was confirmed to be rutile type crystals.

Reference Example 2: Preparation of Colloidal Particles (B1) of Silicon Dioxide-Stannic Oxide Composite Oxide for Coating 77.2 g of JIS No. 3 sodium silicate (containing 29.8% by mass in terms of SiO ₂ ) was added to 668.8 g of pure water. and then 20.9 g of sodium stannate NaSnO ₃ .H ₂ O (containing 55.1% by mass in terms of SnO ₂ ) was dissolved. The resulting aqueous solution was passed through a column packed with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B). Then, 7.2 g of diisopropylamine was added to the obtained water-dispersed sol. The obtained sol was a water-dispersed sol of alkaline silicon dioxide-tin oxide composite oxide colloidal particles (B1), pH 8.0, total metal oxide concentration (SnO ₂ and SnO ₂ ) 1.7 mass. %, and the primary particle size was 1 to 4 nm as observed by a transmission electron microscope.

Reference Example 3: Preparation of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C1) modified with silicon dioxide-stannic oxide composite oxide Zirconium oxychloride ₍ 21.2 mass in terms of ZrO2 % content) was diluted with 501.1 g of pure water to prepare 583.8 g of an aqueous zirconium oxychloride solution (containing 3.0% by mass in terms of ZrO ₂ ). 1516.2 g of water-dispersed sol of stannic composite oxide colloidal particles (A1) was added with stirring. Then, hydrolysis was performed by heating to 95° C. to obtain a water-dispersed sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles having a thin film layer of zirconium oxide formed on the surface. 2041.2 g of the obtained water-dispersed sol was added to 1763.3 g of the water-dispersed sol of the alkaline silicon dioxide-stannic oxide composite oxide colloidal particles (B1) prepared in Reference Example 2 with stirring, and anion exchange was performed. The solution was passed through a column packed with 500 ml of resin (Amberlite (registered trademark) IRA-410, manufactured by Organo Corporation). Then, the water-dispersed sol after passing the liquid was heated at 95° C. for 3 hours and then concentrated by an ultrafiltration membrane method.

Next, the dispersion medium of the obtained water-dispersed sol is replaced with methanol using a rotary evaporator, and the titanium oxide-stannic oxide-zirconium oxide composite oxide modified with the silicon dioxide-stannic oxide composite oxide is obtained. A methanol-dispersed sol of colloidal particles (C1) was obtained. This methanol-dispersed sol has a pH of 5.2, a total metal oxide (TiO ₂ , ZrO ₂ , SnO ₂ , and SiO ₂ ) concentration of 30.5% by mass, a viscosity of 1.8 mPa·s, and a dynamic light scattering method (DLS). The average particle size (dynamic light scattering method particle size) was 20 nm.

Reference Example 4: Preparation of core zirconium oxide-tin oxide composite oxide colloidal particles (A2) The 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 ZrO ₂ ) was gradually added while stirring the aqueous solution. After completion of the addition, the mixture was heated to 85°C, 9.6 g of metastannic acid (containing 86.0% by mass of SnO ₂ ) was gradually added, heat-aged at 105°C for 5 hours, and further heated at 145°C. A hydrothermal treatment was performed for 5 hours. Next, the sol was washed and concentrated by an ultrafiltration device while adding pure water. The resulting sol was a water-dispersed sol of alkaline zirconium oxide-stannic oxide composite oxide colloidal particles (A2), pH 9.4, total metal oxide concentration (total of ZrO ₂ and SnO ₂ ) of 5.5. It was 0% by mass and the average particle size (dynamic light scattering particle size) was 15 nm as determined by the dynamic light scattering method.

Reference Example 5: Preparation of colloidal particles (C2) of zirconium oxide-stannic oxide composite oxide modified with silicon dioxide-stannic oxide composite oxide Alkaline zirconium oxide-stannic oxide obtained in Reference Example 4 830.4 g of the aqueous dispersion of the alkaline silicon dioxide-stannic oxide colloidal particles (B1) prepared in Reference Example 2 was stirred into 1411.7 g of the aqueous dispersion of the colloidal particles of tin composite oxide (A2). added below. Then, after heating to 95 ° C. and holding for 2 hours, the solution was passed through a column packed with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B), and the water-dispersed sol after passing was subjected to ultrafiltration. Concentrated by filtration membrane method.

Next, the dispersion medium of the obtained water-dispersed sol is replaced with methanol using a rotary evaporator, and the zirconium oxide-stannic oxide composite oxide colloidal particles modified with silicon dioxide-stannic oxide composite oxide ( A methanol-dispersed sol of C2) was obtained. This methanol-dispersed sol has a pH of 5.0, a total metal oxide (ZrO ₂ , SnO ₂ , and SiO ₂ ) concentration of 38.5% by mass, a viscosity of 3.3 mPa s, and an average particle size determined by a dynamic light scattering method (DLS). The diameter (dynamic light scattering particle diameter) was 20 nm.

Reference Example 6: Preparation of core stannic oxide colloidal particles (A3) 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 with stirring. 290.3 g of 35% hydrogen peroxide solution and 128.1 g of metal tin powder (contains 99.7% in terms of SnO ₂ ) were added. The hydrogen peroxide solution and metallic tin were alternately added in 10 divisions. First, 29.0 g of 35% hydrogen peroxide solution and then 12.8 g of metallic tin were added. After waiting for the reaction to finish (10-15 minutes), this operation was repeated. The time required for the addition was 2 hours, and after the completion of the addition, the reaction was completed by heating for 2 hours while maintaining the liquid temperature at 90°C. Then, 394.5 g of 35% hydrogen peroxide water was added and the mixture was kept at 90° C. for 5 hours. Next, 5.1 g of isopropylamine was added, and after holding at 50° C. for 3 hours, the solution was passed through a column packed with 500 ml of an anion exchange resin (Amberlite® IRA-410). The resulting sol was a water-dispersed sol of alkaline stannic oxide composite oxide colloidal particles (A3), pH 11.0, SnO ₂ concentration 4.0% by mass, average particle diameter (dynamic It was 20 nm in terms of the particle size (measured by the light scattering method).

Reference Example 7: Preparation of stannic oxide colloidal particles (C3) modified with silicon dioxide-stannic oxide composite oxide 1458.8 g of water-dispersed sol of stannic oxide colloidal particles (A3) obtained in Reference Example 6 514.9 g of the aqueous dispersion sol of the alkaline silicon dioxide-stannic oxide composite oxide colloidal particles (B1) prepared in Reference Example 2 was added to the mixture while stirring. After heating to 95° C. and holding for 2 hours, the solution was passed through a column filled with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B). Then, the water-dispersed sol after passing the liquid was concentrated by an ultrafiltration membrane method.
Next, the dispersion medium of the resulting water-dispersed sol was replaced with methanol using a rotary evaporator to obtain a methanol-dispersed sol of stannic oxide colloidal particles (C3) modified with a silicon dioxide-stannic oxide composite oxide. Obtained. This methanol-dispersed sol has a total metal oxide (SnO ₂ and SiO ₂ ) concentration of 30.5% by mass, a viscosity of 1.3 mPa s, and an average particle size determined by dynamic light scattering (DLS) (dynamic light scattering method particle diameter) was 18 nm.

Production Example 1: Titanium oxide-stannic oxide-zirconium oxide composite oxide colloid particles (C4 ) To 200 g of the methanol-dispersed sol of the silicon dioxide-stannic oxide-modified titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C1) obtained in Reference Example 3, 3.9 g of phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM103) was added with stirring, and heated under reflux at 70° C. for 5 hours. Next, by using an evaporator to distill off methanol while adding methyl ethyl ketone at 180 Torr, the methanol is replaced with methyl ethyl ketone, and a silicon dioxide-stannic oxide formed by bonding an organosilicon compound having a phenyl group on the surface. A methyl ethyl ketone dispersion sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C4) modified with a composite oxide was obtained. This methyl ethyl ketone dispersion sol has a total metal oxide (TiO ₂ , ZrO ₂ , SnO ₂ , and SiO ₂ ) concentration of 30.5% by mass, a viscosity of 0.9 mPa s, and an average particle size ( Dynamic light scattering method particle size) was 19 nm.

Production Example 2: Titanium oxide-stannic oxide-zirconium oxide composite oxide colloid particles (C5 ) To 200 g of the methanol-dispersed sol of the silicon dioxide-stannic oxide-modified titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C3) obtained in Reference Example 3, 4.9 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM503) was added with stirring, and heated under reflux at 70° C. for 5 hours. Next, by using an evaporator to distill off methanol while adding methyl ethyl ketone at 180 Torr, the methanol is replaced with methyl ethyl ketone, and a silicon dioxide-stannic oxide in which an organosilicon compound having a methacrylic group on the surface is bonded. A methyl ethyl ketone dispersion sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C5) modified with the composite oxide was obtained. This methyl ethyl ketone dispersion sol has a total metal oxide (TiO ₂ , ZrO ₂ , SnO ₂ , and SiO ₂ ) concentration of 30.5% by mass, a viscosity of 1.2 mPa s, and an average particle size ( The dynamic light scattering method particle diameter) was 17 nm.

Production Example 3: Titanium oxide-stannic oxide-zirconium oxide composite oxide colloid particles (C6 ) To 200 g of the methanol-dispersed sol of the silicon dioxide-stannic oxide-modified titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C3) obtained in Reference Example 3, 2.4 g of trimethylmethoxysilane (manufactured by Dow Corning Toray Co., Ltd., product name: Z6013) was added with stirring, and heated under reflux at 70° C. for 5 hours. Next, by using an evaporator to distill off methanol while adding methyl ethyl ketone at 180 Torr, the methanol is replaced with methyl ethyl ketone, and an organic silicon compound having a methyl group on the surface is bonded to silicon dioxide-stannic oxide. A methyl ethyl ketone dispersion sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C6) modified with a composite oxide was obtained. This methyl ethyl ketone dispersion sol has a total metal oxide (TiO ₂ , ZrO ₂ , SnO ₂ , and SiO ₂ ) concentration of 30.5% by mass, a viscosity of 8.0 mPa s, and an average particle size determined by dynamic light scattering (DLS). (Dynamic light scattering method particle size) was 45 nm.

Production Example 4: Titanium oxide-stannic oxide-zirconium oxide composite oxide colloid modified with a silicon dioxide-stannic oxide composite oxide, comprising an organic silicon compound having a phenyl group and a glycidyl group bonded to the surface Preparation of particles (C7) Methanol-dispersed sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C3) modified with silicon dioxide-stannic oxide composite oxide obtained in Reference Example 3 To 200 g, 2.0 g of phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM103) and 2.3 g of 3-glycidoxypropyltrimethoxysilane (manufactured by Momentive, trade name SILQUEST A-187T) were added with stirring. was added and heated to reflux at 70° C. for 5 hours. Next, by using an evaporator to distill off methanol while adding propylene glycol monomethyl ether at 80 Torr, methanol is replaced with propylene glycol monomethyl ether, and an organosilicon compound having a phenyl group and a glycidyl group is bonded to the surface. Thus, a propylene glycol monomethyl ether dispersed sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C7) modified with silicon dioxide-stannic oxide composite oxide was obtained. This propylene glycol monomethyl ether dispersion sol has a total metal oxide (TiO ₂ , ZrO ₂ , SnO ₂ , and SiO ₂ ) concentration of 30.5% by mass, a viscosity of 3.4 mPa s, and an average The particle size (dynamic light scattering particle size) was 11 nm.

Production Example 5: Preparation of zirconium oxide-stannic oxide composite oxide colloidal particles (C8) modified with silicon dioxide-stannic oxide composite oxide, in which an organosilicon compound having a phenyl group is bonded to the surface Phenyltrimethoxysilane (Shin-Etsu 4.7 g of KBM103 (trade name, manufactured by Kagaku Kogyo Co., Ltd.) was added with stirring, and heated under reflux at 70° C. for 5 hours. Next, by using an evaporator to distill off methanol while adding methyl ethyl ketone at 180 Torr, the methanol is replaced with methyl ethyl ketone, and a silicon dioxide-stannic oxide formed by bonding an organosilicon compound having a phenyl group on the surface. A methyl ethyl ketone dispersed sol of zirconium oxide-stannic oxide composite oxide colloidal particles (C8) modified with the composite oxide was obtained. This methyl ethyl ketone dispersion sol has a total metal oxide (ZrO ₂ , SnO ₂ , and SiO ₂ ) concentration of 30.5% by mass, a viscosity of 4.1 mPa s, and an average particle size (dynamic light Scattering method particle size) was 33 nm.

Production Example 6: Preparation of Colloidal Particles (C9) of Silicon Dioxide-Stannic Oxide Composite Oxide Modified Stannic Oxide Composite Oxide, Comprising Organosilicon Compounds Having Phenyl Groups on Their Surfaces Reference Example 7 200 g of the methanol-dispersed sol of the colloidal particles (C3) of the silicon dioxide-stannic oxide-modified stannic oxide composite oxide obtained in , was added with phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd. 3.0 g of KBM103) (trade name) was added with stirring, and heated under reflux at 70° C. for 5 hours. Next, by using an evaporator to distill off methanol while adding methyl ethyl ketone at 180 Torr, the methanol is replaced with methyl ethyl ketone, and a silicon dioxide-stannic oxide formed by bonding an organosilicon compound having a phenyl group on the surface. A methyl ethyl ketone dispersion sol of stannic oxide composite oxide colloidal particles (C9) modified with the composite oxide was obtained. This methyl ethyl ketone dispersion sol has a total metal oxide (SnO ₂ and SiO ₂ ) concentration of 30.5% by mass, a viscosity of 3.4 mPa s, and an average particle size determined by dynamic light scattering (DLS) (dynamic light scattering particles diameter) was 20 nm.

Example 1
(Preparation of coating composition)
In a glass container equipped with a magnetic stirrer, 12.0 parts by mass of epoxy-modified organosiloxane (trade name KR470 manufactured by Shin-Etsu Chemical Co., Ltd.) and trimethylolpropane polyglycidyl ether (trade name manufactured by Nagase ChemteX Corporation) EX-321L) 3.0 parts by mass and 30.7 parts by mass of propylene glycol monomethyl ether were added, and the silicon dioxide- 49.2 parts by mass of methyl ethyl ketone dispersion sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C4) modified with stannic oxide composite oxide was added and stirred for 0.5 hour. Then, a propylene glycol monomethyl ether solution of a cationic polymerization initiator (manufactured by Sanshin Chemical Industry Co., Ltd., trade name San-Aid SI-100) (San-Aid SI-100 5.0% by mass) 3.0 parts by mass, storage stabilization aid N-methyl-2-pyrrolidone solution (SI auxiliary agent 5.0% by weight) of (Sanshin Chemical Industry Co., Ltd. trade name SI auxiliary agent), 0.15 parts by weight of polyether-modified silicone oil (Toray Dow Corning Add 2.0 parts by mass of a propylene glycol monomethyl ether solution (L-7001 10.0% by mass) (trade name L-7001 manufactured by Co., Ltd.) and stir for 0.5 hours to prepare a coating liquid (coating composition). bottom.

(Formation and evaluation of cured film)
A glass substrate and a PET film (trade name Cosmoshine A4300 manufactured by Toyobo Co., Ltd.) were prepared, a coating liquid (coating composition) was applied to them by a spin coating method (thickness: 3 μm), and the solvent was removed at 80° C. for 2 minutes. After volatilization, heat treatment was performed at 100° C. for 0.5 hour, and further heat treatment was performed at 120° C. for 2 hours to cure the coating film, thereby forming an optical member having a cured film. The tests shown in (1) to (6) above were carried out. Evaluation results are shown in Tables 1 and 2.

Example 2
In Example 1, the addition amount of epoxy-modified organosiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR470) was added to 10.5 parts by mass, and trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name EX- 321L) was changed to 4.5 parts by mass, a coating composition was prepared and a cured film was formed and evaluated in the same manner as in Example 1.

Example 3
In Example 1, the addition amount of epoxy-modified organosiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR470) was changed to 9.0 parts by mass, and trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name EX- 321L) was changed to 6.0 parts by mass, a coating composition was prepared and a cured film was formed and evaluated in the same manner as in Example 1.

Example 4
In Example 1, the addition amount of epoxy-modified organosiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR470) was changed to 7.5 parts by mass, and trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name EX- 321L) was changed to 7.5 parts by mass, a coating composition was prepared and a cured film was formed and evaluated in the same manner as in Example 1.

Example 5
In Example 1, the addition amount of epoxy-modified organosiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR470) was changed to 6.0 parts by mass, and trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name EX- 321L) was changed to 9.0 parts by mass, a coating composition was prepared and a cured film was formed and evaluated in the same manner as in Example 1.

Example 6
In Example 1, the addition amount of epoxy-modified organosiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR470) was changed to 15.0 parts by mass, and trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name Except for not adding EX-321L), preparation of the coating composition and formation and evaluation of the cured film were carried out in the same manner as in Example 1.

Example 7
In Example 1, the addition amount of epoxy-modified organosiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR470) was changed to 4.5 parts by mass, and trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name EX- 321L) was changed to 10.5 parts by mass, the coating composition was prepared and the cured film was formed and evaluated in the same manner as in Example 1.

Example 8
In Example 2, the amount of trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name EX-321L) was changed to 3.0 parts by mass, and epoxy-modified isocyanurate (Nissan Chemical Co., Ltd. trade name 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 1.5 parts by mass of TEPIC-VL) was added.

Example 9
In Example 1, the added amount of epoxy-modified organosiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR470) was 14.0 parts by mass, and trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name EX- 321L) to 6.0 parts by mass, the amount of propylene glycol monomethyl ether to be added to 29.6 parts by mass, and the organosilicon compound having a phenyl group on the surface obtained in Production Example 1. The addition amount of the methyl ethyl ketone dispersion sol of the titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C4) modified with silicon dioxide-stannic oxide composite oxide was changed to 32.8 parts by mass, and the cationic polymerization was started. Addition amount of propylene glycol monomethyl ether solution (San-Aid SI-100 5.0% by mass) of agent (manufactured by Sanshin Chemical Industry Co., Ltd., trade name San-Aid SI-100) to 4.0 parts by mass, storage stabilization aid The amount of N-methyl-2-pyrrolidone solution (SI aid 5.0% by mass) of (Sanshin Chemical Industry Co., Ltd. trade name SI aid) was changed to 0.20 parts by mass, and methyl ethyl ketone 11 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 4 parts by mass was added.

Example 10
In Example 1, the addition amount of epoxy-modified organosiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR470) was changed to 8.4 parts by mass, and trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name EX- 321L) to 3.6 parts by mass, the amount of propylene glycol monomethyl ether to be added to 24.5 parts by mass, and the organosilicon compound having a phenyl group on the surface obtained in Production Example 1. The addition amount of the methyl ethyl ketone dispersion sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C4) modified with silicon dioxide-stannic oxide composite oxide was changed to 59.0 parts by mass, and cationic polymerization was started. Addition amount of propylene glycol monomethyl ether solution (San-Aid SI-100 5.0% by mass) of agent (manufactured by Sanshin Chemical Industry Co., Ltd., trade name San-Aid SI-100) to 2.4 parts by mass, storage stabilization aid Except for changing the amount of N-methyl-2-pyrrolidone solution (SI Auxiliary 5.0% by mass) of (Sanshin Chemical Industry Co., Ltd. trade name SI Auxiliary) to 0.12 parts by mass, Preparation of the coating composition and formation and evaluation of the cured film were carried out in the same manner as in Example 1.

Example 11
In Example 1, the added amount of epoxy-modified organosiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR470) was changed to 7.0 parts by mass, and trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name EX- 321L) to 3.0 parts by mass, the amount of propylene glycol monomethyl ether to be added to 20.3 parts by mass, and the organosilicon compound having a phenyl group on the surface obtained in Production Example 1. The addition amount of the methyl ethyl ketone dispersion sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C4) modified with silicon dioxide-stannic oxide composite oxide was changed to 65.6 parts by mass, and cationic polymerization was started. Addition amount of propylene glycol monomethyl ether solution (San-Aid SI-100 5.0% by mass) of agent (manufactured by Sanshin Chemical Industry Co., Ltd., trade name San-Aid SI-100) to 2.0 parts by mass, storage stabilization aid Except for changing the amount of N-methyl-2-pyrrolidone solution (SI Auxiliary 5.0% by mass) added to 0.10 parts by mass (manufactured by Sanshin Chemical Industry Co., Ltd. under the trade name of SI Auxiliary), Preparation of the coating composition and formation and evaluation of the cured film were carried out in the same manner as in Example 1.

Example 12
In Example 1, the addition amount of epoxy-modified organosiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR470) was changed to 6.0 parts by mass, and trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name EX- 321L) to 2.6 parts by mass, the amount of propylene glycol monomethyl ether to be added to 17.4 parts by mass, and the organosilicon compound having a phenyl group on the surface obtained in Production Example 1. The addition amount of the methyl ethyl ketone dispersion sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C4) modified with silicon dioxide-stannic oxide composite oxide was changed to 70.3 parts by mass, and cationic polymerization was started. Addition amount of propylene glycol monomethyl ether solution (San-Aid SI-100 5.0% by mass) of agent (manufactured by Sanshin Chemical Industry Co., Ltd., trade name San-Aid SI-100) to 1.7 parts by mass, storage stabilization aid Except for changing the amount of N-methyl-2-pyrrolidone solution (SI Auxiliary 5.0% by mass) added to 0.09 parts by mass (manufactured by Sanshin Chemical Industry Co., Ltd. under the trade name of SI Auxiliary), Preparation of the coating composition and formation and evaluation of the cured film were carried out in the same manner as in Example 1.

Example 13
In Example 2, instead of the colloidal particles (C4) obtained in Production Example 1, the silicon dioxide-stannic oxide composite oxide obtained in Production Example 2 was bonded to the organosilicon compound having a methacrylic group on the surface. A coating composition was prepared and prepared in the same manner as in Example 2, except that 49.2 parts by mass of a methyl ethyl ketone dispersion sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C5) modified with a substance was added. Formation and evaluation of the cured film were carried out.

Example 14
In Example 2, instead of the colloidal particles (C4) obtained in Production Example 1, the organic silicon compound having a methyl group on the surface obtained in Production Example 3 was bonded to the silicon dioxide-stannic oxide composite oxide. A coating composition was prepared and prepared in the same manner as in Example 2, except that 49.2 parts by mass of a methyl ethyl ketone dispersion sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C6) modified with a substance was added. Formation and evaluation of the cured film were carried out.

Example 15
In Example 2, instead of propylene glycol monomethyl ether, 30.7 parts by mass of methyl ethyl ketone was added, and instead of the colloidal particles (C4) obtained in Production Example 1, phenyl groups and glycidyl groups were added to the surface obtained in Production Example 4. Propylene glycol monomethyl ether dispersion sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C7) modified with silicon dioxide-stannic oxide composite oxide, in which an organosilicon compound having 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 49.2 parts by mass was added.

Example 16
In Example 2, instead of the colloidal particles (C4) obtained in Production Example 1, the organic silicon compound having a phenyl group on the surface obtained in Production Example 5 was bonded to the silicon dioxide-stannic oxide composite oxide. Preparation of a coating composition and formation of a cured film were performed in the same manner as in Example 2, except that 49.2 parts by mass of a methyl ethyl ketone dispersion sol of zirconium oxide-stannic oxide composite oxide colloidal particles (C8) modified with a substance was added. Formulation and evaluation were carried out.

Example 17
(Preparation of coating composition)
In Example 14, the amount of propylene glycol monomethyl ether added was changed to 32.9 parts by mass, and a propylene glycol monomethyl ether solution (San-Aid SI -100 5.0% by mass), 0.9 parts by mass of a photocationic polymerization initiator (San-Apro Co., Ltd. trade name CPI-101A) is added, and a storage stabilization aid (Sanshin Chemical Industry Co., Ltd. product A coating composition was prepared in the same manner as in Example 14 except that the N-methyl-2-pyrrolidone solution (SI auxiliary agent 5.0% by mass) was not used.

(Formation and evaluation of cured film)
A glass substrate and a PET film (trade name Cosmoshine A4300 manufactured by Toyobo Co., Ltd.) were prepared, a coating liquid (coating composition) was applied to them by a spin coating method (thickness: 3 μm), and the solvent was removed at 80° C. for 2 minutes. After volatilization, the coating film was cured by ultraviolet treatment for 5 minutes with a high-pressure mercury lamp with an irradiation intensity of 28 mW/cm 2 to form an optical member having a cured film. The tests shown in (1) to (6) above were carried out. Evaluation results are shown in Tables 1 and 2.

Example 18
In Example 2, instead of the colloidal particles (C4) obtained in Production Example 1, the organic silicon compound having a phenyl group on the surface obtained in Production Example 7 was bonded to the silicon dioxide-stannic oxide composite oxide. A coating composition was prepared and a cured film was formed and evaluated in the same manner as in Example 2, except that 49.2 parts by mass of a methyl ethyl ketone dispersion sol of stannic oxide composite oxide colloidal particles (C9) modified with a substance was added. carried out.

Example 19
In Example 15, instead of the colloidal particles (C8) obtained in Production Example 5, the silicon dioxide-stannic oxide composite oxide obtained in Production Example 7 was bonded to the organosilicon compound having a phenyl group on the surface. A coating composition was prepared and a cured film was formed and evaluated in the same manner as in Example 15, except that 49.2 parts by mass of a methyl ethyl ketone dispersion sol of stannic oxide composite oxide colloidal particles (C9) modified with a substance was added. carried out.

Comparative example 1
In Example 1, no epoxy-modified organosiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR470) was added, and the added amount of trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name EX-321L) was 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 content was changed to 15.0 parts by mass.

Comparative example 2
In Example 2, instead of the epoxy-modified organosiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR470), 10.5 parts by mass of epoxy-modified organosiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name X-40-2669) Preparation of the coating composition and formation and evaluation of the cured film were carried out in the same manner as in Example 2 except that the was added.

Comparative example 3
In Example 1, the addition amount of epoxy-modified organosiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR470) was changed to 16.8 parts by mass, and trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name EX- 321L) to 7.2 parts by mass, the amount of propylene glycol monomethyl ether to 31.9 parts by mass, and the cationic polymerization initiator (manufactured by Sanshin Chemical Industry Co., Ltd., trade name San-Aid SI-100) of propylene The amount of glycol monomethyl ether solution (San-Aid SI-100 5.0% by mass) was added to 4.8 parts by mass, and the storage stabilization aid (trade name SI aid manufactured by Sanshin Chemical Industry Co., Ltd.) N-methyl -Modified metal obtained in Production Example 1 by changing the amount of 2-pyrrolidone solution (5.0% by mass of SI auxiliary agent) added to 0.24 parts by mass, and bonding an organosilicon compound having a phenyl group to the surface obtained in Production 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 37.1 parts by mass of methyl ethyl ketone was added instead of colloidal oxide particles (C2).

In Table 1, Shin-Etsu Chemical Co., Ltd. product name KR470 (i), Nagase ChemteX Co., Ltd. product name EX-321L (ii), Nissan Chemical Co., Ltd. product name TEPIC-VL (iii) , trade name X-40-2669 manufactured by Shin-Etsu Chemical Co., Ltd. is indicated by (iv).

[Table 1]
Table 1
―――――――――――――――――――――――――――――――――
Content in composition solid content [parts by mass]
(i) (ii) (iii) (iv) Particles Used Particle Example 1 12.0 3.0 - - 15.0 C4
Example 2 10.5 4.5 - - 15.0 C4
Example 3 9.0 6.0 - - 15.0 C4
Example 4 7.5 7.5 - - 15.0 C4
Example 5 6.0 9.0 - - 15.0 C4
Example 6 15.0 - - - 15.0 C4
Example 7 4.5 10.5 - - 15.0 C4
Example 8 10.5 3.0 1.5 - 15.0 C4
Example 9 14.0 6.0 - - 10.0 C4
Example 10 8.4 3.6 - - 18.0 C4
Example 11 7.0 3.0 - - 20.0 C4
Example 12 6.0 2.6 - - 21.4 C4
Example 13 10.5 4.5 - - 15.0 C5
Example 14 10.5 4.5 - - 15.0 C6
Example 15 10.5 4.5 - - 15.0 C7
Example 16 10.5 4.5 - - 15.0 C8
Example 17 10.5 4.5 - - 15.0 C8
Example 18 10.5 4.5 - - 15.0 C9
Example 19 10.5 4.5 - - 15.0 C9
Comparative Example 1 - 15.0 - - 15.0 C4
Comparative Example 2 - 4.5 - 10.5 15.0 C4
Comparative Example 3 16.8 7.2 － － － －
―――――――――――――――――――――――――――――――――

[Table 2]
Table 2
――――――――――――――――――――――――――――――――――
Curing method Refractive index Hardness Adhesion Transparency Light resistance Storage stability Example 1 Heat 1.65 A A A A A
Example 2 Heat 1.65 A A A A A
Example 3 Heat 1.65 A A A A A
Example 4 Heat 1.65 A A A A A
Example 5 Heat 1.66 A A A A A
Example 6 Heat 1.65 A A A A A
Example 7 Heat 1.66 A A A A B
Example 8 Heat 1.66 A A A A A
Example 9 Thermal 1.61 A A A A A
Example 10 Heat 1.70 A A A A A
Example 11 Thermal 1.72 A A A A A
Example 12 Heat 1.75 A A A A A
Example 13 Thermal 1.64 A A A A A
Example 14 Thermal 1.64 A A A A A
Example 15 Thermal 1.64 A A A A A
Example 16 Heat 1.58 A A A A A
Example 17 Light 1.58 A A A A A
Example 18 Thermal 1.58 A A A A A
Example 19 Light 1.58 A A A A A
Comparative Example 1 Thermal 1.66 C A A A -
Comparative Example 2 Heat - B A D B C
Comparative Example 3 Heat 1.51 C A A A A
―――――――――――――――――――――――――――――――――

As shown in Tables 1 and 2, all of Examples 1 to 19 were excellent in hardness, adhesion, transparency, light resistance, and storage stability of the coating material.

On the other hand, Comparative Examples 1 to 3 were unsatisfactory in terms of hardness, adhesion, transparency, light resistance, and storage stability of the coating material.

Substrates coated with the coating composition of the present invention can be applied to various fields such as optical members, mechanical component materials, electronic component materials, building materials, and molding materials.

Claims (8)

Metal oxide particles (A) having an average particle diameter of 2 nm to 100 nm and surface-coated with a hydrolyzable silane containing a hydrolyzable silane of formula (1a) and / or formula (1b), and formula (2 and a cycloaliphatic epoxy compound (B) of formula (1a) and/or (1b), wherein the hydrolyzable silane of formula (1a) and/or formula (1b) is:

(In formulas (1a) and (1b), R ¹ and R ¹¹ are acryloxy groups, methacryloxy groups, aryl groups, alkyl groups, glycidoxy groups, ureido groups, or alkylene groups having 1 to 10 carbon atoms containing these functional groups. and is bonded to the Si atom with a Si—C bond, R ² and R ¹² are hydrolyzable groups consisting of alkoxy groups, acyloxy groups, or halogen groups, and at least one hydrolyzate of R ² The groups form MO-Si bonds on the surface of the metal oxide particles, and M is Ti, Sn, Zr, Si, Al, Sb, Fe, Cu, Zn, Y, Nb, Mo, In, Ta, Pb , Bi, Hf, Ge, Ce, represents at least one metal selected from the group consisting of W, Y represents an alkylene group, an arylene group, an NH group, or an oxygen atom, a represents an integer of 1 to 3 , d is an integer of 0 to 3, and e is an integer of 0 or 1.), and the alicyclic epoxy compound of formula (2) is:

(In formula (2), R ³ is an alkylene group having 1 to 10 carbon atoms including an epoxycycloalkyl group, R ⁴ represents a hydrogen atom or a methyl group, and R ³ and R ⁴ are the same of Si
It is bonded to an atom with a Si—C bond or Si—H bond, and n is an integer of 3-5. ) and
The metal oxide particles (A) have an average particle diameter of 2 to 100 nm, and are Ti, Sn, Zr, Si, Al, Sb, Fe, Cu, Zn, Y, Nb, Mo, In, Ta, Pb, Bi, Hf, Ge, Ce, and at least one metal oxide or composite oxide (a1) selected from the group consisting of W is used as a nucleus, and the surface thereof has an average primary particle size of 1 to 40 nm. and at least selected from the group consisting of Ti, Sn, Zr, Si, Al, Sb, Fe, Cu, Zn, Y, Nb, Mo, In, Ta, Pb, Bi, Hf, Ge, Ce, W Metal oxide particles (A) coated with at least one layer of particles of one kind of metal oxide or composite oxide (a2), the layer comprising particles of (a1) and particles of (a2) have different metal components or different composite oxides, and (a2) coated on the outermost layer contains Si as a metal component, and
The metal oxide particles (A) are
The particles (a1) are coated with the particles (a2), or
or
An intermediate layer made of the particles (a2) and a coating layer made of the particles (a2) are formed on the particles made of (a1).
The above coating composition. 2. The coating composition according to claim 1, wherein the epoxycycloalkyl group of R3 in formula ( ² ) is an epoxycyclohexyl group. Furthermore, a non-alicyclic epoxy compound (C) of formula (3):

(In the formula (3), T is an m-valent organic group having 1 to 40 carbon atoms, the organic group being a saturated or unsaturated chain, cyclic, or condensed cyclic hydrocarbon group and m represents an integer of 1 to 10.), Among the epoxy compounds consisting of the alicyclic epoxy compound (B) and the non-alicyclic epoxy compound (C), the alicyclic epoxy compound (B) is 10 to 75% by mass, and the non - alicyclic epoxy compound (C) is 25 to 90% by mass. 4. A coating composition according to any one of claims 1 to 3 , further comprising a thermal acid generator and/or a photoacid generator. 5. The coating composition according to any one of claims 1 to 4 , further comprising an amine compound as a quencher. 6. A coating composition according to any one of claims 1 to 5 , further comprising a surfactant. A method for producing a coated substrate, comprising coating a substrate with the coating composition according to any one of claims 1 to 6 . A substrate coated with the coating composition of any one of claims 1-6 .