CN112752802B - Acrylic coating composition comprising inorganic oxide particles - Google Patents

Abstract

The present invention addresses the problem of providing a coating composition that can be cured by heat or light and has improved storage stability for forming a coated substrate that requires refractive index, hardness, adhesion, transparency, light resistance, bendability, scratch resistance, adhesion, and the like. The solution is a coating composition comprising: modified metal oxide particles (A) having an average particle diameter of 2 to 100nm, the metal oxide particles (A) having colloidal particles (a 1) of a metal oxide having an average particle diameter of 2 to 60nm as cores, and the surfaces of the metal oxide particles (A) being coated with a layer containing colloidal particles (a 2) of a metal oxide having an average primary particle diameter of 1 to 40nm, and a polymerizable compound (B) having an unsaturated bond between a carbon atom and a carbon atom. The metal oxide particle (a) further has an intermediate layer containing the particle (a 2) between the core particle (a 1) and the outermost layer containing the particle (a 2). The polymerizable compound (B) is a polymerizable compound having a triazinetrione skeleton and having an unsaturated bond of a carbon atom and a carbon atom. An optical member includes a base material and a coating film formed on the base material.

Description

Acrylic coating composition comprising inorganic oxide particles

technical field

The present invention relates to a thermally curable and photocurable coating composition using an organic-inorganic composite component, and an optical member obtained from the coating composition.

Background technique

The substrate coated with the coating composition is used in various fields such as optical components, mechanical component materials, electronic component materials, construction materials, and molding materials. Refractive index, hardness, adhesiveness, transparency, light resistance, and bendability are required for these coated substrates depending on the application. In addition, the coating liquid used for coating requires storage stability.

For example, an adhesive composition for circuit connection is disclosed, which comprises a radical polymerizable compound, a radical initiator, and a metal oxide, wherein the metal oxide is aluminum, magnesium, zirconium, bismuth, calcium, tin, manganese , antimony, silicon, or titanium oxide (see Patent Document 1).

Also disclosed is an organic-inorganic composite having (A) a (meth)acryloyl group bonded to the surface via a -O-Si-X- bond, (B) an ultraviolet absorber, and (C) a hindered amine-based light stabilizer. (D) The active energy ray curable resin composition of the organic solvent whose boiling point is 70 degreeC - 200 degreeC (refer patent document 2).

In addition, a method of obtaining an optical product by curing a metal oxide sol formed from a hydrolytic condensate of a metal alkoxide selected from titanium, cerium, zirconium, or tin and a polymerizable compound is disclosed (see Patent Document 3).

prior art literature

patent documents

Patent Document 1: International Publication No. 2017/090659

Patent Document 2: Japanese Patent Laid-Open No. 2014-037453

Patent Document 3: Japanese Patent Laid-Open No. 2005-075723

Contents of the invention

The problem to be solved by the invention

The object of the present invention is to provide a coating composition capable of thermosetting and photocuring, and having improved storage stability for forming a coating substrate requiring refractive index, hardness, adhesiveness, transparency, light resistance, and flexibility.

method used to solve the problem

That is, as a first viewpoint in the present invention, it is a coating composition comprising:

Modified metal oxide particles (A) having an average particle diameter of 2 nm to 100 nm, wherein the metal oxide particle (A) uses colloidal particles (a1) of metal oxides having an average particle diameter of 2 nm to 60 nm as a core, The surface thereof is coated with a layer comprising colloidal particles (a2) of metal oxides having an average primary particle diameter of 1 nm to 40 nm; and

A polymerizable compound (B) having an unsaturated bond between carbon atoms and carbon atoms (ie, a carbon-carbon unsaturated bond),

As a second viewpoint, it is the coating composition according to the first viewpoint, wherein the metal oxide particles (A) are modified metal oxide particles (A) having an average particle diameter of 2 nm to 100 nm, and the metal oxide particles (A) having an average particle diameter of 2 nm to 100 nm and selected from Ti, Sn, Zr, Si, Al, Sb, Fe, Cu, Zn, Y, Nb, Mo, In, Ta, Pb, Bi, Hf, Ge , Ce and W at least one metal oxide or composite oxide (a1) as the core, the surface of which has an average primary particle size of 1 nm to 40 nm and is selected from Ti, Sn, Zr, Si, Al, At least one layer of oxide or composite oxide (a2) of at least one metal selected from Sb, Fe, Cu, Zn, Y, Nb, Mo, In, Ta, Pb, Bi, Hf, Ge, Ce, and W For coating, the core particle (a1) and the layer containing the particle (a2) are different in metal composition or different as composite oxides,

As a third viewpoint, in the coating composition according to the first viewpoint or the second viewpoint, the layer containing the particles (a2) covering the outermost layer of the metal oxide particles (A) contains Si as a metal component,

As a fourth viewpoint, it is the coating composition according to any one of the first viewpoint to the third viewpoint, wherein the metal oxide particle (A) is between the core particle (a1) and the outermost layer containing the particle (a2) further having an intermediate layer comprising particles (a2),

As a fifth viewpoint, it is the coating composition according to any one of the first viewpoint to the fourth viewpoint, wherein the polymerizable compound (B) has a triazinetrione skeleton and has an unsaturated bond between carbon atoms and carbon atoms. A polymerizable compound (b1-1), or a polymerizable compound (b1-2) which is an aromatic compound having a urethane bond and has an unsaturated bond between carbon atoms,

As a sixth aspect, it is the coating composition according to any one of the first to fifth viewpoints, wherein the polymerizable compound (B) contains a polymerizable compound (b1-1) represented by formula (b1-1) or a polymerizable compound (b1-2) represented by formula (b1-2),

(In formula (b1-1), R ¹ and R ² represent a hydrogen atom or a methyl group, R ³ represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms, and n ₁ and n ₂ represent a group of 0 to 10 carbon atoms, respectively. integer.

In formula (b1-2), R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ each represent a hydrogen atom or a methyl group. )

As a seventh viewpoint, it is the coating composition according to the sixth viewpoint, wherein the polymerizable compound (B) further includes a polymerizable compound (b2) represented by formula (b2),

(In formula (b2), R ⁴ represents a hydrogen atom or a methyl group, T is a carbon atom, or an aliphatic hydrocarbon group that may contain an ether bond, an aromatic hydrocarbon group, or a combination thereof, and n ₃ represents an integer of 1 to 10 , n ₄ represents an integer from 0 to 5, n ₅ represents an integer from 0 to 2, and n ₆ represents an integer from 0 to 2.)

As an 8th viewpoint, it is the coating composition in any one of a 1st viewpoint - a 7th viewpoint which further contains a photopolymerization initiator or a thermal polymerization initiator as a polymerization initiator (C),

As a ninth viewpoint, it is the coating composition according to the eighth viewpoint, wherein the polymerization initiator (C) is a photoradical polymerization initiator, a thermal radical polymerization initiator, a photocationic polymerization initiator, or a thermal cationic polymerization initiator,

As a tenth aspect, the coating composition according to any one of the first to ninth viewpoints, further comprising a surfactant,

As an eleventh aspect, it is a film composed of a photocured or thermally cured product of the coating composition according to any one of the first to tenth viewpoints,

As a twelfth aspect, it is an optical member comprising a base material, and the film according to the eleventh aspect formed on the base material, and

As a thirteenth viewpoint, it is a method for producing a substrate having a film, which includes the steps of: coating the substrate with the coating composition according to any one of the first viewpoint to the tenth viewpoint; A process of solvent removal; a process of performing light irradiation and/or heating.

The effect of the invention

The present invention is a coating composition comprising:

A colloidal particle (A) having an average particle diameter of 2nm to 100nm, wherein the colloidal particle (A) has a colloidal particle (a1) of a metal oxide as a core and its surface is coated with a layer containing a colloidal particle (a2) of a metal oxide Covered; and

A polymerizable compound (B) having an unsaturated bond between carbon atoms.

Metal oxide particles having a structure in which the surface of the core particle (a1) is coated with at least one layer including the particle (a2) can be used. By using the modified colloidal particles (A) having a coating structure, transparency and hardness can be improved, and the refractive index corresponding to the substrate to be coated can be adjusted.

By using metal oxide particles having a coating structure, multiple functions can be imparted to a coating film containing them as a coating composition.

For example, when metal oxide sols are mixed with each other, the metal oxide component in the film may be biased microscopically, and functionally uniformity may not be achieved due to the bias, but in the present invention, by With a coating structure, each particle is uniform as a metal oxide component, and by exerting the same function throughout the entire coating film, a uniform effect can be expected on any part of the coating film surface.

Furthermore, for functions that cannot be achieved by metal oxide particles alone, the intended functions can be exhibited by forming a coating structure and compounding them. Even if it is a metal oxide particle which is not compatible with the polymeric compound used as a binder component, for example, it can be set as the metal oxide particle with high compatibility by forming a coating structure. In addition, even in the case where the surface of the metal oxide particle has properties that are changed by external force caused by light or heat, as long as the change of the metal oxide can be suppressed by other metal oxides, it can also be exhibited by having a coating structure. Function.

The coating structure of the particles is obtained by mixing and heat-treating particles serving as cores and particles to be coated. For example, by making the surface potential of the core particle opposite to the surface potential of the coating particle, the coating particle can be coated on the surface of the core particle by electrostatic force, and they are heated to form M-O-M' (M, M' represents a metal ) combination. Since the coating structure of the particles having a coating structure does not change even when the solvent is replaced from an aqueous medium to an organic solvent, it is considered to be a reaction substance that forms an interface.

In addition, the polymerizable compound (B) improves light resistance due to the triazinetrione skeleton by using a polymerizable compound having a triazinetrione skeleton. A (meth)acrylate compound having a triazinetrione skeleton has a structure having a (meth)acrylate group in a ratio of 1, 2, or 3 in the molecule, and by having 2 (methyl) groups in the molecule Since the coating composition is applied to the film and cured due to the acrylate group, the adhesiveness of the coating film is high, and it follows the expansion and contraction of the film without cracking or peeling of the coating film, and is excellent in flexibility.

Moreover, scratch resistance and adhesiveness are improved by using the aromatic compound which has a urethane bond as a polymeric compound (B).

Detailed ways

The present invention is a coating composition comprising:

Modified metal oxide particles (A) having an average particle diameter of 2 nm to 100 nm, wherein the metal oxide particle (A) uses colloidal particles (a1) of metal oxides having an average particle diameter of 2 nm to 60 nm as a core, The surface thereof is coated with a layer comprising colloidal particles (a2) of metal oxides having an average primary particle diameter of 1 nm to 40 nm; and

A polymerizable compound (B) having an unsaturated bond between carbon atoms.

The value of the average particle diameter (nm) measured by the dynamic light scattering method (DLS method) can be used for the said core particle (a1) and modified particle (A).

As the above-mentioned coated particles (a2), the average primary particle diameter (nm) measured by a transmission projected image (transmission electron microscope) using electron beams can be used.

A colloidal particle (a1) is a particle (a1) that becomes a nucleus, and is also called a nucleus particle (a1). Colloidal particles (a2) are particles (a2) to be coated, and are also called coated particles (a2). The modified metal oxide particles (A) are modified particles (A), and are also called modified particles (A).

Since the core particle (a1) and the coating particle (a2) react at the particle interface, the core particle (a1)+coating particle (a2) does not necessarily have the particle diameter of the modified particle (A).

The coating composition of the present invention contains a solvent in addition to the above components, and may contain a polymerization initiator, a quencher, a surfactant, and the like as optional components.

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 as a solid content. The term "solid content" here means a component obtained by removing a solvent component from all the components of the coating composition.

Metal oxide particles (A) represent particles composed of metal oxides and composite metal oxides.

The metal oxide particle (A) is a metal oxide particle (A) having an average particle diameter of 2 nm to 100 nm, or 3 nm to 50 nm, and the metal oxide particle (A) has an average particle diameter of 2 nm to 60 nm, or 3 nm to 40 nm. Particle size and at least one metal selected from Ti, Sn, Zr, Si, Al, Sb, Fe, Cu, Zn, Y, Nb, Mo, In, Ta, Pb, Bi, Hf, Ge, Ce and W The oxide or composite oxide (a1) is used as the core, and the surface thereof is coated with a material having an average primary particle size of 1nm to 40nm or 2nm to 20nm and selected from Ti, Sn, Zr, Si, Al, Sb, Fe, Cu , Zn, Y, Nb, Mo, In, Ta, Pb, Bi, Hf, Ge, Ce and W at least one metal oxide or composite oxide (a2) is coated with at least one layer, and the core particles (a1) and the layers containing the particles (a2) differ in metal components or differ as composite oxides.

The case where the metal components of the particles (a1) and the particles (a2) are different means that the particles (a1) and the particles (a2) are different as metal elements. In addition, when the particles (a1) and the particles (a2) are different as composite oxides, even if there is a metal type in which the particles (a1) and the particles (a2) overlap as metal components, the particles (a1) and the particles (a2) are Composite oxides are also different cases.

The thickness of the coating layer depends on the particle diameter of the coating particle (a2), but may be 1 nm to 40 nm depending on the particle diameter of the coating particle (a1).

When different metal elements are used, for example, TiO ₂ is used for the particles (a1) and SnO ₂ is used for the particles (a2).

Even if there are metal types that overlap as metal components, there are cases where the composite oxides are different. For example, TiO ₂ -ZrO ₂ -SnO ₂ is used for the particle (a1), and SnO ₂ -SiO ₂ is used for the particle (a2). .

The same applies to the case where a layer consisting of particles (a2) is used as the outermost layer of the particles (a1) and particles (a2) are further used in the intermediate layer. The particles (a2) used in the intermediate layer can use the same components as those exemplified for the above-mentioned particles (a2), and the core particles (a1) and the outermost layer particles (a2) have different metal components or different composite oxides. .

The values of the average particle diameter and the average primary particle diameter of the metal oxide or composite metal oxide include the value of the average particle diameter (nm) measured by the dynamic light scattering method (DLS method), and the value obtained by transmission projection using electron beams. The value of the average primary particle diameter (nm) observed by the image (transmission electron microscope). Examples of metal oxides and composite oxides include TiO ₂ , SnO ₂ , ZrO ₂ , SiO ₂ , 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 , HfO ₂ , In ₂ O ₃ , GeO ₂ , CeO ₂ , WO ₃ , WO ₃ -Sb ₂ O ₅ , WO ₃ -SnO _2. SnO ₂ -ZrO ₂ , TiO ₂ -SnO ₂ , SnO ₂ -SiO ₂ , TiO ₂ -ZrO ₂ -SnO ₂ , TiO ₂ -CeO ₂ -SnO ₂ , WO ₃ -SnO ₂ -SiO ₂ , etc.

The metal oxide particle (A) may have a structure in which the coating layer formed by (a2) is formed on the particle formed by (a1).

These composite metal oxide particles having a coating structure can use SnO ₂ -ZrO ₂ , TiO ₂ -ZrO ₂ -SnO ₂ as core particles, use SiO ₂ , SnO ₂ -SiO ₂ , WO ₃ -SnO ₂ -SiO ₂ , etc. as core particles. coated particles. For example:

Modified metal oxide particles composed of SnO ₂ -ZrO ₂ as the core particle (a1), WO ₃ -SnO ₂ -SiO ₂ as the coating particle (a2),

Modified metal oxide particles composed of TiO ₂ as the core particle (a1) and TiO ₂ -SnO ₂ as the coating particle (a2);

In addition, modified metal oxide particles composed of TiO ₂ -ZrO ₂ -SnO ₂ as the core particle (a1) and SnO ₂ -SiO ₂ as the coating particle (a2) are mentioned.

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

In addition, in the case of particles composed of a core particle, an intermediate layer, and a coating layer, the core particle (a1), the particle (a2) of the intermediate layer, and the particle (a2) of the coating layer may be in a mass ratio of 1:0.01 to 1. : 0.01 to 1, or 1: 0.1 to 0.5: use in the range of 0.1 to 0.5.

The metal oxide particles (A) can be used as a colloidal solution of metal oxide particles. The colloidal solution (sol) of metal oxide particles can be used as an organic solvent sol by substituting a solvent produced as an aqueous sol with an organic solvent. As the organic solvent, solvents such as methanol, ethanol, 1-propanol, 2-propanol, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate can be used.

The content of the metal oxide particles (A) may be 10 to 1000 parts by mass, or 50 to 500 parts by mass, or 50 to 300 parts by mass relative to 100 parts by mass of the polymerizable compound (B). contain.

The metal oxide particles (A) preferably cover the outermost layer containing the particles (a2) containing Si as the metal component. In this case, it is preferable to include Si as a metal component, that is, to include a SiO ₂ component, and to coat the outermost layer with a silane coupling agent because the reactivity with the silane coupling agent is improved.

The hydrolyzable silane used for the surface coating of the metal oxide particle (A) may contain the hydrolyzable silane of formula (3) and/or the hydrolyzable silane of formula (4). The hydrolyzable silane of formula (3) and the hydrolyzable silane of formula (4) can further use other hydrolyzable silane in combination, the hydrolyzable silane of formula (3) and/or the hydrolyzable silane of formula (4): other hydrolyzable silane The weight ratio can be used in the range of 1:0.1-1.0 or 1:0.5-1.0.

Regarding the surface coating amount of the metal oxide particle (A), the number of Si atoms of the above-mentioned silane compound coated on the surface of the metal oxide particle can be 0.1/nm ² to 10.0/nm ² , 0.1/nm ² -5.0 pieces/nm ² , or in the range of 0.1 pieces/nm ² to 3.0 pieces/nm ² . The above-mentioned surface coating amount is the mass of hydrolyzable silane added to the metal oxide particle (A), and can be calculated from the specific surface area of the metal oxide particle (A) and the added amount of hydrolyzable silane.

R ¹¹ _a Si(R ¹² ) _4-a formula (3)

[R ¹³ _d Si(R ¹⁴ ) _3-d ] ₂ Y _e formula (4)

In formula (3), R ¹¹ includes acryloyloxy group, methacryloyloxy group, aryl group, alkyl group, glycidoxy group, polyethylene glycol group, or a carbon atom number of 1 to 1 including these functional groups. 10 is an alkylene group, and R ¹¹ is bonded to the Si atom through a Si-C bond, R ¹² is a hydrolyzable group composed of an alkoxy group, an acyloxy group, or a halogen atom, and at least one hydrolyzable group of R ¹² is in MO-Si bonds are formed on the surface of the metal oxide particles, and M represents a group selected from Ti, Sn, Zr, Si, Al, Sb, Fe, Cu, Zn, Y, Nb, Mo, In, Ta, Pb, Bi, Hf, Ge , Ce and W at least one metal. a represents an integer of 1-3.

In formula (4), R ¹³ is an alkyl group and is bonded to a silicon atom through a Si-C bond, R ¹⁴ represents an alkoxy group, an acyloxy group, or a halogen atom, and Y represents an alkylene group, an arylene group, an NH A group or an oxygen atom, d represents an integer of 0 to 3, and e is an integer of 0 or 1.

The above-mentioned alkyl group is an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl Base, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl -n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, Cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl -cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n- Pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2, 2-Dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl base, 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 Base-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl , 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n- Propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-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 Base-2-methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl etc.

In addition, the alkylene group includes an alkylene group derived from the above-mentioned alkyl group.

The aryl group includes, for example, phenyl, naphthyl, anthracenyl, etc., and the arylene group is a group derived from the above-mentioned aryl group, and examples thereof include phenylene, naphthylene, anthracenyl, and the like.

Examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-di Methyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1- Methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy , 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butyl Oxygen, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy , 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy and 1-ethyl-2-methyl-n-propoxy, etc., in addition as ring Alkoxy groups like cyclopropoxy, cyclobutoxy, 1-methyl-cyclopropoxy, 2-methyl-cyclopropoxy, cyclopentyloxy, 1-methyl-cyclopropyl Butoxy, 2-methyl-cyclobutoxy, 3-methyl-cyclobutoxy, 1,2-dimethyl-cyclopropoxy, 2,3-dimethyl-cyclopropoxy, 1-Ethyl-cyclopropoxy, 2-ethyl-cyclopropoxy, cyclohexyloxy, 1-methyl-cyclopentyloxy, 2-methyl-cyclopentyloxy, 3-methyl- Cyclopentyloxy, 1-ethyl-cyclobutoxy, 2-ethyl-cyclobutoxy, 3-ethyl-cyclobutoxy, 1,2-dimethyl-cyclobutoxy, 1, 3-Dimethyl-cyclobutoxy, 2,2-dimethyl-cyclobutoxy, 2,3-dimethyl-cyclobutoxy, 2,4-dimethyl-cyclobutoxy, 3,3-Dimethyl-cyclobutoxy, 1-n-propyl-cyclopropoxy, 2-n-propyl-cyclopropoxy, 1-isopropyl-cyclopropoxy, 2-isopropyl Base-cyclopropoxy, 1,2,2-trimethyl-cyclopropoxy, 1,2,3-trimethyl-cyclopropoxy, 2,2,3-trimethyl-cyclopropoxy base, 1-ethyl-2-methyl-cyclopropoxy, 2-ethyl-1-methyl-cyclopropoxy, 2-ethyl-2-methyl-cyclopropoxy and 2-ethyl Base-3-methyl-cyclopropoxy and the like.

Examples of the acyloxy group include acyloxy groups having 2 to 10 carbon atoms, such as methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy Base, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, n-pentylcarbonyloxy, 1-methyl-n-butylcarbonyloxy, 2-methyl-n-butyl Carbonyloxy, 3-methyl-n-butylcarbonyloxy, 1,1-dimethyl-n-propylcarbonyloxy, 1,2-dimethyl-n-propylcarbonyloxy, 2,2- Dimethyl-n-propylcarbonyloxy, 1-ethyl-n-propylcarbonyloxy, n-hexylcarbonyloxy, 1-methyl-n-pentylcarbonyloxy, 2-methyl-n-pentylcarbonyl Oxygen, 3-methyl-n-pentylcarbonyloxy, 4-methyl-n-pentylcarbonyloxy, 1,1-dimethyl-n-butylcarbonyloxy, 1,2-dimethyl- n-butylcarbonyloxy, 1,3-dimethyl-n-butylcarbonyloxy, 2,2-dimethyl-n-butylcarbonyloxy, 2,3-dimethyl-n-butylcarbonyloxy base, 3,3-dimethyl-n-butylcarbonyloxy, 1-ethyl-n-butylcarbonyloxy, 2-ethyl-n-butylcarbonyloxy, 1,1,2-trimethyl -n-propylcarbonyloxy, 1,2,2-trimethyl-n-propylcarbonyloxy, 1-ethyl-1-methyl-n-propylcarbonyloxy, 1-ethyl-2-methyl Base-n-propylcarbonyloxy, phenylcarbonyloxy, and tosylcarbonyloxy, etc.

Fluorine, chlorine, bromine, iodine, etc. are mentioned as said halogen atom.

The above-mentioned hydrolyzable silanes can be exemplified by the following compounds.

In the above formula, R ¹² represents a hydrolyzable group composed of an alkoxy group, an acyloxy group, or a halogen atom, as described in the penultimate paragraph on page 9 above. These are available as a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd.

The compound of formula (4) contains a trimethylsilylating agent, and examples thereof include hexamethyldisilane, hexamethyldisiloxane, hexamethyldisilazane, and the like. These silylation agents are available from Tokyo Chemical Industry Co., Ltd.

The surface treatment of the metal oxide particles (A) with a silane compound can be carried out by adding, for example, a hydrolyzable silane of formula (3) and/or formula (4) to the methanol sol of the metal oxide particles (A) for hydrolysis and surface coating.

In the hydrolysis of the alkoxysilyl group, acyloxysilyl group, or halosilyl group, 0.5 mol to 100 mol, preferably 1 mol to 10 mol of water is used per 1 mol of the hydrolyzable group.

Moreover, 0.001 mol - 10 mol, preferably 0.001 mol - 1 mol of the hydrolysis catalyst can be used per 1 mol of the hydrolyzable group.

The reaction temperature at the time of carrying out hydrolysis and condensation is 20 to 80 degreeC normally.

Hydrolysis may be completely hydrolyzed or partially hydrolyzed. That is, the hydrolyzate and the monomer may remain in the hydrolyzed condensate.

A catalyst can be used for hydrolysis and condensation.

As a hydrolysis catalyst, a chelate compound, an organic acid, an inorganic acid, an organic base, or an inorganic base can be used together.

In the present invention, the polymerizable compound (B) can be a polymerizable compound having a triazinetrione skeleton and an unsaturated bond between carbon atoms and carbon atoms, and a compound having an aromatic urethane bond and having a carbon atom and a carbon atom. A polymeric compound with an unsaturated bond.

As the polymerizable compound (B), a polymerizable compound (b1-1) represented by formula (b1-1) can be used. In formula (b1-1), R ¹ and R ² represent a hydrogen atom or a methyl group, R ³ represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms, and n ₁ and n ₂ represent an integer of 0 to 10, respectively .

As a polymeric compound represented by formula (b1-1), it can illustrate below, for example.

It is preferably a bifunctional acrylate having a triazinetrione skeleton, particularly preferably a compound represented by formula (b1-1-1), and is available as, for example, Toagosei Co., Ltd., trade name Aronix M-215.

Moreover, as a polymeric compound (B), the polymeric compound (b1-2) represented by a formula (b1-2) can be used. In formula (b1-2), R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ each represent a hydrogen atom or a methyl group.

The polymeric compound (b1-2) represented by formula (b1-2) can be illustrated below.

The aromatic compound (b1-2) having a urethane bond has a toluene 2,4-urethane acrylate structure and a toluene 2,6-urethane acrylate structure, usually in a molar ratio of 80 : Contained in a ratio of 20, can be used as their mixture.

The mixture of the compounds represented by the above (b1-2-1) and (b1-2-3) is available as, for example, EBECRYL220 manufactured by Daicel Olenex Corporation.

As the polymerizable compound (B), in addition to the above-mentioned polymerizable compound (b1), a bifunctional or higher acrylate compound can be further used as the polymerizable compound (b2) represented by the formula (b2). Examples of the polymerizable compound (b2) represented by the formula (b2) include bifunctional acrylates, trifunctional acrylates, tetrafunctional acrylates, and pentafunctional or higher acrylates.

As these polyfunctional acrylates, polymerizable compounds (b2) represented by formula (b2) can be used. In formula (b2), R ⁴ represents a hydrogen atom or a methyl group, T is a carbon atom, or an aliphatic hydrocarbon group that may contain an ether bond, an aromatic hydrocarbon group, or a combination thereof, n ₃ represents an integer of 1 to 10, n ₄ represents an integer of 0-5, n ₅ represents an integer of 0-2, and n ₆ represents an integer of 0-2.

Examples of the aliphatic hydrocarbon group include hydrocarbon groups derived from the alkyl groups having 1 to 10 carbon atoms described in the first paragraph on page 10 above. The aromatic hydrocarbon group is an aromatic hydrocarbon group having 6 to 40 carbon atoms, and examples thereof include phenyl, naphthyl, anthracenyl, and pyrenyl.

These polymeric compounds (B) can be illustrated, for example, below.

For example, as a bifunctional acrylate, compounds represented by the following formula (b2-1) and formula (b2-2) can be mentioned, and as a trifunctional acrylate, compounds represented by the following formula (b2-3) can be mentioned. As a compound, the compound represented by following formula (b2-4) is mentioned as tetrafunctional acrylate, and the compound represented by following formula (b2-5) is mentioned as pentafunctional or more acrylate. The compound represented by formula (b2-1) can be obtained as, for example, manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD NPGDA, and the compound represented by formula (b2-2) can be obtained as, for example, manufactured by Nippon Kayaku Co., Ltd., trade name Name KAYARAD R-551, the compound represented by formula (b2-3) can be obtained as, for example, manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD TMPTA, and the compound represented by formula (b2-4) can be obtained as, for example, Japanese Available from Kayaku Co., Ltd. under the trade name KAYARAD T-1420(T), and the compound represented by the formula (b2-5) is available as, for example, Nippon Kayaku Co., Ltd. under the trade name KAYARAD DPHA.

In addition, it is permissible to include the polymerizable compound (b2) as a by-product at the time of synthesis of the polymerizable compound (b1). For example, the polymerizable compound (b2) may be included in the polymerizable compound (b1-2). Pentaerythritol tri(meth)acrylate (b2-6) and pentaerythritol tetra(meth)acrylate (b2-7) are mentioned as this polymeric compound.

The polymerizable compound (b2) is preferably a compound represented by formula (b2-5) which is a pentafunctional or higher acrylate among these polyfunctional acrylates.

As the polymerizable compound (B), the polymerizable compound (b1) can be used alone, and the polymerizable compound (b2) can also be used alone. However, when using the polymerizable compound (b1) and the polymerizable compound (b2) in combination, the polymerizable compound (b1) and the polymerizable compound (b2) may be 100 to 0.1:1, or 100 to 1.0:1, or 20 to 1.3:1, or 10 to 1.3:1 ratio.

In the present invention, a photopolymerization initiator (c1) or a thermal polymerization initiator (c2) may be contained as a polymerization initiator (C).

Polymerization initiator (C) can use photoradical polymerization initiator (c1-1), thermal radical polymerization initiator (c2-1), photocationic polymerization initiator (c1-2), or thermal cationic polymerization initiator ( c2-2).

盐化合物、和噻吨酮化合物等。作为叠氮基化合物，可以举出对叠氮基苯甲醛、对叠氮基苯乙酮、对叠氮基苯甲酸、对叠氮基亚苄基苯乙酮、4,4’-二叠氮基查耳酮、4,4’-二叠氮基二苯基硫化物、和2,6-双(4’-叠氮基亚苄基)-4-甲基环己酮等。作为重氮化合物，可以举出1-重氮-2,5-二乙氧基-4-对甲苯基巯基苯硼氟化物、1-重氮-4-N,N-二甲基氨基苯氯化物、和1-重氮-4-N,N-二乙基氨基苯硼氟化物等。作为联咪唑化合物，可以举出2,2’-双(邻氯苯基)-4,5,4’,5’-四(3,4,5-三甲氧基苯基)1,2’-联咪唑、和2,2’-双(邻氯苯基)4,5,4’,5’-四苯基-1,2’-联咪唑等。作为二茂钛化合物，可以举出二环戊二烯基-钛-二氯化物、二环戊二烯基-钛-双苯基、二环戊二烯基-钛-双(2,3,4,5,6-五氟苯基)、二环戊二烯基-钛-双(2,3,5,6-四氟苯基)、二环戊二烯基-钛-双(2,4,6-三氟苯基)、二环戊二烯基-钛-双(2,6-二氟苯基)、二环戊二烯基-钛-双(2,4-二氟苯基)、双(甲基环戊二烯基)-钛-双(2,3,4,5,6-五氟苯基)、双(甲基环戊二烯基)-钛-双(2,3,5,6-四氟苯基)、双(甲基环戊二烯基)-钛-双(2,6-二氟苯基)、和二环戊二烯基-钛-双(2,6-二氟-3-(1H-吡咯-1-基)-苯基)等。Examples of photoradical polymerization initiators (c1-1) include imidazole compounds, diazo compounds, biimidazole compounds, N-arylglycine compounds, organic azido compounds, titanocene compounds, Aluminate compounds, organic peroxides, N-alkoxypyridines

Salt compounds, and thioxanthone compounds, etc. Examples of azido compounds include p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzylideneacetophenone, 4,4'-diazide Chalcone, 4,4'-diazidodiphenylsulfide, and 2,6-bis(4'-azidobenzylidene)-4-methylcyclohexanone, etc. Examples of diazo compounds include 1-diazo-2,5-diethoxy-4-p-tolylmercaptophenylboronium fluoride, 1-diazo-4-N,N-dimethylaminobenzene chloride Compounds, and 1-diazo-4-N, N-diethylaminophenyl borofluoride, etc. Examples of biimidazole compounds include 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetrakis(3,4,5-trimethoxyphenyl)1,2'- Biimidazole, and 2,2'-bis(o-chlorophenyl) 4,5,4',5'-tetraphenyl-1,2'-biimidazole, etc. As titanocene compounds, dicyclopentadienyl-titanium-dichloride, dicyclopentadienyl-titanium-biphenyl, dicyclopentadienyl-titanium-bis(2,3, 4,5,6-pentafluorophenyl), dicyclopentadienyl-titanium-bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl-titanium-bis(2, 4,6-trifluorophenyl), dicyclopentadienyl-titanium-bis(2,6-difluorophenyl), dicyclopentadienyl-titanium-bis(2,4-difluorophenyl ), bis(methylcyclopentadienyl)-titanium-bis(2,3,4,5,6-pentafluorophenyl), bis(methylcyclopentadienyl)-titanium-bis(2, 3,5,6-tetrafluorophenyl), bis(methylcyclopentadienyl)-titanium-bis(2,6-difluorophenyl), and dicyclopentadienyl-titanium-bis(2 , 6-difluoro-3-(1H-pyrrol-1-yl)-phenyl) and the like.

唑酮、2-巯基苯并咪唑、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、1-羟基-环己基-苯基-酮、和2-苄基-2-二甲基氨基-1-(4-吗啉代苯基)-丁酮等。Examples of photoradical polymerization initiators include 1,3-bis(tert-butyldioxycarbonyl)benzophenone, 3,3',4,4'-tetrakis(tert-butyldioxy Carbonyl) benzophenone, 3-phenyl-5-iso

Azoxazolone, 2-mercaptobenzimidazole, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-one, and 2-benzyl -2-Dimethylamino-1-(4-morpholinophenyl)-butanone and the like.

As these radical photopolymerization agents, it is available as Irgacure TPO (c1-1-1) manufactured by BASF Corporation, for example.

Examples of photocationic polymerization initiators (c1-2) include sulfonate esters, sulfonimide compounds, disulfonyldiazomethane compounds, dialkyl-4-hydroxysulfonium salts, arylsulfonic acid-p- Nitrobenzyl ester, silanol-aluminum complex, (η ⁶ -benzene)(η ⁵ -cyclopentadienyl)iron(II), etc.

As the sulfonimide compound, for example, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-( Camphorsulfonyloxy)succinimide, N-(trifluoromethanesulfonyloxy)naphthalimide, and the like.

Examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, (p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane, etc.

As the photocationic polymerization initiator, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one is also mentioned.

盐化合物、芳香族锍盐化合物、芳香族重氮

盐化合物、芳香族

盐化合物、三嗪化合物和铁芳烃配位化合物等既可以作为光自由基聚合引发剂而使用，也可以作为光阳离子聚合引发剂而使用。In addition, aromatic iodine

Salt compound, aromatic sulfonium salt compound, aromatic diazonium

Salt compounds, aromatic

Salt compounds, triazine compounds, iron arene complexes, and the like can be used as photoradical polymerization initiators or photocation polymerization initiators.

盐化合物，可举出例如二苯基碘

氯化物、二苯基碘

三氟甲烷磺酸盐、二苯基碘

甲磺酸盐、二苯基碘

甲苯磺酸盐、二苯基碘

溴化物、二苯基碘

四氟硼酸盐、二苯基碘

六氟锑酸盐、二苯基碘

六氟砷酸盐、双(对叔丁基苯基)碘

六氟磷酸盐、双(对叔丁基苯基)碘

甲磺酸盐、双(对叔丁基苯基)碘

甲苯磺酸盐、双(对叔丁基苯基)碘

三氟甲烷磺酸盐、双(对叔丁基苯基)碘

四氟硼酸盐、双(对叔丁基苯基)碘

氯化物、双(对氯苯基)碘

氯化物、双(对氯苯基)碘

四氟硼酸盐、以及双(4-叔丁基苯基)碘

六氟磷酸盐等双(烷基苯基)碘

盐、烷氧基羰基烷氧基-三烷基芳基碘

盐(例如，4-[(1-乙氧基羰基-乙氧基)苯基]-(2,4,6-三甲基苯基)-碘

六氟磷酸盐等)、双(烷氧基芳基)碘

盐(例如，(4-甲氧基苯基)苯基碘

六氟锑酸盐等双(烷氧基苯基)碘

盐)。as aromatic iodine

Salt compounds, such as diphenyl iodide

Chloride, diphenyl iodide

Trifluoromethanesulfonate, diphenyl iodide

Methanesulfonate, diphenyl iodide

Tosylate, diphenyl iodide

bromide, diphenyl iodide

Tetrafluoroborate, diphenyl iodide

Hexafluoroantimonate, diphenyl iodide

Hexafluoroarsenate, bis(p-tert-butylphenyl)iodide

Hexafluorophosphate, bis(p-tert-butylphenyl)iodide

Methanesulfonate, bis(p-tert-butylphenyl)iodide

Tosylate, bis(p-tert-butylphenyl) iodide

Trifluoromethanesulfonate, bis(p-tert-butylphenyl)iodide

Tetrafluoroborate, bis(p-tert-butylphenyl)iodide

Chloride, bis(p-chlorophenyl)iodide

Chloride, bis(p-chlorophenyl)iodide

Tetrafluoroborate, and bis(4-tert-butylphenyl)iodide

Bis(alkylphenyl)iodides such as hexafluorophosphate

Salt, alkoxycarbonylalkoxy-trialkylaryl iodide

salt (for example, 4-[(1-ethoxycarbonyl-ethoxy)phenyl]-(2,4,6-trimethylphenyl)-iodine

hexafluorophosphate, etc.), bis(alkoxyaryl) iodide

Salts (e.g., (4-methoxyphenyl)phenyl iodide

Bis(alkoxyphenyl)iodides such as hexafluoroantimonate

Salt).

Examples of aromatic sulfonium salt compounds include triphenylsulfonium chloride, triphenylsulfonium bromide, tris(p-methoxyphenyl)sulfonium tetrafluoroborate, tris(p-methoxyphenyl) )sulfonium hexafluorophosphonate, tris(p-ethoxyphenyl)sulfonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium six Fluorophosphate and other triphenylsulfonium salts, (4-phenylthiophenyl) diphenylsulfonium hexafluoroantimonate, (4-phenylthiophenyl) diphenylsulfonium hexafluorophosphate, bis[4 -(diphenylsulfonium)phenyl]sulfide-bis-hexafluoroantimonate, bis[4-(diphenylsulfonium)phenyl]sulfide-bis-hexafluorophosphate, (4-methyl oxyphenyl) diphenylsulfonium hexafluoroantimonate) and other sulfonium salts.

盐化合物，可举出例如，苯重氮

六氟锑酸盐、苯重氮

六氟磷酸盐、苯重氮

六氟硼酸盐等重氮

盐。as aromatic diazo

Salt compounds, for example, benzenediazonium

Hexafluoroantimonate, benzenediazonium

Hexafluorophosphate, Benzenediazonium

Diazo such as hexafluoroborate

Salt.

盐，可举出三苯基

氯化物、三苯基

溴化物、三(对甲氧基苯基)

四氟硼酸盐、三(对甲氧基苯基)

六氟膦酸盐、三(对乙氧基苯基)

四氟硼酸盐、4-氯苯重氮

六氟磷酸盐、苄基三苯基

六氟锑酸盐等

盐。as aromatic

salt, triphenyl

Chloride, triphenyl

bromide, tris(p-methoxyphenyl)

Tetrafluoroborate, tris(p-methoxyphenyl)

Hexafluorophosphonate, tris(p-ethoxyphenyl)

Tetrafluoroborate, 4-Chlorobenzenediazonium

Hexafluorophosphate, benzyltriphenyl

Hexafluoroantimonate etc.

Salt.

Examples of triazine compounds include 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)- Triazine compounds such as 6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine.

As the iron arene complex, for example, xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, di Toluene-cyclopentadienyl iron (II) tris(trifluoromethylsulfonyl)methanide and other iron arene coordination compounds.

Further, selenium salts such as triphenylselenium hexafluorophosphate, metallocene coordination compounds such as (η ⁵ or η ⁶ -isopropylbenzene) (η ⁵ -cyclopentadienyl) iron (II) hexafluorophosphate It can also be used as a photoradical polymerization initiator, and can also be used as a photocationic polymerization initiator.

As a photocationic polymerization initiator (c1-2), the compound represented by following formula (c1-2-1) - a formula (c1-2-67) is further mentioned, for example.

Examples of the thermal radical polymerization initiator (c2-1) include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2 ,2'-Azobis(2,4-dimethylvaleronitrile), 4,4'-Azobis(4-cyanovaleric acid), 2,2'-Azobis(2-methylpropane acid) dimethyl ester, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] Dihydrochloride, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, etc. They are available from Tokyo Chemical Industry Co., Ltd.

Examples of thermal cationic polymerization initiators (c2-2) include dicyandiamide, cyclohexyl p-toluenesulfonate, methyldiphenylsulfonium tetrafluoroborate, benzyl (4-hydroxyphenyl) Methylsulfonium hexafluoroantimonate, (4-hydroxyphenyl)methyl(2-methylbenzyl)sulfonium hexafluoroantimonate, etc. They are available from Tokyo Chemical Industry Co., Ltd.

The photoinitiator (C) can be used in the range of 0.01-50 mass parts, or 0.1-15 mass parts with respect to 100 mass parts of polymerizable compounds (B).

In the coating composition of the present invention, for radical polymerization, a radical scavenger (quencher) can be used. Furthermore, it can be used for preventing monomer polymerization by light/heat/air etc. during storage. In addition, it can be included in the coating composition to suppress changes in sensitivity and improve pattern accuracy. For example, 4-tert-butylpyrocatechol, tert-butylhydroquinone, 1,4-benzoquinone, 6-tert-butyl-2,4-xylenol, 2,6-di-tert-butyl-p- Cresol, 2,6-di-tert-butylphenol, hydroquinone, 4-methoxyphenol, phenothiazine, etc. Those manufactured by Tokyo Chemical Industry Co., Ltd. can be used.

In the coating composition of the present invention, one or more nitrogen-containing organic compounds may be blended as basic compounds (quenchers) for cationic polymerization.

As the nitrogen-containing organic compound, a compound capable of suppressing the diffusion rate when the acid generated by the acid generator diffuses in the film is suitable. By compounding nitrogen-containing organic compounds, it is possible to suppress the diffusion rate of acid in the film to improve resolution, suppress sensitivity changes after exposure, reduce substrate and environmental dependence, and improve exposure margin and patternability. In addition, the storage stability of the coating composition can be improved.

Examples of such nitrogen-containing organic compounds (quenchers) include primary aliphatic amines, secondary aliphatic amines, tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, Nitrogen-containing compounds with sulfonyl groups, nitrogen-containing compounds with hydroxyl groups, nitrogen-containing compounds with hydroxyphenyl groups, alcoholic nitrogen-containing compounds, amides, imides, carbamates, ammonia, Ammonium salts, sulfonium salts, etc.

唑衍生物(更具体而言，

唑、异

唑等)、噻唑衍生物(更具体而言，噻唑、异噻唑等)、咪唑衍生物(更具体而言，咪唑、4-甲基咪唑、4-甲基-2-苯基咪唑等)、吡唑衍生物、呋咱衍生物、吡咯啉衍生物(更具体而言，吡咯啉、2-甲基-1-吡咯啉等)、吡咯烷衍生物(更具体而言，吡咯烷、N-甲基吡咯烷、吡咯烷酮、N-甲基吡咯烷酮等)、咪唑啉衍生物、咪唑烷衍生物、吡啶衍生物(更具体而言，吡啶、甲基吡啶、乙基吡啶、丙基吡啶、丁基吡啶、4-(1-丁基戊基)吡啶、二甲基吡啶、三甲基吡啶、三乙基吡啶、苯基吡啶、3-甲基-2-苯基吡啶、4-叔丁基吡啶、二苯基吡啶、苄基吡啶、甲氧基吡啶、丁氧基吡啶、二甲氧基吡啶、4-吡咯烷基吡啶、2-(1-乙基丙基)吡啶、氨基吡啶、二甲基氨基吡啶等)、哒嗪衍生物、嘧啶衍生物、吡嗪衍生物、吡唑啉衍生物、吡唑烷衍生物、哌啶衍生物、哌嗪衍生物、吗啉衍生物、吲哚衍生物、异吲哚衍生物、1H-吲唑衍生物、二氢吲哚衍生物、喹啉衍生物(例如喹啉、3-喹啉甲腈等)、异喹啉衍生物、噌啉衍生物、喹唑啉衍生物、喹喔啉衍生物、酞嗪衍生物、嘌呤衍生物、蝶啶衍生物、咔唑衍生物、菲啶衍生物、吖啶衍生物、吩嗪衍生物、1,10-菲咯啉衍生物、腺嘌呤衍生物、腺苷衍生物、鸟嘌呤衍生物、鸟苷衍生物、尿嘧啶衍生物、尿苷衍生物等。Examples of primary aliphatic amines include methylamine, ethylamine, n-propylamine and the like. Examples of secondary aliphatic amines include dimethylamine, diethylamine, di-n-propylamine and the like. As tertiary aliphatic amines, trimethylamine, triethylamine, tri-n-propylamine etc. are mentioned, for example. Examples of aromatic amines and heterocyclic amines include aniline derivatives (more specifically, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-di Methylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline Aniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N,N-dimethyltoluidine, etc.), diphenyl (p-tolyl) Amines, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (more specifically, pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4- Dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.),

Azole derivatives (more specifically,

azole, iso

azole, etc.), thiazole derivatives (more specifically, thiazole, isothiazole, etc.), imidazole derivatives (more specifically, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), Pyrazole derivatives, furoxan derivatives, pyrroline derivatives (more specifically, pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (more specifically, pyrrolidine, N- methylpyrrolidine, pyrrolidone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (more specifically, pyridine, picoline, ethylpyridine, propylpyridine, butyl Pyridine, 4-(1-butylpentyl)pyridine, lutidine, collidine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine , diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 4-pyrrolidinylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethyl aminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives Compounds, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (such as 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.

The content of the quencher can be used within a range of 0.001 to 1 part by mass, or 0.01 to 0.5 parts by mass relative to 100 parts by mass of the polymerizable compound (B).

Surfactants (leveling agents) may be used in the present invention. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ethers, polyoxyethylene Polyoxyethylene alkyl allyl ethers such as vinyl octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, dehydrated Sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, etc. Sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, poly Oxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Non-ionic surfactants such as polyoxyethylene sorbitan fatty acid esters, trade name Eftop EF301 , EF303, EF352 (manufactured by Tochem Prodaku), trade names Megafack F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC), Florard FC430, FC431 ( Fluorine-based surfactants such as Sumitomo Sunrise Co., Ltd.), trade name Asahide AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), and organosiloxane polymerization Product-KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), polyether-modified silicone oil (manufactured by Toray Dow Corning Co., Ltd. L-7001), etc. These surfactants can be added in a ratio of 0.002 to 10 parts by mass or 0.02 to 5 parts by mass with respect to 100 parts by mass of the polymerizable compound (B).

The solvent used in the coating composition of the present invention is not particularly limited as long as it can dissolve the above-mentioned solid content. Examples of such solvents include methanol, ethanol, n-propanol, isopropanol, butanol, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, and propylene glycol monomethyl ether. , Propylene Glycol Monoethyl Ether, Methyl Isobutyl Methanol, Propylene Glycol Monobutyl Ether, Propylene Glycol Monomethyl Ether Acetate, Propylene Glycol Monoethyl Ether Acetate, Propylene Glycol Monopropyl Ether Acetate, Propylene Glycol Monobutyl Ethyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethoxyacetic acid Ethyl ester, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 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 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 dipropylene Dibutyl 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 ester, isobutyl formate, amyl formate, isopentyl formate, methyl acetate, ethyl acetate, amyl acetate, isopentyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate ester, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate , ethyl glycolate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, methoxy Ethyl acetate, ethyl ethoxy acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetic acid Esters, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl 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,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 4-methyl-2-pentanol , and γ-butyrolactone, etc. These solvents may be used alone or in combination of two or more.

As a method for producing the coating composition, a solvent, a colloidal solution of metal oxide particles (A), a polymerizable compound (B), a polymerization initiator (C) if necessary, and a quencher can be added to a container with a stirrer. It is produced by stirring extinguishing agent and surfactant. A polymerization initiator, a photoacid generator, and a nitrogen organic compound as a quencher may be added by dissolving a part of the above-mentioned solvent in advance.

Hereinafter, use of the coating composition of this invention is demonstrated.

Coated on substrates (such as diaphragms, silicon wafer substrates, silicon/silicon dioxide coated substrates, silicon nitride substrates, glass substrates, ITO substrates, polyimide substrates, and low-k materials) substrate, etc.), the coating composition of the present invention is coated by an appropriate coating method such as a spin coater, a coater, and then heated to form a coating film obtained by thermal curing (by the heat of the coating composition film made of cured product). The heating conditions are appropriately selected from a heating temperature of 20° C. to 250° C., or 20° C. to 110° C., and a heating time of 0.3 minutes to 60 minutes. Here, the film thickness of the formed coating film is, for example, 0.01 μm to 10 μm, or 0.02 μm to 8 μm, or 0.05 μm to 6 μm, or 0.1 μm to 5 μm.

In the case of photocuring the coated coating film, in order to remove the solvent, it is dried at 20°C to 100°C for a heating time of 0.3 minutes to 60 minutes, and then, using ultraviolet rays with a wavelength of 500nm to 190nm, the exposure amount is 1mJ/ cm ² to 20000mJ/cm ² , or 10mJ/cm ² to 15000mJ/cm ² , or 50mJ/cm ² to 11000mJ/cm ² to form a coating film obtained by photocuring. The film thickness of the formed coating film is, for example, 0.01 μm to 10 μm, or 0.02 μm to 8 μm, or 0.05 μm to 6 μm, or 0.1 μm to 5 μm.

In the present invention, thermal curing and photocuring can be used together. It can be heat-cured first and then light-cured, or light-cured and then heat-cured.

Example

About the optical member which has a cured film obtained in the Example and the comparative example, each physical property was measured and evaluated by the measuring method shown below.

(1) Refractive index

The reflectance of the cured film formed on the glass substrate was measured using the reflectance measuring machine (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

The hardness HMs [N/mm ² ] of the cured film formed on the glass substrate was measured using a dynamic ultra-micro hardness meter (DUH-211 manufactured by Shimadzu Corporation). Judgment criteria are as follows.

A: The hardness is 250 or more.

B: The hardness is 150 or more and less than 250.

C: The hardness is less than 150.

(3) Transparency

The haze value of the cured film formed on the glass substrate was measured using the haze meter (Nippon Denshoku Industries Co., Ltd. product NDH7000). The judgment criteria are as follows.

A: The haze value is less than 0.3.

B: The haze value is 0.3 or more and less than 1.0.

C: The haze value is 1.0 or more and less than 3.0.

D: The haze value is 3.0 or more and less than 10.0.

E: The haze value is 10.0 or more.

(4) Light fastness test

The transmittance of the obtained optical member (optical member in which a cured film was formed on a glass substrate) was measured using a spectrophotometer (UV-3600 manufactured by Shimadzu Corporation), and the YI value was calculated based on JIS7373. Then, the YI value of the optical member exposed for 120 hours was calculated using a QUV accelerated weathering tester (UVA lamp irradiation intensity: 890 mW/m ² ). ΔYI of the optical member before and after ultraviolet irradiation was calculated. The 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.

(5) Bending test

Using a cylindrical mandrel bending tester (1603/MS manufactured by BEVS Corporation), in a tester in which a test rod with a radius of curvature R=1 mm was placed, the resulting optical member (made on a PET film (manufactured by Toyobo Co., Ltd.) Cosmosyrin A4300, an optical member in which a cured film was formed on a thickness of 100 μm) was bent, and the optical member was clamped and fixed with the main body jig so that the cured film position was outside. The roller is brought close to the test panel, and the handle is turned 180° evenly over a period of 1 second to 2 seconds. Then, the presence or absence of cracks was confirmed using a digital microscope (VHX-6000 manufactured by Keyence Corporation). Judgment criteria are as follows.

1: Cracks are not generated on the cured film.

2: 1 to 9 cracks were formed on the cured film.

3: 10 to 29 cracks were formed on the cured film.

4: 30 or more cracks were formed on the cured film.

(6) Scratch resistance test

Device: Shinto Science Co., Ltd. reciprocating wear tester TRIBOGEAR TYPE: 30S

Scanning speed: 1.2sec/cycle

Scanning distance: 30mm

The surface of the cured film was rubbed 20 back and forth under a load of 250 g/ ^cm2 with steel wool [Bonster (registered trademark) #0000 (super fine) manufactured by Bonstar Trading Co., Ltd.) installed in a reciprocating wear tester, and passed the target. Depending on the degree of the confirmed damage, evaluation was performed according to the following criteria.

1: 5 or less wounds.

2: 6 or more and 20 or less wounds.

3: 21 or more wounds.

(7) Adhesion test

100 grids were applied to the cured film at intervals of 1 mm, and an adhesive tape (cellophane tape, manufactured by Nichiban Co., Ltd.) was strongly attached to the gridded portion, and the adhesive tape was quickly peeled off to investigate peeling. Whether or not the cured film peeled off after the adhesive tape was applied. The evaluation criteria are as follows.

A: No peeling at all, or less than 5 peelings out of 100 were confirmed.

B: Peeling of 5 to 30 frames out of 100 frames can be confirmed.

C: Peeling of 31 to 100 frames out of 100 frames can be confirmed.

(Reference Example 1): Preparation of titanium oxide-tin dioxide composite oxide colloidal particles (a1-1) serving as nuclei.

Dissolve 319.5 g of a 25% by mass tetramethylammonium hydroxide aqueous solution in 947.1 g of pure water, then add 14.8 g of metastannic acid (12.5 g in terms of SnO ₂ ), 236.6 g of titanium tetraisopropoxide (containing 12.5 g in terms of TiO ₂ 66.6 g), and 82.0 g of oxalic acid dihydrate (58.5 g in terms of oxalic acid) were added with stirring. This mixed solution was kept at 80° C. for 2 hours, and the pressure was further reduced to 580 Torr and kept for 2 hours to prepare a mixed solution. The above-mentioned mixed solution was charged into a glass-lined autoclave container, subjected to hydrothermal treatment at 140° C. for 5 hours, cooled to room temperature, and then taken out. The resulting sol is an acidic titanium oxide-tin dioxide composite oxide colloidal particle (A1) water dispersion sol, pH 3.9, and the total metal oxide concentration (TiO ₂ and SnO ₂ ) is 5.0% by mass. The average particle diameter obtained by the scattering method (dynamic light scattering method particle diameter) was 16 nm. The obtained sol was dried at 110° C. to obtain a powder, and X-ray diffraction analysis of the obtained powder confirmed that it was a rutile crystal.

(Reference example 2): Preparation of silica-tin dioxide composite oxide colloidal particles (a2-1) to be a coating.

Dissolve 77.2 g of JIS No. 3 sodium silicate (contains 29.8% by mass in terms of SiO ₂ ) in 668.8 g of pure water, and then dissolves sodium stannate monohydrate NaSnO ₃ ·H ₂ O (contains 55.1% by mass in terms of SnO ₂ ) 20.9g. The resulting aqueous solution was passed through a column filled with a hydrogen-form cation exchange resin (Amberlight (registered trademark) IR-120B, manufactured by Olgano Co., Ltd.). Next, 7.2 g of diisopropylamine was added to the obtained water-dispersed sol. The obtained sol was a water-dispersed sol of basic silica-tin dioxide composite oxide colloidal particles (B1), pH 8.0, and total metal oxide concentration (SnO ₂ and SnO ₂ ) of 1.7% by mass. Observation with a transmission electron microscope revealed that the primary particle size was 1 nm to 4 nm.

(Reference Example 3): Preparation of titania-tin dioxide-zirconia composite oxide colloidal particles (A-1) modified with silica-tin dioxide composite oxide.

82.7 g of zirconium oxychloride (containing 21.2 mass % in terms of ZrO ₂ ) was diluted with 501.1 g of pure water to prepare 583.8 g of zirconium oxychloride aqueous solution (containing 3.0 mass % in terms of ZrO ₂ ), which was prepared in Reference Example 1. 1516.2 g of the water-dispersed sol of the titanium oxide-tin dioxide composite oxide colloidal particles (A1) was added with stirring. Then, hydrolysis was carried out by heating at 95°C, and a water-dispersed sol of titania-tin dioxide-zirconia composite oxide colloidal particles having a thin film layer of zirconia formed on the surface was obtained. Add 2041.2 g of the obtained water-dispersed sol to 1763.3 g of the water-dispersed sol of the basic silica-tin dioxide composite oxide colloidal particles (B1) prepared in Reference Example 2 under stirring, and pour the liquid into the filling A 500 ml column of anion exchange resin (Amberlight (registered trademark) IRA-410, manufactured by Olugano Co., Ltd.) was used. Next, the water-dispersed sol passed through 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 was replaced with methanol using a rotary evaporator to obtain a titanium oxide-tin dioxide-zirconia composite oxide modified with a silica-tin dioxide composite oxide Methanol dispersion sol of colloidal particles (C1). The methanol dispersion sol has a pH of 5.2, a concentration of all metal oxides (TiO ₂ , ZrO ₂ , SnO ₂ , and SiO ₂ ) of 30.5% by mass, a viscosity of 1.8 mPa·s, and an average particle size obtained by dynamic light scattering (DLS). diameter (dynamic light scattering method particle size) 20nm.

The modified metal oxide particle (A-1) has a structure in which an intermediate layer (a-2) of zirconia is formed on the surface of a core particle (a1-1) composed of titanium oxide-tin dioxide composite oxide colloidal particles , formed silica-tin dioxide composite oxide colloidal particles (a2-1) on its surface.

(Reference Example 4) Titanium oxide-tin dioxide-zirconia composite oxide colloidal particles modified with silica-tin dioxide composite oxide were surface-treated with acryloxypropyltrimethoxysilane Modulation of colloidal particles (A-2)

98.4 g of the methanol dispersion sol of the modified metal oxide particles (A-1) obtained in Reference Example 3 was taken into a container, and acryloyloxypropyltrimethoxysilane (KBM manufactured by Shin-Etsu Chemical Co., Ltd. -5103) 6.8 g was added under stirring, and the reaction was carried out under reflux for 5 hours to obtain a methanol dispersion sol 105.2 g. The modified metal oxide particle (A-2) has a structure in which an intermediate layer (a-2) of zirconia is formed on the surface of a core particle (a1-1) composed of titanium oxide-tin dioxide composite oxide colloidal particles , Silica-tin dioxide composite oxide colloidal particles (a2-1) were formed on the surface, and the surface of the particles was further surface-treated with acryloxypropyltrimethoxysilane. The silicon atom of the silane coupling agent corresponds to 3.0 atoms/nm ² per unit surface of the modified metal oxide particle (A-2).

The obtained sol had a specific gravity of 1.070, a viscosity of 1.9 mPa·s, a total metal oxide concentration of 30.5% by mass, a water content of 0.8% by mass, and an average particle size obtained by dynamic light scattering (DLS) (DLS particle size) of 18 nm. .

(Example 1)

(Preparation of coating composition)

Into a glass container equipped with a magnetic stirrer, 13.2 parts by mass of isocyanuric acid EO-modified diacrylate (trade name Aronix M-215 manufactured by Toagosei Co., Ltd.), dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate were added. Acrylate mixture (Nippon Kayaku Co., Ltd. product name KAYARAD DPHA) 4.4 parts by mass, 5.2 parts by mass of methanol, 18.3 parts by mass of propylene glycol monomethyl ether, add the modified metal oxide produced in Reference Example 3 while stirring. Substance (A-1) 57.2 parts by mass of colloidal liquid (30.5 mass % of solid content). Next, 0.9 parts by mass of a photoradical polymerization initiator (trade name Irgacure TPO manufactured by BASF Co., Ltd.) and propylene glycol monomethyl ether of polyether-modified silicone oil (trade name L-7001 manufactured by Toray Dow Corning Co., Ltd.) were added. 0.9 parts by mass of the solution (2.0% by mass as trade name L-7001) was stirred for 0.5 hours to prepare a coating liquid (coating composition).

(Formation and evaluation of cured film)

A glass substrate and a PET film were prepared, and a coating solution (coating composition) was applied on them by a spin coating method. After evaporating the solvent at 80° C. for 5 minutes, a high-pressure mercury lamp with an irradiation intensity of 29 mW/cm ² was used for 6 The coating film was cured by ultraviolet treatment (29 mW/cm ² ×6×60=10440 mJ/cm ² ) for 1 minute, and an optical member having a cured film with a film thickness of 3 μm was formed.

The tests shown in (1) to (5) above were carried out. The evaluation results are shown in Table 2.

(Example 2)

In Example 1, the addition amount of isocyanuric acid EO-modified diacrylate (trade name Aronix M-215 manufactured by Toagosei Co., Ltd.) was changed to 10.5 parts by mass, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate The addition amount of the mixture of acrylates (trade name KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) was changed to 7.0 parts by mass, and the ultraviolet treatment time when the cured film was formed was changed to 3 minutes, except that it was the same as in Example 1 Preparation of a coating composition and formation/evaluation of a cured film were implemented.

(Example 3)

In Example 1, the addition amount of isocyanuric acid EO-modified diacrylate (trade name Aronix M-215 manufactured by Toagosei Co., Ltd.) was changed to 15.8 parts by mass, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate The addition amount of the mixture of acrylates (Nippon Kayaku Co., Ltd. product name KAYARAD DPHA) was changed to 1.8 parts by mass, and the UV treatment time when the cured film was formed was changed to 3 minutes (29mW/ ^cm2 ×3×60=5220mJ /cm ² ), preparation of a coating composition and formation/evaluation of a cured film were carried out in the same manner as in Example 1.

(Example 4)

Into a glass container equipped with a magnetic stirrer, 12.0 parts by mass of isocyanuric acid EO-modified diacrylate (trade name Aronix M-215 manufactured by Toagosei Co., Ltd.), dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate were added. Acrylate mixture (Nippon Kayaku Co., Ltd. product name KAYARAD DPHA) 4.0 parts by mass, 1.5 parts by mass of methanol, 18.4 parts by mass of propylene glycol monomethyl ether, add the modified metal oxide produced in Reference Example 3 while stirring. Substance (A-1) 62.5 parts by mass of colloidal liquid (30.5 mass % of solid content). Next, 0.8 parts by mass of a photoradical polymerization initiator (trade name Irgacure TPO manufactured by BASF Co., Ltd.) and propylene glycol monomethyl ether of polyether-modified silicone oil (trade name L-7001 manufactured by Toray Dou Corning Co., Ltd.) were added. 0.8 parts by mass of the solution (2.0% by mass as trade name L-7001) was stirred for 0.5 hours to prepare a coating liquid (coating composition). Then, preparation of a coating composition and formation and evaluation of a cured film were implemented similarly to Example 1.

(Example 5)

Into a glass container equipped with a magnetic stirrer, 10.6 parts by mass of isocyanuric acid EO-modified diacrylate (trade name Aronix M-215 manufactured by Toagosei Co., Ltd.), dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate were added. Acrylate mixture (Nippon Kayaku (KK) product name KAYARAD DPHA) 3.5 parts by mass, 15.6 parts by mass of propylene glycol monomethyl ether, add the modified metal oxide (A-1 ) 68.9 parts by mass of colloidal liquid (30.5 mass % of solid content). Next, 0.7 parts by mass of a photoradical polymerization initiator (Irgacure TPO manufactured by BASF Co., Ltd.) and a propylene glycol monomethyl ether solution ( As a product name L-7001 (2.0 mass %) 0.7 mass parts, stirring was performed for 0.5 hours, and the coating liquid (coating composition) was produced. Then, preparation of a coating composition and formation and evaluation of a cured film were implemented similarly to Example 1.

(Example 6)

Into a glass container equipped with a magnetic stirrer, 8.8 parts by mass of isocyanuric acid EO-modified diacrylate (trade name Aronix M-215 manufactured by Toagosei Co., Ltd.), dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate were added. Acrylate mixture (Nippon Kayaku (KK) product name KAYARAD DPHA) 2.9 parts by mass, 10.3 parts by mass of propylene glycol monomethyl ether, add the modified metal oxide (A-1 ) 76.8 parts by mass of colloidal liquid (solid content 30.5 mass %). Next, a propylene glycol monomethyl ether solution of 0.6 parts by mass of a photoradical polymerization initiator (trade name IrgacureTPO manufactured by BASF Co., Ltd.) and a polyether-modified silicone oil (trade name L-7001 manufactured by Toray Dou Corning Co., Ltd.) was added. (2.0% by mass as brand name L-7001) 0.6 mass parts were stirred for 0.5 hours to prepare a coating liquid (coating composition). Then, preparation of a coating composition and formation and evaluation of a cured film were implemented similarly to Example 1.

(Example 7)

In Example 1, isocyanuric acid EO-modified diacrylate (trade name Aronix M-215 manufactured by Toagosei Co., Ltd.) was changed to ethoxylated bisphenol A diacrylate (Shin Nakamura Chemical Co., Ltd.) manufacturer name ABE-300), and the addition amount was changed to 8.8 parts by mass. Moreover, the addition amount of the mixture (Nippon Kayaku Co., Ltd. product name KAYARAD DPHA) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate was changed to 8.8 mass parts. Furthermore, preparation of a coating composition and formation/evaluation of a cured film were implemented similarly to Example 1 except having changed the ultraviolet-ray treatment time at the time of cured film formation to 3 minutes.

(Embodiment 8)

In Example 1, isocyanuric acid EO-modified diacrylate (trade name Aronix M-215 manufactured by Toagosei Co., Ltd.) was changed to ethoxylated bisphenol A diacrylate (Shin Nakamura Chemical Co., Ltd.) The manufacture name ABE-300), except having changed the ultraviolet-ray treatment time at the time of cured film formation to 3 minutes, it carried out similarly to Example 1, and implemented the preparation of a coating composition and the formation/evaluation of a cured film.

(Example 9)

In Example 1, isocyanuric acid EO-modified diacrylate (trade name Aronix M-215 manufactured by Toagosei Co., Ltd.) was changed to tris(2-acryloyloxyethyl)isocyanurate ( Hitachi Chemical Co., Ltd. product name FA-731A), except that the ultraviolet treatment time during the formation of the cured film was changed to 3 minutes, the preparation of the coating composition and the formation of the cured film were carried out in the same manner as in Example 1. /evaluate.

(Example 10)

In Example 1, the addition amount of isocyanuric acid EO-modified diacrylate (trade name Aronix M-215 manufactured by Toagosei Co., Ltd.) was changed to 8.8 parts by mass, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate The addition amount of the mixture of acrylates (trade name KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) was changed to 8.8 parts by mass, and the ultraviolet treatment time when the cured film was formed was changed to 3 minutes, except that it was the same as in Example 1 Preparation of a coating composition and formation/evaluation of a cured film were implemented.

(Example 11)

In Example 1, the addition amount of isocyanuric acid EO-modified diacrylate (trade name Aronix M-215 manufactured by Toagosei Co., Ltd.) was changed to 4.4 parts by mass, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate The addition amount of the mixture of acrylates (trade name KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) was changed to 13.2 parts by mass, and the ultraviolet treatment time when the cured film was formed was changed to 3 minutes, except that it was the same as in Example 1 Preparation of a coating composition and formation/evaluation of a cured film were implemented.

(Example 12)

In Example 1, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name KAYARAD DPHA manufactured by Nippon Kayaku (KK)) was not added, and isocyanuric acid EO modified diacrylate (Toya Synthetic ( Co., Ltd. product name Aronix M-215) except that the addition amount was changed to 17.6 parts by mass, the preparation of the coating composition and the formation/evaluation of the cured film were carried out in the same manner as in Example 1.

(Example 13)

(Preparation of high refractive index layer coating composition)

In a container made of glass equipped with a magnetic stirrer, an aromatic compound having a polymerizable unsaturated bond containing a urethane bond (manufactured by Daicel Olenex Co., Ltd., trade name EBECRYL220) was added, and the polymerizable compound contained the formula (b1 2.18 mass parts of the compound shown in -2), the compound shown in the formula (b2-6), the compound shown in the formula (b2-7), 73.94 mass parts of propylene glycol monomethyl ether, while stirring, add in the reference example 8.59 parts by mass of the modified metal oxide (A-2) colloidal liquid (30.5% by mass of solid content) surface-treated with acryloxypropyltrimethoxysilane produced in 4. Next, 10.92 parts by mass of a propylene glycol monomethyl ether solution (1.0% by mass as the trade name Irgacure TPO) of a photoradical polymerization initiator (trade name Irgacure TPO manufactured by BASF Co., Ltd.), polyether-modified silicone oil (Toray Co., Ltd. 4.37 parts by mass of a propylene glycol monomethyl ether solution (trade name L-7001 produced by Dow Corning Co., Ltd. (trade name L-7001)) was stirred for 0.5 hours to prepare a coating solution (coating composition ).

(Preparation of Hard Coating Composition for Scratch Resistance and Adhesion Evaluation)

In a glass container equipped with a magnetic stirrer, 38.1 parts by mass of urethane acrylate (trade name UA-306H manufactured by Kyoeisha Chemical Co., Ltd.) and 58.1 parts by mass of propylene glycol monomethyl ether were added and stirred. While adding 1.9 parts by mass of a photoradical polymerization initiator (trade name Irgacure TPO manufactured by BASF Co., Ltd.), a propylene glycol monomethyl ether solution of polyether-modified silicone oil (trade name L-7001 manufactured by Toray Dou Corning Co., Ltd.) (2.0% by mass as brand name L-7001) 1.9 parts by mass. Then, stirring was performed for 0.5 hours to prepare a coating liquid (coating composition).

(Formation and evaluation of cured film)

(refractive index, transparency evaluation)

A glass substrate was prepared, and a high-refractive-index layer coating liquid (high-refractive-index layer coating composition) was applied by spin coating, and the solvent was volatilized at 80° C. for 5 minutes. The coating film was cured by ultraviolet treatment (19 mW/cm ² x6 x 60=6840 mJ/cm ² ) for 6 minutes with a high-pressure mercury lamp of cm ² to form an optical member having a cured film with a film thickness of 200 nm.

The tests shown in (1) and (3) above were carried out. The evaluation results are shown in Table 4.

(Scratch resistance, adhesion evaluation)

Prepare a polycarbonate substrate, apply a hard coat coating solution (hard coat coating composition) by spin coating so that the film thickness after UV curing becomes 5 μm, and evaporate the solvent at 80° C. for 5 minutes Thereafter, the coating film was cured by ultraviolet treatment (19 mW/cm ² ×30=570 mJ/cm ² ) for 30 ^seconds with a high-pressure mercury lamp with an irradiation intensity of 19 mW/cm 2 , thereby obtaining a hard coat cured film. Then, the high-refractive-index layer coating liquid (high-refractive-index layer coating composition) was coated on the hard coat cured film by the spin coating method, and the solvent was evaporated at 80° C. for 5 minutes, and then, under a nitrogen atmosphere, Use a high-pressure mercury lamp with an irradiation intensity of 19mW/ ^cm2 to perform 6 minutes of ultraviolet treatment (19mW/ ^cm2 ×6×60=6840mJ/ ^cm2 ) to cure the coating film and form a laminated cured film (film thickness: high refractive index layer 200nm , hard coating 5μm).

The tests shown in (7) and (8) above were carried out. The evaluation results are shown in Table 4.

(Example 14)

In Example 13, instead of the modified metal oxide (A-2) colloid liquid prepared in Reference Example 4, which was surface-treated with acryloxypropyltrimethoxysilane, the Modified metal oxide (A-1) colloid liquid (30.5% by mass of solid content) 8.59 mass parts of the modified metal oxide (A-1) produced in, except that, similarly carried out the making of high refractive index layer coating composition and the formation of cured film/ evaluate.

(Example 15)

In Example 13, an isocyanuric acid EO-modified diacrylate was used instead of a urethane bond-containing aromatic compound having a polymerizable unsaturated bond (manufactured by Daicel Olenex Co., Ltd., trade name EBECRYL220). (Toagosei Co., Ltd. product name Aronix M-215) 1.64 parts by mass, and a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Nippon Kayaku Co., Ltd. product name KAYARAD DPHA) 0.55 parts by mass, except In addition, preparation of the high-refractive-index layer coating composition and formation and evaluation of a cured film were implemented similarly.

(comparative example 1)

Into a glass container equipped with a magnetic stirrer, 25.7 parts by mass of isocyanuric acid EO-modified diacrylate (trade name Aronix M-215 manufactured by Toagosei Co., Ltd.), dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate were added. Acrylic ester mixture (Nippon Kayaku Co., Ltd. product name KAYARAD DPHA) 8.6 parts by mass, 17.5 parts by mass of methanol, and 44.8 parts by mass of propylene glycol monomethyl ether. Next, while stirring the above solution, 1.7 parts by mass of a photoradical polymerization initiator (trade name Irgacure TPO manufactured by BASF Co., Ltd.), 1.7 parts by mass of polyether-modified silicone oil (trade name L-7001 manufactured by Toray Dow Corning Co., Ltd.) were added. ) of a propylene glycol monomethyl ether solution (2.0% by mass as trade name L-7001) was stirred for 0.5 hours to prepare a coating liquid (coating composition).

The formation and evaluation of the cured film were performed in the same manner as in Example 1 except that the ultraviolet treatment time at the time of forming the cured film was changed to 3 minutes.

(comparative example 2)

Into a glass container equipped with a magnetic stirrer, 19.9 parts by mass of isocyanuric acid EO-modified diacrylate (trade name Aronix M-215 manufactured by Toagosei Co., Ltd.), dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate were added. Acrylate mixture (Nippon Kayaku Co., Ltd. product name KAYARAD DPHA) 6.6 parts by mass, 26.2 parts by mass of methanol, 17.9 parts by mass of propylene glycol monomethyl ether, while stirring, add (a1-1 ) 26.5 parts by mass of titanium oxide-based sol (solid content 30.0% water dispersion) not subjected to SnO ₂ -SiO ₂ composite formation. Next, 1.3 parts by mass of a photoradical polymerization initiator (trade name Irgacure TPO manufactured by BASF Co., Ltd.) and propylene glycol monomethyl ether of polyether-modified silicone oil (trade name L-7001 manufactured by Toray Dou Corning Co., Ltd.) were added. 1.3 parts by mass of the solution (2.0% by mass as trade name L-7001) was stirred for 0.5 hours to prepare a coating liquid (coating composition). Then, preparation of a coating composition and formation and evaluation of a cured film were implemented similarly to Example 1.

(comparative example 3)

In a container made of glass equipped with a magnetic stirrer, an aromatic compound having a polymerizable unsaturated bond containing a urethane bond (manufactured by Daicel Olenex Co., Ltd., trade name EBECRYL220) was added, and the polymerizable compound contained the formula (b1 4.59 parts by mass of the compound represented by -2), the compound represented by the formula (b2-6), and the compound represented by the formula (b2-7), and 63.30 parts by mass of propylene glycol monomethyl ether. Next, 22.94 parts by mass of a propylene glycol monomethyl ether solution (1.0% by mass as Irgacure TPO as a trade name) of a photoradical polymerization initiator (trade name Irgacure TPO manufactured by BASF Co., Ltd.), 22.94 parts by mass of polyether modified 9.17 parts by mass of a propylene glycol monomethyl ether solution (2.0% by mass as the product name L-7001) of silicone oil (trade name L-7001 manufactured by Toray Dow Corning Co., Ltd.), stirred for 0.5 hours to produce a high refractive index Layer Coating Liquid (High Refractive Index Layer Coating Composition).

The formation and evaluation of the cured film were carried out in the same manner as in Example 13.

(comparative example 4)

In a container made of glass equipped with a magnetic stirrer, an aromatic compound having a polymerizable unsaturated bond containing a urethane bond (manufactured by Daicel Olenex Co., Ltd., trade name EBECRYL220) was added, and the polymerizable compound contained the formula (b1 -2) the compound shown in the compound shown in the formula (b2-6), and the compound shown in the formula (b2-7)) 2.39 parts by mass, 72.89 parts by mass of propylene glycol monomethyl ether, add while stirring 7.97 parts by mass of (a1-1) titanium oxide-based sol (solid content 30.0% water dispersion) not subjected to SnO ₂ -SiO ₂ composite obtained in Example 1. Next, 11.96 parts by mass of a propylene glycol monomethyl ether solution (1.0% by mass as the trade name Irgacure TPO) of a photoradical polymerization initiator (trade name Irgacure TPO manufactured by BASF Co., Ltd.), polyether-modified silicone oil (Toray Co., Ltd. 4.78 parts by mass of a propylene glycol monomethyl ether solution (trade name L-7001 produced by Dow Corning Co., Ltd. (trade name L-7001)) was stirred for 0.5 hours to prepare a coating liquid (coating composition ).

The formation and evaluation of the cured film were carried out in the same manner as in Example 13.

In Table 1, Toagosei Co., Ltd. product name Aronix M-215) is represented by (i),

The Nippon Kayaku Co., Ltd. product name KAYARAD DPHA is represented by (ii),

The brand name ABE-300 manufactured by Shin-Nakamura Chemical Co., Ltd. is represented by (iii),

The brand name FA-731A manufactured by Hitachi Chemical Co., Ltd. is represented by (iv),

The trade name Irgacure TPO manufactured by BASF Co., Ltd. is represented by (v),

The product name L-7001 manufactured by Toray Dow Corning Co., Ltd. is represented by (vi), and the particle (A-1) is represented by (vii),

The particle (a1-1) is represented by (viii),

The particle (A-2) is represented by (ix),

The product name EBECRYL220 manufactured by Daicel Olenex Co., Ltd. is represented by (x). In addition, in Table 1, the addition amount shows the mass parts of each component.

[Table 1]

Table 1

Table 2

table 3

Table 4

The coating film obtained from the coating composition comprising modified metal oxide particles (A) and a polymerizable compound (B) having an unsaturated bond between carbon atoms and carbon atoms has the following properties in terms of refractive index, hardness, transparency, Shows excellent performance in light resistance, flexibility, scratch resistance, and adhesiveness.

A coating film obtained from a coating composition obtained by using a polymerizable compound (b1) and a polymerizable compound (b2) in combination with a polymerizable compound (B) exhibits refractive index, hardness, transparency, light resistance, and flexibility. Excellent performance.

In the polymerizable compound (B), when the polymerizable compound (b1) and the polymerizable compound (b2) are not used together, when the polymerizable compound (b2) is included but the polymerizable compound (b1) is not included, or when the polymerizable compound (b1) is included, When the polymerizable compound (b1) and the polymerizable compound (b2) are used in combination, but the content of the polymerizable compound (b1) is low, the light resistance and the flexibility are slightly lowered in performance.

When the metal oxide particles (A) are not contained, sufficient hardness cannot be obtained, and adjustment of the refractive index is also insufficient.

In addition, the metal oxide particles (A) that do not have a coating structure are insufficient in terms of transparency, light resistance, and flexibility.

In the present invention, by selecting the core particle (a1) and the coating particle (a2), a desired refractive index can be adjusted according to the refractive index of the substrate, and a coating agent corresponding to a high-refractive substrate can be produced. In addition, by containing a silica component in the outermost layer and surface-treating the particle surface with a silane coupling agent, it can be copolymerized with the unsaturated bond of the polymerizable compound that becomes the curing component, and the metal oxide particle can be incorporated into the resin matrix. uniformly immobilized.

Moreover, the composition corresponding to the function required for a coating composition can be manufactured by selecting a polymeric compound (B).

industry availability

The present invention can be heat-cured and photo-cured, and can be coated on a transparent film or a glass substrate to form the required refractive index, hardness, adhesion, transparency, light resistance, flexibility, scratch resistance, adhesion, etc. coated substrate.

Claims (10)

1. A coating composition comprising:

metal oxide particles (A); and

a polymerizable compound (B) having an unsaturated bond of a carbon atom and a carbon atom;

the metal oxide particles (A) are modified metal oxide particles (A) having an average particle diameter of 2nm to 100nm, the metal oxide particles (A) have colloidal particles (a 1) having an average particle diameter of 2nm to 100nm and being an oxide or a composite oxide of at least 1 metal selected from Ti, sn, zr, si, al, sb, fe, cu, zn, Y, nb, mo, in, ta, pb, bi, hf, ge, ce and W, and the surfaces thereof are coated with at least 1 layer of colloidal particles (a 2) having an average primary particle diameter of 1nm to 40nm and being an oxide or a composite oxide of at least 1 metal selected from Ti, sn, zr, si, al, sb, fe, cu, zn, Y, nb, mo, in, ta, pb, bi, hf, ge, ce and W, and the core particles (a 1) and the layer containing the particles (a 2) are different In metal component from each other or are different as a composite oxide;

the polymerizable compound (B) comprises a polymerizable compound (B1-1) represented by the formula (B1-1) or a polymerizable compound (B1-2) represented by the formula (B1-2),

in the formula (b 1-1), R ¹ And R ² Each represents a hydrogen atom or a methyl group, R ³ Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, n ₁ And n ₂ Each represents an integer of 0 to 10;

in the formula (b 1-2), R ²¹ 、R ²² 、R ²³ 、R ²⁴ 、R ²⁵ And R ²⁶ Each represents a hydrogen atom or a methyl group.

2. The coating composition according to claim 1, wherein the layer containing the metal oxide particles (a) that covers the outermost layer of the metal oxide particles (a) contains Si as a metal component.

3. The coating composition according to claim 1 or 2, wherein the metal oxide particle (a) further has an intermediate layer comprising the particle (a 2) between the core particle (a 1) and the outermost layer comprising the particle (a 2).

4. The coating composition according to claim 1, wherein the polymerizable compound (B) further comprises a polymerizable compound (B2) represented by the formula (B2),

in the formula (b 2), R ⁴ Each represents a hydrogen atom or a methyl group, T represents a carbon atom, or an aliphatic hydrocarbon group or an aromatic hydrocarbon group which may contain an ether bond, or a combination thereof, and n ₃ Represents an integer of 1 to 10, n ₄ Represents an integer of 0 to 5, n ₅ Represents an integer of 0 to 2, n ₆ Represents an integer of 0 to 2.

5. The coating composition according to claim 1 or 2, further comprising a photopolymerization initiator or a thermal polymerization initiator as the polymerization initiator (C).

6. The coating composition according to claim 5, wherein the polymerization initiator (C) is a photo radical polymerization initiator, a thermal radical polymerization initiator, a photo cation polymerization initiator or a thermal cation polymerization initiator.

7. The coating composition of claim 1 or 2, further comprising a surfactant.

8. A coating film comprising a photo-cured product or a thermosetting product of the coating composition according to any one of claims 1 to 7.

9. An optical member comprising a base material and the coating film according to claim 8 formed on the base material.

10. A method for producing a substrate having a coating film, comprising the steps of: coating a substrate with the coating composition according to any one of claims 1 to 7; removing the solvent; and (d) performing a light irradiation and/or heating step.