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

Acrylic coating composition containing inorganic oxide particles Download PDF

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Publication number
CN112752802B
CN112752802B CN201980063077.4A CN201980063077A CN112752802B CN 112752802 B CN112752802 B CN 112752802B CN 201980063077 A CN201980063077 A CN 201980063077A CN 112752802 B CN112752802 B CN 112752802B
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particles
metal oxide
coating composition
polymerizable compound
mass
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CN112752802A (en
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安藤优大
山口真人
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size

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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 containing inorganic oxide particles
Technical Field
The present invention relates to a coating composition using an organic-inorganic composite component, which is heat-curable and photocurable, and an optical member obtained from the coating composition.
Background
The substrate coated with the coating composition is used in various fields such as optical members, mechanical part materials, electronic part materials, building materials, and molding materials. Depending on the application, the coated substrate is required to have refractive index, hardness, adhesiveness, transparency, light resistance, and flexibility. Further, the coating liquid used for coating is required to have 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 an oxide of aluminum, magnesium, zirconium, bismuth, calcium, tin, manganese, antimony, silicon, or titanium (see patent document 1).
Further, an active energy ray-curable resin composition having (a) an organic-inorganic complex having a (meth) acryloyl group bonded to the surface thereof via an — O — Si — X-bond, (B) an ultraviolet absorber, (C) a hindered amine light stabilizer, and (D) an organic solvent having a boiling point of 70 to 200 ℃ is disclosed (see patent document 2).
Further, a method of obtaining an optical product by curing a sol containing a metal oxide formed from a hydrolysis-condensation product of a metal alkoxide selected from titanium, cerium, zirconium, or tin and a polymerizable compound is disclosed (see patent document 3).
Documents of the prior art
Patent document
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 publication No. 2005-075723
Disclosure of Invention
Problems to be solved by the invention
The invention provides a coating composition which can be cured by heat and light and has improved storage stability in order to form a coated substrate requiring refractive index, hardness, adhesion, transparency, light resistance and bendability.
Means for solving the problems
That is, as a1 st aspect in the present invention, there 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 a core of colloidal particles (a 1) of a metal oxide having an average particle diameter of 2 to 60nm and having surfaces coated with a layer containing colloidal particles (a 2) of a metal oxide having an average primary particle diameter of 1 to 40 nm; and
a polymerizable compound (B) having an unsaturated bond of a carbon atom and a carbon atom (i.e., a carbon-carbon unsaturated bond),
a2 nd aspect of the coating composition according to the 1 st aspect, wherein 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 a core of an oxide or a composite oxide (a 1) of at least 1 metal 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 and W and a surface thereof is coated with at least 1 layer of an oxide or a composite oxide (a 2) having an average primary particle diameter of 1nm to 40nm and 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 and W, and the core particles (a 1) and the layer containing the particles (a 2) are different from each other In metal component or are different from each other as a composite oxide,
a 3 rd aspect of the coating composition according to the 1 st or 2 nd aspect, wherein the layer containing the particles (a 2) of the metal oxide particles (a) that covers the outermost layer contains Si as a metal component,
the 4 th aspect of the coating composition according to any one of the 1 st to 3 th aspects, wherein the metal oxide particles (A) further have an intermediate layer comprising the particles (a 2) between the core particles (a 1) and the outermost layer comprising the particles (a 2),
the coating composition according to claim 5, which is the coating composition according to any one of claims 1 to 4, wherein the polymerizable compound (B) is a polymerizable compound (B1-1) having a triazinetrione skeleton and having an unsaturated bond between a carbon atom and a carbon atom, or a polymerizable compound (B1-2) having an aromatic compound having a urethane bond and having an unsaturated bond between a carbon atom and a carbon atom,
the 6 th aspect of the coating composition according to any one of the 1 st to 5 th aspects, wherein 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),
Figure BDA0002992056900000031
(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. )
An aspect 7 is the coating composition according to aspect 6, wherein the polymerizable compound (B) further comprises a polymerizable compound (B2) represented by the formula (B2),
Figure BDA0002992056900000041
(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. )
The coating composition according to claim 8, which further comprises a photopolymerization initiator or a thermal polymerization initiator as the polymerization initiator (C),
a9 th aspect of the coating composition according to the 8 th aspect of the present invention is the coating composition according to the 9 th aspect, 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,
the coating composition according to any one of aspects 1 to 9, which is the coating composition according to claim 10, further comprising a surfactant,
the 11 th aspect is a coating film comprising a photo-cured product or a thermosetting product of the coating composition according to any one of the 1 st to 10 th aspects,
viewed from 12 is an optical member comprising a base material and the coating film of viewed from 11 formed on the base material, and
as a 13 th aspect, the present invention provides a method for producing a substrate having a coating film, comprising the steps of: a step of coating a substrate with the coating composition according to any one of aspects 1 to 10; removing the solvent; and (d) performing a light irradiation and/or heating process.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention is a coating composition comprising:
colloidal particles (A) having an average particle diameter of 2nm to 100nm, the colloidal particles (A) having colloidal particles (a 1) of a metal oxide as cores and the surfaces of the colloidal particles (A) being coated with a layer containing colloidal particles (a 2) of a metal oxide; 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 (a 1) is coated with at least 1 layer including the particle (a 2) can be used. By using the modified colloidal particles (a) having a coating structure, transparency and hardness can be improved, and a refractive index corresponding to a substrate to be coated can be adjusted.
By using the metal oxide particles having a coating structure, a coating film containing these particles as a coating composition can impart a plurality of functions.
For example, when metal oxide sols are mixed with each other, the metal oxide component may be offset microscopically in the coating film, and the function may not be uniformized due to the offset, but in the present invention, each particle is uniform as the metal oxide component by having the coating structure, and the uniform effect can be expected in any portion of the coating film surface by performing the same function throughout the entire coating film.
In addition, functions that cannot be achieved by the metal oxide particles alone can be achieved by forming a coating structure and combining the functions to achieve the intended functions. Even metal oxide particles that are not compatible with, for example, a polymerizable compound that is a binder component can be made highly compatible by forming a coating structure. Even when the surface of the metal oxide particle has a property of changing by an external force generated by light or heat, the metal oxide particle can function by having a coating structure as long as the change of the metal oxide can be suppressed by another metal oxide.
The coating structure of the particles is obtained by mixing particles to be cores and particles to be coated, and performing a heat treatment. For example, the surface potential of the core particles is set to be opposite to the surface potential of the coated particles, so that the coated particles are coated on the surface of the core particles by electrostatic force, and they are heated to form a bond of M-O-M '(M, M' represents a metal) at the interface. The particles having a coating structure are considered to be substances that form a reaction at an interface because the coating structure does not change even when the solvent is replaced with an organic solvent from an aqueous medium.
Further, by using a polymerizable compound having a triazinetrione skeleton, the light resistance of the polymerizable compound (B) is improved due to the triazinetrione skeleton. The (meth) acrylate compound having a triazinetrione skeleton has a structure having (meth) acrylate groups at a ratio of 1 to 2 to 3 in a molecule, and has 2 (meth) acrylate groups in a molecule, whereby a coating film obtained by applying a coating composition to a film and curing the coating film has high adhesion, follows expansion and contraction of the film, is free from cracks and peeling of the film, and has excellent flexibility.
In addition, the use of an aromatic compound having a urethane bond as the polymerizable compound (B) improves scratch resistance and adhesion.
Detailed Description
The present invention 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 thereof being coated with a layer containing colloidal particles (a 2) of a metal oxide having an average primary particle diameter of 1 to 40 nm; and
a polymerizable compound (B) having an unsaturated bond between a carbon atom and a carbon atom.
The core particles (a 1) and the modified particles (a) may have an average particle diameter (nm) measured by a dynamic light scattering method (DLS method).
The coated particles (a 2) may have an average primary particle diameter (nm) measured by transmission projection imaging with an electron beam (transmission electron microscope).
The colloidal particles (a 1) are particles (a 1) serving as cores, and are also referred to as core particles (a 1). The colloidal particles (a 2) are particles (a 2) to be coated, and are also referred to as coated particles (a 2). The modified metal oxide particles (a) are modified particles (a), and are also referred to as modified particles (a).
Since the core particle (a 1) and the coated particle (a 2) react at the particle interface, the core particle (a 1) + the coated particle (a 2) do not necessarily have the particle diameter of the modified particle (a).
The coating composition of the present invention may contain 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 contains 0.1 to 60% by mass, or 1 to 50% by mass, or 10 to 45% by mass of a solid content. The solid content here is a component obtained by removing the solvent component from the entire components of the coating composition.
The metal oxide particles (a) are particles formed of metal oxides or composite metal oxides.
The metal oxide particles (A) are metal oxide particles (A) having an average particle diameter of 2nm to 100nm or 3nm to 50nm, wherein the metal oxide particles (A) have an average particle diameter of 2nm to 60nm or 3nm to 40nm and are different from each other or different from each other as a composite oxide, and have an oxide or composite oxide (a 1) of at least 1 metal selected from Ti, sn, zr, si, al, sb, ta, pb, bi, hf, ge, ce and W as a core, and the surface thereof is coated with at least 1 layer of an oxide or composite oxide (a 2) having an average primary particle diameter of 1nm to 40nm or 2nm to 20nm and being 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 from each other or different from each other as a composite oxide.
The case where the metal components of the particles (a 1) and the particles (a 2) are different is the case where the particles (a 1) and the particles (a 2) are different as the metal element. In the case where the particles (a 1) and the particles (a 2) are different as the composite oxide, the particles (a 1) and the particles (a 2) are different as the composite oxide even if there is a metal species in which the particles (a 1) and the particles (a 2) are repeated as the metal component.
The thickness of the coating layer depends on the particle size of the coated particles (a 2), but may be 1nm to 40nm depending on the particle size of the coated particles (a 1).
When the metal element is different from the metal element, tiO is used for the particles (a 1), for example 2 SnO is used as the particles (a 2) 2 That is the case.
Even if there are metal species repeating as the metal component, the composite oxide is different, and examples thereof include the use of TiO as the particles (a 1) 2 -ZrO 2 -SnO 2 SnO is used as the particles (a 2) 2 -SiO 2 The case (1).
The same applies to the case where a layer formed of the particles (a 2) is used as the outermost layer of the particles (a 1), and the particles (a 2) are further used as the intermediate layer. The particles (a 2) used in the intermediate layer may have the same composition as the particles (a 2) exemplified above, and the core particles (a 1) and the outermost particles (a 2) may have different metal components from each other or may be different as a composite oxide.
Examples of the average particle diameter and the average primary particle diameter of the metal oxide or the composite metal oxide include a value of an average primary particle diameter (nm) measured by a dynamic light scattering method (DLS method) and a value of an average primary particle diameter (nm) observed by a transmission projection image (transmission electron microscope) using an electron beam. Examples of the metal oxide and the composite oxide 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 And the like.
The metal oxide particles (a) may have a structure in which a coating layer of (a 2) is formed on the particles of (a 1).
SnO can be used as the composite metal oxide particles having a coating structure 2 -ZrO 2 、TiO 2 -ZrO 2 -SnO 2 As the core particles, siO was used 2 、SnO 2 -SiO 2 、WO 3 -SnO 2 -SiO 2 Etc. as the coated particles. Examples thereof include:
from SnO as core particles (a 1) 2 -ZrO 2 WO as the coated particle (a 2) 3 -SnO 2 -SiO 2 Modified metal oxide particles,
From TiO as core particles (a 1) 2 TiO as the coated particle (a 2) 2 -SnO 2 Modified metal oxide particles of the composition;
further, there may be mentioned: from TiO as core particles (a 1) 2 -ZrO 2 -SnO 2 SnO as coated particles (a 2) 2 -SiO 2 Modified metal oxide particles of the composition.
In the case of particles composed of core particles and a coating layer, the mass ratio of the core particles (a 1) to the coating layer particles (a 2) may be in the range of 1:0.01 to 1, or 1:0.1 to 0.5.
In the case of particles composed of the core particles, the intermediate layer, and the coating layer, the mass ratio of the core particles (a 1) to the particles (a 2) of the intermediate layer to the particles (a 2) of the coating layer may be in the range of 1:0.01 to 1:0.01 to 1, or 1:0.1 to 0.5:0.1 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 replacing a solvent with an organic solvent, which is a substance produced as an aqueous sol. As the organic solvent, a solvent such as methanol, ethanol, 1-propanol, 2-propanol, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, or 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, based on 100 parts by mass of the polymerizable compound (B).
The layer containing the metal oxide particles (a 2) coated on the outermost layer preferably contains Si as a metal component. In this case, si is contained as the metal component, that is, siO is contained 2 Component (c) is preferable because when the outermost layer is coated with a silane coupling agent, reactivity with the silane coupling agent is improved.
The hydrolyzable silane used for coating the surface of the metal oxide particle (a) may include a hydrolyzable silane of the formula (3) and/or a hydrolyzable silane of the formula (4). The hydrolyzable silane of the formula (3) or the hydrolyzable silane of the formula (4) may be further used in combination with other hydrolyzable silanes, a hydrolyzable silane of the formula (3) and/or a hydrolyzable silane of the formula (4): the weight ratio of the other hydrolyzable silanes may be in the range of 1:0.1 to 1.0, or 1:0.5 to 1.0.
The amount of the surface coating of the metal oxide particles (A) may be 0.1 atom/nm as the number of Si atoms of the silane compound coating the surface of the metal oxide particles 2 10.0 pieces/nm 2 0.1 pieces/nm 2 5.0 pieces/nm 2 Or 0.1 molecules/nm 2 3.0 pieces/nm 2 The range of (1) is used. The surface coating amount is the mass of the hydrolyzable silane added to the metal oxide particles (a), and can be calculated from the specific surface area of the metal oxide particles (a) and the addition amount of the 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 the formula (3), R 11 Comprising an acryloyloxy group, a methacryloyloxy group, an aryl group, an alkyl group, a glycidoxy group, a polyethylene glycol group, or an alkylene group having 1 to 10 carbon atoms containing these functional groups, and R 11 Bound to the Si atom by 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 1R 12 The hydrolyzable group of (2) forms an M-O-Si bond on the surface of the metal oxide particle, M represents at least 1 metal 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 and W. a represents an integer of 1 to 3.
In the formula (4), R 13 Being alkyl and bound to the silicon atom by a Si-C bond, R 14 Represents an alkoxy group, an acyloxy group or a halogen atom, Y represents an alkylene group, an arylene group, an NH group or an oxygen atom, d represents an integer of 0 to 3, and e is an integer of 0 or 1.
The alkyl group is an alkyl group having 1 to 10 carbon atoms, examples thereof include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 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, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 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-2-methyl-cyclopropyl, 3234-ethyl-2-methyl-cyclopropyl, 322-ethyl-2-methyl-cyclopropyl and 323-methyl-cyclopropyl.
Examples of the alkylene group include alkylene groups derived from the above-mentioned alkyl groups.
Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group, and examples of the arylene group include a group derived from the above aryl group, a phenylene group, a naphthylene group, and an anthracenylene group.
Examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms, for example, 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-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexoxy, 1-methyl-n-pentoxy, 2-methyl-n-pentoxy, 3-methyl-n-pentoxy, 4-methyl-n-pentoxy, 1,1-dimethyl-n-butoxy, 3265 zxft 65-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 3525-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, n-butyl383256 zxft 3256-dimethyl-n-butoxy, 3579-ethyl-n-propoxy, n-ethyl-methyl-n-propoxy, and n-propoxy, in addition, as the cyclic alkoxy group, a cyclic alkoxy group, examples thereof include cyclopropyloxy, cyclobutyloxy, 1-methyl-cyclopropyloxy, 2-methyl-cyclopropyloxy, cyclopentyloxy, 1-methyl-cyclobutyloxy, 2-methyl-cyclobutyloxy, 3-methyl-cyclobutyloxy, 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-cyclopropoxy, 1,2,2-trimethyl-cyclopropoxy, 5283-trimethyl-zft 5283, 2-trimethyl-cyclopropoxy, 5329-ethyl-methyl-cyclopropoxy, 2-ethyl-methyl-cyclopropoxy, and the like.
Examples of the acyloxy group include an acyloxy group having 2 to 10 carbon atoms, for example, methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, n-pentylcarbonyloxy, 1-methyl-n-butylcarbonyloxy, 2-methyl-n-butylcarbonyloxy, 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-pentylcarbonyloxy, 3-methyl-n-pentylcarbonyloxy, n-propylcarbonyloxy 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, 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-n-propylcarbonyloxy, phenylcarbonyloxy, and tosylcarbonyloxy, and the like.
Examples of the halogen atom include fluorine, chlorine, bromine, iodine, and the like.
Examples of the hydrolyzable silane include the following compounds.
Figure BDA0002992056900000121
In the above formula R 12 As described in the last 2 paragraph on page 9, a hydrolyzable group composed of an alkoxy group, an acyloxy group or a halogen atom is shown. They are available as silane coupling agents manufactured by shin-Etsu chemical industries, ltd.
The compound of formula (4) contains a trimethylsilylating agent, and examples thereof include hexamethyldisilane, hexamethyldisiloxane, and hexamethyldisilazane. These silylating agents can be obtained from Tokyo chemical industry Co.
The surface treatment of the metal oxide particles (a) with a silane compound may be carried out by adding a hydrolyzable silane of the formula (3) and/or the formula (4) to a methanol sol of the metal oxide particles (a) to hydrolyze and coat the surface.
In the hydrolysis of the alkoxysilyl group, acyloxysilyl group, or halosilyl group, water is used in an amount of 0.5 to 100 mol, preferably 1 to 10 mol, per 1 mol of the hydrolyzable group.
The hydrolysis catalyst may be used in an amount of 0.001 to 10 mol, preferably 0.001 to 1 mol, per 1 mol of the hydrolyzable group.
The reaction temperature for the hydrolysis and condensation is usually 20 to 80 ℃.
The hydrolysis may be carried out completely or partially. That is, the hydrolysis product and the monomer may remain in the hydrolysis-condensation product.
A catalyst may be used for the hydrolysis and condensation.
As the hydrolysis catalyst, a chelate compound, an organic acid, an inorganic acid, an organic base, or an inorganic base may be used in combination.
In the present invention, as the polymerizable compound (B), a polymerizable compound having a triazinetrione skeleton and an unsaturated bond of a carbon atom and a carbon atom, or a polymerizable compound having an aromatic urethane bond and an unsaturated bond of a carbon atom and a carbon atom can be used.
As the polymerizable compound (B), a polymerizable compound (B1-1) represented by the formula (B1-1) can be used. 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.
Examples of the polymerizable compound represented by the formula (b 1-1) are shown below.
Figure BDA0002992056900000131
Figure BDA0002992056900000141
The 2-functional acrylate having a triazinetrione skeleton is preferable, and the compound represented by the formula (b 1-1-1) is particularly preferable, and can be obtained, for example, as a product name of アロニックス M-215 manufactured by Tokya synthetic company.
Further, as the polymerizable compound (B), a polymerizable compound (B1-2) represented by the formula (B1-2) can be used. 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.
The polymerizable compound (b 1-2) represented by the formula (b 1-2) can be exemplified by the following.
Figure BDA0002992056900000151
The aromatic compound having a urethane bond (b 1-2) has a toluene 2,4-urethane acrylate structure, and a toluene 2,6-urethane acrylate structure, generally in a molar ratio of 80: the proportion of 20 comprises, and may be used as a mixture thereof.
The mixture of the compounds represented by (b 1-2-1) and (b 1-2-3) can be obtained, for example, as EBECRYL220 manufactured by ダイセルオルネクス.
As the polymerizable compound (B), in addition to the polymerizable compound (B1), an acrylate compound having 2 or more functions may be further used as the polymerizable compound (B2) represented by the formula (B2). Examples of the polymerizable compound (b 2) represented by the formula (b 2) include 2-functional acrylates, 3-functional acrylates, 4-functional acrylates, and 5-or more-functional acrylates.
As these polyfunctional acrylates, the polymerizable compound (b 2) represented by the formula (b 2) can be used. 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.
Examples of the aliphatic hydrocarbon group include hydrocarbon groups derived from an alkyl group having 1 to 10 carbon atoms described in the 1 st paragraph on page 10. The aromatic hydrocarbon group is an aromatic hydrocarbon group having 6 to 40 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group and the like.
Examples of the polymerizable compound (B) are shown below.
For example, the 2-functional acrylate may be a compound represented by the following formula (b 2-1) or (b 2-2), the 3-functional acrylate may be a compound represented by the following formula (b 2-3), the 4-functional acrylate may be a compound represented by the following formula (b 2-4), and the 5-or higher-functional acrylate may be a compound represented by the following formula (b 2-5). The compound represented by the formula (b 2-1) can be obtained, for example, as trade name KAYARAD NPGDA, the compound represented by the formula (b 2-2) can be obtained, for example, as trade name KAYARAD R-551, the compound represented by the formula (b 2-3) can be obtained, for example, as trade name KAYARAD TMPTA, the compound represented by the formula (b 2-4) can be obtained, for example, as trade name KAYA T-1420 (RADT), the compound represented by the formula (b 2-5) can be obtained, for example, as trade name KAYARAD DPHA, the product of Nippon Kagaku corporation.
In addition, it is permissible to include the polymerizable compound (b 2) as a by-product in the synthesis of the polymerizable compound (b 1). For example, the polymerizable compound (b 1-2) may contain a polymerizable compound (b 2). Examples of the polymerizable compound include pentaerythritol tri (meth) acrylate (b 2-6) and pentaerythritol tetra (meth) acrylate (b 2-7).
Figure BDA0002992056900000171
Figure BDA0002992056900000181
Among these polyfunctional acrylates, the polymerizable compound (b 2) is preferably a compound represented by the formula (b 2-5) which is an acrylate having 5 or more functions.
The polymerizable compound (B) may be the polymerizable compound (B1) alone or the polymerizable compound (B2) alone. However, when the polymerizable compound (b 1) and the polymerizable compound (b 2) are used in combination, the mass ratio of the polymerizable compound (b 1) to the polymerizable compound (b 2) 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 in the ratio of 1.
The photopolymerization initiator (C1) or the thermal polymerization initiator (C2) may be contained as the polymerization initiator (C) in the present invention.
As the polymerization initiator (C), a photo radical polymerization initiator (C1-1), a thermal radical polymerization initiator (C2-1), a photo cation polymerization initiator (C1-2), or a thermal cation polymerization initiator (C2-2) can be used.
Examples of the photo radical polymerization initiator (c 1-1) include imidazole compounds, diazo (diazo) compounds, biimidazole compounds, N-arylglycine compounds, organoazido compounds, titanocene compounds, aluminate compounds, organic peroxides, and N-alkoxypyridines
Figure BDA0002992056900000182
Salt compounds, and thioxanthone compounds, and the like. Examples of the azido compound include p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzylideneacetophenone, 4,4' -diazidochalcone, 4,4' -diazidodiphenyl sulfide, and 2,6-bis (4 ' -azidobenzylidene) -4-methylcyclohexanone. Examples of the diazo compound include 1-diazo-2,5-diethoxy-4-p-tolylmercaptophenylboron fluoride, 1-diazo-4-N, N-dimethylaminobenzene chloride, and 1-diazo-4-N, N-diethylaminophenylboron fluoride. Examples of the 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. Examples of the titanocene compound include dicyclopentadienyl-titanium-dichloride, dicyclopentadienyl-titanium-bisphenyl, 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-phenyl).
Examples of the photo radical polymerization initiator include 1,3-di (t-butyldioxycarbonyl) benzophenone, 3,3',4,4' -tetra (t-butyldioxycarbonyl) benzophenone, and 3-phenyl-5-isobenzophenone
Figure BDA0002992056900000192
Oxazolone, 2-mercaptobenzimidazole, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, and the like.
These photoradical polymerization agents are available, for example, as Irgacure TPO (c 1-1-1) which is a trade name of BASF.
Figure BDA0002992056900000191
Examples of the photo-cationic polymerization initiator (c 1-2) include sulfonic acid esters, sulfonimide compounds, disulfonyl diazomethane compounds, dialkyl-4-hydroxysulfonium salts, arylsulfonic acid-p-nitrobenzyl esters, silanol-aluminum complexes, (η) 6 -benzene) (η) 5 Cyclopentadienyl) iron (II), and the like.
Examples of the sulfonimide compound include N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoro-N-butanesulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, and N- (trifluoromethanesulfonyloxy) naphthalimide.
Examples of the disulfonyl diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylbenzenesulfonyl) diazomethane, and methylsulfonyl-p-toluenesulfonyl diazomethane.
Examples of the photo cation polymerization initiator include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one.
In addition, aromatic iodine
Figure BDA0002992056900000201
Salt compound, aromatic sulfonium salt compound, aromatic diazo
Figure BDA0002992056900000202
Salt compound and aromatic compound
Figure BDA0002992056900000203
The salt compound, triazine compound, iron arene complex compound, and the like may be used as a photo radical polymerization initiator or a photo cation polymerization initiator.
As aromatic iodine
Figure BDA0002992056900000204
Examples of the salt compound include diphenyliodine
Figure BDA0002992056900000205
Chloride, diphenyl iodide
Figure BDA0002992056900000206
Trifluoromethanesulfonate, diphenyliodide
Figure BDA0002992056900000207
Methanesulfonic acid salt, diphenyl iodide
Figure BDA0002992056900000208
Tosylate and diphenyl iodide
Figure BDA0002992056900000209
Bromide, diphenyl iodide
Figure BDA00029920569000002010
Tetrafluoroborate and diphenyl iodide
Figure BDA00029920569000002011
Hexafluoroantimonate and diphenyl iodide
Figure BDA00029920569000002012
Hexafluoroarsenate, bis (p-tert-butylphenyl)Iodine
Figure BDA00029920569000002013
Hexafluorophosphate, bis (p-tert-butylphenyl) iodide
Figure BDA00029920569000002014
Methanesulfonate, bis (p-tert-butylphenyl) iodide
Figure BDA00029920569000002015
Tosylate, bis (p-tert-butylphenyl) iodide
Figure BDA00029920569000002016
Trifluoromethanesulfonate bis (p-tert-butylphenyl) iodide
Figure BDA00029920569000002017
Tetrafluoroborate, bis (p-tert-butylphenyl) iodide
Figure BDA00029920569000002018
Chloride, bis (p-chlorophenyl) iodide
Figure BDA00029920569000002019
Chloride, bis (p-chlorophenyl) iodide
Figure BDA00029920569000002020
Tetrafluoroborate and bis (4-tert-butylphenyl) iodide
Figure BDA00029920569000002021
Bis (alkylphenyl) iodides such as hexafluorophosphate
Figure BDA00029920569000002022
Salts, alkoxycarbonylalkoxy-trialkylyaryl iodides
Figure BDA00029920569000002023
Salts (e.g. 4- [ (1-ethoxycarbonyl-ethoxy) phenyl)]- (2,4,6-trimethylphenyl) -iodine
Figure BDA00029920569000002024
Hexafluorophosphate, etc.), bis (alkoxyaryl) iodide
Figure BDA00029920569000002025
Salts (e.g., (4-methoxyphenyl) phenyliodide)
Figure BDA00029920569000002026
Bis (alkoxyphenyl) iodides such as hexafluoroantimonate
Figure BDA00029920569000002027
Salt).
Examples of the aromatic sulfonium salt compound include triphenylsulfonium salts such as triphenylsulfonium chloride, triphenylsulfonium bromide, tris (p-methoxyphenyl) sulfonium tetrafluoroborate, tris (p-methoxyphenyl) sulfonium hexafluorophosphate, tris (p-ethoxyphenyl) sulfonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate and triphenylsulfonium hexafluorophosphate, and sulfonium salts such as (4-phenylthiophenyl) diphenylsulfonium hexafluoroantimonate, (4-phenylthiophenyl) diphenylsulfonium hexafluorophosphate, (4- (diphenylsulfonium) phenyl ] sulfide-bis-hexafluoroantimonate), bis [4- (diphenylsulfonium) phenyl ] sulfide-bis-hexafluorophosphate and (4-methoxyphenyl) diphenylsulfonium hexafluoroantimonate).
As aromatic diazo
Figure BDA0002992056900000211
The salt compound includes, for example, benzenediazonium
Figure BDA0002992056900000212
Hexafluoroantimonate and benzenediazonium
Figure BDA0002992056900000213
Hexafluorophosphate and benzenediazonium salt
Figure BDA0002992056900000214
Diazonium salts such as hexafluoroborate
Figure BDA0002992056900000215
And (3) salt.
As aromatics
Figure BDA0002992056900000216
Salts, for example triphenyl
Figure BDA0002992056900000217
Chloride, triphenyl
Figure BDA0002992056900000218
Bromide, tris (p-methoxyphenyl)
Figure BDA0002992056900000219
Tetrafluoroborate, tris (p-methoxyphenyl)
Figure BDA00029920569000002110
Hexafluorophosphonate, tris (p-ethoxyphenyl)
Figure BDA00029920569000002111
Tetrafluoroborate, 4-chlorophenyldiazo
Figure BDA00029920569000002112
Hexafluorophosphate, benzyltriphenyl
Figure BDA00029920569000002113
Hexafluoroantimonate and the like
Figure BDA00029920569000002114
And (3) salt.
Examples of the triazine compound include triazine compounds such as 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, and 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3,5-triazine.
Examples of the iron arene complex include iron arene complexes such as xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, xylene-cyclopentadienyl iron (II) tris (trifluoromethylsulfonyl) methide, and the like.
Further, selenium salts such as triphenylselenium hexafluorophosphate and (. Eta.), (η) 5 Or η 6 -isopropylbenzene) (η) 5 Metallocene complexes such as cyclopentadienyl iron (II) hexafluorophosphate may be used as photo radical polymerization initiators or as photo cation polymerization initiators.
Examples of the photo cation polymerization initiator (c 1-2) further include compounds represented by the following formulae (c 1-2-1) to (c 1-2-67).
Figure BDA0002992056900000221
Figure BDA0002992056900000231
Figure BDA0002992056900000241
Figure BDA0002992056900000251
Figure BDA0002992056900000261
Figure BDA0002992056900000271
Figure BDA0002992056900000281
Examples of the thermal radical polymerization initiator (c 2-1) 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-methylpropionic acid) dimethyl ester, 2,2' -azobis (2-methylpropionamidine) dihydrochloride, 2,2' -azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride, t-butyl hydroperoxide, isopropylbenzene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, and benzoyl peroxide. They are available from Tokyo chemical industry.
Examples of the thermal cationic polymerization initiator (c 2-2) include dicyandiamide, cyclohexyl p-toluenesulfonate, methyldiphenylsulfonium tetrafluoroborate, benzyl (4-hydroxyphenyl) methylthioninium hexafluoroantimonate, and (4-hydroxyphenyl) methyl (2-methylbenzyl) sulfonium hexafluoroantimonate. They are available from Tokyo chemical industry.
The photopolymerization initiator (C) may be used in a range of 0.01 to 50 parts by mass, or 0.1 to 15 parts by mass, based on 100 parts by mass of the polymerizable compound (B).
In the coating composition of the present invention, a radical scavenger (quencher) can be used for radical polymerization. Further, it can be used for preventing polymerization of the monomer by light/heat/air or the like during storage. In addition, the coating composition can be contained to suppress sensitivity variation and improve pattern accuracy. For example, 4-tert-butyl pyrocatechol, tert-butyl hydroquinone, 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, and the like can be used. These were prepared by Tokyo chemical industry Co., ltd.
In the coating composition of the present invention, 1 or 2 or more nitrogen-containing organic compounds may be blended as the basic compound (quencher) for cationic polymerization.
As the nitrogen-containing organic compound, a compound which can suppress the diffusion rate of an acid generated from an acid generator when the acid diffuses in the film is suitable. By blending the nitrogen-containing organic compound, the diffusion rate of an acid in the film is suppressed to improve the resolution, the sensitivity change after exposure is suppressed, the substrate and environment dependency is reduced, and the exposure margin and patterning properties can be improved. 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 having carboxyl groups, nitrogen-containing compounds having sulfonyl groups, nitrogen-containing compounds having hydroxyl groups, nitrogen-containing compounds having hydroxyphenyl groups, alcoholic nitrogen-containing compounds, amides, imides, carbamates, ammonia, ammonium salts, sulfonium salts, and the like.
Examples of the primary aliphatic amine include methylamine, ethylamine and n-propylamine. Examples of the secondary aliphatic amine include dimethylamine, diethylamine, and di-n-propylamine. Examples of the tertiary aliphatic amine include trimethylamine, triethylamine, and tri-n-propylamine. Examples of the aromatic amines and heterocyclic amines include aniline derivatives (more specifically, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N-dimethyltoluidine, etc.), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, and pyrrole derivatives (more specifically, pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.),
Figure BDA0002992056900000301
The azole derivative (more specifically,
Figure BDA0002992056900000302
oxazole, iso
Figure BDA0002992056900000303
Oxazole and the like), thiazole derivatives (more specifically, thiazole, isothiazole and the like), imidazole derivatives (more specifically, imidazole, 4-methylimidazole4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazan 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, butylpyridine, 4- (1-butylpentyl) pyridine, lutidine, collidine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-t-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 4-pyrrolidinylpyridine, 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 (e.g., 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, 8978 zx8978-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives, and the like.
The amount of the quencher may be in the range of 0.001 to 1 part by mass, or 0.01 to 0.5 part by mass, based on 100 parts by mass of the polymerizable compound (B).
A surfactant (leveling agent) may be used in the present invention. The surfactant includes, for example, <xnotran> , , , , , , / , , , , , , , , , , , , 5725 zxft 5725 EF301, EF303, EF352 (() 3432 zxft 3432 ), 3862 zxft 3862F 171, F173, R-08, R-30, R-30 4232 zxft 4232-40 LM (DIC () ), 4234 zxft 4234 FC430, FC431 ( 5364 zxft 5364 () ), 8652 zxft 8652 AG710, 3265 zxft 3265S-382, SC101, SC102, SC103, SC104, SC105, SC106 ( () ) , -KP341 ( () ), ( 3579 zxft 3579 · 3525 zxft 3525 () L-7001) . </xnotran> These surfactants may be added in a proportion of 0.002 to 10 parts by mass, or 0.02 to 5 parts by mass, based on 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 solid component. <xnotran> , , , , , , , , , , , , , , , , , , , , , , ,2- ,2- -2- , , ,2- -3- ,3- ,3- ,3- ,3- , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , </xnotran> Hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, 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, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, toluene, xylene, methylethylketone, methylpropylketone, methylbutylketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N-dimethylformamide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidone, 4-methyl-2-butyrolactone, γ -pentanol, and the like. These solvents may be used alone or in combination of two or more.
The coating composition can be produced by adding a solvent, a colloidal solution of the metal oxide particles (a), the polymerizable compound (B), and, if necessary, the polymerization initiator (C), a quencher, and a surfactant to a container equipped with a stirrer and stirring the mixture. The polymerization initiator, the photoacid generator, and the nitrogen organic compound as the quencher may be added by dissolving them in a part of the solvent in advance.
The use of the coating composition of the present invention is explained below.
The coating composition of the present invention is applied to a substrate (for example, a film, a silicon wafer substrate, a silicon/silica-coated substrate, a silicon nitride substrate, a glass substrate, an ITO substrate, a polyimide substrate, a low dielectric constant material (low-k material) -coated substrate, or the like) by an appropriate application method such as a spin coater, a coater, or the like, and then heated to form a coating film (coating film composed of a thermoset product of the coating composition) obtained by thermosetting. The heating conditions are appropriately selected from the heating temperature of 20 to 250 ℃ or the heating time of 20 to 110 ℃ for 0.3 to 60 minutes. The film thickness of the formed coating film is, for example, 0.01 to 10 μm, or 0.02 to 8 μm, or 0.05 to 6 μm, or 0.1 to 5 μm.
In the case of photocuring the coated coating film, the coating film is dried at 20 to 100 ℃ for 0.3 to 60 minutes under heating for removing the solvent, and then subjected to an exposure of 1mJ/cm by using ultraviolet rays having a wavelength of 500 to 190nm 2 ～20000mJ/cm 2 Or 10mJ/cm 2 ～15000mJ/cm 2 Or 50mJ/cm 2 ～11000mJ/cm 2 Thereby forming a coating film obtained by photocuring. The film thickness of the formed coating film is, for example, 0.01 to 10 μm, or 0.02 to 8 μm, or 0.05 to 6 μm, or 0.1 to 5 μm.
In the present invention, both heat curing and light curing can be used. The thermosetting may be carried out first and then the photocuring may be carried out, or the photocuring may be carried out and then the thermosetting may be carried out.
Examples
The optical members having cured films obtained in examples and comparative examples were evaluated by measuring the respective physical properties by the following measurement methods.
(1) Refractive index
The reflectance of the cured film formed on the glass substrate was measured using a reflectance measuring instrument (USPM-RU manufactured by オリンパス, inc.). From the measured reflectance, the refractive index of the cured film was calculated using optical simulation.
(2) Hardness test
The hardness of a cured film formed on a glass substrate was measured using a dynamic ultramicro hardness tester (DUH-211, manufactured by Shimadzu corporation) at HMs [ N/mm ] 2 ]. The judgment criterion is 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 of
The haze value of the cured film formed on the glass substrate was measured using a haze meter (NDH 7000 manufactured by japan electrochrome industry, ltd.). 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 resistance test
The transmittance of the obtained optical member (optical member having a cured film formed on a glass substrate) was measured using a spectrophotometer (UV-3600, manufactured by shimadzu corporation), and the YI value was calculated based on JIS 7373. Then, QUV accelerated weathering tester (UVA lamp irradiation intensity 890 mW/m) was used 2 ) Then, the YI value of the optical member exposed for 120 hours was calculated. The Δ YI of the optical member before and after the ultraviolet irradiation was calculated. The judgment criteria are as follows.
A: Δ YI is less than 1.0.
B: Δ YI is 1.0 or more and less than 2.0.
C: Δ YI is 2.0 or more.
(5) Bending test
When the obtained optical member (an optical member having a cured film formed on a PET film (コスモシャイン a4300, 100 μm thick)) was bent using a cylindrical mandrel bar bending tester (1603/MS, manufactured by BEVS) with a test bar having a curvature radius R =1mm placed therein, the optical member was sandwiched and fixed with a main body jig so that the cured film was positioned outside. The roller was brought close to the test plate and the handle was rotated 180 ° equally over a period of 1-2 seconds. Then, whether or not cracks were generated was confirmed by using a digital microscope (VHX-6000, キーエンス Co.). The criteria for determination are as follows.
1: no cracks were generated in the cured film.
2: 1 to 9 cracks were generated in the cured film.
3: 10 to 29 cracks were generated in the cured film.
4: more than 30 cracks were generated in the cured film.
(6) Scratch resistance test
The device comprises the following steps: the reciprocating abrasion tester TRIBOGEAR TYPE manufactured by Xindong science (strain): 30S
Scanning speed: 1.2sec/cycle
Scanning distance: 30mm
Steel wool [ ボンスター casing ボンスター (registered trademark) #0000 (ultra fine) manufactured by strain # 5363 and installed in reciprocating abrasion tester is used for surface of cured film]Application of 250g/cm 2 The load of (2) was rubbed by 20 back and forth, and the degree of damage was visually confirmed, and evaluated according to the following criteria.
1: the number of wounds was 5 or less.
2: the number of the wounds is more than 6 and less than 20.
3: the number of the wounds is more than 21.
(7) Adhesion test
After the cured film was subjected to 100-grid cutting at 1mm intervals and an adhesive tape (cellophane tape, ニチバン, ltd.) was strongly adhered to the cut portions, the adhesive tape was rapidly peeled off, and the presence or absence of peeling of the cured film after peeling of the adhesive tape was examined. The evaluation criteria are as follows.
A: no peeling at all, or peeling of less than 5 out of 100 cells could be confirmed.
B: peeling was observed in 5 to 30 out of 100 cases.
C: peeling was observed in 31 to 100 cells out of 100 cells.
(reference example 1): preparation of titanium oxide-tin dioxide composite oxide colloidal particles (a 1-1) as cores.
319.5g of a 25 mass% tetramethylammonium hydroxide aqueous solution was dissolved in 5363 g of pure water 947.1g, followed by 14.8g of metastannic acid (as SnO) 2 Calculated as 12.5 g), and 236.6g (calculated as TiO) of titanium tetraisopropoxide 2 66.6g in terms of oxalic acid), and 82.0g of oxalic acid dihydrate (58.5 g in terms of oxalic acid) were added under stirring. The mixed solution was kept at 80 ℃ for 2 hours, and further kept at 580 torr under reduced pressure for 2 hours to prepare a mixed solution. The mixed solution was put into a glass-lined autoclave, subjected to hydrothermal treatment at 140 ℃ for 5 hours, cooled to room temperature, and taken out. The obtained sol was an acidic aqueous dispersion sol of titanium oxide-tin dioxide composite oxide colloidal particles (A1), pH3.9, total metal oxide concentration (TiO) 2 And SnO 2 ) 5.0 mass%, and the average particle diameter by dynamic light scattering (particle diameter by dynamic light scattering) was 16nm. The obtained sol was dried at 110 ℃ to obtain a powder, and the obtained powder was analyzed by X-ray diffraction to confirm that the crystal was a rutile crystal.
(reference example 2): preparation of silica-tin dioxide composite oxide colloidal particles (a 2-1) as a coating material.
JIS No. 3 sodium silicate (as SiO) 2 Calculated as 29.8 mass%) of 77.2g was dissolved in 668.8g of pure water, followed by dissolution of sodium stannate monohydrate NaSnO 3 ·H 2 O (in SnO) 2 Converted to 55.1 mass%) of 20.9g. The resulting aqueous solution was passed through a column packed with a hydrogen type cation exchange resin (アンバーライト (registered trademark) IR-120B, オルガノ (manufactured by LTD.). Then, 7.2g of diisopropylamine was added to the obtained aqueous dispersion sol. The obtained sol was an aqueous dispersion sol of basic silica-tin dioxide composite oxide colloidal particles (B1), pH8.0, total metal oxide concentration (SnO) 2 And SnO 2 ) 1.7% by mass. The primary particle diameter is 1 to 4nm as observed by a transmission electron microscope.
(reference example 3): preparation of titanium oxide-tin dioxide-zirconium oxide composite oxide colloidal particles (A-1) modified with a silica-tin dioxide composite oxide.
Zirconium oxychloride (as ZrO) 2 Converted to 21.2 mass%) of 82.7g was diluted with 501.1g of pure water to prepare 5363 g of an aqueous solution of zirconium oxychloride (as ZrO) 583.8g 2 In terms of 3.0 mass%), the aqueous dispersion sol 1516.2g of the titanium oxide-tin dioxide composite oxide colloidal particles (A1) prepared in reference example 1 was added under stirring. Subsequently, the mixture was heated to 95 ℃ to hydrolyze the mixture, thereby obtaining an aqueous dispersion sol of colloidal particles of titanium oxide-tin dioxide-zirconium oxide composite oxide having a zirconium oxide thin film layer formed on the surface thereof. The obtained aqueous dispersion sol 2041.2g was added to aqueous dispersion sol 1763.3g of the basic silica-tin dioxide composite oxide colloidal particles (B1) prepared in reference example 2 under stirring, and the mixture was passed through a column filled with 500 ml of an anion exchange resin (アンバーライト (registered trademark) IRA-410, オルガノ (manufactured by ltd.). Subsequently, the water-dispersed sol after passing through was heated at 95 ℃ for 3 hours, and then concentrated by an ultrafiltration membrane method. Subsequently, the dispersion medium of the obtained water-dispersed sol was replaced with methanol using a rotary evaporator to obtain a methanol-dispersed sol of titanium oxide-tin dioxide-zirconium oxide composite oxide colloidal particles (C1) modified with a silica-tin dioxide composite oxide. The methanol dispersion sol had a pH of 5.2 and was composed of all metal oxides (TiO) 2 、ZrO 2 、SnO 2 And SiO 2 ) A concentration of 30.5% by mass, a viscosity of 1.8 mPas, and an average particle diameter (dynamic light scattering particle diameter) obtained by Dynamic Light Scattering (DLS) of 20nm.
The modified metal oxide particles (A-1) have the following structure: an intermediate layer (a-2) of zirconia is formed on the surface of a core particle (a 1-1) composed of titanium oxide-tin dioxide composite oxide colloidal particles, and silica-tin dioxide composite oxide colloidal particles (a 2-1) are formed on the surface.
Reference example 4 preparation of colloidal particles (A-2) in which titanium oxide-tin dioxide-zirconium oxide composite oxide colloidal particles modified with silica-tin dioxide composite oxide were surface-treated with acryloxypropyltrimethoxysilane
98.4g of the methanol dispersed sol of the modified metal oxide particles (A-1) obtained in reference example 3 was taken in a vessel, and 6.8g of acryloxypropyltrimethoxysilane (KBM-5103, manufactured by shin-Etsu chemical Co., ltd.) was added under stirring and reacted under reflux for 5 hours to obtain 105.2g of the methanol dispersed sol of the modified metal oxide particles (A-2) having acryloxypropyltrimethoxysilane bonded to the surface. The modified metal oxide particles (A-2) have the following structure: the intermediate layer (a-2) of zirconia is formed on the surface of the core particle (a 1-1) composed of titanium oxide-tin dioxide composite oxide colloidal particles, the silica-tin dioxide composite oxide colloidal particles (a 2-1) are formed on the surface, and the surface of the particles is further treated with acryloxypropyltrimethoxysilane. The unit surface area of the silicon atom of the silane coupling agent and the modified metal oxide particles (A-2) corresponds to 3.0 particles/nm 2 。
The obtained sol had a specific gravity of 1.070, a viscosity of 1.9 mPas, a total metal oxide concentration of 30.5% by mass, and a water content of 0.8% by mass, and the average particle diameter (dynamic light scattering particle diameter) obtained by Dynamic Light Scattering (DLS) was 18nm.
(example 1)
(preparation of coating composition)
Into a glass vessel equipped with a magnetic stirrer, 13.2 parts by mass of isocyanuric acid EO-modified diacrylate (trade name アロニックス M-215, manufactured by Toyo Synthesis Co., ltd.), 4.4 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name KAYARAD DPHA, manufactured by Nippon Kagaku K.K.), 5.2 parts by mass of methanol, and 18.3 parts by mass of propylene glycol monomethyl ether were charged, and 57.2 parts by mass of the modified metal oxide (A-1) colloidal fluid (solid content 30.5 mass%) produced in reference example 3 was added with stirring. Then, 0.9 parts by mass of a photoradical polymerization initiator (Irgacure TPO, trade name, manufactured by BASF corporation) and 0.9 parts by mass of a propylene glycol monomethyl ether solution (2.0% by mass, trade name, L-7001, manufactured by DOW レ. ダウコーニング, trade name, manufactured by DOW 4736 zxft 8978) of a polyether-modified silicone oil were added and stirred for 0.5 hour to prepare a coating liquid (coating composition).
(formation and evaluation of cured film)
A glass substrate and a PET film were prepared, a coating liquid (coating composition) was applied to these by a spin coating method, the solvent was evaporated at 80 ℃ for 5 minutes, and then the irradiation intensity was 29mW/cm 2 The high pressure mercury lamp (9) was subjected to ultraviolet ray treatment for 6 minutes (29 mW/cm) 2 ×6×60＝10440mJ/cm 2 ) The coating film was cured to form an optical member having a cured film with a thickness of 3 μm.
The tests shown in (1) to (5) above were carried out. The evaluation results are shown in table 2.
(example 2)
Preparation of a coating composition and formation/evaluation of a cured film were carried out in the same manner as in example 1 except that the amount of the isocyanurate EO-modified diacrylate (trade name アロニックス M-215, manufactured by east asia corporation) was changed to 10.5 parts by mass, the amount of the dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate mixture (trade name KAYARAD DPHA, manufactured by japan chemical corporation) was changed to 7.0 parts by mass, and the ultraviolet treatment time during formation of a cured film was changed to 3 minutes.
(example 3)
In example 1, the amount of isocyanurate EO-modified diacrylate (trade name アロニックス M-215, manufactured by Toyo Synthesis Co., ltd.) added was changed to 15.8 parts by mass, the amount of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name KAYARAD DPHA, manufactured by Nippon chemical Co., ltd.) added was changed to 1.8 parts by mass, and the ultraviolet ray treatment time during formation of a cured film was changed to 3 minutes (29 mW/cm) 2 ×3×60＝5220mJ/cm 2 ) Except for this, the preparation of the coating composition and the formation and evaluation of the cured film were carried out in the same manner as in example 1.
(example 4)
12.0 parts by mass of isocyanuric acid EO-modified diacrylate (trade name アロニックス M-215, manufactured by Toyo Synthesis Co., ltd.) and 4.0 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name KAYARAD DPHA, manufactured by Nippon Chemicals Co., ltd.), 1.5 parts by mass of methanol and 18.4 parts by mass of propylene glycol monomethyl ether were charged into a glass vessel equipped with a magnetic stirrer, and 62.5 parts by mass of the modified metal oxide (A-1) colloidal fluid (solid content 30.5 mass%) produced in reference example 3 was added thereto with stirring. Then, 0.8 part by mass of a photoradical polymerization initiator (trade name Irgacure TPO, manufactured by BASF corporation) and 0.8 part by mass of a propylene glycol monomethyl ether solution (trade name L-7001, manufactured by Chinese envoy レ, ダウコーニング, manufactured by DOW) of a polyether-modified silicone oil (trade name L-7001, manufactured by Chinese envoy) were added and stirred for 0.5 hour to prepare a coating liquid (coating composition). Then, the preparation of the coating composition and the formation and evaluation of the cured film were carried out in the same manner as in example 1.
(example 5)
To a glass vessel equipped with a magnetic stirrer, 10.6 parts by mass of isocyanuric acid EO-modified diacrylate (trade name アロニックス M-215, manufactured by Toyo Synthesis Co., ltd.), 3.5 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name KAYARAD DPHA, manufactured by Nippon Kagaku K.K.) and 15.6 parts by mass of propylene glycol monomethyl ether were added, and 68.9 parts by mass of the modified metal oxide (A-1) colloidal liquid (solid content 30.5 mass%) produced in reference example 3 was added with stirring. Then, 0.7 parts by mass of a photo radical polymerization initiator (Irgacure TPO, manufactured by BASF Co., ltd.) and 0.7 parts by mass of a propylene glycol monomethyl ether solution (2.0% by mass as trade name L-7001, manufactured by DONG レ, ダウコーニング, manufactured by DONG Co., ltd.) were added and stirred for 0.5 hour to prepare a coating liquid (coating composition). Then, the preparation of the coating composition and the formation and evaluation of the cured film were carried out in the same manner as in example 1.
(example 6)
8.8 parts by mass of isocyanuric acid EO-modified diacrylate (trade name アロニックス M-215, manufactured by Toyo Synthesis Co., ltd.), 2.9 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name KAYARAD DPHA, manufactured by Nippon Chemicals, ltd.) and 10.3 parts by mass of propylene glycol monomethyl ether were charged into a glass vessel equipped with a magnetic stirrer, and 76.8 parts by mass of the modified metal oxide (A-1) colloidal liquid (solid content 30.5 mass%) produced in reference example 3 was added thereto with stirring. Subsequently, 0.6 part by mass of a photoradical polymerization initiator (trade name Irgacure TPO, manufactured by BASF corporation) and 0.6 part by mass of a propylene glycol monomethyl ether solution (trade name L-7001, manufactured by Easter レ, ダウコーニング, manufactured by Easter corporation) of a polyether-modified silicone oil (trade name L-7001, manufactured by Easter Ching 5363, ダウコーニング) were added and stirred for 0.5 hour to prepare a coating solution (coating composition). Then, the preparation of the coating composition and the formation and evaluation of the cured film were carried out in the same manner as in example 1.
(example 7)
In example 1, the isocyanurate EO-modified diacrylate (trade name アロニックス M-215, manufactured by Toyo Synthesis Co., ltd.) was changed to ethoxylated bisphenol A diacrylate (trade name ABE-300, manufactured by Newzhongmura chemical Co., ltd.), and the amount added was changed to 8.8 parts by mass. Further, the amount of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name KAYARAD DPHA, manufactured by japan chemical corporation) added was changed to 8.8 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, except that the uv treatment time for forming the cured film was changed to 3 minutes.
(example 8)
Preparation of a coating composition and formation/evaluation of a cured film were carried out in the same manner as in example 1 except that in example 1, the isocyanurate EO-modified diacrylate (trade name アロニックス M-215, manufactured by east asian corporation) was changed to ethoxylated bisphenol a diacrylate (trade name ABE-300, manufactured by shinkamura chemical) and the ultraviolet treatment time at the time of forming a cured film was changed to 3 minutes.
(example 9)
The preparation of a coating composition and the formation/evaluation of a cured film were carried out in the same manner as in example 1 except that in example 1, the isocyanuric acid EO-modified diacrylate (trade name アロニックス M-215, manufactured by Toyo Seiyaku Co., ltd.) was changed to tris (2-acryloyloxyethyl) isocyanurate (trade name FA-731A, manufactured by Hitachi Kagaku K.K.) and the ultraviolet treatment time at the time of forming a cured film was changed to 3 minutes.
(example 10)
A coating composition was prepared and a cured film was formed and evaluated in the same manner as in example 1 except that the amount of the isocyanurate EO-modified diacrylate (trade name アロニックス M-215, manufactured by east asia corporation) added was changed to 8.8 parts by mass, the amount of the dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate mixture (trade name KAYARAD DPHA, manufactured by japan chemical corporation) added was changed to 8.8 parts by mass, and the ultraviolet ray treatment time during formation of the cured film was changed to 3 minutes in example 1.
(example 11)
Preparation of a coating composition and formation/evaluation of a cured film were carried out in the same manner as in example 1 except that the amount of the isocyanurate EO-modified diacrylate (trade name アロニックス M-215, manufactured by east asia corporation) was changed to 4.4 parts by mass, the amount of the dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate mixture (trade name KAYARAD DPHA, manufactured by japan chemical corporation) was changed to 13.2 parts by mass, and the ultraviolet treatment time during formation of a cured film was changed to 3 minutes.
(example 12)
The preparation of a coating composition and the formation/evaluation of a cured film were carried out in the same manner as in example 1 except that the amount of the isocyanurate EO-modified diacrylate (アロニックス M-215, manufactured by east asian corporation) was changed to 17.6 parts by mass without adding a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (KAYARAD DPHA, manufactured by japan chemical corporation).
(example 13)
(preparation of high refractive index layer coating composition)
Into a glass vessel equipped with a magnetic stirrer, 8.59 parts by mass of a modified metal oxide (a-2) colloidal fluid (solid content: 30.5 mass%) surface-treated with acryloyloxypropyltrimethoxysilane, produced in reference example 4, was charged while stirring, the aromatic compound having a urethane bond and a polymerizable unsaturated bond (ダイセルオルネクス, trade name EBECRYL220, manufactured by ダイセルオルネクス, and the polymerizable compound includes 2.18 parts by mass of the compound represented by formula (b 1-2), the compound represented by formula (b 2-6), the compound represented by formula (b 2-7), and 3242 parts by mass of propylene glycol monomethyl ether 73.94. Then, 10.92 parts by mass of a propylene glycol monomethyl ether solution (trade name: irgacure TPO, manufactured by BASF corporation) of a photo radical polymerization initiator (trade name: irgacure TPO, 1.0 part by mass), and 4.37 parts by mass of a propylene glycol monomethyl ether solution (trade name: L-7001, manufactured by DOW レ. ダウコーニング, manufactured by DOW, inc.) of a polyether-modified silicone oil (trade name: L-7001, manufactured by DOW, inc.) were added and stirred for 0.5 hour to prepare a coating solution (coating composition).
(preparation of hard coating composition for evaluation of scratch resistance and adhesion)
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 charged into a glass vessel equipped with a magnetic stirrer, and 1.9 parts by mass of a photo radical polymerization initiator (trade name: irgacure TPO, manufactured by BASF Co., ltd.) and 1.9 parts by mass of a propylene glycol monomethyl ether solution (trade name: L-7001, manufactured by Dode レ, ダウコーニング, manufactured by Dode chemical Co., ltd.) of polyether-modified silicone oil (trade name: L-7001, 2.0 mass%) were charged while stirring. Then, the mixture was stirred for 0.5 hour to prepare a coating liquid (coating composition).
(formation and evaluation of cured film)
(evaluation of refractive index and transparency)
A glass substrate was prepared, a high refractive index layer coating solution (high refractive index layer coating composition) was applied by spin coating, the solvent was volatilized at 80 ℃ for 5 minutes, and then the irradiation intensity was 19mW/cm in a nitrogen atmosphere 2 The high pressure mercury lamp (9 mW/cm) was subjected to ultraviolet treatment for 6 minutes 2 ×6×60＝6840mJ/cm 2 ) The coating film was cured to form an optical member having a cured film with a thickness of 200 nm.
The tests shown in (1) and (3) above were carried out. The evaluation results are shown in table 4.
(evaluation of scratch resistance and adhesion)
A polycarbonate substrate was prepared, a hard coat layer coating liquid (hard coat layer coating composition) was applied by a spin coating method so that the film thickness after UV curing became 5 μm, the solvent was evaporated at 80 ℃ for 5 minutes, and the irradiation intensity was 19mW/cm 2 The high pressure mercury lamp (9 mW/cm) was subjected to ultraviolet treatment for 30 seconds 2 ×30＝570mJ/cm 2 ) The coating film was cured to obtain a hard coat cured film. Then, a high refractive index layer coating liquid (high refractive index layer coating composition) was applied on the hard coat layer cured film by a spin coating method, the solvent was volatilized at 80 ℃ for 5 minutes, and then the irradiation intensity was 19mW/cm under a nitrogen atmosphere 2 The high pressure mercury lamp (9 mW/cm) was subjected to ultraviolet treatment for 6 minutes 2 ×6×60＝6840mJ/cm 2 ) The coating film was cured to form a multilayer cured film (film thickness: high refractive index layer 200nm, hard coat 5 μm).
The tests shown in (7) and (8) above were carried out. The evaluation results are shown in table 4.
(example 14)
In example 13, a high refractive index layer coating composition and formation/evaluation of a cured film were carried out in the same manner as in example 13 except that 8.59 parts by mass of the modified metal oxide (a-1) colloidal fluid (solid content: 30.5% by mass) produced in reference example 3 was used instead of the modified metal oxide (a-2) colloidal fluid surface-treated with acryloyloxypropyltrimethoxysilane produced in reference example 4.
(example 15)
In example 13, a high refractive index layer coating composition and formation/evaluation of a cured film were carried out in the same manner as in example 13 except that 1.64 parts by mass of isocyanurate EO-modified diacrylate (アロニックス M-215, manufactured by east asian corporation) and 0.55 part by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (KAYARAD DPHA, manufactured by japan chemical corporation) were used instead of the urethane bond-containing aromatic compound having a polymerizable unsaturated bond (ダイセルオルネクス, manufactured by japan corporation, trade name EBECRYL 220).
Comparative example 1
25.7 parts by mass of isocyanuric acid EO-modified diacrylate (trade name アロニックス M-215, manufactured by Toyo Synthesis Co., ltd.), 8.6 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name KAYARAD DPHA, manufactured by Nippon Chemicals Co., ltd.), 17.5 parts by mass of methanol, and 44.8 parts by mass of propylene glycol monomethyl ether were charged into a glass vessel equipped with a magnetic stirrer. Subsequently, 1.7 parts by mass of a photoradical polymerization initiator (trade name Irgacure TPO, manufactured by BASF corporation) and 1.7 parts by mass of a propylene glycol monomethyl ether solution (trade name L-7001, manufactured by Chinese envoy レ. ダウコーニング, manufactured by Chinese envoy corporation) (trade name L-7001, 2.0 mass%) were added to the above solution and stirred for 0.5 hour 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 1, except that the uv treatment time for the formation of the cured film was changed to 3 minutes.
Comparative example 2
19.9 parts by mass of isocyanuric acid EO-modified diacrylate (trade name アロニックス M-215, manufactured by Toyo Synthesis Co., ltd.) and 6.6 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name KAYARAD DPHA, manufactured by Nippon Chemicals Co., ltd.) were placed in a glass vessel equipped with a magnetic stirrer, 26.2 parts by mass of methanol and 17.9 parts by mass of propylene glycol monomethyl ether were added thereto, and the resulting mixture (a 1-1) obtained in reference example 1, which had not been SnO-modified, was added thereto with stirring 2 -SiO 2 26.5 parts by mass of a composite titania sol (dispersed in water with a solid content of 30.0%). Then, 1.3 parts by mass of a photoradical polymerization initiator (Irgacure TPO, trade name, manufactured by BASF corporation) and 1.3 parts by mass of a propylene glycol monomethyl ether solution (2.0% by mass, trade name, L-7001, manufactured by DOW レ. ダウコーニング, trade name, manufactured by DOW) of polyether-modified silicone oil were added and stirred for 0.5 hour to prepare a coating liquid (coating composition). Then, the preparation of the coating composition and the formation and evaluation of the cured film were carried out in the same manner as in example 1.
Comparative example 3
4.59 parts by mass of an aromatic compound having a polymerizable unsaturated bond and containing a urethane bond (product name EBECRYL220 manufactured by ダイセルオルネクス, manufactured by Kabushiki Kaisha, including a compound represented by formula (b 1-2), a compound represented by formula (b 2-6), and a compound represented by formula (b 2-7)) and 3242 parts by mass of propylene glycol monomethyl ether (63.30) were charged into a glass vessel equipped with a magnetic stirrer. Then, 22.94 parts by mass of a propylene glycol monomethyl ether solution (trade name: irgacure TPO, manufactured by BASF corporation) of a photo radical polymerization initiator (trade name: irgacure TPO, manufactured by BASF corporation) and 9.17 parts by mass of a propylene glycol monomethyl ether solution (trade name: L-7001, manufactured by DOW レ. ダウコーニング, manufactured by DOW corporation) of a polyether-modified silicone oil (trade name: L-7001, manufactured by DOW CORPORATION) were added to the above solution while stirring the solution, and stirring was carried out for 0.5 hour to prepare a high refractive index layer coating solution (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
Into a glass vessel equipped with a magnetic stirrer were charged an aromatic compound having a polymerizable unsaturated bond and containing a urethane bond (product name EBECRYL220, manufactured by ダイセルオルネクス K.K., containing a compound represented by the formula (b 1-2), a compound represented by the formula (b 2-6), and a compound represented by the formula (b 2-7)) 2.39 parts by mass and propylene glycol monomethyl ether 72.89 parts by mass, and the non-SnO (a 1-1) obtained in reference example 1 were added while stirring 2 -SiO 2 7.97 parts by mass of a composite titania sol (dispersed in water with a solid content of 30.0%). Then, 11.96 parts by mass of a propylene glycol monomethyl ether solution (trade name: irgacure TPO, manufactured by BASF corporation) of a photo radical polymerization initiator (trade name: irgacure TPO, 1.0 part by mass), and 4.78 parts by mass of a propylene glycol monomethyl ether solution (trade name: L-7001, manufactured by DOW レ. ダウコーニング, manufactured by DOW, inc.) of a polyether-modified silicone oil (trade name: L-7001, manufactured by DOW 4736. zxft 4736.8978) were added and stirred for 0.5 hour to prepare a coating solution (coating composition).
The formation and evaluation of the cured film were performed in the same manner as in example 13.
In Table 1, the trade name アロニックス M-215 manufactured by Toyo Synthesis is represented by (i),
the trade name KAYARAD DPHA manufactured by Nippon chemical Co., ltd., (ii) is shown,
the product name ABE-300 manufactured by Nippon Memura chemical Co., ltd. (iii) is shown,
the trade name of FA-731A manufactured by Hitachi chemical Co., ltd is represented by (iv),
the product name Irgacure TPO manufactured by BASF corporation is shown as (v),
the trade name L-7001 manufactured by Chinese envoys レ and ダウコーニング (strain) is represented by (vi), the particles (A-1) are represented by (vii),
the particles (a 1-1) are represented by (viii),
the particles (A-2) are represented by (ix),
the trade name EBECRYL220 manufactured by ダイセルオルネクス (strain) is shown by (x). In table 1, the addition amounts represent parts by mass of the respective components.
[ Table 1]
TABLE 1
Figure BDA0002992056900000451
TABLE 2
Figure BDA0002992056900000461
TABLE 3
Figure BDA0002992056900000462
TABLE 4
Figure BDA0002992056900000471
The coating film obtained from the coating composition containing the modified metal oxide particles (a) and the polymerizable compound (B) having an unsaturated bond between a carbon atom and a carbon atom exhibits excellent properties in terms of refractive index, hardness, transparency, light resistance, bendability, scratch resistance, and adhesion.
The coating film obtained from the coating composition in which the polymerizable compound (B1) and the polymerizable compound (B2) are combined with each other in the polymerizable compound (B) exhibits excellent properties in terms of refractive index, hardness, transparency, light resistance, and bendability.
In the polymerizable compound (B), when the polymerizable compound (B2) is contained but the polymerizable compound (B1) is not used in combination with the polymerizable compound (B1), or when the content of the polymerizable compound (B1) is low while the polymerizable compound (B1) is used in combination with the polymerizable compound (B2), the performance is slightly lowered in light resistance and bendability.
When the metal oxide particles (a) are not contained, sufficient hardness cannot be obtained, and the refractive index adjustment is insufficient.
Further, the metal oxide particles (a) having no coating structure are insufficient in transparency, light resistance and bendability.
In the present invention, by selecting the core particles (a 1) and the coated particles (a 2), 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. Further, by containing a silica component in the outermost layer and subjecting the particle surface to surface treatment with a silane coupling agent, it is possible to copolymerize with the unsaturated bond of the polymerizable compound which becomes the curing component, and it is possible to uniformly immobilize the metal oxide particles in the resin matrix.
Further, by selecting the polymerizable compound (B), a composition corresponding to the function required for the coating composition can be produced.
Industrial applicability
The present invention can be cured by heat or light, and can form a coated substrate requiring refractive index, hardness, adhesion, transparency, light resistance, bendability, scratch resistance, adhesion, and the like by applying the coating to a transparent film or a glass 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),
Figure FDA0003917470430000011
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),
Figure FDA0003917470430000021
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.
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