JP2000256535A - Resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition having excellent curability, and capable of forming coating films excellent in hardness and low curliness, etc., on the surfaces of various base materials, by including specific particles and component(s) selected from a specific urethane compound and others. SOLUTION: This composition is obtained by including (A) particles obtained by binding (i) oxide particles of at least one element selected from silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony, and cerium, to (ii) an organic compound containing a polymerizable unsaturated group and a group of the formula (X is NH, O or S; Y is O or S), and (B) at least one compound selected from (iii) a polyfunctional urethane compound having 2 or more (meta)acryloyl groups and 2 or more [-O-C(=O)-NH-] groups in the molecule, wherein the molecular weight per (meta)acryloyl group is <=400, (iv) a fluorine-based surfactant, and (v) a thermoplastic polymer having a glass transition temperature of >=40 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition and a cured product thereof. More specifically, the present invention provides excellent curability and various substrates [for example, plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetylcellulose, ABS resin, AS resin) resin,
Norbornene resin), metal, wood, paper, glass, slates, etc.] with excellent hardness, scratch resistance, low curl, adhesion and transparency, especially hardness and low curl. The present invention relates to a resin composition capable of forming a film and a cured product thereof. The resin composition of the present invention and a cured product thereof can be used, for example, to prevent scratches (scratch) on plastic optical components, touch panels, film-type liquid crystal elements, plastic containers, flooring materials as building interior materials, wall materials, artificial marble, and the like. It can be suitably used as a protective coating material for preventing contamination; an adhesive for various substrates; a sealing material; a binder material for printing ink;

[0002]

2. Description of the Related Art In recent years, various types of base materials have been used as protective coating materials for preventing scratches (scratch) and contamination on the surface of various base materials; adhesives and sealing materials for various base materials; Hardness, scratch resistance, low curl,
There is a need for a resin composition having excellent curability, which can form a film having excellent adhesion and transparency. Among these demands, various materials containing colloidal silica have been proposed with the aim of improving scratch resistance. For example, US Pat. No. 3,451,838 and US Pat.
No. 4,357 discloses that a composition mainly composed of a hydrolyzate of alkoxysilane and colloidal silica is used as a thermosetting coating material.
For example, Japanese Patent Publication No. 21815/1987 discloses the use of a composition of acrylate and particles obtained by modifying the surface of colloidal silica with methacryloxysilane as a photocurable coating material. A characteristic of these coating materials is that the performance of the coating material is improved by treating the surface of the silica particles with a specific organosilane or specific conditions. However, such a coating material does not satisfy all of the curability as a composition and the hardness, abrasion resistance, low curl, adhesion and transparency when a cured film is formed. . Further, for example, thermosetting coating materials exemplified in the above-mentioned U.S. Pat. No. 3,451,838 and U.S. Pat. No. 2,404,357 require high-temperature and long-time heat treatment, It was difficult to apply to a plastic substrate having low heat resistance.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has excellent curability, and has hardness, abrasion resistance, low curl on surfaces of various substrates. It is an object of the present invention to provide a resin composition capable of forming a film having excellent properties, adhesion and transparency, particularly hardness and low curl property, and a cured product thereof.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object. As a result, (A) an oxide particle of a specific element and an organic compound containing a specific group in a molecule have been developed. And (B) at least one selected from a specific polyfunctional urethane compound, a fluorine-based surfactant, and a thermoplastic polymer having a specific glass transition temperature.
The present inventors have found that a resin composition which satisfies the above-mentioned various properties, particularly, a hardness and a low curl property when a cured product is obtained, can be obtained by using a resin composition, and completed the present invention. That is, the present invention provides the following resin compositions and cured products thereof.

[1] (A) oxide particles of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium, and a polymerizable unsaturated group; Particles (hereinafter, sometimes referred to as “crosslinkable particles (A)”) obtained by bonding an organic compound containing a group represented by the following formula (1) (hereinafter, may be referred to as “specific organic compound”). And

[0006]

Embedded image [In the formula (1), X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. (B) A resin composition containing at least one selected from the following (b1), (b2) or (b3) (hereinafter sometimes referred to as “component (B)”). (B1) having four or more (meth) acryloyl groups in the molecule and having a molecular weight of 4 per (meth) acryloyl group;
00 and not less than 2 and [-OC (= O) -N
(B-2) Fluorosurfactant (b3) Thermoplastic polymer having a glass transition temperature of 40 ° C. or more

[2] When the organic compound is [-OC (=
O) -NH-] group, and further comprises [-OC (= S)
The resin composition according to the above [1], which comprises at least one of a -NH-] group and a -S-C (= O) -NH-] group.

[3] The resin composition according to the above [1] or [2], wherein the organic compound is a compound having a silanol group or a compound generating a silanol group by hydrolysis.

[4] (b1) of the above (B) is a urethane (meth) acrylate obtained by reacting 2 mol of an active hydrogen-containing polymerizable unsaturated compound with 1 mol of a diisocyanate represented by the following formula (3). The resin composition according to [1] or [2].

[0010]

Embedded image R ⁶ —OC (＝ O) NH—R ⁷ —NHCOO—R ⁸ (3) [In the formula (3), R ⁶ and R ⁸ are (meth) derived from an active hydrogen-containing polymerizable unsaturated compound. An organic group containing an acryloyl group,
R ⁷ represents a divalent organic group derived from diisocyanate. ]

[5] The resin according to [1] or [2], wherein (b2) in (B) is a nonionic fluorine-based surfactant and / or an anionic fluorine-based surfactant. Composition.

[6] (B3) of the above (B) is a polystyrene, polymethyl (meth) acrylate, polyamide,
It is at least one selected from the group consisting of polyamide imide, polyester, styrene butadiene copolymer resin, xylene resin, ketone resin, acrylonitrile styrene copolymer resin, methyl (meth) acrylate styrene copolymer resin, norbornene resin and epoxy resin [ 1]
Or the resin composition according to [2].

[7] In addition to the above (A) and (B), (C) a compound containing two or more polymerizable unsaturated groups in the molecule (hereinafter sometimes referred to as “compound (C)”). ) The resin composition according to any one of the above [1] to [6].

[8] The resin composition according to any one of [1] to [7], further comprising (D) a polymerization initiator (hereinafter, sometimes referred to as "polymerization initiator (D)").

[9] The polymerization initiator (D) is (d) 1
The resin composition according to the above [8], which is a radiation polymerization initiator for both or any of an aryl ketone having a hydroxycyclohexyl group and an aryl ketone having an N-morpholino group. In the present invention, "radiation"
The term means infrared rays, visible rays, ultraviolet rays, far ultraviolet rays, X-rays, electron beams, α-rays, β-rays, γ-rays and the like.

[10] A cured product obtained by curing the resin composition according to any one of [1] to [9].

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the resin composition of the present invention and a cured product thereof will be specifically described.

I. Resin composition The resin composition of the present invention contains crosslinkable particles (A) and component (B), and if necessary, compound (C) and a polymerization initiator (D). is there. Hereinafter, each composition component is specifically described.

1. Crosslinkable particles (A) The crosslinkable particles (A) used in the present invention are formed by oxidation of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. It is a crosslinkable particle formed by bonding a product particle and a specific organic compound.

(1) Oxide Particles The oxide particles used in the present invention are preferably silicon, aluminum, zirconium, titanium, zinc, germanium, from the viewpoint of the colorlessness of the cured film of the obtained resin composition.
The oxide particles are at least one element selected from the group consisting of indium, tin, antimony, and cerium.

Examples of these oxides include silica, aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide and cerium oxide. it can. Among them, silica, aluminum oxide, zirconia and antimony oxide are preferred from the viewpoint of high hardness. These may be used alone or 2
More than one species can be used in combination. Further, the oxide particles of such an element are preferably in the form of a powder or a solvent-dispersed sol. In the case of a solvent dispersion sol, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. As such an organic solvent, for example,
Alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl lactate and γ-butyrolactone; ethylene glycol monomethyl ether; Ethers such as diethylene glycol monobutyl ether; benzene, toluene,
Aromatic hydrocarbons such as xylene; amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like can be mentioned. Among them, methanol,
Isopropanol, butanol, methyl ethyl ketone,
Preferred are methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene.

The number average particle diameter of the oxide particles is 0.001.
μm to 2 μm, preferably 0.001 μm to 0.2 μm
Is more preferable, and 0.001 μm to 0.1 μm is particularly preferable. If the number average particle size exceeds 2 μm, the transparency of the cured product tends to decrease, and the surface state of the coating tends to deteriorate. Here, various surfactants and amines may be added to improve the dispersibility of the particles.

Commercially available silicon oxide particles, for example, silica particles, such as colloidal silica, manufactured by Nissan Chemical Industries, Ltd., trade names: methanol silica sol, IPA-ST, MEK-ST, NBA-S
T, XBA-ST, DMAC-ST, ST-UP, ST
-OUP, ST-20, ST-40, ST-C, ST-
N, ST-O, ST-50, ST-OL, and the like. As the powdered silica, trade names: Aerosil 130, Aerosil 30 manufactured by Nippon Aerosil Co., Ltd.
0, Aerosil 380, Aerosil TT600, Aerosil OX50, manufactured by Asahi Glass Co., Ltd. Trade names: Sildex H31, H32, H51, H52, H121, H12
2. Product name: E220A, E, manufactured by Nippon Silica Industry Co., Ltd.
220, manufactured by Fuji Silysia Ltd. Product name: SYLYSI
A470, manufactured by Nippon Sheet Glass Co., Ltd .: SG flake and the like.

Examples of the water-dispersed alumina product include alumina sol-100, manufactured by Nissan Chemical Industries, Ltd.
200, -520; As an aqueous dispersion of zinc antimonate powder, Nissan Chemical Industry Co., Ltd. product name: CELNAX; alumina, titanium oxide, tin oxide, indium oxide; powder of zinc oxide, etc. and solvent dispersion Is a product of Ishihara Sangyo Co., Ltd. as a water dispersion sol of antimony-doped tin oxide.
Trade name: SN-100D; as ITO powder, a product manufactured by Mitsubishi Materials Corporation; as cerium oxide aqueous dispersion, Taki Chemical Co., Ltd., trade name: Niedral. The shape of the oxide particles is spherical, hollow, porous, rod-like, plate-like, fibrous, or irregular, and is preferably spherical. The specific surface area of the oxide particles (by the BET specific surface area measurement method using nitrogen) is preferably 10
１０００1000 m ² / g, more preferably 100１００
500 m ² / g. These oxide particles can be used in the form of dry powder or dispersed in water or an organic solvent. For example, a dispersion liquid of fine oxide particles known in the art as a solvent dispersion sol of the above oxide can be directly used. In particular, use of a solvent-dispersed sol of an oxide is preferred for applications requiring excellent transparency of the cured product.

(2) Specific Organic Compound The specific organic compound used in the present invention includes a polymerizable unsaturated group and a group represented by the above formula (1) (hereinafter referred to as [-XC (= Y)
-NH-] in some cases. ).

The polymerizable unsaturated group is not particularly restricted but includes, for example, acryloyl, methacryloyl, vinyl, propenyl, butadienyl, styryl,
Preferred examples include an ethynyl group, a cinnamoyl group, a maleate group and an acrylamide group. This polymerizable unsaturated group is a structural unit that undergoes addition polymerization using an active radical species.

The group represented by the formula (1) [-XC (= Y)
-NH-] is, specifically, [-OC (= O) -NH
-], [-OC (= S) -NH-], [-SC (=
O) -NH-], [-NH-C (= O) -NH-],
[-NH-C (= S) -NH-] and [-SC (=
S) -NH-]. These groups can be used alone or in combination of two or more. Above all, from the viewpoint of thermal stability, [-OC (= O) -NH
-] Group, [-OC (= S) -NH-] group and [-S
It is preferable to use at least one of -C (= O) -NH-] groups in combination.

The specific organic compound used in the present invention is a compound containing a silanol group (hereinafter, sometimes referred to as a “silanol group-containing compound”) or a compound that forms a silanol group by hydrolysis (hereinafter, a “silanol group”). Group-forming compound "). Examples of such a silanol group-forming compound include compounds having an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom and the like on a silicon atom, and an alkoxy group or an aryloxy group on a silicon atom. Are preferable, that is, a compound containing an alkoxysilyl group or a compound containing an aryloxysilyl group.

The silanol group or the silanol group-forming site of the silanol group-forming compound is a structural unit that bonds to the oxide particles by a condensation reaction or a condensation reaction that occurs after hydrolysis, and the polymerizable unsaturated group is It is a structural unit that undergoes chemical crosslinking between molecules via addition polymerization by an active radical species. Further, the group [-XC (=
Y) -NH-] generates an appropriate cohesive force due to hydrogen bonding between molecules and imparts properties such as excellent mechanical strength, adhesion to a substrate and heat resistance when cured. it is conceivable that.

Preferred specific organic compounds include, for example, compounds represented by the following formula (2).

[0031]

Embedded image

In the formula (2), R ¹ and R ² may be the same or different and each is a hydrogen atom or a C ₁ to C ₈ alkyl or aryl group, for example, methyl, ethyl, propyl, butyl Octyl, phenyl, and xylyl groups. Here, m is 1, 2 or 3.

Examples of the group represented by ^{_{[(R 1 O) m R}} 2 3-m Si-], for example, trimethoxysilyl groups, triethoxysilyl group, triphenoxysilyl group, methyldimethoxysilyl group, dimethylmethoxysilyl And the like. Among these groups, a trimethoxysilyl group or a triethoxysilyl group is preferred.

R ³ is a divalent organic group having a C ₁ to C ₁₂ aliphatic or aromatic structure, and may have a chain, branched or cyclic structure. Such organic groups include, for example, methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene,
Xylylene, dodecamethylene and the like can be mentioned.
Preferred examples among these are methylene, propylene, cyclohexylene, phenylene and the like.

R ⁴ is a divalent organic group.
Molecular weight 14 to 10,000, preferably molecular weight 76 to 50
It is selected from 0 divalent organic groups. For example, chain polyalkylene groups such as hexamethylene, octamethylene, dodecamethylene, etc .; alicyclic or polycyclic divalent organic groups such as cyclohexylene and norbornylene; divalent organic groups such as phenylene, naphthylene, biphenylene and polyphenylene Aromatic groups; and substituted alkyl and aryl groups thereof. In addition, these divalent organic groups may include an atomic group containing an element other than carbon and hydrogen atoms, and include a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, and a compound represented by the formula (1).
May be included.

R ⁵ is an (n + 1) -valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and an unsaturated hydrocarbon group.

Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule which undergoes an intermolecular crosslinking reaction in the presence of an active radical species. For example, acryloyl (oxy) group, methacryloyl (oxy) group, vinyl (oxy) group, propenyl (oxy) group, butadienyl (oxy) group, styryl (oxy) group, ethynyl (oxy) group, cinnamoyl (oxy) group , Maleate group, acrylamide group, methacrylamide group and the like. Among these, an acryloyl (oxy) group and a methacryloyl (oxy) group are preferred. N is preferably a positive integer of 1 to 20, more preferably 1 to 10, and most preferably 1 to 5.

For the synthesis of the specific organic compound used in the present invention, for example, a method described in JP-A-9-100111 can be used. That is, (a) a mercaptoalkoxysilane, a polyisocyanate compound,
It can be carried out by an addition reaction with an active hydrogen group-containing polymerizable unsaturated compound. In addition, (b) the reaction can be carried out by a direct reaction between a compound having an alkoxysilyl group and an isocyanate group in the molecule and an active hydrogen-containing polymerizable unsaturated compound. Furthermore, (c) the compound having a polymerizable unsaturated group and an isocyanate group in a molecule and a mercaptoalkoxysilane or an aminosilane can be directly synthesized by an addition reaction.

In order to synthesize the compound represented by the formula (2), (a) of these methods is suitably used.
More specifically, for example, the method (a): first reacting a mercaptoalkoxysilane with a polyisocyanate compound to form an alkoxysilyl group, a [—S—C (−O) —NH—] group and an isocyanate in the molecule. An intermediate containing a group is formed and then the isocyanate remaining in the intermediate is reacted with a hydroxy group-containing polymerizable unsaturated compound to convert the unsaturated compound into [-OC (= O) -NH A method of bonding via a-] group, method (b); a polyisocyanate compound and a hydroxy group-containing polymerizable unsaturated compound are first reacted to form a polymerizable unsaturated group, [-OC (= O) -NH-] group,
And forming an intermediate containing an isocyanate group, and reacting the intermediate with the mercaptoalkoxysilane to bond the mercaptoalkoxysilane via a [—S—C (＝ O) —NH—] group. Can be. Among them, the method (a) is preferable because there is no decrease in the polymerizable unsaturated group due to the Michael addition reaction.

In the synthesis of the compound represented by the formula (2), the reaction with an isocyanate group results in [-SC (=
Examples of the alkoxysilane capable of forming the O) —NH—] group include compounds having one or more alkoxysilyl groups and one or more mercapto groups in the molecule. Examples of such mercaptoalkoxysilanes include, for example, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethoxymethylsilane, mercaptopropylmethoxydimethylsilane, mercaptopropyltriphenoxysisilane, mercapto Propyl tributoxy silane can be exemplified. Of these, mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane are preferred. Further, an addition product of an amino-substituted alkoxysilane and an epoxy-substituted mercaptan,
An addition product of an epoxysilane and an α, ω-dimercapto compound can also be used.

Examples of the polyisocyanate compound used for synthesizing the specific organic compound include a chain saturated hydrocarbon,
It can be selected from polyisocyanate compounds composed of cyclic saturated hydrocarbons and aromatic hydrocarbons.

Examples of such polyisocyanate compounds include, for example, 2,4-tolylene diisocyanate
2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalenedi isocyanate, m-
Phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate G, 4,4'-biphenylene diisocyanate
1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate, 6- Isopropyl-1,3-phenyldiisocyanate, 4-diphenylpropanediisocyanate, lysine diisocyanate, hydrogenated diphenylmethanediisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, Examples include tetramethylxylylene diisocyanate, 2,5 (or 6) -bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, and the like. Of these, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, and the like are preferable. These are 1
Species can be used alone or in combination of two or more.

In the synthesis of the specific organic compound, the polyisocyanate compound is reacted with [-OC (=
Examples of the active hydrogen-containing polymerizable unsaturated compound that can be bonded via an O) —NH—] group include an [—O—C (＝ O) —NH—] group by an addition reaction with an isocyanate group in the molecule. A compound having at least one active hydrogen atom capable of forming a compound and having at least one polymerizable unsaturated group. As these active hydrogen-containing polymerizable unsaturated compounds, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate,
Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3
Phenyloxypropyl (meth) acrylate, 1,
4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate
G, 4-hydroxycyclohexyl (meth) acryle
G, 1,6-hexanediol mono (meth) acryle
G, neopentyl glycol mono (meth) acryle
G, trimethylolpropane di (meth) acrylate,
Trimethylol ethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like can be mentioned. In addition, alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acryl
And a compound obtained by an addition reaction of a glycidyl group-containing compound such as (g) with (meth) acrylic acid. Among these compounds, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate
Acrylate and the like are preferred. These compounds can be used alone or as a mixture of two or more.

(3) Method for Producing Crosslinkable Particles (A) The method for producing the crosslinkable particles (A) used in the present invention is not particularly limited. For example, the above-mentioned specific organic compound is reacted with oxide particles. Can be mentioned. Oxide particles are known to contain moisture as adsorbed water on the particle surface in a normal storage state, and at least a component that reacts with a silanol group-forming compound such as a hydroxide or a hydrate is present on the surface. It is estimated to be. Therefore, at the time of producing the crosslinkable particles (A), it is also possible to produce the mixture by mixing a silanol group-forming compound and oxide particles, followed by heating and stirring. Note that the reaction is preferably performed in the presence of water in order to efficiently bond the silanol group generation site of the organic compound to the oxide particles. However, when the organic compound has a silanol group, water may not be necessary. Therefore, the crosslinkable particles (A)
Can be produced by a method including an operation of mixing at least an organic compound and oxide particles.

Hereinafter, a preferred method for producing the crosslinkable particles (A) will be described in more detail. The amount of the specific organic compound bonded to the oxide particles in the crosslinkable particles (A) is preferably at least 0.01% by weight, more preferably 0.1% by weight.
It is at least 1% by weight, particularly preferably at least 1% by weight. 0.01% by weight of the specific organic compound bound to the oxide particles
If it is less than 3, the dispersibility of the crosslinkable particles (A) in the composition is not sufficient, and the transparency and abrasion resistance of the obtained cured product may not be sufficient. The ratio of the oxide particles in the raw material at the time of producing the crosslinkable particles (A) is preferably 5 to 9 with the total of the specific organic compound and the oxide particles being 100% by weight.
It is 9% by weight, more preferably 10 to 98% by weight or less. When the proportion of the oxide particles in the raw material at the time of producing the crosslinkable particles (A) exceeds 99% by weight, dispersibility as a composition, applicability, and abrasion resistance when a cured product is obtained may not be sufficient. is there. If the amount is less than 5% by weight, the hardness and scratch resistance of the cured product may not be sufficient.

Hereinafter, the method for producing the crosslinkable particles (A) will be described in more detail by taking an alkoxysilyl group-containing compound (alkoxysilane compound) as an example of the silanol group-forming compound. The amount of water consumed in the hydrolysis of the alkoxysilane compound during the production of the crosslinkable particles (A) is as follows:
It is sufficient that at least one of the alkoxy groups on silicon in one molecule is hydrolyzed. Preferably, the amount of water added or present during the hydrolysis is at least one third of the number of moles of all alkoxy groups on silicon, and more preferably one half of the number of moles of all alkoxy groups. More than three times. The product obtained by mixing the alkoxysilane compound represented by the formula (2) and the oxide particles under the condition that water is completely absent is a product in which the alkoxysilane compound is physically adsorbed on the surface of the oxide particles. In a composition composed of such components, the effect of expressing high hardness and scratch resistance, which is one object of the composition of the present invention, is low.

In the production of the crosslinkable particles (A), the alkoxysilane compound represented by the above formula (2) is separately subjected to a hydrolysis operation, and then this is mixed with the powder oxide particles or the solvent dispersion sol of the oxide particles. A method of mixing, heating and stirring;
Alternatively, a method in which the alkoxysilane compound represented by the formula (2) is hydrolyzed in the presence of oxide particles; and other components such as the component (B), the compound (C), and the polymerization initiator (D ) And the like, a method of performing a surface treatment of the oxide particles, and the like can be selected. Among them, a method of hydrolyzing the alkoxysilane compound represented by the formula (2) in the presence of oxide particles is preferable. When producing the crosslinkable particles (A),
The temperature is preferably from 0 ° C to 150 ° C,
More preferably, the temperature is from 20 ° C to 100 ° C. Processing times are typically in the range of 5 minutes to 24 hours.

When a powdery oxide powder is used during the production of the crosslinkable particles (A), the reaction with the alkoxysilane compound is carried out smoothly and uniformly.
An organic solvent may be added. As such an organic solvent, the same solvent as that used as the dispersion medium of the solvent dispersion sol of the oxide particles can be used. The amount of these solvents to be added is not particularly limited as long as the reaction is carried out smoothly and uniformly.

When a solvent-dispersed sol is used as a raw material of the crosslinkable particles (A), it can be produced by mixing at least the solvent-dispersed sol and an organic compound. Here, an organic solvent that is uniformly compatible with water may be added for the purpose of ensuring uniformity in the initial stage of the reaction and smoothly proceeding the reaction.

In the production of the crosslinkable particles (A),
To promote the reaction, an acid, salt or base may be added as a catalyst. Examples of the acid include hydrochloric acid, nitric acid, sulfuric acid,
Inorganic acids such as phosphoric acid; organic acids such as methanesulfonic acid, toluenesulfonic acid, phthalic acid, malonic acid, formic acid, acetic acid, and oxalic acid; unsaturated organic acids such as methacrylic acid, acrylic acid, and itaconic acid; For example, ammonium salts such as tetramethylammonium hydrochloride and tetrabutylammonium hydrochloride, and bases such as primary, secondary and tertiary such as aqueous ammonia, diethylamine, triethylamine, dibutylamine and cyclohexylamine
And aromatic amines such as tertiary aliphatic amines and pyridine; and quaternary ammonium hydroxides such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and tetrabutylammonium hydroxide. Among these, preferred examples of the acid are organic acids and unsaturated organic acids, and the bases are tertiary amines and quaternary ammonium hydroxides. The amount of the acid, salt or base added is preferably from 0.001 to 1.0 part by weight, more preferably from 0.01 to 0.1 part by weight, based on 100 parts by weight of the alkoxysilane compound. It is. It is also preferable to add a dehydrating agent to promote the reaction. As the dehydrating agent, inorganic compounds such as zeolite, anhydrous silica, and anhydrous alumina, and organic compounds such as methyl orthoformate, ethyl orthoformate, tetraethoxymethane, and tetrabutoxymethane can be used.
Among them, organic compounds are preferable, and orthoesters such as methyl orthoformate and ethyl orthoformate are more preferable. The amount of the alkoxysilane compound bonded to the crosslinkable particles (A) is usually 11% in air as a constant value of the weight loss% when the dry powder is completely burned in air.
It can be determined by thermogravimetric analysis from 0 ° C to 800 ° C.

(4) Compounding Amount of Crosslinkable Particles (A) in the Composition The compounding amount of the crosslinkable particles (A) is 50% based on 100% by weight of the composition [total of (A) and (B)]. ~ 99.9
Preferably, 999% by weight is blended. If the ratio is outside the above range, the hardness of the cured product may be insufficient. In addition, the amount of the crosslinkable particles (A) means a solid content,
When the crosslinkable particles (A) are used in the form of a solvent-dispersed sol, the amount thereof does not include the amount of the solvent.

2. Component (B) Component (B) used in the present invention includes the following (b1), (b)
2) or at least one selected from (b3).

(B1) The molecule has two or more (meth) acryloyl groups in the molecule, the molecular weight per one (meth) acryloyl group is 400 or less, and two or more [—O—C
(= O) -NH-] group-containing polyfunctional urethane compound (hereinafter sometimes referred to as polyfunctional urethane compound (b1)) (b2) Fluorine surfactant (hereinafter, fluorine surfactant (b2) (B3) Thermoplastic polymer having a glass transition temperature of 40 ° C. or higher (hereinafter sometimes referred to as thermoplastic polymer (b3)).

(1) Polyfunctional urethane compound (b1) The polyfunctional urethane compound (b1) used in the present invention is:
It is used to increase the scratch resistance and hardness of the cured product. The polyfunctional urethane compound (b1) has two or more (meth) acryloyl groups in the molecule, has a molecular weight of 400 or less per (meth) acryloyl group, and has two or more [-OC ( ＯO) —NH—] group, is not particularly limited, but may be a urethane (meth) obtained by reacting 2 mol of an active hydrogen-containing polymerizable unsaturated compound with 1 mol of a diisocyanate represented by the following formula (3). ) Acrylates are preferred.

[0055]

Embedded image R ⁶ —OC (＝ O) NH—R ⁷ —NHCOO—R ⁸ (3) [In the formula (3), R ⁶ and R ⁸ are (meth) derived from an active hydrogen-containing polymerizable unsaturated compound. An organic group containing an acryloyl group,
R ⁷ represents a divalent organic group derived from diisocyanate. ]

Specifically, a reaction product of 2-hydroxyethyl (meth) acrylate and 2,4-tolylene diisocyanate, a reaction product of 2-hydroxyethyl (meth) acrylate and isophorone diisocyanate, 2-hydroxybutyl (meth) A) a reaction product of acrylate and 2,4-tolylene diisocyanate, a reaction product of 2-hydroxybutyl (meth) acrylate and isophorone diisocyanate, a reaction product of pentaerythritol tri (meth) acrylate and 2,4-tolylene diisocyanate, A reaction product of erythritol tri (meth) acrylate and isophorone diisocyanate can be used.

These synthesizing methods include a method in which a diisocyanate and an active hydrogen-containing polymerizable unsaturated compound are charged and reacted at once, a method in which an active hydrogen-containing polymerizable unsaturated compound is dropped into diisocyanate and reacted, a method in which diisocyanate and an active A method in which an equimolar amount of the hydrogen-containing polymerizable unsaturated compound is charged and reacted, and then the active hydrogen-containing polymerizable unsaturated compound is reacted again can be exemplified.

The amount of the polyfunctional urethane compound (b1) used in the present invention may be 0.01 to 50% by weight based on 100% by weight of the composition [total of (A) and (B)]. Preferably, it is 0.01 to 40% by weight. If the amount is less than 0.01% by weight, the abrasion resistance may be insufficient, and if it exceeds 50% by weight, the hardness of the cured product may be insufficient.

(2) Fluorinated Surfactant (b2) The fluorinated surfactant (b2) used in the present invention is used to enhance the coating properties of the composition on a substrate. The use of the surfactant (b2) unexpectedly improves the hardness of the cured product. Such a fluorosurfactant is not particularly limited as long as it is a nonionic fluorosurfactant and / or an anionic fluorosurfactant, but is not particularly limited in view of solubility in a solvent. Systems are preferred. Specifically, manufactured by Dainippon Ink and Chemicals, Inc.
F-142D, F-144D, F-171, F-17
2, F-173, F-177, F-178A,
F-178K, F-179, F-179A, F-18
3, F-184, F-191, F-812,
Product name: EFTOP E manufactured by Tochem Products Co., Ltd.
F-101, EF-121, EF-122B, EF
-122C, EF-122A3, EF-121,
EF-123A, EF-123B, EF-126,
EF-127, EF-301, EF-302, E
F-351, EF-352, EF-601, EF-
801 and EF-802.

The amount of the fluorine-based surfactant (b2) used in the present invention is 0.0001 to 5% by weight based on 100% by weight of the composition [total of (A) and (B)]. Is preferable, and 0.001 to 3% by weight is more preferable. If the amount is less than 0.0001% by weight or more than 5% by weight, the hardness of the cured product may be insufficient.

(3) Thermoplastic polymer (b3) The thermoplastic polymer (b3) used in the present invention is used for imparting low curl when a cured product (film) is formed. The thermoplastic polymer (b3) is not particularly limited as long as it has a glass transition temperature of 40 ° C. or higher. For example, polystyrene, polymethyl (meth) acrylate,
Polyamide, polyamide imide, polyester, styrene butadiene copolymer resin, xylene resin, ketone resin,
Acrylonitrile styrene copolymer resin, methyl (meth)
Acrylate styrene copolymer resin, norbornene resin,
Epoxy resins and the like can be mentioned. Among them, polymethyl (meth) acrylate and methyl (meth) acrylate styrene copolymer resin are preferable.

The thermoplastic polymer (b) used in the present invention
The amount of 3) is preferably 1 to 50% by weight, more preferably 2 to 30% by weight, based on 100% by weight of the composition [sum of (A) and (B)]. The amount is 1
If the amount is less than 10% by weight, the low curl property of the cured product (film) may be insufficient, and if it exceeds 50% by weight, the hardness of the cured product may be insufficient.

These (b1), (b2) and (b3)
Can be used alone or in combination of two or more.

3. Compound (C) The compound (C) used in the present invention is a compound containing two or more polymerizable unsaturated groups. This compound (C) is suitably used for enhancing the film forming property of the composition. The compound (C) is not particularly limited as long as it contains two or more polymerizable unsaturated groups, and examples thereof include (meth) acrylic esters and vinyl compounds. Among them, (meth) acrylic esters are preferred. Hereinafter, specific examples of the compound (C) used in the present invention are listed.
(Meth) acrylic esters include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate Acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-butanediol di ( (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, and their starting alcohols Poly (meth) acrylates of ethylene oxide or propylene oxide adducts, oligoester (meth) acrylates having two or more (meth) acryloyl groups in the molecule, oligoether (meth) acrylates, oligourethane (meth) Examples include acrylates and oligoepoxy (meth) acrylates. Of these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylolpropanetetra (meth) acrylate are preferred. Examples of the vinyl compounds include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether.

Commercially available products of such a compound (C) include, for example, trade names: Aronix M-400, M-408, M-450, M-305, manufactured by Toagosei Co., Ltd.
M-309, M-310, M-315, M-32
0, M-350, M-360, M-208, M-21
0, M-215, M-220, M-225, M
-233, M-240, M-245, M-26
0, M-270, M-1100, M-1200, M-
1210, M-1310, M-1600, M-221,
M-203, TO-924, TO-1270, TO-1
231, TO-595, TO-756, TO-123
1, TO-1343, TO-902, TO-904, T
O-905, TO-1330, manufactured by Nippon Kayaku Co., Ltd. Trade name: KAYARAD D-310, D-330, DPH
A, DPCA-20, DPCA-30, DPCA-6
0, DPCA-120, DN-0075, DN-247
5, SR-295, SR-355, SR-399E, S
R-494, SR-9041, SR-368, SR-4
15, SR-444, SR-454, SR-492, S
R-499, SR-502, SR-9020, SR-9
035, SR-111, SR-212, SR-213,
SR-230, SR-259, SR-268, SR-2
72, SR-344, SR-349, SR-601, S
R-602, SR-610, SR-9003, PET-
30, T-1420, GPO-303, TC-120
S, HDDA, NPGDA, TPGDA, PEG400
DA, MANDA, HX-220, HX-620, R-
551, R-712, R-167, R-526, R-5
51, R-712, R-604, R-684, TMPT
A, THE-330, TPA-320, TPA-33
0, KS-HDDA, KS-TPGDA, KS-TMP
TA, manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate PE-4A, DPE-6A, DTMP-4A and the like.

The compounding amount of the compound (C) used in the present invention is preferably 5 to 900 parts by weight based on 100 parts by weight of the composition [total of (A) and (B)].
More preferred is 10 to 250 parts by weight. If the amount is less than 5 parts by weight, the cured product may have insufficient hardness. If the amount is more than 900 parts by weight, the cured product may have insufficient curl. The composition of the present invention may contain, in addition to the compound (C), a compound having one polymerizable unsaturated group in the molecule, if necessary.

4. Polymerization initiator (D) In the present invention, if necessary, the above (A) and (B)
And (D) a polymerization initiator as a compounding component other than the component (C). First, a method for curing the composition of the present invention including the use of the polymerization initiator (D) will be described.

The compositions of the present invention are cured by heat and / or radiation. When using heat, for example, an electric heater, an infrared lamp, hot air or the like can be used as the heat source. In the case of radiation, the radiation source is not particularly limited as long as the composition can be cured in a short time after coating, but as the infrared radiation source, for example, a lamp, a resistance heating plate, Lasers, etc., as visible light sources, for example, sunlight, lamps, fluorescent lamps, lasers, etc., and as UV ray sources, for example, mercury lamps, halide lamps, lasers, etc. As the radiation source, for example, a system using thermoelectrons generated from a commercially available tungsten filament, a cold cathode system generated by applying a high voltage pulse to a metal, and a system generated by collision of ionized gaseous molecules with a metal electrode 2 A secondary electron system using a secondary electron can be used. Alpha, base - as a source of data lines and gamma rays, for example, include fissile material, such as Co ^60, for gamma rays can utilize a vacuum tube or the like which causes accelerated electrons to collide with an anode. These radiations may be irradiated alone or in combination of two or more, or one or more radiations may be irradiated at a fixed time interval. A polymerization initiator (D) may be added to the composition of the present invention in order to shorten the curing time, and such a polymerization initiator (D), for example, generates an active radical species thermally. Commonly used compounds such as compounds and compounds that generate active radical species upon irradiation with radiation can be mentioned.

In the present invention, it is preferable to use a radiation polymerization initiator as the polymerization initiator (D). Among them, (d) aryl ketones having 1-hydroxycyclohexyl group and aryl ketones having N-morpholino group It is more preferable to use a radiation polymerization initiator containing both or either of ketones (hereinafter, sometimes referred to as “radiation polymerization initiator (d)”). When only an aryl ketone having a 1-hydroxycyclohexyl group is added, a cured product with less coloring can be formed in a short time. On the other hand, when only an aryl ketone having an N-morpholino group is added, a cured product having a high surface hardness can be formed in a short time. When both are used together, a cured product having high surface hardness and little coloring can be formed in a short time.

The aryl ketone having a 1-hydroxycyclohexyl group is not particularly limited.
1-hydroxycyclohexyl phenyl ketone, 1-hydroxycyclohexyl isopropyl phenyl ketone,
Examples thereof include 1-hydroxycyclohexyl decyl phenyl ketone. The N used in the present invention
The aryl ketone having a morpholino group is not particularly limited. For example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-
1,2-methyl-1- [4- (methoxy) phenyl]-
2-morpholinopropanone-1, 2-methyl-1-
[4- (2-hydroxyethoxy) phenyl] -2-morpholinopropanone-1,2-methyl-1- [4-
(Dimethylamino) phenyl] -2-morpholinopropanone-1,2-methyl-1- [4- (diphenylamino) phenyl] -2-morpholinopropanone-1,2
-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,3,6-bis (2-methyl-2-morpholinopropionyl) -9-N-octylcarbazole and the like. it can. These radiation polymerization initiators (d) may be used alone or in combination of two or more. However, when a cured product is obtained, the curing speed and hardness of both the surface portion and the inside are improved. Therefore, it is preferable to use a combination of an aryl ketone having a 1-hydroxycyclohexyl group and an aryl ketone having an N-morpholino group. Commercial products of such a radiation polymerization initiator (d) include, for example,
Product name: Ciba Specialty Chemicals Co., Ltd.
Irgacure 184, 907 and the like.

The amount of the radiation polymerization initiator (d) optionally used in the present invention is 0.01 to 20 parts by weight based on 100 parts by weight of the composition (total of (A) and (B)).
It is preferable to mix by weight, more preferably 0.1 to 10 parts by weight. If the amount is less than 0.01 part by weight, the hardness of the cured product may be insufficient,
If the amount exceeds the weight part, the cured product may not be cured to the inside (lower layer).

When an aryl ketone having a 1-hydroxycyclohexyl group and an aryl ketone having an N-morpholino group are used in combination, the mixing ratio of both is preferably from 10:90 to 90:10 by weight. 40: 6
0 to 80:20 is more preferable.

5. Components other than those described above In the present invention, various components other than those described above such as a sensitizer, a solvent, oxide particles other than the crosslinkable particles (A), various additives, and the like may be added as necessary. Can be. Less than,
Examples are listed. (1) Sensitizer Examples of the sensitizer include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, -Isoamyl dimethylaminobenzoate. Commercial products of this sensitizer include KAYACURE DMBI, EP, manufactured by Nippon Kayaku Co., Ltd.
A and the like.

(2) Solvent In addition to the above-mentioned dispersion solvent, a solvent can be added after the composition is prepared for the purpose of improving coating properties, adjusting viscosity, adjusting solid content concentration, and the like. As the solvent, the same solvent as that used as the dispersion solvent can be used.

(3) Oxide particles other than the crosslinkable particles (A) Examples of the oxide particles other than the crosslinkable particles (A) include:
Oxide particles that are not bonded to an organic compound can be given.

(4) Various additives Examples of additives include antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, antioxidants, thermal polymerization inhibitors, coloring agents, leveling agents, and surfactants. And storage stabilizers, plasticizers, lubricants, inorganic fillers, organic fillers, fillers, wettability improvers, coating surface improvers, and the like.

Commercially available antioxidants include Irganox 1010, 1035, 1076, 1222 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), and UV absorbers include Ciba Specialty Chemicals. Chemicals Co., Ltd. Product name: Tinuvin P, 2,
34, 320, 326, 327, 328, 213, 40
0, manufactured by Sumitomo Chemical Co., Ltd. Product name: Sumisorb 11
0, 130, 140, 220, 250, 300, 32
0, 340, 350, 400 and the like. Commercially available light stabilizers are trade names of Tinuvin 292, 144, 62 manufactured by Ciba Specialty Chemicals Co., Ltd.
2LD, manufactured by Sankyo Chemical Industry Co., Ltd. Product name: SANOL LS
−770, 765, 292, 2626, 1114, 74
4 and the like, and examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane.
These commercially available products are trade names: SH6062, SZ603 manufactured by Dow Corning Toray Silicone Co., Ltd.
0, manufactured by Shin-Etsu Silicone Co., Ltd.
KBM803 and the like, and as a commercially available anti-aging agent, trade name: Antigen W, S, P, 3C, 6C, RD-G, FR, AW manufactured by Sumitomo Chemical Co., Ltd.
And the like.

(5) Additives Other than the Above Additives other than the above include epoxy resin, polyamide, polyimide, polyamideimide, polyurethane, polybutadiene, chloroprene, polyether, polyester, pentadiene derivative, styrene / butadiene / styrene block copolymer. Polymer, styrene / ethylene / butene / styrene block copolymer, styrene / isoprene /
Styrene block copolymer, petroleum resin, xylene resin,
Examples include polymers or oligomers such as ketone resins, fluorine oligomers, silicone oligomers, and polysulfide oligomers.

The composition of the present invention is suitable as a coating material. Examples of the substrate to be coated include plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, Triacetyl cellulose, ABS, AS, norbornene resin), metal, wood, paper, glass, slates and the like. The shape of these substrates may be plate-like, film-like or three-dimensionally formed, and the coating method is a usual coating method such as a dipping core.
Coating, spray coating, flow coating, shower coating,
Roll coating, spin coating, brush coating and the like can be mentioned. The thickness of the coating in these coatings,
After drying and curing, the thickness is usually 0.1 to 400 μm, preferably 1 to 200 μm.

The composition of the present invention can be used after being diluted with a solvent from the viewpoint of workability. For example, the viscosity when used as a coating material is usually 0.1 to 50,000 mPa.
S / 25 ° C., preferably 0.5 to 10,000
mPa · s / 25 ° C.

II. Cured Product The cured product of the present invention can be obtained by coating the resin composition on various substrates, for example, a plastic substrate and curing the resin composition. Specifically, the composition can be obtained by coating the composition, preferably drying the volatile components at 0 to 200 ° C., and then performing a curing treatment with heat or / and radiation. Preferred curing conditions in the case of heat are 20 to 150 ° C., and 10 seconds to
Performed within 24 hours. When using radiation, it is preferable to use ultraviolet rays or electron beams. In such a case, the preferable irradiation amount of ultraviolet light is 0.01 to 10 J / c.
m ² , and more preferably 0.1 to ² J / cm ² . In addition, preferable electron beam irradiation conditions are as follows.
0-300 KV, electron density 0.02-0.30 mA /
cm ^2, and electron beam irradiation amount is 1～10Mrad.

The cured product of the present invention has hardness, scratch resistance, low curl, adhesion and transparency, especially hardness and low curl.
It has excellent characteristics to prevent scratches (scratch) and contamination of plastic optical parts, touch panels, film-type liquid crystal elements, plastic containers, flooring materials, wall materials, artificial marble, etc. as building interior materials. Protective coating materials (especially plastic sheets that require transparency,
It is suitably used as a hard coat material such as a plastic film. ); It is suitably used as an adhesive for various substrates, a sealing material, a binder material for printing ink, and the like. Furthermore, front plates of various displays such as a cathode ray tube, a laser display, a photochromic display, an electrochromic display, a liquid crystal display, a plasma display, a light emitting diode display, and an electroluminescent panel, or input device parts thereof, and other cover cases. It can be widely used for applications such as front covers, optical lenses, spectacle lenses, windshields, light covers, and helmet shields.

[0083]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following, parts and% indicate parts by weight and% by weight, respectively, unless otherwise specified. In the present invention, the “solid content” means a portion obtained by removing a volatile component such as a solvent from the composition, and specifically, is obtained by drying the composition on a hot plate at 120 ° C. for 1 hour. It means a residue (non-volatile component).

Synthesis of Organic Compound Synthesis Example 1 A solution consisting of 7.8 parts of mercaptopropyltrimethoxysilane and 0.2 parts of dibutyltin dilaurate in dry air was stirred at 50 ° C. while stirring 20.6 parts of isophorone diisocyanate. After dropwise addition over 1 hour, the mixture was stirred at 60 ° C. for 3 hours. After dropwise adding 71.4 parts of pentaerythritol triacrylate at 30 ° C. over 1 hour, 6
The organic compound (S1) was obtained by heating and stirring at 0 ° C. for 3 hours. The infrared absorption spectrum of the product showed that the absorption peak of 2550 Kaiser characteristic of the mercapto group and the absorption peak of 2260 Kaiser characteristic of the isocyanate group in the raw material disappeared, and [ 1660 characteristic of -OC (= O) -NH-] and [-SC (= O) -NH-] groups.
172 characteristic of peak and acryloyl groups of Kaiser
A peak of 0 Kaiser was observed, and an acryloyl group and a [—S—C (＝ O) —NH—] group as a polymerizable unsaturated group,
It was shown that an organic compound having both [-OC (= O) -NH-] groups was formed.

Synthesis Example 2 Mercaptopropyltrimethoxysilane 3 in dry air
To a solution consisting of 8.4 parts and 0.2 parts of dibutyltin dilaurate, 38.7 parts of 1,3-bis (isocyanatomethyl) cyclohexane was added dropwise with stirring at 50 ° C. over 1 hour. The mixture was heated and stirred at ℃ for 3 hours. This is 2
After dropping 22.7 parts of -hydroxyethyl acrylate over 1 hour at 30 ° C, the mixture was heated and stirred at 60 ° C for 10 hours to obtain an organic compound (S2). Analysis of the amount of residual isocyanate in the product was 0.1% or less, indicating that the reaction was almost quantitatively completed.

Production of Crosslinkable Particles (A) Hereinafter, Production Examples of the crosslinkable particles (A) are shown in Production Examples 1 to 4, and the results are summarized in Table 1.

Production Example 1 Organic compound (S1) synthesized in Synthesis Example 1 under a nitrogen stream
8.7 parts, methyl ethyl ketone silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-ST, number-average particle size: 0,1)
91.3 parts (solid content 2)
7.39 parts), a mixed solution of 0.2 parts of isopropanol and 0.1 parts of ion-exchanged water were stirred at 80 ° C. for 3 hours, and 1.4 parts of orthoformic acid methyl ester was added. By heating and stirring, a colorless and transparent crosslinkable particle (A) dispersion (dispersion a) was obtained. After weighing 2 g of the dispersion a in an aluminum dish, drying it on a hot plate at 120 ° C. for 1 hour and weighing it, the solid content was determined to be 35%.

Production Example 2 Organic compound (S2) synthesized in Synthesis Example 2 under a nitrogen stream
8.3 parts, methyl ethyl ketone silica sol (MEK
-ST) A mixed solution of 91.7 parts (solid content 27.51 parts) and ion-exchanged water 0.8 parts was stirred at 80 ° C for 3 hours,
4.9 parts of orthoformic acid methyl ester were added, and one more part was added.
By heating and stirring at the same temperature (80 ° C.) for a period of time, a translucent crosslinkable particle (A) dispersion (dispersion b) was obtained. The solid content of this dispersion liquid b was determined in the same manner as in Production Example 1 to find that it was 34.
%Met.

Production Example 3 92.5 parts of methanol-alumina sol (number-average particle diameter 0.0075 μm, alumina concentration 30%, water content 5.6%) produced by replacing aqueous alumina sol (produced by C-I Kasei Co., Ltd.) with a solvent. (Solid content: 27.75 parts), a mixture of 7.5 parts of the organic compound (S1) synthesized in Synthesis Example 1 and 0.01 parts of p-methoxyphenol was stirred at 60 ° C. for 3 hours, and then methyl orthoformate was added. 1.3 parts and 41.2 parts of methanol were added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain a dispersion of the crosslinkable particles (A) (dispersion c).
The solid content of this dispersion c was determined in the same manner as in Production Example 1, and found to be 25%.

Production Example 4 8.2 parts of organic compound (S1) synthesized in Synthesis Example 1, 91.8 parts of toluene zirconia sol (number average particle diameter 0.05 μm, zirconia concentration 30%) (solid content 27.54)
Part) and 0.1 part of ion-exchanged water were stirred at 60 ° C. for 3 hours, then 1.3 parts of orthoformic acid methyl ester and 41.2 parts of methyl ethyl ketone were added, and the mixture was further heated and stirred at the same temperature for 1 hour. Thus, a dispersion of the crosslinkable particles (A) (dispersion d) was obtained. The solid content of this dispersion d was determined in the same manner as in Production Example 1, and found to be 25%.

[0091]

[Table 1] () ^* Indicates the amount of solid content. P1: Methyl ethyl ketone silica sol P2: Methanol alumina sol P3: Toluene zirconia sol

Synthesis of Polyfunctional Urethane Compound Synthesis Example 3 Pentaerythritol triacrylate 7 in dry air
To a solution consisting of 1.4 parts and 20.6 parts of isophorone diisocyanate was added 0.2 parts of dibutyltin dilaurate, and the mixture was stirred at room temperature for 1 hour and at 50 ° C. for 3 hours. Pentaerythritol triacrylate 7
After dropping 1.4 parts over 1 hour, the mixture was heated and stirred at 60 ° C. for 3 hours to obtain a polyfunctional urethane compound (b1-1). Analysis of the amount of residual isocyanate in the product was 0.1% or less, indicating that the reaction was almost quantitatively completed.

Synthesis Example 4 Pentaerythritol triacrylate 7 in dry air
1.4 parts, 2,4-tolylene diisocyanate 16.1
Parts of a solution consisting of 0.1 parts of dibutyltin dilaurate.
Two parts were added, and the mixture was stirred at room temperature for 1 hour and at 50 ° C. for 3 hours. To this, 71.4 parts of pentaerythritol triacrylate was added dropwise over 1 hour, and the mixture was heated and stirred at 60 ° C. for 3 hours to obtain a polyfunctional urethane compound (b1-2). Analysis of the amount of residual isocyanate in the product was 0.1% or less, indicating that the reaction was almost quantitatively completed.

Preparation of Composition Hereinafter, preparation examples of the composition of the present invention are shown in Examples 1 to 8,
Comparative preparation examples are shown in Comparative Examples 1 and 2. Table 2 shows the weight ratio of each component. Example 1 257 parts of the dispersion a produced in Production Example 1 (crosslinkable particles 90) were placed in a container shielded from ultraviolet light under a stream of dry air.
Parts), fluorinated surfactants (Dainippon Ink Co., Ltd.)
(Product name: Megafac F-179, solid content 20%)
5 parts (solid content 0.5 part), 9.5 parts of thermoplastic polymer (trade name: Acrypet VH (manufactured by Mitsubishi Rayon Co., Ltd., glass transition temperature 115 ° C., measurement method: in accordance with JIS K7121)), dipenta 80 parts of erythritol hexaacrylate, 1.5 parts of 1-hydroxycyclohexyl phenyl ketone, and 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone-1
1.5 parts was stirred at 50 ° C. for 2 hours to obtain a homogeneous solution composition.

By the same operation method, Example 2 shown in Table 2 was used.
To 8 and Comparative Examples 1 and 2 were obtained.

Evaluation of Cured Product In order to clarify the effects of the composition of the present invention, a cured product obtained by applying, drying and irradiating the above composition was evaluated. The evaluation method is described below. Table 2 shows the evaluation results. 1. Coating, drying and curing conditions After coating the substrate with a bar coater to a dry film thickness of 10 μm, drying it in a hot air dryer at 80 ° C. for 3 minutes, and then using a conveyor type mercury lamp After irradiating with a light amount of 1 J / cm ² using, it was evaluated after storage at 25 ° C. for 24 hours. 2. Substrate In a pencil hardness test, a glass plate,
A polyethylene terephthalate (PET) film having a thickness of 188 μm was used for evaluation of transparency, scratch resistance to steel wool, adhesion, and curl. 3. Evaluation method-Appearance of coating film: Transparency and occurrence of abnormalities such as uneven coating, repelling, foreign matter, white turbidity, and devitrification were visually determined. The case where the film was transparent and there was no abnormality in the coating film was evaluated as “O”, and the case where one or more foreign substances were present or an abnormality occurred was evaluated as “Poor”. Pencil hardness: The coating cured on a glass substrate was evaluated according to JIS K5400. Adhesion (%): Evaluated based on the cross-cut cellophane tape peeling test in JIS K5400, 1 mm square, remaining film ratio in a total of 100 cross-cuts.・ Steel wool (SW) abrasion resistance: A gakushin type abrasion resistance tester manufactured by Tester Sangyo Co., Ltd. was reciprocated 30 times with # 0000 steel wool with a load of 500 g, and the scratched state of the tested coating film surface was evaluated. It was evaluated visually. The case without scratches was evaluated as ○, the case with 1 to 10 scratches as Δ, and the case with more than 10 scratches as X.・ Curl (mm): The composition of the present invention was formed on PET having a thickness of 188 μm immediately after film formation under the above-mentioned application and curing conditions, and cut into 10 cm × 10 cm pieces with a cutter knife.
After standing at 50 ° C. and a relative humidity of 50% for 24 hours, the average value (mm) of the amounts of warpage of the four corners from the reference plane was determined.

[0097]

[Table 2] () ^* Indicates the amount of solid content. P1: methyl ethyl ketone silica sol M1: dipentaerythritol hexaacrylate M2: pentaerythritol tetraacrylate R1: 1-hydroxycyclohexyl phenyl ketone R2: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1

[0098]

Industrial Applicability According to the present invention, it has excellent curability and excellent hardness, scratch resistance, low curl, adhesion and transparency, especially hardness and low curl, on the surface of various substrates. And a cured product thereof capable of forming a cured film. Since the resin composition of the present invention and the cured product thereof have such properties, for example, plastic optical components, touch panels, film-type liquid crystal elements,
Protective coating materials to prevent scratches (scratch) and contamination of plastic containers, floor materials as building interior materials, wall materials, artificial marble, etc .; adhesives for various substrates, sealing materials;
It can be suitably used as a binder for printing ink.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yuichi Eriyama 2-11-24 Tsukiji, Chuo-ku, Tokyo JAE SRL Inc. (72) Inventor Isao Nishiwaki 2-11-24 Tsukiji, Chuo-ku, Tokyo Jae Within Sear Co., Ltd. (72) Inventor Takashi Ukaji 2-11-24 Tsukiji, Chuo-ku, Tokyo JEar S.S.R. Co., Ltd. F-term (reference) EP017 ER007 ET017 EU238 EV087 FB086 FD016 FD017 FD158

Claims (10)

[Claims] (A) silicon, aluminum, zirconium, titanium, zinc, germanium, indium,
Particles obtained by bonding oxide particles of at least one element selected from the group consisting of tin, antimony and cerium with an organic compound containing a polymerizable unsaturated group and a group represented by the following formula (1): 1) [In the formula (1), X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. (B) A resin composition containing at least one selected from the following (b1), (b2) or (b3): (B1) having two or more (meth) acryloyl groups in the molecule and having a molecular weight of 4 per (meth) acryloyl group;
00 and not less than 2 and [-OC (= O) -N
(B-2) Fluorosurfactant (b3) Thermoplastic polymer having a glass transition temperature of 40 ° C. or more 2. The method according to claim 1, wherein the organic compound is [-OC (= O)-
NH-] group, and further comprises [-OC (= S) -NH
The resin composition according to claim 1, wherein the resin composition contains at least one of a-] group and a -S-C (= O) -NH-] group. 3. The resin composition according to claim 1, wherein the organic compound is a compound having a silanol group or a compound that forms a silanol group by hydrolysis. 4. The method of claim 1, wherein (b1) in (B) is a urethane (meth) acrylate obtained by reacting 2 mol of an active hydrogen-containing polymerizable unsaturated compound with 1 mol of a diisocyanate represented by the following formula (3). Item 3. The resin composition according to item 1 or 2. Embedded image R ⁶ —OC (＝ O) —NH—R ⁷ —NHCOO—R ⁸ (3) [In the formula (3), R ⁶ and R ⁸ are derived from an active hydrogen-containing polymerizable unsaturated compound (meth) ) An organic group containing an acryloyl group,
R ⁷ represents a divalent organic group derived from diisocyanate. ] 5. The resin composition according to claim 1, wherein (b2) in (B) is a nonionic fluorosurfactant and / or an anionic fluorosurfactant. 6. A method according to claim 1, wherein (b3) in (B) is polystyrene,
Polymethyl (meth) acrylate, polyamide, polyamide imide, polyester, styrene butadiene copolymer resin, xylene resin, ketone resin, acrylonitrile styrene copolymer resin, methyl (meth) acrylate styrene copolymer resin, norbornene resin and epoxy resin The resin composition according to claim 1, which is at least one selected from the group consisting of: 7. The resin according to claim 1, further comprising (C) a compound containing two or more polymerizable unsaturated groups in a molecule, in addition to (A) and (B). Composition. 8. The method according to claim 1, which further comprises (D) a polymerization initiator.
The resin composition according to any one of the above. 9. The polymerization initiator (D) is either (d) an aryl ketone having a 1-hydroxycyclohexyl group and / or an aryl ketone having an N-morpholino group, or a radiation polymerization initiator thereof. The resin composition according to claim 8. 10. A cured product obtained by curing the resin composition according to claim 1.