JP2001302943A - Reactive particle, curable composition containing the same, and cured item obtained therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide reactive particles which are used for preparing a curable composition which is excellent in applicability and can form a coating film (a cured film) excellent in hardness, scratch resistance, abrasion resistance, low curling properties, adhesiveness, clarity, chemical resistance, and surface appearance, especially in hardness, scratch resistance, low curling properties, and adhesiveness; a curable composition containing the particles; and a cured item thereof. SOLUTION: The reactive particles are prepared by bonding (b-1) an organic compound having a free-radical-generating group and a hydrolyzable group to (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.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a reactive particle, a curable composition containing the same, and a cured product thereof. More specifically, it has excellent coating properties, and various substrates [for example,
Plastics (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, etc.), metal, wood, Paper, glass, slates, etc.] with excellent hardness, scratch resistance, abrasion resistance, low curl, adhesion and chemical resistance, especially hardness, scratch resistance, low curl, The present invention relates to reactive particles used in a curable composition capable of forming a coating film (cured film) having excellent adhesion, a curable composition containing the particles, and a cured product thereof. The curable composition containing the reactive particles of the present invention and the cured product thereof include, for example, plastic optical components, touch panels, film-type liquid crystal elements, plastic containers, flooring materials as building interior materials, wall materials, artificial marble, etc. Hard coating material to prevent scratches (scratch) and contamination; adhesives for various substrates;
Sealing material; can be suitably used as a binder material for printing ink, and the like.

[0002]

2. Description of the Related Art In recent years, various substrate surfaces have been scratched (scratched).
Hard coating material for prevention, contamination prevention and anti-reflection, etc .; adhesives and sealing materials for various substrates; excellent coating properties as a binder material for printing ink; A curable composition capable of forming a cured film having excellent hardness, scratch resistance, abrasion resistance, low curl, adhesion, transparency, chemical resistance and appearance of the coating surface on the surface is required. Have been.

[0003] Various compositions have been proposed to satisfy such demands. However, they have excellent coating properties as a curable composition, and when formed into a cured film, have a high hardness, abrasion resistance,
At present, a material having characteristics such as excellent wear resistance, low curl, adhesion and chemical resistance has not yet been obtained. For example, Japanese Patent Publication No. Sho 62-21815 proposes to use a composition of acrylate and particles obtained by modifying the surface of colloidal silica with methacryloxysilane as a radiation (light) curable coating material. Have been. This type of radiation-curable composition has recently been widely used because of its excellent coating properties. However, in order to cure such a composition, it is usually necessary to use a low molecular weight polymerization initiator. In the case of a cured product, the polymerization initiator remains in the cured product, and the hardness and scratch resistance There is a problem that characteristics such as wear resistance and abrasion resistance are adversely affected.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has excellent coating properties, and has a hardness, abrasion resistance, and abrasion resistance on the surface of various substrates. Coating, excellent in hardness, low curl, adhesion, transparency, chemical resistance, and appearance of coating surface, especially, coating with excellent hardness, scratch resistance, low curl, and adhesion It is an object of the present invention to provide reactive particles used in a curable composition capable of forming a film, a curable composition containing the particles, and a cured product thereof.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, (a) oxide particles of a specific element have been added to (b-1) radical-generating groups in the molecule. The present inventors have found that a curable composition that satisfies all of the above-mentioned properties can be obtained by using reactive particles formed by bonding an organic compound having a hydrolyzable group, and the present invention.
That is, the present invention provides the following reactive particles, a curable composition containing the particles, and a cured product 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;
Reactive particles comprising an organic compound having a radical-generating group and a hydrolyzable group in the molecule.

[2] In addition to the organic compound of the component (b-1), a radical polymerizable unsaturated group and a hydrolyzable group in the molecule are added to the oxide particles of the component (a). The reactive particle according to the above [1], which is formed by binding an organic compound having the following.

[3] The reactive particle according to the above [1] or [2], wherein the organic compound as the component (b-1) is a compound having a silanol group or a compound which forms a silanol group by hydrolysis.

[4] The organic compound (b-1) is a compound having a monovalent organic group represented by the following formula (1) or (2) or any one of the formulas (1) to (1).
The reactive particle according to any one of [3].

[0010]

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[0011]

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[5] The organic compound (b-2) is a compound having a silanol group or a compound that forms a silanol group by hydrolysis.
The reactive particles according to any one of [4].

[6] The organic compound as the component (b-2) contains a [-OC (= O) -NH-] group,
[-OC (= S) -NH-] group and [-SC (=
O) The reactive particle according to any one of [2] to [5], which has at least one of -NH-] group.

[7] The reactive particles (reactive particles (A)) according to any one of the above [1] to [6] in 5 to 80% by weight based on 100% by weight of the total solid content of the curable composition. , And (B)
Compounds having two or more polymerizable unsaturated groups in the molecule
A curable composition containing 95% by weight.

[8] The reactive particles (reactive particles (A)) according to any one of the above [1] to [6] and the above-mentioned (a) in 100% by weight of the total solid content of the curable composition. Mixture 5 to 80 of crosslinkable particles (crosslinkable particles (C)) obtained by bonding the organic compound of component (b-2) to the oxide particles of component (b).
Curable composition comprising, by weight, (B) 20 to 95% by weight of a compound having two or more polymerizable unsaturated groups in the molecule.

[9] A cured product obtained by curing the curable composition according to [7] or [8].

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the reactive particles (hereinafter sometimes referred to as “reactive particles (A)”) of the present invention, curable compositions containing the particles, and cured products thereof will be described below. This will be specifically described. I. Reactive Particle (A) The reactive particle (A) of the present invention comprises (a) at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. Oxide particles (hereinafter sometimes referred to as “oxide particles (a)” or “component (a)”) are provided with (b-1) an organic compound having a radical-generating group and a hydrolyzable group in a molecule (hereinafter referred to as “organic compound”) , "Organic compound (b-1)" or "(b-1) component") and, if necessary, (b-2) a radically polymerizable unsaturated group and a hydrolyzable group in the molecule. Organic compound (hereinafter, sometimes referred to as “organic compound (b-2)” or “component (b-2) component”). Hereinafter, each component will be specifically described.

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

Examples of these oxide particles (a) include silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide,
Examples include particles of indium tin oxide (ITO), antimony oxide, cerium oxide, and the like. Among them, silica, alumina, zirconia and antimony oxide particles are preferable from the viewpoint of high hardness. These can be used alone or in combination of two or more. Further, the oxide particles (a) 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. Such organic solvents include, for example, methanol, ethanol, isopropanol, butanol,
Alcohols such as octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate;
Esters such as γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide ,
Amides such as dimethylacetamide and N-methylpyrrolidone can be mentioned. Among them, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

The number average particle diameter of the oxide particles (a) is 0.1.
001 μm to 2 μm is preferable, and 0.001 μm to 0.
2 μm is more preferable, and 0.001 μm to 0.1 μm
Is particularly preferred. 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. Various surfactants and amines may be added to improve the dispersibility of the particles.

Silicon oxide particles (eg, silica particles)
As commercially available products, for example, as colloidal silica, Nissan Chemical Industries, Ltd. product name: methanol silica sol, IPA-ST, MEK-ST, NB
A-ST, XBA-ST, DMAC-ST, ST-U
P, 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 300, Aerosil 380, Aerosil TT60 manufactured by Nippon Aerosil Co., Ltd.
0, Aerosil OX50, manufactured by Asahi Glass Co., Ltd. Brand name: Sildex H31, H32, H51, H52, H12
1, H122, manufactured by Nippon Silica Industry Co., Ltd. Product name: E2
20A, E220, manufactured by Fuji Silysia K.K.
YLYSIA470, manufactured by Nippon Sheet Glass Co., Ltd .: SG
Flakes and the like.

Examples of the aqueous dispersion of alumina include alumina sol-100, manufactured by Nissan Chemical Industries, Ltd.
200, -520; As alumina isopropanol dispersion, a product name: AS-, manufactured by Sumitomo Osaka Cement Co., Ltd.
150I; As a toluene dispersion of alumina, manufactured by Sumitomo Osaka Cement Co., Ltd .; trade name: AS-150T; As a zirconia dispersion of toluene, manufactured by Sumitomo Osaka Cement Co., Ltd .; trade name: HXU-110JC; zinc antimonate powder As a water dispersion product of Nissan Chemical Industry Co., Ltd.
Trade name: Cellnax; As powders and solvent dispersions of alumina, titanium oxide, tin oxide, indium oxide, zinc oxide, etc., manufactured by C-I Kasei Co., Ltd. Trade name: Nanotech; Antimony-doped tin oxide water dispersion sol ,
Ishihara Sangyo Co., Ltd. Product name: SN-100D; As ITO powder, a product made by Mitsubishi Materials Corporation; As a cerium oxide aqueous dispersion, Taki Chemical Co., Ltd. product name: Neidral Can be.

The shape of the oxide particles (a) is spherical, hollow,
Porous, rod-like, plate-like, fibrous, or irregular shape,
Preferably, it is spherical. The specific surface area of the oxide particles (a) (determined by a BET specific surface area measurement method using nitrogen) is preferably from 10 to 1000 m ² / g, and more preferably from 100 to 500 m ² / g. These oxide particles (a) can be used in the form of powder in a dry state or in a state of being 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) Organic Compound (b-1) The organic compound (b-1) used in the present invention is an organic compound having a radical generating group and a hydrolyzable group in the molecule. -1) has a silano-in the molecule.
Preferably, the compound is a compound having a hydroxyl group or a compound which produces a silanol group by hydrolysis.

Radical-generating group The radical-generating group contained in the organic compound (b-1) is not particularly limited. For example, a monovalent organic group represented by the formula (1) and (2) or any one of the above formulas And the like. These organic groups generate radicals by, for example, radiation. By having the radical-generating group, a composition containing the reactive particles of the present invention can obtain a cured product without using a low molecular weight polymerization initiator.

Hydrolyzable Group The hydrolyzable group contained in the organic compound (b-1) is not particularly limited, and examples thereof include a silanol group and a group that forms a silanol group by hydrolysis. . The organic compound (b-1) is a compound having a silanol group in a molecule (hereinafter referred to as a “silanol group-containing compound”).
Or a compound that produces a silanol group by hydrolysis (hereinafter referred to as "silanol group-forming compound")
Is sometimes preferred). Examples of such a silanol group-forming compound include an alkoxy group, an aryloxy group, an acetoxy group, an amino group,
A compound in which a halogen atom or the like is bonded can be given, and a compound in which an alkoxy group or an aryloxy group is bonded to a silicon atom, that is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable. The silanol group or the silanol group-forming site of the silanol group-forming compound is a constituent unit that bonds to the oxide particles (a) by a condensation reaction or a condensation reaction that occurs after hydrolysis.

Preferred Embodiment Preferred examples of the organic compound (b-1) include, for example,
The compounds represented by the formulas (3) to (8) can be exemplified.

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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The organic compound (b-) is added to the oxide particles (a).
The binding amount of 1) is the reactive particles (A) (total of oxide particles (a), organic compounds (b-1) and (b-2)).
Is 100% by weight, preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and particularly preferably 1% by weight or more. If the amount of the organic compound (b-1) bonded to the oxide particles (a) is less than 0.01% by weight, the resulting cured product may have insufficient hardness and transparency. Here, the binding amount is determined by thermogravimetric analysis from 110 to 800 ° C. as a constant value of the weight loss% when the dry powder of the reactive particles of the present invention is completely burned in air. Means the amount that can be produced. The mixing ratio of the oxide particles (a) in the raw materials at the time of producing the reactive particles (A) is preferably from 5 to 99% by weight, and more preferably from 10 to 98% by weight.

(3) Organic compound (b-2) The organic compound (b) used as required in the present invention
-2) is a compound containing a radically polymerizable unsaturated group in the molecule, containing a [-OC (= O) -NH-] group,
Furthermore, a [-OC (= S) -NH-] group and a [-S-
Preferably, it contains at least one C (１O) —NH—] group. The organic compound (b-2)
Is preferably a compound having a silanol group in the molecule or a compound which forms a silanol group by hydrolysis.

Radical polymerizable unsaturated group The radical polymerizable unsaturated group contained in the organic compound (b-2) is not particularly limited, and examples thereof include an acryloyl group, a methacryloyl group, a vinyl group, a propenyl group, a butadienyl group, Preferred examples include styryl, ethynyl, cinnamoyl, maleate and acrylamide groups. This radically polymerizable unsaturated group is a structural unit that undergoes addition polymerization using an active radical species. Organic compound (b-2) is [-OC (= O) -NH-]
And a group further including at least one of a [-OC (= S) -NH-] group and a [-SC (= O) -NH-] group. 1 type alone or 2
More than one species can be used in combination. Among them, from the viewpoint of thermal stability, a [-OC (= O) -NH-] group,
[-OC (= S) -NH-] group and [-SC (=
O) -NH-] group is preferably used in combination. These groups generate an appropriate cohesive force due to hydrogen bonding between molecules, and when cured, are considered to impart properties such as excellent mechanical strength, adhesion to a substrate, and heat resistance. .

Silanol group or group capable of forming a silanol group by hydrolysis The organic compound (b-2) may be a silanol group-containing compound or a silanol group-forming compound as in the case of the component (b-1). preferable.

Preferred Embodiment Preferred specific examples of the organic compound (b-2) include a compound represented by the following formula (9).

[0039]

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In the formula (9), R ¹ and R ² , which may be the same or different, are a hydrogen atom or a C ₁ -C ₈ alkyl or aryl group, for example, methyl, ethyl, propyl, Examples thereof include butyl, octyl, phenyl, and xylyl groups. Here, p is an integer of 1 to 3.

[0041] Examples of a group represented by _{^{[(R 1 O) p R}} 2 3-p 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. R ⁴ is a divalent organic group, and usually has a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500.
It is selected from valence organic groups. R ⁵ is a (q + 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 in its molecule a polymerizable unsaturated group that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. Also, q is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably 1 to 5
Is an integer.

The synthesis of the organic compound (b-2) optionally used in the present invention is described, for example, in JP-A-9-110011.
No. 1 can be used.

The organic compound (b-
The amount of bonding in 2) is not particularly limited as long as film formation failure does not occur or the hardness becomes insufficient when the composition is cured. The total amount of the organic compound (b-1) and the organic compound (b-2) bonded to the oxide particles (a) is determined by the amount of the reactive particles (A)
(The sum of the oxide particles (a), the organic compound (b-1) and the organic compound (b-2)) as 100% by weight, preferably 0.01% by weight or more, more preferably
It is at least 0.1% by weight, particularly preferably at least 1% by weight. If the total bonding amount to the oxide particles (a) is less than 0.01% by weight, when the composition is cured, the hardness and transparency may be insufficient. In the production of the reactive particles (A) using the organic compound (b-1) and the organic compound (b-2) in combination, the oxide particles (a) are reacted with the organic compound (b-1), and then the organic compound (b-1) is reacted. A method of reacting the compound (b-2), a method of reacting the oxide particles (a) with the organic compound (b-2) and then reacting the organic compound (b-1), or a method of reacting the oxide particles (a ) And the organic compound (b-1) and the organic compound (b-2) at the same time. Organic compound (b-) at the time of production of reactive particles (A)
1) and the compounding ratio of the organic compound (b-2) to the total of the organic compound (b-2) (b-2) / ((b-1) +
(B-2)) is preferably 0.01 to 0.9, and more preferably 0.0 to 0.9.
1-0.8 is more preferred. If the compounding ratio exceeds 0.9, the hardness of the obtained cured product may be insufficient.

II. Curable composition The curable composition of the present invention has a total solid content of 100% by weight,
5 to 80% by weight of the reactive particles (A) and (B) a compound containing two or more polymerizable unsaturated groups in the molecule (hereinafter, referred to as a compound)
"Compound (B)") 20 to 95% by weight
(Hereinafter, may be referred to as “first composition”). Further, the curable composition of the present invention has a reactivity obtained by binding only the organic compound (b-2) to the reactive particles (A) and the oxide particles (a) in 100% by weight of the total solids. 5 to 80% by weight of a mixture with particles (hereinafter, sometimes referred to as “crosslinkable particles (C)”) and compound (B)
A curable composition containing 20 to 95% by weight (hereinafter, referred to as a curable composition)
"May be referred to as a" second composition ").

1. First composition (1) Reactive particles (A) The reactive particles (A) used in the first composition include:
The foregoing can be used. The content (content) of the reactive particles (A) in the first composition is 5 to 80% by weight in the total solid content of 100% by weight of the composition (reactive particles (A) and compound (B)). %, More preferably 10 to 75% by weight. If the amount is less than 5% by weight, low curl properties may be inferior. If the amount exceeds 80% by weight, film formability may be insufficient. In this case, the reactive particles (A)
The total solid content of the composition of the oxide particles (a) constituting
The content in 0% by weight is preferably 0.25 to 79% by weight. The amount of the reactive particles (A) means the solid content as described above. When the reactive particles (A) are used in the form of a solvent-dispersed sol, the amount of the reactive particles (A) includes the amount of the solvent. Absent.

(2) Compound (B) The compound (B) used in the first composition contains 2
It is a compound containing the above polymerizable unsaturated group. Compound (B) is suitably used to enhance the film forming property of the composition. The compound (B) is not particularly limited as long as it contains two or more polymerizable unsaturated groups in the molecule, and examples thereof include (meth) acrylic esters and vinyl compounds. Among them, (meth) acrylic esters are preferred.

Hereinafter, specific examples of the compound (B) used in the first composition 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,
Diethylene 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 (B) 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-320, M
-350, M-360, M-208, M-210, M-
215, M-220, M-225, M-233, M-2
40, M-245, M-260, M-270, M-11
00, M-1200, M-1210, M-1310, M
-1600, M-221, M-203, TO-924,
TO-1270, TO-1231, TO-595, TO
-756, TO-1343, TO-902, TO-90
4, TO-905, TO-1330, manufactured by Nippon Kayaku Co., Ltd. Trade name: Kayarad D-310, D-330, DP
HA, 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.

Compound (B) used in the first composition
Of the composition [total of the reactive particles (A) and the compound (B)] is 100% by weight, and
Preferably, it is added in an amount of from 95 to 95% by weight, more preferably from 25 to 80% by weight. If it is less than 20% by weight or more than 95% by weight, a cured product having high hardness may not be obtained. The first composition may contain a compound having one polymerizable unsaturated group in the molecule, if necessary, in addition to the compound (B).

(3) Radical polymerization initiator The first composition comprises, as reactive particles, oxide particles (a)
In addition, an organic compound having a radical generating group in the molecule (b-
Since the reactive particles (A) to which 1) is bonded are used,
It is characterized in that a cured product having excellent hardness, scratch resistance and the like can be obtained without using a special radical polymerization initiator. However, if necessary, a small amount of a radical polymerization initiator (hereinafter referred to as "radical polymerization initiator") can be obtained. Initiator (D) ")
Is not prevented. Examples of such a radical polymerization initiator (D) include compounds that thermally generate active radical species (thermal polymerization initiators) and compounds that generate active radical species by irradiation of radiation (light) (radiation, etc.). (Light) polymerization initiators) which are widely used.

The radiation (light) polymerization initiator is not particularly limited as long as it is decomposed by light irradiation to generate a radical to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexylphenyl Ketone, 2,2-dimethoxy-
1,2-diphenylethan-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,
4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1-
(4-Isopropylphenyl) -2-hydroxy-2-
Methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1
-[4- (methylthio) phenyl] -2-morpholino-
Propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-
1,4- (2-hydroxyethoxy) phenyl- (2-
(Hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide,
Bis- (2,6-dimethoxybenzoyl) -2,4,4
-Trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like.

Commercially available radiation (light) polymerization initiators include, for example, Ciba Specialty Chemicals Co., Ltd.
Product name: Irgacure 184, 369, 651, 50
0, 819, 907, 784, 2959, CGI 170
0, CGI1750, CGI1850, CG24-6
1, Darocur 1116, 1173, manufactured by BASF
Product name: Lucirin TPO, manufactured by UCB Company name: Jubecryl P36, manufactured by Fratteris Lamberti Company Name: Ezacure KIP150, KIP65LT, K
IP100F, KT37, KT55, KTO46, KI
P75 / B and the like.

When the composition of the present invention is cured, a photopolymerization initiator and a thermal polymerization initiator can be used in combination, if necessary. Preferred thermal polymerization initiators include, for example, peroxides and azo compounds, and specific examples include benzoyl peroxide, t-butyl-peroxybenzoate, and azobisisobutyronitrile. it can.

(4) Method of Applying (Coating) the Composition The first composition is suitable for use as a coating material or an antireflection film. As a substrate to be coated or antireflection, for example, a plastic ( Polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin,
Epoxy, melamine, triacetyl cellulose, AB
S, AS, norbornene resin, etc.), metal, wood, paper,
Glass, slates and the like can be mentioned. The shape of these substrates may be plate-like, film-like or three-dimensionally molded,
Examples of the coating method include ordinary coating methods such as dip coating, spray coating, flow coating, shower coating, roll coating, spin coating, and brush coating. The thickness of the coating film in these coatings after drying and curing is usually 0.1 to 400 μm, preferably 1 to 200 μm.

The first composition can be used after being diluted with a solvent in order to adjust the thickness of the coating film. For example, when used as an antireflection film or a coating material, the viscosity is usually 0.1.
The temperature is 1 to 50,000 mPa · sec / 25 ° C, preferably 0.5 to 10,000 mPa · sec / 25 ° C.

(5) Method of Curing the Composition The first composition can be cured by heat and / or radiation (light). When heat is used, 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 (light), the radiation source is not particularly limited as long as the composition can be cured in a short time after coating. For example, as an infrared radiation source, a lamp, a resistance heating plate, Commercially available as lasers, visible light sources such as sunlight, lamps, fluorescent lamps, lasers, etc., as ultraviolet ray sources, mercury lamps, halide lamps, lasers, etc., and as electron beam sources. Using a hot electron generated from a tungsten filament, a cold cathode method using a high voltage pulse to generate a metal, and a secondary electron method using a secondary electron generated by collision between ionized gaseous molecules and a metal electrode. Can be mentioned. As a source of alpha rays, beta rays and gamma rays, for example, C
can be mentioned fissionable material o ⁶⁰ such, for gamma rays can utilize a vacuum tube or the like which causes accelerated electrons to collide with an anode. These radiations can be used alone or in combination of two or more at the same time or after a certain period of time.

2. Second composition The second composition is composed of 5-80% by weight of a mixture of the reactive particles (A) and the crosslinkable particles (C) and 100-200% by weight of the compound (B) in a total solid content of 100% by weight. It contains 95% by weight. In the second composition, while the first composition uses only the reactive particles (A) as the reactive particles, the reactive particles (A) and the crosslinkable particles (C) are used as the reactive particles.
Is the same as the first composition except that a mixture of The point that the crosslinkable particles (C) are different from the reactive particles (A) is that the reactive particles (A) are added to the oxide particles (a) by an organic compound (b-1) or an organic compound (b-1). While both of the organic compounds (b-2) are combined,
The crosslinkable particles (C) are obtained by bonding the organic compound (b-2) to the oxide particles (a) without bonding the organic compound (b-1). In this case, the mixing ratio (A) / ((A) + (C)) of the reactive particles (A) to the total of the reactive particles (A) and the crosslinkable particles (C) is 0.1 to 0.1.
99 is preferable, and 0.2 to 0.99 is more preferable.
If it is less than 0.1, the hardness of the obtained cured product may be insufficient.

III. Cured Product The cured product of the present invention can be obtained by coating the curable composition on various substrates, for example, a plastic substrate and curing the composition. Specifically, after coating the composition, preferably drying the volatile components at 0 to 200 ° C., the composition can be obtained as a coated molded article by performing the above-described curing treatment with heat and / or radiation. .
The preferable curing condition by heat is 20 to 150 ° C., and the curing is performed in the range of 10 seconds to 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 / cm ² , more preferably 0.1 to ² J
/ Cm ² . Preferred electron beam irradiation conditions are:
Pressing voltage is 10-300KV, electron density is 0.02-
0.30 mA / cm ² and the amount of electron beam irradiation is 1 to 10
Mrad.

Since the cured product of the present invention has excellent characteristics of hardness, scratch resistance, adhesion, and low curl, plastic optical parts, touch panels, film type liquid crystal elements,
It is particularly suitably used as a plastic container, a floor material as a building interior material, a wall material, a hard coating material for preventing scratching (scratching), contamination and reflection of artificial marble and the like.

[0061]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited by these examples. In the following, parts and% indicate parts by weight and% by weight, respectively, unless otherwise specified. Also,
In the present invention, “solid content” means a portion obtained by removing a volatile component such as a solvent from a composition.
It means a residue (non-volatile component) obtained by drying on a hot plate at 20 ° C. for 1 hour.

Synthesis of Organic Compound (b-1) Synthesis Example 1 34.3 parts of isophorone diisocyanate in dry air
Γ-mercaptopropyltrimethoxysilane was added to a solution consisting of 0.5 part of dibutyltin dilaurate.
After dripping 4 parts at 20 ° C. over 1 hour with stirring, 60 parts were added.
Stirred at C for 1 hour. 0.1 parts of triethylamine was added thereto, and the amount of the residual isocyanate in the intermediate after stirring at 60 ° C. for 1 hour was analyzed. As a result, it was 10%, and it was confirmed that the reaction was almost completed quantitatively. Further 1-
[4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one 34.
After adding 7 parts, the mixture was heated and stirred at 60 ° C. for 3 hours to obtain an organic compound (b-1-1). 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 2 2,4-Toluene diisocyanate in dry air
Γ-mercaptopropyltrimethoxysilane 3 in a solution consisting of 2 parts and 0.1 part of dibutyltin dilaurate
After dropping over 3.0 hours at 20 ° C. while stirring 3.0 parts,
The mixture was stirred at 30 ° C. and 60 ° C. for 1 hour each. Analysis of the amount of residual isocyanate in this intermediate revealed that it was 11.3.
%, Indicating that the reaction was almost quantitatively completed. Further, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-
After adding 37.7 parts of 1-one, the mixture was heated and stirred at 60 ° C. for 3 hours to obtain an organic compound (b-1-2). 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 3 38.1 parts of isophorone diisocyanate in dry air
To a solution consisting of 0.1 part of dibutyltin dilaurate, 28.1 parts of 2-hydroxy-2-methyl-1-phenyl-propan-1-one was added dropwise with stirring at 20 ° C. for 1 hour, and then 30 ° C. Each was stirred at 60 ° C. for 1 hour. Analysis of the amount of residual isocyanate in this intermediate was 10.9%, confirming that the reaction was almost quantitatively completed. Further, after adding 33.6 parts of γ-mercaptopropyltrimethoxysilane and 0.1 part of triethylamine, the mixture was heated and stirred at 60 ° C. for 3 hours to obtain an organic compound (b-1-3). Analysis of the amount of residual isocyanate in the product was 0.1% or less, indicating that the reaction was almost quantitatively completed.

Synthesis of Organic Compound (b-2) Synthesis Example 4 20.6 parts of isophorone diisocyanate in dry air
Γ-mercaptopropyltrimethoxysilane 7.8 was added to a solution consisting of 0.2 parts of dibutyltin dilaurate.
The mixture was added dropwise at 50 ° C. over 1 hour while stirring, and then 60 ° C.
For 3 hours. To this, 71.4 parts of pentaerythritol triacrylate was added dropwise at 30 ° C. over 1 hour.
The organic compound (b-2) was heated and stirred at 60 ° C. for 3 hours.
-1) was obtained. 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 Reactive Particles (A) and Crosslinkable Particles (C) Examples of the production of the reactive particles (A) are described in Examples 1 to 6, and the production of the crosslinkable particles (C). Examples are shown in Preparation Example 1, and the results are shown in Table 1.

Example 1 Organic compound (b-1-1) 4.5 synthesized in Synthesis Example 1
Parts, 95.5 parts of methyl ethyl ketone silica sol (a-1) (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-ST, number average particle diameter 0.022 μm, silica concentration 30%), 0.5 parts of ion-exchanged water After stirring at 60 ° C. for 3 hours, 5.0 parts of orthoformic acid methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain a dispersion of colorless and transparent reactive particles (A) (dispersion). Liquid A-1) was obtained. Dispersion A
After weighing 2 g of -1 in an aluminum dish, drying on a hot plate at 120 ° C. for 1 hour, and weighing, the solid content was found to be 31%.

Example 2 2.2 Organic compound (b-1-1) synthesized in Synthesis Example 1
Part, the methyl ethyl ketone silica sol (a-1) (M
EK-ST) 90.4 parts, p-methoxyphenol 0.
A mixture of 01 parts and 0.2 parts of ion-exchanged water was heated at 60 ° C.
After stirring for 3 hours, 7.4 parts of the organic compound (b-2-1) synthesized in Synthesis Example 4 was further added, and the mixture was stirred at 60 ° C. for 3 hours. Further, 2.8 parts of orthoformic acid methyl ester were added, and the mixture was heated and stirred at 60 ° C. for 1 hour to obtain a translucent dispersion liquid of reactive particles (A) (dispersion liquid A-2). The solid content of this dispersion A-2 was determined in the same manner as in Example 1, and found to be 36%.

Example 3 Organic compound (b-1-2) 4.5 synthesized in Synthesis example 2
Part, the methyl ethyl ketone silica sol (a-1) (M
A mixture of 95.5 parts (EK-ST) and 0.5 parts of ion-exchanged water was stirred at 60 ° C for 3 hours. Further, 5.0 parts of orthoformic acid methyl ester were added, and the mixture was heated and stirred at 60 ° C. for 1 hour to obtain a dispersion liquid of translucent reactive particles (A) (dispersion liquid A-3). The solids content of this dispersion A-3 was determined in the same manner as in Example 1, and found to be 31%.

Example 4 Organic compound (b-1-3) 4.5 synthesized in Synthesis example 3
Part, the methyl ethyl ketone silica sol (a-1) (M
EK-ST) A mixture of 95.5 parts and 0.5 parts of ion-exchanged water was stirred at 60 ° C for 3 hours, and 5.0 parts of orthoformic acid methyl ester was added. By heating and stirring for a period of time, a translucent reactive particle (A) dispersion liquid (dispersion liquid A-4) was obtained. The solid content of this dispersion A-4 was determined in the same manner as in Example 1, and found to be 31%.

Example 5 Organic compound (b-1-1) 1.5 synthesized in Synthesis Example 1
Parts, isopropanol alumina sol (a-2) (manufactured by Sumitomo Osaka Cement Co., Ltd., trade name: AS-150I, number average particle diameter 0.013 μm, alumina concentration 15%) 98.5
Parts, and a mixture of 0.2 parts of ion-exchanged water at 60 ° C.
After stirring for 3 hours, 4.0 parts of orthoformic acid methyl ester were added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain a dispersion of reactive particles (A) (dispersion A-5). The solid content of this dispersion A-5 was determined in the same manner as in Example 1.
6%.

Example 6 Organic compound (b-1-1) 1.0 synthesized in Synthesis Example 1
Part, organic compound (b-2-1) synthesized in Synthesis Example 4.
9 parts of 2 parts, toluene zirconia sol (a-3) (number average particle diameter 0.01 μm, zirconia concentration 30%),
A mixture of 0.01 part of p-methoxyphenol, 33.0 parts of methyl ethyl ketone and 0.1 part of ion-exchanged water was added to 60 parts of
After stirring at 3 ° C. for 3 hours, methyl orthoformate 1.2
And the mixture was further heated and stirred at the same temperature for 1 hour to obtain a reactive particle (A) dispersion liquid (dispersion liquid A-6).
The solid content of this dispersion A-6 was determined in the same manner as in Example 1, and found to be 24%.

Preparation Example 1 8.7 of the organic compound (b-2-1) synthesized in Synthesis Example 4
Parts, methyl ethyl ketone silica gel sol (a-1) (M
EK-ST) A mixture of 91.3 parts and 0.1 part of ion-exchanged water was stirred at 80 ° C. for 3 hours, and then 1.4 parts of orthoformic acid methyl ester was added, followed by heating at the same temperature for 1 hour. By stirring, a colorless and transparent crosslinkable particle dispersion (dispersion C-1) was obtained. 2 g of this dispersion C-1 was weighed on an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, weighed, and the solid content was determined in the same manner as in Example 1.
%Met.

[0074]

[Table 1]

The contents of the abbreviations in Table 1 are shown below. a-1: Methyl ethyl ketone silica sol (silica concentration 3
A-2: isopropanol alumina sol (alumina concentration 15%) a-3: toluene zirconia sol (zirconia concentration 30)
%) B-1-1: Organic compound synthesized in Synthesis Example 1 b-1-2: Organic compound synthesized in Synthesis Example 2 b-1-3: Organic compound synthesized in Synthesis Example 3 b-2-1: Organic compound synthesized in Synthesis Example 4

Preparation Examples of Compositions Hereinafter, preparation examples of the composition of the present invention are shown in Examples 7 to 15 and Comparative Example 1. Table 2 shows the weight ratio of each component.

Example 7 155 parts of the dispersion A-1 prepared in Example 1 (48 parts of reactive particles, dispersion medium methyl ethyl ketone (MEK)), 26 parts of dipentaerythritol hexaacrylate, 26 parts of pentaerythritol triacrylate 1 part at 50 ° C
By stirring for a time, a composition of a uniform solution was obtained. This preparation was performed in a room shielded from ultraviolet rays. When the solid content of this composition was determined in the same manner as in Example 1, the solid content was 48%.
Met.

Examples 8 to 15 The compositions of Examples 8 to 15 were obtained in the same manner as in Example 7 except that the compositions shown in Table 2 were used.

Comparative Example 1 The methyl ethyl ketone silica sol (a-
1) 177 parts (53 parts of oxide particles, dispersion medium methyl ethyl ketone (MEK)), 23.5 parts of dipentaerythritol hexaacrylate, 23.5 parts of pentaerythritol triacrylate, 0.5 part of 1-hydroxycyclohexyl phenyl ketone Part, and 2-methyl-1- (4-
By stirring 0.5 part of (methylthio) phenyl-2-morpholinopropanone-1 at 50 ° C. for 2 hours, a homogeneous solution composition was obtained. The solid content of this composition was determined in the same manner as in Example 1 and found to be 45%.

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 with the above composition was evaluated. The evaluation method is described below. Table 2 shows the evaluation results.

1. Coating, drying and curing conditions The compositions obtained in Examples 7 to 15 and Comparative Example 1 in Table 2 were dried on a substrate using a bar coater to a dry film thickness of 10 µm.
After coating in a hot air dryer at 80 ° C,
After drying for 1 minute, use a conveyor-type mercury lamp to
After irradiation with the light amount of ² , storage at 25 ° C. for 24 hours was evaluated.

2. Substrate A glass plate was used in the pencil hardness test, and a thickness of 1 was used in the evaluation of steel wool scratch resistance and adhesion evaluation.
An 88 μm polyethylene terephthalate (PET) film was used, and a 100 μm PET film was used in the curl test.

3. Evaluation method-Pencil hardness: A cured film on a glass substrate was evaluated according to JIS K5400. Adhesion: Evaluated according to the cross-cut cellophane tape peeling test in JIS K5400, the residual film ratio (%) in a total of 100 squares of 1 mm square.・ 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 test: 100 μm thick PE of the composition of the present invention
Immediately after film formation under the above-mentioned coating and curing conditions on T, a 10 cm × 10 cm piece was cut out with a cutter knife and allowed to stand at 25 ° C. and 50% relative humidity for 24 hours. ) Was calculated.

[0084]

[Table 2]

In Table 2, dispersion A-1 * to dispersion A-6 * in reactive particles (A), dispersion C-1 * in crosslinkable particles (C), and oxide particles a-1 * Indicates the solid content (parts by weight) in each dispersion. The contents of the abbreviations in Table 2 are shown below. a-1: Methyl ethyl ketone silica sol (silica concentration 3
0%) B-1: dipentaerythritol hexaacrylate B-2: pentaerythritol triacrylate D-1: 1-hydroxycyclohexylphenyl ketone D-2: 2-methyl-1- [4- (methylthio) phenyl] -2 Morpholinopropanone-1

[0086]

As described above, according to the present invention,
It has excellent coating properties, and has excellent hardness, scratch resistance, abrasion resistance, low curl, adhesion and chemical resistance on the surface of various substrates. The present invention can provide a reactive particle used in a curable composition capable of forming a coating film (cured film) having excellent curl properties and adhesion, a curable composition containing the particles, and a cured product thereof.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08G77 / 22 C08G77 / 22 4J037 77/28 77/28 4J038 C08K 5/10 C08K 5/10 C08L 08 C08L 83/08 // C09D 4/00 C09D 4/00 (72) Inventor Takaro Yatsushiro 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside JAE SuR Co., Ltd. (72) Isao Nishiwaki Tsukiji, Chuo-ku, Tokyo 2-11-11-24 JAE SRL Co., Ltd. (72) Inventor Takashi Ukaji 2-11-24 Tsukiji Chuo-ku, Tokyo F-term in JAE SRL Co., Ltd. 4G042 DA01 DB28 DC03 DE07 DE14 4G076 AA02 AA26 AB02 BB08 BF01 CA18 DA14 4H049 VN01 VP01 VQ49 VR21 VR22 VR23 VR41 VR42 VR43 VU12 VU16 VW02 4J002 CF24Y CH05Y CP05Y CP07W CP09W CP10X CP12X EH07 6 EU186 FD140 FD150 FD200 FD206 4J035 BA11 CA05U CA051 CA13U CA131 CA18U CA182 CA19U CA192 CA29M CA291 LB01 4J037 AA08 AA11 AA18 AA22 AA25 CB04 CB07 FA08 FA1 FA1 FA02 FA17 FA2 FA11 FA2 GA06 GA08 GA15 HA216 JC32 JC33 KA03 KA04 KA07 KA08 KA20 NA01 NA04 NA11 NA12 NA24 PB04 PB05 PB08 PC02 PC03 PC08

Claims (9)

[Claims] (1) oxide particles of at least one element selected from the group consisting of (a) silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium; Reactive particles comprising an organic compound having a radical-generating group and a hydrolyzable group. 2. The oxide particles of the component (a) are added to the particles (b)
The reactive particle according to claim 1, wherein an organic compound having a radically polymerizable unsaturated group and a hydrolyzable group in the molecule (b-2) is bonded in addition to the organic compound as the component (1). 3. The reactive particle according to claim 1, wherein the organic compound as the component (b-1) is a compound having a silanol group or a compound which forms a silanol group by hydrolysis. 4. The method according to claim 1, wherein the organic compound as the component (b-1) is a compound having a monovalent organic group represented by the following formulas (1) and (2) or any one of the formulas. The reactive particle according to any one of the above. Embedded image Embedded image 5. The reactive particles according to claim 2, wherein the organic compound as the component (b-2) is a compound having a silanol group or a compound which forms a silanol group by hydrolysis. 6. The method according to claim 1, wherein the organic compound (b-2) is [-
O—C (＝ O) —NH—] group;
C (= S) -NH-] group and [-SC (= O) -NH
-] Having at least one of the groups.
The reactive particles according to any one of the above. 7. The reactive particles (reactive particles (A)) according to claim 1 in an amount of 5 to 80% by weight, and (B) in 100% by weight of the total solid content of the curable composition. ) 2 in the molecule
20 to 95% by weight of a compound having the above polymerizable unsaturated group
A curable composition comprising: 8. The reactive particles (reactive particles (A)) according to any one of claims 1 to 6 and the oxidation of the component (a) in 100% by weight of the total solid content of the curable composition. 5 to 80% by weight of a mixture with crosslinkable particles (crosslinkable particles (C)) obtained by bonding the organic compound of the component (b-2) to the product particles, and (B) two or more polymerizable molecules in the molecule. A curable composition comprising 20 to 95% by weight of a compound having an unsaturated group. 9. A cured product obtained by curing the curable composition according to claim 7.