JP4872248B2 - Curable composition and cured film thereof - Google Patents

Description

  The present invention relates to a curable composition, a cured film and a laminate thereof. More specifically, the present invention has excellent coating properties, has high hardness and scratch resistance on the surface of various substrates, and has transparency. It is related with the curable composition which can form the coating film (coating film) which was excellent in surface slipperiness and antifouling property, and these durability, and its cured film.

  In recent years, 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, slate, etc. As a protective coating material and anti-reflection coating material for preventing scratches (abrasion) on various substrate surfaces and preventing contamination, it has excellent coating properties, and the surface of various substrates has hardness, There is a demand for a curable composition capable of forming a cured film excellent in any of scratch resistance, abrasion resistance, surface slipperiness, low curling property, adhesion, transparency, chemical resistance and coating surface appearance. ing.

In order to satisfy such a request, various compositions have been proposed, but have excellent coating properties as a curable composition, and have a high hardness and scratch resistance when used as a cured film. The present condition is that the thing which is excellent in transparency and also has the characteristic that it is excellent also in the surface slipperiness stable also with time has not been obtained yet.
As a method for imparting surface slipperiness, for example, a photo-curing resin composed of an acrylic ester of bisphenol A diglycidyl ether polymer, dipentaerythritol monohydroxypentaacrylate, a photopolymerization initiator, inorganic particles, and terminal-reactive polydimethylsiloxane It has been proposed to use the composition as a photocurable coating material (Patent Document 1). However, a cured product using such a composition has a certain improvement in surface slipperiness, but the surface slipperiness changes with time, and the slidability imparting component may bleed out. The hardness and scratch resistance were not always satisfactory.
Patent Document 2 describes a curable composition having improved surface slip by blending a polysiloxane having a (meth) acryloyl group, but there is still room for improvement from the viewpoint of antifouling properties. .

JP-A-11-124514 JP-A-2005-36018

  The present invention has excellent coating properties, and has high hardness and scratch resistance on the surface of various substrates, excellent transparency, surface slipperiness and antifouling properties, and sustainability thereof. It aims at providing the curable composition which can form the outstanding coating film (film), and its cured film.

  As a result of intensive studies to achieve the above object, the present inventors have (A) oxide particles of a specific element having a polymerizable unsaturated group, and (B) having two or more polymerizable unsaturated groups. It has been found that if a curable composition containing an organic compound and (C) a reactive polysiloxane compound having 3 or more polymerizable groups is used, a cured film satisfying the above-mentioned characteristics can be obtained. Was completed.

（式中、Ｒ^１は３以上の重合性不飽和基を有する１価の有機基を示し、Ｒ^２はウレタン結合を有する２価の有機基を示し、Ｒ^３およびＲ^４は各々独立してメチル基またはフェニル基を示し、ｎは１〜１５０の数を示す）
を含有することを特徴とする硬化性組成物を提供するものである。 That is, the present invention has a specific amount of (A) a polymerizable unsaturated group and at least selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. Particles whose main component is an oxide of one element (hereinafter referred to as “reactive particles”), (B) a polymerizable organic compound having two or more polymerizable unsaturated groups, and (C) the following formula ( 1) a compound comprising the structure shown below (hereinafter sometimes referred to as “reactive polysiloxane compound (C)”)

(Wherein R ¹ represents a monovalent organic group having 3 or more polymerizable unsaturated groups, R ² represents a divalent organic group having a urethane bond, and R ³ and R ⁴ are each independently A methyl group or a phenyl group, and n represents a number from 1 to 150)
The curable composition characterized by containing is provided.

  Moreover, this invention provides the cured film formed by hardening said curable composition.

  Furthermore, this invention provides the laminated body formed by laminating | stacking said cured film on a transparent base material.

  As described above, according to the present invention, the surface of various substrates has excellent coating properties, transparency, scratch resistance, high hardness, and surface slipperiness and antifouling properties (fingerprints). It is possible to provide a curable composition capable of forming a coating film (film) excellent in wiping property and oily dye wiping property) and their durability, and a cured film thereof.

1. Curable composition [1] Reactive particles The reactive particles (A) used in the present invention have a polymerizable unsaturated group, and are silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, Particles mainly composed of an oxide of at least one element selected from the group consisting of antimony and cerium. Such reactive particles include particles (Aa) mainly composed of an oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. It can be obtained by reacting an organic compound (Ab) having a polymerizable unsaturated group and a hydrolyzable silyl group in the molecule.

(1) Particles mainly composed of oxide (Aa)
The oxide particles (Aa) used for the production of the reactive particles (A) are silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin from the viewpoint of colorlessness of the cured film of the resulting curable composition. , Particles mainly composed of an oxide of at least one element selected from the group consisting of antimony and cerium.

  Examples of these oxide particles (Aa) include particles of silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, cerium oxide, and the like. Can be mentioned. Of these, particles of silica, alumina, zirconia and antimony oxide are preferred from the viewpoint of high hardness. These can be used alone or in combination of two or more. Furthermore, the oxide particles (Aa) are preferably used in the form of powder or solvent dispersion sol. When used as a solvent-dispersed sol, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone. , Esters such as propylene glycol monomethyl ether acetate and 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, dimethylacetamide, Examples thereof include amides such as N-methylpyrrolidone. Of these, 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 (Aa) is preferably 0.001 μm to 2 μm, more preferably 0.003 μm to 1 μm, and particularly preferably 0.005 μm to 0.5 μm. When the number average particle diameter exceeds 2 μm, the transparency when cured is lowered or the surface state when cured is deteriorated. Various surfactants and amines may be added to improve the dispersibility of the particles.

  Commercially available products as silicon oxide particles (for example, silica particles) include, for example, colloidal silica, methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA- manufactured by Nissan Chemical Industries, Ltd. ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL and the like can be mentioned. As powder silica, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Silex H31, H32, H51, H52, H121, H122, Asahi Glass Co., Ltd. Examples include E220A and E220 manufactured by Fuji Electric, SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.

  Moreover, as an aqueous dispersion product of alumina, Nissan Chemical Industries, Ltd. alumina sol-100, -200, -520; As an alumina isopropanol dispersion product, Sumitomo Osaka Cement Co., Ltd. AS-150I; AS-150T manufactured by Sumitomo Osaka Cement Co., Ltd .; HXU-110JC manufactured by Sumitomo Osaka Cement Co., Ltd. as a toluene dispersion of zirconia; Nissan Chemical Industries, Ltd. as an aqueous dispersion of zinc antimonate powder ) Celnax; Alumina, Titanium oxide, Tin oxide, Indium oxide, Zinc oxide, etc. Powder and solvent dispersion products are nanotech made by CI Kasei Co., Ltd .; Antimony-doped tin oxide water dispersion sol is Ishihara Sangyo ( SN-100D, manufactured by Mitsubishi Materials Corporation, and ITO The aqueous dispersion, mention may be made of Taki Chemical Co., Ltd. Nidoraru like.

The oxide particles (Aa) have a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an indefinite shape, and preferably a spherical shape. The specific surface area of the oxide particles (Aa) (by the BET specific surface area measurement method using nitrogen) is preferably 10 to 1000 m ² / g, and more preferably 100 to 500 m ² / g. These oxide particles (Aa) can be used in a dry state, or dispersed in water or an organic solvent. For example, a dispersion of fine oxide particles known in the art as a solvent dispersion sol of the above oxide can be used directly. In particular, the use of an organic solvent-dispersed sol of an oxide is preferable in applications where the cured product requires excellent transparency.

(2) Organic compound (Ab)
The organic compound (Ab) used in the present invention is a compound having a polymerizable unsaturated group, and is preferably an organic compound containing a group represented by the following formula (2). Further, it includes a [—O—C (═O) —NH—] group, and further includes a [—O—C (═S) —NH—] group and a [—S—C (═O) —NH—] group. It is preferable that at least 1 of these is included. Moreover, it is preferable that this organic compound (Ab) is a compound which has a silanol group in a molecule | numerator, or a compound which produces | generates a silanol group by hydrolysis.

［式（２）中、Ｕは、ＮＨ、Ｏ（酸素原子）又はＳ（イオウ原子）を示し、Ｖは、Ｏ又はＳを示す。］

[In Formula (2), U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. ]

(I) Polymerizable unsaturated group The polymerizable unsaturated group contained in the organic compound (Ab) is not particularly limited, and examples thereof include acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, and ethynyl. Preferred examples include a group, a cinnamoyl group, a maleate group and an acrylamide group.
This polymerizable unsaturated group is a structural unit that undergoes addition polymerization with active radical species.

(Ii) The group represented by the formula (2) The group [—UC— (V) —NH—] represented by the formula (2) contained in the organic compound is specifically represented by [—O—C ( = O) -NH-], [-O-C (= S) -NH-], [-S-C (= O) -NH-], [-NH-C (= O) -NH-], Six types of [—NH—C (═S) —NH—] and [—S—C (═S) —NH—]. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C (═O) — It is preferable to use in combination with at least one of the NH-] groups.
The group [—UC (═V) —NH—] represented by the formula (2) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength and group when cured. It is considered that it gives properties such as adhesion and heat resistance to adjacent layers such as materials and high refractive index layers.

(Iii) Silanol group or group that generates a silanol group by hydrolysis The organic compound (Ab) is preferably a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis. Examples of the compound that generates such a silanol group include compounds in which an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom, and the like are bonded to a silicon atom. A compound having a group bonded thereto, that is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.
The silanol group-generating site of the silanol group or the compound that generates the silanol group is a structural unit that binds to the oxide particles (Aa) by a condensation reaction that occurs following a condensation reaction or hydrolysis.

(Iv) Preferred Embodiment Specific examples of the organic compound (Ab) include compounds represented by the following formula (3).

In the formula (3), R ⁶ and R ⁷ may be the same or different and each represents a hydrogen atom or an alkyl group or aryl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, Examples thereof include phenyl and xylyl groups. Here, j is an integer of 1 to 3.

Examples of the group represented by [(R ⁶ O) _j R ⁷ _3-j Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.
R ⁸ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms and may contain a chain, branched or cyclic structure. Specific examples include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, dodecamethylene and the like.
R ⁹ is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. Specific examples include a chain polyalkylene group such as hexamethylene, octamethylene, and dodecamethylene; an alicyclic or polycyclic divalent organic group such as cyclohexylene and norbornylene; and 2 such as phenylene, naphthylene, biphenylene, and polyphenylene. Valent aromatic group; and these alkyl group-substituted and aryl group-substituted products. These divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and may contain a polyether bond, a polyester bond, a polyamide bond, and a polycarbonate bond.
R ¹⁰ is a (k + 1) -valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.
Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. K is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.

  Specific examples of the compound represented by the formula (3) include compounds represented by the following formulas (4) and (5).

［式（４）及び式（５）中、「Ａｃｒｙｌ」は、アクリロイル基を示す。］

[In the formulas (4) and (5), “Acryl” represents an acryloyl group. ]

  For the synthesis of the organic compound (Ab) used in the present invention, for example, a method described in JP-A-9-100111 can be used. Preferably, mercaptopropyltrimethoxysilane and isophorone diisocyanate are mixed in the presence of dibutyltin dilaurate and reacted at 60 to 70 ° C. for several hours, then pentaerythritol triacrylate is added, and further at 60 to 70 ° C. for several hours. Produced by reacting to some extent.

(3) Preparation of Reactive Particles (A) An organic compound (Ab) having a silanol group or a group that generates a silanol group by hydrolysis is mixed with metal oxide particles (Aa), hydrolyzed, and bonded together. . The proportion of the organic polymer component, ie, hydrolyzable silane hydrolyzate and condensate, in the resulting reactive particles (A) is usually a mass loss% when the dry powder is completely burned in air. The constant value can be obtained, for example, by thermal mass spectrometry from room temperature to usually 800 ° C. in air.

  The amount of binding of the organic compound (Ab) to the oxide particles (Aa) is preferably 100% by mass of the reactive particles (A) (the total of the metal oxide particles (Aa) and the organic compound (Ab)), It is 0.01 mass% or more, More preferably, it is 0.1 mass% or more, Most preferably, it is 1 mass% or more. When the amount of the organic compound (Ab) bound to the metal oxide particles (Aa) is less than 0.01% by mass, the dispersibility of the reactive particles (A) in the composition is not sufficient, and the resulting curing is obtained. The transparency and scratch resistance of the object may not be sufficient. Moreover, the compounding ratio of the metal oxide particles (Aa) in the raw material during the production of the reactive particles (A) is preferably 5 to 99% by mass, and more preferably 10 to 98% by mass. The content of the oxide particles (Aa) constituting the reactive particles (A) is preferably 65 to 95% by mass of the reactive particles (A).

The content of the reactive particles (A) in the curable composition is 5 to 85% by weight, with 100% by weight of the entire composition excluding (E) the organic solvent. Preferably it is 10 to 80% by weight. If it is less than 5% by weight, it may not be possible to obtain a high hardness when cured, and if it exceeds 85% by weight, the film formability may be insufficient.
The content of the reactive particles (A) means a solid content, and when the reactive particles (A) are used in the form of a solvent-dispersed sol, the content does not include the amount of solvent.

[2] (B) Polyfunctional polymerizable organic compound The polyfunctional polymerizable organic compound (B) used in the present invention is suitably used for enhancing the film-forming property of the composition. The polyfunctional polymerizable organic compound (B) is not particularly limited as long as it contains two or more polymerizable unsaturated groups in the molecule, except for the component (C) described later. Examples include acrylic esters and vinyl compounds. Of these, (meth) acrylic esters are preferred.

［式（６）及び式（７）中、「Ａｃｒｙｌ」は、アクリロイル基を示す。］ (Meth) acrylic esters include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) 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, Hydroxyl-containing (meth) such as ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate Acrylates, and poly (meth) acrylates of ethylene oxide or propylene oxide adducts to these hydroxyl groups, oligoesters (meth) acrylates having two or more (meth) acryloyl groups in the molecule, oligoether (meth) acrylates , Oligourethane (meth) acrylates, oligoepoxy (meth) acrylates, compounds represented by the following formulas (6) and (7), and the like. Among them, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, represented by the following formulas (6) and (7) And the like are preferred.

[In the formulas (6) and (7), “Acryl” represents an acryloyl group. ]

  Examples of vinyl compounds include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether.

  As a commercial item of such a polymerizable organic compound (B), Toagosei Co., Ltd. Aronix M-400, M-404, M-408, M-450, M-305, 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-240, M-245 , M-260, M-270, M-1100, 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-904, TO-905, TO-1330, KAYARAD D-310, D-330, DPHA, DPCA-20, DP manufactured by Nippon Kayaku Co., Ltd. A-30, DPCA-60, DPCA-120, DN-0075, DN-2475, SR-295, SR-355, SR-399E, SR-494, SR-9041, SR-368, SR-415, SR- 444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610, SR-9003, PET-30, T-1420, GPO-303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R-526, R -551, R-712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA, Kyoeisha Chemical Co., Ltd. light acrylate PE -4A, DPE-6A, DTMP-4A and the like.

  The content of the polymerizable organic compound (B) used in the present invention is 10 to 90% by weight based on 100% by weight of the entire composition. Preferably it is 15 to 80% by weight. If it is less than 10% by weight or more than 90% by weight, it may not be possible to obtain a high hardness when cured.

[3] (C) Reactive polysiloxane compound The reactive polysiloxane compound (C) is not particularly limited as long as it is a reactive polysiloxane compound other than the component (B) having three or more polymerizable groups. However, a polydimethylsiloxane compound is preferable because it is easily available. The polydimethylsiloxane compound is not particularly limited as long as it is a compound having a polymerizable group and further having two or more dimethylsiloxane structures. A spacer structure may be suitably provided between the polysiloxane chain and the polymerizable group.

  The polymerizable group of the reactive polysiloxane compound (C) used in the curable composition of the present invention is not particularly limited, and examples thereof include acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, Polymerizable unsaturated groups such as a styryl group, an ethynyl group, a cinnamoyl group, a maleate group, and an acrylamide group; and an epoxy group-substituted alkyl or alkoxy group such as a 2,3-epoxypropyloxy group and an epoxycyclohexyl group. Among these, an acryloyl group and a methacryloyl group are preferable from the viewpoint of imparting radiation curability. Further, the polymerizable group of the component (C) may be a group having the same structure or a group having a different structure.

  The polystyrene-reduced number average molecular weight of the reactive polysiloxane compound (C) by GPC method is preferably 800 to 15000, and particularly preferably 1000 to 7000. If the number average molecular weight is less than 800, the surface slipperiness of the cured product of the composition containing this may not be sufficient, and if the number average molecular weight exceeds 15,000, the composition containing it will have a coating property. May be inferior.

  As the reactive polysiloxane compound (C), the following formula (1)

（式中、Ｒ^１は３以上の重合性不飽和基を有する１価の有機基を示し、Ｒ^２はウレタン結合を有する２価の有機基を示し、Ｒ^３およびＲ^４は各々独立してメチル基またはフェニル基を示し、ｎは１〜１５０の数を示す）
で表される化合物が好ましい。

(Wherein R ¹ represents a monovalent organic group having 3 or more polymerizable unsaturated groups, R ² represents a divalent organic group having a urethane bond, and R ³ and R ⁴ are each independently A methyl group or a phenyl group, and n represents a number from 1 to 150)
The compound represented by these is preferable.

Among them, among the components (C) having the structure represented by the formula (1), the number of polymerizable unsaturated groups that the component (C) has is the polymerizable unsaturated group that R ^{1 of the} formula (1) has. Is particularly preferable in that both good transparency and antifouling properties can be achieved (hereinafter, the component (C) having such a structure is referred to as “one-end reactive polysiloxane compound”). In this case, the structure of the molecular terminal different from the terminal represented by R ¹ in the above formula (1) of the reactive polysiloxane is not particularly limited as long as it does not have a polymerizable unsaturated group. Group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, etc., n = 1-30 saturated hydrocarbon group represented by C _n H _{2n + 1} , alicyclic saturated hydrocarbon group such as cyclohexyl group, phenyl An aromatic unsaturated hydrocarbon group such as a benzyl group is preferred.

In the formula (1), R ¹ includes acryloxy group, methacryloxy group, (meth) acrylic acid ester group such as glycidyl (meth) acrylate group, (meth) acrylic acid phenyl group such as benzyl acrylate, and the like. In terms of surface characteristics after curing the composition, a polymerizable unsaturated group such as an acryloxy group or a methacryloxy group is preferable, and an acryloxy group is particularly preferable.

The molecular weight of R ² is preferably 28 to 14,000, particularly preferably 28 to 5,000 from the viewpoint of compatibility with other components. Preferable R ² is an organic group having an aliphatic or aromatic structure which may have a urethane bond, an ether bond, an ester bond, an amide bond, or the like, or an organic group having both such an aliphatic and aromatic structure. Can be mentioned. Here, as the aliphatic structure, for example, a chain structure such as methylene, ethylene, propylene, tetramethylene, hexamethylene, 2,2,4-trimethylhexamethylene, 1- (methylcarboxyl) -pentamethylene, Examples include alicyclic structures such as isophorone, cyclohexylmethane, methylenebis (4-cyclohexane), hydrogenated dienylmethane, hydrogenated xylene, and hydrogenated toluene. Examples of aromatic structures include benzene, toluene, xylene, paraphenylene, Aromatic ring structures such as diphenylmethane, diphenylpropane, naphthalene and the like can be mentioned.

Furthermore, it is preferable that R ² has a urethane bond, since the compatibility between the component (C) and other components is improved and the coating property of the curable composition is improved. One urethane bond may be used, but two or more urethane bonds may be included.

The compound of the formula (1) having a urethane bond in R ² can be produced, for example, by reacting a polyisocyanate with a reactive silicone compound having a hydroxyl group and a hydroxyl group-containing (meth) acrylate.

  Among the polyisocyanates suitable for this purpose, diisocyanates include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5- Naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 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-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, 2, And 5 (or 6) -bis (isocyanatomethyl) -bicyclo [2.2.1] heptane. Of these, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate) and the like are particularly preferable. These may be used alone or in combination of two or more.

The polydimethylsiloxane structure in the compound (C) is introduced using, for example, a silicone compound having a hydroxyl group at the molecular end.
Examples of such silicone compounds include a 3- (2'-hydroxyethoxy) propyl group, a 3- (2 ', 3'-dihydroxypropyloxy) propyl group, and 3- (2'-ethyl-2') at the molecular end. Examples thereof include silicone compounds having an organic group such as -hydroxymethyl-3-hydroxy) propyl group and 3- (2'-hydroxy-3'-isopropylamino) propyl group. These may be used alone or in combination of two or more.

  Silicone compounds having a hydroxyl group at one end as described above can also be obtained as commercial products such as Silaplane FM-0411, FM-0421, FM-0425 manufactured by Chisso Corporation.

Moreover, the (meth) acryloyl group preferable as R < ¹ > of said Formula (1) is required in order to provide radiation curability to the compound (C) used by this invention. The (meth) acryloyl group is introduced, for example, by reacting a hydroxyl group-containing (meth) acrylate with a polyisocyanate.

  Examples of such a hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenyloxypropyl. (Meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl Glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta Meth) acrylate, the following formula (8) or (9)

(Wherein R ¹¹ represents a hydrogen atom or a methyl group, and m represents a number of 1 to 15)
(Meth) acrylate represented by the following. Moreover, the compound obtained by addition reaction with glycidyl group containing compounds, such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate, and (meth) acrylic acid can also be used. Of these hydroxyl group-containing (meth) acrylates, pentaerythritol tri (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like are particularly preferable. These may be used alone or in combination of two or more.

  Examples of the reaction for obtaining the compound (C) having two or more urethane bonds include, for example, a method in which a silicone compound having a hydroxyl group, a polyisocyanate and a hydroxyl group-containing (meth) acrylate are charged and reacted; And a method of reacting a polyisocyanate and then a hydroxyl group-containing (meth) acrylate; a method of reacting a polyisocyanate and a hydroxyl group-containing (meth) acrylate and then reacting the silicone compound. The reaction is preferably performed so that the hydroxyl group equivalent of the hydroxyl group-containing silicone compound and the hydroxyl group-containing (meth) acrylate is substantially the same as the isocyanate equivalent of the polyisocyanate.

Moreover, by adding a polyol to the starting material for the above reaction, a structure such as a polyurethane polyol can be introduced between the polydimethylsiloxane structure and the (meth) acryloyl group.
Examples of the reaction for obtaining the compound (C) having a polyurethane polyol structure include a method in which a silicone compound having a hydroxyl group, a polyol, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate are charged and reacted; A method of reacting the silicone compound and the hydroxyl group-containing (meth) acrylate; a method of reacting the polyisocyanate, the silicone compound and the hydroxyl group-containing (meth) acrylate, and then reacting a polyol; and a method of reacting the polyisocyanate and the silicone compound. A method in which a polyol is reacted, and finally a hydroxyl group-containing (meth) acrylate is reacted; a polyisocyanate and a hydroxyl group-containing (meth) acrylate are reacted; Reacting the polyol, and finally a method of reacting the silicone compound, and the like.

  As the polyol used here, polyether diol, polyester diol, polycarbonate diol, polycaprolactone diol and the like are used, and these polyols can be used in combination of two or more. The bonding mode of the structural units in these polyols is not particularly limited, and may be any of random bonds, block bonds, and graft bonds.

  Specifically, as the polyether diol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, or two or more ion-polymerizable cyclic compounds are opened. Examples thereof include polyether diols obtained by copolymerization. Examples of the ion polymerizable cyclic compound include ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, 3,3-bischloromethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, and tetraoxane. , Cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl methacrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monooxide, isoprene monooxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, glycidyl benzoate And cyclic ethers such as Specific combinations of the two or more ion-polymerizable cyclic compounds include, for example, tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, butene-1 And terpolymers of -oxide and ethylene oxide, tetrahydrofuran, butene-1-oxide and ethylene oxide. Further, a polyether diol obtained by ring-opening copolymerization of the ion polymerizable cyclic compound and a cyclic imine such as ethyleneimine; a cyclic lactone acid such as β-propiolactone or glycolic acid lactide; or a dimethylcyclopolysiloxane. Can also be used. The ring-opening copolymer of these ion-polymerizable cyclic compounds may be bonded at random or may be bonded in a block form.

  Examples of the polyester diol include a polyester diol obtained by reacting a polyhydric alcohol and a polybasic acid. Examples of the polyhydric alcohol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 3- Examples include methyl-1,5-pentanediol, 1,9-nonanediol, and 2-methyl-1,8-octanediol. Examples of the polybasic acid include phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid and the like. Commercially available products of these polyester diols are available as Kuraray Kurapole P-2010, PMIPA, PKA-A, PKA-A2, PNA-2000 and the like.

  Examples of the polycarbonate diol include polytetrahydrofuran polycarbonate and 1,6-hexanediol polycarbonate. Commercially available products are available as Nippon Polyurethane Co., Ltd. DN-980, 981, 982, 983, US PPG PC-8000, BASF PC-THF-CD, and the like.

  Furthermore, examples of polycaprolactone diol include polycaprolactone diol obtained by reacting ε-caprolactone and diol. Examples of the diol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4- Examples include cyclohexanedimethanol and 1,4-butanediol. Examples of commercially available products of these polycaprolactone diols include Plascel 205, 205AL, 212, 212AL, 220, and 220AL manufactured by Daicel Chemical Industries, Ltd.

Examples of polyols other than the above include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol. A, hydrogenated bisphenol F, dimethylol compound of dicyclopentadiene, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, β-methyl-δ-valerolactone, hydroxy-terminated polybutadiene, hydroxy-terminated hydrogenated polybutadiene, castor oil-modified polyol, Examples thereof include a terminal diol compound of polydimethylsiloxane and a polydimethylsiloxane carbitol-modified polyol.
The preferred molecular weight of the polyol is usually 50 to 15,000 in terms of polystyrene-equivalent number average molecular weight, particularly preferably 100 to 8,000.

  As a commercial item of the reactive polysiloxane compound (C), Chisso Corporation Silaplane FM-7711, FM-7721, FM7725 etc. can be mentioned.

The content of the reactive polysiloxane compound (C) used in the present invention is 0.1 to 5% by weight, with 100% by weight of the entire composition excluding (E) the organic solvent. Preferably it is the range of 0.1 to 2 weight%. When the content of the reactive polysiloxane compound (C) is less than 0.1% by weight, the surface slipperiness of the cured product may be insufficient. When the addition amount exceeds 5% by weight, coating such as repellency is applied. May be sexually defective.
In the composition of the present invention, in addition to the reactive particles (A), the polymerizable organic compound (B) and the reactive polysiloxane (C), these components (B), (C ) Other than the component, a compound having one polymerizable unsaturated group in the molecule may be contained.

[4] (D) Radical polymerization initiator In the composition of the present invention, as a component other than the reactive particles (A), the polymerizable organic compound (B), and the reactive polysiloxane compound (C), ( D) A radical polymerization initiator (hereinafter sometimes referred to as “radical polymerization initiator (D)”) is preferably blended.
Examples of such radical polymerization initiator (D) include a compound that thermally generates active radical species (thermal polymerization initiator) and a compound that generates active radical species by radiation (light) irradiation (radiation (light ) Polymerization initiators) and the like can be mentioned.

  The radiation (photo) polymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2 , 2-dimethoxy-1,2-diphenylethane-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, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy Roxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane -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-methyl Vinyl) phenyl) propanone) and the like.

  Examples of commercially available radiation (photo) polymerization initiators include Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG 24-61, Darocur, manufactured by Ciba Specialty Chemicals Co., Ltd. 1116, 1173, BASF's Lucyrin TPO, 8893UCB's Ubekrill P36, Fratelli Lamberti's Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B, and the like.

  The content of the radical polymerization initiator (D) used as necessary in the present invention is preferably 0.01 to 20 parts by weight, and preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the whole composition. Part is more preferable. If it is less than 0.01 part by weight, the hardness when it is a cured product may be insufficient, and if it exceeds 20 parts by weight, the inside (lower layer) may not be cured when it is a cured product.

[5] (E) Organic solvent Examples of the organic solvent (E) include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate and acetic acid Esters such as butyl, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate and 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 And amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

[6] Curing Method When the composition of the present invention is cured, a radiation (light) polymerization initiator and a thermal polymerization initiator can be used in combination as necessary.
Preferable thermal polymerization initiators include, for example, peroxides and azo compounds. Specific examples include benzoyl peroxide, t-butyl-peroxybenzoate, azobisisobutyronitrile, and the like. it can.

  The composition of the present invention is suitable for use as an antireflection film or a coating material. Examples of a base material to be antireflection or coated include plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine). , Triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, slate, and the like. The shape of the substrate may be a plate, a film or a three-dimensional molded body, and the coating method is a normal coating method such as dipping coating, spray coating, flow coating, shower coating, roll coating, spin coating, brush. A paint etc. can be mentioned. The thickness of the coating film in these coatings is usually 0.1 to 400 μm, preferably 1 to 200 μm after drying and curing.

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

The composition of the present invention can be cured by heat and / or radiation (light). When using heat, as the heat source, for example, an electric heater, an infrared lamp, hot air, or the like can be used. 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 lasers, etc., as visible ray sources, sunlight, lamps, fluorescent lamps, lasers, etc., ultraviolet ray sources, mercury lamps, halide lamps, lasers, etc., and electron beam sources Using thermionic electrons generated from the tungsten filament, cold cathode method for generating metal through high voltage pulse, and secondary electron method using secondary electrons generated by collision between ionized gaseous molecules and metal electrode Can be mentioned. Further, as a source of alpha rays, solid rays, and gamma rays, for example, a fission material such as Co ⁶⁰ can be cited, and for the gamma rays, a vacuum tube or the like that causes accelerated electrons to collide with the anode can be used. These radiations can be irradiated alone or in combination of two or more at a certain time.

2. Cured film The cured film of the present invention can be obtained by coating and curing the curable composition on various substrates, for example, plastic substrates. Specifically, after coating the composition and preferably drying the volatile component at 0 to 200 ° C., it can be obtained as a coated molded body by performing a curing treatment with heat and / or radiation. The preferable curing conditions in the case of heat are 20 to 150 ° C., and are performed within a 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 rays is 0.01 to 10 J / cm ² , more preferably 0.1 to ² J / cm ² . Moreover, preferable irradiation conditions of the electron beam are an acceleration voltage of 10 to 300 kV, an electron density of 0.02 to 0.30 mA / cm ² , and an electron beam irradiation amount of 1 to 10 Mrad.

  The cured film of the present invention has characteristics of being able to form a coating film (film) having high hardness and scratch resistance and excellent surface slipperiness depending on the composition. Protective coating material to prevent scratches (scratches) and contamination of recording disks, plastic optical components, touch panels, film-type liquid crystal elements, plastic containers, flooring materials for building interiors, wall materials, artificial marble, etc., or It is particularly suitably used as an antireflection film for film-type liquid crystal elements, touch panels, plastic optical components and the like.

3. Laminated body The laminated body of this invention can be obtained by laminating | stacking said cured film on a transparent base material. A suitable transparent substrate and a laminated method of the cured film are as described above. Since the laminate of the present invention has high transparency and hardness, and is excellent in surface slipperiness and antifouling properties (wipeability of fingerprints and oily dyes) and sustainability thereof, various display devices It is suitable as a surface protective film.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the following, parts and% are parts by weight and% by weight, respectively, unless otherwise specified.

[Synthesis of Organic Compound (A2)]
Synthesis Example 1 (A2-1)
To a solution consisting of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate in dry air, 222 parts of isophorone disoocyanate was added dropwise at 50 ° C. over 1 hour with stirring, followed by heating and stirring at 70 ° C. for 3 hours. . This is composed of NK ester A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Co., Ltd.) comprising 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate. 549 parts were added dropwise at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 10 hours to obtain an organic compound (Ab) containing a polymerizable unsaturated group. When the residual isocyanate content in the product was analyzed by FT-IR, it was 0.1% or less, indicating that the reaction was almost quantitatively completed. In the infrared absorption spectrum of the product, the 2550 Kaiser absorption peak characteristic of the mercapto group in the raw material and the 2260 Kaiser absorption peak characteristic of the raw material isocyanate compound disappeared, and a new urethane bond and S (C = O) A peak of 1660 Kaiser characteristic of NH-group and a peak of 1720 Kaiser characteristic of acryloxy group were observed, and both an acryloxy group as a polymerizable unsaturated group, -S (C = O) NH-, and a urethane bond were observed. It was shown that an acryloxy group-modified alkoxysilane was produced. As a result, 773 parts of the compound (Ab) represented by the formula (4) and 220 parts of pentaerythritol tetraacrylate were obtained.

Production Example 1
[Production of Reactive Particles (A-1)]
2.98 parts of the composition produced in Production Example 1 (including 2.32 parts of an organic compound (Ab) having a polymerizable unsaturated group), silica particle dispersion (Aa) (silica concentration of 32%, MEK-ST, A mixture of 89.90 parts of a number average particle size of 0.022 μm (manufactured by Nissan Chemical Industries, Ltd.), 0.12 part of ion-exchanged water, and 0.01 part of p-hydroxyphenyl monomethyl ether was added at 60 ° C. for 4 hours. After stirring, 1.36 parts of orthoformate methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain reactive particles (dispersion liquid (A-1)). When 2 g of this dispersion (A-1) was weighed on an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour and weighed to determine the solid content, it was 30.7%. Further, 2 g of the dispersion (A-1) was weighed in a magnetic crucible, preliminarily dried on a hot plate at 80 ° C. for 30 minutes, and baked in a muffle furnace at 750 ° C. for 1 hour. The inorganic content was determined to be 95%.

Synthesis example 2
[Synthesis of one-terminal reactive polysiloxane compound (C-1)]
A reaction vessel equipped with a stirrer was charged with 10.4 parts of 2,4-tolylene diisocyanate, 0.08 part of dibutyltin dilaurate and 0.02 part of 2,6-di-t-butyl-p-cresol and brought to 15 ° C. or lower. Cooled down. This is composed of NK ester A-TMM-3LM-N (60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. so that the temperature is kept at 30 ° C. or lower while stirring. Of these, only the pentaerythritol triacrylate having a hydroxyl group is involved in the reaction.) 37.5 parts were added dropwise. After completion of the dropwise addition, the mixture was reacted at 30 ° C for 1 hour. Next, 52.1 parts of α- [3- (2′-hydroxyethoxy) propyl] having a hydroxyl group equivalent of 1,000 and ω-trimethylsilyloxypolydimethylsiloxane (Silaplane FM-0411 manufactured by Chisso Corporation) were added. And stirred at 20-55 ° C. The reaction was terminated when the residual isocyanate was 0.1% by weight or less. When the number average molecular weight of the obtained product was measured by gel permeation chromatography using AS-8020 manufactured by Tosoh Corporation, the polystyrene equivalent number average molecular weight. The same shall apply hereinafter. In addition to the dimethylsiloxane compound, a combination of 1 mole of 20% by weight of tolylene diisocyanate and 2 moles of pentaerythritol triacrylate was observed. The liquid terminal-reactive polydimethylsiloxane compound obtained by this method is designated as C-1.

Synthesis example 3
[Synthesis of a reactive polysiloxane compound (C′-1) having one polymerizable unsaturated group at both ends]
A reaction vessel equipped with a stirrer was charged with 14.3 parts of 2,4-tolylene diisocyanate, 0.08 part of dibutyltin dilaurate and 0.02 part of 2,6-di-t-butyl-p-cresol, and 15 ° C. or less. Cooled to. While stirring, 10.5 parts of hydroxyethyl acrylate was added dropwise so that the temperature was maintained at 30 ° C. or lower. After completion of the dropwise addition, the mixture was reacted at 30 ° C for 1 hour. Next, 37.3 parts of α, ω- [3- (2′-hydroxyethoxy) propyl] polydimethylsiloxane having a hydroxyl group equivalent of 1,000 (Silane Plan FM-4411 manufactured by Chisso Corporation) was added, and 20 to 55 was added. Stir at ° C. The reaction was terminated when the residual isocyanate was 0.1% by weight or less. When the number average molecular weight of the obtained product was measured by gel permeation chromatography using AS-8020 manufactured by Tosoh, the polystyrene equivalent number average molecular weight. The same shall apply hereinafter. In addition to the dimethylsiloxane compound, a combination of 20 mole percent of the product, 1 mole of tolylene diisocyanate and 2 moles of hydroxyethyl acrylate was observed. The liquid both-end reactive polydimethylsiloxane compound obtained by this method is designated as C′-1.

Synthesis example 4
[Synthesis of a reactive polysiloxane compound (C′-2) having one polymerizable unsaturated group at one end]
A reaction vessel equipped with a stirrer was charged with 16.6 parts of 2,4-tolylene diisocyanate, 0.08 part of dibutyltin dilaurate and 0.02 part of 2,6-di-t-butyl-p-cresol, and the temperature was reduced to 15 ° C or lower. Cooled down. While stirring, 8.7 parts of hydroxyethyl acrylate was added dropwise so that the temperature was kept at 30 ° C. or lower. After completion of the dropwise addition, the mixture was reacted at 30 ° C for 1 hour. Next, 74.7 parts of α- [3- (2′-hydroxyethoxy) propyl] having a hydroxyl equivalent weight of 1,000 and ω-trimethylsilyloxypolydimethylsiloxane (Silaplane FM-0411 manufactured by Chisso Corporation) were added. And stirred at 20-55 ° C. The reaction was terminated when the residual isocyanate was 0.1% by weight or less. The number average molecular weight of the obtained polydimethylsiloxane compound was 1400. The liquid end-reactive polydimethylsiloxane compound obtained by this method is designated as C′-2.

Synthesis Example 5: Production of polyfunctional (meth) acrylate represented by formula (6) For a solution comprising 19 parts of isophorone diisocyanate and 0.2 part of dibutyltin dilaurate in a container equipped with a stirrer, NK manufactured by Shin-Nakamura Chemical Co., Ltd. Ester A-TMM-3LM-N (participating in the reaction is only pentaerythritol triacrylate having a hydroxyl group) 93 parts dropwise at 10 ° C. for 1 hour, then at 60 ° C. for 6 hours. The reaction solution was stirred under conditions.
The product in this reaction solution, that is, the amount of residual isocyanate was measured by FT-IR in the same manner as in Production Example 1, and was 0.1% by mass or less, confirming that the reaction was carried out almost quantitatively. did. Moreover, it confirmed that a molecule | numerator contained a urethane bond and an acryloyl group (polymerizable unsaturated group) in a molecule | numerator.
As a result, 75 parts of the compound represented by the formula (6) and 37 parts of pentaerythritol tetraacrylate were obtained.

Synthesis Example 6: Production of polyfunctional (meth) acrylate represented by formula (7) For a solution consisting of 16 parts of 2,4-tolylene diisocyanate and 0.2 part of dibutyltin dilaurate in a container equipped with a stirrer, ND ester A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd. (participating in the reaction is only pentaerythritol triacrylate having a hydroxyl group) was added dropwise at 93 ° C. for 1 hour, then 60 parts. The mixture was stirred at 6 ° C. for 6 hours to prepare a reaction solution.
The product in this reaction solution, that is, the amount of residual isocyanate was measured by FT-IR in the same manner as in Production Example 1, and was 0.1% by mass or less, confirming that the reaction was carried out almost quantitatively. did. Moreover, it confirmed that a molecule | numerator contained a urethane bond and an acryloyl group (polymerizable unsaturated group) in a molecule | numerator.
As a result, 72 parts of the compound represented by the formula (7) and 37 parts of pentaerythritol tetraacrylate were obtained.

[Example of preparation of composition]
Example 1
176.9 parts of reactive silica particle dispersion (A-1) produced in Production Example 1 (54.3 parts as reactive particles (A). 50 parts of silica particles (Aa) and organic compound bonded to the particles (Ab ) 4.3 parts by mass)), dipentaerythritol hexaacrylate (Aronix M-404; Ciba Specialty Chemicals)) 4.8 parts, multifunctional produced in Synthesis Example 5 represented by Formula (6) above 6.1 parts of acrylate, 27.2 parts of polyfunctional acrylate produced in Synthesis Example 6 represented by the formula (7), 3.9 parts of pentaerythritol tetraacrylate, one-end reactive polysiloxane compound produced in Synthesis Example 2 (C-1) 0.2 part, 1-hydroxycyclohexyl phenyl ketone (Irgacure 184) 2.2 part, and 2-methyl-1- (4- (methylthio) A mixture of 1.3 parts of phenyl) -2-morpholinopropan-1-one (Irgacure 907), 10 parts of methyl ethyl ketone (MEK), 70 parts of methyl isobutyl ketone (MIBK) and 20 parts of cyclohexanone at 40 ° C. for 2 hours is homogeneous. A solution was obtained. Among these, pentaerythritol tetraacrylate is derived from pentaerythritol tetraacrylate mixed in the organic compound (Ab) and the polyfunctional acrylate represented by the formula (6). The solid content of this composition was determined to be 24%.
Table 1 shows the blending ratio of each component of the composition.

Comparative Examples 1-3
Each composition was produced in the same manner as in Example 1 except that the composition described in Table 1 was followed.

表１中、反応性粒子（Ａ）の数値は、各粒子分散ゾルの仕込量中に含まれる不揮発成分含有量の重量部を示す。
表１中の略称の内容を下記に示す。
Ａ−１：製造例１で製造した反応性粒子（Ａ）
Ｃ−１：合成例２で製造した片末端反応性ポリジメチルシロキサン化合物（Ｃ）。重合性不飽和基の数は、３である。
Ｃ’−１：合成例３で得られた両末端反応性ポリシロキサン化合物。重合性不飽和基の数は、２である。
Ｃ’−２：合成例４で製造した片末端反応性ポリジメチルシロキサン化合物。重合性不飽和基の数は、１である。

In Table 1, the numerical value of the reactive particle (A) indicates the weight part of the nonvolatile component content contained in the charged amount of each particle-dispersed sol.
The contents of the abbreviations in Table 1 are shown below.
A-1: Reactive particles (A) produced in Production Example 1
C-1: One-terminal reactive polydimethylsiloxane compound (C) produced in Synthesis Example 2. The number of polymerizable unsaturated groups is 3.
C′-1: a double-terminal reactive polysiloxane compound obtained in Synthesis Example 3. The number of polymerizable unsaturated groups is 2.
C′-2: One-end reactive polydimethylsiloxane compound produced in Synthesis Example 4. The number of polymerizable unsaturated groups is 1.

[Evaluation of curable composition and cured film thereof]
In order to clarify the effect of the composition of the present invention, the coating property of the composition was evaluated, and the cured film obtained by coating, drying, and irradiating with the composition was evaluated. The evaluation method is shown below. The evaluation results are shown in Table 2.
(1) Coating, drying, and curing conditions The composition obtained in Example 1 and Comparative Examples 1 to 3 was coated on a substrate using a bar coater so as to have a dry film thickness of 10 μm, and then at 80 ° C. The film was dried in a hot air dryer for 3 minutes and irradiated with a light amount of 1 J / cm ² using a conveyor type mercury lamp to obtain a cured film. Using this cured coating, pencil hardness, adhesion to the substrate, steel wool (SW) scratch resistance, and surface slip were evaluated. The results are shown in Table 2.
Note that a triacetyl cellulose (TAC) film having a thickness of 80 μm was used for evaluation of haze and surface slipperiness.

(2) Evaluation method An evaluation method is shown for each evaluation item. In each evaluation of haze, fingerprint wiping property, and oily dye wiping property, measurement was performed immediately after the production of the laminate, after the wet heat test and after the weather resistance test. Here, the conditions of the wet heat test are 100 hours at 80 ° C. and a relative humidity of 85%, and the conditions of the weather resistance test are a QUV test and 100 hours.

《Haze》
The haze of the laminate was measured according to JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.). The results obtained are shown in Table 1 << Fingerprint Wipeability >>
After pressing the finger on the film cured on the PET film to attach a fingerprint, wipe it back and forth with tissue paper (trade name: Eliere, Daio Paper Co., Ltd.) 40 times to see if the fingerprint remains. Visual observation was performed and the following criteria were evaluated.
A: Can be wiped off within 5 times and no fingerprints remain.
○: Can be wiped off within 20 times and no fingerprints remain.
(Triangle | delta): It can wipe off within 40 times and a fingerprint does not remain.
X: Cannot be wiped off.
<Wipeness of oil-based dyes>
Apply approximately 1 cm ² of the cured film on the PET film with an oil-based dye ink type marking pen (Zebra Co., Ltd., trade name: Mackey) without any gaps. After naturally drying for 1 minute, the portion coated with the marker was wiped off with a non-woven fabric (Bencot), and it was visually observed how many times it was wiped off or not wiped, and was ranked and evaluated according to the following criteria.
(Double-circle): It can wipe off within 5 times and oil-based ink does not remain.
○: Can be wiped off within 20 times, and no oil-based ink remains.
(Triangle | delta): It can wipe off within 40 times and oil-based ink does not remain.
X: Cannot be wiped off.
<Surface slipperiness>
The coating cured on the PET film is cured from the stress when a steel ball with a radius of curvature of 4 mm is attached to a surface property tester manufactured by Shinto Kagaku Co., Ltd. The surface friction was evaluated by calculating the dynamic friction coefficient of the coating surface.

  The curable composition of the present invention comprises a protective coating material and antireflection coating for preventing scratches (scratches) and contamination on the surfaces of various substrates such as plastic, metal, wood, paper, glass, and slate. Suitable as a material.

Claims (6)

The following (A), (B) and (C) with respect to the total amount of the composition:
(A) an oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium, having a polymerizable unsaturated group as a main component 5 to 85% by weight of particles
(B) 10 to 90% by weight of a polymerizable organic compound having two or more polymerizable unsaturated groups other than the following component (C)
(C) 0.1 to 5% by weight of a compound containing a structure represented by the following formula (1)

[In Formula (1), R ¹ represents a monovalent organic group having 3 or more polymerizable unsaturated groups, R ² represents a divalent organic group having a urethane bond, and R ³ and R ⁴ are each Independently, it represents a methyl group or a phenyl group, and n represents a number from 1 to 150. ]
A curable composition comprising: The curable composition according to claim 1, wherein the polymerizable unsaturated group of the component (A) is a group including a structure represented by the following formula (2).

[In Formula (2), U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. ] The curable composition according to claim 1 or 2, wherein the number of polymerizable unsaturated groups contained in the component (C) is equal to the number of polymerizable unsaturated groups contained in R ^{1 of the} formula (1). The curable composition as described in any one of Claims 1-3 whose polymerizable unsaturated group which the said (C) component has is a (meth) acryloyl group. The cured film which consists of hardened | cured material of the curable composition as described in any one of Claims 1-4. The laminated body formed by laminating | stacking the cured film of Claim 5 on a transparent base material.