JP2008081575A - Curable composition, cured film and laminated form - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition excellent in coatability, and capable of forming coating film that has high hardness and scratch resistance, excellent in transparency and also in stainproofness and weatherability, low in curling tendency and high in flexibility on various base materials, and to provide its cured film. <P>SOLUTION: The curable composition comprises the following components (A) to (D): (A) particles bound to an organic compound (Ab) having in the molecule polymerizable unsaturated group(s) and consisting mainly of oxide(s) of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium; (B) a compound having two or more urethane linkages and two or more polymerizable unsaturated groups; (C) a polysiloxane compound having one or more polymerizable groups; (D) a compound having two or more polymerizable unsaturated groups other than the components B and C. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a curable composition, a cured film thereof, and a laminate.

  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 each substrate has hardness, There is a demand for a curable composition capable of forming a cured film having excellent scratch resistance, abrasion resistance, surface slipperiness, low curling properties, adhesion, transparency, chemical resistance, and coating film appearance. ing.

In order to satisfy such a request, various compositions have been proposed, but have excellent coating properties as a curable composition, and when it is a cured film, has high hardness and scratch resistance, 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 slipperiness by blending a polysiloxane having a (meth) acryloyl group, but there is room for further 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, excellent antifouling properties and weather resistance, and low curl properties. An object of the present invention is to provide a curable composition capable of forming a coating film (film) having excellent flexibility and a cured film thereof.

  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, (B) two or more urethane bonds and two or more. A compound having a polymerizable unsaturated group of (C), a polysiloxane compound having one or more polymerizable unsaturated groups, and (D) two or more other than the components (A), (B) and (C) By using a curable composition containing a compound having a polymerizable unsaturated group, it was found that a cured film satisfying the above-mentioned characteristics could be obtained, and the present invention was completed.

［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。］
４．前記成分（Ｃ）のガスパーミエーションクロマトグラフィー法（ＧＰＣ）によるポリスチレン換算数平均分子量が５００以上である上記１〜３のいずれかに記載の硬化性組成物。
５．成分（Ｃ）が、下記式（１）

［式（１）中、Ｒ^１は１個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及びＲ^４は各々独立してメチル基又はフェニル基を示し、Ｒ^５は１個以上の重合性不飽和基を有する１価の有機基、炭素数１〜３０の飽和炭化水素基、炭素数１〜３０の脂環式飽和炭化水素基又は炭素数１〜３０の芳香族不飽和炭化水素基を示し、ｎは１〜１５０の数を示す。］
で示される構造を含む化合物である上記１〜４のいずれかに記載の硬化性組成物。
６．前記式（１）で示される化合物が、Ｒ^１のみにおいて重合性不飽和基を有する、上記５に記載の硬化性組成物。
７．前記（Ｃ）成分が有する重合性不飽和基が、（メタ）アクリロイル基である、上記１〜６のいずれかに記載の硬化性組成物。
８．前記成分（Ｂ）が、下記式（６）及び／又は（７）

［式（６）及び式（７）中、「Ａｃｒｙｌ」は、アクリロイル基を示す。］
である上記１〜７のいずれかに記載の硬化性組成物。
９．さらに、（Ｅ）ラジカル重合開始剤を含有する上記１〜８のいずれかに記載の硬化性組成物。
１０．さらに、（Ｆ）有機溶剤を含有する上記１〜９のいずれかに記載の硬化性組成物。
１１．上記１〜１０のいずれかに記載の硬化性組成物の硬化物からなる硬化膜。
１２．透明基材上に上記１２に記載の硬化膜を積層してなる積層体。 That is, this invention provides the following curable composition, cured film, and laminated body.
1. The following components (A) to (D):
(A) At least one selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium, bonded to an organic compound (Ab) having a polymerizable unsaturated group in the molecule Particles mainly composed of elemental oxides (B) Compound having two or more urethane bonds and two or more polymerizable unsaturated groups (C) Polysiloxane compound having one or more polymerizable groups (D ) A curable composition containing a compound having two or more polymerizable unsaturated groups other than the components (A), (B) and (C).
2. When the total solid content in the composition is 100% by weight, the component (A) is in the range of 5 to 85% by weight, the component (B) is in the range of 5 to 50% by weight, and the component (C ) In a range of 0.01 to 5% by weight and the component (D) in a range of 1 to 87% by weight.
3. Curing of said 1 or 2 whose organic compound (Ab) which has a polymerizable unsaturated group and a hydrolysable silyl group in the molecule | numerator of said (A) component is a compound containing the structure shown to following formula (2). Sex composition.

[In Formula (2), U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. ]
4). The curable composition according to any one of 1 to 3 above, wherein the component (C) has a polystyrene-reduced number average molecular weight of 500 or more by gas permeation chromatography (GPC).
5. Component (C) is represented by the following formula (1)

[In Formula (1), R ¹ represents a monovalent organic group having one 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 represents a methyl group or a phenyl group, and R ⁵ represents a monovalent organic group having one or more polymerizable unsaturated groups, a saturated hydrocarbon group having 1 to 30 carbon atoms, and a fat having 1 to 30 carbon atoms. A cyclic saturated hydrocarbon group or a C1-C30 aromatic unsaturated hydrocarbon group is shown, n shows the number of 1-150. ]
The curable composition in any one of said 1-4 which is a compound containing the structure shown by these.
6). 6. The curable composition according to 5 above, wherein the compound represented by the formula (1) has a polymerizable unsaturated group only in R ¹ .
7). The curable composition in any one of said 1-6 whose polymerizable unsaturated group which the said (C) component has is a (meth) acryloyl group.
8). The component (B) is represented by the following formula (6) and / or (7)

[In the formulas (6) and (7), “Acryl” represents an acryloyl group. ]
The curable composition according to any one of 1 to 7 above.
9. Furthermore, (E) The curable composition in any one of said 1-8 containing a radical polymerization initiator.
10. Furthermore, (F) The curable composition in any one of said 1-9 containing the organic solvent.
11. The cured film which consists of hardened | cured material of the curable composition in any one of said 1-10.
12 A laminate obtained by laminating the cured film described in 12 above on a transparent substrate.

  The present invention has excellent coating properties, the surface of various substrates, excellent transparency and scratch resistance, high hardness, surface slipperiness and antifouling properties (fingerprint wiping and oiliness) It is possible to provide a curable composition capable of forming a coating film (film) excellent in dye wiping property) and sustainability thereof, and a cured film thereof.

1. Curable composition The curable composition of this invention may contain the following component (A)-(G). Components (A) to (D) are essential components, and components (E) to (G) are optional components that can be added as necessary.
(A) At least one selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium, bonded to an organic compound (Ab) having a polymerizable unsaturated group in the molecule Particles mainly composed of elemental oxides (hereinafter referred to as “reactive particles”)
(B) Compound having two or more urethane bonds and two or more polymerizable unsaturated groups (hereinafter referred to as “urethane bond-containing compound”)
(C) a polysiloxane compound having one or more polymerizable groups (hereinafter referred to as “reactive polysiloxane compound”)
(D) A compound having two or more polymerizable unsaturated groups other than the components (A), (B) and (C) (hereinafter referred to as “polyfunctional polymerizable unsaturated group-containing compound”).
(E) Radical polymerization initiator (F) Organic solvent (G) additive Hereinafter, each component is demonstrated.

[1] Reactive particles The reactive particles (A) used in the present invention are oxidized of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. Silicon, aluminum, zirconium, which has a polymerizable unsaturated group, obtained by reacting a particle (Aa) containing a product as a main component with an organic compound (Ab) having a polymerizable unsaturated group in the molecule, The particles are mainly composed of an oxide of at least one element selected from the group consisting of titanium, zinc, germanium, indium, tin, antimony and cerium.

(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. Among these, silica, alumina, zirconia and antimony oxide particles are preferable from the viewpoint of high hardness. These may be used alone or in combination of two or more. Furthermore, the oxide particles (Aa) are preferably used as a powder or solvent-dispersed 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., Nippon Silica Industry, Nippon Aerosil 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 ) Cellax: Alumina, titanium oxide, tin oxide, indium oxide, zinc oxide and other powders 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 Corp .; cerium oxide The dispersion can be exemplified 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 indeterminate 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 ratio of the organic polymer component, that is, the hydrolyzable silane hydrolyzate and condensate in the resulting reactive particles (A) is usually the weight loss% when the dry powder is completely burned in air. The constant value can be obtained, for example, by thermogravimetric analysis from room temperature to usually 800 ° C. in air.

  The amount of the organic compound (Ab) bound to the oxide particles (Aa) is preferably 100% by weight of the reactive particles (A) (the total of the metal oxide particles (Aa) and the organic compound (Ab)), It is 0.01% by weight or more, more preferably 0.1% by weight or more, and particularly preferably 1% by weight or more. When the amount of the organic compound (Ab) bound to the metal oxide particles (Aa) is less than 0.01% by weight, 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 weight, and more preferably 10 to 98% by weight. The content of the oxide particles (Aa) constituting the reactive particles (A) is preferably 65 to 95% by weight of the reactive particles (A).

The content of the reactive particles (A) in the curable composition is 5 to 85% by weight, with the total solid content excluding the organic solvent being 100% by weight. 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.
In addition, content of the reactive particle (A) means solid content, and when the reactive particle (A) is used in the form of a solvent-dispersed sol, the content does not include the amount of solvent.

[2] Urethane bond-containing compound The urethane bond-containing compound used in the present invention is a compound (B) having two or more urethane bonds and two or more polymerizable unsaturated groups. By blending this compound, The resulting cured film exhibits low curl and high flexibility and contributes to high hardness. By having a urethane group, high hardness can be expressed and flexibility with respect to bending can be imparted even though the crosslink density is lower than that of ordinary polyfunctional (meth) acrylate.

［式（６）及び式（７）中、「Ａｃｒｙｌ」は、アクリロイル基を示す。］ The urethane bond-containing compound is not particularly limited as long as it has two or more urethane bonds and two or more polymerizable unsaturated groups, preferably a (meth) acryloyl group. However, diisocyanates such as tolylene diisocyanate ( A polyaddition product of TDI) or isophorone diisocyanate (IPDI) and a hydroxyl group-containing (meth) acrylate such as monohydroxypentaerythritol triacrylate is preferable. As a preferable urethane bond containing compound, the compound shown by following formula (6) and (7) is mentioned, for example. When a urethane bond-containing compound having an isophorone diisocyanate skeleton is used, particularly weathering yellowing can be reduced.

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

  The content of the urethane bond-containing compound (B) used in the composition of the present invention is 5 to 50% by weight, preferably 10 to 40% by weight, with the total solid content excluding the organic solvent being 100% by weight. is there. If it is less than 5% by weight, scratch resistance (steel wool resistance) may be reduced, and if it exceeds 50% by weight, pencil hardness may be reduced.

[3] (C) Reactive polysiloxane compound The reactive polysiloxane compound (C) is not particularly limited as long as it is a compound having one or more polymerizable groups and having two or more siloxane structures. A spacer structure such as a urethane bond may be appropriately provided between the polysiloxane chain and the polymerizable group. By introducing a urethane bond, compatibility with other components is improved, and large layer separation that adversely affects optical properties can be suppressed.

  The polymerizable group of the reactive polysiloxane compound used in the curable composition of the present invention is not particularly limited. For example, an acryloyl group, a methacryloyl group, a vinyl group, a propenyl group, a butadienyl group, a styryl group, Examples thereof include polymerizable unsaturated groups such as ethynyl group, cinnamoyl group, maleate group, and acrylamide group; and epoxy group-substituted alkyl or alkoxy groups such as 2,3-epoxypropyloxy group and epoxycyclohexyl group. Among these, an acryloyl group and a methacryloyl group are preferable from the viewpoint of imparting radiation curability. When the component (C) has two or more polymerizable groups, the polymerizable groups may be groups having the same structure or different structures. By having a polymerizable group, it is possible to form a chemical bond with the polymerizable unsaturated group of other components, causing bleed-out during the durability test and wear test, and antifouling properties and slippage of the resulting cured film. There is no decline in sex.

  The number average molecular weight in terms of polystyrene by GPC method of the reactive polysiloxane compound is preferably 500 or more, more preferably 800 to 15000, and particularly preferably in the range of 1000 to 7000. When the number average molecular weight is less than 500, the antifouling property and surface slipping property of the cured product of the composition containing the composition may not be sufficient. When the number average molecular weight exceeds 15,000, the composition containing the cured product The coatability may be inferior.

（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及びＲ^４は各々独立してメチル基又はフェニル基を示し、Ｒ^５は１個以上の重合性不飽和基を有する１価の有機基、炭素数１〜３０の飽和炭化水素基、炭素数１〜３０の脂環式飽和炭化水素基又は炭素数１〜３０の芳香族不飽和炭化水素基を示し、ｎは１〜１５０の数を示す） As the reactive polysiloxane compound (C), a compound represented by the following formula (1) is preferable.

(In the formula, 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 R ⁵ represents a monovalent organic group having one or more polymerizable unsaturated groups, a saturated hydrocarbon group having 1 to 30 carbon atoms, an alicyclic saturated carbon atom having 1 to 30 carbon atoms. A hydrogen group or an aromatic unsaturated hydrocarbon group having 1 to 30 carbon atoms, and n represents a number from 1 to 150)

Of the reactive polysiloxane compounds having the structure represented by the formula (1), if only R ¹ has a polymerizable unsaturated group, the resulting cured film can have both good transparency and antifouling properties. Particularly preferred (hereinafter, the component (C) having such a structure is referred to as “one-terminal reactive polysiloxane compound”). In this case, the molecular terminal structure of the reactive polysiloxane represented by R ⁵ in the above formula (1) is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or the like. , A saturated hydrocarbon group of n = 1 to 30 represented by C _n H _{2n + 1} , an alicyclic saturated hydrocarbon group such as a cyclohexyl group, an aromatic unsaturated hydrocarbon group such as a phenyl group and a benzyl group, and the like.

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. Preferred 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. There may be one urethane bond, but there may be two or more.

The compound of the formula (1) having a urethane bond in R ² can be produced, for example, by reacting a polyisocyanate, 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 polysiloxane structure in the reactive polysiloxane compound is introduced using, for example, a silicone compound having a hydroxyl group at the molecular end.
Examples of such a silicone compound include a 3- (2′-hydroxyethoxy) propyl group, a 3- (2 ′, 3′-dihydroxypropyloxy) propyl group, and 3- (2′-ethyl-2 ′) at the molecular end. Examples include silicone compounds having organic groups 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)

(In the formula, 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. It is preferable to make the reaction so that the hydroxyl group equivalent of the silicone compound having a hydroxyl group and the hydroxyl group-containing (meth) acrylate and the isocyanate equivalent of the polyisocyanate substantially coincide.

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 together and reacted; A method in which the silicone compound and the hydroxyl group-containing (meth) acrylate are reacted; a method in which the polyisocyanate, the silicone compound and the hydroxyl group-containing (meth) acrylate are reacted, and then a polyol is reacted; 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, and then a polyol It reacted, 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 composition of the present invention is 0.01 to 5% by weight based on 100% by weight of the total solid content excluding the organic solvent. Preferably it is 0.05 to 3 weight% of range. When the content of the reactive polysiloxane compound (C) is less than 0.01% 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.

[4] (D) Polyfunctional polymerizable unsaturated group-containing compound The polyfunctional polymerizable unsaturated group-containing compound (D) used in the present invention is suitably used for enhancing the film-forming property of the composition. As the polyfunctional polymerizable unsaturated group-containing compound (D), as long as it contains two or more polymerizable unsaturated groups in the molecule, the aforementioned components (A), (B) and (C) are excluded. In addition, although there is no restriction | limiting in particular, (meth) acrylic esters and vinyl compounds can be mentioned, for example. Of these, (meth) acrylic esters are preferred.

  (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 And oligoepoxy (meth) acrylates. Among these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate and the like are preferable.

  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 polyfunctional polymerizable unsaturated group containing compound (D), 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, Nippon Kayaku Co., Ltd. KAYARAD D-310, D-330, DPHA, DPC -20, DPCA-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 polyfunctional polymerizable unsaturated group-containing compound (D) used in the composition of the present invention is 1 to 87% by weight based on 100% by weight of the total solid content excluding the organic solvent. Preferably it is 15 to 80% by weight. If it is less than 1% by weight or more than 87% by weight, it may not be possible to obtain a high hardness when cured.

  In the composition of the present invention, in addition to the reactive particles (A), the urethane bond-containing compound (B), the reactive polysiloxane compound (C) and the polyfunctional polymerizable unsaturated group-containing compound (D). If necessary, a compound having one polymerizable unsaturated group in the molecule other than these components may be contained.

[5] (E) Radical Polymerization Initiator In the composition of the present invention, (E) a radical polymerization initiator (hereinafter referred to as “radical polymerization initiator (E) as a blending component other than the above components (A) to (D). It is preferable to blend in some cases.
Examples of such radical polymerization initiator (E) 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.

  As a commercial item of a radiation (photo) polymerization initiator, for example, Ciba Specialty Chemicals Co., Ltd. Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG 24-61 , Darocur 1116, 1173, BASF's Lucillin 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 (E) used as needed in the composition of the present invention is preferably 0.01 to 20 parts by weight based on 100 parts by weight of the total solid content excluding the organic solvent. 0.1 to 10 parts by weight 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.

[6] (F) Organic solvent The composition of the present invention can be used after being diluted with an organic 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.
Examples of the organic solvent (F) 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 include amides such as N-methylpyrrolidone.

  The content of the organic solvent (F) used as necessary in the composition of the present invention is preferably 50 to 10,000 parts by weight with respect to 100 parts by weight of the total solid content excluding the organic solvent. -1,000 parts by weight is more preferable, and 80-500 parts by weight is even more preferable.

[7] (G) Additive In addition to the above components, a thermal polymerization initiator, an antioxidant, an ultraviolet absorber, a leveling agent, and the like can be added to the composition of the present invention 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.

[8] Curing Method 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 tungsten filaments, 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. Moreover, as a source of alpha rays, solid rays, and gamma rays, for example, a fission material such as Co ⁶⁰ can be cited. For gamma rays, a vacuum tube that collides accelerated electrons with the anode can be used. These radiations can be irradiated alone or in combination of two or more at a certain time.

  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. These substrates may be in the form of a plate, film or three-dimensional molded body, and the coating method may be 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.

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 such as high hardness and scratch resistance, and can form a coating film having excellent surface slipperiness depending on the composition. Recording discs, plastic optical components, touch panels, film-type liquid crystal elements, plastic containers, floor materials as building interior materials, wall materials, protective coating materials for preventing scratches (scratches) and preventing contamination of artificial marble, 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 its sustainability, 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% respectively represent parts by weight and% by weight unless otherwise specified.

Synthesis example 1
[Synthesis of Organic Compound (Ab)]
To a solution consisting of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate in dry air, 222 parts of isophorone diisocyanate was added dropwise over 1 hour at 50 ° C. with stirring, followed by heating and stirring at 70 ° C. for 3 hours. NK ester A-TMM-3LM-N (60% by weight of pentaerythritol triacrylate and 40% by weight of pentaerythritol tetraacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. Among them, the one involved in the reaction is pentaerythritol having a hydroxyl group. 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 amount of residual isocyanate in the product was analyzed by FT-IR, it was 0.1% or less, indicating that the reaction was almost quantitatively completed. Infrared absorption spectrum of the product disappeared absorption peaks characteristic 2260 cm ^-1 to the absorption peak and the raw material isocyanate compounds characteristic 2550 cm ^-1 mercapto group in the raw material, new urethane bond and S (C = O) NH- peaks characteristic 1720 cm ^-1 to a peak and an acryloxy group of characteristic 1660 cm ^-1 based on observed, acryloxy group and -S (C = O as a polymerization unsaturated group) NH-, It was shown that an acryloxy group-modified alkoxysilane having a urethane bond was formed. As a result, a total of 773 parts of the organic compound (Ab) represented by the formulas (4) and (5) and 220 parts of pentaerythritol tetraacrylate were obtained.

Synthesis example 2
[Production of Reactive Particles (A-1)]
2.98 parts of the composition produced in Synthesis 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 3
[Synthesis of Reactive Polysiloxane Compound (C-1) Having Three Acrylyl Groups at One Terminal]
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 the temperature was reduced to 15 ° C. or lower. Cooled down. This is composed of NK ester A-TMM-3LM-N (60% by weight of pentaerythritol triacrylate and 40% by weight of pentaerythritol tetraacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. so that the temperature is maintained 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 (Silane Plain 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 4
[Synthesis of reactive polysiloxane compound (C-2) having one acryloyl group at each end]
A reaction vessel equipped with a stirrer was charged with 14.4 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 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 terminal reactive polydimethylsiloxane compound obtained by this method is designated as C-2.

Synthesis example 5
[Synthesis of Reactive Polysiloxane Compound (C-3) Having One Acrylyl 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-3.

Synthesis Example 6
[Production of urethane bond-containing polyfunctional (meth) acrylate (B-1) represented by formula (6)]
NK ester A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd. (which has a hydroxyl group is involved in a solution consisting of 19 parts isophorone diisocyanate and 0.2 part dibutyltin dilaurate in a vessel equipped with a stirrer. (Only pentaerythritol triacrylate.) 93 parts were added dropwise at 10 ° C. for 1 hour, and then stirred at 60 ° C. for 6 hours to obtain 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 weight 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 7
[Production of urethane bond-containing polyfunctional (meth) acrylate (B-2) represented by formula (7)]
To a solution consisting of 16 parts of 2,4-tolylene diisocyanate and 0.2 part of dibutyltin dilaurate in a vessel equipped with a stirrer, NK ester A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical) Is only pentaerythritol triacrylate having a hydroxyl group.) 93 parts were added dropwise at 10 ° C. for 1 hour, and then stirred at 60 ° C. for 6 hours to obtain 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 weight 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 Synthesis Example 2 (including 54.3 parts as reactive particles (A) and 122.6 parts by weight of methyl ethyl ketone. Reactive particles (A) are , 50 parts of silica particles (Aa) and 4.3 parts by weight of organic compound (Ab) bonded to the particles.), Dipentaerythritol hexaacrylate (Aronix M-404; Ciba Specialty Chemicals)) 4.8 parts 6.1 parts of urethane bond-containing polyfunctional acrylate (B-1) produced in Synthesis Example 6 represented by Formula (6), and urethane bond-containing polyfunctional product produced in Synthesis Example 7 represented by Formula (7) 27.2 parts of acrylate (B-2), 3.9 parts of pentaerythritol tetraacrylate, 0.2 part of the one-terminal reactive polysiloxane compound (C-1) produced in Synthesis Example 3, 1 2.2 parts hydroxycyclohexyl phenyl ketone (Irgacure 184), 1.3 parts 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one (Irgacure 907), 10 parts methyl ethyl ketone (MEK) Then, 70 parts of methyl isobutyl ketone (MIBK) and 20 parts of cyclohexanone were stirred at 40 ° C. for 2 hours to obtain a uniform solution. 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 31%.
Table 1 shows the blending ratio of each component of the composition.

Examples 2-4 and Comparative Examples 1-2
Each composition was produced in the same manner as in Example 1 except that the composition described in Table 1 was followed.

In Table 1, the numerical value of the reactive particles (A-1) indicates parts by weight 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 produced in Synthesis Example 2 (A)
C-1: One-terminal reactive polydimethylsiloxane compound (C) produced in Synthesis Example 3. The number of polymerizable unsaturated groups is three.
C-2: Both-ends reactive polysiloxane compound (C) obtained in Synthesis Example 4. The number of polymerizable unsaturated groups is two.
C-3: One-terminal reactive polydimethylsiloxane compound produced in Synthesis Example 5. The number of polymerizable unsaturated groups is one.

[Evaluation of curable composition and cured film thereof]
(1) Coating, drying, and curing conditions The composition obtained in each Example and Comparative Example was coated on a substrate using a bar coater so as to have a dry film thickness of 20 μm, and then heated at 80 ° C. with hot air. The film was dried in the machine 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 film, transmittance, haze, antifouling property, pencil hardness, steel wool (SW) resistance, curling property, flexibility, weather resistance (yellowing and change in haze) were evaluated. The results are shown in Table 2.
The substrate was a triacetyl cellulose (TAC) film having a thickness of 80 μm for haze evaluation.

(2) Evaluation method An evaluation method is shown for each evaluation item. Haze and antifouling properties (fingerprint wiping property and oily dye wiping property) were measured and evaluated immediately after production of the laminate. Here, the conditions of the wet heat test were 100 ° C. at 80 ° C. and 85% relative humidity. It is time, and the conditions of the weather resistance test are a QUV test and 100 hours.

(I) Transmittance The transmittance was measured in accordance with JISK7105 using the obtained TAC hard coat film using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.). The obtained light transmittance value was evaluated according to the following criteria.
◎: Light transmittance 95% or more ○: Light transmittance 90% or more and less than 95% Δ: Light transmittance 85% or more and less than 90% ×: Light transmittance less than 85%

(Ii) Haze The haze of the laminate was measured according to JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.).
◎: Less than 0.3 ○: 0.3 or more and less than 0.6 Δ: 0.6 or more and less than 1.2 ×: 1.2 or more

(Iii) Antifouling (fingerprint wiping)
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.

(Iii) Antifouling property (wiping property of oil-based dye)
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.

(Iv) Pencil hardness Using a pencil hardness tester, the hardness of the core of the hardest pencil that was scratched five times under the condition of a load of 500 g and was not damaged four times or more was used as an evaluation value.

(V) Scratch resistance test (steel wool resistance test)
The obtained cured film was attached with steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.). The surface was repeatedly rubbed 10 times under the condition of a load of 500 g, and the presence or absence of scratches on the surface of the cured film was visually confirmed according to the following criteria. The evaluation criteria are as follows.
A: The cured film is not damaged.
◯: Almost no peeling or scratching of the cured film is observed, or slight thin scratches are observed on the cured film.
Δ: Streaky scratches are observed on the entire surface of the cured film.
X: Peeling of the cured film occurs.

(Vi) Curling property The obtained TAC film with hard coat was cut into a size of 10 cm square, placed horizontally, and the average of the floats from the horizontal surfaces of the four corners was taken as the curl value, and evaluated according to the following criteria.
◎: 0 mm or more and less than 10 mm ○: 10 mm or more and less than 30 mm Δ: 30 mm or more and less than 50 mm x: 50 mm or more

(Vii) Flexibility The obtained hard-coated TAC film was cut into a size of 10 cm × 1 cm, wound around a metal rod, and the minimum diameter of the metal rod for which no crack was visually confirmed was taken as an evaluation value.
◎: 1 mm or more and less than 5 mm ○: 5 mm or more and less than 15 Δ: 15 mm or more and less than 25 mm x: 25 mm or more

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

Claims (12)

The following components (A) to (D):
(A) At least one selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium, bonded to an organic compound (Ab) having a polymerizable unsaturated group in the molecule Particles mainly composed of elemental oxides (B) Compound having two or more urethane bonds and two or more polymerizable unsaturated groups (C) Polysiloxane compound having one or more polymerizable groups (D ) A curable composition containing a compound having two or more polymerizable unsaturated groups other than the components (A), (B) and (C).   When the total solid content in the composition is 100% by weight, the component (A) is in the range of 5 to 85% by weight, the component (B) is in the range of 5 to 50% by weight, and the component (C ) In the range of 0.01 to 5% by weight and the component (D) in the range of 1 to 87% by weight. The organic compound (Ab) having a polymerizable unsaturated group and a hydrolyzable silyl group in the molecule of the component (A) is a compound containing a structure represented by the following formula (2). Curable composition.

[In Formula (2), U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. ]   The curable composition according to any one of claims 1 to 3, wherein the component (C) has a polystyrene-reduced number average molecular weight of 500 or more by gas permeation chromatography (GPC). Component (C) is represented by the following formula (1)

[In Formula (1), R ¹ represents a monovalent organic group having one 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 represents a methyl group or a phenyl group, and R ⁵ represents a monovalent organic group having one or more polymerizable unsaturated groups, a saturated hydrocarbon group having 1 to 30 carbon atoms, and a fat having 1 to 30 carbon atoms. A cyclic saturated hydrocarbon group or a C1-C30 aromatic unsaturated hydrocarbon group is shown, n shows the number of 1-150. ]
The curable composition according to any one of claims 1 to 4, which is a compound having a structure represented by: The curable composition according to claim 5, wherein the compound represented by the formula (1) has a polymerizable unsaturated group only in R ¹ .   The curable composition of any one of Claims 1-6 whose polymerizable unsaturated group which the said (C) component has is a (meth) acryloyl group. The component (B) is represented by the following formula (6) and / or (7)

[In the formulas (6) and (7), “Acryl” represents an acryloyl group. ]
The curable composition according to any one of claims 1 to 7.   Furthermore, (E) The curable composition of any one of Claims 1-8 containing a radical polymerization initiator.   Furthermore, the curable composition of any one of Claims 1-9 containing the organic solvent (F).   The cured film which consists of hardened | cured material of the curable composition of any one of Claims 1-10.   The laminated body formed by laminating | stacking the cured film of Claim 11 on a transparent base material.