JP2008024808A - Curable composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition which is excellent in applicability and is capable of forming a coating film (coating) with a high hardness and a scratch resistance on surfaces of various substrates, and a cured product thereof. <P>SOLUTION: The curable composition comprises (A) a particle (Aa) which essentially comprises silica, has a number average particle size of 30-200 nm and is surface-treated with an organic compound (Ab) having a polymerizable unsaturated group, (B) a compound having at least three (meth)acryloyl groups within the molecule and (C) an organic solvent. The proportion of the silica particle (Aa) in the component (A) is ≥30 mass% against 100 mass% total solid content of the composition, and methyl isobutyl ketone (MIBK) accounts for ≥50 mass% of the component (C). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a curable composition and a cured product thereof. More specifically, the present invention has excellent coating properties, and has high hardness and scratch resistance on the surface of various substrates. The present invention relates to a curable composition capable of forming a coating film (film) having excellent properties and a cured product thereof.

  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 demand, various compositions have been proposed, but when the cured film has excellent coating properties as a curable composition, high hardness and scratch resistance, or The present condition is that the thing with the characteristic that it is excellent also in surface slipperiness has not been obtained yet. As a method for imparting surface slipperiness, for example, Patent Document 1 includes a bisphenol A diglycidyl ether polymer acrylate ester, dipentaerythritol pentaacrylate, a photopolymerization initiator, inorganic particles, and terminal-reactive polydimethylsiloxane. It has been proposed to use the photocurable resin composition as a photocurable coating material. However, a cured product using such a composition is not necessarily satisfactory in terms of hardness and scratch resistance, although a certain improvement in surface slipperiness is recognized.

JP-A-11-124514

  The present invention provides a curable composition having excellent coating properties and capable of forming a coating film (film) having high hardness and scratch resistance on the surface of various substrates, and a cured product thereof. For the purpose.

  As a result of intensive studies to achieve the above object, the present inventors have (A) particles (Aa) containing silica as a main component and surface-treated with an organic compound (Ab) having a specific organic group. , (B) a compound having three or more (meth) acryloyl groups in the molecule, and (C) a ratio of particles (Aa) containing an organic solvent and having silica as a main component, and (C) identification in the organic solvent By using a curable composition having a ratio of the organic solvent in a predetermined range, it was found that a cured product satisfying the above-mentioned various characteristics could be obtained, and the present invention was completed.

［一般式（１１）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。］で示される基を有する上記１又は２に記載の硬化性組成物。
４．さらに、（Ｄ）放射線重合開始剤を含有する上記１〜３のいずれかに記載の硬化性組成物。
５．さらに、（Ｅ）重合性不飽和基を有する有機化合物（Ｅｂ）によって表面処理されていてもよい、シリカを主成分とする数平均粒子径が１ｎｍ以上３０ｎｍ未満の粒子（Ｅａ）を含有する上記１〜４のいずれかに記載の硬化性組成物。
６．上記１〜５のいずれかに記載の硬化性組成物を硬化させてなる硬化物。 According to the present invention, the following curable composition and its cured product are provided.
1. The following components (A) to (C):
(A) Particles (Aa) having a number average particle diameter of 30 nm or more and 200 nm or less mainly composed of silica, which is surface-treated with an organic compound (Ab) having a polymerizable unsaturated group
(B) A curable composition containing a compound (C) an organic solvent having three or more (meth) acryloyl groups in the molecule,
When the total solid content in the composition is 100% by mass, the proportion of silica particles (Aa) in the component (A) is 15% by mass or more, and 50% by mass or more of the component (C). A curable composition wherein is methyl isobutyl ketone (MIBK).
2. 2. The curable composition according to 1 above, wherein the organic compound (Ab) having a polymerizable unsaturated group is a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis.
3. The compound (Ab) having a polymerizable unsaturated group is further represented by the following formula (11):

[In General Formula (11), U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. The curable composition of said 1 or 2 which has group shown by this.
4). Furthermore, (D) The curable composition in any one of said 1-3 containing a radiation polymerization initiator.
5. Furthermore, (E) the above-mentioned containing particles (Ea) having a number average particle diameter of 1 nm or more and less than 30 nm, the main component of which may be surface-treated with an organic compound (Eb) having a polymerizable unsaturated group The curable composition in any one of 1-4.
6). Hardened | cured material formed by hardening | curing the curable composition in any one of said 1-5.

  ADVANTAGE OF THE INVENTION According to this invention, the curable composition which gives the hardened | cured material which has the outstanding coating property on the surface of various base materials, and has abrasion resistance and high hardness, and its hardened | cured material can be provided.

  Embodiments of the curable composition of the present invention and the cured product thereof will be described below.

1. Curable composition The curable composition of this invention (henceforth the composition of this invention) may contain the following component (A)-(F). Among these components, (A) to (C) are essential components, and (D) to (F) are optional components that can be added as necessary.
(A) Particles (Aa) having a number average particle diameter of 30 nm to 200 nm, the surface of which is modified with an organic compound (Ab) having a polymerizable unsaturated group, the main component of which is silica.
(B) Compound having three or more (meth) acryloyl groups in the molecule (C) Organic solvent (D) Polymerization initiator (E) Organic compound (Eb) having a polymerizable unsaturated group was used for surface modification. Particles having a number average particle diameter of 1 nm or more and less than 30 nm (Ea) mainly composed of silica
(F) Other additives

In the composition of the present invention, a cured film having a high hardness can be provided by blending a specific amount of silica particles having a specific particle diameter, which is surface-modified with an organic compound having a polymerizable unsaturated group. .
These components will be described below.

(A) Particles (Aa) having a number average particle diameter of 30 nm or more and 200 nm or less mainly composed of silica, which is surface-treated with an organic compound (Ab) having a polymerizable unsaturated group
The component (A) used in the present invention is a silica particle (Aa) having a number average particle diameter of 30 nm or more and 200 nm or less, which is surface-treated with an organic compound (Ab) having a polymerizable unsaturated group, that is, polymerizable on the surface. Silica particles having an unsaturated group (hereinafter referred to as “reactive particles” or “reactive particles (Aab)”). By containing such reactive particles (Aab), the hardness and scratch resistance of a cured product obtained by curing the curable composition can be improved.

(Aa) Silica particles Known silica particles can be used as the silica particles used in the present invention. The shape may be spherical or indefinite, and is not limited to ordinary colloidal silica, and may be hollow particles, porous particles, core-shell type particles, or the like.
Further, the number average particle diameter of the silica particles determined by the dynamic light scattering method is 30 nm or more, more preferably 30 to 200 nm, and particularly preferably 40 to 80 nm. There exists a possibility that the hardness of a cured film may fall that the number average particle diameter of a silica particle is less than 30 nm.
The silica particles are preferably colloidal silica having a solid content of 10 to 40% by mass and a pH of 2.0 to 6.5.

  The dispersion medium of silica particles is preferably water or an organic solvent. Examples of organic solvents include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide and dimethyl Examples include amides such as acetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; and organic solvents such as ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in admixture of two or more as a dispersion medium.

  As a commercial item of a silica particle (Aa), Nissan Chemical Industries Ltd. MEK-ST-L, IPA-ST-L, IPA-ST-ZL etc. can be mentioned as colloidal silica, for example.

(Ab) Organic compound having a polymerizable unsaturated group Component (A) used in the present invention is reactive silica particles (Aab). The reactive particles (Aab) are obtained by surface-treating the silica particles (Aa) with an organic compound (Ab) having a polymerizable unsaturated group (hereinafter referred to as “organic compound (Ab)”). The organic compound (Ab) used for the production of the reactive particles (Aab) is a compound having a polymerizable unsaturated group, preferably an ethylenically unsaturated group, and further contains a group represented by the following general formula (11). An organic compound is preferred. 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 one 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.

［一般式（１１）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 General Formula (11), U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. ]

[1] Ethylenically unsaturated group Although there is no restriction | limiting in particular as an ethylenically unsaturated group contained in an organic compound (Ab), For example, an acryloyl group, a methacryloyl group, and a vinyl group can be mentioned as a suitable example.
This ethylenically unsaturated group is a structural unit that undergoes addition polymerization with active radical species.

[2] Group represented by Formula (11) The group [—UC— (V) —NH—] represented by Formula (11) 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 (11) 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.

[3] Silanol group or group that generates a silanol group by hydrolysis The organic compound (Hb) 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 silica particles by a condensation reaction that occurs following a condensation reaction or hydrolysis.

[4] Preferred Embodiment As a preferred specific example of the organic compound (Hb), for example, a compound represented by the following formula (12) can be mentioned.

In formula (12), R ²¹ and R ²² 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 ²¹ O) _j R ²² _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 ²³ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms, and may include a chain, branched, or cyclic structure. Specific examples include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, dodecamethylene and the like.
R ²⁴ 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 ²⁵ 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 (12) include compounds represented by the following formula (13) or the following formula (14).

［式（１３）及び（１４）中、「Ａｃｒｙｌ」は、アクリロイル基を示す。「Ｍｅ」は、メチル基を示す。］

[In the formulas (13) and (14), “Acryl” represents an acryloyl group. “Me” represents a methyl 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. Typically, a mixture of the compound represented by formula (13) and the compound represented by formula (14) is obtained.

(Aab) Reactive Particles An organic compound (Ab) is mixed with silica particles (Aa), hydrolyzed, and bonded together. The ratio of the organic polymer component in the resulting reactive particles (Aab), that is, the hydrolyzate and condensate of hydrolyzable silane, is usually the mass loss% when the dry powder is completely burned in air. The constant value of can be determined, for example, by thermal mass spectrometry from room temperature to usually 800 ° C. in air.

  The amount of the organic compound (Ab) bound to the silica particles (Aa) is preferably 0.01% by mass or more, more preferably 0.1% by mass, based on 100% by mass of the reactive particles (Aab). As described above, it is particularly preferably 1% by mass or more. When the binding amount of the organic compound (Ab) bound to the silica particles (Aa) is less than 0.01% by mass, the dispersibility of the reactive particles (Aab) in the composition is insufficient, and the cured product obtained Scratch resistance may not be sufficient. Moreover, the compounding ratio of the silica particles (Aa) in the raw material during the production of the reactive particles (Aab) is preferably 5 to 99% by mass, and more preferably 10 to 98% by mass. The content of the silica particles (Aa) constituting the reactive particles (Aab) is preferably 65 to 95% by mass of the reactive particles (Aab).

  In the composition of the present invention, the amount of component (A), that is, the reactive silica particles (A) is 5 to 80 masses when the total solid content in the composition is 100 mass%. % Is preferable, and 10 to 80% by mass is more preferable. By containing the component (A) in the range of 5 to 80% by mass, the scratch resistance of a cured product obtained by curing the composition can be improved. In addition, the quantity of a component (A) means solid content, and when a component (A) is used with the form of a dispersion liquid, the quantity of a dispersion medium is not included in the compounding quantity.

(B) Compound having 3 or more (meth) acryloyl groups in the molecule Compound having 3 or more (meth) acryloyl groups in the molecule (hereinafter referred to as polyfunctional (meth) acrylate compound) has a curable composition. Used to increase the hardness and scratch resistance of a cured product obtained by curing the product.

  The component (B) is not particularly limited as long as it is a compound containing at least three (meth) acryloyl groups in the molecule. Examples of the compound having three or more (meth) acryloyl groups include tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, and trimethylol. Propane tri (meth) acrylate, ethylene oxide (hereinafter referred to as “EO”) modified trimethylolpropane tri (meth) acrylate, propylene oxide (hereinafter referred to as “PO”) modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl ether end (meth) acrylic acid adduct, 1,4-butanediol di (meth) acrylate, 1 6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, EO Modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, EO modified water It can be exemplified bisphenol A di (meth) acrylate, PO-modified hydrogenated bisphenol A di (meth) acrylate, EO-modified bisphenol F di (meth) acrylate, phenol novolak polyglycidyl ether (meth) acrylate.

  Examples of commercially available products of these multifunctional monomers include SA1002 (manufactured by Mitsubishi Chemical Corporation), biscoat 195, biscoat 230, biscoat 260, biscoat 215, biscoat 310, biscoat 214HP, biscoat 295, biscoat 300, Biscoat 360, Biscoat GPT, Biscoat 400, Biscoat 700, Biscoat 540, Biscoat 3000, Biscoat 3700 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Kayarad R-526, HDDA, NPGDA, TPGDA, MANDA, R-551, R-712, R-604, R-684, PET-30, GPO-303, TMPTA, THE-330, DPHA, DPHA-2H, DPHA-2C, DPHA-2I, D-310, D-330, DPCA 20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, T-1420, T-2020, T-2040, TPA-320, TPA-330, RP-1040, RP-2040, R-011, R-300, R-205 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-220, M-233, M-240, M-215, M-305, M- 309, M-310, M-315, M-325, M-400, M-6200, M-6400 (above, manufactured by Toagosei Co., Ltd.), light acrylate BP-4EA, BP-4PA, BP-2EA, BP-2PA, DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.), New Frontier BPE-4, BR-42M, GX-8345 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), ASF 400 (above, manufactured by Nippon Steel Chemical Co., Ltd.), Lipoxy SP-1506, SP-1507, SP-1509, VR-77, SP-4010, SP-4060 (above, Showa Polymer Co., Ltd.), NK ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd.).

  Of these, pentaerythritol triacrylate (PETA) is particularly preferable as the compound having three (meth) acryloyl groups in the molecule. In the composition of the present invention, it is more preferable to use a compound having 4 or more (meth) acryloyl groups in the molecule. The four or more compounds can be selected from tetra (meth) acrylate compounds, penta (meth) acrylate compounds, hexa (meth) acrylate compounds and the like exemplified above, and among these, dipentaerythritol. Hexaacrylate (DPHA), pentaerythritol hydroxytriacrylate, and trimethylolpropane triacrylate are particularly preferred. Each of the above compounds can be used alone or in combination of two or more.

  These polyfunctional (meth) acrylate compounds may contain a fluorine atom. Examples of such compounds are perfluoro-1,6-hexanediol di (meth) acrylate, octafluorooctane-1,6-di (meth) acrylate, octafluorooctanediol and 2- (meth) acryloyloxyethyl. One kind alone or a combination of two or more kinds such as an isocyanate, 2- (meth) acryloyloxypropyl isocyanate, an adduct with 1,1- (bisacryloyloxymethyl) ethyl isocyanate may be mentioned.

(B) Although it does not restrict | limit especially about the addition amount of a component, When the total amount of solids in the composition of this invention is 100 mass%, it is 5-70 mass% normally. The reason for this is that when the addition amount is less than 5% by mass, the scratch resistance of the cured product obtained by curing the curable composition may be lowered, whereas when the addition amount exceeds 70% by mass. The hardness of the cured product of the curable composition may be reduced.
For this reason, the amount of component (B) added is more preferably 10 to 60% by mass, and still more preferably 20 to 50% by mass.

(C) Organic solvent The composition of the present invention contains an organic solvent, and when the total amount of the organic solvent is 100% by mass, the proportion of methyl isobutyl ketone (MIBK) is 50% by mass or more, It is preferably 100% by mass, and more preferably 65-90% by mass. The hardness of a coating film becomes high by making the ratio of methyl isobutyl ketone 50 mass% or more.

  Specific examples of organic solvents other than methyl isobutyl ketone include ketones such as acetone, methyl ethyl ketone, cyclohexanone and methyl amyl ketone, esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methanol, One or more selected from alcohols such as ethanol, sec-butanol, t-butanol, 2-propanol and isopropanol, aromatics such as benzene, toluene and chlorobenzene, and aliphatics such as hexane and cyclohexane Combinations are listed. Among these, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, methyl amyl ketone, esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methanol, ethanol, sec-butanol , T-butanol, 2-propanol, isopropanol and the like are preferable, and methyl isobutyl ketone, methyl amyl ketone and t-butanol are used alone or in combination of two or more.

  The total addition amount of the (C) organic solvent containing methyl isobutyl ketone is not particularly limited, but is preferably 100 to 100,000 parts by mass with respect to 100 parts by mass of the solid content. This is because when the addition amount is less than 100 parts by mass, it may be difficult to adjust the viscosity of the curable composition. On the other hand, when the addition amount exceeds 100,000 parts by mass, the curable composition is used. This is because the storage stability of the resin may decrease, or the viscosity may decrease excessively, making handling difficult.

(D) Radiation polymerization initiator The radiation (photo) polymerization initiator used in the present invention is not particularly limited as long as it can be decomposed by light irradiation to generate radicals and initiate polymerization, and examples thereof include acetophenone and 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, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy- 2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2 -Hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2) -Methyl-1- (4- (1-methylvinyl) phenyl) pro Mention may be made of a non), 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 radiation (photo) polymerization initiator (D) used as necessary in the present invention is 0.01 to 20% by mass when the total solid content in the composition is 100% by mass. Is preferable, and 0.1-10 mass% is further more preferable. If it is less than 0.01% by mass, the hardness when cured may be insufficient, and if it exceeds 20% by mass, the cured product may not be cured to the inside (lower layer).

  When curing the composition of the present invention, 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.

(E) Particles (Ea) that may be surface-treated with an organic compound (Eb) having a polymerizable unsaturated group and that have a number average particle diameter of 1 nm or more and less than 30 nm mainly composed of silica
(1) Particles (Ea) having a number average particle diameter of 1 nm or more and less than 30 nm mainly composed of silica
In the composition of the present invention, reactive particles which are surface treated with an organic compound (Ab) having a polymerizable unsaturated group and are particles (Aa) having a number average particle diameter of 30 nm or more mainly composed of silica (Aab) is essential, but the surface treatment is performed by particles (Ea) having a number average particle diameter of 1 nm or more and less than 30 nm and / or an organic compound (Eb) having a polymerizable unsaturated group. You may mix | blend the reactive particle (Eab) which is made | formed and is a particle | grain (Ea) whose number average particle diameter which has a silica as a main component and is 1 nm or more and less than 30 nm. By blending particles (E) whose main component is silica having a number average particle diameter of 1 nm or more and less than 30 nm, the scratch resistance of the cured product obtained by curing the composition of the present invention, particularly the steel wool resistance, is improved. be able to.
As particles (Ea) containing silica as a main component, known particles can be used, and if the shape is spherical, not only ordinary colloidal silica but also hollow particles, porous particles, core / shells. It may be mold particles. However, hollow particles and porous particles are preferable from the viewpoint of reducing the refractive index of the composition, and it is particularly preferable that one or both of the components (A) and (E) are hollow particles. Moreover, it is not limited to a spherical shape, and may be an irregularly shaped particle. Colloidal silica having a solid content of 10 to 40% by mass is preferred. About a preferable dispersion medium and a commercial item, it is as having demonstrated with the component (A).

Moreover, what carried out surface treatments, such as chemical modification, on the colloidal silica surface can be used, for example, a hydrolyzable silicon compound having one or more alkyl groups in the molecule or one containing a hydrolyzate thereof. Can be reacted. Such hydrolyzable silicon compounds include trimethylmethoxysilane, tributylmethoxysilane, dimethyldimethoxysilane, dibutyldimethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, 1,1. , 1-trimethoxy-2,2,2-trimethyl-disilane, hexamethyl-1,3-disiloxane, 1,1,1-trimethoxy-3,3,3-trimethyl-1,3-disiloxane, α-trimethylsilyl -Ω-dimethylmethoxysilyl-polydimethylsiloxane, α-trimethylsilyl-ω-trimethoxysilyl-polydimethylsiloxane hexamethyl-1,3-disilazane, and the like. A hydrolyzable silicon compound having one or more reactive groups in the molecule can also be used. Hydrolyzable silicon compounds having one or more reactive groups in the molecule are, for example, urea propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl having NH ₂ groups as reactive groups. Trimethoxysilane or the like having an OH group, bis (2-hydroxyethyl) -3aminotripropylmethoxysilane or the like having an isocyanate group, 3-isocyanatopropyltrimethoxysilane or the like having a thiocyanate group 3 As thiocyanate propyltrimethoxysilane and the like having an epoxy group (3-glycidoxypropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like having a thiol group 3 -Mercaptopropyltrimethoxy Sisilane etc. can be mentioned. A preferred compound is 3-mercaptopropyltrimethoxysilane.

  The particles (Ea) containing silica as the main component may have been surface-treated with an organic compound (Eb) having a polymerizable unsaturated group. Such surface treatment enables co-crosslinking with the UV curable acrylic monomer and improves the scratch resistance. As the organic compound (Eb) having a polymerizable unsaturated group, the organic compound (Ab) having a polymerizable unsaturated group is preferable.

(E) As for the compounding quantity of a component, when the solid content whole quantity in a composition is 100 mass%, it is preferable to mix | blend 5-50 mass%, and 10-40 mass% is further more preferable.
In addition, the quantity of (E) component means solid content, and when a particle | grain is used with the form of a solvent dispersion | distribution sol, the quantity of a solvent is not included in the compounding quantity.

(F) Additive In the composition of the present invention, inorganic particles other than silica particles, a photosensitizer, a thermal polymerization initiator, a polymerization inhibitor, and a polymerization initiation auxiliary agent are within the range not impairing the object and effect of the present invention. , Leveling agents, wettability improvers, surfactants, plasticizers, UV absorbers, antioxidants, antistatic agents, silane coupling agents, pigments, dyes, slip agents, etc. .
In particular, the inorganic particles are effective for improving the coating strength, and when added, the number average particle diameter is preferably in the range of 1 to 100 nm, and spherical, beaded, and amorphous particles can be used, and Porous and hollow particles having voids in the internal structure can also be used. As the inorganic particles that can be used, inorganic oxides or fluorides are preferable, and examples thereof include alumina, titania, zirconia, and magnesium fluoride. Moreover, the surface of these inorganic particles may be surface-modified with an arbitrary organic group, and by being modified with a (meth) acrylic group, compatibility with the curable composition is improved, and other properties at the time of curing It becomes possible to co-crosslink with the curable composition, and it is possible to improve the scratch resistance of the cured film.

  The thermal polymerization initiator is a compound that generates active species by heat, and examples thereof include a thermal radical generator that generates radicals as active species. Examples of thermal radical generators include benzoyl peroxide, tert-butyl-oxybenzoate, azobisisobutyronitrile, acetyl peroxide, lauryl peroxide, tert-butyl peracetate, cumyl peroxide, tert-butyl peroxide , Tert-butyl hydroperoxide, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc. The combination of the above can be mentioned.

  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.

  The composition of the present invention contains (C) an organic solvent, and the viscosity of the composition can be adjusted by adjusting the amount of the organic solvent added 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 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, beta rays, and gamma rays, for example, a fission material such as Co ⁶⁰ can be cited, and for 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.

The cured product 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 . Further, the preferable electron beam irradiation conditions 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.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, the scope of the present invention is not limited to description of these Examples. “Part” and “%” mean “part by mass” and “% by mass” unless otherwise specified. Further, in the present invention, the “solid content” means a part obtained by removing volatile components such as a solvent from the composition, and specifically, obtained by drying the composition on a hot plate at a predetermined temperature for 1 hour. It means a residue (nonvolatile component).

(Production Example 1)
Production of organic compound (Ab) having polymerizable unsaturated group In a dry air, 60.0 parts of isophorone diisocyanate is stirred with respect to a solution consisting of 23.0 parts of mercaptopropyltrimethoxysilane and 0.5 parts of dibutyltin dilaurate. After dropwise addition at 50 ° C. over 1 hour, the mixture was stirred at 70 ° C. for 3 hours. This consists 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. (Only triacrylate.) After adding 202.0 parts dropwise at 30 ° C. over 1 hour, specific organic compound (S1) was obtained by heating and stirring at 60 ° C. for 3 hours.
In the infrared absorption spectrum of the product, the absorption peak at 2550 cm ⁻¹ characteristic for the mercapto group in the raw material and the absorption peak at 2260 cm ⁻¹ characteristic for the isocyanate group disappear, and [−O—C (= O) -NH-] group and [-S-C (= O) -NH-] peak characteristic 1720 cm ^-1 to the carbonyl in the group the peak and acryloyl groups characteristic 1660 cm ^-1 - click is observed And a specific organic compound having both an acryloyl group as a polymerizable unsaturated group, a [—S—C (═O) —NH—] group, and a [—O—C (═O) —NH—] group is formed. Showed that.

(Production Example 2)
Production of Reactive Silica Particles (Component (Aab)) 9.36 parts of the composition produced in Production Example 1 (containing 7.28 parts of an organic compound (Ab) having a polymerizable unsaturated group), silica particle dispersion ( Aa) (silica concentration 31%, Nissan Chemical MEK sol) 98.07 parts, 0.13 parts of ion-exchanged water, and 0.01 parts of p-hydroxyphenyl monomethyl ether were stirred at 60 ° C. for 4 hours. Then, 1.45 parts of orthoformate methyl ester was added, and a dispersion of reactive particles was obtained by heating and stirring at the same temperature for 1 hour. 2 g of this dispersion was weighed on an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour, and weighed to determine the solid content, which was 35.7%. Further, 2 g of the dispersion was weighed in a magnetic crucible, preliminarily dried on an 80 ° C. hot plate for 30 minutes, and calcined in a muffle furnace at 750 ° C. for 1 hour to obtain the inorganic content in the solid content. As a result, it was 77.7%.
The average particle size of the silica-based particles was 40 nm. Here, the average particle diameter was measured with a transmission electron microscope.

(Production Example 3)
Production of reactive particles ((Eab) component) 9.36 parts of the composition produced in Production Example 1 (containing 7.28 parts of an organic compound (Ab) having a polymerizable unsaturated group), silica particle dispersion (Aa ) (Silica concentration 31%, Shin Nakamura Chemical MEK sol) 89.69 parts, ion-exchanged water 0.12 parts, and p-hydroxyphenyl monomethyl ether 0.01 parts after stirring at 60 ° C. for 4 hours Then, 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 a dispersion of reactive particles. 2 g of this dispersion was weighed in an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour, and weighed to determine the solid content, which was 36.6%. Further, 2 g of the dispersion was weighed in a magnetic crucible, preliminarily dried on an 80 ° C. hot plate for 30 minutes, and calcined in a muffle furnace at 750 ° C. for 1 hour to obtain the inorganic content in the solid content. As a result, it was 77.7%.
The average particle size of the silica-based particles was 10 nm. Here, the average particle diameter was measured with a transmission electron microscope.

(Example 1)
109.36 parts of the reactive particles (Aab) produced in Production Example 2, 10.06 parts of dipentaerythritol hexaacrylate, 0.9 parts of Irg184, and 60.0 parts of methyl isobutyl ketone were placed in a flask and stirred at room temperature for 30 minutes. A homogeneous mixture was obtained. This mixture was concentrated under reduced pressure using a vacuum evaporator at a reduced pressure of 80 hPa until the weight became 100.0 parts, and the composition shown in Example 1 was obtained.

(Examples 2-4, Comparative Examples 1-3)
Each curable composition was obtained in the same manner as in Example 1 except that the composition shown in Table 1 below was used.

<Manufacture of cured film>
Each composition manufactured in Examples 1 to 4 and Comparative Examples 1 to 3 was coated on a TAC substrate using a 30 mil bar coater to obtain a coating film having a thickness of 12 μm. This was placed in an oven at 80 ° C. for 1 minute and dried. Thereafter, the film was cured by passing through a high-pressure mercury lamp conveyor four times at a radiation speed of 50 mJ / cm ² using a high-pressure mercury lamp in the air, and irradiating a total of 200 mJ / cm ² .

<Characteristic evaluation of cured film>
Each cured film obtained was evaluated for pencil hardness.
The evaluation method was based on JIS K5600-5-4 and evaluated the film hardened on the glass substrate. Evaluation was carried out 5 times for each of the hardnesses of 3H and 4H, and “good” was indicated when passing 3 times or more, and “impossible” was indicated otherwise.

The product names in Table 1 represent the following.
DPHA: Dipentaerythritol hexaacrylate PETA: Pentaerythritol triacrylate Irg 184: 1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by Ciba Specialty Chemicals MEK: Methyl ethyl ketone MIBK: Methyl isobutyl ketone

  From the results in Table 1, it can be seen that a cured film having high hardness can be obtained by blending a specific amount of particles having a specific particle diameter.

Since the cured product of the present invention has high hardness and scratch resistance, recording disks such as CD, DVD, and MO, plastic optical components, touch panels, film-type liquid crystal elements, plastic containers, flooring materials as building interior materials, It can be particularly suitably used as a protective coating material for preventing scratches (scratching) and contamination of wall materials, artificial marble and the like, or an antireflection film for film-type liquid crystal elements, touch panels, plastic optical components and the like.

Claims (6)

The following components (A) to (C):
(A) Particles (Aa) having a number average particle diameter of 30 nm or more and 200 nm or less mainly composed of silica, which is surface-treated with an organic compound (Ab) having a polymerizable unsaturated group
(B) A curable composition containing a compound (C) an organic solvent having three or more (meth) acryloyl groups in the molecule,
When the total solid content in the composition is 100% by mass, the proportion of silica particles (Aa) in the component (A) is 15% by mass or more, and 50% by mass or more of the component (C). A curable composition wherein is methyl isobutyl ketone (MIBK).   The curable composition according to claim 1, wherein the organic compound (Ab) having a polymerizable unsaturated group is a compound having a silanol group in a molecule or a compound that generates a silanol group by hydrolysis. The compound (Ab) having a polymerizable unsaturated group is further represented by the following formula (11):

[In General Formula (11), U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. The curable composition of Claim 1 or 2 which has group shown by this.   Furthermore, (D) The curable composition of any one of Claims 1-3 containing a radiation polymerization initiator.   And (E) a particle (Ea) having a number average particle diameter of 1 nm or more and less than 30 nm, the main component of which may be surface-treated with an organic compound (Eb) having a polymerizable unsaturated group. Item 5. The curable composition according to any one of Items 1 to 4. Hardened | cured material formed by hardening | curing the curable composition of any one of Claims 1-5.