JP2006233170A - Radiation-curing resin composition and cured film thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-curing resin composition which has excellent curability and can form a coating film excellent in hardness, scratch resistance, resistance to curling, adhesion, transparency or excellent in especially hardness and resistance to curling and to provide a cured film thereof. <P>SOLUTION: The radiation-curing resin composition comprises (A) particles prepared by bonding particles of an oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony, and cerium with an organic compound containing a polymerizable unsaturated group and a group represented by formula (1) (in formula (1), U is NH, O (oxygen atom), or S (sulfur atom); and V is O or S), (B) a compound containing two or more polymerizable unsaturated groups, (C) a fluorine-containing surfactant, and (D) an organic solvent selected from the group consisting of methanol, methyl isobutyl ketone, and n-butanol. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a radiation curable resin composition and a cured film thereof. More specifically, the present invention has excellent curability and various substrates [for example, plastic (polycarbonate, polymethacrylate, polymethylmethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetylcellulose, ABS resin, AS resin. , Norbornene resin, etc.), metal, wood, paper, glass, slate, etc.] to form a film having excellent hardness, scratch resistance, low curl, adhesion and transparency, especially hardness and low curl The present invention relates to a radiation curable resin composition and a cured film thereof.

In recent years, protective coating materials to prevent scratches (scratches) and contamination on various substrate surfaces; adhesives and sealing materials for various substrates; as binder materials for printing inks, There is a need for a radiation curable resin composition having excellent curability that can form a film having excellent scratch resistance, low curl properties, adhesion, and transparency. Of these requirements, various materials containing colloidal silica have been proposed with the aim of improving the scratch resistance. These include thermosetting materials (Patent Documents 1 and 2) and radiation curable materials (Patent Documents 3 and 4). These coating materials are characterized by improving the performance of the coating material by treating the surface of the silica particles with a specific organosilane or specific conditions.
However, it is difficult to obtain a uniform film thickness when such a coating material is applied by the dip coating method, as well as the curability as a composition and the hardness and scratch resistance when a cured film is formed. However, it did not satisfy all of the properties, low curl property, adhesion and transparency. In addition, thermosetting coating materials require high-temperature and long-time heat treatment, and are difficult to apply to plastic substrates with low heat resistance.
U.S. Pat. No. 3,451,838 U.S. Pat. No. 2,404,357 Japanese Patent Publication No.62-21815 JP 2000-256535 A

  The present invention has been made in view of the above-mentioned problems, and has excellent curability and has hardness, scratch resistance, low curl properties, adhesion and transparency, particularly hardness and surface, on the surfaces of various substrates. It is an object of the present invention to provide a radiation curable resin composition capable of forming a film excellent in low curling property and a cured film thereof.

［式（１）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。］
（Ｂ）２以上の重合性不飽和基を含む化合物、
（Ｃ）フッ素原子を有する界面活性剤、及び
（Ｄ）メタノール、メチルイソブチルケトン及びｎ−ブタノールからなる群から選択される一以上を、全溶剤中に５０質量％以上含有する有機溶剤
を含有することを特徴とする放射線硬化性樹脂組成物。
２．前記有機化合物が、［−Ｏ−Ｃ（＝Ｏ）−ＮＨ−］基を含み、さらに、［−Ｏ−Ｃ（＝Ｓ）−ＮＨ−］基及び［−Ｓ−Ｃ（＝Ｏ）−ＮＨ−］基の少なくとも１を含むものである１記載の放射線硬化性樹脂組成物。
３．前記有機化合物が、シラノール基を有する化合物又は加水分解によってシラノール基を生成する化合物である１又は２記載の放射線硬化性樹脂組成物。
４．前記（Ｃ）フッ素原子を有する界面活性剤が、含フッ素アクリル残基とポリジメチルシロキサン残基を含む１〜３のいずれか記載の放射線硬化性樹脂組成物。
５．前記（Ｄ）成分が、メタノール、メチルイソブチルケトン及びｎ−ブタノールの混合物である１〜４のいずれか記載の放射線硬化性樹脂組成物。
６．１〜５のいずれか記載の放射線硬化性樹脂組成物に放射線を照射せしめて得られる硬化膜。
７．透明基材及び６記載の硬化膜からなる層を有する積層体。 As a result of earnest research to achieve the above-mentioned object, the present inventors have determined from specific components including particles formed by binding oxide particles of specific elements and organic compounds containing specific groups in the molecules. The present invention was completed by discovering that a composition satisfying the above-mentioned properties, particularly hardness and low curl properties when used as a cured film, can be obtained by the radiation curable resin composition.
That is, the present invention provides the following radiation curable resin composition and cured film thereof.
1. (A) Oxide particles of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium, a polymerizable unsaturated group, and the following formula (1) Particles formed by bonding an organic compound containing a group

[In Formula (1), U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. ]
(B) a compound containing two or more polymerizable unsaturated groups,
(C) A surfactant having a fluorine atom, and (D) an organic solvent containing at least 50% by mass in all solvents selected from the group consisting of methanol, methyl isobutyl ketone and n-butanol. A radiation curable resin composition characterized by that.
2. The organic compound includes a [—O—C (═O) —NH—] group, and further includes a [—O—C (═S) —NH—] group and a [—S—C (═O) —NH. -] The radiation curable resin composition according to 1, which comprises at least one group.
3. 3. The radiation curable resin composition according to 1 or 2, wherein the organic compound is a compound having a silanol group or a compound that generates a silanol group by hydrolysis.
4). The radiation curable resin composition according to any one of 1 to 3, wherein the surfactant (C) having a fluorine atom contains a fluorine-containing acrylic residue and a polydimethylsiloxane residue.
5. The radiation curable resin composition according to any one of 1 to 4, wherein the component (D) is a mixture of methanol, methyl isobutyl ketone and n-butanol.
A cured film obtained by irradiating the radiation curable resin composition according to any one of 6.1 to 5 with radiation.
7). A laminate having a layer comprising a transparent substrate and the cured film described in 6.

According to the present invention, a radiation curable composition suitable for coating by a dip coating method can be obtained. Specifically, it is possible to obtain a coating film having no coating unevenness and repellency and having a uniform film thickness at the center and end of the cured film.
Since the radiation curable resin composition and the cured film thereof according to the present invention have such characteristics, for example, a hard coat for an antireflection plate, a hard coat for an optical sheet such as a touch panel, and a display of a mobile device such as a mobile phone. It can be suitably used as a material such as a hard coat for a protective plate used in the part.

  Hereinafter, embodiments of the radiation curable resin composition, the cured film and the laminate of the present invention will be specifically described.

I. Radiation curable resin composition The radiation curable resin composition of the present invention comprises (A) specific oxide particles, (B) a compound containing two or more polymerizable unsaturated groups in the molecule, and (C) a fluorine atom. And (D) a specific solvent as an essential component, and (E) a polymerization initiator and the like as a non-essential component. Hereinafter, each composition component is demonstrated concretely.

1. Specific metal oxide particles (A)
Component (A) used in the present invention is composed of oxide particles of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium, and a specific organic compound. Are particles (hereinafter referred to as “reactive particles”).

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

  Examples of these oxides include silica, aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide. Among these, silica, aluminum oxide, zirconia, and antimony oxide are preferable from the viewpoint of high hardness. These can be used singly or in combination of two or more. Furthermore, the oxide particles of such elements are preferably in the form of powder or solvent dispersion sol. In the case of a solvent dispersion sol, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. 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 ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone it can. 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 is preferably 0.001 μm to 2 μm, more preferably 0.001 μm to 0.2 μm, and particularly preferably 0.001 μm to 0.1 μm. When the number average particle diameter exceeds 2 μm, the transparency when the cured film is formed tends to be lowered, or the surface state when the film is formed tends to be deteriorated. Here, various surfactants and amines may be added to improve the dispersibility of the particles.

  As a product marketed as silicon oxide particles, for example, silica particles, for example, colloidal silica, manufactured by Nissan Chemical Industries, Ltd. Product names: methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST , DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, and the like. Further, as powder silica, product names manufactured by Nippon Aerosil Co., Ltd .: Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Asahi Glass Co., Ltd. Product names: Sildex H31, H32, H51, H52, H121 H122, manufactured by Nippon Silica Kogyo Co., Ltd. Trade names: E220A, E220, manufactured by Fuji Silysia Co., Ltd., trade names: SYLYSIA470, manufactured by Nippon Sheet Glass Co., Ltd.

Moreover, as an aqueous dispersion of alumina, product names manufactured by Nissan Chemical Industries, Ltd .: Product names: Alumina Sol-100, -200, -520; As aqueous dispersions of zinc antimonate powder, product names manufactured by Nissan Chemical Industries, Ltd. : Cellax; Alumina, Titanium oxide, Tin oxide, Indium oxide; As powder and solvent dispersions such as zinc oxide, manufactured by CI Kasei Co., Ltd. Product name: Nanotech; As an aqueous dispersion sol of antimony-doped tin oxide, Ishihara Product name: SN-100D manufactured by Sangyo Co., Ltd .; as ITO powder, product manufactured by Mitsubishi Materials Corporation; as cerium oxide aqueous dispersion, product name: Nidral manufactured by Taki Chemical Co., Ltd. it can. The oxide particles have a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an indefinite shape, preferably a spherical shape. The specific surface area of the oxide particles (by the BET specific surface area measurement method using nitrogen) is preferably 10 to 1000 m ² / g, more preferably 100 to 500.
m ² / g. These oxide particles can be used in a dry powder, 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, use of a solvent-dispersed sol of an oxide is preferable in applications that require excellent transparency in a cured film.

(2) Specific organic compound (Ab)
The specific 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 (1). 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. The specific organic compound (Ab) is preferably a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis.

［式（１）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 (1), 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 specific organic compound (Ab) is not particularly limited. For example, an acryloyl group, a methacryloyl group, a vinyl group, a propenyl group, a butadienyl group, a styryl group, Preferred examples include ethynyl group, cinnamoyl group, maleate group, and 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 (1) The group [—UC— (V) —NH—] represented by the formula (1) 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 (1) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength and group when formed into a cured film. 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) A compound having a silanol group or a compound producing a silanol group by hydrolysis The specific organic compound (Ab) is preferably a compound having a silanol group in the molecule or a compound producing 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 As a preferred specific example of the specific organic compound (Ab), for example, a compound represented by the following formula (2) can be exemplified.

In the formula (2), 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 (2) include compounds represented by the following formulas (3-1) and (3-2).

［式（３−１）及び（３−２）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 (3-1) and (3-2), “Acryl” represents an acryloyl group. “Me” represents a methyl group. ]

  For the synthesis of the specific 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) Production method of reactive particles (A) A specific 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 both Combine. The ratio of the organic polymer component, that is, the hydrolyzable silane hydrolyzate and condensate in the resulting reactive particles (A) is usually a mass loss% when the dry powder is completely burned in air. The constant value can be obtained, for example, by thermal mass spectrometry from room temperature to usually 800 ° C. in air.

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

  The amount (inclusive) of the reactive particles (A) in the curable composition is preferably 5 to 70% by mass, more preferably 20 to 60% by mass, with the total amount of the composition excluding all solvents being 100% by mass. When it is less than 5% by mass, the hardness of the cured film is insufficient, and when it exceeds 70% by mass, the film formability may be insufficient. The amount of the reactive particles (A) means a solid content, and when the reactive particles (A) are used in the form of a dispersion, the amount of the reactive particles does not include the amount of the dispersion medium.

Compound (B) containing 2.2 or more polymerizable unsaturated groups
The compound (B) used in the present invention is a compound containing two or more polymerizable unsaturated groups. This compound (B) is suitably used for enhancing the film formability of the composition. The compound (B) is not particularly limited as long as it contains two or more polymerizable unsaturated groups, and examples thereof include (meth) acrylic esters and vinyl compounds. Of these, (meth) acrylic esters are preferred.
Specific examples of the compound (B) used in the present invention are listed below.
(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, Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, and starting alcohols thereof Poly (meth) acrylates of adducts with ethylene oxide or propylene oxide, oligoesters (meth) acrylates having two or more (meth) acryloyl groups in the molecule, oligoethers (meth) acrylates, oligourethanes (meth) Examples include acrylates and oligoepoxy (meth) acrylates.
Among these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate 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 compound (B), Toagosei Co., Ltd. product name: Aronix M-400, 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-1231, TO-1343, TO-902, TO-904, TO-905, TO-1330, manufactured by Nippon Kayaku Co., Ltd. Trade names: KAYARAD D-310, D-330, D HA, DPCA-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-71 , 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. product name: Light acrylate PE-4A, DPE-6A, DTMP-4A and the like can be mentioned.

The compounding amount of the compound (B) used in the present invention is preferably 20 to 80% by mass, more preferably 40 to 75% by mass, with the total amount of the composition excluding all solvents being 100% by mass. . If it is less than 20% by mass, the hardness may be insufficient when it is a cured film, and if it exceeds 80% by mass, it may cause curing distortion when it is a cured film.
In addition to the compound (B), the composition of the present invention may contain a compound having one polymerizable unsaturated group in the molecule, if necessary. The kind of compound having one polymerizable unsaturated group in the molecule is not particularly limited.

3. Surfactant having fluorine atom (C)
The fluorosurfactant (C) used in the present invention is used to enhance the coating property of the composition to the base material. By using this fluorosurfactant (C), it is surprising. In addition, the hardness of the cured film is improved. Such a fluorosurfactant is not particularly limited as long as it is a nonionic fluorosurfactant and / or an anionic fluorosurfactant, but nonionic from the viewpoint of solubility in a solvent. A system is preferred.
Specifically, Dainippon Ink and Chemicals, Inc. product name: MegaFuck F-142D, F-144D, F-171, F-172, F-173, F-177, F-178A, F- 178K, F-179, F-179A, F-183, F-184, F-191, F-812, F-815, F-1405, F410, F-443, F-445, F-450, F- 471, F-472SF, F475, F-479, F-482, R-30, MCF-350, TF1025, manufactured by Gemco Co., Ltd. Trade names: EFTOP EF-101, EF-121, EF-122B, EF-122C , EF-122A3, EF-121, EF-123A, EF-123B, EF-126, EF-127, EF-301, EF-302, EF-351, EF-352, EF-6 1, EF-801, EF-802, manufactured by Neos Co., Ltd. Product names: Footage 250, 251, 222F, FTX-218, 212M, 245M, 290M, FTX-207S, FTX-211S, FTX-220S, FTS- 230S, FTX-209F, FTX-213F, FTX-233F, FTX-245F, FTX-208G, FTX-218G, FTX-230G, FTS-240G, FTX-204D, FTX-208D, FTX-212D, FTX-216D, FTX-218D, FTX-220D, FTX-222D, FTX-720C, FTX-740C, manufactured by Seimi Chemical Co., Ltd. Trade names: Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, S-145, S-381 S-383, S-393, S-101, KH-40, SA-100, and the like. Among these, Megafac F-179, F-470 and the like are preferable from the viewpoint of applicability by the dip coating method.

  The blending amount of the fluorosurfactant (C) used in the present invention is preferably 0.0001 to 5% by weight, based on 100% by mass of the total composition excluding all solvents, and preferably 0.001 to 3% by weight. % Is more preferable. If the blending amount is less than 0.0001% by weight or more than 5% by weight, the hardness of the cured film may be insufficient.

4). Solvent (D)
The composition of the present invention contains a specific solvent, that is, (D) the solvent contains at least one mass selected from the group consisting of methanol, methyl isobutyl ketone and n-butanol in an amount of 50% by mass or more of the total solvent. It is necessary to be, and preferably 80% by mass or more. When these compositions (D) are less than 50% by mass of the total solvent, when the composition is applied to a transparent substrate by a dip coating method, depending on the type of the transparent substrate, it is easy to dissolve in the solvent. The transparency of the resulting cured film or laminate is reduced, making it unsuitable for optical applications. For example, when only methyl ethyl ketone is used as a solvent, when a transparent substrate of polycarbonate or polymethyl methacrylate is immersed in the composition by the dip coating method, the resin constituting the transparent substrate is partially dissolved, so that the obtained curing Membranes and laminates become cloudy. (D) The solvent is particularly preferably a mixture comprising methanol, methyl isobutyl ketone and n-butanol.

5. (E) Polymerization initiator In the present invention, if necessary, (E) a polymerization initiator may be blended as a blending component other than the components (A), (B), (C) and (D). it can. First, the curing method of the composition of the present invention including the use of the (E) polymerization initiator will be described.

The composition of the present invention is cured by heat and / or radiation.
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, the radiation source is not particularly limited as long as the composition can be cured in a short time after coating. Examples of the infrared radiation source include a lamp, a resistance heating plate, Lasers, etc., visible light sources such as sunlight, lamps, fluorescent lamps, lasers, etc. Ultraviolet ray sources such as mercury lamps, halide lamps, lasers, etc. Examples of the radiation source include a method using thermoelectrons generated from a commercially available tungsten filament, a cold cathode method in which a metal is generated through a high voltage pulse, and a collision between an ionized gaseous molecule and a metal electrode 2. A secondary electron system using secondary electrons can be mentioned. Examples of the source of alpha rays, beta rays, and gamma rays include fission materials such as ⁶⁰ Co. For gamma rays, a vacuum tube that collides accelerated electrons with the anode can be used. These radiations may be irradiated alone or in combination of two or more, or one or more kinds of radiation may be irradiated after a certain period. In order to shorten the curing time, a polymerization initiator (E) may be added to the composition of the present invention. As such a polymerization initiator (E), for example, an active radical species is generated thermally. Commonly used compounds such as compounds and compounds that generate active radical species upon irradiation can be mentioned.

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

Although there is no restriction | limiting in particular as aryl ketones which have 1-hydroxy cyclohexyl group, For example, 1-hydroxy cyclohexyl phenyl ketone, 1-hydroxy cyclohexyl isopropyl phenyl ketone, 1-hydroxy cyclohexyl dodecyl phenyl ketone etc. can be mentioned. The aryl ketones having an N-morpholino group used in the present invention are not particularly limited. For example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2 -Methyl-1- [4- (methoxy) phenyl] -2-morpholinopropanone-1, 2-methyl-1- [4- (2-hydroxyethoxy) phenyl] -2-morpholinopropanone-1, 2- Methyl-1- [4- (dimethylamino) phenyl] -2-morpholinopropanone-1, 2-methyl-1- [4- (diphenylamino) phenyl] -2-morpholinopropanone-1, 2-benzyl- 2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1,3,6-bis (2-methyl-2-morpholinopropionyl) -9-N An octyl carbazole. These radiation polymerization initiators (e) may be used singly or in combination of two or more, but when used as a cured film, the curing rate and hardness of both the surface portion and the inside thereof are improved. For this purpose, it is preferable to use a combination of an aryl ketone having a 1-hydroxycyclohexyl group and an aryl ketone having an N-morpholino group.
As a commercial item of such a radiation polymerization initiator (e), Ciba Specialty Chemicals Co., Ltd. product name: Irgacure 184,907 etc. can be mentioned, for example.

  In the present invention, the polymerization initiator (E) used as necessary is preferably blended in an amount of 0.01 to 20% by mass, with the total amount of the composition excluding all solvents being 100% by mass, 10 mass% is further more preferable. When it is less than 0.01% by mass, the hardness when it is a cured film may be insufficient, and when it exceeds 20% by mass, the inside (lower layer) may not be cured when it is a cured film.

  In addition, when the aryl ketone having a 1-hydroxycyclohexyl group and the aryl ketone having an N-morpholino group are used in combination, the mixing ratio of both is preferably 10:90 to 90:10, and 40:60 ~ 80: 20 is more preferred.

6). Ingredients other than the above (F)
In the present invention, various blending components other than the above, such as a sensitizer, oxide particles other than the reactive particles (A), and an antioxidant, can be blended as necessary. Examples are listed below.
(1) Sensitizer Examples of the sensitizer include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4 -Isoamyl dimethylaminobenzoate etc. can be mentioned. Examples of commercially available products of this sensitizer include Nippon Kayaku Co., Ltd. trade name: KAYACURE DMBI, EPA, and the like.

(2) Oxide particles other than reactive particles (A) Examples of oxide particles other than reactive particles (A) include oxide particles that are not bonded to an organic compound.

(3) Various additives Examples of additives include antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, anti-aging agents, thermal polymerization inhibitors, colorants, leveling agents, surfactants, and storage stability. Agents, plasticizers, lubricants, inorganic fillers, organic fillers, fillers, wettability improvers, coating surface improvers, and the like.

  Examples of commercially available antioxidants include Ciba Specialty Chemicals Co., Ltd. trade names: Irganox 1010, 1035, 1076, 1222, etc., and UV absorbers include Ciba Specialty Chemicals Co., Ltd. Product name: Tinuvin P, 234, 320, 326, 327, 328, 213, 400, manufactured by Sumitomo Chemical Co., Ltd. Product name: Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350 400, and the like. Commercially available light stabilizers are manufactured by Ciba Specialty Chemicals Co., Ltd. Trade names: Tinuvin 292, 144, 622LD, Sankyo Chemical Industry Co., Ltd. Trade name: Sanol LS- 770, 765, 292, 2626, 1114, 744, etc. Examples of the pulling agent include γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. Examples of these commercially available products include Toray Dow Corning Silicone ( Product name: SH6062, SZ6030, Shin-Etsu Silicone Co., Ltd. Product name: KBE903, KBM803, etc. As commercial products of anti-aging agents, Sumitomo Chemical Co., Ltd. product name: Antigen W , S, P, 3C, 6C, RD-G, FR, AW, and the like.

  The composition of the present invention is suitable as a coating material. Examples of the base material to be coated include plastics (polycarbonate, polymethacrylate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, slate and the like. The shape of these substrates may be a plate, film or three-dimensional molded body, and the coating method is a normal coating method such as dipping coating, spray coating, flow coating, shower coating, roll coating, spin coating, brush coating, 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.

II. Cured film The cured film of the present invention can be obtained by coating and curing the radiation curable resin composition on various substrates, for example, plastic substrates. Specifically, it can be obtained as a coated molded body by coating the composition, preferably drying the volatile component at 0 to 200 ° C., and then performing a curing treatment with heat or / and 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. In the present invention, “radiation” means infrared rays, visible rays, ultraviolet rays, far ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays and the like. When curing by 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, the preferable irradiation conditions of an electron beam are a pressurization voltage of 10-300 KV, an electron density of 0.02-0.30 mA / cm < ² >, and an electron beam irradiation amount of 1-10 Mrad.

  Since the cured film of the present invention has excellent characteristics in hardness, scratch resistance, low curling property, adhesion and transparency, particularly hardness and low curling property, plastic optical parts, touch panels, film type liquid crystal elements Protective coating materials to prevent scratches (scratches) and contamination of plastic containers, flooring materials as building interior materials, wall materials, artificial marble, etc. (especially plastic sheets and plastic films that require transparency) It is preferably used as a hard coating material.); Adhesives and sealing materials for various substrates; Furthermore, the front plate of various displays such as cathode ray tubes, laser displays, photochromic displays, electrochromic displays, liquid crystal displays, plasma displays, light emitting diode displays, electroluminescent panels, etc. It can be widely used for applications such as front covers, optical lenses, eyeglass lenses, windshields, light covers, helmet shields and the like.

III. Laminated body The cured film of the present invention is usually used by being laminated on a substrate as a hard coat layer, and further antireflection by laminating a high refractive index layer and a low refractive index layer thereon. A laminate suitable as a film can be formed. The antireflection film may further include layers other than these. For example, a plurality of combinations of a high refractive index film and a low refractive index film are provided to provide a relatively uniform reflectance with respect to light in a wide wavelength range. A so-called wideband antireflection film having characteristics may be used, and an antistatic layer may be provided.
Although there is no restriction | limiting in particular as a base material, When using as an anti-reflective film, for example, the above-mentioned plastics (polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin) AS resin, norbornene-based resin, and the like.
Examples of the high refractive index film used in the laminate of the present invention include a cured coating material film containing metal oxide particles such as zirconia particles having a refractive index of 1.65 to 2.20. .
Examples of the low refractive index film used in the laminate of the present invention include a metal oxide film such as magnesium fluoride and silicon dioxide having a refractive index of 1.38 to 1.45, a fluorine-based coating material cured film, and the like. Can be mentioned

As a method for forming a low refractive index film on a high refractive index cured film obtained by curing the curable composition of the present invention, for example, in the case of a metal oxide film, vacuum deposition, sputtering, etc. In the case of a fluorinated coating material cured film, the same method as the method for applying (coating) the composition described above can be used.
Thus, by laminating the high refractive index cured film and the low refractive index film on the substrate, reflection of light on the substrate surface can be effectively prevented.
The laminate of the present invention has high hardness, low curling properties, excellent flexibility, low reflectivity, and excellent chemical resistance, so that it is an antireflection film for film-type liquid crystal elements, touch panels, plastic optical components, etc. Particularly preferably used.

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

Production Example 1: Synthesis of a specific organic compound In a dry air, a solution consisting of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate was added dropwise at 50 ° C. over 1 hour while stirring 222 parts of isophorone diisocyanate. The mixture was heated and stirred at 70 ° C. for 3 hours. This is composed of NK ester A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Co., Ltd.) comprising 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate. 549 parts were added dropwise at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 10 hours to obtain an organic compound (Ab) containing a polymerizable unsaturated group. When the residual isocyanate content in the product was analyzed by FT-IR, it was 0.1% or less, indicating that the reaction was almost quantitatively completed. In the infrared absorption spectrum of the product, the 2550 Kaiser absorption peak characteristic of the mercapto group in the raw material and the 2260 Kaiser absorption peak characteristic of the raw material isocyanate compound disappeared, and a new urethane bond and S (C = O) A peak of 1660 Kaiser characteristic of NH-group and a peak of 1720 Kaiser characteristic of acryloxy group were observed, and both an acryloxy group as a polymerizable unsaturated group, -S (C = O) NH-, and a urethane bond were observed. It was shown that an acryloxy group-modified alkoxysilane was produced. As a result, 773 parts of the compound (Ab) represented by the formulas (3-1) and (3-2) were obtained in total, and 220 parts of pentaerythritol tetraacrylate that was not involved in the reaction was mixed. .

Production Example 2 Preparation of Reactive Silica Particle Dispersion (A-1) 2.32 parts of an organic compound (Ab) containing a polymerizable unsaturated group produced in Production Example 1, silica particle dispersion (manufactured by Nissan Chemical Co., Ltd., trade name) Methanol silica sol) (Aa) (silica concentration 32%) 89.90 parts, ion-exchanged water 0.12 parts, and p-hydroxyphenyl monomethyl ether 0.01 parts after stirring at 60 ° C. for 4 hours, Reactive particles (dispersion liquid (A-1)) were obtained by adding 1.36 parts of methyl orthoformate and further stirring with heating at the same temperature for 1 hour. 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 90%.

Example 1
According to Table 1, the reactive silica particles (A-1) and dipentaerythritol tetraacrylate (B-1) were mixed and stirred at 40 ° C. for 2 hours to obtain a uniform solution. The solution was concentrated under reduced pressure using a rotary evaporator so that the solid concentration was about 80%, and then the other components shown in Table 1 were added to obtain a uniform solution composition. The solid content of this composition was determined to be 39.4%.

  Except having changed the component according to Table 1, it carried out similarly to Example 1, and obtained each composition of Examples 2-7 shown in Table 1, and Comparative Examples 1-4.

Evaluation of Cured Film In order to clarify the effect of the composition of the present invention, the cured film obtained by coating, drying, and light irradiation was evaluated using the above composition. The evaluation method is shown below. The evaluation results are shown in Table 1.
1. Preparation of cured film for evaluation (1) Base material A polycarbonate plate having a thickness of 50 × 100 × 2 mm was used.
(2) Coating, drying, and curing conditions Using a dip coater on the substrate, coating was performed so that the dry film thickness was 6 μm under the conditions of a pulling speed of 300 mm / min and an immersion time of 60 seconds, and then hot-air drying at 80 ° C. After drying for 3 minutes in the machine, it was irradiated with a light amount of 1 J / cm ² using a conveyor type mercury lamp, and then evaluated after storage at 25 ° C. for 24 hours.
2. Evaluation method (1) Hajiki:
The degree of mottle due to local abnormalities in the thickness of the cured film was visually determined. When the whole coating film was observed, the case where there was no cissing was marked as ◯, the case where there was repellency of 1 or more and 3 or less, and the case where there was cissing or 4 or more, x. The repellency is generated during dip coating when the wettability between the coating film of the composition and the substrate is insufficient. (2) Film thickness uniformity:
The film thickness of the coating film at the central part of the substrate and the film thickness of the coating film at the lower end part were measured with a thickness meter, and the difference (μm) was obtained to obtain an evaluation value. When the thickness is 2 μm or less, the liquid is well-dissipated and is suitably used as a substrate with a hard coat.
(2) Film thickness uniformity:
The film thickness of the coating film at the central part of the substrate and the film thickness of the coating film at the lower end part were measured with a thickness meter, and the difference (μm) was obtained to obtain an evaluation value. When the thickness is 2 μm or less, the liquid is well-dissipated and is suitably used as a substrate with a hard coat.
(3) Transparency The transparency of the obtained cured film was visually determined. A case where no turbidity was observed was indicated by “◯”, and a case where turbidity was clearly observed was indicated by “X”.

F179: Megafac F-179; Dainippon Ink & Chemicals, Inc. F470: Megafac F-470; Dainippon Ink & Chemicals, Inc. EF351: EFTOP EF-351; Gemco TR- 701: Polyoxyalkylene condensate of ethylenediamine, Adekapururonic TR-701; Asahi Denka B-1: Dipentaerythritol tetraacrylate E-1: 1-hydroxycyclohexyl phenyl ketone (Irgacure 184)
E-2: 2-methyl-1- (4- (methylthio) phenyl) -2-morpholino-propanone-1 (Irgacure 907)
F-1: Irganox 1010; pentaerythrityl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
F-2: Sanol LS-765; bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate MIBK: methyl isobutyl ketone MEK: methyl ethyl ketone

  The radiation curable resin composition and the cured film thereof according to the present invention include, for example, a hard coat for an antireflection plate, a hard coat for an optical sheet such as a touch panel, and a hard plate for a protective plate used in a display unit of a mobile device such as a mobile phone. Materials such as coatings Plastic optical parts, touch panels, film-type liquid crystal elements, plastic containers, flooring materials for building interior materials, wall materials, protective coating materials for preventing scratches (scratching) and contamination prevention of artificial marble, etc .; It can be suitably used as an adhesive for a substrate, a sealing material, a binder material for printing ink, and the like. The radiation curable resin composition of the present invention is particularly excellent in uniform coating properties when applied by a dip coating method, and therefore can be used for both large display devices such as projection televisions and small devices such as mobile phones. Can also be suitably used.

Claims (7)

(A) Oxide particles of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium, a polymerizable unsaturated group, and the following formula (1) Particles formed by bonding an organic compound containing a group

[In Formula (1), U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. ]
(B) a compound containing two or more polymerizable unsaturated groups,
(C) A surfactant having a fluorine atom, and (D) an organic solvent containing at least 50% by mass in all solvents selected from the group consisting of methanol, methyl isobutyl ketone and n-butanol. A radiation curable resin composition characterized by that.   The organic compound includes a [—O—C (═O) —NH—] group, and further includes a [—O—C (═S) —NH—] group and a [—S—C (═O) —NH. The radiation curable resin composition according to claim 1, which contains at least one of the —] groups.   The radiation curable resin composition according to claim 1, wherein the organic compound is a compound having a silanol group or a compound that generates a silanol group by hydrolysis.   The radiation curable resin composition according to any one of claims 1 to 3, wherein the surfactant (C) having a fluorine atom contains a fluorine-containing acrylic residue and a polydimethylsiloxane residue.   The radiation curable resin composition according to any one of claims 1 to 4, wherein the component (D) is a mixture of methanol, methyl isobutyl ketone and n-butanol.   A cured film obtained by irradiating the radiation curable resin composition according to any one of claims 1 to 5 with radiation.   The laminated body which has a layer which consists of a transparent base material and the cured film of Claim 6.