JP2006348194A - Curable composition, cured product thereof and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition having excellent coating properties and capable of forming a coating film (film) having excellent antistatic property on a surface of various substrates even under a high temperature and high humidity environment, and its A cured product and a laminate excellent in antistatic properties are provided.
SOLUTION: (A) 30 to 70% by mass of a compound having one ethylenically unsaturated group, (B) 20 to 60% by mass of a compound having two or more ethylenically unsaturated groups, (C) photopolymerization 0.1 to 10% by weight of initiator and (D) 1 to 10% by weight of aliphatic quaternary ammonium salt having no polymerizable group, and the glass transition temperature of the cured product of the composition is 160 to 200 ° C. A radiation curable liquid composition.
[Selection] None

Description

  The present invention relates to a curable composition, a cured product thereof, and a laminate. More specifically, it has excellent coating properties and various transparent substrates [for example, plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS Resin, norbornene-based resin, etc.), metal, wood, paper, glass, slate, etc.], and is capable of forming a coating (film) with excellent antistatic properties on the surface of a transparent substrate. The present invention relates to a composition, a cured product thereof, and a laminate excellent in antistatic properties.

In recent years, protective coating materials for preventing contamination of various substrate surfaces; adhesives and sealing materials for various substrates; as a binder material for printing inks, and having excellent coating properties, There is a demand for a curable composition that can form a cured film excellent in all of adhesion, transparency, chemical resistance, antistatic property, and appearance of a coating film surface.
In addition to the above requirements, a curable composition capable of forming a cured film having a high refractive index is required in addition to the above-described requirements in applications of antistatic films such as film-type liquid crystal elements, touch panels, and plastic optical components.

  Various compositions have been proposed in order to satisfy such demands. However, the composition has excellent coating properties as a curable composition, and is stable even in a high-temperature and high-humidity environment when used as a cured film. The present condition is that the thing provided with the characteristic that it is excellent in antistatic property is not yet obtained.

  For example, a quaternary ammonium salt that is an antistatic agent is known to have a type having no polymerizable group and a type having a polymerizable group such as a (meth) acryloyl group or a vinyl group. Patent Documents 1 and 2 describe thermosetting antistatic coating materials to which a long-chain aliphatic quaternary ammonium alkyl sulfate having no polymerizable group is added as an antistatic agent. Patent Documents 3 to 4 describe radiation curable antistatic coating resin compositions to which a quaternary ammonium salt having a polymerizable group is added.

  However, when an antistatic agent such as a long-chain aliphatic quaternary ammonium alkyl sulfate having no polymerizable group is blended in the radiation curable composition, a sufficient amount is added to effectively impart antistatic properties. Due to insufficient compatibility with the binder resin, the antistatic agent precipitates (bleeds out) on the surface of the cured resin, particularly in a high temperature and high humidity environment. As a result, the antistatic property deteriorates over time. In addition, there are many defects such as a decrease in transparency of the cured resin.

JP-A-2-185541 JP-A-4-1271 Japanese Patent Laid-Open No. 9-165555 JP-A-7-258628

  The present invention has been made in view of the above-mentioned problems, has an excellent coating property, and has a stable antistatic coating film (coating film) on the surface of various transparent substrates even in a high-temperature and high-humidity environment. It is an object of the present invention to provide a curable composition capable of forming a), a cured product thereof, and a laminate having low reflectivity and excellent antistatic properties.

In order to achieve the above-mentioned object, the present inventors have conducted intensive research and added a long-chain aliphatic quaternary ammonium salt having no polymerizable group to a predetermined radiation-curable composition. As a result, the inventors have found that stable antistatic properties can be obtained, and have completed the present invention.
According to the present invention, the following curable composition, a cured film thereof and a laminate can be provided.

［式（１）中、Ｒは、炭素数８〜２２のアルキル基またはアルケニル基、Ａは炭素数１〜４のアルキル基である。］
［３］前記（Ｂ）エチレン性不飽和基含有化合物が、（Ａ）成分の全量に対して、３個以上のエチレン性不飽和基を有する化合物を２０〜６０質量％含有する、上記［１］又は［２］に記載の硬化性組成物；
［４］上記［１］〜［３］のいずれかに記載の硬化性組成物の硬化物からなる硬化膜；
［５］透明基材上に、上記［４］に記載の硬化膜からなる層を有する、積層体。 [1] Based on the total amount of the composition, (A) 30 to 70% by mass of a compound having one ethylenically unsaturated group, (B) 20 to 60% by mass of a compound having two or more ethylenically unsaturated groups (C) 0.1-10 mass% of photoinitiators and (D) 1-10 mass% of aliphatic quaternary ammonium salt which does not have a polymeric group, The glass transition temperature of the hardened | cured material of a composition A curable composition having a temperature of 160 to 200 ° C .;
[2] The curable composition according to the above [1], wherein the component (D) is a compound represented by the following formula (1);

[In Formula (1), R is an alkyl group or alkenyl group having 8 to 22 carbon atoms, and A is an alkyl group having 1 to 4 carbon atoms. ]
[3] The above [1], wherein the (B) ethylenically unsaturated group-containing compound contains 20 to 60% by mass of a compound having 3 or more ethylenically unsaturated groups based on the total amount of the component (A). Or the curable composition according to [2];
[4] A cured film comprising a cured product of the curable composition according to any one of [1] to [3] above;
[5] A laminate having a layer made of the cured film according to [4] above on a transparent substrate.

  According to the present invention, a coating film having excellent coating properties and having excellent antistatic properties and adhesion to a substrate, a low refractive index layer, and other hard coat layers on the surface of various substrates ( A curable composition capable of forming a coating), a cured product thereof, and a laminate excellent in antistatic properties can be provided.

Hereinafter, embodiments of the curable composition, the cured product and the laminate of the present invention will be specifically described.
I. Curable composition The curable composition of the present invention comprises (A) a compound having one ethylenically unsaturated group, (B) a compound having two or more ethylenically unsaturated groups, and (C) initiation of photopolymerization. And (D) an aliphatic quaternary ammonium salt having no polymerizable group.
Hereinafter, each structural component of the curable composition of this invention is demonstrated concretely.

1. (A) Compound having one ethylenically unsaturated group The component (A) used in the composition of the present invention is a compound having one ethylenically unsaturated group. Component (A) is suitably used for enhancing the film-forming property of the composition. The compound (A) is not particularly limited as long as it has one ethylenically unsaturated group, and examples thereof include (meth) acrylic esters and vinyl compounds. Of these, (meth) acrylic esters are preferred.

  Hereinafter, specific examples of the compound (A) used in the present invention include, for example, vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam; isobornyl (meth) acrylate, bornyl (meth) acrylate, and tricyclodecanyl. (Meth) acrylate, alicyclic structure-containing (meth) acrylate such as dicyclopentanyl (meth) acrylate; benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, vinylimidazole, vinylpyridine, etc. Can be mentioned. Furthermore, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) ) Acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) ) Acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodec (Meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate , Ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol ( (Meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate , Methoxypolypropylene glycol (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, Diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, hydroxybutyl vinyl ether, lauryl vinyl ether Cetyl vinyl ether, 2-ethylhexyl vinyl ether, and the like. Among these, vinyl group-containing lactams and alicyclic structure-containing (meth) acrylates having relatively high glass transition temperatures of homopolymers are preferable, and N-vinylpyrrolidone, N-vinylcaprolactam, and the like are more preferable.

  VP (BASF JAPAN) etc. can be used as a commercial item of these (A) components.

  The compound having one ethylenically unsaturated group as component (A) is usually blended in an amount of 10 to 70% by mass, more preferably 10 to 50% by mass, particularly preferably 10%, based on the total amount of the composition. -40 mass% is mix | blended.

2. (B) Compound having two or more ethylenically unsaturated groups The component (B) used in the composition of the present invention is a compound having two or more ethylenically unsaturated groups. Component (B) is preferably used for enhancing the film-forming property of the composition. The compound (B) is not particularly limited as long as it has two or more ethylenically unsaturated groups, and examples thereof include (meth) acrylic esters and vinyl compounds. Of these, (meth) acrylic esters are preferred.

（式（２）においてＲ^１は水素原子、またはフッ素を除くハロゲン原子を示し、Ｒ^３は−ＣＨ_２−、−Ｓ−または−Ｃ（ＣＨ_３）_２−を示す） 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 thereof include acrylates, oligoepoxy (meth) acrylates, and polyfunctional (meth) acrylates including a structure represented by the following formula (2).

(In Formula (2), R ¹ represents a hydrogen atom or a halogen atom excluding fluorine, and R ³ represents —CH ₂ —, —S—, or —C (CH ₃ ) ₂ —).

Specific examples of polyfunctional (meth) acrylates having the structure represented by the above formula (2) include ethylene oxide-added bisphenol A (meth) acrylate, ethylene oxide-added tetrabromobisphenol A (meth) acrylate, propylene oxide Addition bisphenol A (meth) acrylic acid ester, propylene oxide addition tetrabromobisphenol A (meth) acrylic acid ester, bisphenol A epoxy (meth) obtained by epoxy ring-opening reaction of bisphenol A diglycidyl ether and (meth) acrylic acid Tetrabromobisphenol A epoxy (meth) acrylate, bisphenol obtained by epoxy ring-opening reaction of acrylate, tetrabromobisphenol A diglycidyl ether and (meth) acrylic acid Bisphenol F epoxy (meth) acrylate obtained by epoxy ring-opening reaction between diglycidyl ether and (meth) acrylic acid, tetrabromo obtained by epoxy ring-opening reaction between tetrabromobisphenol F diglycidyl ether and (meth) acrylic acid Bisphenol F epoxy (meth) acrylate etc. are mentioned.
Among the components (B) listed above, a polyfunctional (meth) acrylate containing a structure represented by the above formula (2) such as bisphenol A epoxy (meth) acrylate, which has a relatively high glass transition temperature of the homopolymer, Trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are preferable.

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

  As a commercial item of such a compound (B), for example, Sanwa Chemical Co., Ltd. product name: Nikarac MX-302, 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-1343, TO-902, TO-904, TO-905, TO-1330, manufactured by Nippon Kayaku Co., Ltd. Trade name: KAYARAD D 310, D-330, DPHA, 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-62 R-551, R-712, R-167, R-526, R-551, R-712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA KS-TPGDA, KS-TMPTA, manufactured by Kyoeisha Chemical Co., Ltd. Trade name: Light acrylate PE-4A, DPE-6A, DTMP-4A, and the like.

  The compound having two or more ethylenically unsaturated groups as component (B) is usually blended in an amount of 20 to 80% by mass, more preferably 40 to 80% by mass, particularly preferably based on the total amount of the composition. 50-80 mass% is mix | blended.

  (B) It is preferable to mix | blend the compound which has a 3 or more ethylenically unsaturated group in a component. The compounding quantity of the compound which has a 3 or more ethylenically unsaturated group is 20-60 mass% normally with respect to the whole quantity of (B) component, Preferably it is 20-50 mass%.

3. (C) Photopolymerization initiator The photopolymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl Phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4 ′ -Dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, -Hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- Propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2 , 4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like. Kill.

  As a commercial item of a photoinitiator, for example, Ciba Specialty Chemicals Co., Ltd. trade name: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG 24-61, Darocur 1116, 1173, manufactured by BASF, Inc. Product name: Lucillin TPO, manufactured by UCB, Inc. Product name: Ubekrill P36, manufactured by Fratteri Lamberti, Inc. Product names: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B, etc. be able to.

When hardening the composition of this invention, a photoinitiator and a thermal-polymerization initiator can be used together as needed.
Preferable thermal polymerization initiators include, for example, peroxides and azo compounds. Specific examples include benzoyl peroxide, t-butyl-peroxybenzoate, azobisisobutyronitrile, and the like. it can.

  The photopolymerization initiator as component (C) is usually blended in an amount of 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total amount of the composition. If it is less than 0.1% by mass, the film formability may be insufficient, and if it exceeds 10% by mass, a cured product with high hardness may not be obtained.

4). (D) Aliphatic quaternary ammonium salt having no polymerizable group The component (D) used in the composition of the present invention is an aliphatic quaternary ammonium salt having no polymerizable group. Component (D) is blended to impart antistatic properties to a cured film obtained by curing the composition.

［式（１）中、Ｒは、炭素数８〜２２のアルキル基またはアルケニル基、Ａは炭素数１〜４のアルキル基である。］
本発明の（Ｄ）成分は、重合性基を有しないことが必要である。重合性基を有しないことにより、硬化膜中である程度移動することができ、硬化膜の帯電防止性により効果的に寄与することができる。 (D) As a typical example of a component, a long-chain aliphatic quaternary ammonium alkyl sulfate can be mentioned, Preferably the compound shown by following formula (1) can be mentioned.

[In Formula (1), R is an alkyl group or alkenyl group having 8 to 22 carbon atoms, and A is an alkyl group having 1 to 4 carbon atoms. ]
The component (D) of the present invention needs to have no polymerizable group. By not having a polymerizable group, it can move to some extent in the cured film, and can contribute more effectively to the antistatic properties of the cured film.

［式（３）中、Ｒは、式（１）のＲに同義である。］ As the component (D) of the present invention, a modified aliphatic dimethylethylammonium ethosulphate represented by the following formula (3) is preferable. As a commercial item of this compound, Elegan 264-WAX (Nippon Yushi Co., Ltd.) can be mentioned.

[In Formula (3), R is synonymous with R of Formula (1). ]

  The photopolymerization initiator as component (D) is usually blended in an amount of 1 to 10% by mass, more preferably 1 to 5% by mass, based on the total amount of the composition. When the amount is less than 1% by mass, the antistatic property may be insufficient. When the amount exceeds 10% by mass, the component (D) is difficult to dissolve in the composition, so that it is difficult to obtain a uniform composition. Sometimes.

5. Other components In the curable composition of the present invention, as long as the effects of the present invention are not impaired, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, an interface, as necessary. An activator, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, an inorganic filler, a pigment, a dye, and the like can be appropriately blended.
The composition of the present invention contains a photopolymerization initiator (C) as a polymerization initiator. In addition, a compound that generates a cationic species thermally and / or a thermally active radical species is added. A thermal polymerization initiator such as a compound to be generated can be blended.
Examples of the compound that generates a cationic species thermally include, for example, aliphatic sulfonic acid, oxyaliphatic sulfonate, aliphatic carboxylic acid, aliphatic carboxylate, aromatic carboxylic acid, aromatic carboxylate, alkylbenzene sulfone. Examples thereof include compounds such as acids, alkylbenzene sulfonates, phosphate esters, and metal salts.
These can be used alone or in combination of two or more.

  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.

6). Glass transition temperature of composition The glass transition temperature (Tg) of the cured product of the composition of the present invention is preferably 160 to 200 ° C, and more preferably 170 to 190 ° C. The glass transition temperature here is defined as a temperature indicating a maximum value of loss tangent (tan δ) measured at a vibration frequency of 1 kHz by a dynamic viscoelasticity measuring apparatus. Tg is obtained by measuring the maximum value of tan δ with respect to temperature by the vibron method. When Tg is in the above range, the compatibility with the component (D) is improved.

7). Composition (Coating) Method of Composition The composition of the present invention is suitable for use as an antistatic film or a coating material. Examples of the base material to be antistatic or coated include plastics (polycarbonate, polymethacrylate, polystyrene). Polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, slate and the like. The shape of 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 0.01 to 400 μm, preferably 0.1 to 200 μm after drying and curing.

The composition of the present invention can be used after diluted with a solvent in order to adjust the thickness of the coating film. For example, the viscosity when used as an antistatic film or a coating material is usually 0.1 to 50,000 mPa · sec / 25 ° C., and preferably 0.5 to 10,000 mPa · sec / 25 ° C.
Examples of the solvent that can be used for adjusting the coating thickness 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 , Esters such as ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene Amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. Moreover, the usage-amount of this solvent in particular is although it does not restrict | limit, It is 5-100,000 mass parts normally with respect to 100 mass parts of compositions of this invention, Preferably it is 10-10,000 mass parts.

8). Method of Curing Composition 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. For the gamma rays, a vacuum tube or the like that causes accelerated electrons to collide with the anode can be used. These radiations can be irradiated alone or in combination of two or more at a certain time.

II. Cured film 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 the above-described curing treatment with heat and / or radiation. . The preferable curing conditions in the case of heat are 20 to 150 ° C., and are performed within a range of 10 seconds to 24 hours. When using radiation, it is preferable to use ultraviolet rays or electron beams. In such a case, the preferable irradiation amount of ultraviolet rays is 0.01 to 10 J / cm ² , more preferably 0.1 to ² J / cm ² . Moreover, as for the irradiation conditions of a preferable electron beam, a pressurization voltage is 10-300 KV, an electron density is 0.02-0.30 mA / cm < ² >, and an electron beam irradiation amount is 1-10 Mrad.

The cured film of the present invention has the characteristics that it has a high hardness and a high refractive index, and can form a coating film (film) excellent in scratch resistance and adhesion to the substrate and the low refractive index layer. Therefore, it is particularly suitably used as a hard coat or an antistatic film for film type liquid crystal elements, touch panels, plastic optical parts and the like.
Further, the cured film of the present invention is excellent in antistatic properties and is also useful as an antistatic film in various plastic optical parts.

III. Laminate The laminate of the present invention is particularly suitable as an antistatic film obtained by laminating a cured film obtained by curing the curable composition on a transparent substrate.
The transparent substrate used in the laminate of the present invention is not particularly limited. For example, the aforementioned plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, PET resin) , ABS resin, AS resin, norbornene resin, etc.).

  Since the laminate of the present invention is excellent in antistatic properties, it is particularly suitably used as a surface coat film for film type liquid crystal elements, touch panels, plastic optical components and the like.

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to the description of these examples. Moreover, unless otherwise indicated, the compounding quantity of each component in an Example means the mass part and the mass%.

[Preparation of curable composition]
Example 1
In a container shielded from ultraviolet rays, 15 parts of trimethylolpropane triacrylate, 40 parts of bisphenol type epoxy diacrylate, 23 parts of N-vinylpyrrolidone, 20 parts of dipentaerythritol hexaacrylate, 3 parts of hydroxycyclohexyl phenyl ketone, and IRGANOX 1035 3 parts, 0.1 part of diethylamine and 0.15 part of polyoxyalkylene alkyl ether phosphate ester were added, and quaternary ammonium salt modified aliphatic dimethylethylammonium ethosulphate (Elegan 264-WAX; Nippon Oil & Fats Co., Ltd.) 4 0.0 part was added and the composition of the uniform solution was obtained by stirring at 60 degreeC for 1 hour.

Comparative Examples 1-6
Each composition of Comparative Examples 1-6 was obtained by the same method as Example 1 except having changed into the composition shown in Table 1.

[Create laminate]
Example 2
The composition obtained in Example 1 was coated on a PET substrate using an applicator bar. Next, in the atmosphere, using a metal halide lamp, the coating film was UV-cured under light irradiation conditions of 220 mW / cm ² and 0.4 J / cm ² , and a cured film having a thickness of 200 μm was laminated on the PET substrate. Got the body.
The surface resistance of this laminate was measured using a high resistance meter (Agilent Technology Co., Ltd. Agilent 4339B) and Resistivity Cell 16008B (Agilent Technology Co., Ltd.) under an applied voltage of 100V. . The surface resistance value was 3 × 10 ¹³ Ω / □.

Comparative Examples 7-12
A laminated body was produced in the same manner as in Example 2 except that the compositions obtained in Comparative Examples 1 to 6 were used in place of the composition in Example 1.

<Characteristic evaluation of laminate>
1. Glass transition temperature of cured film For the laminates obtained in Example 1 and Comparative Examples 7-12, the loss was measured at a vibration frequency of 1 kHz using a dynamic viscoelasticity measuring device after cutting the laminate to 3 mm × 3.6 cm. The temperature showing the maximum value of tangent (tan δ) was measured (Vibron method: Leo Vibron, Orientec Co., Ltd.), and the maximum value of tan δ with respect to temperature was taken as the glass transition temperature (Tg).
2. Presence / absence of bleed material For the laminates obtained in Example 2 and Comparative Examples 7 to 12, the laminates were immediately after film formation and after standing at 80 ° C. and 85% relative humidity for 1 day and 1 week. The presence or absence of a bleed material on the surface was visually determined. The case where no bleed was found was judged as “none”, and the case where a bleed was found was judged as “present”.

Trimethylolpropane triacrylate: Biscoat TMP-3A # 295 (Osaka Organic Chemical Industry Co., Ltd.)
Bisphenol type epoxy diacrylate: VR-77 (Showa Polymer Co., Ltd.)
N-vinyl pyrrolidone: VP (BASF JAPAN)
Dipentaerythritol hexaacrylate: KAYARAD DPHA (Nippon Kayaku Co., Ltd.)
Phenoxytetraethylene glycol acrylate: PHE-4S (Daiichi Kogyo Seiyaku Co., Ltd.)
Hydroxycyclohexyl phenyl ketone: Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.)
Irganox 1035: Thiodiethylenebis [3-3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Ciba Specialty Chemicals Co., Ltd.)
Diethylamine: (Mitsubishi Gas Chemical Co., Ltd.)
Polyoxyalkylene alkyl ether phosphate: Prisurf A208F (Daiichi Kogyo Seiyaku Co., Ltd.)
Modified Aliphatic Dimethylethylammonium Ethosulphate: Elegan 264-WAX (Nippon Yushi Co., Ltd.)

  From the results of Table 1 above, when the laminate is exposed to a high-temperature and high-humidity environment, in the laminate of the example, no bleed material is generated on the surface of the laminate. It can be seen that bleeding occurs.

The curable composition of the present invention, the cured product, and the laminate are, for example, scratches such as plastic optical parts, touch panels, film-type liquid crystal elements, plastic containers, floor materials as building interior materials, wall materials, artificial marble, etc. Protective coating materials for preventing scratches and preventing contamination; Antistatic films for film-type liquid crystal elements, touch panels, plastic optical components, etc .; Adhesives and sealing materials for various base materials; It can be suitably used as a film.
Further, since the laminate of the present invention is excellent in antistatic properties, it can be used for the purpose of preventing the adhesion of dust for various panels such as CRT, liquid crystal display panel, plasma display panel, electroluminescence display panel, etc. It is also useful as an electromagnetic shield and as an antistatic film for these.

Claims (5)

For the total amount of the composition
(A) 10 to 70% by mass of a compound having one ethylenically unsaturated group,
(B) 20-80% by mass of a compound having two or more ethylenically unsaturated groups,
(C) Photopolymerization initiator 0.1 to 10% by mass, and (D) Aliphatic quaternary ammonium salt 1 to 10% by mass having no polymerizable group.
And a glass transition temperature of a cured product of the composition is 160 to 200 ° C. The curable composition according to claim 1, wherein the component (D) is a compound represented by the following formula (1).

[In Formula (1), R is an alkyl group or alkenyl group having 8 to 22 carbon atoms, and A is an alkyl group having 1 to 4 carbon atoms. ]   The said (B) ethylenically unsaturated group containing compound contains 20-60 mass% of compounds which have a 3 or more ethylenically unsaturated group with respect to the whole quantity of (B) component. The curable composition as described.   The cured film which consists of hardened | cured material of the curable composition as described in any one of Claims 1-3.   The laminated body which has a layer which consists of a cured film of Claim 4 on a transparent base material.