JP2005343119A - Manufacturing method of coated plastic article, coated plastic article and photo-curable coating liquid composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a plastic article coated by a photocurable hard coat film superior in a scratch resistance and an adhesion and especially a manufacturing method of a heat curable plastic lens for glasses. <P>SOLUTION: The coated plastic articles are produced by applying a photocurable coating liquid containing (A) a compound having at least two (meth)acryloyl groups in a molecule, (B) an ionic photopolymerization initiator and (C) a photocurable coating liquid containing a metallic oxide particles of at least one metal selcted from Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, Ti and Ge to the surface of a plastic substrate and by photochemically curing by radiating a radioactive ray. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a coated plastic article, particularly a method for producing a coated plastic article in which a coating liquid for hard coat for imparting scratch resistance is applied to the surface of a transparent resin substrate such as a plastic spectacle lens, and cured. The present invention relates to a coated plastic article obtained by the production method and a photocurable coating liquid composition for the production method.

  Glasses for spectacles are becoming plastic instead of those using conventional glass because of their features such as being hard to break and light. However, plastic lenses are hard to break, but the surface is easily scratched, so it is common to perform a hard coat treatment on the surface.

  Compared to thermoplastics such as polycarbonate (refractive index 1.58 Abbe number 30) as a material for plastic lenses, the high refractive index thermosetting resin developed for spectacle lenses has a high Abbe number, resulting in improved optical performance. It is excellent and is preferably used for glasses. Examples of the high refractive index thermosetting resin include diethylene glycol bisallyl carbonate resin (refractive index: 1.50, Abbe number: 58) using the monomer “CR-39” of PPG. By using a monomer containing a ring, a lens having a higher refractive index is manufactured, and a lens having a small thickness is a major measure. For example, using lenses (refractive index 1.55, Abbe number 40) using fumaric acid ester resin monomer “NK-55” manufactured by NOF Corporation and thiourethane resin monomer “MR-6” manufactured by Mitsui Chemicals, Inc. Lenses (refractive index 1.60, Abbe number 36), lenses using “MR-7” (refractive index 1.66, Abbe number 32), and the like.

  The hard coating on the resin lens substrate is generally performed by applying a hard coating solution mainly composed of a metal oxide and a silicone compound and heat curing. For high refractive index resin lenses, high refractive index metal oxides such as titanium, zirconium, and tin are used to make the refractive index of the hard coat film as close as possible to the refractive index of the substrate so that interference fringes are not noticeable. Hard coating treatment is performed using a coating solution containing a product. (For example, Patent Document 1)

However, the above hard coat takes a long time to cure for heat curing and requires large-scale equipment. Lenses, especially lenses with a high refractive index, are easily deformed during heating, resulting in a decrease in manufacturing yield. There is a problem that causes it. As a hard coat which can solve these problems and can be cured in a short time with a small-scale facility, a manufacturing method is disclosed in which a coating liquid mainly composed of an ultraviolet curable resin and a photopolymerization initiator is cured at a low temperature. . For example, Patent Document 2 discloses a composition containing a polyfunctional acrylate such as pentaerythritol triacrylate, a metal oxide fine particle such as antimony oxide, and a photopolymerization initiator such as 1-hydroxycyclohexyl phenyl ketone as a resin base material. It is described that a hard coat film-coated resin article is obtained by applying to the surface and curing at low temperature by light irradiation.
JP-A-8-48940 JP-A-8-179123

  However, the above hard coat film has large cure shrinkage at the time of photocuring, especially when a thermosetting resin is used as a base material, the adhesiveness is inferior, and it is easy to cause problems such as film peeling after the moisture resistance test. It is inferior to practical use as compared with the hard coat film. Accordingly, there is a need for a photocurable hard coat film that can adjust the refractive index for thermosetting lenses and has excellent adhesion and scratch resistance.

  An object of the present invention is to provide a method for producing a photocurable hard coat film-coated plastic article excellent in scratch resistance and adhesion, particularly a method for producing a thermosetting resin plastic lens for spectacles, and a coated plastic article obtained by this production method. And providing a photocurable coating liquid composition for the manufacturing method.

  That is, the present invention relates to (A) a compound having at least two (meth) acryloyl groups in the molecule, (B) an ionic photopolymerization initiator, and (C) Si, Al, Sn, Sb, Ta, Ce, A photocurable coating solution containing oxide particles of at least one metal selected from La, Fe, Zn, W, Zr, In, Ti and Ge is applied to the surface of a plastic substrate, and photocured by irradiation. A method for producing a coated plastic article.

  The hard coat liquid in the present invention comprises (A) a compound having at least two (meth) acryloyl groups in the molecule, (B) an ionic photopolymerization initiator, and (C) Si, Al, Sn, Sb, Ta, It contains oxide particles of at least one metal selected from Ce, La, Fe, Zn, W, Zr, In, Ti and Ge. Each component will be described below.

  Examples of compounds having at least two (meth) acryloyl groups in the molecule as component (A) include (meth) acrylic acid ester monomers, urethane (meth) acrylates, polyester (meth) acrylates, and epoxy (meth) acrylates. , Silicone (meth) acrylate, and copolymer acrylate. In this specification, an acryloyl group or a methacryloyl group is referred to as a (meth) acryloyl group, an acrylate or methacrylate is referred to as a (meth) acrylate, and acrylic acid or methacrylic acid is referred to as (meth) acrylic acid.

  Examples of the poly (meth) acrylate monomer include 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Ethylene glycol di (meth) acrylate, tripropylene glycolidi (meth) acrylate, neopentyl glycol di (meth) acrylate, poly (butanediol) di (meth) acrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol di (Meth) acrylate, triethylene glycol di (meth) acrylate, triisopropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate Di (meth) acrylates such as trimetholpropane; triacrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol monohydroxytriacrylate and trimethylolpropane triethoxytriacrylate; pentaerythritol tetra (meth) acrylate and di Mention may be made of tetra (meth) acrylates such as trimethylolpropane tetraacrylate; and pentaacrylates such as pentaerythritol (monohydroxy) pentaacrylate. These are used singly or in combination of two or more. When a trifunctional or higher acrylate (triacrylate, tetraacrylate) is used, the hardness of the hard coat film is generally improved, but the viscosity of the hard coat liquid is increased, and cracks are likely to occur in the hard coat film. Or In consideration of the function and workability of the membrane, the above compounds may be used alone or in combination.

  Urethane (meth) acrylate is a compound comprising a polyol, an isocyanate moiety, and a (meth) acrylate moiety as a main chain. Examples of the main chain include polyester polyols, polyether polyols, and isocyanate moieties such as toluene diisocyanate, monomeric 4,4′diphenylmethane diisocyanate, polymeric 4,4′diphenylmethane diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane 4,4 ′ diisocyanate. Can be mentioned. As these, the following commercial products can be used. Kyoeisha Chemical Co., Ltd. AH-600, AT-600, UA-306H, AI-600, UA-101TUA-101I, UA-306T, UA-306I; Photomer 6008, Photomer 6010, Photomer manufactured by San Nopco 6019, Photomer 6022, Photomer 6060; Aronix M-1100, Aronix M-1200, Aronix M-1210, Aronix M-1310 Aronix, M-1600 manufactured by Toagosei Co., Ltd. Art Resin UN manufactured by Negami Kogyo Co., Ltd. -3320HA, Art Resin UN-3320HB, Art Resin UN-3320HC, Art Resin UN-3320HS; KAYARAD UX-2201, KAYARAD UX-2301, KAYARAD UX-3204, manufactured by Nippon Kayaku Co., Ltd. AYARAD UX-3301, KAYARAD UX-4101, KAYARAD UX-6101, KAYARAD UX-7101, KAYARAD UX-8810, Ebecryl230, Ebecryl2244, Ebecryl2244, Ebecryl2244 , Ebecryl 4830, Ebecryl 4835, Ebecryl 4858, Ebecryl 4883, Ebecryl 8402, Ebecryl 8804, Ebecryl 8807, Ebecryl 8803, Ebecryl 8807, Ebec 8808, Ebec 54, Ebecryl264, Ebecryl265, Ebecryl294 / 35HD, Ebecryl1259, Ebecryl1264, Ebecryl4866, Ebecryl9240, Ebecryl8210, Ebecryl, Ebecryl1290, Ebecryl1290K, Ebecryl5129, Ebecryl2000, Ebecryl2001, Ebecryl2002, Ebecryl2100, EbecrylKRM7222, EbecrylKRM7735, Ebecryl4842, Ebecryl210, Ebecryl215, Ebecryl4827, Ebecryl4849, Ebecryl 6700, Ebecryl 6700-20T, Ebecryl 204, Ebecryl 205, Such as becryl6602, Ebecryl220, Ebecryl4450.

  The urethane acrylate has a yellowing type and a non-yellowing type, but the non-yellowing type is preferred when transparency is particularly required, but the yellowing type is considered in consideration of the balance of functions such as film hardness and adhesion. If it seems to be preferable, a yellowing type may be used.

  Polyester (meth) acrylate is an esterified compound of polyester polyol and (meth) acrylic acid having a terminal hydroxyl group. As these, the following commercial products can be used. Aeonix M-7100, Aronix M-8030, Aronix M-8060 manufactured by Toagosei Chemical Industry Co., Ltd. Ebecryl800, Ebecryl805, Ebecryl808, Ebecryl810, Ebecryl812, Ebecryl1657, Ebecryl1810, EbecrylIRR302, Ebecryl450, Ebecryl670, Ebecryl830, Ebecryl835, Ebecryl870, Ebecryl1830, Ebecryl1870, Ebecryl287 , Such as EbecrylIRR267, Ebecryl813, EbecrylIRR483, Ebecryl811.

  Epoxy (meth) acrylate is a compound obtained by reaction of polyglycidyl ether such as polyester polyol or polyether polyol and (meth) acrylic acid. As these, the following commercial products can be used. Epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 200PA, epoxy ester 80MFA, epoxy ester 3002M, epoxy ester 3002A, epoxy ester 1600A, epoxy ester 3000M, epoxy ester 3000A, epoxy ester 200EA manufactured by Kyoeisha Chemical Co., Ltd. , Epoxy ester 400EA, Ebecryl 600, Ebecryl 601, Ebecryl 604, Ebecryl 605, Ebecryl 607, Ebecryl 608, Ebecyl 608, Ebecyl 608, Ebecyl 608, Ebecyl Ec 0, Ebecryl1606, Ebecryl1608, Ebecryl1629, Ebecryl1940, Ebecryl2958, Ebecryl2959, Ebecryl3404, Ebecryl3411, Ebecryl3412, Ebecryl3415, Ebecryl3502, Ebecryl3600, Ebecryl3603, Ebecryl3604, Ebecryl3605, Ebecryl3608, Ebecryl3700, Ebecryl3700-20H, Ebecryl3700-20T, Ebecryl3700-25R, Ebecryl3701, Ebecryl 3701-20T, Ebecryl 3703, Ebecryl 3702, Ebecryl 3708, Ebecryl RDX 6318 , Such as Ebecryl6040, EbecrylIRR419.

  The above compound can be expressed as an ester compound of (meth) acrylic acid and polyol, but the (meth) acrylic acid moiety becomes an acrylic acid oligomer such as dimer acid or trimer acid for the purpose of reducing skin irritation. Polyol polyacrylic acid oligomer ester may be used.

  As the ionic photopolymerization initiator which is the component (B) in the present invention, a cationic photopolymerization initiator or an anionic photopolymerization initiator is used. Examples of the cationic photopolymerization initiator include arylsulfonium salts, aryliodonium salts, diazonium salts, and metallocene derivatives.

  The arylsulfonium salt in the present invention is a salt comprising a cation moiety having at least one bond between an aryl group and a trivalent sulfur cation, and an anion moiety. Examples of the aryl group include a phenyl group, a tolyl group, an anisyl group, an isopropylphenyl group, a butylphenyl group, an alkylphenyl group, an alkenylphenyl group, and an alkanylphenyl group. The aryl group may contain, for example, naphthalene, anthracene and the like in which two or more aromatic rings are condensed. These aromatic rings may be heterocycles containing oxygen, nitrogen, sulfur, selenium, tellurium, phosphorus and the like. Any arylsulfonium salt having one aryl group or two or more aryl groups may be used, and the arylsulfonium salt is appropriately selected depending on the solubility, reactivity, wavelength of the irradiation light source used, and the like.

Examples of the counter ion of the arylsulfonium salt include BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , ClO ₄ ⁻ , BrO ₄ ⁻ , IO ₄ ⁻ , ClO ₃ ⁻ , BrO ₃ ⁻ , IO ₃ ⁻ , ClO ₂ ⁻ , BrO ₂ ⁻ , IO ₂ ⁻ , ClO ⁻ , BrO ⁻ , IO ⁻ , Cl ⁻ , Br ⁻ , I ^{− and the} like.

  Examples of the arylsulfonium salt include 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate and 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl). Sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4- Methylphenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4- (α-hydroxyethoxy) phenyl) sulfonium hexafluoroantimonate, 4- (2 Methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (3-methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4 -(2-Fluoro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, fluorofluoro-4- (2,3,5,6-tetramethyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,6-dichloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,6- Dimethyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,3-dimethyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (3-methyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoro Antimonate, 4- (2-fluoro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, fluoro-4- (2,3,5,6-tetramethyl-4-ben Ylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,6-dichloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2, 6-dimethyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,3-dimethyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate 4- (2-chloro-4-acetylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenyldiphenylsulfate Nitrohexafluoroantimonate, 4- (2-chloro-4- (4-fluorobenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenyldiphenyl Sulfonium hexafluoroantimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) phenylbis (4-fluorophenyl) sulfonium Hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro- 4- (4-Fluorobenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium Hexafluoroantimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) phenylbis (4 -Chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- 4-fluorobenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4- ( 2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium perchlorate 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium trifluoromethanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluorophosphate, 4 -(2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium perchlorate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium trifluoromethanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophene) Nyl) sulfonium p-toluenesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium camphorsulfonate, 4- (2-chloro-4-benzoylphenylthio) Phenylbis (4-fluorophenyl) sulfonium nonafluorobutanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-) Benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium perchlorate, 4- (2-chloro-4-benzo) Rufeniruchio) phenyl bis (4-chlorophenyl) sulfonium trifluoromethanesulfonate, and the like.

  The following commercially available products can be used as the arylsulfonium salt. “CYRACURE” UVI-6950, UVI-6970, UVI-6974, UVI-6990, manufactured by Union Carbide Corporation, “Adekaoptomer” SP-150, SP-152, SP-170, SP-, manufactured by Asahi Denka Kogyo Co., Ltd. 172, “Sun Aid SI-60L” manufactured by Sanshin Chemical Industries, Ltd., “WPAG-281”, “WPAG-336”, “WPAG-367” manufactured by Wako Pure Chemical Industries, Ltd.

The aryliodonium salt in the present invention is a salt composed of a cation moiety having at least one bond between an aryl group and a divalent iodine cation, and an anion moiety. Examples of the aryl group include a phenyl group, a tolyl group, an anisyl group, an alkylphenyl group, an alkenylphenyl group, and an alkanylphenyl group. The aryl group may contain, for example, naphthalene, anthracene and the like in which two or more aromatic rings are condensed. These aromatic rings may be heterocycles containing oxygen, nitrogen, sulfur, selenium, tellurium, phosphorus and the like. Any aryliodonium salt having one aryl group or two or more aryl groups may be used, and the aryliodonium salt is appropriately selected depending on the solubility, reactivity, wavelength of the irradiation light source used, and the like.
Examples of the counter ion of the aryl iodonium salt include BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , ClO ₄ ⁻ , BrO ₄ ⁻ , IO ₄ ⁻ , ClO ₃ ⁻ , BrO ₃ ⁻ , IO ₃ ⁻ , ClO ₂ ⁻ , BrO ₂ ⁻ , IO ₂ ⁻ , ClO ⁻ , BrO ⁻ , IO ⁻ , Cl ⁻ , Br ⁻ , I ^{− and the} like.

Examples of the aryliodonium salt include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and the like. The following commercially available products can be used as the aryl iodonium salt. "IRGACURE250" manufactured by Ciba Specialty Chemicals Co., Ltd., Wako Pure Chemical Industries "WPI-113", Toyo Gosei Kogyo "DTBPI-PFBS", etc.
Usually, the aryl iodonium salt is added to the photocurable coating solution, but the aryl iodonium salt may be generated in the system of the photocurable coating solution.

The diazonium salt in the present invention is a salt containing a C═N ⁺ ═N ⁻ bond in the molecule. Other substituents are selected optimally depending on the solubility, reactivity, wavelength of the light source used, and the like. Examples of the structure of the diazonium salt include BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , ClO ₄ ⁻ , BrO ₄ ⁻ , IO ₄ ⁻ , ClO ₃ ⁻ , BrO ₃ ⁻ , IO ₃ ⁻ , ClO ₂ ⁻ and BrO. _{^{2 -, IO 2 -, ClO}} -, BrO -, IO -, Cl -, Br -, I - , etc. may be included as a counter ion, also a betaine structure cation portion and an anion portion in a molecule coexist It may be. Examples of the cation moiety include 2,5-diethoxy-4- (p-toluylmercapto) benzene, 2,4-dichlorobenzene, D-nitrobenzene, p-chlorobenzene, p- (N morpholino) benzene, 2,5-di Examples include chlorobenzene and o-nitrobenzene, and examples of the anion moiety include BF ₄ ⁻ , FeCl ₄ ⁻ , PF ₆ ⁻ and SbF ₆ ⁻ . The following commercially available products can be used as the diazonium salt. Wako Pure Chemical Industries WPAG-145, WPAG-170, WPAG-199, and Midori Chemical Industries DAM-101, DAM-102, etc.

  The metallocene derivative in the present invention is a compound having a structure in which at least one anion having a cyclopentadienyl skeleton is coordinated to a metal at the center. As the center metal, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, W, Re , Os, Ir, Pt, Au and the like. Examples of commercially available metallocene derivatives include “IRGACURE261” manufactured by Ciba Specialty Chemicals.

  Examples of the anionic photopolymerization initiator in the present invention include a cobalt amine complex, o-nitrobenzyl alcohol carbamate, oxime ester and the like.

  Among the above ionic photopolymerization initiators, since the yellowing of the hard coat film is small, arylsulfonium salts and aryliodonium salts are preferably used.

The component (C) of the hard coat liquid in the present invention is a component that increases the hardness of the hard coat film and prevents the occurrence of cracks in the film. Si, Al, Sn, Sb, Ta, Ce, La, Fe, These are oxide particles of at least one metal selected from Zn, W, Zr, In, Ti, and Ge. Examples of these metal oxides include SiO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Ta ₂ O ₅ , CeO ₂ , La ₂ O ₃ , Fe ₂ O ₃ , ZnO, WO ₃ and ZrO _2. , In ₂ O ₃ , TiO ₂ , GeO _{2 and the} like. The component (C) may be a simple substance of these metal oxide fine particles or a mixture thereof, a composite oxide fine particle composed of two or more kinds, or a mixture thereof. As the metal oxide fine particles, those having a particle size of 1 to 100 nm are preferably used.

As composite oxide fine particles, composite oxide fine particles of titanium and silicon (TiO 2 · SiO 2), composite oxide fine particles of titanium, cerium and silicon (TiO 2 · CeO 2 · SiO 2), composite oxide fine particles of titanium, iron and silicon (TiO 2)・ Fe2O3 ・ SiO2), composite oxide fine particles of titanium, zirconium and silicon (TiO2 ・ ZrO2 ・ SiO2), composite oxide fine particles of titanium, antimony and silicon (Sb2O3 ・ ZrO2 ・ SiO2), composite oxidation of titanium, aluminum and silicon And fine particles (TiO2, Al2O3, SiO2) and the like. These composite oxide fine particles preferably contain 5 mol% or more of SiO2 component (molar ratio metal: SiO ₂ = 9.5: 0.5 or more).

  The metal oxide fine particles are preferably used by being dispersed in a solvent so that the solid content is 10 to 50% by mass. In order to improve the dispersibility in the solvent, the surface of the metal oxide fine particles may be modified with an organosilane compound. The addition amount of the organosilane compound is 0 to 20% by mass with respect to the fine particle mass. The surface modification treatment is performed without hydrolysis or by mixing the hydrolyzed organosilane compound with the metal oxide fine particles and then heating or drying.

Specific examples of the organosilane compound used for the surface modification include the following (a), (b), (c), and (e).
(A) Monofunctional silane represented by R ₃ SiX (R is an organic group having an alkyl group, phenyl group, vinyl group, methacryloxy group, mercapto group, amino group, epoxy group, and X is a hydrolyzable group) );
For example, trimethylmethoxysilane, triethylmethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylmethoxysilane, diphenylmethylmethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, vinyldimethylmethoxysilane, vinyldimethylethoxysilane, γ- Acryloxypropyldimethylmethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-mercaptopropyldimethylmethoxysilane, γ-mercaptopropyldimethylethoxysilane, N-β (aminoethyl) γ-aminopropyldimethylmethoxysilane, γ-amino Propyldimethylmethoxysilane, γ-aminopropyldimethylethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycol De propyl dimethoxy silane, a beta-(3.4-epoxycyclohexyl) ethyl dimethyl methoxysilane.

(A) a bifunctional silane represented by R ₂ SiX ₂ ;
For example, dimethyldimethoxysilane, diethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, γ-acryloxy Propylmethyldimethoxysilane, γ-methacryloxypropyldimethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyl Methyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethoxydiet Shishiran a beta-(3.4-epoxycyclohexyl) ethyl methyl dimethoxysilane.

(C) a trifunctional silane represented by RSiX ₃ ;
For example, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl (β-methoxyethoxy) silane , Γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane , Beta-glycidoxypropyl triethoxy silane, beta-(3.4-epoxycyclohexyl) ethyltrimethoxysilane.
(D) a tetrafunctional silane represented by SiX ₄ ;
For example, tetraethyl orthosilicate, tetramethyl orthosilicate, and tetra n-butyl orthosilicate.

  Water; saturated aliphatic alcohols such as methanol, ethanol, isopropyl alcohol, n-butanol, 2-butanol; cellosolves such as methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve; propylene glycol Derivatives such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl acetate; esters such as methyl acetate, ethyl acetate, butyl acetate; ethers such as diethyl ether, methyl isobutyl ether; ketones such as acetone, Methyl isobutyl ketone; aromatics such as xylene, toluene; other organic solvents such as ethylene glycol, tetrahydrofuran, N, N, -di Chill formamide, dichloroethane, dichloromethane, chloroform, carbon tetrachloride.

Examples of commercially available SiO ₂ fine particles include Nalco 1057 (manufactured by Nalco, average particle size 20 nm, solid content 30%, propoxyethanol dispersion), Snowtex O-40 (manufactured by Nissan Chemical Co., Ltd., average particle size 20 nm, An aqueous dispersion having a solid content of 40%) and IPA-ST (manufactured by Nissan Chemical Co., Ltd., isopropyl alcohol dispersion having an average particle size of 20 nm and a solid content of 30%) can be used.

Commercially available products of Al ₂ O ₃ fine particles include, for example, Nissan Chemical Industries Co., Ltd. water dispersion: Alumina sol-100, -200, -520; Sumitomo Osaka Cement Co., Ltd. isopropanol dispersion: AS-150I; Sumitomo Osaka Cement Co., Ltd. toluene dispersion product: AS-150T etc. can be mentioned.

The SnO ₂ fine particles of commercially available products, for example Ishihara Sangyo Co., Ltd. antimony-doped tin oxide aqueous dispersion sol: can be mentioned SN-100D. As a commercially available product of CeO ₂ fine particles, for example, cerium oxide aqueous dispersion: Nidraral manufactured by Taki Chemical Co., Ltd. can be mentioned. As a commercial item of ZrO ₂ fine particles, for example, Sumitomo Osaka Cement Co., Ltd. zirconia toluene dispersion: HXU-110JC can be mentioned. Examples of commercially available fine particles of titanium oxide, indium oxide, and zinc oxide include powders and solvent dispersions manufactured by CI Kasei Co., Ltd .: Nanotech.

  The hard coat liquid used in the present invention is represented by 10 to 99.4% by weight of the component (A) as a solid content with respect to the total solid content, the component (B) as the component (A), the component (B) and ( C) 0.1 to 20% by weight, more preferably 0.2 to 10 parts by weight, and more preferably 0.5 to 70% by weight, and more preferably 0.5 to 70% by weight, based on the total solid content. Contains 3 to 60 parts by weight. If the component (B) is too small, curing will be insufficient and adhesion and film hardness will be insufficient. Conversely, if it is too large, the main component will be too small and sufficient film hardness will not be obtained. When the amount of the component (C) is too small, the hardness of the hard coat film is insufficient, or the hard coat film is too hard to shrink and the hard coat film is likely to be whitened or cracked. Moreover, when there are too many, the contact site | part of a reaction active site | part and a base material will decrease, and adhesiveness will fall.

  When the difference between the refractive index of the hard coat film and the refractive index of the base resin is large, the interference fringes are easy to see, so that the interference fringes are not noticeable by making this refractive index difference as small as possible. It is preferable to control the refractive index of the hard coat film by adjusting the type and content of the component (C) according to the type of the base resin. When it is desired to lower the refractive index of the hard coat film, it is preferable to use Si oxide fine particles or composite metal oxide fine particles mainly composed thereof. When it is desired to increase the refractive index of the film, at least one metal oxide fine particle selected from Ti, Zr, Hf, V, Ce, Fe, Zn, and Sb or a composite oxide fine particle containing this as a main component is used. Is preferred.

The hard coat liquid of the present invention is preferably prepared as a dispersion in a liquid medium containing the above components (A), (B) and (C) in a predetermined amount. The hard coat liquid is preferably used after the solid content concentration is adjusted to, for example, 2 to 50% by weight. The liquid medium is used for adjusting the viscosity of the hard coat liquid and the film thickness of the hard coat film. As the liquid medium, water, alcohols, or other organic solvents and monofunctional monomers are used. Examples of the organic solvent include the following saturated aliphatic alcohols, cellosolves, propylene glycol derivatives, esters, ethers, ketones, aromatics, and other solvents.
(A) Examples of saturated aliphatic alcohols Examples of methanol, ethanol, isopropyl alcohol, n-butanol, 2-butanol (I) cellosolves Examples of methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve (c) propylene glycol derivatives Examples of propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl acetate (d) esters Examples of methyl acetate, ethyl acetate, butyl (o) ethers Diethyl ether, methyl isobutyl ether, tetrahydrofuran, tetrahydropyran, methyl Examples of tetrahydrofuran, dimethoxyethane (ca) ketones Examples of acetone, methyl ethyl ketone, methyl isobutyl ketone (ki) aromatics Benzene, xylates , Toluene, nitrobenzene, chlorobenzene, dichlorobenzene (viii) Other examples of ethylene glycol, N, N, - dimethylformamide, dichloroethane, dichloromethane, chloroform, carbon tetrachloride, acetonitrile, etc.

Among the above solvents, it is preferable to use a saturated aliphatic alcohol system in consideration of the solubility, safety and volatility of the ionic photopolymerization initiator which is the component (B).
When a thermoplastic material such as polycarbonate is used as the base material, use of a ketone-based or halogen-based solvent tends to cause problems such as whitening by attacking the base material. It is preferable to pay attention to this.

  The monofunctional monomer is mainly used for adjusting the viscosity of the hard coat solution. Unlike the solvent, the monofunctional monomer reacts during curing and does not remain in the final hard coat film. Accordingly, when it is desired to further improve the water resistance and solvent resistance of the hard coat film, the monofunctional monomer is preferably used as a diluting compound rather than a solvent. In addition, since the monofunctional monomer has low volatility, it is preferably used for the purpose of reducing the volatile organic compound (VOC). Further, when the hard coat film has a large cure shrinkage and the film is likely to crack, a monofunctional monomer is preferably used. However, it is preferable to be careful since monofunctional monomers tend to reduce the hardness of the hard coat film.

Examples of the monofunctional monomer include (meth) acrylates, compounds having an epoxy group, compounds having a vinyl group, compounds having an episulfide group, compounds having a thiol group, and compounds having an allyl group.
(1) Examples of (meth) acrylates;
(Meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meta ) Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 2-ethoxyethyl ( (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 3-methoxybutyl (meth) acrylate, benzyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, etc.

(2) Examples of compounds having an epoxy group;
Allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, ethoxyphenyl glycidyl ether, diethoxyphenyl glycidyl ether, triethoxyphenyl glycidyl ether, tetraethoxyphenyl glycidyl ether, pentaethoxyphenyl glycidyl ether, t-butylphenyl glycidyl ether, Lauryl alcohol EO adduct glycidyl ether, stearyl alcohol glycidyl ether, stearyl alcohol EO adduct glycidyl ether, lauryl alcohol glycidyl ether, oleyl alcohol glycidyl ether, oleyl alcohol EO adduct glycidyl ether, etc.

(3) Examples of compounds having a vinyl group;
Vinyl acetate, vinyl propionate, vinyl benzoate (4) Examples of compounds having an episulfide group;
Examples of compounds having an epoxy group in which the oxygen atom of the epoxy is changed to a sulfur atom. (5) Examples of compounds having a thiol group;
Thiomalic acid, 2-mercaptonaphthalene, stearyl mercaptan, 2-mercaptoethyloctanoic acid ester, thiosalicylic acid, 4-mercaptopyridine, 4-mercaptophenol, pt-butylthiophenol, o-thiocresol, 2,4-dimethyl Thiophenol 2-mercaptopropionic acid, dimethylaminoethanethiol hydrochloride, β-mercaptoisobutyric acid, phenylthioethanethiol, methyl 6-mercaptohexylate, etc. (6) Examples of compounds having an allyl group;
Allyl chloride, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, allyl bromide, allyl iodide, etc.

In addition to the components (A), (B), (C) and the liquid medium, the hard coat liquid of the present invention has at least 2 reactive sites with a cationic photopolymerization initiator as described in detail below. Individual compounds, radical photopolymerization initiators, photopolymerization accelerators, leveling agents, UV absorbers / UV stabilizers, and the like can be contained.

(1) A compound having at least two functional groups that can react with a cationic photopolymerization initiator; the above functional group is, for example, an epoxy group, a vinyl group, an episulfide group, a thiol group, or an allyl group. The plurality of functional groups in the molecule of the compound may be the same or different from each other. This compound can be contained in the hard coat solution at 50% by weight or less based on the component (A).
A compound having at least two epoxy groups is used, for example, when it is desired to increase the hydrophilicity of the hard coat film and to improve the washability and dyeability. Examples of this compound include glycidyl ethers such as trimethylolpropane triglycidyl ether, alicyclic polyepoxides such as bis- (3,4-epoxycyclohexyl) adipate, and general epoxy resins. As commercial products, Asahi Denka Kogyo Co., Ltd. trade name: “ADEKA RESIN”, Japan Epoxy Resin Co., Ltd. trade name: “Epicoat”, “Epiletts” and the like can be mentioned.

  A compound having at least two vinyl groups is used, for example, when a ene-thiol reaction is desired in combination with a compound containing a thiol group. Examples of the compound having at least two vinyl groups include divinyl ethers such as triethylene glycol divinyl ether, butanediol divinyl ether, and cyclohexanedimethanol divinyl ether.

  A compound having at least two episulfide groups is used, for example, when only the metal oxide of component (C) cannot sufficiently increase the refractive index of the hard coat film and further increases the refractive index. Examples of this compound include 1,2,6,7-diepithio-4-thiaheptane, 2- (2-β-epithiopropylthio) -1,3-bis (β-epithiopropylthio) propane, and the like. Can be mentioned.

  The compound having at least two thiol groups is used, for example, when it is desired to further increase the refractive index of the hard coat film in the same manner as the compound having at least two episulfide groups. A compound having at least two thiol groups is used in combination with, for example, a compound containing a vinyl group, an allyl group or a (meth) acryloyloxy group to cause an ene-thiol reaction. Examples of the compound having at least two thiol groups include dimercaptoethyl sulfide, pentaerythritol tetrakis (3-mercaptopropionate), 4-mercaptomethyl-3,6-dithio-1,8-octanedithiol, and the like. be able to.

  A compound having at least two allyl groups is used, for example, when a ene-thiol reaction is desired in combination with a compound containing a thiol group. Examples of the compound having at least two allyl groups include polyallyl ethers such as 1,1,2,2-tetraallyloxyethane, triallyl cyanurate, and 1,6-hexanediol divinyl ether. .

(2) Radical Photopolymerization Initiator The ionic photopolymerization initiator (B) is excellent in the surface curing of the hard coat film. However, by using the radical photopolymerization initiator in combination with the component (B), a film excellent not only in surface curing of the hard coat film but also in internal curing can be produced. In addition, functions such as weather resistance of the film can be improved. Examples of radical photopolymerization initiators include α-hydroxyketone, α-aminoketone, acylphosphine oxide, benzyldimethyl ketal, benzophenone, thioxanthone, anthraquinone, and the like. It can be contained in the hard coat solution in the range of 20% to 5 times.

  Examples of commercially available products of α-hydroxyketone include Irgacure 184, Darocur 1173, Irgacure 500, Irgacure 1000, and Irgacure 2959 manufactured by Ciba Specialty Chemicals. Examples of commercially available products of α-aminoketone include Irgacure 907 and Irgacure 369 manufactured by Ciba Specialty Chemicals. Examples of commercially available acylphosphine oxide include Irgacure 1700, Irgacure 149, Irgacure 1800, Irgacure 1850, and Irgacure 819 manufactured by Ciba Specialty Chemicals. As a commercial item of benzyl dimethyl ketal, for example, Irgacure 651 manufactured by Ciba Specialty Chemicals can be mentioned. Examples of commercial products of benzophenone include KAYACURE BP-100, KAYACURE BMS, KAYACURE BTC, and KAYACURE ABQ manufactured by Nippon Kayaku Co., Ltd. Examples of commercially available thioxanthone include KAYACURE DETX-S and KAYACURE CTX manufactured by Nippon Kayaku Co., Ltd. As a commercial item of anthraquinone, Nippon Kayaku Co., Ltd. KAYACURE 2-EAQ etc. can be mentioned, for example.

(3) Photopolymerization accelerator The photopolymerization accelerator is used when the hard coat film is not sufficiently cured by using only the component (B) or the combination of the component (B) and the radical photopolymerization initiator. Examples of the photopolymerization accelerator include commercially available products such as KAYACURE DMBI and KAYACURE EPA manufactured by Nippon Kayaku Co., Ltd. The photopolymerization accelerator is preferably 2 to 100 weights with respect to the amount of the component (B) or the total amount of the component (B) and the radical photopolymerization initiator when a radical photopolymerization initiator is used. % Is used.

(4) Leveling agent Fluorine-based, silicone-based, hydrocarbon-based leveling agents are used to exhibit the appearance, surface slip performance, antifouling performance, etc. of the hard coat film. The leveling agent is preferably used at a ratio of 0.01% to 20% with respect to the amount of the coating liquid.
Commercially available fluorine-based leveling agents include, for example, “Megafuck” manufactured by Dainippon Ink Co., Ltd., “Florad” manufactured by Sumitomo 3M Co., Ltd., “Zonyl” manufactured by DuPont Co., Ltd., “Futgent” manufactured by Neos Co., Ltd., Asahi Glass “Surflon” manufactured by Daikin Corporation, “Zeffle” manufactured by Daikin Industries, Ltd.
Examples of commercially available silicone leveling agents include “NUC Silicone” manufactured by Nippon Unicar Co., Ltd., “Paintad” manufactured by Dow Corning, “SH” “SB” manufactured by Toray Dow Corning Silicone, and the like.
Examples of commercially available hydrocarbon leveling agents include “Surfinol” manufactured by Daishin Chemical Co., Ltd., “Polyflow” manufactured by Kyoeisha Chemical, “Adecanol”, “Adecatol” manufactured by Asahi Denka Kogyo, and the like.

(5) UV absorber and UV stabilizer An UV absorber and UV stabilizer are used for the purpose of improving the weather resistance of the coating film and preventing yellowing. Examples of the UV absorber and UV stabilizer include salicylic acid, benzophenone, benzotriazole, cyanoacrylate, and hindered amine.
Examples of salicylic acid-based ultraviolet absorbers include phenyl salicylate, pt-butyl ferryl salicylate, p-octylphenyl salicylate, and the like.
Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, and 2,2′-dihydroxy-4. -Methoxybenzophenone, 2,2'-dihydroxy-4,4'-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane and the like. .

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′- Hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3) ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t-aminophenyl) benzotriazole, 2- {2'-hydroxy-3,5 '-Di-t-aminophenyl} benzotriazole, 2- {2'-hydroxy-3'-(3 ', 4', 5 ', 6') tetrahydrophthal Imidomethyl} -5′-methylphenyl} benzotriazole, 2,2-methylenebis {4- (1,1,3,3, -tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol}, And 2 (2′-hydroxy-5′-methacryloxyphenyl) -2H-benzotriazole.

Examples of cyanoacrylate-based ultraviolet absorbers include 2-ethylhexyl 2-cyano-3,3′-diphenyl acrylate, ethyl-2-cyano-3,3′-diphenyl acrylate, and the like.
Examples of the hindered amine UV stabilizer include nickel bis (octylphenyl) sulfide, {2,2′-thiobis (4-t-octylphenolate)}-n-butylamine nickel, nickel complex-3, 5-dit- Examples thereof include butyl-4-hydroxybenzyl, phosphoric acid monoethylate, nickel dibutyldithiocarbamate, hindered amine and the like.

  The hard coat liquid is applied to the surface of a plastic substrate, for example, one or both surfaces of a transparent resin lens substrate having a thickness of 1 to 5 mm. Application may be performed by, for example, dip coating, flow coating, spray coating, gravure coating, bar coating, spin coating, roll coating, flexographic printing, screen printing, brush coating, and the like. it can. The application is preferably performed with a thickness such that the film thickness after curing is 0.05 to 10 μm, preferably 1.0 to 10 μm. If the thickness is less than 0.05 μm, the hardness of the film is not sufficient. On the other hand, if the thickness is more than 10 μm, whitening and flexibility decrease.

After coating, a hard coat film cured by irradiation with radiation (active energy rays) such as ultraviolet rays and electron beams is formed. Various ultraviolet lamps such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a xenon lamp, and a carbon arc lamp, laser light, and the like can be used for ultraviolet irradiation. The irradiation conditions of ultraviolet rays are, for example, such that ultraviolet rays having a wavelength of about 200 to 400 nm and illuminance of several tens to 100 mW / cm ² (wavelength 365 nm) have a total ultraviolet irradiation energy of 300 to 3000 (mJ / cm ² ). For several seconds to 30 minutes. An ozone removing device can be provided in order to prevent ozone from being generated during light irradiation and inhibiting the curing reaction of the coating film.

  In order to improve the adhesion and the like of the hard coat film, the plastic substrate may be heated to 30 to 100 ° C. and then applied and irradiated with light. In addition, a known pretreatment, for example, the surface of the substrate may be previously treated with an alkali, an acid or a surfactant, polished with inorganic or organic fine particles, plasma-treated, or a primer treatment described later may be performed. Furthermore, you may heat to 30 to 200 degreeC after application | coating of a hard-coat liquid and light irradiation hardening, for example.

In order to further improve the adhesion, dyeability, impact resistance, weather resistance, etc. of the hard coat film to the plastic substrate, a primer layer can be provided between the plastic substrate surface and the hard coat film. As this primer layer, for example, the following formula (1)
R ¹ nSi (R ² ) _4-n (1)
Here, R ¹ is an organic functional group having a functional group selected from a methacryloxy group, an acryloxy group, a vinyl group, an allyl group, and an amino group, and R ² is one or more selected from an alkoxyl group, an acetoxyl group, and chlorine. N is an integer of 1 to 3,
It is obtained by applying a primer layer treatment liquid containing an organosilicon compound represented by the following formula to the surface of a plastic substrate and drying it. An amino group is preferably used as R ¹ in the above formula (1), a mixture of a silicon compound in which R ¹ is an amino group and a silicon compound in which R ¹ is a vinyl group, and two types in which both R ¹ are amino groups A mixture of these silicon compounds is more preferably used because it further improves adhesion. The preferable thickness of this primer layer is 2 to 50 nm. The solvent for the primer layer treatment solution may be water in addition to an organic solvent such as alcohol. The concentration of the organosilicon compound in the primer layer treatment liquid is determined by the thickness of the primer layer and the coating method, but is usually 0.2 to 5% by weight. The coating method may be any of dipping method, spray method, flow coating method, roll coating method, spin coating method and the like.

On the hard coat film in the present invention, a single-layer or multilayer antireflection film can be formed to a thickness of 20 nm to 1000 nm (total thickness in the case of two or more layers). As the composition of each layer of the antireflection film, metal oxides such as Si, Al, Sn, Nb, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti are preferably used.
Examples of the coating method for the antireflection film include chemical vapor deposition (CVD) and physical vapor deposition (PVD). Examples of the CVD method include a plasma CVD method, and examples of the PVD method include a vacuum deposition method, a sputtering method, and an ion plating method.

  In the present invention, as the plastic substrate, transparent thermosetting resins such as thermosetting thiourethane resin, thermosetting urethane resin, diethylene glycol bisallyl carbonate resin, and thermoplastic transparent resin are used. Of these, thermosetting thiourethane resin and diethylene glycol bisallyl carbonate resin are preferably used. As the plastic substrate, those having a flat plate shape, a curved plate shape, a film shape and the like are used.

  The coated plastic article in the present invention has spectacle lenses, architectural transparent resin plates, mobile phone light guide plates, displays (notebook personal computers, monitors, PDP, PDA outermost surface treatment), touch panel monitors, mobile phone windows, and high optical properties. Used for required parts, transparent parts for automobiles, etc.

  In the method for producing a coated plastic article of the present invention, an ionic photopolymerization initiator that is not inhibited by oxygen as a photopolymerization initiator contained in the photocurable coating liquid is used. As compared with the conventional radical photopolymerization initiators, the crosslink density is higher, and a hard coat film having excellent hardness can be obtained both before and after the moisture resistance test. In addition, by using metal oxide as a filler and filler for adjusting the refractive index, it is possible to provide a hard coat film in which interference fringes are difficult to see on both the high refractive index substrate and the low refractive index substrate. become. Furthermore, due to the high reactivity of ionic photopolymerization initiators, especially cationic photopolymerization initiators, the hard coat film is strongly bonded or interacts with the substrate surface, and the shrinkage of curing is small, so that the adhesiveness has been conventionally reduced. Excellent adhesion can be obtained even on a base material of a thermosetting resin that is difficult to obtain. According to the present invention, it is possible to provide a protective film capable of adjusting the refractive index, which has good productivity, excellent moisture resistance, and scratch resistance.

The embodiment of the present invention will be specifically described below with reference to examples.
The plastic substrates used in the examples and comparative examples, the preparation of the hard coat solution, the application and curing of the hard coat solution, the application and curing of the primer solution, the formation of the antireflection layer, the evaluation method, etc. are as follows.

[Plastic substrate]
(A1) A plastic spectacle lens substrate made of a thermosetting thiourethane resin. Molded and thermally cured using a monomer “MR-6” manufactured by Mitsui Chemicals, Inc. (refractive index 1.60, Abbe number 36).
(A2) A plastic spectacle lens substrate made of a thermosetting thiourethane resin. Molded and heat-cured using Mitsui Chemicals' monomer “MR-7” (refractive index 1.66, Abbe number 32).
(A3) A plastic spectacle lens substrate made of a thermosetting thiourethane resin. Molded and thermally cured using a monomer “MR-20” manufactured by Mitsui Chemicals, Inc. (refractive index 1.60, Abbe number 43).
(B) A plastic spectacle lens substrate made of diethylene glycol bisallyl carbonate. Molded and heat-cured using PPG monomer “CR-39” (refractive index 1.50, Abbe number 58).

[Preparation of hard coat solution]
Preparation of hard coat solution 1 284 g of methanol and 284 g of methoxypropanol are placed in a beaker equipped with a stir bar and stirred vigorously. 240 g of urethane acrylate “KAYARAD UX-3204” (manufactured by Nippon Kayaku Co., Ltd.) is gradually added, and further 170 g of 30 wt% methanol dispersion (hereinafter referred to as sol A) of silicon oxide fine particles (particle size: 10 to 20 nm), And 18 g of arylsulfonium salt “ADEKA OPTMER SP-170” (manufactured by Asahi Denka Kogyo Co., Ltd., triarylsulfonium hexafluoroantimonate, 50 wt% propylene carbonate solution) as a cationic photopolymerization initiator and stirred vigorously Finally, 4 g of a 10% methoxypropanol solution of a silicone leveling agent “NUC Silicone L-77” (manufactured by Nippon Unicar Co., Ltd.) was added to obtain a hard coat solution 1. The refractive index of the hard coat solution after coating and curing was 1.49.

Preparation of Hard Coat Solution 2 186 g of methanol and 186 g of methoxypropanol are put into a beaker equipped with a stir bar and stirred vigorously. 156 g of urethane acrylate “KAYARAD UX-3204” (manufactured by Nippon Kayaku Co., Ltd.) is gradually added, and a composite oxide of titanium oxide, iron oxide and silicon oxide (TiO ₂ : Fe ₂ O ₃ : SiO ₂ = in molar ratio) 98: 2: 10) 30 wt% methanol dispersion (hereinafter referred to as Sol B)) 450 g, “Adekaoptomer SP-170” 18 g was added, stirred vigorously, and finally “NUC Silicone L-77” 10 4 g of a% methoxypropanol solution was added to obtain a hard coat solution 2. The refractive index of the hard coat solution after coating and curing was 1.66.

Preparation of hard coat liquid 3 Methanol 129.8g, methoxypropanol 216.4g and tetrahydrofurfuryl acrylate ("light acrylate THF-A" (manufactured by Kyoeisha Chemical Co., Ltd.)) 86.5g was put in a beaker equipped with a stir bar. Stir vigorously, 66 g of 1,6 hexanediol diacrylate ("Light acrylate 1, 6HX-A", manufactured by Kyoeisha Chemical Co., Ltd.) and 120 g of "KAYARAD UX-3204" are gradually added to this, and further titanium oxide, oxidized 350 g of 30% methanol dispersion (hereinafter referred to as Sol C) of antimony and silicon oxide composite oxide (molar ratio TiO ₂ : Sb ₂ O ₃ : SiO ₂ = 90: 10: 10), cationic photopolymerization initiator Arylsulfonium Salt “Sun-Aid SI-60L” (Sanshin Chemical Co., Ltd.) 27.3 g of a triarylsulfonium hexafluoroantimonate 33% by weight propylene carbonate solution manufactured by the same manufacturer) and 4 g of 10% methoxypropanol solution of “NUC Silicone L-77” were added to the hard coat solution. The refractive index of the hard coat solution after coating and curing was 1.59.

Preparation of Hard Coat Solution 4 459.2 g of methoxypropanol and 114.8 g of phenoxydiethylene glycol acrylate (“NK ester AMP-20GY”, manufactured by Shin-Nakamura Chemical Co., Ltd.) are placed in a beaker equipped with a stir bar and stirred vigorously. 235.5 g of trimethylolpropane triacrylate (“Light acrylate TMP-A”, manufactured by Kyoeisha Chemical Co., Ltd.) is gradually added thereto, and 170 g of sol A and aryliodonium salt “IRGACURE250” as a cationic photopolymerization initiator are added. (Ciba Chemical Specialties, iodonium, [4- (2-methylpropyl) phenyl] (4-methylphenylhexafluorophosphate) 75 wt% propylene carbonate solution) 12 g and α as radical photopolymerization initiator -4.5 g of "IRGACURE184" which is a hydroxyketone, 1-hydroxycyclohexylphenylphenylketone manufactured by Ciba Specialty Chemicals, and vigorously stirred. Finally, 4 g of a 10% by weight methoxypropanol solution of a fluorine-based leveling agent “Florad FC-4430” (manufactured by Sumitomo 3M Limited) was added thereto to obtain a hard coat solution 4. The refractive index of the hard coat solution after coating and curing was 1.49.

Preparation of the hard coat solution 5 The same procedure as in the preparation of the hard coat solution 4 was performed except that the sol B used in the preparation of the hard coat solution 2 was used instead of the sol A used in the preparation of the hard coat solution 4. A hard coat solution 5 was obtained. The refractive index of the hard coating solution after coating and curing was 1.59.

Preparation of Hard Coat Solution 6 132.3 g of methoxypropanol, 189 g of “NK ester AMP-20GY” and 56.7 g of “light acrylate THF-A” are placed in a beaker equipped with a stir bar and stirred vigorously. 156 g of epoxy acrylate “epoxy ester 3002M” (manufactured by Kyoeisha Chemical Co., Ltd.) is gradually added thereto, and further a composite oxide of titanium oxide, zirconium oxide and silicon oxide (TiO ₂ : ZrO ₂ : SiO ₂ = 98 in molar ratio). : 2: 8) 30 wt% methanol dispersion (hereinafter referred to as Sol D) 450 g and “IRGACURE250” 12 g were added and vigorously stirred. Finally, 4 g of a 10 wt% methoxypropanol solution of “Florad FC-4430” was added thereto to obtain a hard coat solution 6. The refractive index of the hard coat solution after coating and curing was 1.66.

Preparation of Hard Coat Solution 7 152.95 g of methoxypropanol, 218.5 g of “NK ester AMP-20GY” and 65.55 g of “light acrylate THF-A” are placed in a beaker equipped with a stir bar and stirred vigorously. 180 g of “epoxy ester 3002M” is gradually added thereto, and 370 g of sol A and a diazonium salt “WPAG-145” (manufactured by Wako Pure Chemical Industries, Ltd., bis (cyclohexylsulfonyl) diazomethane) as a cationic photopolymerization initiator 9 g And stirred vigorously. Finally, 4 g of a 10 wt% methoxypropanol solution of “Florad FC-4430” was added thereto to obtain a hard coat solution 7. The refractive index of the hard coat solution after coating and curing was 1.48.

Preparation of Hard Coat Solution 8 306 g of methoxypropanol and 306 g of methanol are placed in a beaker equipped with a stir bar and stirred vigorously. Polyester acrylate “Ebecryl 657” (Daicel UCB Co., Ltd.) 255 g is gradually added thereto, 120 g of sol A, and aryliodonium salt “WPI-113” (Wako Pure Chemicals, Ltd.) as a cationic photopolymerization initiator. 9 g of bis (alkyl (C = 10-14) phenyl) iodonium hexafluorophosphate) manufactured by the same company was added and stirred vigorously. Finally, 4 g of a 10 wt% methoxypropanol solution of “NUC silicone L-77” was added to obtain a hard coat solution 8. The refractive index of the hard coat solution after coating and curing was 1.49.

Preparation of Hard Coat Solution 9 260.5 g of methoxypropanol and 260.5 g of methanol are placed in a beaker equipped with a stir bar and stirred vigorously. 216 g of “Ebecryl 657” was gradually added thereto, and further 250 g of sol D and metallocene derivative “IRGACURE261” as a cationic photopolymerization initiator (η5-cyclopentadienyl-η6-cumyl-iron (1+, manufactured by Ciba Specialty Chemicals) ) -Hexafluorophosphate) 9 g was added and stirred vigorously. Finally, 4 g of a 10 wt% methoxypropanol solution of “NUC silicone L-77” was added to obtain a hard coat solution 9. The refractive index of the hard coating solution after coating and curing was 1.59.

Preparation of Hard Coat Solution 10 Methanol (208 g) and methoxypropanol (208 g) are placed in a beaker equipped with a stir bar and stirred vigorously. 51 g of 1,6-hexanediol diglycidyl ether (“Denacol EX-212”, manufactured by Nagase ChemteX Corp.) and 120 g of “KAYARAD UX-3204” were gradually added thereto, and 400 g of Sol A and a photoanion generator were further added. 9 g of a certain carbamate o-nitrobenzyl alcohol ester was added and stirred vigorously. Finally, 4 g of a 10% methoxypropanol solution of “NUC silicone L-77” was added to obtain a hard coat solution 10. The refractive index of the hard coat solution after coating and curing was 1.48.

Preparation of hard coat solution 11 Hard coat solution except that 9 g of “IRGACURE 184” used in preparation of hard coat solution 4 was used instead of 18 g of “adekatopomer SP-170” used in the preparation of hard coat solution 1 1 was performed in the same manner as in Preparation 1 to obtain a hard coat solution 11.
Preparation of hard coat liquid 12 Hard coat liquid except that 9 g of “IRGACURE 184” used in the preparation of hard coat liquid 4 was used instead of 18 g of “Adekaoptomer SP-170” used in the preparation of hard coat liquid 2 The hard coat liquid 12 was obtained in the same manner as the preparation of No. 2.
Preparation of hard coat solution 13 “Sun Aid SI-60L” used in the preparation of hard coat solution 3 27 g of “IRGACURE 184” used in the preparation of hard coat solution 4 was used in place of 27 g. It carried out like preparation and the hard-coat liquid 13 was obtained.

Preparation of hard coat liquid 14 Instead of using 12 g of “IRGACURE250” and 4.5 g of “IRGACURE184” used in the preparation of hardcoat liquid 4, all except for using “IRGACURE250” and 9 g of “IRGACURE184” It carried out like preparation of the liquid 4, and the hard-coat liquid 14 was obtained.
Preparation of hard coat solution 15 Instead of using 12 g of “IRGACURE250” and 4.5 g of “IRGACURE184” used in the preparation of hardcoat solution 5, all except for using “IRGACURE250” and 9 g of “IRGACURE184” It carried out similarly to preparation of the liquid 5, and the hard-coat liquid 15 was obtained.
Preparation of hard coat liquid 16 All of the same as the preparation of hard coat liquid 6 except that 12 g of “IRGACURE250” and 270 g of sol D used in the preparation of hard coat liquid 6 were used, and 9 g of “IRGACURE184” and 450 g of sol A were used. Thus, a hard coat liquid 16 was obtained.

Preparation of hard coat solution 17 The hard coat solution was prepared in the same manner as the hard coat solution 7 except that 9 g of “IRGACURE 184” was used instead of 9 g of “WPAG145” used in the preparation of the hard coat solution 7. 17 was obtained.
Preparation of Hard Coat Solution 18 In place of 9 g of “WPI-113” used in the preparation of Hard Coat Solution 8 except that 9 g of “IRGACURE 184” was used, A coating solution 18 was obtained.
Preparation of hard coat liquid 19 Instead of 9 g of “WPI-113” used in the preparation of hard coat liquid 9, “Darocur 1173” (produced by Ciba Specialty Chemicals, 2-hydroxy-) as a radical photopolymerization initiator Except for using 2-methyl-1-phenyl-propan-1-one), the same procedure as in the preparation of the hard coat solution 9 was performed to obtain a hard coat solution 19.

Preparation of hard coat solution 20 All of the same procedures as in the preparation of hard coat solution 10 except that 9 g of “Darocur 1173” was used instead of 9 g of carbamic acid o-nitrobenzyl alcohol ester used in the preparation of hard coat solution 10. The hard coat liquid 20 was obtained.
Preparation of hard coat liquid 21 Except for not using the α-hydroxyketone ("IRGACURE184") used in the preparation of the hard coat liquid 5, everything was carried out in the same manner as the preparation of the hard coat liquid 5 to obtain the hard coat liquid 21. Obtained.

  The compositions of the sols A to D used in the preparation and the compositions of the hard coat liquids 1 to 21 are shown in Table 1 and Table 2, respectively.

[Table 1]
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Sol A: 30% methanol dispersion of silicon oxide Sol B: Composite oxide of titanium oxide, iron oxide and silicon oxide (TiO ₂ : Fe ₂ O _{3 in} molar ratio:
SiO ₂ = 98: 2: 10) 30% methanol dispersion solution sol C: Composite oxide of titanium oxide, antimony oxide and silicon oxide (TiO _{2 in} molar ratio:
Sb ₂ O ₃ : SiO ₂ = 90: 10: 10) 30% methanol dispersion solution sol D: Composite oxide of titanium oxide, zirconium oxide and silicon oxide (TiO ₂ : ZrO ₂ : SiO ₂ = 98 in molar ratio) 2: 8) 30% methanol dispersion ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

[Application and curing of hard coat solution]
The hard coat solutions 1 to 21 are applied at a rotational speed of 2,500 rpm by a spin coating method, and then light is applied to the sample placed on the conveyor by a metal halide lamp, and the speed of the conveyor is adjusted so that the amount of light is 1 J / cm. Was adjusted to cure the coating film. After applying and curing on the convex surface of the lens substrate, it was applied and cured on the concave surface. In addition, a cold filter was provided in front of the metal halide lamp to shield infrared light so that the temperature of the lens base material did not increase during light irradiation.

[Application and curing of primer solution]
As an easy-adhesion layer that improves the adhesion between the base material and the hard coat film, “CP620” (manufactured by Nippon Air Sea Co., Ltd.), a urethane primer solution, is pulled up by the dipping method at a speed of 10 cm / min. It was applied on the surface and cured by heating at 50 ° C. for 30 minutes to form a 1.0 μm thick primer layer.

[Formation of antireflection layer]
The surface of the hard coat film-coated lens is vacuum deposited (electron beam heating), beam power is 2.0 kW, deposition rate is 270 nm / min, deposition distance is 25 cm, vapor pressure is 10 ^-4 Torr. A TiO ₂ film was formed. The refractive index of the TiO ₂ film was 2.30. On the TiO ₂ film, a vacuum deposition method (electron beam heating method) is used. The beam power is 5.0 kW, the deposition rate is 15000 nm / min, the deposition distance is 25 cm, and the vapor pressure is 10 ⁻⁴ Torr. ₂ was deposited. The refractive index of the SiO ₂ film was 1.46. In order from the first layer, a two-layer structure of TiO ₂ (nd = 110 nm) / SiO ₂ (nd = 140 nm) was formed. The values in parentheses indicate the optical film thickness (refractive index n × physical film thickness d).

[Evaluation methods]
The evaluation methods of the coated films obtained in the following examples and comparative examples are as follows.
(A) Adhesion test: A cross cut test was performed according to JIS K5400. That is, a cellophane tape manufactured by Nichiban Co., Ltd. was applied on the hard coat film, and then peeled off vigorously, before the moisture resistance test (initial) and in the moisture resistance test (50 ° C., 95% RH for 10 days). ) Evaluation of adhesion (easy adhesion) and moisture permeation resistance of the subsequent coating, 100% (z / 100) by the number z of the squares that did not peel out of the 100 squares of the hard coat film Judged.

(B) Humidity resistance test: The sample was left in a constant temperature and humidity chamber with an atmospheric temperature of 50 ° C. and a relative humidity of 98% RH for 500 hours, and the adhesion and scratch resistance were evaluated in the same manner as in the initial stage.
(C) Scratch property (abrasion resistance): A commercially available steel wool (# 0000) was used to rub the 10 reciprocating surfaces under a load of 1 kg, and the scratch was evaluated visually. The evaluation results were expressed in five stages 1-5 as follows.
━━━━━━━━━━━━━━━━━
5: Not scratched at all 4: Slightly scratched 3: Scratched 2: Severely scratched 1: Scratched to the substrate ━━━━━━━━━━━━━━━━

(D) Degree of interference fringe The degree of interference fringe was visually evaluated in the following three stages under fluorescence, etc. ━━━━━━━━━━━━━━━━━
3: Almost no interference fringes are observed 2: Somewhat thin interference fringes can be confirmed 1: Interference fringes are conspicuous ━━━━━━━━━━━━━━━━━

(E)
Coloring of hard coat film The transparency of the hard coat film was judged by measuring the yellowing degree (YI). The smaller the YI value, the lower the yellow coloring and the higher the transparency.

[Example 1]
The lens substrate B was coated with the hard coat solution 1 and photocured to form a hard coat film having a thickness of 3 μm. The obtained hard coat-coated plastic lens was measured for the degree of interference fringes before the moisture resistance test, adhesion, scratch resistance, adhesion after the moisture resistance test, and scratch resistance. The results are shown in Table 3.

[Comparative Example 1]
The lens substrate B was coated with the hard coat solution 11 and photocured to form a hard coat film having a thickness of 3 μm. Various performances of the obtained hard coat-coated plastic lens were measured in the same manner as in Example 1. The results are shown in Table 3.
[Examples 2 to 13, Comparative Examples 2 to 10]
Hard coat liquids 1 to 21 were applied to the lens base material A1, A2, A3 or B as shown in Table 3 and photocured to form a hard coat film having a thickness of 3 μm. Various performances of the obtained hard coat-coated plastic lens were measured in the same manner as in Example 1. The results are shown in Table 3. In addition, about Example 12, the primer liquid was apply | coated and hardened | cured before apply | coating the hard-coat liquid 5 (Example 5) using base material A3. Moreover, about Example 13, the base material A1 was used, and the antireflection layer was formed on the hard coat film which applied and hardened hard coat liquid 4 (Example 4). For Example 4 and Example 11, the scratch resistance (scratch resistance) test was performed separately with the load condition changed to 2 kg. The initial scratch resistance was 5 for both Examples 4 and 11, The scratch resistance after the moisture resistance test was 5 in Example 4 and 4 in Example 11, and it was found that Example 4 was more excellent in moisture resistance than Example 11.

From the results shown in Table 3, it can be seen that in Examples 1 to 13, no interference fringes are visible and the film adhesion, scratch resistance, transparency, and weather resistance (moisture resistance) are excellent. On the other hand, in the comparative example, the film adhesion is inferior (Comparative Examples 4, 5, and 10), the scratch resistance is inferior (Comparative Examples 1, 2, 3, 6, 7, and 10), and the moisture resistance is inferior (Comparative Example). 1 to 10) and interference fringes are conspicuous (Comparative Example 6).

Claims (10)

(A) a compound having at least two (meth) acryloyl groups in the molecule, (B) an ionic photopolymerization initiator, and (C) Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn , W, Zr, In, Ti, and a coated plastic article that is coated with a photocurable coating liquid containing oxide particles of at least one metal selected from Ge, and is photocured by irradiation with radiation. Production method. The photo-curing coating liquid represents the component (A) as a solid content with respect to the total solid content of 10 to 99.4% by weight, the component (B) as the component (A), the component (B) and the component (C). The method for producing a coated plastic article according to claim 1, comprising 0.1 to 20% by weight based on the total of the components and 0.5 to 70% by weight of the component (C) based on the total solid content. The method for producing a coated plastic article according to claim 1, wherein the component (A) is a poly (meth) acrylate monomer, urethane (meth) acrylate, polyester (meth) acrylate, or epoxy (meth) acrylate. The component (B) is an arylsulfonium salt, aryliodonium salt, diazonium salt, metallocene derivative, cobaltamine-based complex, carbamate o-nitrobenzyl alcohol ester, or oxime ester. Of manufacturing a coated plastic article. The method for producing a coated plastic article according to any one of claims 1 to 3, wherein the component (B) is an arylsulfonium salt or an aryliodonium salt. The method for producing a coated plastic article according to any one of claims 1 to 5, wherein the plastic substrate is made of a thermosetting resin. The method for producing a coated plastic article according to claim 1, wherein the plastic substrate is a plastic lens substrate. The method for producing a coated plastic article according to claim 6 or 7, wherein the plastic substrate is made of a thiourethane resin. The coated plastic article obtained by the manufacturing method of any one of Claims 1-8. (A) a compound having two or more (meth) acryloyl groups in the molecule;
(B) an ionic photopolymerization initiator and (C) at least one metal selected from Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, Ti, and Ge Oxide particles,
The photocurable coating liquid composition for the manufacturing method of the coated plastic article of any one of Claims 1-8 containing this.