TW201832936A - Hard coat laminate having high hardness - Google Patents

Abstract

To provide a laminate provided with a hard coat layer that has high scratch resistance and hardness. A high-hardness hard coat laminate that comprises a substrate, a primer layer above the substrate, and a hard coat layer above the primer layer. The primer layer comprises a cured product of a primer layer-forming composition containing (A) a polyfunctional compound selected from the group consisting of active energy ray-curable polyfunctional monomers and polymers, (B) inorganic fine particles, and (C) a polymerization initiator that generates radicals by means of active energy rays. The hard coat layer comprises a cured product of a curable composition containing (a) an active energy ray-curable polyfunctional monomer, (b) a perfluoropolyether in which an active energy ray-polymerizable group is bonded to both ends thereof via a poly(oxyalkylene) group or via a poly(oxyalkylene) group and one urethane bonding group in this order, and (c) a polymerization initiator that generates radicals by means of active energy rays. Also provided is a method for producing the high-hardness hard coat laminate.

Description

High hardness hard coating laminate

[0001] The present invention relates to a high hardness hard coat layer having a hard coat layer having excellent scratch resistance and a method for producing the same.

[0002] In the past, on a lithographic display such as a personal computer, a portable telephone, a portable game machine, or an ATM, a product equipped with a touch panel has been commercialized. In particular, the introduction of a smart phone or tablet PC has enabled the electrostatic capacitive touch panel with multi-touch capability to expand its number of mounts. [0003] The surface of the touch panel display is thinned tempered glass, so that the glass is scattered and the protective film is attached to the surface of the display. Since the protective film is likely to cause scratches due to the glass due to the use of the plastic film, it is necessary to provide a hard coating layer excellent in scratch resistance on the surface. A method of imparting scratch resistance to the surface of a plastic film, for example, a method of forming a highly crosslinked structure, that is, a crosslinked structure having a low molecular mobility to increase surface hardness and impart resistance to external force, or the like can be used. Among the hard coating layer forming materials, most of the polyfunctional acrylate materials which are currently used most are liquid monomers which are liquid at normal temperature, and are subjected to radicals generated by a photopolymerization initiator. Three-dimensional cross-linking. The acrylate type has a characteristic that it can be cured by ultraviolet rays (UV), and the time for irradiating UV is extremely short, thereby saving energy and high productivity. A method of forming a hard coat layer on a surface of a plastic film, for example, applying a polyfunctional acrylate, a photopolymerization initiator, and a solution containing an organic solvent to a plastic film via gravure coating or the like to cause an organic solvent After drying, it is cured by ultraviolet rays to form a hard coat layer. In the hard coating layer to be formed, the function of hardness, scratch resistance, and the like is practically not problematic, and the thickness of the hard coat layer is usually 1 to 15 μm. Further, there has been disclosed a technique of adding reactive cerium oxide microparticles as a component imparting high hardness to a polyfunctional acrylate resin, particularly when a higher hardness is sought for a hard coating layer for display protection use. Patent Document 1 and Patent Document 2). [0004] However, the electrostatic capacity type touch panel operates in a contact manner using people's fingers. Therefore, when the operation is performed, the fingerprint is often attached to the surface of the touch panel, which causes a problem that the image recognition of the display is significantly impaired or the appearance of the display is defaced. The fingerprint contains oil derived from moisture and sebum produced by sweat, so that it is hard to adhere to any of these, that is, it is strongly expected to be provided on the hard coating layer on the surface of the display to impart water repellency and oil repellency. . Based on these points of view, it is highly desirable to have antifouling properties for fingerprints and the like on the surface of a touch panel display. However, since the electrostatic capacitive touch panel is in contact with a finger every day, even if a certain degree of antifouling property can be achieved at an early stage, in use, the function is often lowered. Therefore, durability against the antifouling property during use is a problem. [0005] Conventionally, a method of imparting antifouling properties to the surface of a hard coat layer, for example, a method of adding a fluorine-based surface modifier to a coating liquid for forming a hard coat layer. The fluorine-based compound to be added is biased on the surface of the hard coat layer based on its low surface energy, so that water repellency and oil repellency can be imparted. For the fluorine-based compound, for example, in view of water repellency and oil repellency, an oligomer having a number average molecular weight of about 1,000 to 5,000, which is a perfluoropolyether having a poly(oxoperfluoroalkylene) chain, is generally used. However, since the perfluoropolyether has a high fluorine concentration, it is usually difficult to dissolve in the organic solvent used for the coating liquid which forms the hard coat layer. Moreover, in the hard coating layer formed, agglomeration also occurs. Among these perfluoropolyethers, a method of adding an organic moiety to a perfluoropolyether is often used from the viewpoint of imparting solubility to an organic solvent and dispersibility in a hard coat layer. Further, from the viewpoint of imparting scratch resistance, a method of bonding an active energy ray-curable portion represented by a (meth) acrylate group is often used. Heretofore, in the antifouling hard coat layer having scratch resistance, the component which imparts antifouling property to the surface of the hard coat layer has been disclosed as being used at both ends of the poly(oxoperfluorocyclohexane) chain. A technique of using a compound having a (meth)acryloyl group bonded to a plurality of urethane bond groups having a heterophorone skeleton as a surface modifier (Patent Document 3). [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2010- 828

[Problems to be Solved by the Invention] [0007] In the methods disclosed in Patent Document 1 and Patent Document 2, although the reactive cerium oxide microparticles can be compounded at a high concentration to obtain higher hardness, The reason why the fine particles are formed is that fine irregularities are formed on the surface, and there is a problem that sufficient scratch resistance cannot be obtained. Further, in the method specifically described in Patent Document 3, in order to provide scratch resistance and antifouling properties to the surface of the hard coat layer, there has been no specific research on how to produce high hardness. . [Means for Solving the Problems] [0008] The present inventors have conducted intensive studies to solve the above problems, and have found that when a primer layer containing inorganic fine particles is provided between a substrate and a hard coat layer, hard coat can be imparted. The coating has a higher hardness. That is, a poly(oxyalkylene) group or a poly(oxyalkylene) group and one urethane bond are used at both ends of a molecular chain to be contained in a poly(oxoperfluoroalkylene) group. The perfluoropolyether having a base-bonded active energy ray-polymerizable group, which is a curable composition of a fluorine-based surface modifier, is excellent in scratch resistance as a material for forming a hard coat layer, and can be formed. A laminate having a hard coat layer having a high hardness is thus completed. [0009] That is, a first aspect of the present invention relates to a high-hardness hard-coating laminate comprising a substrate, a primer layer above the substrate, and a hard coating layer over the primer layer. The formed high hardness hard coat layer characterized in that the primer layer is selected from the group consisting of (A) an active energy ray-curable polyfunctional monomer and an active energy ray-curable polyfunctional polymer. 100 parts by mass of the polyfunctional compound, (B) 100 to 1,000 parts by mass of the inorganic fine particles, and (C) a total of 100 masses of the polymerization initiator which generates a radical via the active energy ray with respect to the component (A) and the component (B) Further, the inorganic fine particles of the component (B) are formed of a cured material of a composition for forming a primer layer having particles of an active energy ray polymerizable group; the hard coat layer Is a poly(oxyalkylene) group via a terminal of a molecular chain containing (a) an active energy ray-curable polyfunctional monomer, (b) a poly(oxoperfluoroalkylene) group-containing molecular chain, or Directly bonding a poly(oxyalkylene) group and a urethane linkage group to bond the active energy ray 0.1 to 10 parts by mass of a perfluoropolyether substrate, and (c) 1 to 20 parts of the formed mass of a radical polymerization initiator is cured curable composition produced by the active energy ray. According to a second aspect, the high hardness hard coat layer according to the first aspect, wherein the inorganic fine particles of the component (B) are particles having an average particle diameter of 10 to 100 nm. According to a third aspect, the high hardness hard coat layer according to the first aspect or the second aspect, wherein the inorganic fine particles of the component (B) are cerium oxide fine particles. The high hardness hard coat layer according to any one of the first aspect to the third aspect, wherein the polyfluoropolyether of the component (b) is poly(oxoperfluoroalkylene) Base, with -[OCF ₂ ]-and-[OCF ₂ CF ₂ ]- as the basis of the repeating unit. The high hardness hard coat layer according to any one of the first aspect to the fourth aspect, wherein the poly(polyoxyalkylene) group of the perfluoropolyether of the component (b) is agglomerated (Exhaloethylene) base. The high hardness hard coat layer according to any one of the first aspect to the fifth aspect, wherein the polyfunctional monomer of the component (A) is a polyfunctional (meth)acrylic acid. At least one selected from the group consisting of an ester compound and a polyfunctional urethane (meth) acrylate compound. The high hardness hard coat layer according to any one of the first aspect to the sixth aspect, wherein the polyfunctional monomer of the component (a) is a polyfunctional (meth)acrylic acid. At least one selected from the group consisting of an ester compound and a polyfunctional urethane (meth) acrylate compound. The high hardness hard coat layer according to any one of the above aspects, wherein the component (C) is a polymerization initiator which generates a radical via an active energy ray. Alkyl phenone polymerization initiator. The high hardness hard coat layer according to any one of the first aspect to the eighth aspect, wherein the component (c) is a polymerization initiator which generates a radical via an active energy ray. Alkyl phenone polymerization initiator. A tenth aspect relates to a method for producing a high-hardness hard-coating laminate comprising a primer layer on a surface of at least one of the substrates and a high hardness of the hard coating layer above the primer layer A method for producing a hard coat layer comprising a step of forming a coating film by coating a composition for forming a primer layer on a substrate, and a coating film for irradiating the composition for forming a primer layer with an active energy ray. a step of forming the primer layer to form a primer layer, a step of applying a curable composition on the primer layer, forming a coating film, and irradiating the coating film of the curable composition with an active energy ray. The coating film is cured to form a hard coat layer; and the primer layer forming composition is composed of (A) an active energy ray-curable polyfunctional monomer and an active energy ray-curable polyfunctional polymer. 100 parts by mass of the polyfunctional compound selected by the group, (B) 100 to 1,000 parts by mass of the inorganic fine particles, and (C) a polymerization initiator which generates a radical via the active energy ray, with respect to the component (A) and the component (B) 100 parts by mass in total, 1 to 20 parts by mass, The inorganic fine particles of the component (B) are particles having an active energy ray polymerizable group, and the curable composition contains (a) 100 parts by weight of the active energy ray-curable polyfunctional monomer, and (b) contains poly(oxygen). The terminal of the molecular chain of the perfluoroalkylene group is bonded via a poly(oxyalkylene) group or a poly(oxyalkylene) group and a urethane-bonding group, respectively. 0.1 to 10 parts by mass of the perfluoropolyether of the active energy ray polymerizable group, and (c) 1 to 20 parts by mass of a polymerization initiator which generates a radical via an active energy ray. [Effects of the Invention] According to the description of the present invention, it is possible to provide a laminate of a hard coat layer having a high hardness and a film having a thickness of about 1 to 15 μm and having excellent scratch resistance. [Form of the Invention] The high-hardness hard coat layer of the present invention is formed of a base material, a primer layer above the base material, and a hard coat layer above the primer layer. . Further, in the high-hardness hard-coating laminate of the present invention, the primer layer is formed of a cured product of a composition for forming a primer layer, and the hard coating layer is formed of a cured product of a curable composition. Hereinafter, the contents of the respective layers constituting the high hardness hard coat layer of the present invention will be described in detail. [Substrate] The substrate in the high hardness hard coat layer of the present invention is not particularly limited, for example, plastic (polycarbonate, polymethyl acrylate, polymethyl methacrylate (PMMA)). , polystyrene, polyester, PET (polyethylene terephthalate), polyolefin, epoxy resin, melamine resin, triethylenesulfonyl cellulose, ABS (acrylonitrile-butadiene-styrene copolymer ), AS (acrylonitrile-styrene copolymer), norbornene resin, etc.), metal, wood, paper, glass, cerium oxide, slate, and the like. The shape of the substrates may be a plate shape, a film shape or a three-dimensional molded body. Among them, in the present invention, the substrate is preferably PET or PMMA. The thickness of the above substrate is not particularly limited, and may be, for example, 10 to 1,000 μm or the like. [Primer layer] <Purchase layer forming composition> The primer layer in the high hardness hard coat layer of the present invention is formed of a primer layer containing the following (A) to (C) It is formed of a cured product of the composition: (A) 100 parts by mass of the polyfunctional compound selected from the group consisting of active energy ray-curable polyfunctional monomer and active energy ray-curable polyfunctional polymer, (B) inorganic 100 to 1,000 parts by mass of the fine particles, and (C) a polymerization initiator which generates a radical via the active energy ray is 1 to 20 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B). Hereinafter, each component (A) to (C) will be described. [(A) A polyfunctional compound selected from the group consisting of an active energy ray-curable polyfunctional monomer and an active energy ray-curable polyfunctional polymer] Active energy ray-curable polyfunctional monomer and active energy The line curable polyfunctional polymer refers to a monomer and a polymer which can be polymerized and cured by irradiation with an active energy ray such as ultraviolet rays. Further, in the (a) active energy ray-curable polyfunctional monomer in the curable composition described later, the compound listed in the following "active energy ray-curable polyfunctional monomer" in the (A) polyfunctional compound can be used. A compound that is the same content. <Active energy ray-curable polyfunctional monomer> In the curable composition of the present invention, a preferred active energy ray-curable polyfunctional monomer is, for example, a polyfunctional (meth) acrylate compound and A monomer selected from the group of functional urethane (meth) acrylate compounds. Further, in the present invention, the (meth) acrylate compound means both an acrylate compound and a methyl acrylate compound. For example, (meth)acrylic means the meaning of acrylic acid and methacrylic acid. [0016] The above polyfunctional (meth) acrylate compound, for example, trimethylolpropane tri(meth) acrylate, di-trimethylolpropane tetra(meth) acrylate, pentaerythritol di(methyl) Acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate monostearate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol six (a) Acrylate, glycerol tri(meth)acrylate, propoxylated glycerol tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylol Propane tri(meth)acrylate, pentoxide tetraol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethoxylated glycerol tri(meth)acrylate, ethoxylated bisphenol A Di(meth)acrylate, ethoxylated bisphenol F di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylic acid Ester, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2-methyl-1,8-octyl Diol (meth) acrylate, 1,9-nonanediol di(meth) acrylate, 1,10-decanediol di(meth) acrylate, neopentyl glycol di(methyl) Acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, Propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, bis(2-hydroxyethyl)isocyanate di(meth)acrylate, tris(2-hydroxyethyl) Cyanurate di(meth)acrylate, tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane dimethanol di(meth)acrylate, dioxanediol di(meth)acrylate, 2-hydroxy-1-propenyloxy-3-methylpropenyloxypropane, 2-hydroxyl -1,3-bis(meth)acryloxypropane, 9,9-bis[4-(2-(methyl)propenyloxyethoxy)phenyl]indole, bis[4-( Methyl)propenylthiophenyl]thioether, bis[2-(methyl)propenylthioethyl]thioether, 1,3-adamantanediol di(meth)acrylate, 1,3 -adamantane dimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tris(2-(methyl)acryloxyethyl) Phosphate and ε-caprolactone denatured tris(2-hydroxyethyl)isocyanate tri(meth)acrylate and the like. Among them, preferred are, for example, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like. [0017] The polyfunctional urethane (meth) acrylate compound has a plurality of acryl fluorenyl groups or methacryl fluorenyl groups in one molecule, and has one or more urethane bonds ( -NHCOO-) compound. For example, the above polyfunctional urethane (meth) acrylate compound, for example, obtained by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group, is composed of a polyfunctional isocyanate and a hydroxyl group (A) The acrylate is reacted with a polyalcohol to obtain a compound, etc., and is not limited to the exemplified examples of the functional urethane (meth) acrylate compound which can be used in the present invention. Further, the polyfunctional isocyanate is, for example, tolyl diisocyanate, isophorone diisocyanate, xylene diisocyanate, hexamethyl diisocyanate or the like. Further, a (meth) acrylate having the above hydroxyl group, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol-5 ( Methyl) acrylate, tripentaerythritol hepta (meth) acrylate, and the like. Further, the polyhydric alcohol is, for example, a glycol such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol or dipropylene glycol; These polyesters are polyester polyols of a reaction product of an aliphatic dicarboxylic acid or a dicarboxylic acid anhydride such as succinic acid, maleic acid or adipic acid; a polyether polyol; a polycarbonate diol or the like. <Active Energy Ray-Curable Polyfunctional Polymer> The active energy ray-curable polyfunctional polymer has a plurality of acrylonitrile groups or methacryl fluorenyl groups in a polymer side chain, and has a weight average molecular weight (Mw). It is a compound of more than 10,000. For example, the above active energy ray-curable polyfunctional polymer, for example, a polymer having a glycidyl group (meth) acrylate (co)polymer reacted with (meth)acrylic acid, and a (meth)acrylic acid having a hydroxyl group A polymer in which an ester (co)polymer is reacted with a (meth) acrylate having an isocyanate group, a (meth) acrylate (co)polymer having an isocyanate group, and a (meth) acrylate having a hydroxyl group are reacted. a polymer, a polymer which selectively polymerizes only a vinyl ether group having a vinyl ether group and a (meth) acrylonitrile group, but an active energy ray curable polyfunctional compound which can be used in the present invention The polymer is not limited by these illustrations. [0020] Commercially available products of the active energy ray-curable polyfunctional polymer, for example, manufactured by DAICEL-ALLNEX Co., Ltd., polymer acrylate: ACA Z200M, same as Z230AA, same Z250, same Z251, same Z300, same Z320, the same Z254F; DIC (share) system, polymer type acrylate: UNIDIC (registered trademark) V-6840, the same V-6841, the same WHV-649, with EKS-675; Dacheng precision chemical (stock) system, UV Hardening type polymer: 8KX-012C, 8KX-014C, 8KX-018C, 8KX-052C, 8KX-056C, 8KX-058, 8KX-077, 8KX-078, 8KX-089; Hitachi Chemical Co., Ltd., polymer Type acrylate: HIDEROIDE (registered trademark) 7975, the same 7975D, the same 7798; Asia Industrial Co., Ltd., polymer type acrylate: RUA-049, RUA-054, KX50-200 and the like. In the present invention, the (A) polyfunctional compound may be a single one selected from the group consisting of an active energy ray-curable polyfunctional monomer and an active energy ray-curable polyfunctional polymer, or two kinds thereof. The combination of the above. Further, as the active energy ray-curable polyfunctional monomer, a single one selected from the group consisting of the above polyfunctional (meth) acrylate compound and the above polyfunctional urethane (meth) acrylate compound can be used. , or a combination of two or more. From the viewpoint of increasing the hardness of the obtained cured product, (A) a polyfunctional compound is preferably at least an active energy ray-curable polyfunctional polymer, particularly in combination with an active energy ray-curable polyfunctional polymer and an active energy ray. A curable polyfunctional monomer is preferred. In this case, the active energy ray-curable polyfunctional monomer is preferably a combination of a polyfunctional (meth) acrylate compound and the above polyfunctional urethane (meth) acrylate compound. Further, the polyfunctional (meth) acrylate compound is preferably a combination of a polyfunctional (meth) acrylate compound having 5 or more functional groups and a polyfunctional (meth) acrylate compound having 4 or less functional groups. In the above (A) polyfunctional compound, the active energy ray-curable polyfunctional polymer and the active energy ray-curable polyfunctional monomer are preferably used in a mass ratio of from 100:0 to 25:75. [0022] In the above active energy ray-curable polyfunctional monomer, when a polyfunctional (meth) acrylate compound is used in combination with the above polyfunctional urethane (meth) acrylate compound, it is relatively multifunctional ( It is preferable to use 30 to 70 parts by mass of the polyfunctional urethane (meth) acrylate compound in an amount of 20 to 100 parts by mass, based on 100 parts by mass of the methyl acrylate compound. Further, in the above polyfunctional (meth) acrylate compound, when the above-mentioned five-functional or more polyfunctional (meth) acrylate compound is used in combination with the above-described tetrafunctional or lower polyfunctional (meth) acrylate compound, 100 parts by mass of the polyfunctional (meth) acrylate compound having a functional or higher functional group is preferably 10 to 100 parts by mass of a tetrafunctional or lower polyfunctional (meth) acrylate compound, and preferably 20 to 60 parts by mass. . [0023] wherein, the active energy ray-curable polyfunctional polymer and the active energy ray-curable polyfunctional monomer are in a mass ratio of 95:5 to 25:75, and relative to the polyfunctional (meth) acrylate. 100 parts by mass of the compound, 20 to 100 parts by mass of the polyfunctional urethane (meth) acrylate compound, and 4 parts or less with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound having 5 or more functional groups. The polyfunctional (meth) acrylate compound is preferably used in an amount of 10 to 100 parts by mass, preferably 20 to 60 parts by mass, particularly an active energy ray-curable polyfunctional polymer and an active energy ray-curable polyfunctional monomer. a mass ratio of 95:5 to 25:75, and 30 to 70 parts by mass of the polyfunctional urethane (meth) acrylate compound, and 100 parts by mass of the polyfunctional (meth) acrylate compound, and It is preferable to use 10 to 100 parts by mass of a polyfunctional (meth)acrylate compound having 4 or less functional groups, preferably 20 to 60 parts by mass, per 100 parts by mass of the polyfunctional (meth) acrylate compound having 5 or more functional groups. . [(B) Inorganic fine particles] The inorganic fine particles (B) used in the present invention are not particularly limited as long as they are particles having an active energy ray polymerizable group to be described later, for example, cerium oxide ( Silica; metal oxide fine particles such as alumina, zirconia, titania, zinc oxide, cerium oxide, indium oxide, tin oxide, indium tin oxide, cerium oxide, cerium oxide; magnesium fluoride, sodium fluoride, etc. Metal fluoride microparticles; metal sulfide microparticles; metal nitride microparticles; metal microparticles, and the like. [0025] When the inorganic fine particles (B) are used for the purpose of improving the dispersibility in the composition for forming a primer layer, or for improving the adhesion to the substrate or the hard coat layer and forming a uniform primer layer, Alternatively, the microparticles may be surface-treated for the purpose of forming a primer layer of a hard coat layer of higher hardness. For the surface treatment, for example, a decane-based coupling agent such as vinyl decane or amino decane; a titanate-based coupling agent; an aluminate-based coupling agent; and an activity having a (meth) acrylonitrile group, a vinyl group, or the like can be used. An organic compound of a reactive functional group such as an energy ray polymerizable group or an epoxy group; a surface treatment agent such as a fatty acid or a fatty acid metal salt; or the like. In the above (B) inorganic fine particles used in the present invention, when inorganic fine particles having an active energy ray polymerizable group after surface treatment with a surface treatment agent having an active energy ray-polymerizable group are used, the primer can be formed. The polyfunctional compound selected from the group consisting of the active energy ray-curable polyfunctional monomer and the active energy ray-curable polyfunctional polymer of the component (A) of the layer, forms a crosslinked structure with the inorganic fine particles, and is promoted The hardness of the laminated structure of the primer layer and the hard coat layer. The average particle diameter of the inorganic fine particles of the component (B) can be obtained from the viewpoint of obtaining a hardness improving effect, and the transparency of the primer layer can be maintained at 300 nm or less, for example, 1 to 200 nm, particularly 5 to 5 100nm is preferred. Here, the average particle diameter referred to herein means a specific surface area (m) measured by a nitrogen adsorption method (BET method). ² ), the value calculated by the calculation formula of the average particle diameter = (2720 / specific surface area). Further, the shape of the inorganic fine particles is not particularly limited. For example, it may be a spherical shape, a spherical shape, or an amorphous shape such as a powder. It may be preferably a spherical shape, and more preferably an aspect ratio. Slightly spherical particles of 1.5 or less are preferably spherical particles. [0027] In the (B) inorganic fine particles used in the present invention, it is preferable to use a primer layer having a hard coat layer having a higher hardness, and it is preferable to use an inorganic oxide particle having a Mohs hardness of 6 or more, for example. Preferably, cerium oxide microparticles, titanium oxide microparticles, zirconia fine particles, alumina fine particles, and the like are preferred. [0028] As the inorganic fine particles, colloidal particles of inorganic fine particles can be used. For example, as the cerium oxide microparticles, a cerium oxide gel dispersed by a dispersion medium or a commercially available colloidal cerium oxide can be suitably used. The cerium oxide gel, for example, an aqueous cerium oxide gel obtained by a known method using an aqueous solution of sodium citrate as a raw material, and water used as a dispersion medium of the aqueous cerium oxide gel, using an organic solvent A substituted organic cerium oxide gel or the like. Examples of the organic solvent (dispersion medium) in the above organic cerium oxide gel, for example, lower alcohols such as methanol, ethanol, isopropanol, butanol; ethylene glycol, ethyl cellosolve, and c a solvate such as a cellosolve, propylene glycol monomethyl ether (PGME) or propylene glycol monomethyl ether acetate (PGMEA); a ketone such as methyl ethyl ketone (MEK) or methyl isobutyl ketone (MIBK); Aromatic hydrocarbons such as toluene and xylene; N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone ( An amine such as NMP); an ester such as ethyl acetate, butyl acetate or γ-butyrolactone; an ether such as tetrahydrofuran or 1,4-dioxane; and the like. Among the above-mentioned inorganic fine particles, a commercially available product of a preferred cerium oxide microparticle (cerium oxide gel), for example, manufactured by Nissan Chemical Industries Co., Ltd.: organic cerium oxide gel (registered trademark) MEK-AC -2140Z, with MEK-AC-4130Y, with MEK-AC-5140Z, with PGM-AC-2140Y, with PGM-AC-4130Y, with MIBK-AC-2140Y, with MIBK-SD, with MIBK-SD-L, etc. . The cerium oxide microparticles are those having an active energy ray polymerizable matrix. The amount of the inorganic fine particles added to the component (B) is 100 parts by mass or more, preferably 200 parts by mass or more, and more preferably 400%, based on 100 parts by mass of the component (A). More than one. On the other hand, from the viewpoint of crack resistance, it is preferably 1,000 parts by mass or less, more preferably 900 parts by mass or less, and particularly preferably 800 parts by mass or less. Further, the amount of (B) inorganic fine particles added is preferably such that the volume fraction of the inorganic fine particles (B) is 50 to 90% by volume based on the entire volume of the primer layer. [(C) A polymerization initiator which generates a radical via an active energy ray] A polymerization initiator which generates a radical via an active energy ray in the composition for forming a primer layer used in the present invention (hereinafter, also The term "(C) polymerization initiator") can be, for example, an active energy ray such as an electron beam, an ultraviolet ray or an X-ray, or a polymerization initiator which can generate a radical via ultraviolet ray irradiation. Further, (c) a polymerization initiator which generates a radical via an active energy ray in the curable composition to be described later, a polymerization initiator which is the same as the compound exemplified in the (C) polymerization initiator. [0032] The above (C) polymerization initiator, for example, benzoquinones, alkyl benzophenones, 9-oxosulfur Class, azo, azide, diazo, o-quinonediazide, phosphine oxide, oxime ester, organic peroxide, benzophenone, double incense Beans, biimidazoles, ferrocenes, thioethers, halogenated hydrocarbons, trichloromethyl three Classes, barium salts, barium salts, etc. These may be used alone or in combination of two or more. In the present invention, from the viewpoints of transparency, surface hardenability, and film curability, an alkylphenone polymerization initiator which uses (C) as a polymerization initiator is preferred. When an alkyl phenone polymerization initiator is used, a cured film having more excellent scratch resistance can be obtained. The above alkyl benzophenone polymerization initiator, for example, 1-hydroxycyclohexyl=phenyl=ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy- 1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionamidine) Α-hydroxyalkylphenones such as benzyl)phenyl)-2-methylpropan-1-one; 2-methyl-1-(4-(methylthio)phenyl)-2- α-Amine alkylphenones such as morpholinylpropan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one; , 2-dimethoxy-1,2-diphenylethane-1-one; phenylglyoxylate methyl, and the like. [0034] The (C) polymerization initiator in the present invention is selected from the group consisting of the active energy ray-curable polyfunctional monomer and the active energy ray-curable polyfunctional polymer. The total amount of the compound and (B) inorganic fine particles is preferably from 1 to 20 parts by mass, preferably from 2 to 10 parts by mass, per 100 parts by mass. [(D) Solvent] The composition for forming a primer layer used in the present invention may be in the form of a coating (film forming material) containing (D) a solvent. In the above-mentioned solvent, for example, it is considered that the components (A) to (C) are dissolved, and workability at the time of coating, drying property before and after curing, and the like which are performed when a cured product (primer layer) is formed later is considered. Suitable choices are, for example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, tetrahydronaphthalene, etc.; n-hexane, n-heptane, mineral spirits, cyclohexane Aliphatic or alicyclic hydrocarbons; methyl chloride, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene Halogenated hydrocarbons such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, etc. Ester or ester ether; diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n- An ether such as propyl ether, propylene glycol monoisopropyl ether or propylene glycol mono-n-butyl ether; a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butanone or cyclohexanone; methanol , Alcohols such as ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol, etc.; N,N-dimethyl a guanamine such as methotrexate or N,N-dimethylacetamide; an anthracene such as dimethyl hydrazine; a heterocyclic compound such as N-methyl-2-pyrrolidone; Two or more kinds of mixed solvents and the like. The amount of the solvent (D) to be used is not particularly limited. For example, the solid content of the primer layer-forming composition used in the present invention may be from 1 to 70% by mass, preferably from 10 to 60. The mass concentration is used in a manner. Here, the solid content concentration (also referred to as a non-volatile component concentration) means the components (A) to (D) (and other additives expected) of the primer layer-forming composition used in the present invention. Total mass (total mass), the content of the solid component (after removal of the solvent component from the total component). [Other Additives] Further, in the composition for forming a primer layer to be used in the present invention, it is possible to appropriately add an additive which is generally added, for example, a polymerization accelerator, as long as it does not impair the effects of the present invention. , polymerization inhibitor, photo sensitizer, leveling agent, surfactant, adhesion imparting agent, plasticizer, ultraviolet absorber, antioxidant, storage stabilizer, antistatic agent, inorganic filler, pigment, dye, etc. . In particular, in the composition for forming a primer layer used in the present invention, since the inorganic fine particles are added, the surface of the coating film when the primer layer is formed is smoothed to prevent damage to the coating appearance or transparency. In view of the occurrence of defects, it is preferable to add a leveling agent. As the leveling agent, a known polyfluorene-based, fluorine-based, acrylic-based, or vinyl-based one can be used. The above-mentioned leveling agent, for example, an acrylic leveling agent, a polyfluorene type leveling agent, a fluorine type leveling agent, a polyfluorene/acrylic copolymer-based leveling agent, a fluorine-denatured acrylic type leveling agent, and a fluorine denaturation agent. a polyfluorene-based leveling agent, and an alkoxy group, a mercaptooxy group, a halogen group, an amine group, a vinyl group, an epoxy group, a methyl group such as a methoxy group or an ethoxy group, which are introduced into the leveling agents. A leveling agent of a functional group such as an acryloxy group, an acryloxy group or an isocyanate group. In the case where a leveling agent is added, the polyfunctional compound selected from the group consisting of the active energy ray-curable polyfunctional monomer and the active energy ray-curable polyfunctional polymer and (B) the inorganic fine particles are When the total amount is 100 parts by mass, it is preferably 5 parts by mass or less, more preferably 0.001 to 2 parts by mass, even more preferably 0.01 to 1 part by mass, from the viewpoints of transparency, coating appearance, adhesion, hardness, and the like. [Hard Coat Layer] <Curable Composition> The hard coat layer in the high hardness hard coat layer of the present invention is obtained from the curable composition containing the following (a) to (c). The cured product (ie, the cured film) is formed. (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer; (b) a terminal of a molecular chain containing a poly(oxoperfluoroalkylene) group via a poly(oxyalkylene) group, or 0.1 to 10 parts by mass of a perfluoropolyether having an active energy ray-polymerizable group bonded to a poly(oxyalkylene) group and one urethane-bonding group, and (c) generating a radical via an active energy ray The polymerization initiator is 1 to 20 parts by mass. Hereinafter, each component of the above (a) to (c) will be described. [(a) Active energy ray-curable polyfunctional monomer] (a) Active energy ray-curable polyfunctional monomer used in the curable composition used in the present invention means active energy via ultraviolet rays or the like In the case of the (A) polyfunctional compound added to the primer layer forming composition, the <active energy ray-curable polyfunctional monomer> is the same as the monomer which is hardened by the polymerization reaction. The content of the compound, that is, the monomer selected from the group consisting of the aforementioned polyfunctional (meth) acrylate compound and polyfunctional urethane (meth) acrylate compound. [0041] In the curable composition, the (a) active energy ray-curable polyfunctional monomer may be used singly from the above polyfunctional (meth) acrylate compound and the above polyfunctional urethane (methyl). One type selected from the group consisting of acrylate compounds, or a combination of two or more types may be used. From the viewpoint of the scratch resistance of the obtained cured product, it is preferred to use a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound in combination. Further, in the above polyfunctional (meth) acrylate compound, a polyfunctional (meth) acrylate compound having 5 or more functional groups and a polyfunctional (meth) acrylate compound having 4 or less functional groups are preferably used in combination. Further, when the polyfunctional (meth) acrylate compound is used in combination with the above polyfunctional urethane (meth) acrylate compound, it is used in an amount of 100 parts by mass based on the polyfunctional (meth) acrylate compound. The polyfunctional urethane (meth) acrylate compound is preferably 20 to 100 parts by mass, and preferably 30 to 70 parts by mass. Further, in the above polyfunctional (meth) acrylate compound, when the above-described pentafunctional or higher polyfunctional (meth) acrylate compound is used in combination with the above-described tetrafunctional or lower polyfunctional (meth) acrylate compound, It is preferable to use 10 to 100 parts by mass of a polyfunctional (meth)acrylate compound having 4 or less functional groups, and to use 20 to 60 parts by mass, based on 100 parts by mass of the polyfunctional (meth) acrylate compound having 5 or more functional groups. Preferably. Further, the polyfunctional urethane (meth) acrylate compound is used in an amount of 20 to 100 parts by mass based on 100 parts by mass of the polyfunctional (meth) acrylate compound, and is relatively polyfunctional with respect to 5 or more functional groups. 100 parts by mass of a (meth) acrylate compound, 10 to 100 parts by mass of a polyfunctional (meth) acrylate compound having 4 or less functional groups, and 100 parts by mass of a polyfunctional (meth) acrylate compound, and a polyfunctional amine is used. 20 to 100 parts by mass of the carbamic acid ester (meth) acrylate compound, and a polyfunctional (meth) group having 4 or less functional groups is used with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound having 5 or more functional groups. 20 to 60 parts by mass of the acrylate compound, and 30 to 70 parts by mass of the polyfunctional urethane (meth) acrylate compound with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound, and relative to 100 parts by mass of a polyfunctional (meth) acrylate compound having 5 or more functional groups, 10 to 100 parts by mass of a polyfunctional (meth) acrylate compound having 4 or less functional groups, and a polyfunctional (meth) acrylate compound 100 The amount of the polyfunctional urethane (meth) acrylate compound is 30 to 70 parts by mass, and the amount of the functional group is less than or equal to 100 parts by mass based on 100 parts by mass of the polyfunctional (meth) acrylate compound. The polyfunctional (meth) acrylate compound is preferably 20 to 60 parts by mass. [(b) a molecular chain containing a poly(oxoperfluoroalkylene) group is bonded to both ends via a poly(oxyalkylene) group, or sequentially via a poly(oxyalkylene) group and one a urethane-bonding group, a perfluoropolyether bonded to an active energy ray-polymerizable group] In the present invention, the component (b) is used for a molecular chain containing a poly(oxoperfluoroalkylene) group. At both ends, through a poly(oxyalkylene) group, or sequentially via a poly(oxyalkylene) group and a urethane linkage group, a perfluoropoly group bonded to an active energy ray polymerizable group Ether (hereinafter, also referred to as "(b) perfluoropolyether having a polymerizable group at both ends). The component (b) has a function as a surface modifier in the hard coat layer using the curable composition used in the present invention. The number of carbon atoms of the alkylene group in the poly(oxoperfluoroalkylene) group is not particularly limited, and is preferably from 1 to 4 carbon atoms. That is, the above poly(oxoperfluoroalkylene) group means a group having a structure in which a divalent fluorinated carbon group having 1 to 4 carbon atoms and an oxygen atom are mutually linked, and an oxoperfluoroalkylene group means The divalent fluorinated carbon group having 1 to 4 carbon atoms and the oxygen atom have a structure in which a structure is bonded. Specifically, for example, -[OCF ₂ ]-(Oxo-perfluoromethyl), -[OCF ₂ CF ₂ ]-(oxoperfluoroextended ethyl), -[OCF ₂ CF ₂ CF ₂ ]-(oxoperfluoropropane-1,3-diyl-yl), -[OCF ₂ C (CF ₃ a group such as F]-(oxoperfluoropropane-1,2-diyl-yl). The oxoperfluoroalkylene group may be used singly or in combination of two or more. In this case, a plurality of oxoperfluoroalkylene groups may be bonded to each other. Or any of the random bonds can be used. Among these, from the viewpoint of producing a cured film having good scratch resistance, the poly(oxoperfluoroalkylene) group is used to have -[OCF ₂ ]-(Oxo-perfluoromethyl) and -[OCF ₂ CF ₂ It is preferred that both - (oxoperfluoroextended ethyl) be used as the basis of the repeating unit. Wherein, the above poly(oxoperfluoroalkylene) group has a molar ratio of [repeating unit: -[OCF] ₂ ]-]:[Repeat unit:-[OCF ₂ CF ₂ ]-]=2:1~1:2 ratio of repeating units: -[OCF ₂ ]-and-[OCF ₂ CF ₂ Preferably, the base is preferably a base having a ratio of approximately 1:1. The bonding of the repeating units may be any one of a block bond and a random bond. The number of repeating units of the oxoperfluoroalkylene group is preferably in the range of 5 to 30 in terms of the number of repeating units, and preferably in the range of 7 to 21. Moreover, the weight average molecular weight (Mw) measured by polystyrene conversion of the poly(oxoperfluoroalkylene) group gel permeation chromatography is 1,000 to 5,000, preferably 1,500 to 2,000. The number of carbon atoms of the alkylene group in the poly(oxyalkylene) group is not particularly limited, and is preferably from 1 to 4 carbon atoms. That is, the above poly(oxyalkylene) group means a group in which an alkylene group having 1 to 4 carbon atoms and an oxygen atom have an interconnected structure, and an oxyalkyl group means a divalent extension having 1 to 4 carbon atoms. The alkyl group and the oxygen atom have a group having a bonded structure. The above alkyl group is, for example, an ethyl group, a methyl group, a methyl group, a methyl group, a tetramethyl group or a tetramethyl group. The above oxyalkyl groups may be used singly or in combination of two or more. In this case, the bonding of the plurality of oxyalkyl groups may be either block bonding or random bonding. Can be. Among them, the above poly(oxyalkylene) group is preferably a poly(ethylene oxide) group. The number of repeating units of the oxyalkyl group in the poly(oxyalkylene) group may be, for example, in the range of 1 to 15, and may be, for example, in the range of 5 to 12, and preferably in the range of 7 to 12, for example. [0046] an active energy ray-polymerizable group bonded via a poly(oxyalkylene) group or a poly(oxyalkylene) group and a urethane-bonding group, for example, Methyl) acrylonitrile, urethane (meth) acrylonitrile, vinyl, and the like. The active energy ray polymerizable group is not limited to an active energy ray polymerizable portion having one (meth) acryl fluorenyl moiety, and may have two or more active energy ray polymerizations. The functional part is, for example, the structures of A1 to A5 shown below, and the structure in which the acryl fluorenyl group in these structures is substituted by a methacryl fluorenyl group. [0048] The (b) perfluoropolyether having a polymerizable group at both terminals is industrially easy to manufacture, and the compound shown below and the propylene sulfonyl group in the compounds are replaced by a methacryl fluorenyl group. The compounds are preferably exemplified. Further, in the structural formula, A represents one of the structures represented by the above formulas [A1] to [A5], PFPE represents the poly(oxoperfluoroalkylene) group, and n each independently represents an oxyethylene group. The number of repeating units is preferably from 1 to 15, more preferably from 5 to 12, and particularly preferably from 7 to 12. [0050] wherein, (b) the perfluoropolyether having a polymerizable group at both ends, and the two ends of the molecular chain containing a poly(oxoperfluoroalkylene) group, sequentially through the poly( An alkoxyalkylene group and a urethane linkage group, that is, a poly(oxyalkylene) group is bonded to each of the two ends of the molecular chain containing a poly(oxoperfluoroalkylene) group, and A urethane bond group is bonded to each of the poly(oxyalkylene) groups at the two ends, and the active energy ray polymerization is bonded to each of the urethane bonds at the two ends. The fluorinated polyether is preferred. Further, in the perfluoropolyether, a perfluoropolyether having a base of an active energy ray polymerizable portion having at least two or more active energy ray-polymerizable groups is preferred. In the present invention, (b) a perfluoropolyether having a polymerizable group at both terminals is used in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the (a) active energy ray-curable polyfunctional monomer. The ratio is preferably 0.2 to 5 parts by mass. The perfluoropolyether having a polymerizable group at both ends of the above (b), for example, can be used for a poly(oxo-perpendane) group having a hydroxyl group via a poly(oxyalkylene) group. In the compound, 2-(methyl)propenyloxyisocyanate or 1,1-bis((meth)acryloxymethyl)isocyanate or the like is used for the hydroxyl group at both ends. Method for performing urethanization reaction of an isocyanate compound having a polymerizable group, a method for dehydrochlorinating (meth)acrylic acid chloride or chloromethylstyrene, and a method for dehydrating (meth)acrylic acid It is obtained by subjecting isoconic anhydride to an esterification reaction or the like. Wherein, in the compound having a poly(oxyalkylene) group-containing hydroxyl group at both ends of the poly(oxoperfluoroalkylene) group, 2-(meth)acrylofluorene is used for the hydroxyl group at both ends a method of performing a urethanization reaction of an isocyanate compound having a polymerizable group such as ethyl isocyanate or 1,1-bis((meth)acryloxymethyl)isocyanate; or It is particularly preferable that the hydroxyl group is subjected to a dehydrochlorination reaction using (meth)acrylic acid chloride or chloromethylstyrene, and the reaction is easily carried out. Further, in the curable composition used in the present invention, the (b) molecular chain containing a poly(oxoperfluoroalkylene) group is bonded to both ends via a poly(oxyalkylene) group, or sequentially. The poly(oxygenated perfluoroalkylene) may be further contained in addition to the perfluoropolyether bonded to the active energy ray-polymerizable group via a poly(oxyalkylene) group and one urethane linkage group. One of the molecular chains of the group has an active energy ray-polymerizable group via a poly(oxyalkylene) group or a poly(oxyalkylene) group and a urethane-bonding group. And a perfluoropolyether having a hydroxyl group at the other end or a poly(oxyalkylene) group at both ends of the molecular chain containing the poly(oxoperfluoroalkylene) group A perfluoropolyether having a hydroxyl group [a compound which does not bond an active energy ray polymerizable group]. [(c) Polymerization initiator for generating a radical via an active energy ray] The curable composition used in the present invention is preferably a polymerization initiator which generates a radical via an active energy ray (hereinafter, only It is called "(c) polymerization initiator"), for example, an active energy ray such as an electron beam, an ultraviolet ray, an X-ray or the like, particularly a polymerization initiator which generates a radical by ultraviolet irradiation, which can be used and added thereto. The (C) polymerization initiator of the aforementioned primer layer forming composition is the same starting agent. Among them, in the present invention, from the viewpoints of transparency, surface hardenability, and film hardenability, it is preferred to use (c) an alkyl benzophenone as a polymerization initiator. When an alkyl phenone polymerization initiator is used, a cured film which is more excellent in scratch resistance can be obtained. In the present invention, (c) the polymerization initiator is used in an amount of from 1 to 20 parts by mass, preferably from 2 to 10 parts by mass, per 100 parts by mass of the active energy ray-curable polyfunctional monomer. It is appropriate. [(d) Solvent] The curable composition used in the present invention may further contain (d) a solvent, that is, a form of a coating material (film forming material). In the above-mentioned solvent, for example, it is possible to dissolve the components (a) to (c), and to form a cured film (hard coat layer), which will be described later, workability at the time of coating, dryness before and after curing, and the like. The choice may be, for example, an aromatic hydrocarbon such as benzene, toluene, xylene, ethylbenzene or tetrahydronaphthalene; an aliphatic group such as n-hexane, n-heptane, mineral spirit or cyclohexane; Alicyclic hydrocarbons; halogenated hydrocarbons such as methyl chloride, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene, etc. Ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, ester or ester ether Diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol An ether such as isopropyl ether or propylene glycol mono-n-butyl ether; a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butanone or cyclohexanone; methanol, ethanol, n- Propanol Alcohols such as isopropanol, n-butanol, isobutanol, tert-butanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol, etc.; N,N-dimethylformamide, N,N - anthracene such as dimethylacetamide; an anthracene such as dimethyl hydrazine; a heterocyclic compound such as N-methyl-2-pyrrolidone; and two or more of these Mix solvents and the like. The amount of the solvent (d) to be used is not particularly limited. For example, the solid content of the curable composition used in the present invention may be from 1 to 70% by mass, preferably from 5 to 50% by mass. concentration. Wherein the solid component concentration (also referred to as the non-volatile component concentration) refers to the total mass of the above components (a) to (d) (and other additives expected) relative to the curable composition used in the present invention ( Total mass), the content of the solid component (the solvent component is removed from the total component). [Other Additives] Further, in the curable composition used in the present invention, a general additive such as a polymerization accelerator or a polymerization inhibitor may be appropriately added as needed, without departing from the scope of the effects of the present invention. Light sensitizer, leveling agent, surfactant, adhesion imparting agent, plasticizer, ultraviolet absorber, antioxidant, storage stabilizer, antistatic agent, inorganic filler, pigment, dye, and the like. [High Hardness Hard Coat Laminate] As described above, the high hardness hard coat laminate of the present invention is composed of a substrate, a primer layer above the substrate, and a top layer of the primer layer. A laminate of 3 layers formed by a hard coating layer. The high hardness hard coat layer of the present invention comprises: (i) a step of forming a coating film by coating a composition for forming a primer layer on a substrate, and (ii) forming the primer layer by irradiation with an active energy ray. a coating film of the composition, a step of curing the coating film to form a primer layer, (iii) applying a curable composition on the primer layer to form a coating film, and (iv) using active energy The line is irradiated with the coating film of the curable composition to be hardened to form a hard coat layer. Among them, the composition for forming a primer layer and the curable composition are each of the above-mentioned compositions. [0058] The coating layer forming composition and the curable composition coating method in the steps (i) and (iii), the mold coating method, the spin coating method, the flat coating method, and the like can be appropriately selected. Dipcoat method, roll coating method, strip coating method, die coating method, spray coating method, curtain coating method, inkjet method, printing method (embossing, gravure, For the lithographic printing, screen printing, etc., it is also possible to use a roll-to-roll method, and it is preferable to use a relief printing method, particularly a gravure coating method, from the viewpoint of film coating properties. The primer layer-forming composition and the curable composition used therein may be suitably used as long as they are in the form of the above-mentioned coating material. In addition, it is preferable to use a filter having a pore size of about 2 μm in advance to filter the primer layer-forming composition and the curable composition. [0059] After applying the composition for forming a primer layer in the above step (i), and after applying the curable composition in the step (iii), it is preferred to continue using a hot plate or an oven, etc., by pre-drying. The solvent is removed (solvent removal step). The conditions for heating and drying at this time are preferably, for example, 40 to 120 ° C and 30 seconds to 10 minutes. After drying, the step (ii) or (iv) is irradiated with an active energy ray such as ultraviolet rays, and photocured to form a primer layer and a hard coat layer. Active energy rays, for example, ultraviolet rays, electron wires, X-rays, and the like. As the light source used for the ultraviolet irradiation, for example, a solar ray, a chemical lamp, a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, a UV-LED, or the like can be used. Subsequently, post-baking is performed, specifically, heating is performed using a hot plate, an oven, or the like to complete polymerization and polycondensation. In the laminate of the present invention obtained in this manner, the thickness of the primer layer is not particularly limited, and may be, for example, 0.1 to 1,000 μm, preferably 1 to 100 μm. Further, the thickness of the hard coat layer is not particularly limited, and is, for example, in the range of 1 to 30 μm, preferably 1 to 20 μm, more preferably 3 to 10 μm.

[Examples] Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited by the following examples. Further, in the examples, the apparatus and conditions used for the production and physical property analysis of the samples are as follows. (1) Strip coating and coating device: PM-9050MC manufactured by SMT (coating): Coating speed of 4 m/min, bar 1 (bar1): A-Bar OSP-25 manufactured by OSG system (share) Maximum wet film thickness 25μm (scratch bar #10 equivalent) Bar 2 (bar2): OSG system manufacturing (stock) A-Bar OSP-30, maximum wet film thickness 30μm (scraping bar #12 equivalent) Bar 3 (bar3 ): OSG system manufacturing (stock) A-Bar OSP-52, maximum wet film thickness 52μm (scratch bar #20 equivalent) Scraper 4 (bar4): OSG system manufacturing (stock) A-Bar OSP-100, maximum Wet film thickness 100μm (scratch bar #37 equivalent) (2) Oven device: ADVANTEC Toyo (stock) dust-free dryer DRC433FA (3) UV irradiation device: HERAEUS (share) system CV-110QC-G lamp: HERAEUS (shares) High-pressure mercury lamp H-bulb (4) scratch test device: Xindong Science (stock) system round-trip friction test machine TRIBOGEAR TYPE: 30S load: 1kg / cm ² scan speed: 3m / minute (5) pencil hardness device: ( Stock) Electric pencil drawing hardness tester made by Yasuda Seiki Co., Ltd. No.553-M Load: 750g Pencil: UNI (registered trademark) manufactured by Mitsubishi Pencil Co., Ltd. Measurement temperature: 20 ° C (6) Gel permeation chromatography (GPC) ) Device: HTC-8220GPC tube made by Tosoh Co., Ltd. : Showa Denko (registered trademark) GPC KF-804L, GPC KF-805L Column temperature: 40 ° C Dissolution: Tetrahydrofuran detector: RI (7) Film thickness device: (share) Nikon digital measurement Long-distance DEGIMICRO MH-15M+ measuring instrument TC-101A (8) Full light transmittance, fog value device: Japan Electric Color Industry (stock) fog value test table NDH5000 (9) Contact angle device: Concord Interface Science (shares) DropMaster DM-501 Measurement temperature: 20 ° C [0063] Again, the abbreviation indicates the following meaning. PFPE1: a perfluoropolyether having a hydroxyl group at both ends via a poly(oxyalkylene) group (repeating unit number 8 to 9) [Fluorolink 5147X manufactured by Solvay Specialty Polymers Co., Ltd.] BEI: 1,1-bis(propyleneoxyloxy group) Methyl)ethyl isocyanate [Karenz (registered trademark) BEI, manufactured by Showa Denko Co., Ltd.] DBTDL: Dibutyltin laurate [Tokyo Chemical Industry Co., Ltd.] 4ELA: Tetraethylene glycol monolaurate acrylate [Day Oil (stock) PLUMER (registered trademark) ALE-200] HDDA: 1,6-hexanediol diacrylate [Naka Nakamura Chemical Industry Co., Ltd. NK ester A-HD-N] LA: Acrylic acid lauryl [ PLUMER (registered trademark) LA] ADVN: 2,2'-azobis(2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] C6FA: Acrylic acid 2-(Perfluorohexyl)ethyl ester [FAMAT-6 manufactured by UNIMATEC] EGDMA: Ethylene glycol diacrylate [1G manufactured by Shin-Nakamura Chemical Co., Ltd.] VEEA: 2-(2-vinyloxy acrylate) Ethoxyethyl)ethyl ester [(Febrication) VEEA by Japanese Catalyst] MAIB: dimethyl 2,2'-azobisisobutyl ester [MAIB manufactured by Otsuka Chemical Co., Ltd.] AA1: Polyacrylic acrylate [ DIC (share) system UNIDIC (registered trademark) V-6840, effective ingredient 50 quality %MIBK solution] AA2: Polyacrylic acrylate [ACAZ-ALLNEX (ACA Z200M, active ingredient 50% by mass PGME solution] AA3: Polyacrylic acrylate [DAICEL-ALLNEX ACA Z230AA, active ingredient 50% by mass PGME solution] DPHA: dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture [KAYALAD DN-0075, manufactured by Nippon Kayaku Co., Ltd.] PETA: pentaerythritol triacrylate/pentaerythritol tetraacrylate mixture [Xinzhongcun Chemical Industry] (Stock) NK ester A-TMM-3LM-N] UA: 6-functional aliphatic urethane acrylate oligomer [EBECRYL (registered trademark) 5129 by DAICEL-ALLNEX) IP1: Containing active energy Linear polymerizable cerium oxide gel [PGM-AC-2140Y, 40% by mass PGME dispersion, primary average particle size 10-15 nm, cerium oxide specific gravity 1.24] IP2: active Energy ray polymerizable group of cerium oxide gel [MIBK-SD manufactured by Nissan Chemical Industries Co., Ltd., 33% by mass MIBK dispersion, primary average particle diameter of 10 to 15 nm, cerium oxide specific gravity of 0.99 to 1.03] IP3: two Yttrium oxide gel [Nissan Chemical Industry Co., Ltd. PGM-ST, 33% by mass PGME Liquid, primary average particle size 10 to 15 nm, cerium oxide specific gravity 1.11 to 1.15] LA1: non-fluorine leveling agent [Kyoeisha Chemical Co., Ltd. reflow soldering No. 77] SM2: having a perfluoropolyether structure UV-reactive fluorine-based surface modifier [DIC (trade) RS-75, active ingredient 40% by mass MEK/MIBK solution] I184: 1-hydroxycyclohexyl = phenyl = ketone [ BASF Japan (stock) IRGACURE (registered trademark) 184] I2959: 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one [BASF Japan (shares) ) IRGACURE (registered trademark) 2959] EPA: p-dimethylamino benzoic acid ethyl [KAYACURE EPA manufactured by Nippon Kayaku Co., Ltd.] PET: One side is easily treated with polyethylene terephthalate (PET)膜 MOS MOS MOS MOS COS MOS COS MOS COS MOS COS MOS COS MOS COS MOS COS MOS COS MOS COS MOS COS MOS COS Ethyl ketone MIBK: methyl isobutyl ketone PGME: propylene glycol monomethyl ether [Production Example 1] propylene fluorenyl group bonded at both ends via a poly(oxyalkylene) group and one urethane bond Perfluoropolyether SM1 Built in screw tube placed PFPE1 1.05g (0.5mmol), BEI 0.26g (1.0mmol), DBTDL 10mg (0.016mmol), and MEK 1.30g. The mixture was stirred at room temperature (about 23 ° C) for 24 hours using a stir bar. The reaction mixture was diluted with MEK 3.93 g to obtain a 20% by mass MEK solution of SM1 of the objective compound. The weight average molecular weight Mw of the obtained SM1 measured by using GPC in terms of polystyrene was 3,400, and the degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) was 1.2. [Production Example 2] The high-branched polymer LA2 having a long-chain alkyl group was produced in a 200 mL reaction flask, and placed in a MIBK (54 g), and a nitrogen gas was introduced for 5 minutes while stirring, and heated until the internal liquid was refluxed (the temperature was about 116 ° C). ). In a separate 100 mL reaction flask, 6.7 g (30 mmol) of HDDA, 3.6 g (15 mmol) of LA, 18.6 g (45 mmol) of 4ELA, 6.0 g (24 mmol) of ADVN, and 54 g of MIBK were placed, and nitrogen gas was introduced for 5 minutes while stirring. The nitrogen was replaced and cooled to 0 ° C in an ice bath. Using the drip pump, the above 100 mL reaction flask containing HDDA, LA, 4ELA, and ADVN was placed, and the contents were dropped into MIBK refluxed in the above 200 mL reaction flask over 30 minutes. After the completion of the dropwise addition, the mixture was further stirred for 1 hour. The reaction mixture was cooled to room temperature (about 23 ° C) to obtain 143.0 g of a MIBK solution having a polymer concentration of the target high branched polymer (LA2) of 25% by mass. The weight average molecular weight of the obtained highly branched polymer LA2 in terms of polystyrene measured by GPC: Mw was 7,300, and the degree of dispersion: Mw/Mn was 4.6. [Production Example 3] Production of a highly branched polymer LA3 having a fluoroalkyl group was carried out in a 200 mL reaction flask, and 59 g of toluene was placed, and nitrogen gas was introduced for 5 minutes while stirring, and heated until the internal liquid was refluxed (about 110 ° C). . In another 100 mL reaction flask, EGDMA 4.0 g (20 mmol), C6FA 5.2 g (12.5 mmol), VEEA 1.9 g (10 mmol), MAIB 2.8 g (12 mmol), and toluene 59 g were placed, and the mixture was stirred for 5 minutes. Nitrogen was replaced with nitrogen and cooled to 0 ° C in an ice bath. Using the dropping pump, the above 100 mL reaction flask of EGDMA, C6FA, VEEA, MAIB was placed, and the contents were dropped into toluene refluxed in the above 200 mL reaction flask over 30 minutes. After the completion of the dropwise addition, the mixture was further stirred for 1 hour. The reaction mixture was added to 277 g of hexane to precipitate the polymer in a slurry state. The slurry was filtered under reduced pressure and dried in vacuo to give 6.6 g of white powder of the desired high-branched polymer (LA3). The weight average molecular weight of the obtained highly branched polymer LA3 in terms of polystyrene measured by GPC: Mw was 8,400, and the degree of dispersion: Mw/Mn was 2.5. [Production Examples 4-1 to 4-8] Preparation of primer composition (primer layer-forming composition) According to Table 1, the following components were mixed to obtain a solid component described in Table 1. The primer composition of the concentration (PR1 to PR8). Further, the solid component thereof means a component other than the solvent. In the table, [parts] means [parts by mass] and [%] means [% by mass]. (1) Polyfunctional compound: The polyfunctional polymer and/or monomer described in Table 1 are in the amounts described in Table 1 (in terms of active ingredient). (2) Inorganic fine particles: The inorganic fine particles described in Table 1 are in the amounts shown in Table 1 ( (3) Polymerization initiator: 5 parts by mass of the polymerization initiator described in Table 1 (4) Polymerization accelerator: EPA The amount described in Table 1 ("-" indicates no addition). (5) Leveling agent: The amount of the leveling agent described in Table 1 is in accordance with the amount shown in Table 1 (solid composition or active ingredient conversion) (6) Solvent: PGME The amount described in Table 1 (in the table, a negative value indicates evaporation) Distillate solvent). [0068] [Production Examples 5-1 to 5-2] Preparation of Hard Coating Composition (Curable Composition) According to the description of Table 2, the following components were mixed to obtain a hard coating having a solid content concentration of 40% by mass. Composition (HC1 to HC2). Further, the solid component thereof means a component other than the solvent. In the table, [parts] means [parts by mass] and [%] means [% by mass]. (1) Polyfunctional monomer: 50 parts by mass of DPHA, 30 parts by mass of UA, and 20 parts by mass of PETA (2) Surface modifier: 1 part by mass of the surface modifier described in Table 2 (solid content or active ingredient conversion) (3) Polymerization initiator: I2959 5 parts by mass (4) Polymerization accelerator: EPA 0.1 parts by mass (5) Solvent: PGME According to the amount described in Table 2 [0070] [Examples 1 to 6 and Comparative Examples 1 to 5] The primer compositions described in Table 3 were coated on the substrate described in Table 3 using the bar shown in Table 3 (PET is an easy-to-handle surface). Strip coating was carried out to obtain a coating film. The coating film was dried in an oven at a drying temperature as described in Table 3 for 1 minute to remove the solvent. The obtained film was irradiated with UV light having an exposure amount of 100 mJ/cm ² in an air atmosphere, and subjected to exposure treatment to form a primer layer (cured film) having a thickness shown in Table 3. Further, in Comparative Example 1, since the primer layer was cracked, the subsequent operation was interrupted. The hard coat composition shown in Table 3 was applied to the primer layer by strip coating using the bar shown in Table 3 to obtain a coating film. The coating film was dried in an oven at a drying temperature as described in Table 3, and dried for 3 minutes to remove the solvent. The obtained film was irradiated with UV light having an exposure amount of 300 mJ/cm ² under a nitrogen atmosphere, and subjected to exposure treatment to obtain a hard coat layer having a hard coat layer (hardened film) having a thickness shown in Table 3. . Further, in Comparative Example 3, a primer layer was not formed, and a hard coat layer was formed directly on the substrate. Further, in Comparative Example 5, the hard coat layer was not formed, and a hard coat layer having only the primer layer was formed. The resulting hard coat laminate was evaluated for scratch resistance, pencil hardness, total light transmittance, haze value, and contact angle of water. The order of evaluation of scratch resistance, pencil hardness, and contact angle is as follows. Also, the results are shown in Table 4. [Scratch Resistance] The hard-coating was carried out at a load of 1 kg/cm ² using a round-trip abrasion tester equipped with steel wool [BONSTAR (registered trademark) #0000 (superfine)]. The surface of the layer was subjected to 1,000 reciprocating frictions, and an oily mic pen [Macaque (blue) made of ZEBRA) and a side of the thin side were used to draw the line. Subsequently, the drawing line was wiped using a non-woven blade [BEMCOT (registered trademark) M-1 manufactured by Asahi Kasei Co., Ltd.), and the degree of the scratch was visually confirmed on the basis of the following criteria for evaluation. Moreover, in the case where the hard coat layer is set to be practical, it needs to be at least a grade of B and a grade of A. A: There is no scar, it can cleanly remove the line drawn by the oily microphone. B: There are only a few scars, but the line drawn by the oily microphone can be cleanly removed. C: The ink of the oily pen is deep into the scar and cannot be wiped clean. [Pencil Hardness] The pencil hardness (scratch hardness) was measured in accordance with JIS 5600-5-4. Further, in the case where the hard coat layer is set to be practical, it is required to be at least 5H or more, and more preferably 7H or more. [Contact Angle] 1 μL of water was attached to the surface of the hard coat layer, and the contact angle θ at 5 points was measured after 5 seconds, and the average value thereof was used as the contact angle value. [0076] [0077] [0078] As shown in Tables 1 to 4, as a surface modifier, a poly(oxyalkylene) group and a urethane bond group are bonded to both ends to bond an acrylonitrile group. The perfluoropolyether SM1, in the case of forming a hard coat layer, has excellent scratch resistance in the laminate 1 to the laminate 6 of Examples 1 to 6 in which the primer layer containing the inorganic fine particles is provided, and the pencil The hardness is also such that it can satisfy the quality of practical use and is a laminate having excellent transparency. On the other hand, in the case where the primer layer was made of inorganic fine particles having no active energy ray polymerizable group (Comparative Example 1), cracking occurred at the time of forming the primer layer, and the laminate could not be formed. Further, in the primer layer, the content of the inorganic fine particles was less than the predetermined amount (Comparative Example 2), and the case where the primer layer was not provided (Comparative Example 3) showed the same as the laminate of the present invention. It is scratch-resistant, but its pencil hardness is low, and the expected hardness cannot be obtained. Further, in the case where the surface modification agent used the UV-reactive fluorine-based surface modifier SM2 having a perfluoropolyether structure in the hard coat layer (Comparative Example 4), although the pencil hardness can achieve a good effect, it cannot be obtained. Expected scratch resistance. Further, in the case where the hard coat layer was not provided, and only the surface modifier SM1 of the hard coat layer was added to the primer layer (Comparative Example 5), a layer having a higher hardness than that of the inorganic fine particles was obtained. However, it is impossible to obtain a layer having scratch resistance. [0079] As described above, as shown in the results of the examples, a laminate having a surface-modifying agent using a hard coating layer of a specific perfluoropolyether can be obtained by providing a primer layer containing inorganic fine particles. A laminate having excellent scratch resistance and high hardness.

Claims (10)

A high hardness hard coat laminate which is a high hardness hard coat laminate formed from a substrate, a primer layer over the substrate, and a hard coat layer over the primer layer, characterized The primer layer is 100 parts by mass of a polyfunctional compound selected from the group consisting of (A) an active energy ray-curable polyfunctional monomer and an active energy ray-curable polyfunctional polymer, (B) inorganic 100 to 1,000 parts by mass of the fine particles, and (C) the polymerization initiator which generates a radical via the active energy ray is 1 to 20 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B); The inorganic fine particles of the component (B) are formed of a cured product of a primer layer forming composition of particles having an active energy ray polymerizable group; and the hard coat layer is hardened by containing (a) an active energy ray. 100 parts by mass of the functional monomer, (b) the terminal of the molecular chain containing the poly(oxoperfluoroalkylene) group is bonded via a poly(oxyalkylene) group, or sequentially via a poly(oxyalkylene) group and One urethane bond group, bonding active energy 0.1 to 10 parts by mass of a perfluoropolyether of the polymerizable group, and (c) 1 to 20 parts of the formed mass of a radical polymerization initiator is cured curable composition produced by the active energy ray. The high hardness hard coat layer of claim 1, wherein the inorganic fine particles of the component (B) are particles having an average particle diameter of 10 to 100 nm. The high hardness hard coat layer of claim 1 or claim 2, wherein the inorganic fine particles of the component (B) are cerium oxide fine particles. The high-hardness hard-coating laminate according to any one of Claims 1 to 3, wherein the poly(oxyperfluoroalkylene) group of the perfluoropolyether of the above component (b) has a group of -[ OCF ₂ ]- and -[OCF ₂ CF ₂ ]- are used as the basis of the repeating unit. The high-hardness hard-coating laminate according to any one of Claims 1 to 4, wherein the poly(polyoxyalkylene) group of the perfluoropolyether of the above component (b) is a poly(ethylene oxide) group. . The high hardness hard coat layer according to any one of Claims 1 to 5, wherein the polyfunctional monomer of the above component (A) is a polyfunctional (meth) acrylate compound and a polyfunctional amine group. At least one selected from the group consisting of formate (meth) acrylate compounds. The high-hardness hard-coating laminate according to any one of Claims 1 to 6, wherein the polyfunctional monomer of the aforementioned component (a) is a polyfunctional (meth) acrylate compound and a polyfunctional amine group. At least one selected from the group consisting of formate (meth) acrylate compounds. The high-hardness hard-coating laminate according to any one of Claims 1 to 7, wherein the polymerization initiator of the component (C) which generates a radical via an active energy ray is a polymerization of an alkyl phenone. Starting agent. The high-hardness hard-coating laminate according to any one of Claims 1 to 8, wherein the polymerization initiator which generates a radical via the active energy ray of the component (c) is an alkyl phenone polymerization. Starting agent. A method for producing a high-hardness hard-coating laminate comprising a primer layer on a surface of at least one of the substrates, and a hard coat layer of a hard coat layer on the hard coat layer above the primer layer A manufacturing method comprising the steps of: forming a coating film by coating a composition for forming a primer layer on a substrate; and irradiating the coating film for forming the composition for forming the primer layer with an active energy ray to harden the coating film And forming a primer layer, coating the curable composition on the primer layer to form a coating film, and irradiating the coating film of the curable composition with an active energy ray to harden the coating film. a step of forming a hard coat layer; the primer layer-forming composition contains: (A) selected from the group consisting of an active energy ray-curable polyfunctional monomer and an active energy ray-curable polyfunctional polymer 100 parts by mass of the polyfunctional compound, (B) 100 to 1,000 parts by mass of the inorganic fine particles, and (C) a total of 100 parts by mass of the polymerization initiator which generates a radical via the active energy ray with respect to the component (A) and the component (B) 1 to 20 parts by mass, the inorganic fine particles of the component (B) are particles having an active energy ray polymerizable group; and the curable composition contains (a) an active energy ray-curable polyfunctional monomer 100 mass. And (b) a molecular chain containing a poly(oxoperfluoroalkylene) group at both ends via a poly(oxyalkylene) group, or sequentially a poly(oxyalkylene) group and an amine group The formate bond group, 0.1 to 10 parts by mass of the perfluoropolyether bonded to the active energy ray-polymerizable group, and (c) 1 to 20 parts by mass of a polymerization initiator which generates a radical via an active energy ray.