TW200904899A - Composition and method of forming protecting film, laminate and method for manufacturing same - Google Patents

Abstract

This invention provides a method of forming protecting film in short time, and the said method could form inorganic transparent protecting film with the properties of film of wearing resistance and like. The said method of forming protecting film is to coat the photocureable composition containing aromatic sulfonium acid generator (B) of formula (1) and at least one kind of (A) selected from siloxane oligomer, organic silane series and alkyl silicate series on a substrate, and then to cure the photocureable composition with irradiating. (wherein R1, R2, R3 represent H, organic group of 1 to 10 carbon numbers, halogen or hydroxyl respectively; R4 represent aliphat alkyl of 1 to 10 carbon numbers; R5 represent aromatic alkyl or aromatic alkyl with substituent; X- represent counter anion. )

Description

[Technical Field] The present invention relates to a method for forming a protective film of an excellent transparent protective film capable of forming scratch resistance in a short period of time, a composition used in the method, and a protective film formed thereon The laminated body and its method of production. [Prior Art] In recent years, transparent plastic materials such as acrylic resin and polycarbonate resin which are excellent in crush resistance and light weight have been widely used in place of transparent glass. However, when the transparent plastic material is compared with glass, the surface hardness is low, and there is a problem that the surface is easily injured. Therefore, in the past, many attempts have been made to improve the scratch resistance of plastic materials. One of the most common methods, there is a widely known method (refer to Patent Documents 1, 2), which utilizes the hydrolysis of an alkoxydecane compound and subsequent condensation reaction to form a bond having a decane on the surface of the substrate. A method of protecting a film composed of an inorganic polymer. However, in such a method, since it takes tens of minutes to several hours of heating time to form the protective film, there is a problem in productivity. In order to solve such problems, for example, there is a proposal (for example, refer to Patent Documents 3 and 4) to disclose a composition containing a decyl alcohol group having a siloxane skeleton in a molecule and having reactivity, an alkoxy decane. A moxa oxide oligomer such as a base or an active energy-inductive cationic polymerization initiator is used as an essential component, and is cured by irradiation of an active energy ray to form a protective film in a short time. Specifically, the composition is coated on a substrate by irradiating an active energy ray such as ultraviolet ray 200904899 and an acid generated by a cationic polymerization initiator as a catalyst, and in the academy alcohol base, A sand oxide bond is formed and hardened to form a protective film. According to this method, although the film can be formed in a short period of time, the physical properties of the protective film obtained in accordance with the type and amount of the active energy ray-initiating cationic polymerization initiator to be used and the irradiation method of the active energy ray are significant. The change 'can't show the problem of physical properties such as scratch resistance. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. 5-8-9 - 1 0695 No. 8 SUMMARY OF INVENTION Technical Problem The present invention has been made to solve the above prior art. That is, an object of the present invention is to provide a protective film forming method, a composition used in the protective film forming method, and a laminated body formed by forming the protective film, which can form a resistant film in a short time. An inorganic transparent protective film having excellent film properties such as scratch resistance. Means for Solving the Problem In order to achieve the above object, the inventors of the present invention repeated the results of intensive deliberation, and found that the aromatic mirror salt-type acid generator of a specific structure can form a chopped oxygen bond very efficiently by irradiating the active energy ray. An active energy ray-curable group 200904899 containing a compound obtained by forming a specific oxyalkylene bond such as a decane oxide oligomer and an aromatic mirror salt type acid generator having a specific structure is applied to the substrate, and the activity is irradiated. The energy ray can be hardened in a short time to form a protective film having excellent film properties, and the present invention has been completed. That is, the present invention is a method for forming a protective film by coating at least one (A) selected from the group consisting of a siloxane oxide, an organic decane, and an alkyl phthalate, and a general formula (1) ) the aromatic sulfonium-type acid generator (B)' shown and hardens the photocurable composition by light irradiation.

(wherein R1, R2 and R3 each represent hydrogen, an organic group having 1 to 10 carbon atoms, a halogen group or a hydroxyl group, R4 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R5 represents a substituent which may have a substituent. The aromatic hydrocarbon group, χ_ is a relative anion). Further, the present invention is a method for forming a protective film, wherein when the active energy ray hardening composition is cured by irradiation of an active energy ray, when the active energy ray is irradiated, after the active energy ray is irradiated, or both, The active energy ray-curable composition is heated. Further, the present invention is a composition for active energy ray hardening, which comprises at least one selected from the group consisting of a siloxane oxide, an organic decane, and an alkyl phthalate (A), and a formula (1) ) an aromatic phosphonium salt type acid generator (B),

200904899 (wherein R1, R2 and R3 each represent hydrogen, an organic group having 1 to 10 carbon atoms, a hydroxy group or a hydroxyl group, R4 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R5 means that it may have a substitution. The aromatic hydrocarbon group, the X' system represents a relative anion). Furthermore, the present invention relates to a laminated body comprising a cured film of the composition for active energy ray hardening on the surface of a substrate. Further, the present invention relates to a method for producing a laminate in which a protective film is provided on a surface of a substrate by the above-described method for forming a protective film. According to the present invention, an inorganic protective film excellent in appearance, transparency, scratch resistance, and the like can be formed in a short period of time. [Embodiment] The component (A) of the active energy ray-curing composition of the present invention is at least one selected from the group consisting of a siloxane oxide oligomer, an organic decane, and an alkyl phthalate. The oxirane oligomer used in the present invention contains an acid derived from an aromatic sulfonium type acid generator (B) as a catalyst in a molecule containing a decane bond as a main skeleton and irradiated with light. An oligomer of a decyl alcohol group or an alkoxycarbenyl group which can be condensed. The oligomer-containing stanol group is condensed with a stanol group or an alkoxycarbenyl group to form a decane bond. The alkoxyalkyl group containing an oligomer can also be directly bonded to a stanol group, and can also be condensed with a stanol group or an alkoxycarbenyl group to form a decane bond after being hydrolyzed to a stanol group. The alkoxycarbenyl group may, for example, be methoxymethylidene alkyl group, ethoxy group 200904899 formamyl group or propoxymethyl group. From the viewpoint of the hydrolysis rate of the hydrolysis, the condensation rate is preferably methoxymercaptoalkyl or ethoxymethylcarbonyl. The molecular weight of the decane oligomer is not particularly limited. The weight average molecular weight is preferably 500 to 50, preferably in the range of ruthenium. When the weight average molecular weight is 50,000 or more, the film formability of the composition can be improved, and the scratch resistance and crack resistance of the obtained protective film can be improved. Further, by 50 or less, the uniformity and transparency of the obtained protective film can be improved. In particular, the weight average molecular weight is from 800 to 10, more preferably in the range of ruthenium. The oxirane oligomer may be used singly or in combination of plural kinds. The oxirane oligomer can be used as it is, and can be used as a raw material by various commercially available decanes or alkyl phthalates, and can be synthesized by hydrolysis and condensation. It is preferred that the organic decane represented by the formula (2) and the compound of any one or more of the alkyl esters of the formula (3) are hydrolyzed and precipitated. R6aSi(OR7)4.a (2) (wherein R6 represents an organic group having 1 to 10 carbon atoms, R7 represents a carbon number] 5 or an alkyl group having a carbon number of 1 to 4' a represents 〇 An integer of any of ~3, R8 — Ο OR10 ISi — Ο IOR11 R9 (3) n (wherein R8, R9, R1Q, and R11 each independently represent an alkyl group of 1 to 5-10-200904899 η It is an integer representing any of 2 to 20.) Specific examples of the organic decanes include tetraethoxydecane, tetramethoxydecane, methyltriethoxydecane, methyltrimethoxydecane, phenyltriethoxydecane, and phenyltrimethoxydecane. , vinyl triethoxy decane, vinyl trimethoxy decane, 2-(3,4-ethoxycyclohexyl)ethyl triethoxy decane, 2-(3,4-ethoxycyclohexyl) Ethyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxy Decane, 3-methacryloxypropyltrimethoxydecane, 3-propenyloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, p-vinylalkylene Ethoxy decane, p-vinyl alkyltrimethoxy decane, dimethyl diethoxy decane, dimethyl dimethoxy decane, and the like. Among them, from the hydrolysis and condensation reaction, 'tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, dimethyl dimethoxy decane, two Methyldiethoxydecane, phenyltrimethoxyanthracene and phenyltriethoxycasting temple are preferred. Specific examples of the alkyl phthalate include methyl decanoate, ethyl decanoate, isopropyl citrate, n-propyl decanoate, isobutyl phthalate, and n-butyl phthalate. Among these, from the viewpoint of the hydrolysis and the condensation reaction, it is preferred that all of R8 to R11 are methyl decanoate and all of r8 to rM are ethyl ethyl oleate. The organodecanes of the component (A) of the present invention are exemplified by the organodecanes represented by the formula (2) which are exemplified above as the raw material of the decane oxide oligomer. In the organic decane-based decanoic acid-based vinegar of the component (A) of the present invention, the alkyl phthalate ester represented by the above formula exemplified as the raw material of the decane oxide oligomer is exemplified. class. In the present invention, the aromatic onium salt type acid generator (B) represented by the formula (1) is used.

(wherein R1, R2 and R3 each represent hydrogen, an organic group having 1 to 1 carbon atoms, a halogen group or a hydroxyl group, R4 represents an aliphatic hydrocarbon group having 1 to 1 carbon number, and R5 represents a substitution or substitution. The aromatic hydrocarbon group of the group, X. represents a relative anion). Specific examples of X- are SbF〆, PF6_, AsF6·, BF4·, CF3S〇3· and the like. In terms of activity, SbF6_ and PF6_ are preferred. By using the aromatic sulfonium salt type acid generator represented by the formula (1), the siloxane oxide-based inorganic film can be efficiently formed in a short time by light irradiation. Good film properties can be obtained as compared with the case where a photoacid generator is applied using other light sensations. Even when an active energy ray-curable composition containing an organic decane or an alkyl phthalate and a usual active energy ray-inducing cationic polymerization initiator is applied to a substrate and irradiated with an active energy ray, the film formation property of the composition is low. , The protective film cannot be formed. However, the active energy ray-inducing cationic polymerization initiator can form a protective film by using the aromatic sulfonium salt type acid generator represented by the general formula (1) to improve the film formability of the composition. -12- 200904899 When organic decanes or alkyl phthalates are used, these may be used singly or in addition to the water necessary for hydrolysis. The component (A) is preferably at least one selected from the group consisting of a halogenated alkane oligomer and at least one selected from the group consisting of an organic decane and an alkyl phthalate. By increasing the content of the siloxane oligomer, the crack resistance of the cured film can be improved. By increasing the content of organic decanes or alkyl phthalates, the scratch resistance and hardness of the cured film can be improved. When at least one of the siloxane oxide oligomers and at least one selected from the group consisting of organic decanes and alkyl phthalates is used, only the combined materials may be used, and organic decanes or alkyl citrates may be added. The ester is used by adding water necessary for water decomposition. Further, when the active energy ray-curable composition is cured by irradiation with an active energy ray, the film performance can be improved when the active energy ray is irradiated, after the active energy ray is irradiated, or both are heated. Specific examples of the aromatic onium salt type acid generator include, for example, benzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, and hexafluoroarsenic acid. .Benzyl hydroxyphenylmethyl hydrazine, benzyl-4-hydroxyphenylmethyl hydrazine tetrafluoroborate, methoxy sulfonic acid; -4-methyl phenylmethyl mirror, p-toluene acid expansion; 4-Hydroxyphenylmethylhydrazine, benzyl benzyl hydroxy-4-hydroxyphenylmethyl hydrazine, methylbenzyl-4-hydroxyphenylmethyl sulfonium hexafluorophosphate, hexafluoroantimonic acid 4 醯Oxyphenyl benzyl methyl hydrazine, hexafluoroantimonic acid 4-ethoxylated phenyl dimethyl hydrazine, hexafluoroantimonic acid benzyl 4-methyl methoxy phenyl methyl hydrazine, hexafluoroantimonic acid benzyl 2-methyl-4-hydroxyphenylmethyl mirror, hexafluoroarsenic acid kaki-3-chloro-4-phenylmethyl mirror, hexafluoro acid; -3-methyl-4- 5--5-butylphenylmethylhydrazine, hexafluoro-petic acid 4-methoxybenzyl 4-hydroxyphenylmethylhydrazine, hexafluoroantimonate dibenzyl-4-hydroxyphenyl-13 - 200904899 锍, dibenzyl-4-hydroxyphenylphosphonium hexafluorophosphate, 4-ethenyloxyphenyl 1-carbyl hexafluoroantimonate, six gas recording one card base-4-methyl basic microscope Six gas chain acid nitrobenzyl-4- Hydroxyphenylmethylhydrazine, hexafluoroantimonic acid 3,5·dinitrobenzyl-4-hydroxyphenylmethylhydrazine, hexafluoroantimonic acid/3-naphthylmethyl-4 hydroxyphenylmethylhydrazine , hexafluorophosphoric acid/3-naphthylmethyl-4-hydroxyphenylmethylhydrazine, hexafluoroantimony acid α-naphthylmethyl-4-hydroxyphenylmethylhydrazine, hexafluorophosphorylnaphthylmethyl-4 -Hydroxyphenylmethylhydrazine and the like. Among them, from the viewpoint that the curing speed of light irradiation is fast and the scratch resistance of the obtained protective film is good, it is preferable to have a structure in which a hydroxyphenyl group is directly bonded to a sulfur atom (S). Specific examples thereof include hexafluoroantimonic acid/3-naphthylmethyl-4-hydroxyphenylmethylhydrazine, hexadefluorophosphorylnaphthylmethyl-4-hydroxyphenylmethylhydrazine, and hexafluorodecanoic acid naphthyl 4-Hydroxyphenylmethylhydrazine, bismuth hexafluorophosphate: -naphthylmethyl-4-hydroxyphenylmethylhydrazine, hexafluoroantimonic acid methylbenzyl-4-hydroxyphenylmethylhydrazine, hexafluoro Methylbenzyl-4-hydroxyphenylmethylhydrazine, benzyl-4-hydroxyphenylmethylhydrazine hexafluoroantimonate and benzyl-4-hydroxyphenylmethyl hexafluorophosphate. The aromatic onium salt type acid generator can be, for example, a phenylmethyl sulfide having a phenylmethyl sulfide or a substituent, an aromatic methyl chloride or an aromatic methyl chloride having a substituent. After reacting at 35 ° C for 20 hours in the presence of water, ethyl acetate was added thereto, and salt exchange (for example, NaSbF 6) was carried out at 150 t for 30 minutes, and it was produced by a well-known method such as concentration of an ethyl acetate layer. Further, a commercially available product can also be used. Commercially available aromatic sulfonium-type acid generators represented by the formula (1) include, for example, "SANEIDO SI-6", "SANEIDO SI-80", "SANEIDO SI-l〇〇j, "SANEIDO Sl" -ll〇" (above, -14- 200904899 Sanxin Chemical Industry Co., Ltd. 'trade name'). The amount of the aromatic sulfonium-type acid generator (B) is not particularly limited, and is 100 parts by mass based on the solid content of the component (A) (the total of the decane oligomer, the organodecane, and the alkyl phthalate). The fraction is preferably in the range of 0.01 to 10 parts by mass. However, the solid content referred to herein means a compound obtained by completely hydrolyzing and condensing the component (A), and the same applies to the following description. When the hydrolyzation and the polycondensate (hereinafter referred to as the following) are contained, it is preferably in the range of 0.01 to 10 parts by mass based on 100 parts by mass of the solid component of (A) and 100 parts by mass of the solid component of (H). When the amount is 0.01 parts by mass or more, light irradiation can be hardened for a short period of time, and a good protective film can be obtained. In addition, when it is 10 parts by mass or less, the protective film obtained by curing tends to have less coloration and good surface hardness or scratch resistance. In addition, the amount of the protective film which is excellent in curability and can provide good performance is a solid relative to the component (A) (a total of a siloxane oligomer, an organic decane, and an alkyl phthalate). 100 parts by mass of the component is more preferably in the range of 0.05 to 5 parts by mass. The composition used in the present invention may contain other reactive compounds insofar as the effects of the present invention are not impaired. Specifically, it is an epoxy compound (C) capable of cationic polymerization, a vinyl ether compound (D), and the like. Further, it may contain a monomer (E) having a radical polymerizable double bond and a photopolymerizable radical polymerization initiator (F). The epoxy compound (C) is not particularly limited as long as it contains an epoxy group in the molecule. Specific examples thereof include ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether, and triethylene glycol propylene glycol diepoxypropyl-15-200904899 ether. , polypropylene glycol diepoxypropyl ether, hydrazine, 4-butanediol diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, ι, 6-hexanediol diepoxypropyl ether, glycerin Diepoxypropyl ether, diglycerol tetraepoxypropyl ether, trimethylolpropane triepoxypropyl ether, 2,6-dioxypropyl phenyl ether, sorbitol triepoxypropyl ether 'Trimeric isocyanate triglycidyl ester, diepoxypropylamine, diepoxypropylbenzylamine, diepoxypropyl phthalate, bisphenol A diglycidyl ether, dibutyl butyl Diene, dicyclopentadiene dioxide, 3,4-epoxycyclohexenecarboxylic acid and ethylene glycol diester, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane Carboxylic acid ester, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, adipic acid bis(3,4-epoxy ring Hexylmethyl)ester, epoxidized dicyclopentadienol epoxypropyl ether, neopentyl alcohol polyepoxypropyl ether, bisphenol A epoxy resin An adduct with ethylene oxide, a phenol novolac type epoxy resin, and a cresol novolak type epoxy resin. Among them, since the curing rate is fast and the abrasion resistance of the obtained protective film is good, an aromatic epoxy compound containing two or more epoxy groups in the molecule is preferred. The epoxy compound may be used alone or in combination of two or more. The vinyl ether compound (D) is a compound containing a vinyl ether group in the molecule. Specific examples of the vinyl ether compound include n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, octadecyl vinyl ether, and cyclohexyl group. Vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, 1,9-nonanediol divinyl ether, cyclohexyl Glycol divinyl ether, cyclohexane dimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol vinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, trimethylolpropane triethylene Ether and -16- 200904899 pentaerythritol tetravinyl ether and the like. When the monomer (E) having a radical polymerizable double bond has a radical polymerizable double bond, the structure thereof is not particularly limited. In particular, a monofunctional or polyfunctional (meth) acrylate compound having a high polymerization rate and containing an acryl fluorenyl group or a methacryl fluorenyl group in the molecule is preferred. Specific examples of the monofunctional (meth) acrylate compound include phenyl (meth) acrylate, benzyl (meth) acrylate, phenyl ethyl (meth) acrylate, and phenoxy B (meth) acrylate. Ester, p-cumylphenol oxirane modified (meth) acrylate, isodecyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Dicyclopentyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (meth)acrylic acid Butyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-hexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth)acrylic acid Hydroquinone ester and phosphorus ethyl (meth)acrylate. Specific examples of the polyfunctional (meth) acrylate compound include ethylene glycol di(meth) acrylate, diethylene glycol di(meth) acrylate, triethylene glycol di(meth) acrylate, and polyethylene B. Diol (meth) acrylate, tri-propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, 1,3-butanediol Di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2,2-bis[4-(methyl)propene oxide Phenyl]-propane, 2,2-bis[4-(methyl)propene oxime-17- 200904899-ethoxyethoxyphenyl]-propane, 2,2-bis[4-(methyl) propylene oxime Oxydiethoxyphenyl]-propane, 2,2-bis[4-(methyl)propenyloxypentaethoxyphenyl]-propane, 2,2-bis[4-(methyl) Propylene methoxyethoxy-3-phenylphenyl]-propene, bis[4-(methyl)propanoid thiol]sulfate, bis[4-(methyl)propanyloxybenzene Base]-Maple, bis[4-(methyl)acryloxyethoxyethoxyphenyl]-anthracene, bis[4-(methyl)acryloxyloxydiethyl Phenyl]-indole, bis[4-(methyl)-propyl decyloxypentaethoxyphenyl]-indole, bis[4-(methyl) propylene methoxy ethoxy-3-phenyl Phenyl]-indole, bis[4-(methyl)acryloxyethoxyethoxy-3,5-dimethylphenyl]-indole, bis[4-(methyl)acryloxyphenyl] - bismuth, bis[4-(methyl) propyl decyloxyethoxy phenyl]-sulfuric acid, bis[4-(methyl)-propyl decyloxypentaethoxyphenyl]-thioether, double [4-(Methyl)acryloxyethoxyethoxy-3-phenylphenyl]-thioether, bis[4-(methyl)acryloxyethoxyethoxy-3,5-dimethylbenzene - sulfuric acid, 2,2-bis[4.(methyl)propionic acid oxyethoxy-3,5-dibromophenylpropane], trimethylolpropane tri(meth)acrylate, Tetramethylolmethane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Among them, polyfunctional (meth) acrylate is more preferable because of good curability and excellent scratch resistance of the obtained protective film. The monomer (E) containing a radical polymerizable double bond may be used alone or in combination of plural types. The photo-inductive radical polymerization initiator (F) is a component which induces an active radical species such as visible light rays or ultraviolet rays to generate an active radical species to cause polymerization of a monomer (E) containing a radical polymerizable double bond. Specific examples of the photo-sensitive radical polymerization initiator (F) include 3,3-dimethyl- 4--18- 200904899 methoxy-diphenyl ketone and benzyl dimethyl ketal. p-Isoamyl dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, diphenyl ketone, p-methoxydiphenyl ketone ' 2,2-diethoxy 'ethyl benzene, 2, 2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, methyl phenyl glyoxylate, ethyl phenyl glyoxylate, 2-hydroxy- 2-methyl-1-phenylpropan-1-one, 2-methyl-^[4-(methylthio)phenyl]-2-sodium acetonide-1,2,4,6-trimethyl Benzopyridinium diphenylphosphine oxide and the like. Among them, from the fast curing rate, methyl phenyl glycolate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2, 2 _ Dimethoxy-1,2-diphenylethane-1-one, benzyldimethylketal and 2,4,6-trimethylbenzimidyldiphenylphosphine oxide are preferred. These photo-sensitive radical polymerization initiators (F) may be used alone or in combination of two or more. The amount of the photo-induced radical polymerization initiator (F) is not particularly limited, and is preferably in the range of 1 to 10 parts by mass based on 100 parts by mass of the component (E). In the case where the curing rate of the irradiation active energy ray is fast, the amount is preferably 0.01 part by mass or more, and the abrasion resistance of the film is preferably 1 part by mass or less. It is more preferably in the range of 5 to 5 parts by mass. The active energy ray-curable composition used in the present invention is also preferably a polymer compound (G). By blending the polymer compound (G), it is possible to impart flexibility to the film to suppress the occurrence of cracks. The polymer compound (G) may, for example, be a polyacrylic polymer, a polyethylene polymer, a polyether polymer or a polydialkylsiloxane (anthracene resin). Among them, a polyether polymer is preferably used, and specific examples thereof include polyethylene glycol. The amount of the polymer compound (G) to be blended is not particularly limited, and is 100 parts by mass based on the solid content of the components (the total of the oxane oligomer, the organodecane, and the alkyl decanoate) of (A) -19-200904899. It is preferably in the range of 0 to 50 parts by mass, more preferably in the range of 1 to 1 part by mass. Further, in the active energy ray-curable composition used in the present invention, polymer microparticles, colloidal cerium oxide, colloidal metal, and photosensitizer (for example, an anthraquinone compound, a thioxanthone compound, or the like) may be blended as necessary. Lanthanide compounds, naphthalene compounds and lanthanoid compounds, etc., pigments, dyes, pigments, pigment dispersants, flow regulators, leveling agents, antifoaming agents, UV absorbers, light stabilizers, antioxidants, heat Inductive radical polymerization initiator, inductive cationic polymerization initiator, and the like. In order to improve the abrasion resistance of the cured product of the active energy ray-curable composition used in the present invention, the organic sand garden of the organic sand chamber represented by the general formula (4) and the tannic acid represented by the general formula (5) are contained. It is preferred that the compound of any one or more of the alkyl esters is hydrolyzed and the polycondensate (H) of colloidal cerium oxide having a number average particle diameter of 5 to 200 nm. When the component (H) is contained, the solid content of the solid component of the component (A) (the total of the decane oligomer, the organodecane, and the alkyl phthalate) and the solid component of the component (H) are 9: 1~5: 5 is good' with 8: 2~6: 4 is especially good. R12bSi(OR13)4-b (4) (wherein R12 represents an organic group having 1 to 10 carbon atoms, r13 represents an alkyl group having 1 to 5 carbon atoms or a fluorenyl group having 1 to 4 carbon atoms, and b represents 〇~ Integer of 3) -20- 200904899 R14 〇, OR16 ISi-0 I OR17 R15 (5) m (wherein r14, R15, R16 and R17 each independently represent an alkyl group of 1 to 5, and m represents 2 Specific examples of any of ~20) ° Specific examples of the organic decanes and alkyl phthalates include the above-mentioned ones. The colloidal cerium oxide may, for example, be an aqueous silica sand sol in which cerium oxide microparticles are uniformly dispersed in water, and an organic cerium oxide sol which is dispersed in a dispersion solvent. Examples of the dispersing solvent include alcohols such as methanol, ethanol, 2-propanol, 1-butanol, and ethylene glycol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; methyl acetate and acetic acid; An glycerin such as ethyl acetate or butyl acetate, or an aromatic hydrocarbon such as benzene, toluene or xylene, or a glyceryl ether such as ethylene glycol monoalkyl ether or propylene glycol monoalkyl ether. The dispersing solvent may be used singly or in combination of two or more.

The number average particle diameter in the colloidal ceria is 5 to 200 nm. By using a colloidal silica sand having a number average particle diameter of 5 nm or more, it is possible to impart scratch resistance and hardness to the hardened film. Further, the transparency of the cured film can be controlled by using a colloidal cerium oxide having an average particle diameter of 200 nm or less. The number average particle diameter of the colloidal cerium oxide is preferably from 10 to 100 nm. Further, the method of measuring the number average particle diameter is, for example, a method of observation using an electron microscope. The active energy ray-curable composition used in the present invention may contain an organic solvent for the purpose of adjusting the concentration of the solid component, improving the dispersion stability, and coating properties, and enhancing the adhesion to the substrate, etc. - 21 - 200904899. The organic solvent may, for example, be an alcohol, a ketone, an ether, an ester, a cellosolve or an aromatic compound. Specific examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol 't-butanol, benzyl alcohol, 2-methoxyethanol, and 2- Ethoxyethanol, 2-(methoxymethoxy)ethanol, 2-butoxyethanol, decyl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, di-propanol, di-propanol monomethyl ether Alcohol monoethyl acid, triethylene glycol monomethyl ether, diacetone alcohol, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone ' 2- Heptone, 4-heptanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, acetophenone, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, two Hexyl ether 'anisole, phenethyl ether, tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, two Glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, glyceryl ether, methyl acetate, ethyl acetate, propyl acetate, acetic acid Propyl ester, butyl acetate, isobutyl acetate, second butyl acetate, amyl acetate, isoamyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate Ester, methyl propionate, ethyl propionate, butyl propionate, 7-butyrolactone, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-phenoxyethyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, benzene, toluene and xylene. These organic solvents may be used singly or in combination of two or more. -22- 200904899 The content of the organic solvent is preferably in the range of 〇1 to 1 part by mass, based on 100 parts by weight of the total of the components (A) to (Η), in terms of 〇1 to 1 part by mass. The range is better. When the amount is less than 1,000 parts by mass, the problem that the coating film is thinned due to the low solid content is less likely to occur, and the protective film having a good scratch resistance tends to be obtained. The active energy ray-curable composition used in the present invention can be applied to the surface of a material made of plastic or the like at a thickness of about 0.5 to 100 μm, for example, and then irradiated with an active energy ray to be cured. Protect the film. The application of the active energy ray-curable composition can be carried out by a previously known method, for example, using a sprayer, a roll coater, a gravure coater, a flexographic printer, a screen printer, a spin coater, a coater, and an electrostatic coating. . Examples of the active energy ray include vacuum ultraviolet rays, ultraviolet rays, visible rays, and the like. Specific examples include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, incandescent bulbs, xenon lamps, halogen lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, gallium lamps, and excimer lasers. Light, light, etc. as a light source. Among them, light with a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, and a halogenated metal lamp as a light source is preferred. The activation ray can be used alone or in combination of different types. Further, the active energy ray-curable composition used in the present invention can be heated by irradiation with an active energy ray, and can be effectively hardened. In general, when such a reaction using a photoacid generator is known, it is possible to promote hardening by irradiation with light -23-200904899 or heating after light irradiation. However, in the case of the component (A) of the present invention, in addition to the acid generator of the present invention, it is not observed that heating has a large effect on promoting hardening. On the other hand, when the acid generator of the present invention is used, it is observed that heating has a large promoting effect. Heating can be performed by heating the active energy ray, or by heating the active energy ray. Further, it is also possible to heat both of them. The heating can be performed by using an infrared heater or the like, or the hot air can be circulated to heat. Further, the heating in the case of irradiating the active energy ray of the present invention includes not only heating simultaneously with irradiation but also heating the curable composition before irradiation, and irradiating the active energy ray with the curable composition at a high temperature. When the heating is performed before the irradiation of the active energy ray, the temperature of the active energy ray-curable composition is preferably in the range of 50 to 100 °C. It is preferable that the temperature of the active energy ray-curable composition is from 50 to 100 ° C when it is heated simultaneously with the irradiation activity. When heating after irradiating the active energy ray, it is preferred to heat it at 50 to 100 ° C for 1 to 60 minutes. In the present invention, the composition can be applied as a coating material or an ink material to a metal material such as a metal plate or a metal can, a natural material such as paper or wood, an inorganic material such as ceramics, an acrylic resin, or a polymer. A plastic molded product such as a carbonate resin, a film such as a film of PET or polyolefin, a composite material such as an electrodeposition coating plate or a laminate, and the like are formed, and a protective film is formed on the substrate by curing. EXAMPLES Hereinafter, the examples of the present invention will be described in detail, but the present invention is not limited thereto. The "parts" described below indicate "parts by mass. -24 - 200904899 &lt;Synthesis Example&gt;&lt;Synthesis Example 1 &gt; Synthesis of siloxane oxide oligomer A 1 18.0 g of methyltrimethoxy sand was added.垸 (Shin-Etsu Chemical Industry Co., Ltd., molecular weight 136·2), 2.97 g of phenyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 198.3), 1 〇. 异丙 isopropyl alcohol, water' and stirring A uniform solution was obtained, and 15.9 g of water was added thereto, and the mixture was heated at 80 C for 9 hours while stirring, and then hydrolyzed and condensed to become an ophthalmic oligomer. Further, isopropyl alcohol was added to make the whole of 54_1 g. When the weight average molecular weight is measured by GPC, the molecular weight of the polyphenylene carbonate is about 2, 〇〇〇. However, the solid is referred to herein as a solid component concentration of 20% by mass. The component concentration means the mass fraction of the azide oligomer obtained at the time of completely hydrolyzing and condensing the entire solution, and the following alumoxane oligomers A2 and A3 are also the same. <Synthesis Example 2> The synthesis of the oxirane oligomer A2 is converted into 1 0 · 0 g Methyl decanoate having a cerium oxide concentration of 53% by mass (manufactured by COLCOAT (manufactured by COLCOAT, average about heptamer, average molecular weight of about 7 89, trade name: METHYLSILICATE 53 A) and 17.3 g of methyltrimethoxydecane) Add 10.0 g of isopropyl alcohol and stir to form a homogeneous solution. Also, add 1 〇. 5 g of water and heat at 80 ° C for 3 hours while stirring to carry out hydrolysis and condensation to form a low oxime. Further, isopropyl alcohol was added in an amount of 69.2 g to obtain a decane alkane oligomer A2 having a solid concentration of 20% by mass, and when the weight average molecular weight was measured by GPC, the molecular weight converted to polystyrene was about 6,500. &lt;Synthesis Example 3&gt; Synthesis of oxane oligomer A3-25-200904899 16.34 g of methyltrimethoxydecane, 5.95 g of phenyltrimethoxyanthracene, 10.0 g of isopropyl alcohol, and stirred to be uniform were added. In addition, 1 6 · 2 g of water was added and heated at 80 ° C for 9 hours while stirring to carry out hydrolysis and condensation to form a decane oligomer, and isopropyl alcohol was added to make the whole 59.6 g. To obtain a solid concentration of 20% by mass When the weight average molecular weight is measured by GPC, the molecular weight converted to polystyrene is about 1,700. <Synthesis Example 4> Hydrolysis and polycondensation of organic decane and colloidal cerium oxide Synthesis of the material 1 in a 500 ml eggplant flask with a stirrer and a cooler. Adding isopropyl alcohol dispersed colloidal cerium oxide (manufactured by Nissan Chemical Industries Co., Ltd., trade name: SNOTEX IPA- ST-L), 6.8 g of methyltrimethoxydecane, 5.4 g of pure water and 74.6 g of isopropyl alcohol, and heated and stirred at 80 ° C for 4 hours in a water bath to carry out hydrolysis and condensation to obtain a solid concentration of 2 0% by mass of the polycondensate Η 1 solution. However, the term "solid content concentration" as used herein means the hydrolysis and condensation of organic decane or alkyl decanoate and colloidal cerium oxide obtained by total hydrolysis and condensation. The same applies to the following Η2 and Η3. &lt;Synthesis Example 5 &gt; Synthesis of water-decomposed alkyl phthalate and colloidal cerium oxide, synthesis of polycondensate Η 2 Addition of 100 g colloidal cerium oxide in a 500 ml eggplant flask having a stirrer and a cooler Propylene alcohol dispersion colloidal cerium oxide (manufactured by Nissan Chemical Industry Co., Ltd., trade name: SNOTEX IPA-ST), 11.75 g phthalic acid methyl -26-200904899 ester tetramer (COLCOAT (trade name), trade name: METHYLSILICATE 5 1), 9.0 g of pure water and 59.2 g of isopropyl alcohol' were heated and stirred at 80 ° C for 4 hours using a water bath to carry out hydrolysis and condensation to obtain a polycondensate H2 solution having a solid concentration of 20% by mass. &lt;Synthesis Example 6&gt; Synthesis of Compound A4: 14.72 g of methyltrimethoxysilane, 2 to 68 g of phenyldimethoxydecane, and 1.64 g of dimethyldimethoxydecane (TORAY-DOWCORNING) Molecular weight 120.2), 16.84 g of isopropyl alcohol and 14.12 g of pure water were added and stirred to obtain a compound A4 having a solid concentration of 20% by mass. However, the term "solid content concentration" as used herein means a hydrolyzed or polycondensate of an organic decane or an alkyl phthalate obtained by completely hydrolyzing and condensing the entire solution, in the following A5 to A7. The same is true. &lt;Synthesis Example 7&gt; Synthesis of Compound A5 In 17.73 g of methyltrimethoxydecane and 1.94 g of phenyltrimethoxydecane, 15.81 g of isopropyl alcohol, 15.1 g of pure water and stirring were added. The compound A 5 having a solid concentration of 20% by mass was obtained. &lt;Synthesis Example 8 &gt; Synthesis of Compound A 6 at 9.16 g of methyltrimethoxydecane, 3.08 g of phenyltrimethoxybutane, and 4.92 g of 3-glycidoxypropyltrimethoxydecane (Shin-Etsu Chemical) Industrial (stock) system, molecular weight 236.1), 21.64 g of isopropyl alcohol and 11.20 g of pure water were added and stirred to obtain a compound A6 ° having a solid concentration of 20% by mass. [Synthesis Example 9 &gt; Synthesis of Compound A7 at 1.78 g As a ceria having a concentration of 53% by mass of phthalic acid methyl -27-200904899 ester, 13.32 g of methyl trimethoxy decane, 2.42 g of phenyl trimethoxy decane, and 1.48 g of dimethyl dimethoxy decane, 16.92 was added. Isopropyl alcohol, 14.08 g of pure water, and stirred to obtain a compound A 7 having a solid concentration of 20% by mass. &lt;Synthesis Example 1 〇&gt; Hydrolysis of organic decane and colloidal cerium oxide, synthesis of polycondensate H3 In a 500 ml eggplant type flask equipped with a stirrer and a cooler, 100 g of colloidal cerium oxide was added thereto. Isopropanol dispersion colloidal cerium oxide (manufactured by Nissan Chemical Industry Co., Ltd., trade name: SNOTEX IPA-ST), 6.8 g of methyltrimethoxy decane, 5.4 g of pure water and 7 4.6 g of isopropyl alcohol, and The mixture was heated and stirred at 80 ° C for 4 hours in a water bath to carry out hydrolysis and condensation to obtain a polycondensate Η 3 solution having a solid concentration of 20% by mass. &lt;Example 1&gt; [Preparation of active energy ray-curable composition] The solid content of the oxime oligomer Α1 obtained in Synthesis Example 1 was 20% by mass (solid content) In a 10.0 part), 0.4 parts by weight of a 50% by mass 丫-butyrolactone solution of benzyl-4-hydroxyphenylmethyl hydrazine hexafluoroantimonate (solid content: 0.2 parts) and 10.0 parts of a solvent are mixed. Isopropanol, 15.0 parts of r-butyrolactone, 10.0 parts of butyl sedum (buty 1 ce 11 〇s ο 1 ve), 0.01 part of a leveling agent sand-based surfactant (TORAY-DOWCORNING) , trade name L-700 1 ), as an active energy ray-curable composition. [Formation of Photocurable Composition Film] The active energy ray-curable composition was appropriately dropped on an acrylate board (MITSUBISHI RAYON) having a length of 10-28-200904899 cm, a width of 10 cm, and a thickness of 3 mm. Co., Ltd., product name "ACRYLAIT EX"), applied by a hard coating method (using a bar coater No. 26), dried to a thickness of 3 to 4 μm, and naturally dried at room temperature for about 60 minutes. . [Formation of protective film] A high-pressure mercury lamp (manufactured by OAK Co., Ltd., UV irradiation device, HANDY-UV-1 2 00, QRU-2161) equipped with a conveyor of 120 W/cm was used, and the cumulative amount of light was 1000 mJ/cm 2 . Ultraviolet rays are hardened to obtain a protective film. The cumulative amount of light was measured using an ultraviolet light meter (manufactured by OAK Co., Ltd., UV-351 type). The maximum temperature of the sample irradiated with ultraviolet light is 3 3 t. [Evaluation of Film] The obtained protective film was evaluated by the following method. 1) Appearance The transparency, crack, and whitening of the acrylate plate having the protective film were visually observed, and the following criteria were used for evaluation. "〇": transparent and crack-free, whitening defects (good). "X": There are opaque parts, cracks, whitening and other defects (poor). 2) Film thickness The film thickness was measured by observing the cross section of the acrylate plate having the protective film using a scanning electron microscope. 3) Scratch resistance using # 〇0 〇〇 steel wool on the acrylate plate with the protective film, the surface of Table -29- 200904899 was rubbed and rubbed 10 times with a pressure of 9.8x1 04 Pa, and evaluated in Ixlcm according to the following criteria. The number of scars produced by the range. A: Scars (shiny face) B: 1 to 9 scars (glossy face) C+: Scars ~ 49 (glossy faces) C-: 50 to 99 scars (glossy faces) D: Scars 1 Above the root (glossy side) E: The shiny side disappears 4) Pencil hardness The pencil hardness of the protective film is evaluated in accordance with TIS-K5600 (pencil scratch test). As a result, the film system of the present embodiment has a good appearance and scratch resistance. The results are shown in Table 1. &lt;Examples 2 to 5&gt; The preparation of the active energy ray-curable composition and the photocurability were carried out in the same manner as in Example 1 except that the components (A) and (B) were prepared in accordance with Table i. Formation of a composition film, formation of a protective film, and evaluation of a film. The results are shown in Table 1. &lt;Example 6&gt; The preparation of the active energy ray-curable composition and the photocurable composition film was carried out in the same manner as in Example 1, and the sample was heated with a halogen lamp while irradiating ultraviolet rays. 7 (rc), the film was cured. Then, the film was evaluated in the same manner as in Example! The results are shown in Table 1. -30-200904899 &lt;Example 7 &gt; In the same manner as in Example 1, ' The formation of the active energy ray-curable composition and the photocurable composition film is carried out, and the film is cured by irradiation with ultraviolet ray. Further, it is post-cured using a hot air dryer and dried at 90 ° C for 1 〇 minute. The protective film was formed in the same manner as in Example 。. The results are shown in Table 1. &lt;Example 8&gt; In the same manner as in Example 6, the active energy ray-curable composition was prepared. The photocurable composition film was formed, and the film was cured by irradiation with ultraviolet rays. Further, it was post-cured using a hot air dryer and dried at 90 ° C for 10 minutes to form a protective film. Then, the film was evaluated in the same manner as in Example i. The results are shown in Table 1. <Comparative Examples 1 to 3> Except that the components (A) and (B,) were prepared in Table 2, and Examples In the same manner, the active energy ray-curable composition and the photocurable composition film were formed, and the film was cured by irradiation with ultraviolet rays, and the film was evaluated. The results are shown in Table 2. Comparative Example 4 &gt; In addition to the components described in Table (2) and (B,), the composition of Table 2 is adjusted, and the active energy ray-curable composition and photocurable composition are prepared. The protective film was formed by irradiating ultraviolet rays to form a protective film. The evaluation of the film was carried out in the same manner as in Example. The results are shown in Table 2. &lt;Comparative Example 5&gt; -31-200904899 In the same manner as in the seventh embodiment, the composition of the component (A) and the component (B') was prepared in the same manner as in the case of the seventh embodiment, and the formation of the active energy-generating material and the photocurable composition film was carried out. Hardened by the illuminating film, and After the aging, the protective film was formed to evaluate the film in the same manner as in Example 1. [Comparative Example 6 &gt; In addition to (A) component and (B') component formulation table 2 In the same manner as in Example 1, the formation of the protective active energy product and the photocurable composition film was carried out in the same manner as in Example 1, and the protective film was formed by curing the film and curing the film. Evaluation of the film was carried out. &lt;Comparative Example 7&gt; The preparation of the active energy product and the formation of the photocurable composition film were carried out in the same manner as in Example 1. Further, the photocuring was replaced by heating for 120 minutes. The film was evaluated in the same manner as in Example 1 in which the film was hardened. As a result, as seen from the examples and the comparative examples, in the case of the formation method of the present invention, it is possible to form a protective film having excellent externality by short-time light irradiation. On the other hand, when the acid generator is clearly known, it is difficult to exhibit good scratch resistance. In the case of the photocurable composition used in the present invention, it is known that the protective film is excellent in appearance and scratch resistance, and the line curable group is irradiated with ultraviolet rays. Subsequently, the results were as shown in Table 2, and the line hardening group was irradiated with ultraviolet rays. Subsequently, the results were as shown in Table 2, the line hardening group, and subjected to 90 °C. Subsequently, as shown. Protective film, scratch resistance, other light, as in Comparative Example 7, only heating -32- 200904899 [Table i]

Ingredients ΐ 1 2 3 4 5 6 7 8 (A) Ingredients (parts) (solid content (parts)) Α1 50.0 (10.0) Α1 50.0 (10.0) Α1 50.0 (10.0) Α1 50.0 (10.0) Α2 50.0 (10.0) Α1 50.0 (10.0) A1 50.0 (10.0) A1 50.0 (10.0) (B) Composition (parts) (solid content (parts)) Β1 0.4 (0.2) Β2 0.4 (0.2) Β3 0.4 (0.2) Β4 0.4 (0.2) Β1 0.4 (0.2) Β1 0.4 (0.2) B1 0.4 (0.2) B1 0.4 (0.2) UV irradiation (mJ/cm2) 1000 1000 1000 1000 1000 1000 1000 1000 Heating during UV irradiation - - - - - 70 °C - 7〇°c post-curing - - - - - - 90 °C '10 minutes 90. . 10 minutes Appearance 〇 〇 〇 〇 〇 〇 〇 〇 Film thickness (micron) 3.4 4.0 3.7 3.3 3.8 3.4 3.9 3.2 Scratch resistance C+ C+ C+ C+ Β Β B B Pencil hardness 5Η 5Η 5Η 5Η 5Η 4Η 6H 4H

[Table 2]

Ingredient Comparative Example 1 2 3 4 5 6 7 (A) Component A1 A1 A1 A1 A1 A1 A1 Formulation amount (parts) 50.0 50.0 50.0 50.0 50.0 50,0 50.0 (solid content (parts)) (10.0) (10.0) (10.0 (10.0) (10.0) (10.0) (10.0) (B) Component B1 Formulation amount (parts) - - - Ink - - 0.4 (solid content (parts)) (0.2) (B'戚分ΒΊ B'2 B , 3 ΒΊ B,1 B,1 Amount (parts) 0.4 0.4 0.4 0.4 0.4 0.4 - (solid content (parts)) (0.2) (0.2) (0.2) (0.2) (0.2) (0.2) UV exposure ( mJ/cm2) 1000 1000 1000 1000 1000 1000 * Heating during UV irradiation - - - 70 ° C - 70 ° C - Post-curing - - - - 90 ° C, 10 minutes 90 °, 10 minutes 90 ° C, 10 minutes Appearance 〇〇〇〇〇〇〇 film thickness (micron) 3.2 3.3 3.4 3.1 3.9 3.2 3.4 Scratch resistance DEEDDDE Pencil hardness 3H 4H 3H 3H 3H 3H 3H -33- 200904899 [Table 3] — I..··. — Table The acridine oligomer A1 obtained in Synthesis Example 1 has a solid content concentration of 20% by mass. The alkoxysilane oligomer A1 obtained in Synthesis Example 2 has a solid content concentration of 20% by mass. Solution _ B1 hexafluoroantimony 50% by mass of benzyl-4-hydroxyphenylmethylhydrazine r-butyrolactone solution - B2 hexafluoroantimonate 50% by mass of n-naphthylmethyl-4-hydroxyphenylmethylhydrazine Ester solution ___ B3 hexafluoroantimonate methylbenzyl-4-hydroxyphenylmethyl hydrazine 50% by mass r-butyrolactone solution _ B4 hexafluorophosphate benzyl-4-hydroxyphenyl hydrazine 50 mass % r -butyrolactone solution _ B,1 bis(hexafluorophenyl)-S,S,S',S'-tetraphenyldifluorene and diphenyl hexafluorophosphate 50% by mass of propylene carbonate solution of (4-phenylthiophenyl)anthracene (manufactured by Dow Chemical Japan Co., Ltd., trade name: "CYRACURE UVI-6992") —_ B'2 hexafluorophosphate dimethyl-4- 50% by mass of hydroxyphenyl hydrazine r-butyrolactone solution B, 3 hexafluorophosphate 1-(4-methylphenyl)[4-(2-methylpropyl)phenyl]iodonium (Iodonium, ( 4-methylphenyl)[4-(2-methylpr〇pyl)phenyl]-hexaflurophosphate(l-)) (manufactured by CIBA SPECIALTY CHEMICALS, trade name: "IRGACURE250 丨) A3 The solid content concentration obtained in Synthesis Example 3 is 20 mass. % of decane oligomer A3 solution HI The solid content concentration obtained in Synthesis Example 4 was 20 % by mass of polycondensate H1 solution (hydrolysis of organic decane and colloidal cerium oxide, polycondensate) H2 Polycondensate H2 solution having a solid content concentration of 20% by mass obtained in Synthesis Example 5 (alkyl citrate and colloid) Hydrolysis of a cerium oxide, a polycondensate) A4 Compound A4 solution A5 having a solid concentration of 20% by mass in Synthesis Example 6 Compound A5 solution A6 having a solid concentration of 20% by mass obtained in Synthesis Example 7 was synthesized. The compound A6 solution A7 obtained in Example 8 having a solid content concentration of 20% by mass The compound A7 solution H3 obtained in Synthesis Example 9 having a solid content concentration of 20% by mass The polycondensate having a solid content concentration of 20% by mass obtained in Synthesis Example 10 H3 solution (hydrolysis and condensation of organic decane and colloidal cerium oxide) &lt;Example 9 &gt; [Preparation of active energy ray-curable composition] The component (A) was 3 5.0 parts in Synthesis Example 3. A solid content concentration of 20% by mass of a solution of the siloxane oxide A3 (solid content: 7.0 parts) and (H) component of 15.0 parts of a solid of the siloxane oligomer Η 1 obtained in Synthesis Example 4 were obtained. ingredient a solution of 50% by mass of γ-butyrolactone of benzyl-4-hydroxyphenylmethyl hexafluoroantimonate in a solution of 20 parts by mass (3.0 parts by weight) of a mixture of 〇4 parts (Β) Ingredients: 0.2 parts), 10.0 parts of solvent isopropanol, 15.0 parts of r-butyrolactone, 10.0 parts of butyl serotonin, 〇·〇ι parts of leveling agent 矽 界 -34- 200904899 surfactant ( The product name l- manufactured by TORAY-DOWCORNING Co., Ltd. is an active energy ray-curable composition. The formation of the photocurable composition and the formation and evaluation of the protective film were carried out in the same manner as in Example 7. The protective film was also evaluated for abrasion resistance. The results are shown in Table 4. [Protective film] 6) Abrasion resistance The turbidity 値 after the Taber abrasion test (using a side of 500 gram load, CS. product name), a wear wheel, a rotation speed of 60 rpm, and a test number of 500 times was measured. Further, 値 represented by (turbidity 试验 after the test) - (pre-test 値) is expressed as abrasion resistance (%). Further, in Examples 6 and 7, the abrasion resistance was additionally evaluated. Results Example 6 was 2 1 %, and Example 7 was 18%. &lt;Examples 10 to 13&gt; The active energy ray-curable composition was prepared in the same manner as in Example 9 except that the components (A) and (B) were prepared in the same manner as described in Table 4; The film and the photocurable composition were formed, and the film was formed by curing and post-curing of the film irradiated with ultraviolet rays, and then the film was evaluated. The results are shown in Table 4. &lt;Example 14&gt; The preparation of the active energy-sensitive composition and the photocurable composition film was carried out in the same manner as in Example 13, and the halogen lamp was used for heating test by the external wire. Sample to about 70 ° C, to harden. Not post-maturing. Subsequently, evaluation of the film was carried out in the same manner as in Example 3. The results are shown in Table 4. 7001), sample introduction and, • 10F (the turbidity of the commercial test, the amount of the implementation, the shape protection of the film is shown. The line hardening irradiates the purple film, -35- 200904899 &lt;Comparative Example 8 (9) In the same manner as in Example 9, except that the components (A), (Η), and (B') were prepared in accordance with the blending amounts described in Table 5, the preparation activity was carried out in the same manner as in Example 9. The formation of the energy ray-curable composition, the photocurable composition film, and the formation of the protective film by curing and aging of the film irradiated with ultraviolet rays, and then evaluation of the film were carried out. The results are shown in Table 5. 4] Ingredient 9 (Α) Ingredients (parts) (solid content (parts)) (Η) Ingredients (parts) (solid content (parts)) (Β戚份量(份) Individual ingredients (parts) UV irradiation amount (mJ/cm2) Curing appearance after heating by UV irradiation _ Film thickness (micron) Scratch resistance Pencil hardness abrasion resistance (%) A3 35.0 (7.0) H1 15.0 (3.0) B1 0.4 (0.2) 1000 9 (TC, 10 minutes)

〇 3.5 C+ 4H A3 40.0 (8.0) H2 10.0 (2.0) B1 0.4 (0.2) 1000 90°C, 10 minutes

〇 4.1 C+ 4H Example 11 A3 35.0 (7.0) H1 15.0 (3.0) B3 0.4 (0.2) 1000 90. . , 10 minutes 〇 3.8 C+ 4H 10

-36- 200904899 [Table 5] Composition Comparison Example 8 9 (A) Component A3 A3 Formulation amount (parts) 35.0 35.0 Individual component (parts) (7.0) (7.0) (H) Component H1 H1 Formulation amount (parts) 15.0 15.0 Carcass Ingredients (parts)) (3.0) (3.0) (B'戚B' 1 B,3 Formulation (dress) 0.4 0.4 Individual ingredients (parts) (0.2) (0.2) UV exposure (mJ/ Cm2) 1000 1000 UV irradiation heating _ - Post-curing 90 ° C '90 ° C ' 10 minutes 10 minutes Appearance film thickness (micron) 4.2 3.6 Scratch resistance DD Recording hardness 4H 4H Wear resistance (%) 53 42 &lt;Example 1 5 &gt; In the component (A), 50.0 parts of the compound A4 obtained in Synthesis Example 6 was dissolved in a solid content of 20% by mass (solid content: 1 part), and 0.4 parts (B) was mixed. 50% by mass γ·butyrolactone solution of hexafluoroantimonate benzyl-4-hydroxyphenylmethylhydrazine (solid content: 份. 2 parts), 10.0 parts of solvent isopropanol, 1 5.0 parts r - Butyrolactone, 1 〇 〇 butyl 赛赛苏, 〇. 〇 1 part of the leveling agent lanthanide surfactant (manufactured by TORAY-DOWCORNING Co., Ltd., trade name L-700I), as active energy ray hardenability CompositionIn the same manner as in Example 6, the formation of the photocurable composition and the formation and evaluation of the protective film were carried out. The results are shown in Table 6. &lt;Examples 16 to 20&gt; The active energy ray-curable composition-37-200904899 was carried out in the same manner as in Example 15 except that the components (A) and (B) were prepared in the same manner as in Table 6. Preparation, formation of a photocurable composition film, and evaluation of a film. The results are shown in Table 6. &lt;Example 21&gt; The preparation of the active energy ray-curable composition and the photocurable composition film was carried out in the same manner as in Example 166, and the film was cured by irradiation with ultraviolet rays. Further, it was post-cured by drying in a hot air dryer at 90 ° C for 10 minutes to form a protective film. Subsequently, the film was evaluated in the same manner as in Example 1. The results are shown in Table 6. &lt;Example 22&gt; The component (A) was 35.0 parts of the compound A4 obtained in Synthesis Example 6 and had a solid content concentration of 20% by mass (solid content: 7.0 parts) and (H) component: 15.0 parts. 10 parts of the obtained polycondensate Η3 solid content concentration 20% by mass solution (solid content: 3.0 parts), mixed with 0.4 parts of (Β) component of hexafluoroantimonate methylbenzyl-4-hydroxyphenylmethyl hydrazine 50 mass %γ-butyrolactone solution (solid content: 0.2 parts), 10.0 parts of solvent isopropanol, 15.0 parts of r-butyrolactone, 1 〇. 丁基butyl butyl sulcata, 0.01 part of leveling agent A surfactant (trade name: L-700 1 manufactured by TORAY-DOWCORNING Co., Ltd.) is used as an active energy ray-curable composition. The formation of the photocurable composition and the formation and evaluation of the protective film were carried out in the same manner as in Example 15. The results are shown in Table 6. &lt;Comparative Example 1 〇~1 2 &gt; In the same manner as in Example 15, except that the components (A) and (B') were prepared in Table 7, the active energy ray-curable composition was prepared. The photocurable composition film is formed and irradiated with ultraviolet rays, but the film is not hard-38-200904899. The results are shown in Table 7. &lt;Comparative Example 1 3 &gt; The preparation of the active energy ray-curable composition and the photocurable composition film were carried out in the same manner as in Example 2 except that the (B') component was prepared in Table 7 The formation of ultraviolet rays, but the film is not hardened. The results are shown in Table 7. <Example 23 &gt; The component (A) was 1 5 _ 0 parts of a solid content concentration of 20% by mass of a siloxane oxide oligomer A1 obtained in Synthesis Example 1 (solid content: 3 〇 part), 350 parts The solid content concentration of the compound A 5 obtained in Example 7 was 2% by mass. The solution (solid content: 7.0 parts) was mixed with 4 parts of the component (B) of hexafluoroantimonic acid kaki-4-phenyl group. Molecular 50% by mass γ-butane vinegar solution (solid content is 〇·2 parts), 10.0 parts of solvent isopropanol, 1 5 · 〇 part of r-butyrol vinegar, 1 〇 · 〇 butyl赛路苏, 0 _ 0 1 leveling agent sand-based surfactant (manufactured by TORAY-DOWCORNING Co., Ltd., trade name L-7 00 1 ), as an active energy ray-curable composition. The formation of the photohardenable composition and the formation and evaluation of the protective film were carried out in the same manner as in Example 6. The results are shown in Table 8. &lt;Example 24&gt; The preparation of the active energy ray-curable composition and the photocurability composition were carried out in the same manner as in Example 23 except that the components (A) and (B) were prepared in Table 8. Formation of a film and evaluation of a film. The results are shown in Table 8. &lt;Example 25&gt; -39-200904899 In a component (A), 12.0 parts of a solution having a solid content concentration of 20% by mass of a siloxane oxide oligomer A1 obtained in Synthesis Example 1 (solid content: 2.4 parts), 28.0 parts The solid content concentration of the compound A 5 obtained in Synthesis Example 7 was 20% by mass, the solution (solid content: 5.6 parts), and the (H) component was 1 part. The solid content concentration of the polycondensate H3 obtained in Synthesis Example 10 was 20 mass. In a solution of % (solid content: 2.0 parts), 0.4 parts of a component (B) of hexafluoroantimonate benzyl-4-hydroxyphenylmethylhydrazine in a 5 〇 mass / / - butyrolactone solution (solid content is 0.2 parts), 10.0 parts of solvent isopropanol, 15.0 parts of τ-butyrolactone, 1 part 〇 butyl celecoxib, 0.01 part of leveling agent lanthanide surfactant (TO R AY-D Ο WC ORN IN G company, trade name L-7001), as an active energy ray-curable composition. Subsequently, formation of a photohardenable composition, formation of a protective film, and evaluation were carried out in the same manner as in Example 23. The results are shown in Table 8. &lt;Comparative Example 1 4, 1 5 &gt; In the same manner as in Example 15, except that the components (A) and (B,) were prepared in accordance with Table 9, the active energy ray-curable composition was subjected to Modulation, formation of a photocurable composition film, and hardening of a film irradiated with ultraviolet rays. The results are shown in Table 9. -40- 200904899 [Table 6]

Ingredient Example 15 16 17 18 19 20 21 22 (A) Component A4 A4 A4 A5 A6 A7 A4 A4 Formulation amount (parts) 50.0 50.0 50.0 50.0 50.0 50.0 50.0 35.0 (solid content (parts)) (10.0) (10.0) ( 10.0) (10.0) (10.0) (10.0) (10.0) (7.0) (H 戚 H3 ration (parts) - - - - - - 15.0 (solid content (parts)) (3.0) (8) Component B1 B3 B4 B3 B3 B3 B3 B3 Formulation amount (parts) 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Individual components (parts)) (0.2) (0.2) (0.2) (0.2) (0.2) (0.2) (0.2) (0.2) UV irradiation (mJ/cm2) 1000 1000 1000 1000 1000 1000 1000 1000 Heating at 70 °C during UV irradiation 70°C 70°C 70°C 70°C 70°C 70°C 70°C Post-curing - - - - - - 90 °C, 10 minutes - Appearance film thickness (micron) 3.5 3.2 3.6 3.7 3.9 3.8 3.3 4.0 Scratch resistance C+ C+ C+ BB c+ BB Pencil hardness 4H 4H 4H 4H 5H 4H 5H 6H

[Table 7] Ingredient Comparative Example 10 11 12 13 (A 戚 A4 A4 A4 A4 A4 Amount (parts) 50.0 50.0 50.0 35.0 (solid content (parts)) (10.0) (10.0) (10.0) (7.0) (H) Ingredient H3 Formulation (Parts) - - - 15.0 Ingredient (parts)) (3.0) (B'戚B* 1 B' 2 B' 3 B' 1 Formulation (parts) 0.4 0.4 0.4 0.4 Carcass ()) (0.2) (0.2) (0.2) (0.2) UV irradiation (mJ/cm2) 1000 1000 1000 1000 Heat 70 when UV irradiation. . 70. . After 70 ° C 70 ° C post-curing - - - - Appearance can not be formed into a film can not be formed into a film can not be filmed film thickness (micron) - - - - scratch resistance - - - - pencil hardness - - - - -41 - 200904899

[Table 8] Ingredient Example 23 24 25 (A) Component i weekly dosing amount (parts) (solid content (parts)) A1 15.0 (3.0) A1 15.0 (3.0) A1 12.0 (2.4) A5 35.0 (7.0) A6 35.0 (7.0) A5 28.0 (5.6) (H) Ingredients (parts) Individual components (parts) - - H3 10.0 (2.0) (8) Ingredients (parts) (solid content (parts)) B1 0.4 (0.2) B1 0.4 (0.2) B1 0.4 (0.2) UV irradiation amount (mJ/cm2) 1000 1000 1000 Heating at 70 ° C 70 during UV irradiation. . 70°C Appearance 〇 〇 膜 Film thickness (micron) 3.3 3.5 4.1 Scratch resistance B B B Pencil hardness 5H 5H 6H

[Table 9] Ingredient Comparative Example 14 15 (A) Ingredients (parts) (solid content (parts)) A1 15.0 (3.0) A1 15.0 (3.0) A5 35,0 (3.0) A6 35.0 (3.0) (8) Composition Amount (parts) (solid content (parts)) - - (B' splitting amount (parts) carcass component (parts)) B' 1 0.4 (0.2) B' 2 0.4 (0.2) UV irradiation amount (mJ/ Cm2) 1000 1000 UV irradiation, heating 70 ° C 70 ° C Appearance film thickness (micron) 3.5 3.2 Scratch resistance DD Pencil hardness 4H 4H -42- 200904899 Industrial use possibility The laminate of the present invention can be adapted Optical parts such as automotive parts for headlight lenses or convertible tops, windshields for locomotives, windows for railway vehicles or airplanes, highway soundproof panels, lenses or filters, mobile phones or information machine housings , functional films such as optical discs, monitors or touch screens. [Simple description of the diagram] and 0 [Description of main component symbols] 4FR1 〇 j \ w -43-

Claims (1)

200904899 X. Patent application scope: 1. A composition for active energy ray hardening, which comprises at least one selected from the group consisting of a siloxane oligomer, an organic decane, and an alkyl phthalate (A), and An aromatic vegetable salt type acid generator (B) represented by the formula (1), (wherein R'R2 and R3 each represent hydrogen, an organic group having 1 to 10 carbon atoms, a halogen group or a hydroxyl group, R4 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R5 represents an aromatic hydrocarbon group or may be An aromatic hydrocarbon group having a substituent, and X is a relative anion). A method for forming a protective film by coating at least one type (A) selected from the group consisting of a decane oxide oligomer, an organic chopping class, and a phthalic acid ester based on a base material, and a method represented by the formula (1) The active energy ray-curable composition of the aromatic sulfonium-type acid generator (B) is cured by irradiating an energy ray to the active energy ray-curable composition. (wherein R^R2 and R3 each represent an organic group having hydrogen, a carbon number of 1 to 1 fluorene, a halogen group or an aliphatic hydrocarbon group having a carbon number of 1 to 1 Å through a radical R, and R5 represents an aromatic group. A hydrocarbon group or an aromatic hydrocarbon group which may also have a substituent, χ--44-200904899 means a relative anion). 3. The protective film forming method according to the second aspect of the invention, wherein the oxirane oligomer is an organic decane represented by the formula (2) and an alkyl decanoate represented by the formula (3) Hydrolysis of a compound or a polycondensate 'R6aSi(OR7)4.a (2) (wherein R6 represents an organic group having a carbon number of 1 to 10, and R7 represents an alkyl group having 1 to 5 carbon atoms or a fluorenyl group having 1 to 4 carbon atoms, a is an integer representing any one of 〇3 to 3) R8—Ο OR10 ISi-0 I OR11 R9 (3) n (wherein R8, R9, R1Q, and R11 are independent The ground represents an alkyl group of 1 to 5, and n is an integer of 2 to 20). 4. The protective film forming method according to claim 2, wherein the organic decane organodecane represented by the formula (4) and the alkyl decanoate represented by the formula (5) are further further contained. Any one or more of the compounds and the colloidal cerium oxide having a number average particle diameter of 5 to 200 nm are hydrolyzed, and the active energy ray-curable composition of the polycondensate (Η) is hardened, R12bSi(OR13)4.b (4) Wherein R12 represents an organic group having 1 to 10 carbon atoms, R13 represents an alkyl group having 1 to 5 carbon atoms or a fluorenyl group having 1 to 4 carbon atoms, and b represents an integer of any of 〇3 to 3; ), -45- 200904899 R14-0 OR16ISi—OI OR17 R15 (5) m (wherein R14, R15, R16, and R17 each independently represent 1, base, and m represents any of 2 to 2 Integer). 5. The protective film method according to any one of claims 2 to 4, wherein when the active energy composition is cured by irradiation of an active energy ray, the irradiation energy line is irradiated Thereafter, or both, heating the active energy ray-curable composition 16. The method for forming a protective film according to claim 1 of the patent application, wherein one step comprises containing the organodecane organodecane represented by the formula (4) and Hydrolysis of any one or more of the alkyl phthalate esters and colloidal cerium oxide having a diameter of 5 to 200 nm, and (H) active energy ray-curable composition hardening 'R12bSi(OR13)4- b (4) (wherein R12 represents an organic group having 1 to 10 carbon atoms, R13 is an alkyl group of Tables 1 to 5, or a fluorenyl group of carbon number 4 is an integer of 〇~3) -5 The alkane forms a square wire hardening activity. More in the general formula (5) The average granule polycondensate shows the carbon number R14—Ο OR16 I•Si—Ο I OR17 Λ R15 (5) m 5 alkane (wherein R14, R15, R16 and R17 are Each of them independently represents a 1 group, and m represents an integer of 2 to 20). -46-200904899 7. A laminated body having a cured film of a composition for active energy ray hardening according to the first or sixth aspect of the patent application. The method of forming a laminate is to provide a protective film on the surface of the substrate by the protective film forming method according to any one of claims 2 to 5. -47- 200904899 VII. Designation of representative representatives: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: te 〇 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: