JPWO2008126902A1 - Composition, protective film forming method, laminate and production method thereof - Google Patents

Abstract

As a protective film forming method capable of forming an inorganic transparent protective film excellent in film performance such as scratch resistance in a short time, at least one selected from siloxane oligomers, organosilanes and alkylsilicates (A), And the photocurable composition containing the aromatic sulfonium salt type | mold acid generator (B) shown by General formula (1) is apply | coated to a base material, The said photocurable composition is hardened by light irradiation. (In the formula, R1, R2, and R3 each represent hydrogen, an organic group having 1 to 10 carbon atoms, a halogen group, and a hydroxyl group; R4 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms; (It represents an aromatic hydrocarbon group which may have a substituent. X- represents a counter anion.)

Description

  The present invention relates to a protective film forming method capable of forming a transparent protective film excellent in scratch resistance in a short time, a composition therefor, a laminate on which the protective film is formed, and a method for producing the same.

  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 as an alternative to transparent glass. However, since the transparent plastic material has a lower surface hardness than glass, it has a problem that the surface is easily damaged.

  Thus, many attempts have been made to improve the scratch resistance of plastic materials. As one of the most common methods, a method of forming a protective film made of an inorganic polymer having a siloxane bond on the surface of a substrate by utilizing hydrolysis of an alkoxysilane compound and subsequent condensation reaction is widely known. (See Patent Documents 1 and 2). However, these methods have a problem in productivity because a heating time of several tens of minutes to several hours is required to form a protective film.

  In order to solve these problems, for example, a siloxane oligomer having a siloxane skeleton in the molecule and having a reactive silanol group, alkoxysilane group, etc. and an active energy ray-sensitive cationic polymerization initiator are contained as essential components. And the composition which hardens | cures by active energy ray irradiation and forms a protective film in a short time is proposed (for example, refer patent document 3, 4).

Specifically, a siloxane bond is formed between a silanol group and an alkoxysilane group using an acid generated from a cationic polymerization initiator as a catalyst by applying such a composition to a substrate and irradiating active energy rays such as ultraviolet rays. Is formed and cured to form a protective coating. According to this method, a film can be formed in a short time, but depending on the type and amount of the active energy ray-sensitive cationic polymerization initiator used and the active energy ray irradiation method, the physical properties of the protective film to be obtained may be different. There was a problem that the physical properties such as scratch resistance were not exhibited.
JP 48-26822 A JP 55-94971 A JP-A-53-97098 JP 56-106958 A

  The present invention has been made to solve the above-described problems in the prior art. That is, an object of the present invention is to provide a protective film forming method capable of forming an inorganic transparent protective film excellent in film performance such as scratch resistance in a short time, a composition therefor, and a laminate on which the protective film is formed. There is to do.

  As a result of intensive studies to achieve the above object, the present inventors have found that an aromatic sulfonium salt type acid generator having a specific structure is extremely effective for the formation of siloxane bonds by irradiation with active energy rays, By applying an active energy ray-curable composition containing a compound capable of forming a specific siloxane bond, such as a siloxane oligomer, and an aromatic sulfonium salt acid generator having a specific structure to a substrate and irradiating the active energy ray, The present inventors have found that a protective coating having excellent coating performance can be formed by curing in a short time, and has led to the present invention.

  That is, the present invention contains at least one selected from siloxane oligomers, organosilanes and alkyl silicates (A), and an aromatic sulfonium salt acid generator (B) represented by the general formula (1). In this method, the active energy ray-curable composition is applied to a substrate and the active energy ray-curable composition is cured by irradiation with active energy rays.

(In the formula, R ¹ , R ² and R ³ each represent hydrogen, an organic group having 1 to 10 carbon atoms, a halogen group or a hydroxyl group, and R ⁴ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms. And R ⁵ represents an aromatic hydrocarbon group or an aromatic hydrocarbon group having a substituent, and X ⁻ represents a counter anion.)

  Furthermore, the present invention provides a protection for heating the active energy ray-curable composition during active energy ray irradiation, after active energy ray irradiation, or both when curing the active energy ray curable composition by active energy ray irradiation. This is a film forming method.

  Further, the present invention is an activity containing at least one (A) selected from siloxane oligomers, organosilanes and alkyl silicates, and an aromatic sulfonium salt acid generator (B) represented by the general formula (1). It is a composition for energy ray curing.

(In the formula, R ¹ , R ² and R ³ each represent hydrogen, an organic group having 1 to 10 carbon atoms, a halogen group or a hydroxyl group, and R ⁴ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms. And R ⁵ represents an aromatic hydrocarbon group or an aromatic hydrocarbon group having a substituent, and X ⁻ represents a counter anion.)

  Furthermore, this invention relates to the laminated body which has the cured film of the said composition for active energy ray hardening on the surface of a base material.

  Furthermore, this invention relates to the manufacturing method of the laminated body which provides a protective film on the surface of a base material with the said protective film formation method.

  According to the present invention, an inorganic protective film excellent in appearance, transparency, and scratch resistance can be formed in a short time.

  As the component (A) in the composition for curing active energy rays of the present invention, at least one selected from siloxane oligomers, organosilanes, and alkyl silicates is used.

  The siloxane oligomer used in the present invention has a siloxane bond as a main skeleton, and a silanol group or alkoxysilyl group that can be condensed with an acid generated from an aromatic sulfonium salt acid generator (B) upon irradiation with light as a catalyst. It is an oligomer contained in The oligomer-containing silanol group is condensed with a silanol group or an alkoxysilyl group to form a siloxane bond. The oligomer-containing alkoxysilyl group can be condensed directly with a silanol group, or once hydrolyzed to a silanol group, it can be condensed with a silanol group or an alkoxysilyl group to form a siloxane bond. is there.

  Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, and a propyloxysilyl group. Preferably, it is a methoxysilyl group or an ethoxysilyl group from the viewpoint of a rapid hydrolysis rate and condensation rate.

  The molecular weight of the siloxane oligomer is not particularly limited, but is preferably in the range of 500 to 50,000 in terms of weight average molecular weight. By setting the weight average molecular weight to 500 or more, the film formability of the composition can be improved, and the scratch resistance and crack resistance of the resulting film can be improved. Moreover, the uniformity and transparency of the protective film obtained can be improved by setting it as 50,000 or less. In particular, the weight average molecular weight is more preferably in the range of 800 to 10,000.

  One type of siloxane oligomer can be used alone, or a plurality of types can be used in combination.

  As the siloxane oligomer, those commercially available from various manufacturers can be used as they are, or those synthesized by hydrolysis and condensation using various organosilanes, alkyl silicates and the like as raw materials can also be used.

  Preferably, it is a hydrolysis or condensate of one or more compounds of organosilanes represented by general formula (2) and alkylsilicates represented by general formula (3).

(In the formula, R ⁶ represents an organic group having 1 to 10 carbon atoms, R ⁷ represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, and a is any one of 0 to 3) Represents an integer.)

(Wherein R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ independently represent an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 2 to 20)

  Specific examples of organosilanes include tetraethoxysilane, tetramethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloyl Oxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, p-vinyl Phenylene Rent triethoxysilane, p- vinylphenylene Rent trimethoxysilane, dimethyl diethoxy silane, dimethyl dimethoxy silane, and the like.

  Among these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, etc., from the point of quick hydrolysis and condensation reaction. preferable.

  Specific examples of alkyl silicates include methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate, isobutyl silicate, n-butyl silicate and the like.

Of these, methyl silicate in which all of R ^{8 to} R ¹¹ represent a methyl group and ethyl silicate in which all of R ^{8 to} R ¹¹ represent an ethyl group are preferable in that the speed of hydrolysis and condensation reaction is high.

  Examples of the organosilanes in the component (A) of the present invention include organosilanes represented by the general formula (2) exemplified as the raw material for the siloxane oligomer.

  Examples of the alkyl silicates in the component (A) of the present invention include alkyl silicates represented by the general formula (3) exemplified as the raw material of the siloxane oligomer.

  In the present invention, the aromatic sulfonium salt type acid generator (B) represented by the general formula (1) is used.

(In the formula, R ¹ , R ² and R ³ each represent hydrogen, an organic group having 1 to 10 carbon atoms, a halogen group or a hydroxyl group, and R ⁴ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms. And R ⁵ represents an aromatic hydrocarbon group or an aromatic hydrocarbon group having a substituent, and X ⁻ represents a counter anion.)

Specific examples of X ⁻ include SbF ₆ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , BF ₄ ⁻ and CF ₃ SO ₃ ⁻ . From the viewpoint of activity, SbF ₆ ⁻ and PF ₆ ⁻ are preferable.

  By using the aromatic sulfonium salt type acid generator represented by the general formula (1), a siloxane inorganic coating can be efficiently formed in a short time by irradiation with active energy rays. Good film properties can be obtained as compared with the case of using other photosensitive photoacid generators.

  Even if an active energy ray-curable composition containing organosilanes or alkylsilicates and a general active energy ray-sensitive cationic polymerization initiator is applied to a substrate and irradiated with active energy rays, the composition of the composition is not affected. The film property is low and a protective film cannot be formed. However, by using the aromatic sulfonium salt type acid generator represented by the general formula (1) as the active energy ray-sensitive cationic polymerization initiator, the film formability of the composition is improved and a protective film is formed. Can do.

  When organosilanes or alkyl silicates are used, they may be used alone or in addition to the water required for their hydrolysis.

  As the component (A), it is preferable to use at least one siloxane oligomer in combination with at least one selected from organosilanes and alkyl silicates. Increasing the content of the siloxane oligomer improves the crack resistance of the cured coating. By increasing the content of organosilanes and alkyl silicates, the scratch resistance and hardness of the cured coating are improved. When using at least one siloxane oligomer in combination with at least one selected from organosilanes and alkyl silicates, only those combinations may be used, or hydrolysis of organosilanes or alkyl silicates may be used. You may add and use the water required for decomposition | disassembly.

  Moreover, when hardening the said active energy ray curable composition by active energy ray irradiation, a film performance can further be improved by heating at the time of active energy ray irradiation, after active energy ray irradiation, or both.

  Specific examples of the aromatic sulfonium salt type acid generator include, for example, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, benzyl-4-hydroxyphenylmethylsulfonium hexanium. Fluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium tetrafluoroborate, benzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium p-toluenesulfonate, methylbenzyl-4- Hydroxyphenylmethylsulfonium hexafluoroantimonate, methylbenzyl-4-hydroxyphenylmethylsulfonate Hexahexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4- Hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, benzyl-3-methyl-4-hydroxy-5-tert-butylphenylmethylsulfonium hexafluoroantimonate 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, dibenzyl-4-hydro Roxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, nitrobenzyl-4-hydroxyphenyl Methylsulfonium hexafluoroantimonate, 3,5-dinitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, β-naphthylmethyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, β-naphthylmethyl-4-hydroxyphenyl Methylsulfonium hexafluorophosphate, α-naphthylmethyl-4-hydroxy Examples include siphenylmethylsulfonium hexafluoroantimonate and α-naphthylmethyl-4-hydroxyphenylmethylsulfonium hexafluophosphate.

  Among these, those having a structure in which a 4-hydroxyphenyl group is directly bonded to a sulfur atom (S) are preferable from the viewpoint of a high curing rate by light irradiation and good scratch resistance of the obtained protective coating. Specific examples include β-naphthylmethyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, β-naphthylmethyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, α-naphthylmethyl-4-hydroxyphenylmethylsulfonium hexafluoro. Antimonate, α-naphthylmethyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, methylbenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, methylbenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, benzyl-4 -Hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfoniu It includes hexafluorophosphate.

These aromatic sulfonium salt type acid generators, for example, phenylmethyl sulfide or phenylmethyl sulfide having a substituent and aromatic methyl chloride or aromatic methyl chloride having a substituent at 35 ° C. in the presence of water. After reacting for 20 hours, it can be produced by a known method such as addition of ethyl acetate and salt exchange (for example, NaSbF ₆ ) at 15 ° C. for 30 minutes and concentration from the ethyl acetate layer.

  Moreover, a commercial item can also be purchased and used. As a commercial item of the aromatic sulfonium salt type acid generator represented by the general formula (1), for example, “Sun-Aid SI-60”, “Sun-Aid SI-80”, “Sun-Aid SI-100”, “Sun-Aid SI-” 110 ”(trade name, manufactured by Sanshin Chemical Industry Co., Ltd.).

  The blending amount of the aromatic sulfonium-type acid generator (B) is not particularly limited, but is 0.1% relative to 100 parts by mass of the solid content of the component (A) (total of siloxane oligomer, organosilanes, and alkyl silicates). The range of 01-10 mass parts is preferable. However, the solid content mentioned here means a compound obtained when the component (A) is completely hydrolyzed and condensed, and the same applies to the following description. When the hydrolysis and condensate (H) described later is included, the amount is preferably within a range of 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the solids of (A) and (H). . If it is 0.01 mass part or more, it will harden | cure in a short time by light irradiation, and it exists in the tendency for a favorable protective film to be obtained. Moreover, if it is 10 mass parts or less, about the physical property of the protective film obtained by hardening, there is especially little coloring and it exists in the tendency for surface hardness and abrasion resistance to become favorable. Furthermore, the compounding amount is 100 parts by mass of the solid content of the component (A) (total of siloxane oligomer, organosilanes and alkyl silicates) from the point that the curability is good and a protective film with good performance is obtained. In contrast, a range of 0.05 to 5 parts by mass is more preferable.

  The composition used in the present invention may contain other reactive compounds as long as the effects of the invention are not hindered. Specific examples include an epoxy compound (C) and a vinyl ether compound (D) that can be cationically polymerized. Furthermore, you may contain the radical polymerization initiator (F) which has a radically polymerizable double bond group containing monomer (E), and photosensitivity.

  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 diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol. Diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, diglycerin tetraglycidyl ether, trimethylolpropane triglycidyl ether, 2,6-diglycidyl phenyl ether, sorbitol triglycidyl ether, triglycidyl isocyanurate , Diglycidylamine, diglycidylbenzylamine, diglycidyl phthalate Bisphenol A diglycidyl ether, butadiene dioxide, dicyclopentadiene dioxide, 3,4-epoxycyclohexenecarboxylic acid and ethylene glycol diester, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene epoxide glycidyl ether, pentaerythritol polyglycidyl ether , Adduct of bisphenol A type epoxy resin and ethylene oxide, phenol novolac type epoxy resin, cresol novolac type epoxy resin, etc. It can be mentioned. Among them, an aromatic epoxy compound containing two or more epoxy groups in the molecule is preferable from the viewpoint that the curing speed is high and the resulting protective film has good scratch resistance. An epoxy compound may be used individually by 1 type, or may be used in combination of 2 or more type.

  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, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, 1,4-butanediol diester. Vinyl ether, 1,6-hexanediol divinyl ether, 1,9-nonanediol divinyl ether, cyclohexanediol divinyl ether, cyclohexanedimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol vinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, Trime Trivinyl ether, pentaerythritol - can be exemplified Le tetravinylether, and the like.

  The structure of the radical polymerizable double bond-containing monomer (E) is not particularly limited as long as it has a radical polymerizable double bond group. In particular, a monofunctional or polyfunctional (meth) acrylate compound containing an acryloyl group or a methacryloyl group in the molecule is preferable from the viewpoint of a high polymerization rate.

  Specific examples of monofunctional (meth) acrylate compounds include phenyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, phenoxyethyl (meth) acrylate, paracumylphenol ethylene oxide modified (meth) acrylate, Isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (Meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethyl Sil (meth) acrylate, n-hexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Tetrahydrofurfuryl (meth) acrylate, phosphoethyl (meth) acrylate, etc. are mentioned.

  Specific examples of the polyfunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, 2,2-bis [4- (meth) acryloyloxyphenyl] -propane, 2,2-bis [4- (meth) acryloyloxyethoxyphenyl] -propane, 2,2-bis 4- (meth) acryloyloxydiethoxyphenyl] -propane, 2,2-bis [4- (meth) acryloyloxypentaethoxyphenyl] -propane, 2,2-bis [4- (meth) acryloyloxyethoxy-3 -Phenylphenyl] -propane, bis [4- (meth) acryloylthiophenyl] sulfide, bis [4- (meth) acryloyloxyphenyl] -sulfone, bis [4- (meth) acryloyloxyethoxyphenyl] -sulfone, bis [4- (meth) acryloyloxydiethoxyphenyl] -sulfone, bis [4- (meth) acryloyloxypentaethoxyphenyl] -sulfone, bis [4- (meth) acryloyloxyethoxy-3-phenylphenyl] -sulfone, Bis [4- (meth) acryl Yloxyethoxy-3,5-dimethylphenyl] -sulfone, bis [4- (meth) acryloyloxyphenyl] -sulfide, bis [4- (meth) acryloyloxyethoxyphenyl] -sulfide, bis [4- (meth) Acryloyloxypentaethoxyphenyl] -sulfide, bis [4- (meth) acryloyloxyethoxy-3-phenylphenyl] -sulfide, bis [4- (meth) acryloyloxyethoxy-3,5-dimethylphenyl] -sulfide, 2 , 2-bis [4- (meth) acryloyloxyethoxy-3,5-dibromophenylpropane], trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, Examples include dipentaerythritol hexa (meth) acrylate.

  Among these, polyfunctional (meth) acrylates are more preferable from the viewpoints of good curability and excellent scratch resistance of the resulting protective coating. As the radical polymerizable double bond-containing monomer (E), one kind may be used alone, or several kinds may be mixed and used.

  Photosensitive radical polymerization initiator (F) is a component that generates active radical species in response to active energy rays such as visible light and ultraviolet light, and initiates polymerization of the radical polymerizable double bond-containing monomer (E). is there. Specific examples of the photosensitive radical polymerization initiator (F) include 3,3-dimethyl-4-methoxy-benzophenone, benzyldimethyl ketal, isoamyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, benzophenone, p-methoxybenzophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, methylphenylglyoxylate, ethylphenylglyoxylate, 2 -Hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2,4,6-trimethylbenzoyldiphenylphosphine Examples include oxides. Among them, methylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzyl Dimethyl ketal and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are more preferable from the viewpoint of curing rate. One of these photosensitive radical polymerization initiators (F) may be used alone, or two or more thereof may be mixed and used.

  Although the compounding quantity of a photosensitive radical polymerization initiator (F) is not specifically limited, The inside of the range of 0.01-10 mass parts is preferable with respect to 100 mass parts of (E) component. When the blending amount is 0.01 parts by mass or more, it is preferable from the viewpoint of the curing rate by active energy ray irradiation, and when it is 10 parts by mass or less, it is preferable from the viewpoint of scratch resistance of the resulting film. More preferably, it exists in the range of 0.05-5 mass parts.

  The active energy ray-curable composition used in the present invention preferably further contains a polymer compound (G). By mix | blending this, a softness | flexibility is provided to a film and generation | occurrence | production of a crack is suppressed. Examples of the polymer compound (G) include polyacrylic polymers, polyvinyl polymers, polyether polymers, polydialkylsiloxanes (silicone resins), and the like. Among these, polyether polymers can be preferably used, and specific examples include polyethylene glycol.

  Although the compounding quantity of a high molecular compound (G) is not specifically limited, It is 0-50 mass parts with respect to 100 mass parts of solid content of (A) component (total of a siloxane oligomer, organosilanes, and alkylsilicates). Within the range is preferable, and within the range of 1 to 10 parts by mass is more preferable.

  The active energy ray-curable composition used in the present invention includes polymer fine particles, colloidal silica, colloidal metals, photosensitizers (for example, anthracene compounds, thioxanthone compounds, anthraquinone compounds) as necessary. Compounds, naphthalene compounds, pyrene compounds, etc.), fillers, dyes, pigments, pigment dispersants, flow regulators, leveling agents, antifoaming agents, UV absorbers, light stabilizers, antioxidants, heat-sensitive radicals You may mix | blend a polymerization initiator, a heat-sensitive cationic polymerization initiator, etc.

  In order to improve the abrasion resistance of the cured product of the active energy ray-curable composition used in the present invention, the organosilanes represented by the general formula (4) and the alkyl silicates represented by the general formula (5) It is preferable to contain a hydrolyzed, condensate (H) of any one or more of the above compounds and colloidal silica having a number average particle diameter of 5 to 200 nm. When the component (H) is contained, the preferred ratio of the solid content of the component (A) (total of siloxane oligomer, organosilanes and alkylsilicates) to the solid content of the component (H) is 9: 1 to 5: 5. Particularly preferred is 8: 2 to 6: 4.

(In the formula, R ¹² represents an organic group having 1 to 10 carbon atoms, R ¹³ represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, and b represents an integer of 0 to 3). .)

(In formula, R <^14> , R <^15> , R <^16> and R < ¹⁷ > represent a C1-C5 alkyl group independently, and m represents the integer in any one of 2-20.)

  Specific examples of the organosilanes and alkyl silicates include those described above.

  Examples of the colloidal silica include an aqueous silica sol in which silica fine particles are uniformly dispersed in water and an organosilica sol in which the silica fine particles are uniformly dispersed in a dispersion solvent. Examples of the dispersion 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; and esters such as methyl acetate, ethyl acetate, and butyl acetate. , Aromatic hydrocarbons such as benzene, toluene and xylene, and glycol ethers such as ethylene glycol monoalkyl ether and propylene glycol monoalkyl ether. The dispersion solvent can be used alone or in combination of two or more.

  The number average particle size in the colloidal silica is 5 to 200 nm. By using colloidal silica having a number average particle diameter of 5 nm or more, scratch resistance and hardness can be imparted to the cured film. Moreover, the fall of the transparency of a cured film can be suppressed by using colloidal silica with a number average particle diameter of 200 nm or less. The number average particle diameter of the colloidal silica is preferably 10 to 100 nm. In addition, as a measuring method of a number average particle diameter, the method by electron microscope observation is mentioned, for example.

  The active energy ray-curable composition used in the present invention may contain an organic solvent for the purpose of adjusting the solid content concentration, improving the dispersion stability, improving the coating property, and improving the adhesion to the substrate. Examples of the organic solvent include alcohols, ketones, ethers, esters, cellosolves, aromatic compounds, and the like.

  Specifically, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, benzyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxy Methoxy) ethanol, 2-butoxyethanol, furfuryl 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 Propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol Rumonomethyl ether, diacetone alcohol, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, acetophenone, diethyl ether, di Propyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, anisole, phenetole, tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , Diethylene glycol dibutyl ether, glycerin ether, methyl acetate, ethyl acetate, acetate Pill, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isopentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, methyl propionate, ethyl propionate, butyl propionate Γ-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, xylene and the like. These organic solvents may be used alone or in combination of two or more.

  The content of the organic solvent is preferably within a range of 0 to 1000 parts by mass, and more preferably within a range of 0 to 100 parts by mass with respect to 100 parts by mass as a total of the components (A) to (H). If this is 1000 parts by mass or less, the problem that the solid content becomes too low and the coating film becomes thin is less likely to occur, and a protective coating with good scratch resistance tends to be obtained.

  The active energy ray-curable composition used in the present invention is applied to the surface of a base material made of, for example, plastic (film thickness of about 0.5 to 100 μm), and then irradiated with active energy rays to be cured, A protective coating can be formed.

  Application | coating of an active energy ray curable composition can be performed by a conventionally well-known method, for example, a spray, a roll coater, a gravure coater, a flexo, a screen, a spin coater, a flow coater, electrostatic coating etc.

  As the active energy ray, for example, vacuum ultraviolet rays, ultraviolet rays, visible rays, or the like can be used. Specific examples include low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, incandescent bulb, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, gallium lamp, excimer laser, sunlight, etc. As a light source. Among them, light using a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, or a metal halide lamp as a light source is preferable. One type of active energy ray may be used alone, or a plurality of different types may be used.

  Moreover, the active energy ray-curable composition used in the present invention can be effectively cured by heating together with the curing by active energy ray irradiation. In general, in this type of reaction using a photoacid generator, it has been known that curing can be promoted by heating simultaneously with light irradiation or after light irradiation. However, in the case of the component (A) of the present invention, the acceleration effect by heating is not so much seen except for the acid generator of the present invention. On the other hand, when the acid generator of the present invention is used, a large acceleration effect by heating is observed.

  Heating may be performed at the time of irradiation with active energy rays, or may be performed after irradiation with active energy rays. Moreover, you may heat by both. The heating may be performed using an infrared heater or the like, or may be performed by circulating hot air.

  In addition, the heating at the time of irradiation with active energy rays in the present invention is not only heating at the same time as the irradiation, but also heating the curable composition before the irradiation so that the curable composition is maintained at a high temperature. It includes irradiation with energy rays.

  When heating before active energy ray irradiation, it is preferable to make the temperature of an active energy ray curable composition into the range of 50-100 degreeC. When heating simultaneously with active energy ray irradiation, it is preferable to make the temperature of an active energy ray curable composition into the range of 50-100 degreeC. When heating after irradiation with active energy rays, it is preferable to heat in an atmosphere of 50 to 100 ° C. for 1 to 60 minutes.

  In the present invention, the composition includes, for example, metal materials such as metal plates and metal cans, natural materials such as paper and wood, inorganic materials such as ceramics, plastic moldings such as acrylic resins and polycarbonate resins, PET, polyolefins, and the like. It can be applied as a coating material or ink material to a base material made of a composite material such as a film, an electrodeposition coating plate, a laminate plate, etc., and a protective film is formed on the base material by curing it. Can do.

  Examples of the present invention will be described in detail below, but the present invention is not limited thereto. In the following description, “part” means “part by mass”.

<Synthesis example>
<Synthesis Example 1> Synthesis of Siloxane Oligomer A1 Methyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., molecular weight 136.2) 18.0 g, Phenyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., molecular weight 198.3) 2.97 g, 10.0 g of isopropyl alcohol and water were added and stirred to obtain a uniform solution. Further, 15.9 g of water was added, and the mixture was heated at 80 ° C. for 9 hours with stirring, followed by hydrolysis and condensation to obtain a siloxane oligomer. Further, isopropyl alcohol was added to make 54.1 g as a whole, and a siloxane oligomer A1 solution having a solid content concentration of 20% by mass was obtained. Furthermore, when the weight average molecular weight was measured by GPC, the molecular weight in terms of polystyrene was about 2,000.

  However, the solid content concentration mentioned here means the mass fraction of the siloxane oligomer obtained in the case of complete hydrolysis and condensation, and the same applies to the following siloxane oligomers A2 and A3.

<Synthesis Example 2> Synthesis of Siloxane Oligomer A2 Methyl silicate having a silica equivalent concentration of 53% by mass (manufactured by Colcoat Co., average about 7-mer, average molecular weight of about 789, trade name: methyl silicate 53A) 10.0 g, methyl tri 10.0 g of isopropyl alcohol was added to 17.3 g of methoxysilane and stirred to obtain a uniform solution. Furthermore, 10.5 g of water was added, and the mixture was superheated at 80 ° C. for 3 hours with stirring, followed by hydrolysis and condensation to obtain a siloxane oligomer. Furthermore, isopropyl alcohol was added to make 69.2 g as a whole, and a siloxane oligomer A2 solution having a solid concentration of 20% by mass was obtained. Furthermore, when the weight average molecular weight was measured by GPC, the molecular weight in terms of polystyrene was about 6,500.

<Synthesis Example 3> Synthesis of Siloxane Oligomer A3 16.34 g of methyltrimethoxysilane, 5.95 g of phenyltrimethoxysilane and 10.0 g of isopropyl alcohol were added and stirred to obtain a uniform solution. Further, 16.2 g of water was added, and the mixture was heated at 80 ° C. for 9 hours with stirring to perform hydrolysis and condensation to obtain a siloxane oligomer. Further, isopropyl alcohol was added to make a total of 59.6 g, and a siloxane oligomer A3 solution having a solid concentration of 20% by mass was obtained. Furthermore, when the weight average molecular weight was measured by GPC, the molecular weight in terms of polystyrene was about 1,700.

Synthesis Example 4 Hydrolysis of Organosilane and Colloidal Silica, Synthesis of Condensate H1 Isopropyl alcohol-dispersed colloidal silica (Nissan Chemical Industries, Ltd.) as colloidal silica in a 500 ml eggplant type flask equipped with a stirrer and a condenser Manufactured, trade name: Snowtex IPA-ST-L) 100 g, methyltrimethoxysilane 6.8 g, pure water 5.4 g and isopropyl alcohol 74.6 g were charged and heated at 80 ° C. for 4 hours using a water bath. Hydrolysis and condensation were carried out with stirring to obtain a condensate H1 solution having a solid content concentration of 20% by mass.

  However, the solid content concentration referred to here means the mass fraction of the hydrolyzed organocondens or alkyl silicates obtained by complete hydrolysis and condensation and colloidal silica, and the mass of the condensate with respect to the total solution. The same applies to H2 and H3 below.

<Synthesis Example 5> Hydrolysis of alkyl silicate and colloidal silica, synthesis of condensate H2 Isopropyl alcohol-dispersed colloidal silica (Nissan Chemical Industry Co., Ltd.) as colloidal silica in a 500 ml eggplant type flask equipped with a stirrer and a condenser Manufactured, trade name: Snowtex IPA-ST) 100 g, methyl silicate tetramer (manufactured by Colcoat Co., Ltd., trade name: methyl silicate 51) 11.75 g, pure water 9.0 g and isopropyl alcohol 59.25 g were charged. Hydrolysis and condensation were carried out by heating and stirring for 4 hours at 80 ° C. using a water bath to obtain a condensate H2 solution having a solid content concentration of 20 mass%.

Synthesis Example 6 Synthesis of Compound A4 Methyltrimethoxysilane 14.72 g, phenyltrimethoxysilane 2.68 g, dimethyldimethoxysilane (manufactured by Toray Dow Corning Co., Ltd., molecular weight 120.2) 1.64 g, isopropyl alcohol 16 .84 g and 14.12 g of pure water were added and stirred to obtain a compound A4 solution having a solid concentration of 20% by mass. However, the solid content concentration referred to here means hydrolysis of organosilanes and alkyl silicates obtained when completely hydrolyzed and condensed, and mass fraction with respect to the whole solution of the condensate. The same applies to A7.

<Synthesis Example 7> Synthesis of Compound A5 A compound having a solid content concentration of 20% by mass was added to 17.73 g of methyltrimethoxysilane and 1.94 g of phenyltrimethoxysilane with addition of 15.18 g of isopropyl alcohol and 15.14 g of pure water and stirred. An A5 solution was obtained.

<Synthesis Example 8> Synthesis of Compound A6 9.16 g of methyltrimethoxysilane, 3.08 g of phenyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 236.1) To 92 g, 21.64 g of isopropyl alcohol and 11.20 g of pure water were added and stirred to obtain a compound A6 solution having a solid content concentration of 20% by mass.

<Synthesis Example 9> Synthesis of Compound A7 1.78 g of methyl silicate having a silica equivalent concentration of 53% by mass, 13.32 g of methyltrimethoxysilane, 2.42 g of phenyltrimethoxysilane, 1.48 g of dimethyldimethoxysilane, and 16.8 g of isopropyl alcohol. 92 g and 14.08 g of pure water were added and stirred to obtain a compound A7 solution having a solid concentration of 20% by mass.

<Synthesis Example 10> Hydrolysis of organosilane and colloidal silica, synthesis of condensate H3 In a 500 ml eggplant type flask equipped with a stirrer and a condenser, isopropyl alcohol-dispersed colloidal silica as a colloidal silica (Nissan Chemical Industry Co., Ltd.) Manufactured, trade name: Snowtex IPA-ST) 100 g, methyltrimethoxysilane 6.8 g, pure water 5.4 g and isopropyl alcohol 74.6 g were charged and heated and stirred at 80 ° C. for 4 hours using a water bath. Then, hydrolysis and condensation were performed to obtain a condensate H3 solution having a solid content concentration of 20% by mass.

<Example 1>
[Preparation of active energy ray-curable composition]
As component (A), 50.0 parts of a 20% by mass solid content concentration of the siloxane oligomer A1 obtained in Synthesis Example 1 (10.0 parts as a solid content) and benzyl-4-hydroxyphenyl as a component (B) Methylsulfonium hexafluoroantimonate 50 mass% γ-butyrolactone solution 0.4 part (0.2 parts as solid content), isopropyl alcohol 10.0 parts, γ-butyrolactone 15.0 parts, butyl cellosolve 10.0 parts As a leveling agent, 0.01 part of a silicone surfactant (trade name L-7001, manufactured by Toray Dow Corning Co., Ltd.) was mixed to obtain an active energy ray-curable composition.

[Formation of Photocurable Composition Film]
An appropriate amount of this active energy ray-curable composition is dropped on an acrylic plate (product name “Acrylite EX”, manufactured by Mitsubishi Rayon Co., Ltd.) having a length of 10 cm, a width of 10 cm, and a thickness of 3 mm, and a bar coating method (bar coater No. .26 use) was applied so that the thickness after drying was 3 to 4 μm, and was naturally dried at room temperature for about 60 minutes.

[Formation of protective coating]
Furthermore, using a 120 W / cm high-pressure mercury lamp equipped with a conveyor (manufactured by Oak Manufacturing Co., Ltd., ultraviolet irradiation device, handy UV-1200, QRU-2161 type), ultraviolet light with an integrated light quantity of 1000 mJ / cm ² is irradiated, Cured to obtain a protective coating. The integrated light quantity was measured using an ultraviolet light quantity meter (manufactured by Oak Manufacturing Co., Ltd., UV-351 type). The maximum temperature of the sample by ultraviolet irradiation was 33 ° C.

[Evaluation of coating]
The obtained protective film was evaluated by the following method.

1) Appearance The acrylic plate having a protective coating was visually observed for the presence of transparency, cracks, and whitening, and evaluated according to the following criteria.
“◯”: Transparent, free from cracks and whitening defects (good).
“X”: An opaque part, a defect such as a crack or whitening (defect).

2) Film thickness The cut surface of the acrylic board which has a protective film was observed with the scanning electron microscope, and the film thickness was measured.

3) Scratch resistance The surface of the acrylic plate having a protective coating was rubbed 10 times with # 0000 steel wool with a pressure of 9.8 × 10 ⁴ Pa applied, and the number of scratches generated in the range of 1 × 1 cm. Evaluation was made according to the following criteria.
A: 0 scratches (with glossy surface)
B: 1 to 9 scratches (with glossy surface)
C +: 10 to 49 scratches (with glossy surface)
C-: 50 to 99 scratches (with glossy surface)
D: 100 or more scratches (with glossy surface)
E: Glossy surface disappears

4) Pencil hardness The pencil hardness of the protective coating was evaluated according to JIS-K5600 (pencil scratch test).

  As a result, the coating film of this example had good appearance, scratch resistance, and pencil hardness. The results are shown in Table 1.

<Examples 2 to 5>
(A) Preparation of active energy ray-curable composition, formation of photocurable composition film, protective coating, in the same manner as in Example 1, except that the components listed in Table 1 are blended as the component (B) and component (B) The formation of the film and the evaluation of the film were carried out. The results are shown in Table 1.

<Example 6>
In the same manner as in Example 1, preparation of an active energy ray-curable composition and formation of a photocurable composition film were performed, and further, the sample was heated to about 70 ° C. with a halogen heater at the same time as being irradiated with ultraviolet rays. Was cured. Thereafter, the coating was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 7>
In the same manner as in Example 1, preparation of an active energy ray-curable composition, formation of a photocurable composition film, and curing of the film by ultraviolet irradiation were performed. Furthermore, it heated as a post-cure with a hot air dryer at 90 degreeC for 10 minutes, and formed the protective film. Thereafter, the coating was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 8>
In the same manner as in Example 6, preparation of the active energy ray-curable composition, formation of a photocurable composition film, and ultraviolet curing and film curing were performed. Furthermore, as a post cure, it heated at 90 degreeC with the hot air dryer for 10 minutes, and formed the protective film. Thereafter, the coating was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Comparative Examples 1-3>
Preparation of active energy ray-curable composition, formation of photocurable composition film, ultraviolet ray, in the same manner as in Example 1, except that the components shown in Table 2 are blended as the component (A) and the component (B ′) The film was cured by irradiation and the film was evaluated. The results are shown in Table 2.

<Comparative example 4>
Preparation of an active energy ray-curable composition, formation of a photocurable composition film, ultraviolet rays, in the same manner as in Example 6, except that the components described in Table 2 are blended as the component (A) and the component (B ′) The film was cured by irradiation and heating to form a protective film. Thereafter, the coating was evaluated in the same manner as in Example 1. The results are shown in Table 2.

<Comparative Example 5>
Preparation of an active energy ray-curable composition, formation of a photocurable composition film, ultraviolet rays, in the same manner as in Example 7, except that the components described in Table 2 are blended as the component (A) and the component (B ′) The film was cured by irradiation and post-cured to form a protective film. Thereafter, the coating was evaluated in the same manner as in Example 1. The results are shown in Table 2.

<Comparative Example 6>
(A) Preparation of active energy ray-curable composition, formation of photocurable composition film, ultraviolet ray, in the same manner as in Example 8, except that the components listed in Table 2 are blended as the component (B). The film was cured by irradiation and heating and post-cured to form a protective film. Thereafter, the coating was evaluated in the same manner as in Example 1. The results are shown in Table 2.

<Comparative Example 7>
In the same manner as in Example 1, preparation of an active energy ray curable composition and formation of a photocurable composition film were performed. Further, instead of the light irradiation, the film was cured by heating at 90 ° C. for 120 minutes. Thereafter, the coating was evaluated in the same manner as in Example 1. The results are shown in Table 2.

  As can be seen from the examples and comparative examples, according to the protective film forming method of the present invention, a protective film excellent in appearance and scratch resistance can be formed by light irradiation in a short time. On the other hand, when other photoacid generators are used, it is clear that it is difficult to develop good scratch resistance. In addition, as shown in Comparative Example 7, the photocurable composition used in the present invention could not form a protective film excellent in appearance and scratch resistance only by heating.

<Example 9>
[Preparation of active energy ray-curable composition]
As component (A), 35.0 parts of a 20% by mass solid content concentration solution of siloxane oligomer A3 obtained in Synthesis Example 3 (7.0 parts as solid content), obtained as Synthesis Component 4 as (H) component In addition, 15.0 parts (3.0 parts as a solid content) of a 20 mass% solid content concentration solution of the condensate H1 was added to 50% by mass of benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate as a component (B). 0.4 parts of butyrolactone solution (0.2 parts as solid content), 10.0 parts of isopropyl alcohol as solvent, 15.0 parts of γ-butyrolactone, 10.0 parts of butyl cellosolve, silicone surfactant as leveling agent (Toray Dow) Corning Co., Ltd., trade name: L-7001) 0.01 part was mixed to obtain an active energy ray-curable composition. Hereinafter, in the same manner as in Example 7, formation of a photocurable composition film, formation of a protective film, and evaluation were performed. Furthermore, abrasion resistance was also evaluated as a film evaluation. The results are shown in Table 4.

[Evaluation of coating]
6) Abrasion resistance The value of the haze after the Taber abrasion test (the test was carried out using a 500 g load on one side, a wear wheel of CS-10F (trade name) at a rotational speed of 60 rpm and 500 tests) was measured. And the numerical value represented by (the haze value after the test) − (the haze value before the test) was shown as wear resistance (%).

  In Examples 6 and 7, the wear resistance was additionally evaluated. As a result, it was 21% in Example 6 and 18% in Example 7.

<Examples 10 to 13>
Preparation of an active energy ray-curable composition in the same manner as in Example 9 except that the components (A), (H), and (B) described in Table 4 are added in the amounts shown in Table 4. Then, a protective film was formed by forming a photocurable composition film, curing the film by ultraviolet irradiation, and post-curing. Thereafter, the coating was evaluated. The results are shown in Table 4.

<Example 14>
In the same manner as in Example 13, the preparation of the active energy ray-curable composition and the formation of the photocurable composition film were performed, and the sample was heated to about 70 ° C. with a halogen heater at the same time as the ultraviolet ray was irradiated. Was cured and no post cure was performed. Thereafter, the coating was evaluated in the same manner as in Example 13. The results are shown in Table 4.

<Comparative Examples 8 and 9>
The active energy ray-curable composition of (A), (H), and (B ′) is the same as in Example 9 except that the components listed in Table 5 are blended in the blending amounts listed in Table 5. Preparation, formation of a photocurable composition film, curing of the film by ultraviolet irradiation, and post-curing were performed to form a protective film. Thereafter, the coating was evaluated. The results are shown in Table 5.

<Example 15>
As component (A), 50.0 parts (10.0 parts as solid content) of a 20% by weight solid content concentration of compound A4 obtained in Synthesis Example 6 was added to benzyl-4-hydroxyphenylmethyl as component (B). 0.4 parts of a 50% by weight γ-butyrolactone solution of sulfonium hexafluoroantimonate (0.2 parts as a solid content), 10.0 parts of isopropyl alcohol, 15.0 parts of γ-butyrolactone, 10.0 parts of butyl cellosolve, 0.01 parts of a silicone surfactant (trade name: L-7001, manufactured by Toray Dow Corning Co., Ltd.) was mixed as a leveling agent to obtain an active energy ray-curable composition. Thereafter, in the same manner as in Example 6, formation of a photocurable composition film, formation of a protective film, and evaluation were performed. The results are shown in Table 6.

<Examples 16 to 20>
Preparation of active energy ray-curable composition, formation of photocurable composition film, protective coating, in the same manner as in Example 15 except that the components described in Table 6 are blended as the component (A) and the component (B). The formation of the film and the evaluation of the film were carried out. The results are shown in Table 6.

<Example 21>
In the same manner as in Example 16, preparation of an active energy ray-curable composition, formation of a photocurable composition film, curing of the film by ultraviolet irradiation and heating were performed. Furthermore, as a post cure, it heated at 90 degreeC with the hot air dryer for 10 minutes, and formed the protective film. Thereafter, the coating was evaluated in the same manner as in Example 1. The results are shown in Table 6.

<Example 22>
As component (A), 35.0 parts of a solid content concentration 20% by mass solution of compound A4 obtained in Synthesis Example 6 (7.0 parts as solid content), and as component (H), obtained in Synthesis Example 10 A solid content concentration 20% by weight solution of condensate H3 (15.0 parts (3.0 parts as solid content)), and 50% by weight γ-methylbenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate as component (B) 0.4 parts of butyrolactone solution (0.2 parts as solid content), 10.0 parts of isopropyl alcohol as solvent, 15.0 parts of γ-butyrolactone, 10.0 parts of butyl cellosolve, silicone surfactant as leveling agent (Toray Dow) Corning Co., Ltd., trade name: L-7001) 0.01 part was mixed to obtain an active energy ray-curable composition. Thereafter, in the same manner as in Example 15, formation of a photocurable composition film, formation of a protective film, and evaluation were performed. The results are shown in Table 6.

<Comparative Examples 10-12>
(A) Preparation of active energy ray-curable composition, formation of photocurable composition film, ultraviolet ray in the same manner as in Example 15 except that the components listed in Table 7 are blended as the component (B). Irradiation and the like were performed, but the film was not cured. The results are shown in Table 7.

<Comparative Example 13>
(B ′) Except for blending the components listed in Table 7, the preparation of an active energy ray-curable composition, the formation of a photocurable composition film, and ultraviolet irradiation were performed in the same manner as in Example 22. However, the film did not cure. The results are shown in Table 7.

<Example 23>
As component (A), the solid content of the siloxane oligomer A1 obtained in Synthesis Example 1 having a solid content of 200% by mass of 15.0 parts (3.0 parts as the solid content) and the solid content of Compound A5 obtained in Synthesis Example 7 To a solution of 35.0 parts of a 20 mass% solution (7.0 parts as a solid content), 0.4 parts of a 50 mass% γ-butyrolactone solution of benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate as the component (B) ( 0.2 parts as solids), 10.0 parts isopropyl alcohol, 15.0 parts γ-butyrolactone, 10.0 parts butyl cellosolve, silicone surfactant as leveling agent (product of Toray Dow Corning Co., Ltd.) Name: L-7001) 0.01 part was mixed to obtain an active energy ray-curable composition. Thereafter, in the same manner as in Example 6, formation of a photocurable composition film, formation of a protective film, and evaluation were performed. The results are shown in Table 8.

<Example 24>
(A) Preparation of active energy ray-curable composition, formation of photocurable composition film, protective coating, in the same manner as in Example 23, except that the components listed in Table 8 are blended as the component (B). The formation of the film and the evaluation of the film were carried out. The results are shown in Table 8.

<Example 25>
As component (A), the solid content of the siloxane oligomer A1 obtained in Synthesis Example 1 having a solid content of 20% by mass of 12.0 parts (2.4 parts as the solid content) and the solid content of Compound A5 obtained in Synthesis Example 7 28.0 parts of a 20% strength by weight solution (5.6 parts as a solid content), 10.0 parts of a 20% strength by weight solid solution of the condensate H3 obtained in Synthesis Example 10 as a component (H) (solid content) As a component (B), 0.4 part of a 50 mass% γ-butyrolactone solution of benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate as a component (B) (0.2 part as a solid content), and isopropyl as a solvent. 10.0 parts of alcohol, 15.0 parts of γ-butyrolactone, 10.0 parts of butyl cellosolve, a silicone surfactant as a leveling agent (trade name: L, manufactured by Toray Dow Corning Co., Ltd.) -7001) 0.01 part was mixed and it was set as the active energy ray curable composition. Thereafter, in the same manner as in Example 23, formation of a photocurable composition film, formation of a protective film, and evaluation were performed. The results are shown in Table 8.

<Comparative Examples 14 and 15>
Preparation of active energy ray-curable composition, formation of photocurable composition film, ultraviolet ray, in the same manner as in Example 15 except that the components described in Table 9 are blended as the component (A) and the component (B ′) The film was cured by irradiation and the film was evaluated. The results are shown in Table 9.

  The laminated body of the present invention includes automotive parts such as headlamp lenses and sunroofs, windshields for motorcycles, windows for railway vehicles and aircraft, sound insulation plates for highways, optical equipment parts such as lenses and filters, mobile phones and information equipment. It is suitable for a housing, an optical disk, a functional film for a display or a touch panel.

Claims (8)

For active energy ray curing containing at least one selected from siloxane oligomers, organosilanes and alkyl silicates (A), and an aromatic sulfonium salt acid generator (B) represented by the general formula (1) Composition.

(In the formula, R ¹ , R ² and R ³ each represent hydrogen, an organic group having 1 to 10 carbon atoms, a halogen group or a hydroxyl group, and R ⁴ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms. And R ⁵ represents an aromatic hydrocarbon group or an aromatic hydrocarbon group having a substituent, and X ⁻ represents a counter anion.) Active energy ray-curable composition containing at least one selected from siloxane oligomers, organosilanes and alkylsilicates (A), and an aromatic sulfonium salt-type acid generator (B) represented by the general formula (1) The protective film formation method which apply | coats a thing to a base material and hardens the said active energy ray curable composition by active energy ray irradiation.

(In the formula, R ¹ , R ² and R ³ each represent hydrogen, an organic group having 1 to 10 carbon atoms, a halogen group or a hydroxyl group, and R ⁴ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms. And R ⁵ represents an aromatic hydrocarbon group or an aromatic hydrocarbon group having a substituent, and X ⁻ represents a counter anion.) The protective coating according to claim 2, wherein the siloxane oligomer is a hydrolysis or condensate of one or more compounds selected from the group consisting of organosilanes represented by the general formula (2) and alkyl silicates represented by the general formula (3). Forming method.

(In the formula, R ⁶ represents an organic group having 1 to 10 carbon atoms, R ⁷ represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, and a is any one of 0 to 3) Represents an integer.)

(Wherein R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ independently represent an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 2 to 20) Furthermore, any one or more compounds of the organosilanes represented by the general formula (4) and the alkyl silicates represented by the general formula (5), and colloidal silica having a number average particle diameter of 5 to 200 nm The method for forming a protective film according to claim 2 or 3, wherein the active energy ray-curable composition containing the hydrolysis and condensate (H) is cured.

(In the formula, R ¹² represents an organic group having 1 to 10 carbon atoms, R ¹³ represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, and b represents an integer of 0 to 3). .)

(In formula, R <^14> , R <^15> , R <^16> and R < ¹⁷ > represent a C1-C5 alkyl group independently, and m represents the integer in any one of 2-20.)   The active energy ray-curable composition is heated at the time of active energy ray irradiation, after active energy ray irradiation, or both when curing the active energy ray curable composition by active energy ray irradiation. The protective film formation method in any one. Furthermore, any one or more compounds of the organosilanes represented by the general formula (4) and the alkyl silicates represented by the general formula (5), and colloidal silica having a number average particle diameter of 5 to 200 nm The composition for active energy ray hardening of Claim 1 containing a hydrolysis and a condensate (H).

(In the formula, R ¹² represents an organic group having 1 to 10 carbon atoms, R ¹³ represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, and b represents an integer of 0 to 3). .)

(In formula, R <^14> , R <^15> , R <^16> and R < ¹⁷ > represent a C1-C5 alkyl group independently, and m represents the integer in any one of 2-20.)   The laminated body which has the cured film of the composition for active energy ray hardening of Claim 1 or 6 on the surface of a base material.   The manufacturing method of the laminated body which provides a protective film in the surface of a base material with the protective film formation method in any one of Claims 2-5.