JP6062661B2 - Active energy ray-curable coating resin composition - Google Patents

Description

  The present invention has good adhesion, excellent solvent resistance and chemical resistance to materials that cannot be heated excessively, such as plastic moldings and films, while having high surface hardness and scratch resistance. The present invention relates to an active energy ray-curable resin composition excellent in flexibility.

  In recent years, plastic materials such as acrylic resin, polycarbonate resin, and PET resin have been widely used as an alternative to metal and glass. However, these plastic materials have a problem of low surface hardness and insufficient chemical resistance. Therefore, a technique of applying various coating materials to the surface of the plastic material to improve performance has been taken.

  For example, there is a method of applying a thermosetting urethane coating and forming a coating film at a temperature lower than the heat resistance temperature of the plastic substrate (Patent Document 1). However, in order to obtain surface hardness and chemical resistance, it is necessary to increase the crosslinking density, and the hydroxyl value is designed to be high. Thereby, there exists a problem which the adhesiveness with respect to plastics, such as a polycarbonate, falls.

  Another method for increasing surface hardness and chemical resistance is to apply a copolymer containing an alkoxysilyl group and obtain a cured film with an organometallic compound such as an organotin compound under heating conditions. (Patent Document 2). However, under conditions that are lower than the heat resistant temperature of the plastic substrate, heating for a long time is required to obtain a sufficient cured film, and there is a problem in productivity.

  On the other hand, a method in which a polyfunctional monomer or oligomer is used as a main constituent and UV curing is performed using a photo radical generator has also been reported (Patent Document 3). Since this method does not require heat drying for curing, there is an advantage that a film having a high hardness can be obtained in a short time without damaging the plastic substrate. However, the obtained film becomes too hard, the adhesion to the plastic substrate is not sufficient, the followability is not obtained, and in some cases the influence on the human body is concerned by the monomer used, etc. is there.

  For this reason, the development of a coating agent having high transparency, chemical resistance, and high surface hardness has been demanded.

JP 2008-296539 A JP 2003-231223 A Japanese Patent Laid-Open No. 5-230397

  The problem to be solved by the present invention is that a transparent cured coating film having good solvent resistance and chemical resistance, excellent adhesion to a plastic substrate can be formed, and has high surface hardness and scratch resistance. It is to provide an active energy ray-curable resin composition that can be cured for a short time with an active energy ray or the like that has excellent flexibility while having it.

  As a result of intensive studies to solve the above problems, the present inventors have found that a (meth) acrylic copolymer having a hydrolyzable silyl group and an isocyanate group, and a coating resin composition containing a specific photoacid generator However, a transparent cured coating film is formed in a short time by UV irradiation using a high-pressure mercury lamp, etc., and the obtained coating film exhibits excellent solvent resistance and chemical resistance, and is excellent in scratch resistance and plastic material. It was found that good adhesion was exhibited. Furthermore, the obtained coating film also discovered having the outstanding softness | flexibility.

That is, this application
The main chain is a (meth) acrylic copolymer, and the general formula (I):
-SiR ² _a (OR ¹ ) _3-a (I)
Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl having 7 to 12 carbon atoms. A monovalent hydrocarbon group selected from a group, wherein a is an integer of 0 to 2.) having two or more silicon groups bonded to a hydrolyzable group represented by: An active energy ray-curable composition comprising a copolymer (A) component having two or more isocyanate groups in the side chain, (B) a photoacid generator, and (C) a dehydrating agent (claimed) Item 1).
The said copolymer (A) component contains 5-50 silicon groups couple | bonded with the hydrolysable group represented by general formula (I) in one molecule | numerator, It is characterized by the above-mentioned. An active energy ray-curable composition (Claim 2).
The active energy ray-curable composition according to claim 1 or 2, wherein the copolymer (A) component contains 3 to 50 isocyanate groups in one molecule.
The active energy ray-curable composition according to any one of claims 1 to 3, wherein the photoacid generator (B) component is an aromatic sulfonium salt or an aromatic iodonium salt. 4).
The active energy ray-curable property according to any one of claims 1 to 4, wherein the counter anion of the photoacid generator (B) component is a fluorophosphonate or fluorosulfonate. A composition (claim 5).
The active energy ray-curable composition according to any one of claims 1 to 5, wherein the dehydrating agent (C) component is an orthocarboxylic acid ester and / or a highly active silane compound. 6).
The coating body which coated the active energy ray curable composition as described in any one of Claims 1-6 (Claim 7).
A curable composition for active energy ray hard coat containing the curable composition according to any one of claims 1 to 6 (claim 8).
The manufacturing method of the coating film which apply | coats the active energy ray curable composition as described in any one of Claims 1-6 to a base material, and irradiates an active energy ray (Claim 9).
The active energy ray-curable composition according to the present invention can be applied to a substrate and irradiated with active energy rays to form a cured film.
By applying and curing the active energy ray-curable composition according to the present invention on the surface of the substrate, a laminate having a cured film formed on the surface of the substrate can be produced.
The active energy ray-curable composition according to the present invention can be suitably used as a one-component curable composition.
When the active energy ray-curable composition according to the present invention is used, after coating, UV irradiation using a high-pressure mercury lamp, a metal halide lamp, a light-emitting diode, etc., in a short time, the surface hardness is high, and excellent solvent resistance and resistance. A chemical film and good adhesion to a plastic material can be obtained, and furthermore, a coating film having good scratch resistance and flexibility can be obtained.

  Since the coating resin composition of the present invention has high storage stability under light shielding, a one-pack type paint form is possible. The composition of the present invention can be cured for a short time with active energy rays such as UV light, has high surface hardness, good solvent resistance and chemical resistance, fingerprint wiping property, A transparent cured coating film having excellent adhesion to a plastic substrate can be formed.

Hereinafter, the present invention will be described in detail based on an embodiment thereof.
(A) Vinyl copolymer The vinyl copolymer (A) that can be used in the present invention includes (a) a hydrolyzable silyl group-containing vinyl monomer and (b) an isocyanate group-containing vinyl monomer. (C) It is obtained by polymerizing other polymerizable vinyl monomers.

(A) Hydrolyzable silyl group-containing vinyl monomer The hydrolyzable silyl group may be bonded to the end of the main chain of the copolymer (A) component, or may be bonded to a side chain. , May be bonded to the end of the main chain and the side chain.
As the hydrolyzable silyl group-containing vinyl monomer (a), a vinyl monomer having an alkoxysilyl group represented by the following general formula (I) is useful.
-SiR ² _a (OR ¹ ) _3-a (I)
Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl having 7 to 12 carbon atoms. A monovalent hydrocarbon group selected from the group, and a is an integer of 0 to 2.)
In the general formula (I), (OR ¹ ) _3-a is preferably 0 or 1 from the viewpoint that the curability of the composition of the present invention is improved. When a plurality of OR ¹ or R ² are present, they may be the same or different.

  Specific examples of the hydrolyzable silyl group-containing vinyl monomer (a) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (n-propoxy) silane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltris. (Β-methoxyethoxy) silane, allyltriethoxysilane, trimethoxysilylpropylallylamine, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxy Propyltriisopropoxysilane, γ- (meth) acryloxypropyltris (β-methoxyethoxy) silane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (Meta) Acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropyldimethylethoxysilane, N-vinylbenzyl-γ-aminopropyltrimethoxysilane, 2-styrylethyltrimethoxysilane, 3- (N-styrylmethyl-2- Aminoethylamino) propyltrimethoxysilane, (meth) acryloxyethyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, vinyltriacetoxysilane, vinyltrichlorosilane, etc. Γ- (meth) acryloxypropyltrimethoxysilane and γ- (meth) acryloxypropyltriethoxysilane, which are group-containing monomers, are preferable from the viewpoint of stability. The above (meth) acryloxy means methacryloxy and / or acryloxy in the present specification.

  These hydrolyzable silyl group-containing vinyl monomers (a) may be used alone or in combination of two or more. The hydrolyzable silyl group-containing vinyl monomer contains 2 to 50, particularly preferably 5 to 30, silicon groups bonded to the hydrolyzable group per molecule of the vinyl copolymer (A). Is preferably used from the viewpoint of providing sufficient solvent resistance and chemical resistance and improving scratch resistance. The monomer (a) is preferably used in an amount of 5 to 80 parts by weight, particularly preferably 10 to 60 parts by weight, based on 100 parts by weight of all monomer units of the vinyl copolymer (A).

(B) Isocyanate group-containing vinyl monomer The isocyanate group may be bonded to the main chain terminal of the copolymer (A) component, may be bonded to the side chain, the main chain terminal and the side. It may be bound to a chain.

  As the isocyanate group-containing vinyl monomer (b), α, β-ethylenically unsaturated monoisocyanate is useful.

  Specific examples of the α, β-ethylenically unsaturated monoisocyanate include (meth) acryloxy isocyanate, β- (meth) acryloxyethyl isocyanate, γ-isopropenyl-α, α'-dimethylbenzyl isocyanate and the like. It is done.

  In addition, polyfunctional isocyanates and hydroxyl group-containing vinyl polymerizable monomers such as 2-hydroxyethyl (meth) acrylate and secondary amino groups such as N-methylaminopropyl (meth) acrylate and N-methyl (meth) acrylamide An isocyanate-containing polymerizable monomer may be obtained by forming a urethane bond after reacting with the vinyl-containing polymerizable monomer in advance.

  Among these, β- (meth) acryloxyethyl isocyanate is preferable from the viewpoints of stability and curability.

  These isocyanate group-containing vinyl monomers (b) may be used alone or in combination of two or more.

  Further, the amount used is designed so that it contains 2 to 100, particularly preferably 3 to 50, isocyanate groups per molecule of the vinyl copolymer (A). Is preferable in that it can be obtained. The monomer (b) is preferably used in an amount of 3 to 80 parts by weight, particularly preferably 5 to 60 parts by weight, based on 100 parts by weight of all the monomer units of the vinyl copolymer (A).

(C) Other polymerizable vinyl monomers Other specific examples of the copolymerizable monomer (c) include (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i -Butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, 3, 3 , 5-trimethylcyclohexyl (meth) acrylate, glycidyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-butoxymethyl (meth) Acrylamide, N, N- Acrylamides such as dimethyl (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, (meth) acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2 -Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxystyrene vinyl toluene, Allonics 5700, 4 manufactured by Toagosei Chemical Industry Co., Ltd. -Hydroxystyrene, manufactured by Nippon Shokubai Chemical Industry Co., Ltd. HE-10, HE-20, HP-1 and HP-2 (all of which are acrylate oligomers having a hydroxyl group at the terminal), manufactured by Nippon Oil & Fats Co., Ltd. Blur Ε-caprolactone-modified hydroxyalkyl vinyl copolymer compound PlaccelFM-1 obtained by reaction of a polyalkylene glycol (meth) acrylate derivative such as the Mer PP series, Blemmer PE series, Blemmer PEP series, etc., a hydroxyl group-containing compound and ε-caprolactone , FM-4 (manufactured by Daicel Chemical Industries, Ltd.), TONEM-201 (manufactured by UCC), HEAC-1 (manufactured by Daicel Chemical Industries, Ltd.), and the like. Mer and / or its derivatives.

Furthermore, (meth) acrylic compounds containing a phosphate ester group, such as condensation products of hydroxyalkyl esters of (meth) acrylic acid and phosphoric acid or phosphate esters, (meth) acrylates containing urethane bonds or siloxane bonds, etc. (Meth) acrylic acid ester compounds; aromatic hydrocarbon vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, 4 - hydroxystyrene, vinyltoluene; maleic acid, fumaric acid, itaconic acid, Unsaturated carboxylic acids such as (meth) acrylic acid, salts of these alkali metal salts, ammonium salts, amine salts, etc .; acid anhydrides of unsaturated carboxylic acids such as maleic anhydride, these acid anhydrides and 1 to 1 carbon atoms Diesters with 20 linear or branched alcohols or amines or Esters of unsaturated carboxylic acids such as half esters; Vinyl esters and allyl compounds such as vinyl acetate, vinyl propionate and diallyl phthalate; Amino group-containing vinyl compounds such as vinyl pyridine and aminoethyl vinyl ether; Itaconic acid diamide and crotonic acid amide Amide group-containing vinyl compounds such as maleic acid diamide, fumaric acid diamide, N-vinylpyrrolidone; (meth) acrylonitrile, 2-hydroxyethyl vinyl ether, methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene And other vinyl compounds such as isoprene, fluoroolefin maleimide, N-vinylimidazole, and vinyl sulfonic acid.

  One or a mixture of two or more selected from these groups can be used. The monomer (c) is preferably used in an amount of 1 to 90 parts by weight, particularly preferably 3 to 50 parts by weight, based on 100 parts by weight of all the monomer units of the vinyl copolymer (A).

  Further, the vinyl polymer (A) obtained by polymerizing the monomers (a) to (c) above has a glass transition temperature of -20 to 80 ° C., which is chemical resistance and scratch resistance. From the viewpoint of excellent balance.

  When the glass transition temperature is −20 ° C. or lower, tack remains in the coating film and the solvent resistance and chemical resistance tend to deteriorate. On the other hand, when the glass transition temperature is 80 ° C. or higher, although the solvent resistance and chemical resistance are excellent, the coating film becomes brittle and the scratch resistance is not sufficient.

  The solvent used in the liquid composition containing the vinyl polymer obtained by polymerizing the monomers (a) to (c) is not particularly limited, and is a known aromatic, aliphatic hydrocarbon, Solvents such as ether, ketone, ester, alcohol, and water can be used. Toluene, xylene, butyl acetate and aliphatic hydrocarbon-containing solvents are preferably used from the viewpoint of the solubility of the vinyl copolymer.

  The method for producing the vinyl polymer is not particularly limited as long as it is a method for obtaining a copolymer liquid composition from the monomer. Examples of the polymerization method include a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, and the like, and the solution polymerization method is preferable from the viewpoint of ease of synthesis.

  Examples of the initiator used for the polymerization include known ones such as organic peroxides such as cumene hydroperoxide, azo compounds such as azobis-2-methylbutyronitrile, potassium persulfate, and the like. Inorganic peroxide-based initiators, redox-based initiators combining peroxides and reducing agents, and the like.

  The degree of polymerization of the obtained vinyl polymer is preferably 2,000 to 25,000 in terms of number average molecular weight. The degree of polymerization can be adjusted by the type and amount of the radical generator, the polymerization temperature, and the use of a chain transfer agent. As the chain transfer agent, n-dodecyl mercaptan, t-dodecyl mercaptan, γ-mercaptopropyltrimethoxysilane and the like can be preferably used. When the number average molecular weight is less than 2,000, an unpolymerized monomer tends to remain, which is not preferable. On the other hand, when the number average molecular weight exceeds 25,000, the resulting curable resin composition often has defects such as stringing during coating.

(B) Photoacid generator The photoacid generator that is the component (B) in the present invention is a compound that generates an acid when exposed to active energy rays, such as toluenesulfonic acid or boron tetrafluoride. Onium salts such as strong acids, sulfonium salts, ammonium salts, phosphonium salts, iodonium salts or selenium salts; iron-allene complexes; silanol-metal chelate complexes; disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethane And sulfonic acid derivatives such as imide sulfonates and benzoin sulfonates; and compounds such as organic halogen compounds that generate an acid upon irradiation with radiation as disclosed in JP-A-5-134411.

  Among the above photoacid generators, an aromatic sulfonium salt or an aromatic iodonium salt is preferable because the composition with the copolymer (A) is highly stable and easily available. Examples of the sulfonic acid derivatives include sulfonic acid esters such as benzoin tosylate, nitrobenzyl tosylate, and succinimide tosyl sulfonate disclosed in US Pat. No. 4,618,564; US Pat. No. 4,540,598 and JP-A-6-67433. Oxime sulfonates such as α- (4-tosyloxyimino) -4-methoxybenzylcyanide shown in Japanese Patent Publication No. 6-348015; tris (methanesulfonyloxy) benzene shown in Japanese Patent Publication No. 6-348015; And 9,10-dialkoxyanthracenesulfonic acid nitrobenzyl ester shown in No. 18143; N- (p-dodecylbenzenesulfonyloxy) -1,8-naphthalimide and the like. Examples of the organic halogen compounds include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-dimethoxystyryl) -4,6- Bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-methylfuran-2-yl) vinyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, etc. Halogen-containing triazine compounds disclosed in JP-A-55-32070, JP-A-48-36281, and JP-A-63-238339; 2-pyridyl-tri described in JP-A-2-304059 Halogen-containing sulfone compounds such as bromomethylsulfone; tris (2-chloropropyl) phosphate, tris (2,3-dichloropropyl) phosphate, tri Halogenated alkyl phosphates such as (2,3-dibromopropyl) phosphate; halogen-containing heterocyclic compounds such as 2-chloro-6- (trichloromethyl) pyridine; 1,1-bis [p-chlorophenyl] -2 , 2,2-trichloroethane, vinylidene chloride copolymers, vinyl chloride copolymers, halogen-containing hydrocarbon compounds such as chlorinated polyolefins, and the like.

  Above all, when the counter anion of the aromatic sulfonium salt or aromatic iodonium salt is a fluorophosphonate, fluoroantimonate or fluorosulfonate, the curing is quick and the adhesion to the plastic substrate is excellent. To preferred. In view of safety, a fluorophosphonate or fluorosulfonate is particularly preferable.

  (B) Although the addition amount of a component needs adjustment according to the generation amount and generation | occurrence | production speed of the acid to produce | generate, 0.05-30 weight part is preferable with respect to 100 weight part of solid content of a copolymer (A). More preferably, the amount is 0.1 to 10 parts by weight. If the amount is less than 0.05 parts by weight, the acid generated is insufficient, and the resulting coating film tends to have insufficient solvent resistance and chemical resistance. If the amount exceeds 30 parts by weight, problems such as deterioration of the coating film appearance and coloring may occur. Tend to occur.

(C) Dehydrating agent Since the vinyl copolymer (A) component having a hydrolyzable silyl group and an isocyanate group has reactivity with moisture, the storage stability of the composition can be improved by further adding a dehydrating agent. Can be improved.

  Examples of the dehydrating agent include alkyl orthoformate such as methyl orthoformate, ethyl orthoformate or butyl orthoformate; alkyl orthoacetate such as methyl orthoacetate, ethyl orthoacetate or butyl orthoacetate; or methyl orthoborate, ethyl orthoborate, Examples thereof include orthocarboxylic acid esters such as alkyl orthoborate such as butyl orthoborate, and highly active silane compounds such as tetramethoxysilane, tetraethoxysilane, and methyltrimethoxysilane.

  The amount of the dehydrating agent used is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the solid content of the vinyl polymer (A).

  Moreover, a photosensitizer can be used for the coating agent composition of this invention as needed for the purpose of improving the photosensitivity of (B) component. Although it does not specifically limit as a photosensitizer, For example, anthracene derivative, a benzophenone derivative, a thioxanthone derivative, an anthraquinone derivative, a benzoin derivative etc. are mentioned, More specifically, a 9, 10- dialkoxy anthracene, 2-alkyl thioxanthone, Examples include 2,4-dialkylthioxanthone, 2-alkylanthraquinone, 2,4-dialkylanthraquinone, p, p′-aminobenzophenone, 2-hydroxy-4-alkoxybenzophenone, benzoin ether, and the like. More specifically, anthrone, anthracene, 9,10-diphenylanthracene, 9-ethoxyanthracene, pyrene, perylene, coronene, phenanthrene, benzophenone, benzyl, benzoin, methyl 2-benzoylbenzoate, butyl 2-benzoylbenzoate, Benzoin ethyl ether, benzoin-i-butyl ether, 9-fluorenone, acetophenone, p, p'-tetramethyldiaminobenzophenone, p, p'-tetraethylaminobenzophenone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethyl Thioxanthone, phenothiazine, acridine orange, benzoflavin, cetoflavin-T, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-ni Roaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramid, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1,2-benzanthraquinone 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis (5,7-dimethoxycarbonylcoumarin), 9,10 -Dibutoxyanthracene, 9,10-dipropoxyanthracene, etc. are mentioned. A photosensitizer may be used independently and 2 or more types may be used together.

  As the photosensitizer, one that can absorb light in a wavelength region that cannot be absorbed by the component (B) to be used is more efficient.

  The addition amount of the photosensitizer may be appropriately adjusted according to the intended curing rate, but is preferably 0.1 to 10 parts by weight, more preferably 100 parts by weight of the photoacid generator (B) component. Is an amount of 0.5 to 5 parts by weight. If the amount is less than 0.1 part by weight, the effect of the intended sensitizer is difficult to obtain, and if it exceeds 5 parts by weight, the coating film is colored or the cost is increased.

In this active energy ray-curable composition, a silicon compound represented by the following general formula (II) and / or a partial hydrolysis condensate thereof is used for the purpose of imparting surface characteristics to the obtained coating film or increasing the hardness. can do.
(R ³ O) _4-b SiR ⁴ _b (II)
Wherein R ³ is the same or different, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, R ⁴ is the same or different and has 1 carbon atom. C-10 alkyl group, C6-C10 aryl group, or C7-C10 aralkyl group, b is an integer of 0-2.)
Examples of silicon compounds and / or partial hydrolysis condensates thereof include tetramethyl silicate, tetraethyl silicate, tetra-n-propyl silicate, tetra-i-propyl silicate, tetra-n-butyl silicate, and tetra-i-butyl silicate. Tetraalkyl silicates such as tetra-t-butyl silicate; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyl Triethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyl Ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, octadecyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxy Trialkoxysilanes such as silane, vinyltrimethoxysilane, vinyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane Sialkoxysilanes such as 3- (meth) acryloxypropylmethyldimethoxysilane and 3- (meth) acryloxypropylmethyldiethoxysilane Emissions and / or one or more partially hydrolyzed condensate chosen from silanes and the like. These may be used alone or in combination of two or more.

Among the above silicon compounds and / or partial hydrolysis condensates thereof, a compound represented by the following general formula (III) and / or an organosilicate which is a partial hydrolysis condensate thereof and / or a modified product thereof is a coating film: It is preferable because it is excellent in the effect of imparting hardness to the surface and developing hydrophilicity on the surface.
(R ³ O) ₄ Si (III)
(Wherein R ³ is the same or different and is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms).

  Examples of the organosilicate include tetramethyl silicate, tetraethyl silicate, tetra-n-propyl silicate, tetra-i-propyl silicate, tetra-n-butyl silicate, tetra-i-butyl silicate, tetra-t-butyl silicate, etc. Examples thereof include tetraalkyl silicates and one or more partially hydrolyzed condensates selected from these.

R ³ organosilicate is the number of carbon atoms is large, and because the reaction of hydrolysis and condensation is reduced in some of the branches, considering the hardness and curability of the resulting coating film, the number 1 to 2 carbon Alkyl groups are preferred.

  Moreover, if it is set as a partial hydrolysis-condensation product, the hydrophilic property of the coating-film surface can be improved. The degree of condensation is 2-20, preferably 3-15.

  The amount of the silicon compound and / or its partially hydrolyzed condensate used is 0 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, based on 100 parts by weight of the component (A). is there. If it exceeds 100 parts, the coating film made of the coating agent composition may become cloudy, the curability may be lowered, or the flexibility of the resulting coating film may be insufficient and become brittle.

  Examples of active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, and γ rays, but the reaction rate is fast and the energy ray generator is relatively inexpensive. Is most preferable from ultraviolet rays. As the irradiation amount of the active energy ray, an integrated light amount of 50 mJ to 10,000 mJ is preferable, and an integrated light amount of 100 mJ to 2,000 mJ is more preferable.

  In the obtained active energy ray-curable composition, additives used for usual paints such as inorganic pigments and organic pigments, plasticizers, solvents, dispersants, wetting agents, thickeners, antifoaming agents, etc., if necessary Can also be added.

  The obtained active energy ray curable composition is, for example, a metal, ceramics, glass, cement, ceramic base material, plastic, film, sheet, wood, paper, fiber, etc. It can be suitably used for painting. In particular, it can be suitably used for substrates such as plastics such as acrylic resins, polycarbonate resins, and PET resins, films, and sheets because of easy irradiation with active energy rays.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto.

(Materials used)
(Polymer (A) having at least two silicon groups bonded to hydrolyzable groups)
A reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas introduction pipe and a dropping funnel was charged with the component (a) in Table 1, and the temperature was raised to 110 ° C. while introducing nitrogen gas. The mixture of the component (a) was dropped at a constant rate from the dropping funnel over 5 hours. Next, the mixed solution of the component (c) was dropped at a constant rate over 1 hour. Then, after stirring at 110 degreeC for 2 hours continuously, it cooled to room temperature. Finally, component (C) in Table 1 was added and stirred to synthesize polymer (A).

  Table 1 shows the solid content concentration of the obtained polymer (A-1 to 4) and the number average molecular weight measured by GPC. The polymer (A-1 to 4) was once diluted with a polymerization solvent so that the solid content concentration became 50%, and proceeded to the next blending.

  Furthermore, in order to modify the isocyanate to the polymer A-3, Duranate D101 (Asahi Kasei Chemicals Co., Ltd. polyisocyanate (NCO% = 19.7%)) was used, so that the NCO / OH ratio was 2, The mixture was stirred under a nitrogen stream at 80 ° C. for 3 hours to synthesize a polymer having 11.5 silicon groups bonded to hydrolyzable groups and 4.6 isocyanate groups. After confirming that the absorption of NCO was reduced by half by IR, it was diluted with a polymerization solvent so that the solid content concentration became 50% to obtain a polymer (A-5).

(Method for preparing coating resin composition)
As shown in Table 2, the component (B) and other components were added to the component (A) and mixed at 1000 rpm for 3 minutes using a stirrer to obtain a coating resin composition.

In addition, the symbols of the compounds in Table 2 are as follows.
CPI-100P: Propylene carbonate solution of triarylsulfonium / PF ₆ salt manufactured by San Apro Co., Ltd. CPI-101A: Propylene carbonate solution of triarylsulfonium / SbF ₆ salt manufactured by San Apro Co., Ltd. MPI-105: manufactured by Midori Chemical Co., Ltd. Diaryliodonium / CF ₃ SO ₃ salt MS51: Condensation product of tetramethoxysilane manufactured by Mitsubishi Chemical Corporation (SiO ₂ content: 52% by weight)
MS56: Mitsubishi Chemical Corp. condensate of tetramethoxysilane (Si0 ₂ content: 56 wt%)
U-ES: Reaction product of dioctyl tin salt and silicate manufactured by Nitto Kasei Co., Ltd.

(Evaluation of the physical properties)
The polycarbonate resin, PMMA plate and ABS plate were coated with the coating resin composition prepared in Table 2 using a bar coater to a dry film thickness of about 15 μm, and dried at 80 ° C. for 3 minutes to remove the solvent. did. Next, using an electrodeless lamp bulb (Light Hammer: manufactured by Fusion UV Systems Japan Co., Ltd.) in the air, irradiation with active energy rays is performed at 240 mW so that the integrated light quantity at a wavelength of 310 to 390 nm is 500 mJ / cm ^2. Was cured to obtain a test piece.

  On the other hand, in Comparative Example 3, a metal catalyst was used and thermally dried at 80 ° C. for 30 minutes to obtain a test piece.

  Moreover, it apply | coated to the polyethylene sheet by the same method, and it was set as the test piece for sclerosis | hardenability (gel fraction) measurement.

・ Curing property (gel fraction)
One day after the irradiation, a free film was cut into a size of about 50 × 50 mm from the test piece for measuring the curability, wrapped in a 200 mesh stainless steel wire mesh (W0) that was precisely weighed in advance, and weighed precisely (W1). Next, extraction is performed by immersion in acetone for 24 hours, followed by drying and precise weighing (W2).
Gel fraction (%) =
{((W2) − (W0)) / ((W1) − (W0))} × 100
Based on the above, the gel fraction (%) was determined.

-Adhesiveness One day after irradiation, a cross-cut adhesion test at 1 mm intervals was performed in accordance with JIS K5600 (primary adhesion). Furthermore, it was immersed in 23 degreeC water for 1 week, and the adhesiveness immediately after taking out was also evaluated (secondary adhesion).

-Hardness Pencil hardness was evaluated according to JIS K5600 14 days after irradiation of the PMMA plate coating test piece.

・ Abrasion resistance Using an eraser abrasion tester (manufactured by Mitsumoto Seisakusho Co., Ltd.) after 14 days of irradiation, an ABS plate coating test piece was reciprocated 30 times with a load of 250 g / cm ² on steel wool # 0000. The number of scratches remaining on the membrane was observed.
○: No or few scratches Δ: Shallow scratches from several to 10 ×: Ten or more scratches or deep scratches

-Flexibility An ABS plate (length: 150 mm) coating specimen was bent 14 days after irradiation, and the height from a horizontal plane when a crack occurred in the coating film was measured.
○: 5 cm or more Δ: 1 to 5 cm x 1 cm

・ Solvent resistance, chemical resistance Using a polycarbonate plate test piece, 7 days after irradiation, the solvent and chemicals shown in Table 2 are spotted. In the case of solvent resistance, the chemical resistance is maintained until the solvent evaporates at room temperature. In this case, after standing at 80 ° C. for 1 hour, the state of the wiping film was observed with absorbent cotton.
○: No change Δ: Spot mark remains ×: The coating film is swollen (dissolved)

The following were used as Copatone and Nivea.
Copatone: Copatone SPF50
Nivea: Nivea SPF47.

  In Examples 1 to 7, high curability was exhibited immediately after irradiation, and very excellent solvent resistance and chemical resistance were obtained. Sufficient solvent resistance and chemical resistance were observed after 7 days of curing. In terms of adhesion, good adhesion was observed for plastic substrates such as polycarbonate and ABS. Further, in the test after 14 days of curing, it was confirmed to have high pencil hardness and scratch resistance (steel wool), and it was further found that the flexibility of the coating film was excellent.

  On the other hand, in Comparative Examples 1 and 2 having no isocyanate group in the polymer, the pencil hardness was at a level close to that of the example, but the flexibility was poor and cracking occurred with light bending. Further, in Comparative Example 3 in which the polymer (A-2) was cured by thermosetting, although it was excellent in flexibility, it was not a satisfactory level in adhesion, hardness, scratch resistance, solvent resistance, and chemical resistance. .

  As described above, the coating film obtained from the present active energy ray-curable composition can be cured in a short time without excessive heating, and has excellent adhesion to a plastic substrate, solvent resistance and chemical resistance. It was confirmed to give an excellent coating film. In addition, it was confirmed that the coating agent was excellent in hardness and scratch resistance, further provided with flexibility, and suitable for workability and handling.

Claims (9)

The main chain is a (meth) acrylic copolymer, and the general formula (I):
-SiR ² _a (OR ¹ ) _3-a (I)
Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl having 7 to 12 carbon atoms. A monovalent hydrocarbon group selected from a group, wherein a is an integer of 0 to 2.) having two or more silicon groups bonded to a hydrolyzable group represented by: and / or a copolymer having two or more isocyanate groups in the side chain (a), (B) a photoacid generator, an active energy ray-curable composition characterized in that it contains (C) a dehydrating agent Including plastic coating agent . 2. The plastic according to claim 1, wherein the copolymer (A) component contains 5 to 30 silicon groups bonded to the hydrolyzable group represented by the general formula (I) in one molecule. Coating agent . The coating agent for plastics according to claim 1 or 2, wherein the copolymer (A) component contains 3 to 50 isocyanate groups in one molecule. The plastic acid coating agent according to any one of claims 1 to 3, wherein the photoacid generator (B) component is an aromatic sulfonium salt or an aromatic iodonium salt. The plastic coating agent according to any one of claims 1 to 4, wherein the counter anion of the photoacid generator (B) is a fluorophosphonate or fluorosulfonate. The plastic coating agent according to any one of claims 1 to 5, wherein the dehydrating agent (C) component is an orthocarboxylic acid ester and / or a highly active silane compound. Painted bodies painted a coating agent for plastics according to any one of claims 1 to 6. The active energy ray hard coating curable composition containing a plastic coating agent according to any one of claims 1 to 6. The plastic coating agent according to any one of claims 1 to 6 applied to a substrate, the manufacturing method of the coating film is irradiated with active energy rays.