JP2015232054A - Active energy ray-curable coating resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inexpensive one-component coating resin composition which can thermally form a transparent cured coating film having good adhesivity, excellent pencil hardness and scratch resistance, and good chemical resistance, and can cure with active energy rays and the like in a short time.SOLUTION: Provided is a coating resin composition comprising a (meth)acrylic copolymer containing a hydrolyzable silicon group, a specified photo-acid generator, and hydrophilic silica particulates having an average particle size of primary particles of 5 nm or more and 100 nm or less, produced by any of a flame hydrolysis method, an arc method, a plasma method, or a molten solid method. Also provided are a transparent cured film formed by UV irradiation using a high-pressure mercury lamp and the like, and a laminate thereof.

Description

  The present invention is a transparent cured coating film having good adhesion, excellent pencil hardness, scratch resistance, and good chemical resistance to materials that cannot be heated excessively, such as plastic moldings and films. The present invention relates to an inexpensive one-component coating resin composition that can be thermally formed and that can be cured for a short time with an active energy ray or the like.

  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 that their surface hardness and scratch resistance are low and their chemical resistance is not sufficient. Therefore, a technique has been adopted in which various coating materials are applied to the surface of the plastic material to improve the performance. 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 that the adhesiveness with respect to plastics, such as a polycarbonate, falls.

  As another method for increasing surface hardness, scratch resistance and chemical resistance, a copolymer containing an alkoxysilyl group is applied, and a cured film is formed with an organometallic compound such as an organotin compound under heating conditions. There is a method to obtain (Patent Document 2). However, under conditions below the heat resistance temperature of the plastic substrate, there is a problem in productivity because heating for a long time is required to obtain a sufficient cured film.

  On the other hand, a method of UV curing using a polyfunctional monomer or oligomer as a main component and using a photo radical generator has also been reported, but there are problems such as curing inhibition by oxygen and lowering of adhesion due to curing shrinkage ( Patent Document 3).

  In addition, as a material for forming another transparent cured film other than the photo radical generator, for example, a hydrolyzate of non-polymerizable alkoxysilane, a hydrolyzate of alkoxysilane having an acrylic group or a glycidyl group, and photoacid generation The photocurable resin composition comprised from an agent is disclosed (patent document 4). Also disclosed is a photocurable resin composition comprising a hydrolyzate of an alkoxysilane having an acrylic group or a glycidyl group, colloidal silica, a non-silyl organic acrylate, and a photoacid generator (patent) Reference 5). Moreover, the photocurable resin composition comprised from 25 mol% or more of organic polymerizable alkoxysilane, a metal alkoxide condensate, and a photo-acid generator is disclosed (patent document 6). Further, a photocurable resin composition comprising an epoxy group-containing alkoxysilane, an alkylalkoxysilane hydrolyzate, colloidal silica, and a photoacid generator is disclosed (Patent Document 7). Furthermore, a photocurable resin composition comprising a hydrolyzed silane compound, a hydrolyzable silicon group-containing vinyl polymer, and a photoacid generator is disclosed (Patent Document 8). However, the suppression of curing shrinkage due to the condensation reaction of alkoxysilane or its hydrolyzate is insufficient, and problems such as warping and deformation occur when coated on a thin film such as a film. Since wet silica is porous and has a large amount of adhering water, high viscosity and storage stability are problems. There is a problem that colloidal silica is an expensive material.

  There is a strong demand for low-cost production from users, and in the plastic molding field, thermoforming such as insert molding is possible, high-temperature heat drying that damages the plastic substrate is not required, and a film with high hardness in a short time There is no warp due to suppression of curing shrinkage due to condensation reaction of alkoxysilane or its hydrolyzate, adhesion is improved, and development of an inexpensive coating agent with excellent pencil hardness, scratch resistance, and chemical resistance is required. It has been.

JP 2008-296539 A JP 2003-231223 A Japanese Patent Laid-Open No. 5-230397 Japanese Patent Publication No.57-500247 Japanese Patent Publication No.57-500984 US Pat. No. 5,385,955 JP-A-2-187176 Japanese Patent Laid-Open No. 2000-109695

  The problems to be solved by the present invention include good adhesion, excellent pencil hardness and scratch resistance, and further, a transparent cured coating film having good chemical resistance can be thermally formed, and active energy rays and the like. It is an object to provide an inexpensive one-pack type coating resin composition that can be cured for a short time.

  The present inventor has a hydrolyzable silicon group-containing (meth) acrylic copolymer, a specific photoacid generator, a flame hydrolysis method in which the average particle size of primary particles is 5 nm to 100 nm, an arc method, a plasma method, or A transparent cured coating film can be obtained in a short time by performing UV irradiation using a high-pressure mercury lamp or the like on an inexpensive coating resin composition containing hydrophilic silica fine particles produced by any method of the molten solid method. It was found that the obtained coating film was excellent in surface hardness, scratch resistance, and chemical resistance, and also exhibited excellent adhesion to plastic materials.

In the active energy ray-curable composition according to the present invention, the main chain is a (meth) acrylic copolymer, and the main chain terminal and / or side chain has 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 copolymer (A) component having one or more silicon groups bonded to a hydrolyzable group represented by a monovalent hydrocarbon group selected from a group, wherein a is an integer of 0 to 2. , (B) a photoacid generator, and (C) hydrophilic silica fine particles having an average primary particle diameter of 5 nm to 100 nm, from a flame hydrolysis method, an arc method, a plasma method, or a molten solid method It contains hydrophilic silica fine particles produced by at least one method selected from the group consisting of:
(B) As a photo-acid generator, an aromatic sulfonium salt or an aromatic iodonium salt can be used suitably. As the counter anion of the photoacid generator, a fluorophosphonate or fluorosulfonate can be suitably used.
The component (C) is finely dispersed in the component (A), and the fine dispersion treatment is selected from the group consisting of an ultrasonic dispersion method, a high-speed stirring dispersion method, a high-speed shear force dispersion method, and a bead mill dispersion method. And at least one method.
(A) 12 to 100 parts by weight of component (C) is included with respect to 100 parts by weight, and the water content of component (C) by the loss on drying method is 3% or less.
The hydrolyzable silicon group-containing monomer is 15 to 85 in 100 parts by weight of all monomers forming the (meth) acrylic copolymer having at least one silicon group bonded to the hydrolyzable group of (A). Part by weight can be preferably used.
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 can be suitably used as a 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 and scratch resistance are high, and excellent An inexpensive coating film having chemical properties and good adhesion to a plastic material 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 excellent surface hardness and scratch resistance, has good chemical resistance, and can be applied to a plastic substrate. An inexpensive transparent cured coating film excellent in adhesion can be formed.

Hereinafter, the present invention will be described in detail based on an embodiment thereof.
(A) Copolymer having at least one silicon group bonded to a hydrolyzable group The copolymer (A) component usable in the present invention contains a hydrolyzable silicon group bonded to a carbon atom. It only has to be.

  The silicon group bonded to the hydrolyzable group may be bonded to the end of the main chain of the copolymer (A) component, may be bonded to the side chain, and may be bonded to the end of the main chain and the side chain. It may be bonded. The number of hydrolyzable silicon groups is preferably 1 or more, and more preferably 2 or more, per molecule of the copolymer (A). As a method for introducing a silicon group bonded to a hydrolyzable group, a method of copolymerizing a monomer containing a silicon group bonded to a hydrolyzable group with another monomer, a method of reacting a silicate compound, or a hydroxyl group There is a method of reacting a silicate compound with the containing copolymer. Among them, a simple method is a method of copolymerizing a monomer containing a silicon group bonded to a hydrolyzable group and another monomer.

Examples of the hydrolyzable group in the silicon group bonded to the hydrolyzable group include a halogen group and an alkoxy group. Among them, an alkoxy group represented by the following general formula (I) is useful because of easy reaction control.
-SiR ² _a (OR ¹ ) _3-a (I)
In the formula, 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 group having 7 to 12 carbon atoms. A monovalent hydrocarbon group selected from Among these, R ¹ is preferably an alkyl group having 1 to 4 carbon atoms from the viewpoint that the curability of the composition of the present invention is excellent.

In the general formula (I), (OR ¹ ) _3-a is selected such that 3-a is 1 or more and 3 or less, that is, a is 0 to 2, but the composition of the present invention is cured. A is preferably 0 or 1 from the viewpoint of improving the properties. Therefore, the number of bonds of R ² is preferably 0 or 1. When the number of OR ¹ or R ² is plural, they may be the same or different. Specific examples of the hydrolyzable silicon group bonded to the carbon atom represented by the general formula (I) include, for example, a hydrolyzable silicon group-containing vinyl monomer copolymerized with a copolymer (A) component described later. Examples include groups contained in the monomer.

  Next, an example of a manufacturing method of a copolymer (A) component is demonstrated.

The copolymer (A) component is, for example, a radical polymerization of a hydrolyzable silicon group-containing vinyl monomer (a) component and another copolymerizable monomer (b) component such as azobisisobutyronitrile. It can be produced by copolymerization using a solution polymerization method or the like using an initiator.
Specific examples of the hydrolyzable silicon group-containing vinyl monomer (a) component include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, and vinyltris (2-methoxyethoxy) silane. , Vinyltriisopropoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxy Propylmethyldiethoxysilane, γ- (meth) acryloxypropyltri-n-propoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, vinyltriacetoxysilane, β- (meth) acryloxyethyltrimethoxysilane Etc. It is. These hydrolyzable silicon group-containing vinyl monomers (a) may be used alone or in combination of two or more.

  Γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- from the viewpoint of easy handling, cost and polymerization stability, and excellent curability of the resulting composition (Meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, and the like are particularly preferable.

  The hydrolyzable silicon group-containing monomer (a) component is used in an amount of 15 to 85 parts by weight, more preferably 20 to 80 parts by weight, and even more preferably 30 to 70 parts by weight in 100 parts by weight of the total monomers. Copolymerization is preferred. If it is less than 15 parts by weight, sufficient initial curability is hardly exhibited, and the weather resistance may not be improved. On the other hand, if it exceeds 85 parts by weight, the storage stability tends to deteriorate.

  Specific examples of the copolymerizable monomer (b) component 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, α-ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methyl (meth) acrylamide, N Acrylamide such as 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, N-methylol (meth) acrylamide, 4-hydroxystyrene vinyltoluene, Aronics 5700 manufactured by Toagosei Co., Ltd., 4-hydroxystyrene, Nippon Shokubai Chemical Industry HE-10, HE-20, HP-1 and HP-2 (all of which are acrylic ester oligomers having a hydroxyl group at the terminal), Blemmer PP series and Blemmer P manufactured by Nippon Oil & Fats Co., Ltd. Polyalkylene glycol (meth) acrylate derivatives such as E series and Blemmer PEP series, ε-caprolactone-modified hydroxyalkylvinyl copolymer compounds PlaccelFM-1, FM-4 (obtained by reaction of a hydroxyl group-containing compound with ε-caprolactone Hydroxyl-containing vinyl monomers such as polycarbonate-containing vinyl compounds such as Daicel Chemical Industries, Ltd., Tonemu-201 (UCC), HEAC-1 (Daicel Chemical Industries, Ltd.) and / or the like. And derivatives thereof.

  As a copolymer (A) component, it is preferable to have a hydrogen bondable functional group in a molecule | numerator from a viewpoint of ensuring affinity with a silica fine particle (C) component. Hydrogen bondable functional groups include alcoholic hydroxyl groups, phenolic hydroxyl groups, amino groups, carbonyl groups, carboxyl groups, and other functional groups, as well as amide bonds, ester bonds, carbonate bonds, urethane bonds, imide bonds, ether bonds, etc. This structure is also included. Such a hydrogen bonding functional group has a strong interaction with silanol present on the surface of the silica particles, and thus can stably hold the silica particles for a long period of time. The number of hydrogen-bonding functional groups is preferably 1 or more and 15 or less, more preferably 2 or more and 10 or less in one molecule of the copolymer (A). The copolymer (A) having a hydrogen bonding functional group can be synthesized by copolymerizing a hydrogen bonding functional group-containing vinyl monomer. Copolymerization is carried out using a hydrogen-bonding functional group-containing vinyl monomer, preferably 3% by weight or more, more preferably 7% by weight or more, based on 100% by weight of the total monomer of the copolymer (A). Preferably it is done.

  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.

  These other monomer (b) components may be used alone or in combination of two or more.

  The copolymer (A) component thus obtained has a number average molecular weight from the viewpoint of excellent physical properties such as curability and chemical resistance of a coating film formed using the composition of the present invention. It is preferable that it is 1000-20000 especially 500-25000, and a copolymer (A) component may be used independently and may use 2 or more types of copolymers together. At this time, the molecular weight may be adjusted using a chain transfer agent such as n-dodecyl mercaptan, γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane, if necessary.

  Note that the main chain of the copolymer (A) component is an acrylic copolymer means 50% by weight or more of the units constituting the main chain of the copolymer (A) component, more preferably 70%. It means that% by weight or more is formed from (meth) acrylic monomer units. In the present invention, (meth) acrylic is a general term for acrylic and methacrylic.

(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 fast and the adhesion to the plastic substrate is excellent. To preferred. In view of safety, a fluorophosphonate or fluorosulfonate is particularly preferable.

  The amount of (B) added needs to be adjusted according to the amount of acid generated and the rate of generation, but is 0.05 to 30 parts by weight, preferably 100 parts by weight of the solid content of the copolymer (A). 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 and chemical resistance tend to be insufficient. If the amount exceeds 30 parts by weight, problems such as deterioration of the coating film appearance and coloration tend to occur. It is in.

  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 number of blended photosensitizers is preferably 1 to 300% by weight, more preferably 10 to 100% by weight, based on 100% by weight of the photoinitiator.

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. The amount of irradiation energy is preferably 100 mJ / cm ² or more, more preferably 200 mJ / cm ² or more, but the upper limit is preferably 2000 mJ / cm ² or less because deformation of the substrate film is likely to occur.

The average particle diameter of the primary particles of the silica fine particle (C) component is 5 nm or more and 100 nm or less. Setting the average particle diameter of the primary particles within this range is preferable from the following viewpoints.
(I) From the viewpoint of transparency of the coating film.
(Ii) The viewpoint of the aggregate of the coating film.
(Iii) The viewpoint of the viscosity of the coating agent.

  The average particle diameter of the primary particles of the silica fine particle (C) component is preferably 12 nm or more and 70 nm or less, more preferably 15 nm or more and 60 nm or less. The average particle diameter of the primary particles of the silica fine particle (C) component is observed using a transmission electron microscope and is measured based on an image copied on a monitor. The particle diameter of each primary particle is measured in a situation where there are at least 100 or more primary particles imaged on the monitor. Either a method of taking a photograph and measuring it or a method of processing using image processing software can be adopted.

  The particle shape of the silica fine particle (C) component is not particularly limited. For example, a spherical shape, a flat shape, a needle shape, an amorphous shape, or a shape having a protrusion on the surface can be given. In particular, spherical particles are preferable from the viewpoint of wear resistance.

  The silica fine particle (C) component is preferably nonporous ultrafine particles. In the embodiment of the present invention, the nonporous ultrafine particles are those having a pore volume (value determined from an adsorption isotherm of nitrogen at −196 ° C.) of less than 0.1 ml / g when measured by a nitrogen adsorption method. Define. The use of such nonporous ultrafine particles suppresses the phenomenon that the composition viscosity is excessively increased when blended with the copolymer (A) component, and sufficiently maintains the mechanical strength of the ultrafine particles. It is preferable from the viewpoint.

The specific surface area of the silica fine particle (C) component is preferably 10 m ² / g or more and 1000 m ² / g or less. More preferably, 50 m ² / g or less 800 m ² / g or less, still more preferably not more than 100 m ² / g or more 500m ² / g. Setting the value of the specific surface area to such a range is suitable from the viewpoint of achieving both dispersibility and organic-inorganic composite. In addition, the specific surface area in the form of this invention is a value calculated | required based on a BET formula from the adsorption isotherm of nitrogen at -196 degreeC.

From the viewpoint of realizing the nonporous ultrafine particles described above, the silica fine particle (C) component is an ultrafine particle produced by any one of the flame hydrolysis method, the arc method, the plasma method, and the molten solid method. preferable. The flame hydrolysis method, the arc method, and the plasma method are also called a thermal decomposition method or a high heat method (dry method). Of these, the flame hydrolysis method is particularly preferred.
The silica fine particle (C) component preferably has a water content of 3% or less as measured by a loss on drying method at 105 ° C. for 2 hours, and in the presence of water, the hydrolyzed silicon group proceeds with a hydrolysis reaction and further a condensation reaction. More preferably, it is 2% or less, and further preferably 1% or less.
The silica fine particle (C) component is preferably in a hydrophilic state in which silanol groups are present on the surface thereof. This silanol group forms a siloxane bond by a condensation reaction with a silanol group obtained by hydrolyzing the hydrolyzable silicon group of the copolymer (A), and organic-inorganic complex formation is promoted. If this organic-inorganic composite formation is promoted, the coating film having excellent pencil hardness and scratch resistance and excellent chemical resistance can be obtained.

  A simple method of distinguishing hydrophilic fine particles from hydrophobic fine particles is a method of observing dispersibility in water. About 150 ml of water is put into a glass container, and about 3 g of fine particles are put into the container from above the water. Then, it stirs at 50 rotations per minute for 5 minutes using the stirring element put into water. It is observed that hydrophilic fine particles are dispersed in water, but hydrophobic fine particles are separated and floated on water. Even in the case of hydrophobic fine particles, when agitated vigorously, water molecules are taken into the particle surface and air is taken in at the same time, so that a phenomenon that the dispersed liquid appears to expand greatly is observed. The hydrophilic fine particle is defined as a fine particle having a volume expansion coefficient ((V1-V0) / V0) of 20% or less, where V0 is an initial volume of water and V1 is a volume after the fine particles are dispersed. be able to.

  The blending amount of the silica fine particles (C) is preferably 15% by weight or more and 70% by weight or less, and more preferably 20% by weight or more and 60% by weight or less with respect to the coating weight.

  The silica fine particle (C) component can be used in combination with other inorganic fine particles, but the closer the refractive index is to that of the copolymer (A) and the smaller the particle diameter, the better the transparency and the better. Examples of such inorganic fine particles include alumina, zirconium oxide, barium titanate, strontium titanate, titanium oxide, silicon nitride, boron nitride, silicon carbide, chromium oxide, vanadium oxide, tin oxide, bismuth oxide, and germanium oxide. , Compounds containing as a main component at least one selected from the group consisting of aluminum borate, nickel oxide, molybdenum oxide, tungsten oxide, iron oxide, and cerium oxide. These can be used alone or in combination of two or more. The number of blended parts of the other inorganic fine particles is preferably 15% by weight or more, more preferably 20% by weight or more with respect to 100% by weight of the copolymer (A).

  As a method for finely dispersing the component (C) in the component (A), it is preferable to use an ultrasonic dispersion method, a high-speed stirring dispersion method, a high-speed shear force dispersion method, a bead mill dispersion method, or the like. The ultrasonic dispersion method is a method of dispersing by generating cavitation, the high-speed stirring dispersion method is a method of dispersing by stirring the fluid, the high-speed shearing force dispersion method is a method of dispersing by shearing force, and the bead mill dispersion method is beads (grinding media). It is a method to disperse by colliding. When fine particles are dispersed in a highly viscous liquid resin, a three-roll method which is a high-speed shearing force dispersion method is preferable.

  If necessary, additives such as inorganic pigments and organic pigments, plasticizers, solvents, dispersants, wetting agents, thickeners and antifoaming agents are added to the resulting coating composition. You can also.

  The obtained coating agent composition can be suitably used for plastics, films and sheets, in particular because of the ease of irradiation with active energy rays. Further, for example, it can be suitably used for coating buildings, home appliances, industrial equipment and the like made of metal, ceramics, glass, cement, ceramic base materials, plastics, films, sheets, wood, paper, fibers and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, these do not limit this invention at all. In the following description, “part” or “%” represents “part by weight” and “% by weight”, respectively, unless otherwise specified.

  Measurement and evaluation in Examples and Comparative Examples were performed using the following conditions and methods.

(1) Polymerization conversion rate The obtained acrylic polymer (D) latex was dried in a hot air dryer at 120 ° C. for 1 hour to determine the amount of solid components, and polymerized by 100 × solid component amount / charged monomer. Conversion (%) was calculated.

(2) Gel content rate of acrylic resin composition The gel content rate in the acrylic resin composition is obtained by multiplying the gel content rate (%) of the acrylic polymer (D) by the blending ratio of the acrylic polymer (D). Calculated.

As for the gel content of the acrylic polymer (D), a predetermined amount of the dry resin powder of the acrylic polymer (D) was sampled on a 100 mesh wire net, immersed in methyl ethyl ketone for 48 hours, and dried under reduced pressure to remove the methyl ethyl ketone. Thereafter, the constant weight was read and calculated according to the following formula (1).
Gel content (%) of acrylic polymer (D)
= (Weight after re-drying / weight of sample collected) × 100 (1)
The gel content (%) in the acrylic resin composition is obtained by multiplying the gel content (%) of the acrylic polymer (D) by the blending ratio of the acrylic polymer (D), from the following formula (2). Calculated.
Gel content in acrylic resin composition (%)
= (Gel content (%) of acrylic polymer (D) x (ratio of acrylic polymer (D))) (2).

(3) Glass transition temperature Values described in "Polymer Hand Book (J. Brandrup, Interscience, 1989)" (MMA: 105 ° C, BA: -54 ° C, ST: 100 ° C, 2-hydroxy Ethyl methacrylate: 55 ° C., 2-ethylhexyl acrylate: −85 ° C., glycidyl methacrylate: 46 ° C., 3-methacryloxypropyltrimethoxysilane: 43 ° C., 3-acryloxypropyltrimethoxysilane: unknown and not calculated) Calculation was performed using the formula of Fox, except that the polyfunctional monomer, initiator, and surfactant were not included.

(4) Graft rate 1 g of the dry resin powder of the acrylic polymer (D) is dispersed and dissolved in 50 ml of methyl ethyl ketone (MEK), and the insoluble and soluble components are separated with a centrifuge (30,000 rpm × 2 Hrs). The insoluble matter was sufficiently dried by vacuum drying, and the weight was measured as the rubber / graft content.
Graft rate (%)
= ((Weight of rubber / graft-weight of crosslinked acrylic polymer (D-1)) / weight of crosslinked acrylic polymer (D-1)) × 100.

(5) Weight average particle diameter of acrylic polymer (D) Temperature of 23 ° C. ± 2 ° C., humidity obtained by diluting the obtained acrylic polymer (D) latex to a solid content concentration of 0.02% The weight average particle diameter was determined from the light transmittance at a wavelength of 546 nm using a spectrophotometer (manufactured by HITACHI, Spectrophotometer U-2000) at 50% ± 5%.

(6) Reduced viscosity Methyl ethyl ketone (MEK) soluble content was measured at 30 ° C using a 0.3% N, N'-dimethylformamide solution. The unit is dl / g.

(7) Solid content hydroxyl value of resin It computed from the following formula from the monomer composition of resin.
Solid content hydroxyl value = KOH mg / total amount of resin not containing KOH mg: mol number of hydroxyl group-containing vinyl monomer and / or derivative thereof × 56100 × N (N: hydroxyl group-containing vinyl monomer and / or derivative thereof Number of hydroxyl groups).

(8) Mass average molecular weight of resin HLC8220GPC (manufactured by Tosoh Corporation) is used, and GPC column is connected with three TSKgel Super H5000, H4000, H3000 (manufactured by Tosoh Corporation), and THF (with stabilizer) is used as a solvent. ) And measured in terms of polystyrene. Other conditions are measurement temperature: INLET OVEN 40 ° C., sample amount: 10 μl, liquid amount: 0.6 ml / min, detector: RI.

(9) 120 ° C tensile elongation%
Autograph AGS10KNG (manufactured by Shimadzu Corporation), TERMOSATATIC CHAMBER is Model: TCRI-200SP (manufactured by Shimadzu Corporation), and the size of the thermoformed film sample in which the cured resin layer is laminated is 10 × 100 mm. The distance between chucks is 50 mm, the pulling speed is 200 mm / min, and the constant temperature bath temperature is set to 120 ° C. After the sample is set, a tensile test is performed when reaching 120 ° C., and the elongation until cracks occur in the coating layer (F) is measured. .

(10) Chemical resistance A test was carried out on the coating layer (F) under the following conditions, and surface chemicals were wiped off and evaluated.
Each chemical and test conditions (i) VW solution: An equivalent mixed test solution of Octyl Methyl cinnamate / Octocrylene / Homosalate / DEET was placed in a case and evaluated after 80 ° C. × 24 hours.
(Ii) Nutriologist SPF45 was dropped and evaluated after 80 ° C. × 1 hour.
Evaluation ○: No lifting occurred, gloss maintained ×: Lifted, no gloss

(11) Thickness of cured resin layer The thickness of the curable resin layer was calculated from the difference in thickness with or without coating, and the film thickness was measured according to JIS B 7503.

(12) Pencil hardness The pencil hardness of the surface of the curable resin layer was measured according to JIS K5600-5-4 (ISO / DIN 15184).

(13) Haze value (initial haze value%)
A thermoforming film in which a curable resin layer was laminated on one side of a thermoplastic acrylic film (P-1) was set in a color measuring device (NIPPON DENSHOKU 300A), and a haze value was measured. The measurement area was 1 cm, and the condition without film was the standard.

(14) Solid content concentration%
The obtained hydrolyzable silicon group-containing acrylic copolymer (A) is dried in a hot air dryer at 150 ° C. for 2 hours to determine the amount of solid components, and the solid content is determined by 100 × solid component amount / initial sample amount. Concentration (%) was calculated.

(15) Adhesion test In accordance with JIS K5600, a grid adhesion test at 1 mm intervals was performed 5 days after irradiation (primary adhesion). Furthermore, the adhesion was also evaluated after 3 days at 85 ° C. and a relative humidity of 85% (secondary adhesion).

(16) Scratch resistance (haze value% after scratch test)
A scratch test was performed using a film for thermoforming laminated with a curable resin layer.
Specifically, a curable resin layer is laminated on one side of a thermoplastic acrylic film (P-1) and a thermoplastic PET film by an eraser wear tester (SONY Mechanical Parts Standards Technical Committee 1982.4 established Manufacturing Honko Seisakusho). A scratch test was conducted on the thermoformed film.

  Both ends of the film are fixed to the resin plate with double-sided tape so that the curable resin layer becomes the surface layer, and set and fixed to the above-described eraser abrasion tester. After carrying out a scratch test of 0000 200 times with a load of 500 g, only the film was removed and set in a color measuring device (NIPPON DENSHOKU 300A), and the haze value was measured. The measurement area was 1 cm, and a thermoformed film without a curable resin layer was used as a standard.

(17) Warpage An area test piece having a diagonal length of 7 inches was placed on a flat table, the gap between the table and the four corners was measured with a ruler, and the average value (mm) was calculated.

(18) Coating stability The coating agent (F) in Table 3 was allowed to stand at 30 ° C. for 7 days and then applied to a glass plate to confirm the presence or absence of irregularities.
Evaluation: No stuff ⇒ ○, ⇒ ⇒ ×.

(Manufacturing method of acrylic polymer (D): P-1)
200 parts by weight of water and OSA were added in the amounts shown in Table 1 into an 8 liter polymerization vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, monomer supply tube, and reflux condenser, and the inside of the vessel was sufficiently filled with nitrogen gas. After the substitution to make it substantially free of oxygen, the internal temperature was set to 40 ° C., 5 parts by weight of the mixture (d-1-1) shown in Table 1 was added all at once, and after stirring for 10 minutes, the following substance sodium Formaldehyde sulfoxylate 0.11 part by weight Ferrous sulfate dihydrate 0.004 part by weight Ethylenediaminetetraacetic acid-2-sodium 0.001 part by weight was charged, and the mixture (d-1-2) shown in Table 1 was prepared. After continuously adding and polymerizing at a rate of 10 parts by weight / hour, the polymerization was continued for another 0.5 hours, and the mixture (d-1-3) shown in Table 1 was added at 12.7 parts by weight / hour. After continuously adding and polymerizing at a ratio, 1 more After continuing the polymerization for 0 hour, the polymerization conversion rate is set to 98% or more, the internal temperature is set to 60 ° C., and the mixture (d-2-1) shown in Table 1 is continuously added at a rate of 16.7 parts by weight / hour. After the polymerization, the polymerization was further continued for 1.0 hour, and then the polymerization conversion rate was set to 98% or more to terminate the polymerization, whereby an acrylic polymer (F) latex was obtained. The obtained latex was salted out with calcium chloride, washed with water and dried to obtain a dry powder (P-1) of an acrylic polymer (D).

Each abbreviation in Table 1 represents the following substance.
OSA; Dioctyl sodium sulfosuccinate BA; Butyl acrylate MMA; Methyl methacrylate ST; Styrene CHP; Cumene hydroperoxide AMA; Allyl methacrylate tDM; Tertiary decyl mercaptan.

(Method for producing thermoplastic film)
After blending the dry powder of P-1 obtained as an acrylic polymer (D) and a methacrylic resin (trade name: Sumipex EX-A manufactured by Sumitomo Chemical Co., Ltd.) at a ratio of 40 parts by weight / 60 parts by weight, , 1 part of UV absorber: TINUVIN234 (manufactured by Ciba Specialty Chemicals Co., Ltd.) and 0.4 part of antioxidant: AO60 (manufactured by ADEKA Co., Ltd.) with respect to 100 parts by weight of the total of P-1 and methacrylic resin. After blending at a blending ratio of parts, extrusion was carried out at a 240 ° C. setting of a vented extruder, pelletizing, and further, a T-die extruder was used to form an extruder at 230 ° C. and a die at 240 ° C. (thickness 125 μm).

(Production method of hydrolyzable silicon group-containing acrylic copolymer (A): A-1 to A-6)
In a reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas introduction pipe and a dropping funnel, the components (a) in Table 2 were charged, and the temperature was raised to 105 ° C. while introducing nitrogen gas. The mixture of components a) was dropped from the dropping funnel at a constant rate over 5 hours. Next, the mixed solution of the component (c) was dropped at a constant rate over 1 hour. Then, after stirring at 105 degreeC for 2 hours subsequently, it cooled to 50 degreeC and synthesize | combined the polymer (A). Table 2 shows the solid content concentration of the obtained polymers (A-1 to 6), the number average molecular weight measured by GPC, the glass transition temperature obtained by calculation, and the solid content hydroxyl value obtained by calculation. In (A-5 to 6), solvent deaeration was performed by an evaporator, and the solid content concentration was set to 95% or more.

  (In the table, the amounts of the components (a) to (c) are parts by weight).

(Production method of resin-dispersed silica: C-1 to C-3)
A hydrolyzable silicon group-containing acrylic copolymer (A-5-6) and 20% by weight of each silica particle were blended and then premixed with a disper (IKA: Eurostar power control-visc), and then stocked. A table-type three roll mill manufactured by Kodaira Seisakusho Co., Ltd. was dispersed in two passes with model RIII-1C to form a water tank. Further, each silica particle was premixed with a disper so as to be 30% by weight, and dispersed by passing two passes with a table type three roll mill model RIII-1C manufactured by Kodaira Manufacturing Co., Ltd. The silica dispersion (C-2) is further premixed with a disperser so that each silica particle is mixed at a weight ratio of 40%, and is subjected to two passes with a table type three roll mill model RIII-1C manufactured by Kodaira Manufacturing Co., Ltd. Distributed. Each dispersion was diluted to a 20% methyl ethyl ketone solution and confirmed to have a dispersity of 10 μm or less with a 100 μm particle gauge.

  After mixing the hydrolyzable silicon group-containing acrylic copolymer (A) with the silica fine particle-containing (C) component shown in Table 3, the diluent solvent and the photocatalyst (B) component are sequentially mixed, and the mixture is mixed at 1000 rpm using a stirrer. The mixture was mixed for 3 minutes to obtain a coating resin composition. However, SNOWTEX O-40 as component (C-4) is mixed with a diluting solvent, and then mixed with a hydrolyzable silicon group-containing acrylic copolymer (A) and a photocatalyst at a rate of 1000 rpm using a stirrer. The mixture was mixed for 3 minutes to obtain a coating resin composition (F).

The obtained coating resin composition (F) was coated on one side of a thermoplastic acrylic film with a coating agent having a concentration of 30% using a bar coater corresponding to each film thickness, and dried at 80 ° C. for 3 minutes. After removing, using a high-pressure mercury lamp in the air, it is cured by irradiating with active energy rays at 240 mW / cm so that the integrated light quantity of wavelength 310 to 390 nm is 1000 mJ / cm ^2, and after 5 days of room temperature curing The specimen was evaluated. No. 4 bar thickness with 4 bar coater. The thickness was 7 μm with an 8 bar coater.
-CPI-100P: Triarylsulfonium manufactured by San Apro Co., Ltd.-Propylene carbonate solution of PF ₆ salt-CPI-200K: Triarylsulfonium manufactured by San Apro Co., Ltd.-Propylene carbonate solution of special phosphorus salt-AEROSIL50: Nippon Aerosil Co., Ltd. Hydrophilic silica fine particles (flame hydrolysis method, average primary particle size 50 nm, moisture content <1% by drying loss method at 105 ° C. for 2 hours)
AEROSIL OX-50: Nippon Aerosil Co., Ltd. hydrophilic silica fine particles (flame hydrolysis method, average primary particle size 50 nm, moisture content <1% by drying loss method at 105 ° C. for 2 hours)
・ NIPGEL CX-200: Tosoh Silica hydrophilic silica fine particles (wet method, moisture content ≧ 5% by drying loss method at 105 ° C. for 2 hours)
Snowtex 0-40: Colloidal silica aqueous solution manufactured by Nissan Chemical Co., Ltd. (average particle size: 10 to 20 nm, hydrophilic silica particles 40% solid content% = 40%)
IPA-ST: Nissan Chemical Co., Ltd. organosilica sol isopropyl alcohol solution (average particle size: 10 to 20 nm, silica particles 30% solid content% = 30%)
MEK-AC-2101: An organosilica sol methyl ethyl ketone solution manufactured by Nissan Chemical Industries, Ltd. (average particle size: 10 to 15 nm, silica particles 30% solid content% = 30%).

(Evaluation of the physical properties)
In Examples 1-6, the result of the 1 liquid coating agent which was excellent in transparency and adhesiveness, excellent in pencil hardness, scratch resistance, chemical resistance, and curvature, and was able to perform favorable heat formation was obtained.

  On the other hand, in Comparative Examples 1 to 7 in which silica fine particles of the flame hydrolysis method are not used or the blending amount is small, adhesion, pencil hardness, scratch resistance, chemical resistance, warpage, storage stability and the like cannot be achieved. In particular, in Comparative Examples 1 to 3, dissolution of the coating film was observed by a chemical resistance test. In Comparative Examples 4 and 7, it was confirmed that storage stability was deteriorated due to water mixing from silica fine particles. In Comparative Examples 4 and 5, it was confirmed that the adhesion to the substrate film was deteriorated due to the mixing of the polar solvent derived from the silica fine particles. As described above, the coating resin composition of the present invention has good adhesion to materials that cannot be heated excessively, such as plastic moldings and films, and has excellent pencil hardness and scratch resistance, and even better. Further, it was confirmed that the transparent cured coating film having chemical resistance can be thermally formed and is an inexpensive one-pack type coating resin composition that can be cured for a short time with an active energy ray or the like.

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 copolymer (A) having one or more silicon groups bonded to a hydrolyzable group represented by a monovalent hydrocarbon group selected from a group, wherein a is an integer of 0 to 2. (B) a photoacid generator, and (C) hydrophilic silica fine particles having an average primary particle size of 5 nm to 100 nm, and comprising a flame hydrolysis method, an arc method, a plasma method, or a molten solid method An active energy ray-curable composition comprising hydrophilic silica fine particles produced by at least one method selected from:   The component (C) is a component that is finely dispersed in the component (A), and the fine dispersion treatment includes an ultrasonic dispersion method, a high-speed stirring dispersion method, a high-speed shear force dispersion method, and a bead mill dispersion method. The active energy ray-curable composition according to claim 1, which is at least one method selected from the above.   The active energy ray-curable composition according to claim 1 or 2, comprising 12 to 100 parts by weight of the component (C) with respect to 100 parts by weight of the (A).   4. The active energy ray-curable composition according to claim 1, wherein the component (C) has a moisture content of 3% or less by a loss on drying method at 105 ° C. for 2 hours.   In 100 parts by weight of all monomers forming the (meth) acrylic copolymer having at least one silicon group bonded to the hydrolyzable group (A), 15 hydrolyzable silicon group-containing monomers are present. It is -85 weight part, The active energy ray curable composition in any one of Claim 1 to 4.   The coating body which coated the active energy ray curable composition as described in any one of Claims 1-5.   A curable composition for active energy ray hard coat containing the curable composition according to any one of claims 1 to 5.   A laminate obtained by applying the curable composition according to any one of claims 1 to 5 to a rubber particle-containing film.   The manufacturing method of the coating film which apply | coats the active energy ray curable composition as described in any one of Claims 1-5 to a base material, and irradiates an active energy ray.