JP5092907B2 - Active energy ray curable resin composition, active energy ray curable hard coating agent, cured film using these, and article having cured film - Google Patents

Description

The present invention is obtained by curing an active energy ray-curable resin composition that is cured by active energy rays such as ultraviolet rays and electron beams, a hard coat agent containing the active energy ray-curable resin composition, and curing the hard coat agent. The present invention relates to a cured coating and an article having a cured coating.

The active energy ray-curable resin composition is applied to the surface of various articles, is easily cured by irradiation with active energy rays such as ultraviolet rays, and is a hardened film having high hardness and excellent scratch resistance and transparency. It is widely used as a hard coat agent for protecting the surface of a plastic material or the like.

In recent years, as seen in various electrical products, cosmetic containers and automotive interior / exterior parts, the metal surface is subjected to vacuum deposition or plating to give it a metallic color or luster, or a combination of plastic and metal materials. For example, a hard coat treatment is performed on an article having a decorative or design property on its surface. However, when a conventional active energy ray-curable resin composition is used, adhesion to a metal surface is insufficient, and hard coat properties suitable for protecting these (high hardness, scratch resistance, abrasion resistance, etc.) ) Is difficult to form.

Therefore, for the purpose of improving the adhesion to a metal surface or the like, for example, an active energy containing a compound (A) having two or more (meth) acryloyl groups in the molecule as a monomer component and silica (B) The technique (patent document 1) etc. which further contain a phosphoric acid group containing ethylenically unsaturated compound (C) in the linear curable resin composition is proposed, but the improvement of the further adhesiveness is calculated | required.

JP 2007-016145 A

  The present invention relates to an active energy ray-curable resin composition (hard coat) capable of forming a cured film (hard coat film) having high adhesion on a wide range of materials, particularly metal surfaces such as metal plating surfaces and metal vapor deposition surfaces. The purpose is to provide an agent.

  As a result of intensive studies to solve the above problems, the present inventor has identified a specific reaction product (A), colloidal silica (B), a specific phosphoric acid compound (C), and a polyfunctional (meth) acrylic compound (D). And (meth) (meth) acrylic equivalent of the entire resin composition (“(meth) acrylic” means “acrylic” or “methacrylic”, the same shall apply hereinafter). The inventors have found that the above-mentioned problems can be solved by using an active energy ray-curable resin composition obtained by adjusting the amount in a specific range, and have completed the present invention.

That is, in the present invention, a carboxyl group-containing (meth) acrylic compound (a2) is added to a polymer obtained by polymerizing a polymerization component containing a vinyl compound (a1) having an epoxy group in the molecule. Active energy ray containing reaction product (A), colloidal silica (B), phosphoric acid compound (C) containing 1 or 2 vinyl groups in the molecule, and polyfunctional (meth) acrylic compound (D) It is a curable resin composition, and the use ratio ((A) / (B)) of the reaction product (A) to the colloidal silica (B) is 0.25 to 1.75 by weight ratio, the resin composition as a whole The active energy ray-curable resin composition having a (meth) acrylic equivalent of 320 to 550; the use ratio of the reaction product (A) to the colloidal silica (B) ((A) / (B)) Is heavy The active energy ray-curable resin composition according to claim 1, which has a ratio of 0.30 to 1.00; The active energy ray-curable resin composition having an average primary particle diameter of colloidal silica (B) of 6 to 100 nm. Further comprising the active energy ray-curable resin composition containing a photopolymerization initiator (E); a hard coat agent containing the active energy ray-curable resin composition; a cured film obtained by curing the hard coat agent; . An article having the cured coating on its surface and an article whose surface is a metal surface.

The hard coating agent using the active energy ray-curable resin composition of the present invention has excellent adhesion to the surface of various articles such as various plastic films, molded articles and glass, and has high hardness and scratch resistance and abrasion resistance. It is possible to form a cured film (hard coat film) excellent in hard coat properties such as properties. In particular, because it has a wide range of excellent adhesion to metal surfaces, it protects articles with metal surfaces such as metal materials such as aluminum, iron and copper, plating surfaces with silver and chromium, and metal deposition surfaces. It is useful as a hard coat agent.

The active energy ray-curable resin composition of the present invention comprises a carboxyl group-containing (meth) acrylic compound (a2) in a polymer obtained by polymerizing a polymerization component containing a vinyl compound (a1) having an epoxy group in the molecule. ) Reaction product (A), colloidal silica (B), phosphoric acid compound (C) containing 1 or 2 vinyl groups in the molecule, and polyfunctional (meth) acrylic compound (D ) -Containing active energy ray-curable resin composition, wherein the use ratio ((A) / (B)) of the reaction product (A) to the colloidal silica (B) is 0.25 to 1. 75, (meth) acryl equivalent is 320-550, It is characterized by the above-mentioned.

Reaction product (A)
The reaction product (A) used in the active energy ray-curable resin composition of the present invention (hereinafter referred to as “component (A)”) is a polymerization component containing a vinyl compound (a1) having an epoxy group in the molecule. The resulting polymer is subjected to an addition reaction with a carboxyl group-containing (meth) acrylic compound (a2). The component (a1) is not particularly limited as long as it is a radically polymerizable vinyl monomer and has one epoxy group and one vinyl group, and a known one can be used. Specific examples include glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether. These may be used alone or in combination of two or more. Among these, glycidyl (meth) acrylate is preferable from the viewpoint of hard coat properties of the obtained cured film.

  Furthermore, as the polymerization component of the polymer, components other than the component (a1) (hereinafter referred to as other polymerization components) can be used. Other polymerization components are not particularly limited as long as they can be copolymerized with the component (a1) and do not have a functional group reactive with an epoxy group in the molecule. Can be used. Examples of other polymerization components include (meth) acrylic acid esters having a chain alkyl group such as methyl methacrylate and ethyl methacrylate, and alicyclic (meth) acrylic acid esters such as isobornyl (meth) acrylate. And (meth) acrylic acid esters including nitrogen-containing acrylic acid esters such as acryloylmorpholine, and aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene. Among these, methyl methacrylate and ethyl methacrylate are preferable in terms of improving the water resistance and heat resistance of the resulting cured film.

The use ratio of the component (a1) and the other polymerization component is not particularly limited, but the cured film obtained by adjusting the component (a1) and the other polymerization component to about 10/0 to 2/8 by weight ratio. It is preferable that the wear resistance and heat resistance are balanced, and it is particularly preferable to set the ratio to 10/0 to 5/5.

As a method for producing a polymer (polymerization method), for example, a known radical polymerization method may be employed. For example, it is produced by heating the component (a1) and other polymerization components in the presence of a radical polymerization initiator. can do. It does not specifically limit as a radical polymerization initiator, A well-known thing can be used. Specifically, for example, inorganic peroxides such as hydrogen peroxide, ammonium persulfate and potassium persulfate, organic peroxides such as benzoyl peroxide, dicumyl peroxide and lauryl peroxide, 2,2′-azobis And azo compounds such as isobutyronitrile and dimethyl-2,2′-azobisisobutyrate. These may be used alone or in combination of two or more. In addition, it is preferable that the usage-amount of a radical polymerization initiator shall be about 0.01-8 weight part with respect to 100 weight part of all the polymerization components ((a1) component and other polymerization components total). In addition, you may use a chain transfer agent etc. as needed. Examples of the chain transfer agent include lauryl mercaptan, dodecyl mercaptan, 2-mercaptobenzothiazole, bromotrichloromethane, and the like. These may be used alone or in combination of two or more. The amount of the chain transfer agent used is preferably about 0.01 to 5 parts by weight with respect to 100 parts by weight of all the polymerization components used.

The polymer thus obtained has a weight average molecular weight (polystyrene conversion value by gel permeation chromatography) of about 6,000 to 40,000, and an epoxy equivalent of about 142 to 710 g / eq in terms of solid content. Is preferred. In the present invention, the epoxy equivalent is a value defined in JIS-K-7236.

The component (a2) to be subjected to addition reaction with the polymer is not particularly limited as long as it is a (meth) acrylic compound having at least one carboxyl group in the molecule, and known compounds can be used. For example, (meth) acrylic acid, crotonic acid, etc. are mentioned. Among these, it is preferable to use acrylic acid from the viewpoint that the photocurability of the resin composition is good. The amount of the component (a2) used is not particularly limited, but it prevents the remaining after irradiation with active energy rays, ensures hard coat properties such as scratch resistance and abrasion resistance of the resulting cured coating, and preserves the resin. From the viewpoint of property, it is preferable that the amount is approximately equimolar with the epoxy group in the component (A).

The reaction between the polymer and the component (a2) is an epoxy ring-opening reaction, and known reaction conditions can be employed. For example, it can be obtained by heating in the presence of a catalyst as required. Examples of the catalyst include phosphines such as triphenylphosphine and tricyclohexylphosphine; quaternary ammonium salts such as tetramethylammonium chloride, trimethylbenzylammonium chloride and tetramethylammonium bromide, trimethylamine, triethylamine, benzylmethylamine, tributylamine and the like. Amines; imidazoles such as 2-methylimedazole; and lauric acid esters such as dibutyltin laurate. Although the usage-amount of a catalyst is not specifically limited, Usually, it is preferable to set it as about 0.01-5 weight part with respect to 100 weight part of total weights of a polymer and (a2) component. In addition, you may use an organic solvent and a polymerization inhibitor as needed. As an organic solvent, if it does not react with a polymer and (a2) component, it will not specifically limit and a well-known thing can be used. Specific examples include alcohols such as ethyl alcohol and propanol; lower ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as toluene and benzene; butyl acetate, ethyl acetate, chloroform, dimethylformamide and the like. These may be used individually by 1 type, and may mix and use 2 or more types. Examples of the polymerization inhibitor include methoquinone, hydroquinone, trimethylhydroquinone, N-nitrosophenylhydroxylamine and the like. The amount of the polymerization inhibitor used is not particularly limited, but the polymerizability of the resulting coating agent may be deteriorated. Therefore, it is usually 1 weight with respect to 100 weight parts of the total weight of the polymer and the component (a2). It is preferable to set it to about part or less. In order to prevent polymerization, air may be blown into the reaction system.

The reactive organism (A) thus obtained has a weight average molecular weight (polystyrene conversion value by gel permeation chromatography) of about 9,000-60,000 and a (meth) acryl equivalent of 214-782 g / eq. The acid value is preferably about 5 mgKOH / g or less from the viewpoint of hard coat properties such as scratch resistance and abrasion resistance of the resulting cured film, adhesion, and storage stability of the resin.

(Colloidal silica (B))
As colloidal silica (B) (henceforth (B) component) used for this invention, it does not specifically limit and the commercial item which used the organic solvent etc. as the dispersion medium can be used. The average primary particle size of the component (B) is preferably about 6 to 100 nm, and more preferably 20 to 80 nm. When the average primary particle diameter is less than 6 nm, the surface hardness tends to be insufficient and the scratch resistance tends to be lowered, and when it exceeds 100 nm, the storage stability tends to be insufficient, and the adhesion and transparency tend to be deteriorated. The average primary particle diameter is a value determined by a dynamic light scattering method. Specific examples of the component (B) include, for example, Snowtex (manufactured by Nissan Chemical Industries, Ltd.), Quartron (manufactured by Fuso Chemical Industries, Ltd.), Aerosil (manufactured by Nippon Aerosil Co., Ltd.), Sildex ( Asahi Glass Co., Ltd.), and Silysia 470 (Fuji Silysia Chemical Co., Ltd.). In order to simplify production, it is preferable to use an organosilica sol dispersed in an organic solvent in advance, for example, IPA-ST, IPA-ST-MS, IPA-ST-L, IPA-ST-ZL (above, Isopropanol dispersion manufactured by Nissan Chemical Industries, Ltd.), MA-ST-M (methanol dispersion manufactured by Nissan Chemical Industries, Ltd.), Quattron PL-2-IPA (isopropanol dispersion manufactured by Fuso Chemical Industries, Ltd.), etc. Is mentioned.

The use ratio of the component (A) and the component (B) is in the range of 0.25 to 1.75 by weight as the ratio of the component (A) to the component (B) ((A) / (B)). It is necessary to adjust so that. When the use ratio ((A) / (B)) is less than 0.25, the adhesion of the cured film obtained is insufficient, and when it exceeds 1.75, the hard coat property is lowered. From the same viewpoint, the use ratio is more preferably 0.30 to 1.00, still more preferably 0.35 to 0.85. In addition, the usage-amount of (B) component in the usage-amount ((B) / (A)) of (A) component and (B) component means the amount of solid content.

(Phosphate compound containing one or two vinyl groups in the molecule (C))
The phosphoric acid compound (C) (hereinafter referred to as component (C)) containing one or two vinyl groups in the molecule used in the present invention has one or two vinyl groups in the molecule. Any phosphoric acid compound can be used without particular limitation. For example, 2-methacryloyloxyethyl acid phosphate (trade name Light Ester P-1M, Light Ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.), phosphoric acid-containing epoxy methacrylate (trade name New Frontier S-23A Daiichi Kogyo Seiyaku Co., Ltd. And phosphoric acid (meth) acrylates such as vinyl phosphonic acid (trade names VPA-90, VPA-100 manufactured by BASF) and the like.
The amount of component (C) used is not particularly limited, but is usually 0.01 to 5% by weight relative to the total amount of components of the resin composition (total amount of components (A) to (D)). The degree is preferred, more preferably 0.1 to 3% by weight.

(Polyfunctional (meth) acrylic compound (D))
The polyfunctional (meth) acrylic compound (D) (hereinafter referred to as “component (D)”) used in the present invention is a compound having two or more (meth) acryloyl groups in one molecule, and the component (C) Anything other than those can be used without particular limitation. Specifically, for example, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, etc., dipentaerythritol pentaacrylate, pentaerythritol Also included are polyfunctional urethane (meth) acrylates obtained by reacting a polyfunctional (meth) acrylate oligomer having a hydroxyl group such as triacrylate with a compound having two or more isocyanate groups in one molecule. These polyfunctional (meth) acrylates can be used alone or in combination of two or more. In these, the compound which has a (meth) acryloyl group more than trifunctional from the viewpoint of the hardness of the cured film obtained, and abrasion resistance is preferable. Although it does not specifically limit as the usage-amount of (D) component, Usually, about 20 to 40 weight% is preferable with respect to the structural-component total amount ((A)-(D) component total amount) of a resin composition, More preferably, it is 25 to 35% by weight.

The (meth) acryl equivalent of the active energy ray-curable resin composition thus obtained needs to be adjusted in the range of 320 to 550. When the (meth) acrylic equivalent is less than 320, a cured film having high adhesion to a metal or the like cannot be obtained, and when the (meth) acrylic equivalent exceeds 550, the scratch resistance, wear resistance, pencil height, etc. are reduced and hard coat is applied. A highly cured film cannot be obtained.
In the present invention, the (meth) acryl equivalent is the weight per mole of (meth) acryloyl group, and in the composition, a value represented by the reciprocal of the (meth) acryloyl group concentration (mol / g). It is.

The active energy ray-curable resin composition of the present invention contains the components (A) to (D), and further includes various photosensitizers, antioxidants, light stabilizers, leveling agents, pigments and the like. You may contain a well-known additive, a photoinitiator (E), etc.

(Photopolymerization initiator (E))
As a photoinitiator (E) (henceforth (E) component), it does not specifically limit but a well-known thing can be used. Specifically, for example, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl -Propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphos Examples include fin oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone, etc. . These may be used alone or in combination of two or more. In addition, although (E) component is used when performing ultraviolet curing, it is not necessarily required when performing electron beam curing. Although the usage-amount in the case of using (E) component is not specifically limited, Usually, it is preferable to set it as about 1-10 weight part with respect to 100 weight part of total amounts of (A)-(D) component.

The active energy ray-curable resin composition of the present invention is suitable as a hard coat agent, and is the surface of various articles (articles processed into various shapes such as films and sheets according to various purposes and applications). A cured coating can be formed by applying an active energy ray such as an ultraviolet ray or an electron beam to cause reaction curing. The resulting cured film has high hardness and excellent hard coat properties such as scratch resistance, abrasion resistance and transparency, and adhesion to the article surface.

The cured coating of the present invention has a hard coating agent containing the active energy ray-curable resin composition on the surface of various articles, and the weight after drying is about 0.1 to 30 g / m ² , preferably 1 to 20 g. It is obtained by irradiating with active energy rays after coating to / m ² and drying.

The material of the article surface to which the hard coat agent of the present invention can be applied is not particularly limited. For example, plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS, etc. Resin, AS resin, norbornene resin, etc.), glass, paper (art paper, cast coated paper, foam paper, PPC paper, high quality coated paper, kraft paper, polyethylene laminated paper, glassine paper, etc.) It can also be used for metal surfaces such as metal materials such as aluminum, iron and copper, plating surfaces such as silver and chromium, and metal deposition surfaces.

Examples of the coating method include bar coater coating, wire bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.

Examples of active energy rays used for curing include ultraviolet rays and electron beams. As an ultraviolet light source, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, or a metal halide lamp can be used. The light amount, light source arrangement, transport speed, etc. can be adjusted as necessary. For example, when a high-pressure mercury lamp is used, the transport speed is 5 to 50 m for one lamp having a light amount of about 80 to 160 W / cm. It is preferable to cure at about / min. On the other hand, in the case of an electron beam, it is preferable to cure at an conveyance speed of about 5 to 50 m / min with an electron beam accelerator having an acceleration voltage of about 10 to 300 kV.

EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated concretely, this invention is not limited only to this Example. In each example, parts and% are based on weight.
In this example, the weight average molecular weight is determined by gel permeation chromatography (trade name “HLC-8220” manufactured by Tosoh Corporation, column: manufactured by Tosoh Corporation, trade names “TSKgel superHZ2000”, “TSKgel superHZM”. -M "indicates the value measured.

Synthesis Example 1 (Synthesis of reaction product (A1))
In a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube, 250 parts of glycidyl methacrylate (hereinafter referred to as GMA) and 7.5 parts of 2,2-azobisisobutyronitrile (hereinafter referred to as AIBN) After charging 1.3 parts of lauryl mercaptan and 1000 parts of butyl acetate, the system was heated to a temperature of about 90 ° C. over about 1 hour under a nitrogen stream, and kept for 1 hour. Next, from a dropping funnel previously charged with a mixed solution consisting of 750 parts of GMA, 3.7 parts of lauryl mercaptan and 22.5 parts of AIBN, the mixed liquid was dropped into the system under a nitrogen stream for about 2 hours, and the same for 3 hours. After keeping the temperature, 10 parts of AIBN were charged and kept for 1 hour. Then, it heated up at 120 degreeC and heat-retained for 2 hours. Then, after cooling the reaction system to 60 ° C., the nitrogen inlet tube was replaced with an air inlet tube, 507 parts of acrylic acid, 2.3 parts of methoquinone and 6.0 parts of triphenylphosphine were charged and mixed, and then under air bubbling The temperature was raised to 110 ° C. Subsequently, after heat-retaining at the same temperature for 8 hours, 1.6 parts of methoquinone was added, it cooled, and ethyl acetate was added so that a non volatile matter might be 50%, and the reaction product (A1) was obtained. The reaction product (A1) obtained had a weight average molecular weight (polystyrene equivalent) of 35,000, an epoxy equivalent of 142, and a (meth) acrylic equivalent of 214.

Synthesis Example 2 (Synthesis of reaction product (A2))
In the same reaction vessel as in Synthesis Example 1, 125 parts of GMA, 125 parts of methyl methacrylate (hereinafter referred to as MMA), 7.5 parts of AIBN, 1.3 parts of lauryl mercaptan and 1000 parts of methyl isobutyl ketone (hereinafter referred to as MIBK) were charged. Thereafter, the system was heated to a temperature of about 120 ° C. over about 1 hour under a nitrogen stream, and kept warm for 1 hour. Next, from a dropping funnel previously charged with a mixed liquid consisting of 375 parts of GMA, 375 parts of MMA, 3.7 parts of lauryl mercaptan and 22.5 parts of AIBN, the mixed liquid was dropped into the system in about 2 hours under a nitrogen stream, After keeping the same temperature for 3 hours, 10 parts of AIBN was charged and kept warm for 1 hour. Then, it heated up at 120 degreeC and heat-retained for 2 hours. Then, after cooling the reaction system to 60 ° C., the nitrogen introduction tube was replaced with an air introduction tube, and 254 parts of acrylic acid (hereinafter referred to as AA), 2.3 parts of methoquinone and 6.0 parts of triphenylphosphine were charged and mixed. Then, the temperature was raised to 110 ° C. under air bubbling. Next, after keeping at the same temperature for 8 hours, 1.6 parts of methoquinone was added and cooled, and MIBK was added so that the non-volatile content was 50% to obtain a reaction product (A2). The obtained reaction product (A2) had a weight average molecular weight (polystyrene equivalent) of 24,000, an epoxy equivalent of 284, and a (meth) acrylic equivalent of 355.

Synthesis Example 3 (Synthesis of polyfunctional (meth) acrylic compound (D))
A reaction vessel equipped with a stirrer and a dropping funnel was charged with 189 parts of isophorone diisocyanate, 812 parts of pentaerythritol triacrylate, 0.6 part of tin octylate, and 1 part of methoquinone, and then the temperature of the system was increased to 80 ° C. Warm and incubate for 3 hours. The reaction was terminated when the isocyanate peak disappeared by infrared spectroscopy (IR) to obtain urethane acrylate (D1).

Example 1 (Preparation of active energy ray-curable resin composition)
33 parts of the reaction product (A1) obtained in Synthesis Example 1 as the component (A) and isopropanol-dispersed colloidal silica (SiO2 non-volatile content 30%, trade name IPA-ST manufactured by Nissan Chemical Industries, Ltd.) as the component (B) 100 parts (in terms of solid content), as component (C) 2-methacryloxyethyl acid phosphate (trade name: Light Ester P-2M, manufactured by Kyoeisha Chemical Co., Ltd.), 1 part, as component (D) pentaerythritol triacrylate 33 5 parts of 1-hydroxy-cyclohexyl-phenyl ketone (trade name Irgacure 184, manufactured by Ciba Japan Co., Ltd.) as component (E), and propylene glycol monomethyl ether so that the non-volatile content is 30% Diluted with (hereinafter referred to as PM) and (meth) acrylic equivalent of 380 g / eq active energy The curable resin composition was prepared.

(Preparation of active energy ray-curable resin composition)
Examples 2-7 and Comparative Examples 1-10
An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that the type and amount of each component in Example 1 were changed as shown in Table 1 or Table 2.
In addition, the (meth) acryl equivalent of the obtained active energy ray-curable resin composition is divided by the number of moles of acrylic acid present in each component used with respect to the total solid weight of the resin composition. Asked.

(Production of cured film)
The active energy ray-curable resin composition obtained in each of the examples and comparative examples was applied onto a 2 mm thick aluminum plate using a bar coater # 16 and dried at 80 ° C. for 1 minute. Next, the obtained coating film is passed under a high-pressure mercury lamp (UV irradiation amount: 400 mJ / cm ² ) in the atmosphere (conveying speed: 10 m / min) to cure the coated surface, thereby producing a cured film. did. The obtained cured film was evaluated by the following method. Note that Comparative Example 8 was not evaluated because cracks occurred in the coating.

(1) The hardness cured film was evaluated by a pencil scratch test with a load of 500 g according to JIS K 5600. The pencil hardness was measured according to JIS K 5600.

(2) The scratch-resistant cured film was rubbed 30 times with a 300 g weight having steel wool adhered to the bottom in the range of 10 mm × 10 mm, the appearance was observed, and the following criteria were evaluated.
○: No change.
Δ: There are fine scratches.
×: There is a large scratch.

(3) Adhesion JIS K
A cross cellophane tape peeling test was conducted by the method described in 5600. The result was evaluated by the number (numerator) that was not peeled off from the 100-cell grid cellophane tape (denominator). Further, a cured film was formed on the silver-plated metal plate, and the adhesion was similarly evaluated.

The description in each table is as follows.
Phosphoric acid methacrylate (vinyl group number 2): Light ester P-2M Kyoeisha Chemical Co., Ltd. Phosphoric acid methacrylate (vinyl group number 1): Light ester P-1M Kyoeisha Chemical Co., Ltd. Phosphoric acid methacrylate (vinyl group number 3): Biscoat 3PA Osaka Organic Chemical Industrial Co., Ltd. PET3A: Pentaerythritol triacrylate

Claims (8)

Reaction product (A) obtained by adding a carboxyl group-containing (meth) acrylic compound (a2) to a polymer obtained by polymerizing a polymerization component (a1) containing a vinyl compound having an epoxy group in the molecule An active energy ray-curable resin composition containing colloidal silica (B), a phosphoric acid compound (C) containing 1 or 2 vinyl groups in the molecule, and a polyfunctional (meth) acrylic compound (D) The ratio of use of the reaction product (A) to the colloidal silica (B) ((A) / (B)) is 0.25 to 1.75 by weight, ) An active energy ray-curable resin composition having an acrylic equivalent of 320 to 550. 2. The active energy ray-curable resin composition according to claim 1, wherein the use ratio ((A) / (B)) of the reaction product (A) to the colloidal silica (B) is 0.30 to 1.00 by weight. . The active energy ray-curable resin composition according to claim 1 or 2, wherein the colloidal silica (B) has an average primary particle diameter of 6 to 100 nm. Furthermore, the active energy ray hardening-type resin composition in any one of Claims 1-3 containing a photoinitiator (E). The hard-coat agent containing the active energy ray hardening-type resin composition in any one of Claims 1-4. A cured film obtained by curing the hard coating agent according to claim 5. An article having the cured coating according to claim 6 on its surface. The article according to claim 7, wherein the surface is a metal surface.