JP6805489B2 - Active energy ray-curable resin composition, cured product, film, cured layer and molded product. - Google Patents

Description

The present invention relates to an active energy ray-curable resin composition, a cured product, a film, a cured layer, and a molded product using the active energy ray-curable resin composition.

Conventionally, molding technology using a decorative film has been mass-produced in order to impart a functional layer such as designability and scratch resistance to the surface of articles such as electric appliances, automobile exteriors, automobile interior parts, and daily necessities. It is praised in terms of sex and production cost. For example, in the construction methods listed in Patent Document 1 and Patent Document 2, a decorative film capable of following a complicated shape and stretching of deep drawing (called deep drawing) is required, and the functional layer is not easily scratched by the conventional method. In addition, the elongation is required so that the functional layer does not crack even when stretched to 100% or more.

The functional layer is required to have scratch resistance (called hard coat property) to prevent the pattern ink layer and the like arranged under the layer from being destroyed or deteriorated due to the influence of external stress, etc., and this functional layer is molded. By being provided on the outermost surface of the object, the design and beautiful appearance of the molded product can be maintained for a long period of time. Conventionally, thermoplastic resins, thermosetting resins, and active energy ray-curable resins have been used as functional layers. Thermoplastic resins have excellent elongation during processing but are weak in chemical resistance and are thermosetting. Sex resins tend to have slightly weak elongation and scratch resistance, and active energy ray-curable resins have excellent scratch resistance and chemical resistance, but when cured before molding, they have poor elongation and cracks. It is likely to occur and the shape of the molded product is limited. On the other hand, when the active energy ray-curable resin is cured after molding, there are problems such as poor handling and a decrease in production efficiency due to an increase in the number of steps of irradiating the molded product with active energy rays.

For these, a method has been proposed in which both processability and physical properties of a cured film are compatible by two-component curing of an active energy ray polymer having a hydroxyl group and a (meth) acryloyl group and a polyfunctional isocyanate (see Patent Document 3). ). However, it has not reached the workability required by the vacuum crimping method. Further, it is necessary to irradiate the surface of the molded product after processing and molding with active energy rays to form a cured film, but in the case of a complicated shape, it is difficult to uniformly irradiate the entire surface, and curing defects are likely to occur in production. The sex is also poor.

Further, a resin composition of a compound having a total of two or more active methylene groups and / or active methine groups in one molecule, a compound having a (meth) acryloyl group, and a photopolymerization initiator has been proposed (Patent Documents). 4). However, as in Patent Document 1, it is necessary to cure by irradiation with active energy rays after processing and molding, and the processability and productivity are poor.

Further, a method of imparting processability by blending a non-reactive resin having no radically polymerizable double bond with a (meth) acrylic monomer has also been proposed (see Patent Document 5). However, when such a non-reactive resin or a plastic resin is blended, although it becomes flexible and the processability is improved, it tends to be scratch-resistant and have insufficient chemical resistance.

A method of controlling the crosslink density by a compounding composition of a trifunctional or higher (meth) acrylic oligomer and a mono-bifunctional (meth) acrylic monomer can also be mentioned (see Patent Document 6). According to this method, a hard coat film having both high surface hardness and flexibility capable of following deformation during molding can be obtained, but it is difficult to achieve both surface hardness and elongation at a high level.

Japanese Patent No. 2957573 Japanese Patent No. 5604569 Japanese Unexamined Patent Publication No. 10-58895 Japanese Unexamined Patent Publication No. 2005-206778 Japanese Unexamined Patent Publication No. 2008-208154 Japanese Unexamined Patent Publication No. 2011-148964

INDUSTRIAL APPLICABILITY The present invention exhibits high elongation during heat treatment, can be laminated on the surface of a molded product without causing cracks even in a complicated shape, and has excellent hard coat property and chemical resistance on the surface of the molded product. The present invention is to provide an active energy ray-curable resin composition capable of providing an active energy ray-curable film that imparts the above. Therefore, it can be suitably used in a method of heat-treating a decorative film and then attaching it to the surface of a molded product or a method of transferring and decorating the film.

That is, the present invention relates to the active energy ray-curable resin composition, the cured product, the film, the cured layer, and the molded product shown in the following items 1 to 8.

Item 1. Ethylene unsaturated monomers (A), metal compounds (B), and other ethylenically unsaturated monomers having at least one functional group selected from primary hydroxyl groups, secondary hydroxyl groups, carboxyl groups and phosphoric acid groups ( An active energy ray-curable resin composition containing C) and a photopolymerization initiator (D).

Item 2. The active energy ray-curable resin composition according to item 1 above, wherein the metal compound (B) is at least one of a metal salt compound of aluminum and / or zirconium, a metal alkoxide compound, and a metal chelate compound.

Item 3. The other ethylenically unsaturated monomer (C) is any one of a nitrogen-containing vinyl-containing monomer, an alkyl mono (meth) acrylate, a cyclic ester mono (meth) acrylate, and a polyalkylene glycol mono (meth) acrylate. The active energy ray-curable resin composition according to the above item 1 or 2.

Item 4. A cured product formed by curing the active energy ray-curable resin composition according to any one of items 1 to 3 above with active energy rays.

Item 5. A film having a resin layer made of the active energy ray-curable resin composition according to any one of the above items 1 to 3.

Item 6. A cured layer obtained by curing a resin layer made of the active energy ray-curable resin composition according to any one of items 1 to 3 above with active energy rays.

Item 7. A laminated film in which the cured layer according to item 6 above is formed on at least one surface of a base material.

Item 8. A molded product obtained by coating the surface of the cured product according to item 6 above.

When the active energy ray resin composition of the present invention is used, an excellent cured film elongation of 100% or more is exhibited by heating, so that cracks do not occur even in a complicated shape or deep drawing, and molding is performed. It is possible to create a decorative film capable of imparting excellent hard coat property and chemical resistance to the surface of an object.

The present invention refers to an ethylenically unsaturated monomer (A) having at least one functional group selected from a primary hydroxyl group, a secondary hydroxyl group, a carboxyl group and a phosphoric acid group (hereinafter, also referred to as "component (A)"). , Metallic compound (B) (hereinafter, also referred to as "(B) component"), other ethylenically unsaturated monomer (C) (hereinafter, also referred to as "(C) component"), and photopolymerization initiator (D). ) (Hereinafter, also referred to as “component (D)”), which is an active energy ray-curable composition.

By using the above-mentioned active energy ray-curable composition, in the process of softening the decorative film by heating, excellent elongation is exhibited, and cracks occur even when the decorative film is bonded to the surface of a molded product having a complicated shape and transferred. It is possible to decorate the surface of a high-quality molded product without generating it, and it is possible to impart excellent properties such as hard coatability and chemical resistance to the surface of the processed molded product.

The component (A) is not particularly limited as long as it is an ethylenically unsaturated monomer having at least one functional group selected from a primary hydroxyl group, a secondary hydroxyl group, a carboxyl group and a phosphoric acid group. As a result, in addition to the polymerization of the (meth) acryloyl group, a cured product using the component (B) as a cross-linking agent can be obtained. Among these, the carboxyl group-containing ethylenically unsaturated monomer has a suitable reactivity with the component (B), so that it is easy to obtain a cured film having excellent chemical resistance, which is more preferable.

Examples of the ethylenically unsaturated monomer having a primary hydroxyl group or a secondary hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl. (Meta) acrylate, polycaprolactone (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyethylene glycol-propylene glycol-mono (meth) acrylate, polyethylene glycol-tetramethylene glycol-mono (meth) ) Acrylate, propylene glycol-polybutylene glycol-mono (meth) acrylate, 1,4-cyclohexanedimethanol monoacrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, hydroxyethyl acrylamide, 3-hydroxy-1-adamantyl Examples include (meth) acrylate. Among these, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and hydroxyethyl acrylamide are preferable from the viewpoint of easy availability.

Examples of the ethylenically unsaturated monomer having a carboxyl group include (meth) acrylic acid, (meth) acrylic acid dimer, (meth) acrylic acid trimmer, 2- (meth) acryloyloxyethyl succinic acid, and EO-modified succinic acid. Acid mono (meth) acrylate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl tetrahydrophthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloy Loxypropyl phthalate, 2- (meth) acryloyloxypropyl tetrahydrophthalate, 2- (meth) acryloyloxypropyl hexahydrophthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, 2- (meth) Examples thereof include acryloyloxyethyl-2-hydroxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, and 2- (meth) acryloyloxyethyl-2-hydroxypropyl hexahydrophthalate. Among these, (meth) acrylic acid trimmer, 2- (meth) acryloyloxyethyl succinic acid, EO-modified mono (meth) succinate, 2- (meth) acryloyloxyethyl because of its low skin irritation. Phtalate, 2- (meth) acryloyloxyethyl tetrahydrophthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxypropyl tetrahydrophthalate, 2- (Meta) acryloyloxypropyl hexahydrophthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl hexahydrophthalate, 2-( Preferable are meta) acryloyloxyethyl-2-hydroxypropylphthalate and 2- (meth) acryloyloxyethyl-2-hydroxypropylhexahydrophthalate.

Examples of the ethylenically unsaturated monomer having a phosphate group at the end include ethyl (meth) acrylate acid phosphate, 3-chloro-2-acid phosphoxypropyl (meth) acrylate, and polyoxyethylene glycol (meth). Examples thereof include acrylate acid phosphate, 2-hydroxyethyl (meth) acrylate acid phosphate, and 2- (meth) acryloyloxyethyl acid phosphate.

As the component (B), any known metal compound having a coordination bond ability can be used without particular limitation. Specific examples thereof include metal salt compounds, metal chelate compounds, metal alcoholates, and metal acylates. The metal chelate compound includes its partial alcoholate or partial acylate, the metal alcoholate includes its hydrolyzate and condensate, and the metal acylate includes its hydrolyzate and condensate. Among these, any one of a metal chelate compound and a metal alcoholate in that the compatibility with the components (A) and (C) is good and the reactivity with the component (A) is good. The above is preferable. More preferably, it is a metal alcoholate.

Examples of the metal constituting the component (B) include aluminum, zirconium, titanium, magnesium, chromium, cobalt, copper, iron, nickel, vanadium, zinc, indium, calcium, manganese, and tin. Among these, aluminum and / or zirconium are preferable from the viewpoint of easy availability.

Examples of the metal chelate compound include aluminum ethylacetate acetate diisopropyrate, alkylacetate acetate aluminum diisopropyrate, aluminum trisethylacetone acetate, aluminum monoacetylacetone bisethylacetone acetate, aluminum trisacetylacetoneate, and aluminum monoiso. Aluminum compounds of propoxymonooleoxyethylacetone acetate; zirconium compounds such as zirconium tetraacetylacetone, zirconium tributoxymonoacetylacetone, zirconium monobutoxyacetylacetone bisethylacetone acetate, zirconium dibutoxybisethylacetone acetate; ethoxy-acetylacetonate Zinc, bisacetylacetonate zinc, propoxy-acetylacetonate zinc, butoxy-acetylacetonate zinc, ethoxy-ethylacetoneacetate zinc, bisethylacetoneacetate zinc, propoxy-ethylacetoneacetate zinc, butoxy-ethylacetoneacetate zinc, etc. Examples include zinc compounds.

Examples of the metal alcoholate include aluminum ethylate, aluminum propylate, aluminum isopropyrate, aluminum diisopropyrate monosec butyrate, aluminum monoisopropirate disec butyrate, and aluminum compounds of aluminum secbutyrate; Zinc compounds such as dibutoxyzinc; examples thereof include zirconium compounds such as zirconium ethylate, zirconium propylate, zirconium isopropylate and zirconium butyrate. Examples of the condensate of the metal alcoholate include cyclic aluminum oxide isopropylate, cyclic aluminum oxide octylate, and cyclic aluminum oxide stearate. Among these, aluminum propylate, aluminum isopropylate, aluminum diisopropyrate monosec butyrate, aluminum monoisopropyrate disec butyrate, aluminum secbutyrate, zirconium in terms of reactivity with component (A) and easily available. Propyrate, zirconium isopropylate and zirconium butyrate are preferred.

Examples of the metal acylate include zirconium monopropyl tristearate, zirconium dipropyl distearate, zirconium tripropyl monostearate, zirconium monobutoxy tristearate, zirconium dibutoxy distearate, zirconium tributoxy monostearate and the like. Zirconium compounds can be mentioned.

Good cured film physical properties can be obtained by using the component (B) at a ratio of 0.1 mol to 0.8 mol with respect to 1 mol of the component (A). When the component (C) is 0.1 mol or more, the scratch resistance and chemical resistance are improved, and when the component is 0.8 mol or less, the thermal elongation of the cured film can be improved. it can.

By setting the total amount of the component (A) and the component (B) to be 30 to 90% by weight in the active energy ray resin composition, the cured film is not easily scratched and the chemical resistance is preferable.

The component (C) is not particularly limited as long as it is an ethylenically unsaturated monomer other than the component (A), but is a nitrogen-containing monovinyl-based monomer, an alkyl mono (meth) acrylate, and a cyclic ester mono (meth). ) It is preferable to combine any one or more of acrylate and alkylene glycol mono (meth) acrylate in terms of resistance to scratches and more suppression of cracks.

Examples of the nitrogen-containing vinyl-based monomonomer include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate quaternized product, dimethylacrylamide, acryloylmorpholin, isopropylacrylamide, diethylacrylamide, and the like. Examples thereof include dimethylaminopropylacrylamide and pentamethylpiperidinyl (meth) acrylate.

Examples of the alkyl mono (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl ( Meta) acrylate, isodecyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (meth) ) Acrylate can be mentioned.

Examples of the cyclic mono (meth) acrylate include isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and (2-methyl-). 2-Ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclohexanespiro-2- (1,3-dioxolan-4-yl) methyl (meth) acrylate, 3-ethyl-3-oxetanylmethyl (Meta) acrylate, 1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, γ-butyllactone (meth) acrylate, dicyclopentenyl ( Examples thereof include meta) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and nonylphenoxypolyethylene glycol (meth) acrylate.

Examples of the alkylene glycol mono (meth) acrylate include methoxypolyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, and octoxypolyethylene. Glycol-propylene glycol-mono (meth) acrylate, lauroxypolyethylene glycol- (meth) acrylate, stearoxypolyethylene glycol (meth) acrylate, tetramethylene glycol-mono (meth) acrylate, propylene glycol-polybutylene glycol-mono (meth) ) Acrylate can be mentioned.

The amount of the component (C) used is not particularly limited, but when the total weight of the components (A) and (B) is 100 parts, by using 10 parts or more of the component (C), the cured film is heated. The elongation can be made excellent, and by using it in 150 parts or less, it is possible to improve the scratch resistance and the chemical resistance.

The component (D) is not particularly limited as long as it can generate radicals by active energy rays to initiate polymerization, and known components can be used. Specific examples of the component (D) include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexylphenylketone, and 2-hydroxy-2-methyl-1-phenyl-propane-1. -On, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one 2-hirodoxy-1- {4- [4- (2-hydroxy-) 2-Methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, phenylglycylic acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1-[ 4- (4-morpholinyl) phenyl] -1-butanone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone , 1- [4- (4-benzoylphenylsulfanyl) fanyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one, 1,2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), etc. Can be mentioned. As the component (D), these can be used alone or in combination of two or more.

The amount of the component (D) used is preferably 0.1 to 10% by weight, more preferably 0.2 to 8% by weight, based on 100 parts by weight of the present composition. By setting the ratio of the component (D) to 0.1% by weight or more, curing failure due to ultraviolet irradiation can be prevented, and by setting the ratio to 10% by weight or less, odor generation due to the decomposition product of the component (D) can be prevented. It can be reduced and the coloring of the cured layer can be prevented.

The production of the present composition is carried out by mixing the above components (A) to (D) in a desired ratio. The mixing method and the order of addition of each component are not particularly limited. Further, the component (A) and the component (B) may be reacted by putting them in a reaction vessel and heating them at room temperature or if necessary while stirring, and then the components (C) and (D) may be mixed.

The present composition can be diluted with various organic solvents, and the dilution can be adjusted to a viscosity range suitable for coating. As the organic solvent, one or more conventionally known organic solvents such as alcohols, ethers, esters, amides, ketones, acetic acid esters, and hydrocarbons can be used. From the viewpoint of dryness, an organic solvent having a boiling point of 50 ° C. to 160 ° C. is preferable.

Further, the composition can contain various additives, if necessary, as long as the effects of the present invention are not impaired. For example, it contains additives such as surface conditioners, surfactants, UV absorbers, antioxidants, inorganic fillers, silane coupling agents, colloidal silica, defoaming agents, wetting agents, rust preventives, and stabilizers. be able to.

As a light source of the active energy rays used for curing the composition, for example, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, or the like is used, and the amount of light, the arrangement of the light source, etc. are adjusted as necessary. To. When a high-pressure mercury lamp is used, it is preferable to cure one lamp having a light amount of 80 to 160 W / cm at a transport speed of 5 to 50 m / min. In other words, typically, more it is preferred to perform ultraviolet irradiation in the conditions integral illuminance of ultraviolet rays becomes 300~3,000mJ / cm ^2, the conditions integral illuminance of ultraviolet rays becomes 500~1,500mJ / cm ² is preferable. On the other hand, when curing with an electron beam, it is preferable to cure with an electron beam accelerator having an acceleration voltage of 10 to 300 kV at a transport speed of 5 to 50 m / min.

The present invention is also a cured product formed by curing the above composition with active energy rays. The cured product of the present invention has good scratch resistance and chemical resistance at room temperature, and exhibits high elongation when heated.

The present invention is also a film having a resin layer made of the above composition. The film of the present invention can be laminated on the surface of a molded product having a complicated shape such as deep drawing without causing cracks in the stretching process during heating, and can decorate the surface of the molded product with high quality. It is possible to impart scratch resistance and chemical resistance.

The present invention is also a cured layer obtained by curing a resin layer composed of the above composition with active energy rays. The cured layer is obtained by applying the above resin layer by a known method, drying / or drying, and then irradiating with active energy rays to cure.

The present invention is also a film formed by forming the cured layer on at least one surface of a substrate. The film of the present invention can be laminated on the surface of a molded product having a complicated shape such as deep drawing without causing cracks in the stretching process during heating, and can decorate the surface of the molded product with high quality. It is possible to impart scratch resistance and chemical resistance. The thickness of the cured layer is not particularly limited, but is usually about 1 to 1000 μm on average, preferably 3 to 500 μm. By setting the thickness within this range, it is possible to improve the dryness, scratch resistance, and workability, and it can be used as a decorative film.

The base material of the film is not particularly limited, and for example, polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene-based resin and the like may be used. Can be done.

Examples of the method for applying the composition to a film include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, and the like. The coating amount is not particularly limited, but usually, the weight after drying is in the range of 1 to 1000 g / m ² , preferably 3 to 500 g / m ² .

A molded product obtained by coating the surface of the cured film is also one of the present inventions. Examples of the molded product include an automobile interior molded product, an exterior of a mobile terminal product, and an exterior of a home electric appliance. Examples of the base material that can be used in the molded product include various known plastics. For example, in addition to plastics with relatively high surface polarity used in conventional vapor-deposited molded products such as ABS resin, AS resin, and polypropylene resin, conventional plastics with low surface polarity have been considered unsuitable for vapor-deposited molded products. Polypropylene resin and the like can also be mentioned.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following description, parts and% are based on weight.

<Manufacturing example 1>
In a four-necked flask equipped with a stirrer, a thermometer, a decompression pump and a distiller, 50 parts of toluene, 38.85 parts of 2-acryloyloxyethyl hexahydrophthalate (hereinafter referred to as MAHP) as a component (A), (hereinafter, MAHP). B) 11.65 parts of aluminum-sec-butoxide (hereinafter referred to as ASBD) and 0.1 part of hydroquinone were charged as components, heated to 80 ° C., and reacted for 2 hours. Then, the pressure inside the flask was reduced to distill off the solvent to obtain a reaction product of the component (A) and the component (B).
<Manufacturing example 2>
59.3 parts of methyl isobutyl ketone (hereinafter referred to as MIBK) was charged into a four-necked flask equipped with a stirrer, a thermometer, a reflux cooler, a nitrogen inlet and a dropping funnel, and nitrogen gas was flowed in to stir at 110 ° C. The temperature was raised to. Next, 9.8 parts of methyl methacrylate (hereinafter, MMA), 9.8 parts of glycidyl methacrylate (hereinafter, GMA), and 1 part of azobisisobutyronitrile (hereinafter, AIBN) were added and reacted at 90 ° C. for 24 hours. After that, 20 parts of acrylic acid and 0.1 part of triphenylphosphine were added and reacted for another 10 hours to obtain an acrylic acid adduct solution of a GMA: MMA copolymer polymer having a resin content of 40% (hereinafter, polymer acrylate A).
<Examples 1 to 7>
Examples 1 to 7 were blended according to the blending ratio shown in Table 1, and all were diluted with methyl ethyl ketone (hereinafter, MEK) to a solid content of 40% to obtain an active energy ray resin composition.

MAES: 2-acryloyloxyethyl succinate HEAA: hydroxyethyl acrylamide MAEP: 2-acryloyloxyethyl acid phosphate IBXA: isobornyl acrylate ACMO: acryloyl morpholine TBA: tert-butyl acrylate MPE: Osaka Organic Chemical Industry Co., Ltd. ) Bismer MPE400A
AL-D: Aluminum monoacetylacetonate Bisethylacetate Zr-B: Zirconium tetranormalbutoxide Zr-P: Zirconium tetranormal propoxide Zr-Ac: Zirconium tetracetylacetonate Zr-BS: Zirconium tributoxymonostearate Irg184 : BASF Irgacure 184

<Comparative example 1>
The thermoplastic acrylic resin "BR-107" (manufactured by Mitsubishi Rayon Co., Ltd.) was diluted with MEK to a solid content of 40%.
<Comparative example 2>
100 parts of the polymer acrylate A obtained in Production Example 2, 2 parts of Irg184, and 5 parts of MEK were added to obtain an active energy ray resin composition having a solid content of 40%.
<Comparative Examples 3 to 5>
Comparative Examples 3 to 5 were blended according to the blending ratio shown in Table 2, and all were diluted with methyl ethyl ketone (hereinafter, MEK) to a solid content of 40% to obtain an active energy ray resin composition.

The active energy ray resin compositions of Examples 1 to 7 and Comparative Examples 1 to 5 were placed on an easily adhesive polyethylene terephthalate film, and the bar coater No. Using No. 26, hand coating was performed so that the dry film thickness was about 10 μm, and heat treatment was performed at 80 ° C. for 3 minutes to prepare a dry film.

<Preparation of cured film>
The dry films of Examples 1 to 7 and Comparative Examples 2 to 5 were irradiated with a cumulative irradiation amount of 450 mJ / cm ² using one high-pressure mercury lamp 80W to prepare a cured film, and the following evaluation was performed.

<Elongation of cured film at high temperature>
A test piece obtained by cutting a cured film film into strips having a length of 100 mm and a width of 7 mm is set in a tensile tester (model number "AGS-10KNX" manufactured by Shimadzu Corporation) with a chuck-to-chuck distance of 50 mm, and in an environment of 150 ° C. , Pull the test piece at a tensile speed of 10 mm / min, stop at the point where the distance between chucks reaches 150 mm (elongation 150%), visually observe the presence or absence of cracks in the cured film, and if there are no cracks, ○, cracks If was generated, it was evaluated as x. By measuring the elongation of the cured film, the processability of the cured film during heat can be evaluated. If the cured film does not generate cracks when stretched by 150%, it is possible to obtain a laminated molded product having a good cured film surface without causing cracks even during the actual molding process. On the other hand, if the cured film has cracks when stretched by 150%, it will be a molded product with cracks on the surface.

<Pencil hardness>
Pencil hardness was evaluated according to JIS-K-5600. Those having a pencil hardness of H or more were evaluated as having excellent hardness to sufficiently satisfy the hard coat property, and those having a pencil hardness of less than F were evaluated as having inferior hard coat properties.

Regarding the evaluation of the chemical resistance of the cured film, the resistance was evaluated using the following two types of chemicals.

<Solvent resistance>
After impregnating MEK with absorbent cotton and rubbing the surfaces of various cured films 10 times back and forth with a load of 4.9 N, those that did not change on the surface of the cured film before and after the test were evaluated as ◯, and those that did change were evaluated as x.

<Sunscreen resistance>
Apply 0.2 g of sunscreen (Ultra Sheer Dry Touch Sunblock SPF45 manufactured by Newdrogina) evenly over 5 cm ² area, let stand at 50 ° C for 12 hours, then rinse the sunscreen with a large amount of water and cure. It was visually confirmed whether there was any abnormality in the appearance of the film. Those without abnormality were marked with ◯, and those with abnormality were marked with x.

The evaluation results of Examples 1 to 7 and Comparative Examples 1 to 5 are shown in Table 3.

Claims (6)

Ethylene unsaturated monomer (A) having at least one functional group selected from a primary hydroxyl group, a secondary hydroxyl group, a carboxyl group and a phosphoric acid group, an ethylenically unsaturated monomer other than the metal compound (B) and (A) components A resin composition for an active energy ray-curable hard coat , which comprises a monomer (C) and a photopolymerization initiator (D) .
The component (B) is a metal alkoxide compound and / or a metal chelate compound of aluminum and / or zirconium.
The component (C) is at least one of a nitrogen-containing vinyl monomer, an alkyl mono (meth) acrylate, a cyclic ester mono (meth) acrylate, and a polyalkylene glycol acrylate.
The total amount of the components (A) and (B) used is 30 to 90% by weight in the resin composition for active energy ray-curable hard coat.
The total weight of the component (A) and the component (B) is 100 parts, and the component (C) is 10 to 150 parts by weight.
The amount of the component (D) used is 0.1 to 10% by weight based on 100 parts by weight of the resin composition for active energy ray-curable hard coat.
Resin composition for active energy ray-curable hard coat . A cured product formed by curing the resin composition for an active energy ray-curable hard coat according to claim 1 with an active energy ray. A film having a resin layer made of the resin composition for an active energy ray-curable hard coat according to claim 1 . A cured layer obtained by curing a resin layer made of the active energy ray-curable hard coat resin composition according to claim 1 with active energy rays. A laminated film in which the cured layer according to claim 4 is formed on at least one surface of a base material. A molded product obtained by coating the surface of the cured product according to claim 2 .