JP2629732B2 - Laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a laminate, and more particularly, to a laminate having excellent surface hardness, surface gloss, weather resistance, and chemical resistance, and also having thermoformability. The present invention relates to a laminate suitable for various industrial members such as automobiles and electric appliances, building members, furniture members and the like.

[Conventional technology and its problems]

Refrigerator doors, molding machine housings, car bodies,
Conventionally, in the case of steel furniture, the surface of the steel plate is white or red,
The ones that are color painted in black etc. are used. In order to improve the coldness and low surface gloss of these color coated steel sheets in accordance with the individualization and diversification of products, the rigidity and heat resistance of the steel sheets and the appearance, workability, etc. It is conceivable to use a laminated body in which both are integrally bonded by utilizing the points of excellent properties and lightness.

However, since the thermoplastic resin has insufficient scratch resistance on the surface, it may be rubbed by contact depending on the method of use and application,
There is a problem that the surface is easily damaged by scratching or the like.

[Specific means to solve the problem]

In the present invention, in order to improve the scratch resistance of the thermoplastic resin film, an ultraviolet-curable resin composition is applied to the surface of the thermoplastic resin film, and the composition is irradiated with ultraviolet light, and the composition is light-cured to form a pencil. A hard film having a hardness of H to 4H is formed to improve scratch resistance and to further improve surface smoothness and gloss.

That is, the present invention has a structure in which a resin adhesive layer (C), a thermoplastic resin film layer (B), and an acrylic ultraviolet curable resin layer (A) are bonded and laminated in this order on a base metal plate (D). Wherein the acrylic ultraviolet-curable resin layer (A) is obtained by photo-curing the following ultraviolet-curable resin composition. is there.

Component (a): Methyl methacrylate homopolymer, methyl methacrylate-based copolymer having a methyl methacrylate content of 80% by weight or more, and side chain of methyl methacrylate-based copolymer having a methyl methacrylate content of 80% by weight or more At least one selected from modified products obtained by introducing a (meth) acryloyl group into
(B) component: a polyfunctional acrylate containing 50% by weight or more of dipentaerythritol hexaacrylate, (c) component: solvent, and (d) component: photopolymerization initiator, An ultraviolet-curable resin composition wherein the weight ratio of component (a) / component (b) is in the range of 0.1 to 10.

In the present invention, the ultraviolet curable acrylic resin composition for forming the layer (A) is a polyolefin sheet directly without a primer, even if the thermoplastic resin sheet (B) is a polypropylene or polyethylene having no polar group. The acrylic curable resin layer (A) can be provided by applying the photocurable resin composition on (B), drying and photocuring.

This UV-curable acrylic resin composition comprises: (a) a component: a methyl methacrylate homopolymer, a methyl methacrylate-based copolymer having a methyl methacrylate content of 80% by weight or more, and a methyl methacrylate content of 80% by weight or more At least one selected from modified products obtained by introducing a (meth) acryloyl group into the side chain of a methyl methacrylate-based copolymer
(B) component: a polyfunctional acrylate containing 50% by weight or more of dipentaerythritol hexaacrylate, (c) component: solvent, and (d) component: photopolymerization initiator And an ultraviolet curable resin composition wherein the weight ratio of component (a) / component (b) is in the range of 0.1 to 10.

The “(meth) acryloyl group” described in this specification is a general term for an acryloyl group and a methacryloyl group. Also,
“(Meth) acrylic acid” described in the present specification is a general term for acrylic acid and methacrylic acid, and similar descriptions, for example, descriptions of “ethyl (meth) acrylate” and the like also apply thereto.

The component (a) is a methyl methacrylate homopolymer,
Methyl methacrylate-based copolymer having a methyl methacrylate content of 80% by weight or more, and a modified product obtained by introducing a (meth) acryloyl group into a side chain of a methyl methacrylate-based copolymer having a methyl methacrylate content of 80% by weight or more At least one polymer selected from the group consisting of:

Examples of the monomer to be copolymerized with methyl methacrylate having a methyl methacrylate content of 80% by weight or more or methyl methacrylate for obtaining a modified product thereof include (meth) acrylic acid; methyl acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylate 2
-Ethylhexyl, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) And (meth) acrylic acid esters such as 2-hydroxypropyl acrylate. These monomers may be used in combination of two or more kinds as necessary.

Examples of the modified product in which a (meth) acryloyl group is introduced into a side chain of a methyl methacrylate copolymer having a methyl methacrylate content of 80% by weight or more include, for example, epoxy (meth) acrylate and urethane (meth) ) Modified products into which acrylate is introduced. Modified products in which the epoxy (meth) acrylate is introduced, for example,
A method in which (meth) acrylic acid is added to a copolymer obtained by copolymerizing 80% by weight or more of methyl methacrylate and glycidyl (meth) acrylate, or 80% by weight.
Glycidyl (meth) acrylate is added to the copolymer obtained by copolymerizing methyl methacrylate and (meth) acrylic acid as described above. Modified products in which urethane (meth) acrylate is introduced are, for example, 80
% By weight of a copolymer obtained by copolymerizing methyl methacrylate and 2-hydroxyethyl (meth) acrylate is equimolar with tolylene diisocyanate or isophorone diisocyanate and 2-hydroxyethyl (meth) acrylate. It can be obtained by subjecting the copolymer reacted at a ratio to an addition reaction to 2-hydroxyethyl (meth) acrylate of the copolymer.

(A) The methyl methacrylate homopolymer, the methyl methacrylate copolymer, and the methyl methacrylate copolymer used as a raw material for obtaining the modified product are used as the component (a). Must be at least 80% by weight. If the content of methyl methacrylate is less than 80% by weight, both the adhesion of the cured coating film of the photocurable resin composition to polyolefin and polyester and the abrasion resistance become insufficient.

Next, the component (b) is a polyfunctional acrylate containing 50% by weight or more of dipentaerythritol hexaacrylate. The polyfunctional acrylate may consist of dipentaerythritol hexaacrylate alone, but is a mixture of 50% by weight or more of dipentaerythritol hexaacrylate and less than 50% by weight of another polyfunctional acrylate. There is no problem. Other polyfunctional acrylates that can be used in combination with the dipentaerythritol hexaacrylate include, for example, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 2,2-bis [ 4- (acryloyloxydiethoxy)
Phenyl] propane, bis (acryloyloxyethyl)
Hydroxyethyl isocyanurate, tricyclodean dimethyl diacrylate, trimethylolpropane triacrylate, pentaerythritol tolacrylate, trimethylolpropane propylene oxide adduct triacrylate, tris (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate, Dipentaerythritol pentaacrylate, dipentaerythritol, caprolactone adduct acrylate, bisphenol A type epoxy resin acrylic acid adduct, novolak type epoxy resin acrylic acid adduct. Further tolylene diisocyanate,
An isocyanate prepolymer obtained by reacting a polyisocyanate such as isophorone diisocyanate or hexamethylene diisocyanate with a polyol such as polypropylene glycol, polytetramethylene glycol, polycaprolactone, or a condensation polymer of adipic acid and ethylene glycol is reacted with 2-isocyanate. Adducts obtained by performing an addition reaction with hydroxyl group-containing acrylates such as hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate are exemplified. Two or more of these other functional acrylates can be used in combination with dipentaerythritol hexaacrylate.

The ratio of the component (a) to the component (b) is expressed as:
The weight ratio of the component (b) is in the range of 0.1 to 10. When the weight ratio is less than 0.1, the adhesion of the cured coating film to polyolefin and polyester becomes insufficient, and when the weight ratio exceeds 10, the scratch resistance of the cured coating film becomes insufficient.

The solvent of the component (c) may be any solvent that can dissolve the components (a) and (b). Examples of the solvent include the aforementioned aromatic hydrocarbon solvents such as benzene, toluene, and xylene; halogenated hydrocarbon solvents such as chloroform and ethylene dichloride; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; and other dioxane and cellosolve solvents.
These solvents may be used in combination of two or more as appropriate.

These solvents are blended for adjusting the viscosity of the photocurable resin composition, and the amount of the solvent used is desirably a ratio that provides the optimum coating viscosity.

Next, as the photopolymerization initiator of the component (d), for example, the above-mentioned benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diethoxyacetophenone, benzyldimethyl ketal, 2-hydroxy-2-methylpropion Phenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, Michler's ketone, isoamyl N, N-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethyloxanthone, and the like. These photopolymerization initiators are two or more kinds. Can also be used in combination as appropriate. The amount of the photopolymerization initiator used is based on the component (b).
0.1 to 10 parts by weight, preferably 1 to 5 parts by weight.

The photocurable resin composition may contain, in addition to the components described above, if necessary, for example, a thermal polymerization inhibitor (for example, hydroquinone, hydroquinone monomethyl ether, benzoquinone, Catechol, pt-butyl catechol, phenothiazine, etc.), UV absorbers (for example, UV absorbers such as salicylic acid type, benzophenone type, benzotriazole type, cyanoacrylate type) for improving the properties of the coating film, and UV stabilizers ( For example, hindered amine ultraviolet stabilizers), anti-blocking agents, slip agents,
Various additives, such as repelling agents, that are incorporated into such compositions can be included.

Known methods such as brush coating, roll coating, spray coating, and dip coating can be used for applying the photocurable resin composition to the thermoplastic resin film (B). In short,
Depending on the shape of the thermoplastic resin film (B) to be coated,
Coating is performed by appropriately selecting a coating method capable of obtaining a desired uniform thickness and a smooth coating surface.

The laminated body coated with the photocurable resin composition is then dried by an appropriate means to remove the solvent by volatilization, and then the dried coating film is subjected to, for example, a xenon lamp, a low-pressure mercury lamp, Light such as a mercury lamp, an ultra-high pressure mercury lamp, a carbon arc lamp, a tungsten lamp, a halogen lamp, and sunlight, particularly ultraviolet rays, is irradiated to crosslink and cure the coating resin.

The thickness of the cured coating is usually 1 to 50 μm, preferably 2.
It is desirable to set it to about 5 to 30 μm. If the thickness of the cured coating film is too thin, sufficient scratch-resistant surface hardness cannot be obtained, and if the thickness is too thick, cracks are liable to be produced.

(Thermoplastic resin film) As the material of the thermoplastic resin film (B) to which the ultraviolet-curable acrylic resin composition is applied, polyester resin such as polyethylene terephthalate and polybutylene terephthalate; polyolefin such as polypropylene and polyethylene; Vinyl, ABS, etc. are used. The thermoplastic resin film layer (B) imparts smoothness and impact resistance to the ultraviolet-curable resin layer (A), and the resin layer (A)
At the same time, water resistance is imparted to the metal plate (D).

The thermoplastic resin film may be provided with a drawn pattern or a checkered pattern on the surface by compression molding or vacuum molding.
Further, they may contain pigments, inorganic fillers, stabilizers, plasticizers, UV absorbers and the like. Furthermore, a single-layer film or a laminated film structure of two or more sheets may be used. For example, in the case of a laminated film structure, the film on the side on which the ultraviolet-curable resin composition is applied is a smooth transparent polypropylene or polyethylene terephthalate film having a thickness of 30 to 80 μm containing no pigment or inorganic filler, and an intermediate layer. A polypropylene or polyethylene terephthalate film (thickness 130 μ) containing 10% by weight of pigment red gold, and a polypropylene or polyethylene terephthalate film (thickness 20) containing 3% by weight of carbon black on the back side.
0 to 1800 µ), the appearance of the obtained laminate can be made to have a wine-red metallic luster.

The thickness of this thermoplastic resin film is 4-2,000μ,
Preferably it is 20-100 micrometer.

(Resin Adhesive) As a resin adhesive for bonding the metal plate (D) and the thermoplastic resin film (B), adhesives such as an epoxy resin, a urethane resin, a polyester resin, and an acrylic resin;
Alternatively, an adhesive film such as an ethylene-acrylic acid-glycidyl acrylate copolymer is used.

 The thickness of the resin adhesive layer (C) is 1 to 100 μ.

(Metal plate) As the metal plate (D), a steel plate, a stainless steel plate, an aluminum plate, a copper plate, or the like is used. Their wall thickness is 8-2,
000μ. The surface of these metal plates may be subjected to a chemical treatment, a plating treatment, a sand blast treatment or the like.

(Laminate) The laminate is formed by bonding a metal plate (D) and a preformed thermoplastic resin film (B) using a resin adhesive (C),
Then, an ultraviolet-curable acrylic resin composition is applied on the film (B), dried and the solvent (c) is scattered, and if necessary, a pattern of the dried resin composition is provided. By irradiating.

In addition, for bonding the metal plate and the thermoplastic resin film, a liquid resin adhesive (so-called “primer”) is applied to the metal plate in advance, and then the thermoplastic resin film melted on the primer surface is extrusion-laminated. The laminate may be obtained by applying, drying, and photocuring the photocurable acrylic resin composition.

Further, an acrylic UV-curable resin layer may be provided on a thermoplastic resin film in advance, and then bonded to a metal plate using an adhesive to obtain a laminate.

Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, parts and% mean parts by weight and% by weight, respectively.

Example 1 A mixture of 100 parts of methyl methacrylate and 100 parts of toluene was heated and heated to 80 ° C., 2 hours after the temperature was raised, and 4 hours after the same, and azobisisobutyronitrile was added.
0.15 parts were added, and reacted at a temperature of 80 ° C. for 6 hours.
A 50% toluene solution of a methyl methacrylate homopolymer was obtained.

100 parts of a 50% toluene solution of the obtained homopolymer, 40 parts of dipentaerythritol hexaacrylate, 10 parts of neopentyl glycol diacrylate, 100 parts of toluene,
And 2 parts of dimethylbenzyl ketal were mixed and dissolved to obtain a photocurable resin composition.

This photocurable resin composition was applied to a 25 μm thick polyester film so as to have a coating amount of 10 μm, dried at 80 ° C. for 5 minutes, and then passed through a high-pressure mercury lamp sample having an output of 2 KW and an output density of 80 W / cm. Using an irradiation device installed vertically, the composition was cured at a conveyor speed of 6 m / min at a position 9 cm below the light source to obtain a laminate.

Polyester film layer of this laminate, thickness 0.4mm
Was press-formed at a temperature of 190 ° C. through a 30 μm-thick adhesive film made of an ethylene-acrylic acid-glycidyl acrylate copolymer to obtain a laminate.

 Table 1 shows the evaluation results of the laminate.

Example 2 A laminate was obtained by a press molding method in the same manner as in Example 1 except that the thickness of the polyester film to which the acrylic ultraviolet curable resin composition was applied was changed to 5 μm.

 Table 1 shows the evaluation results of the laminate.

Example 3 A laminate was obtained by a press molding method in exactly the same manner as in Example 1 except that the thickness of the polyester film to which the acrylic UV-curable resin composition was applied was changed to 50 μm.

 Table 1 shows the evaluation results of the laminate.

Example 4 Example 1 was repeated except that the thickness of the polyester film to which the acrylic UV-curable resin composition was applied was changed to 100 μm.
A laminate was obtained by a press molding method in exactly the same manner as described above.

 Table 1 shows the evaluation results of the laminate.

Comparative Example 1 Thickness of 50 without Acrylic UV Curable Resin Composition
A polyester film of μ was laminated in the same manner as in Example 1 by a press molding method to obtain a laminate.

 Table 1 shows the evaluation results of the laminate.

Test method ・ Pencil hardness JIS K5401 compliant ・ 60 ° C gloss level JIS Z8741 compliant ・ Cellotape peeling Acrylic UV curable resin layer is made with 100 cutters at 1mm intervals with a cutter, and Nichiban adhesive tape Cellotape (trade name) ) Is pressed and then strongly peeled off, and the number of gobangs remaining without peeling is displayed.

Example 5 An epoxy-based primer was applied on a 0.4 mm-thick steel plate at 2 g / m ^2.
Then, a polypropylene film having a thickness of 60 μm was melt-extruded at 300 ° C. and laminated on the primer surface.

Then, the photocurable resin composition used in Example 1 was applied to a polypropylene film of this laminate using a No. 25 bar coater, dried at 80 ° C. for 5 minutes, and then output at 2 KW and output. Using an irradiation device equipped with a high-pressure mercury lamp with a density of 80 W / cm perpendicular to the sample passing direction, and
Irradiated at a position of the conveyor speed of 6 m / min to cure the coating film.

The grain adhesion, pencil hardness, and gloss of the cured coating film to the polypropylene sheet were as follows.

Cellophane tape peeling test 100/100 Pencil hardness 2H Mitsuzawa 85% Example 6 A mixture of 85 parts of methyl methacrylate, 15 parts of cyclohexyl methacrylate and 100 parts of toluene was heated and heated to 80 ° C. and from the same temperature. Two hours and four hours later, 0.15 parts of azobisisobutyronitrile was added, and the mixture was reacted at a temperature of 80 ° C. for 6 hours to obtain a 50% toluene solution of a methyl methacrylate copolymer. Was. The methyl methacrylate content of this copolymer was about 85%.

100 parts of a 50% toluene solution of the obtained copolymer, 50 parts of dipentaerythritol hexaacrylate, 20 parts of tris (acryloyloxyethyl) isocyanurate, 170 parts of toluene, 1 part of dimethylbenzyl ketal, and 1 part of
1 part of hydroxycyclohexyl phenyl ketone was mixed and dissolved to obtain a photocurable resin composition.

Using this resin composition, a cured coating film was formed on a polypropylene film in the same manner as in Example 5 except for the above. The same test as in Example 5 was performed on the cured coating film, and the results were as follows.

Cellophane tape peel test 100/100 Pencil hardness 3H Hikarizawa 89% Example 7 90 parts of methyl methacrylate, glycidyl methacrylate 10
Part, and a mixture of 105 parts of toluene was heated and heated to 80 ° C., 2 hours after the temperature was raised, and 4 hours later, 0.15 parts each of azobisisobutyronitrile was added,
The reaction was performed at 80 ° C. for 6 hours. After the temperature of the reaction product was raised to 110 ° C, 5 parts of acrylic acid and 0.5 part of tetramethylammonium bromide (catalyst) were added, and the mixture was reacted at 110 ° C for 6 hours to obtain a modified product having an acryloyl group introduced into a side chain. Of 50
% Toluene solution was obtained. In this case, the methyl methacrylate content of the copolymer before modification was about 90%, and the methyl methacrylate content of the copolymer after modification was 85.7%.

100 parts of a 50% toluene solution of the obtained modified product, 30 parts of dipentaerythritol hexaacrylate, 130 parts of toluene
And 1 part of 1-hydroxycyclohexylphenyl ketone were mixed and dissolved to obtain a photocurable resin composition.

Using this resin composition, a cured coating film was formed on a polypropylene film in the same manner as in Example 5, except that
The same test as in Example 5 was performed on the cured coating film. The results were as follows.

Cellophane tape peeling test 100/100 Pencil hardness 3H Higasawa 87% Example 8 Polypropylene base film (thickness 200μ) containing 3% by weight of carbon black and pigment “Red Gold” 10
Parts by weight of a polypropylene intermediate layer film (thickness 10
0μ) and polypropylene surface layer film (wall thickness 60μ)
The photocurable resin composition used in Example 1 was applied to the surface layer of the three-layer laminated film, and dried to provide an ultraviolet-curable resin layer having a thickness of about 14 μm on the laminated film.

Next, the surface of the ultraviolet curable resin layer of the laminated film was smoothed using a super calender, and then irradiated with ultraviolet rays to be cured.

This laminate and a steel sheet having a thickness of 0.2 mm were bonded and laminated using a liquid urethane-based adhesive (3 g / m ² ) to obtain a laminate having a wine red metallic luster.

Cellophane tape peel test 100/100 Pencil hardness 2H Mitsuzawa 95% Reference Example 1 A mixture of 70 parts of methyl methacrylate, 30 parts of cyclohexyl methacrylate, and 100 parts of toluene was heated and heated to 80 ° C. and then to the same temperature Two hours and four hours later, 0.15 parts of azobisisobutyronitrile was added, and the mixture was reacted at 80 ° C. for 6 hours to obtain a 50% toluene solution of a methyl methacrylate copolymer. The methyl methacrylate content of this copolymer was about 70%.

100 parts of a 50% toluene solution of the obtained copolymer, 50 parts of dipentaerythritol hexaacrylate, 15 parts of toluene
0 parts and 2 parts of dimethylbenzyl ketal were mixed and dissolved to obtain a photocurable resin composition.

Using this curable resin composition, a cured coating film was formed on a polypropylene film in the same manner as in Example 5 except for the above, and the same test was performed on the coating film. The results were as shown below.

Cellophane tape peeling test 0/100 Pencil hardness B Comparative Example 2 Aronix M, a polyfunctional polyester acrylate
Press molding in the same manner as in Example 1 except that a photocurable resin composition obtained by mixing and dissolving 2 parts of dimethylbenzyl ketal in 100 parts of -8060 (trade name, manufactured by Toa Gosei Chemical Industry Co., Ltd.) is used. A laminate was obtained by the method.

 Table 2 shows the evaluation results of the laminate.

Comparative Example 3 NK ester U-4H which is a polyfunctional urethane acrylate
A (manufactured by Shin-Nakamura Chemical Co., Ltd. (trade name)) was press-molded in the same manner as in Example 1 except that a photocurable resin composition obtained by mixing and dissolving 2 parts of dimethylbenzyl ketal in 100 parts was used. A laminate was obtained.

 Table 2 shows the evaluation results of the laminate.

Comparative Example 4 Aronix M, a polyfunctional polyester acrylate
A cured coating film was formed on a polypropylene film in the same manner as in Example 5, except that a photocurable resin composition obtained by mixing and dissolving 2 parts of dimethylbenzyl ketal in 100 parts of -8060 was used. Table 2 shows the results of the same test as in Example 5 for the cured coating film.

Comparative Example 5 NK ester U-4H which is a polyfunctional urethane acrylate
Example 5 except that a photocurable resin composition obtained by mixing and dissolving 2 parts of dimethylbenzyl ketal in 100 parts of A was used.
A cured coating film was formed on a polypropylene film in the same manner as described above. Table 2 shows the results of the same test as in Example 5 for the cured coating film.

Reference Example 2 Instead of using a 25 μm-thick polyester film, a 1 mm-thick polyvinyl chloride film was used, and Aronix M-860 100, a polyfunctional polyester acrylate, was used.
Using a photocurable resin composition obtained by mixing and dissolving 2 parts of dimethylbenzyl ketal in each part, a laminate was obtained by press molding in the same manner as in Example 1.

 Table 2 shows the evaluation results of the laminate.

Reference Example 3 A light obtained by mixing and dissolving 2 parts of dimethylbenzyl ketal in 100 parts of NK ester U-4HA, a polyfunctional urethane acrylate, having a polyvinyl chloride film of 1 mm thickness instead of using a 25 μm thick polyester film. Using the curable resin composition, a laminate was obtained by press molding in the same manner as in Example 1.

 Table 2 shows the evaluation results of the laminate.

 ──────────────────────────────────────────────────の Continuation of the front page (72) Inventor Masataka Noro 1 Tohocho, Yokkaichi-shi, Mie Mitsubishi Plastics Co., Ltd. Resin Research Laboratory Co., Ltd. (56) References JP-A-60-206640 (JP, A)

Claims (2)

(57) [Claims] 1. A structure in which a resin adhesive layer (C), a thermoplastic resin film layer (B), and an acrylic ultraviolet curable resin layer (A) are bonded and laminated in this order on a metal plate (D) as a base material. A laminate, wherein the acrylic UV-curable resin layer (A) is obtained by photocuring the following UV-curable resin composition. Component (a): Methyl methacrylate homopolymer, methyl methacrylate-based copolymer having a methyl methacrylate content of 80% by weight or more, and side chain of methyl methacrylate-based copolymer having a methyl methacrylate content of 80% by weight or more At least one selected from modified products obtained by introducing a (meth) acryloyl group into
(B) component: a polyfunctional acrylate containing 50% by weight or more of dipentaerythritol hexaacrylate, (c) component: solvent, and (d) component: photopolymerization initiator, And an ultraviolet curable resin composition wherein the weight ratio of component (a) / component (b) is in the range of 0.1 to 10. 2. The thermoplastic resin film layer (B) has a thickness of 4
μ-2,000μ, acrylic UV curable resin layer (A) thickness 1μ-50μ, resin adhesive layer (C) thickness 1-100
2. The laminate according to claim 1, wherein the thickness of the metal plate (D) is 8 to 2,000 [mu], and the thickness of the laminate is 14 to 4,150 [mu].