JP6487287B2 - Metal sheet covering decorative sheet - Google Patents

Description

The present invention relates to a decorative sheet for covering a metal plate. More specifically, the decorative sheet has a glass-like design and can provide a decorative metal plate excellent in boiling water resistance, elixir resistance, and smoothness when used for coating a metal plate. About.

In recent years, glass has opened and closed the front panel of the door body that opens and closes the opening of the main body and the opening of the main body plane of articles such as refrigerators, washing machines, cupboards, and clothes racks because of its deep design feeling. It attracts attention as a member constituting the flat panel of the lid. However, glass has a problem that it has low impact resistance and is easily broken. Then, this inventor considered covering the metal plate which comprises the front panel of a door body, etc. with the decorative sheet which has a glass-like design. As the decorative sheet for covering a metal plate having a transparent layer on the outermost surface side and having good boiling water resistance, “a base layer (A layer) made of a resin containing a pigment and a transparent stretched polyester resin” A laminated sheet having at least two surface layers (B layer) having a thickness of 100 μm or less, wherein the A layer is 3 to 15% by mass, with the total mass of the resin component in the A layer being 100% by mass. Non-polyester thermoplastic elastomer having an epoxy group (a-1 component), 21 to 48% by mass of polybutylene terephthalate resin (a-2 component), and 42 to 73% by mass of substantially amorphous "A laminated sheet for covering a metal plate made of a polyester resin (a-3 component)" is proposed (Patent Document 1). However, the design of the sheet has an inadequate design feeling.

JP 2006-297758 A

The object of the present invention is to have a glass-like design, and when used for coating a metal plate, it is possible to obtain a decorative metal plate excellent in boiling water resistance, elixir resistance, and smoothness. It is to provide a decorative sheet.

As a result of intensive studies, the present inventor has found that the above-described problems can be achieved by a specific decorative sheet.

That is, the present invention comprises (A) a layer of a biaxially stretched polyethylene terephthalate resin film having a thickness of 10 to 200 μm in order from the surface side;
(B) Constitution derived from terephthalic acid, 45 to 50 mol%, structural unit derived from isophthalic acid, 5 to 0 mol%, and 1,4-cyclohexanedimethanol A polyester copolymer comprising 25 to 45 mol% of units and 25 to 5 mol% of structural units derived from 2,2,4,4, -tetramethyl-1,3-cyclobutanediol, and having a thickness of 50 to 3000 μm A layer of transparent polyester resin film; and (D) a layer of colored resin film;
Is a decorative sheet.

2nd invention is the layer of the biaxially-stretched polyethylene terephthalate-type resin film of thickness (A) 10-200 micrometers in order from the surface side;
(B) Constitution derived from terephthalic acid, 45 to 50 mol%, structural unit derived from isophthalic acid, 5 to 0 mol%, and 1,4-cyclohexanedimethanol A polyester copolymer comprising 25 to 45 mol% of units and 25 to 5 mol% of structural units derived from 2,2,4,4, -tetramethyl-1,3-cyclobutanediol, and having a thickness of 50 to 3000 μm A layer of transparent polyester resin film;
(C) a transparent resin layer containing a high brightness pigment; and (D) a layer of a colored resin film;
Is a decorative sheet.

According to a third aspect of the present invention, there is provided a transparent resin layer containing the above (C) high brightness pigment,
(C1) 100 parts by mass of a transparent resin; and (c2) a glass having an average particle diameter of 10 to 250 μm and having a surface coated with one or more selected from the group consisting of titanium oxide, indium oxide, zinc oxide, and tin oxide The decorative sheet according to the second aspect of the present invention, comprising a resin composition containing 0.01 to 10 parts by mass of particles.

4th invention is a metal plate containing the decorative sheet of any one of 1st-3rd invention.

5th invention is an article | item containing the metal plate as described in 4th invention.

The decorative sheet of the present invention has a design with a deep glass tone, and when used for coating a metal plate, a decorative metal plate excellent in boiling water resistance, elixir resistance, and smoothness can be obtained. it can. In addition, the decorative metal plate obtained using the decorative sheet of the present invention includes a front plate of a door body that opens and closes an opening of a main body of an article such as a refrigerator, a washing machine, a cupboard, and a clothes rack, and an opening of a main body plane. It can be suitably used for a flat plate of a lid that opens and closes

In this specification, the term “film” is used as a term including sheets and plates. The term “resin” is used as a term including a resin mixture containing two or more resins and a resin composition containing components other than resins.

The decorative sheet of the present invention, in order from the surface side,
(A) a layer of a biaxially stretched polyethylene terephthalate resin film having a thickness of 10 to 200 μm;
(B) Constitution derived from terephthalic acid, 45 to 50 mol%, structural unit derived from isophthalic acid, 5 to 0 mol%, and 1,4-cyclohexanedimethanol A polyester copolymer comprising 25 to 45 mol% of units and 25 to 5 mol% of structural units derived from 2,2,4,4, -tetramethyl-1,3-cyclobutanediol, and having a thickness of 50 to 3000 μm A layer of transparent polyester resin film;
And (D) a layer of a colored resin film.
Preferably, in order from the surface side,
(A) a layer of a biaxially stretched polyethylene terephthalate resin film having a thickness of 10 to 200 μm;
(B) Constitution derived from terephthalic acid, 45 to 50 mol%, structural unit derived from isophthalic acid, 5 to 0 mol%, and 1,4-cyclohexanedimethanol A polyester copolymer comprising 25 to 45 mol% of units and 25 to 5 mol% of structural units derived from 2,2,4,4, -tetramethyl-1,3-cyclobutanediol, and having a thickness of 50 to 3000 μm A layer of transparent polyester resin film;
(C) a transparent resin layer containing a high brightness pigment; and (D) a layer of a colored resin film.

The layer (A) is a layer of a biaxially stretched polyethylene terephthalate resin film having a thickness of 10 to 200 μm, and functions to improve the smoothness and scratch resistance of the decorative sheet of the present invention.

From the viewpoint of smoothness, the thickness of the biaxially stretched polyethylene terephthalate resin film is 10 μm or more, preferably 20 μm or more. On the other hand, from the viewpoint of workability, it is 200 μm or less, preferably 100 μm or less, and more preferably 50 μm or less.

The biaxially stretched polyethylene terephthalate resin film is widely available on the market, and any film can be used.

The layer of the (B) transparent polyester resin film is composed of 45 to 50 mol% of structural units derived from terephthalic acid, 5 to 0 mol% of structural units derived from isophthalic acid, and 100 mol% of the total amount of monomers. Polyester copolymer containing 25 to 45 mol% of structural units derived from 1,4-cyclohexanedimethanol and 25 to 5 mol% of structural units derived from 2,2,4,4, -tetramethyl-1,3-cyclobutanediol It is a layer of a film having a thickness of 50 to 3000 μm made of a resin mainly containing a polymer (usually 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more).

Since the said polyester-type copolymer is highly transparent, the decorative sheet of this invention has a design with the depth of a glass tone. In addition, the decorative sheet of the present invention has excellent boiling water resistance because it is amorphous or low crystalline and has a high glass transition temperature (preferably 100 ° C. or higher, more preferably 110 ° C. or higher).

In this specification, a Diamond DSC type differential scanning calorimeter manufactured by PerkinElmer Japan Co., Ltd. is used, and after holding the sample at 320 ° C. for 5 minutes, the sample is cooled to −50 ° C. at a temperature decreasing rate of 20 ° C./min, The second melting curve (melting curve measured in the last heating step) measured by a temperature program of holding at 5 ° C. for 5 minutes and then heating to 320 ° C. at a heating rate of 20 ° C./min, Polyesters of 10 J / g or less were defined as amorphous, and polyesters of 10 J / g or more and 60 J / g or less were defined as low crystallinity.

In this specification, the glass transition temperature is measured by using a Diamond DSC type differential scanning calorimeter of Perkin Elmer Japan Co., Ltd., heating the sample to 200 ° C. at a heating rate of 50 ° C./min, and at 200 ° C. for 10 minutes. After the temperature is maintained, the temperature is lowered to 50 ° C. at a rate of temperature decrease of 20 ° C./min, held at 50 ° C. for 10 minutes, and then heated to 200 ° C. at a rate of temperature increase of 20 ° C./min. The glass transition temperature appearing in the curve measured in FIG. 2 is the midpoint glass transition temperature calculated by drawing according to FIG. 2 of ASTM D3418.

The ratio of the structural unit derived from each component in the polyester-based copolymer can be determined using ¹³ C-NMR or ¹ H-NMR. An example of ¹ H-NMR measurement is shown in FIG.

^{The 13} C-NMR spectrum can be measured, for example, by dissolving 20 mg of a sample in 0.6 mL of chloroform-d ₁ solvent and using a 125 MHz nuclear magnetic resonance apparatus under the following conditions.
Chemical shift standard Chloroform-d ₁ : 77 ppm
Measurement mode Single pulse proton broadband decoupling pulse width 45 ° (5.00 μs)
64K points
Observation range 250ppm (-25 to 225ppm)
Repeat time 5.5 seconds Accumulation 256 times Measurement temperature 23 ° C
Window function exponential (BF: 1.0Hz)

^{The 1} H-NMR spectrum can be measured, for example, by dissolving 20 mg of a sample in 0.6 mL of chloroform-d ₁ solvent and using a 400 MHz nuclear magnetic resonance apparatus under the following conditions.
Chemical Shift Standard Chloroform: 7.24ppm
Measurement mode Single pulse pulse width 45 ° (5.14 μs)
Number of points 16k
Measurement range 15 ppm (-2.5 to 12.5 ppm)
Repeat time 7.8 seconds Accumulation 64 times Measurement temperature 23 ° C
Window function exponential (BF: 0.18Hz)

The attribution of the peak is “Polymer Analysis Handbook (First Edition, September 20, 2008, edited by Japan Analytical Chemistry Society, Polymer Analysis Research Meeting, Asakura Shoten Co., Ltd.), especially pages 496-503” and “ The NMR database (http://polymer.nims.go.jp/NMR/) of the National Institute for Materials Science, National Institute for Materials Science, is used as a reference, and the peak area ratio of each component in the above component (a) is determined. The percentage can be calculated. In addition, the measurement of ¹³ C-NMR and ¹ H-NMR can also be performed in an analysis organization such as Mitsui Chemical Analysis Center.

Examples of commercially available polyester-based copolymers include “Tritan FX100 (trade name)” of Eastman Chemical Company, glass transition temperature 110 ° C .; “Tritan FX200 (trade name)”, glass transition temperature 119 ° C., etc. Can give.

The polyester-based copolymer can contain other components as desired, as long as the object of the present invention is not adversely affected. Optional components that can be included include thermoplastic resins other than the above polyester copolymers; pigments, inorganic fillers, organic fillers, resin fillers; lubricants, antioxidants, weathering stabilizers, thermal stabilizers, mold release agents, charging And additives such as an inhibitor and a surfactant. The amount of these optional components is usually 25 parts by mass or less, preferably about 0.01 to 10 parts by mass when the polyester copolymer is 100 parts by mass.

The thickness of the transparent polyester resin film for forming the layer (B) is 50 μm or more, preferably 100 μm or more, more preferably 200 μm or more, and further preferably 300 μm or more from the viewpoint of design. On the other hand, from the viewpoint of workability, it is 3000 μm or less, preferably 2000 μm or less, more preferably 1000 μm or less, and still more preferably 600 μm or less.

The method of obtaining the said transparent polyester-type resin film for forming the said layer (B) using the said polyester-type copolymer is not restrict | limited, Arbitrary methods can be used. For example, a T-die coextrusion method can be mentioned. If desired, uniaxial stretching or biaxial stretching may be performed. Two or more transparent polyester resin films may be laminated.

The decorative sheet of the present invention preferably includes (C) a transparent resin layer containing a high-luminance pigment. The design feeling of the decorative sheet can be improved.

Examples of the high brightness pigment include metals such as aluminum, brass, iron, copper, silver, gold, titanium, indium, zinc, and tin; metal oxides such as titanium oxide, indium oxide, zinc oxide, and tin oxide. Mica; pearls; fine particles such as glass.

The transparent resin layer containing the (C) high brightness pigment is preferably
(C1) 100 parts by mass of a transparent resin; and (c2) a glass having an average particle diameter of 10 to 250 μm and having a surface coated with one or more selected from the group consisting of titanium oxide, indium oxide, zinc oxide, and tin oxide A resin composition containing 0.01 to 10 parts by mass of particles.
The design feeling of the decorative sheet can be further improved.

The component (c1) functions to include a high brightness pigment. In addition, the component (c1) is transparent in order to effectively exhibit the design effect by coloring the high brightness pigment and the layer (D). As a component (c1), if it is excellent in the inclusion property of a high-intensity pigment and is transparent, it will not be restrict | limited, Arbitrary resin can be used.

Examples of the component (c1) include a transparent thermoplastic resin for extrusion molding. Examples of the transparent thermoplastic resin include polyester resins such as aromatic polyesters and aliphatic polyesters; acrylic resins; polycarbonate resins; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; cellophane, triacetyl cellulose, Cellulose resins such as diacetylcellulose and acetylcellulose butyrate; polystyrene, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), styrene / ethylene / butadiene / styrene copolymer, styrene / ethylene / butadiene / styrene copolymer, etc. Styrene resin; polyvinyl chloride resin; polyvinylidene chloride resin; fluorine-containing resin such as polyvinylidene fluoride; other, polyvinyl alcohol, ethylene vinyl alcohol There may be mentioned polyether ether ketone, nylon, polyamide, polyimide, polyurethane, polyether imide, polysulfone, and polyethersulfone and the like. Among these, amorphous or low crystalline aromatic polyester resins and polyvinyl chloride resins are preferable from the viewpoint of design. As said transparent thermoplastic resin, these 1 type, or 2 or more types of mixtures can be used.

Examples of the component (c1) include a transparent adhesive. The transparent adhesive does not become opaque not only when producing decorative sheets, but also when decorating and decorating metal plates using decorative sheets, and when decorated decorative metal plates are processed into articles. It is preferably transparent.

The transparent adhesive is not limited except that it has sufficient adhesive strength and is transparent, and any adhesive can be used. For example, polyester, polyurethane, polyvinyl chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, epoxy, polychloroprene, polyacryl, polymethacryl, polystyrene, polyamide, cellulose, And an adhesive such as a styrene-butadiene copolymer system. Among these, from the viewpoint of adhesive strength and transparency, polyester-based, polyurethane-based, polyvinyl chloride-based, polyacryl-based, polymethacryl-based, and polyvinyl acetate-based adhesives are preferable. As the transparent adhesive, one or a mixture of two or more of these can be used.

In the present specification, the “transparent adhesive” means an adhesive having a visible light transmittance of 50% or more, preferably 70% or more, more preferably 85% or more. Here, the visible light transmittance is a transmission spectrum at a wavelength of 380 to 780 nanometers of an adhesive using a spectrophotometer “SolidSpec-3700 (trade name)” manufactured by Shimadzu Corporation and a quartz cell having an optical path length of 10 mm. This is a value calculated as a ratio of the integral area of the transmission spectrum of the adhesive to the integral area of the transmission spectrum when it is assumed that the transmittance in the entire range of wavelengths from 380 to 780 nanometers is 100%. Further, the term “adhesive” is used as a term including an adhesive.

The component (c2) functions as a high-brightness pigment to impart a high-brightness design to the decorative sheet and to effectively exhibit the design effect due to the coloring of the layer (D).

The component (c2) is a glass particle whose surface is coated with one or more metal oxides selected from the group consisting of titanium oxide, indium oxide, zinc oxide, and tin oxide. The glass and the metal oxide are transparent materials, and the light reflected by the component (c2), that is, the light reflected on the surface of the glass particles or the surface of the metal oxide coating layer is a small amount. Depending on whether it is reflected by the surface of the metal or the metal oxide coating layer, a large path difference occurs, so that even a small amount makes the human eye feel high brightness. Moreover, since much light permeate | transmits a component (c2), the design effect by coloring of the said layer (D) is exhibited effectively, and the design feeling is not impaired.

Among the metal oxides, titanium oxide is preferable from the viewpoint of design.

The component (c2) preferably has an average particle size of 10 to 250 μm. When the average particle size is preferably 10 μm or more, more preferably 20 μm or more, and still more preferably 40 μm or more, it is possible to achieve both a high brightness feeling and a design effect by coloring the layer (D). Moreover, the effect which makes the dispersion | distribution nonuniformity of a component (c2) inconspicuous can be acquired because it is preferably 250 micrometers or less, More preferably, it is 200 micrometers or less, More preferably, it is 120 micrometers or less. Moreover, the design effect by coloring of the said layer (D) can be acquired.

In this specification, the average particle size is the cumulative particle size from the smaller particle in the particle size distribution curve measured using a laser diffraction / scattering particle size analyzer “MT3200II (trade name)” manufactured by Nikkiso Co., Ltd. The particle diameter is 50% by mass.

The amount of the component (c2) is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (c1). When the amount is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and still more preferably 0.1 parts by mass or more, a high luminance feeling can be obtained. Moreover, the design effect by coloring of the said layer (D) can be favorably acquired by being preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and further preferably 1 part by mass or less.

As a commercial example of the said component (c2), the "Metashine (brand name)" etc. of Nippon Sheet Glass Co., Ltd. can be mentioned.

The resin composition containing the high-intensity pigment can further contain an optional component other than the component (c1) and the component (c2) as desired, as long as the object of the present invention is not adversely affected. . Examples of the optional component include a photopolymerization initiator, a compound having two or more isocyanate groups in a molecule, an antistatic agent, a surfactant, a leveling agent, a thixotropic agent, an antifouling agent, and a printability improving agent. And additives such as antioxidants, weather resistance stabilizers, light resistance stabilizers, ultraviolet absorbers, heat stabilizers, pigments other than component (c2), and fillers. The compounding quantity of the said arbitrary component is about 0.01-10 mass parts with respect to 100 mass parts of components (c1).

When the component (c1) is a transparent thermoplastic resin for extrusion, the resin composition for the layer (C) comprises the component (c1), the component (c2), and as desired. Can be obtained by melt-kneading using an arbitrary melt-kneader (for example, a single-screw extruder, a twin-screw extruder, a roll, a mixer, various kneaders, etc.).

When the component (c1) is a transparent thermoplastic resin for extrusion molding, the method for forming the layer (C) using the resin composition is not particularly limited, and any method can be used. . For example, using the above resin composition, after forming a film using an arbitrary method such as T-die coextrusion, on the layer (B) or the layer (D), directly or via an anchor coat or the like , Dry laminating or heat laminating method; feed block containing the resin composition and the transparent polyester resin for forming the layer (B) and / or the following colored resin for forming the layer (D) Or T-die coextrusion method by multi-manifold method or stack plate method;
Examples thereof include an extrusion laminating method in which the layer (B) or the layer (D) is used as a film base and the resin composition is melt-extruded thereon.

When the component (c1) is a transparent adhesive, the resin composition for the layer (C) includes the component (c1), the component (c2), and an optional component used as desired. It can be obtained by mixing and stirring.

When the said component (c1) is a transparent adhesive, the method in particular of forming the said layer (C) using the said resin composition is not restrict | limited, A well-known web coating method can be used. Specifically, methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating can be used. At this time, any dilution solvent such as 1-methoxy-2-propanol, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and acetone can be used as necessary.

The (D) colored resin film layer is a layer composed of a colored resin film, and gives a decorative design effect by coloring the decorative sheet, and also smoothes the decorative decorative surface by absorbing the unevenness of the metal plate as a base film. Or hiding a color or pattern that is not preferable for the design of the metal plate.

The colored resin film is not limited and any colored resin film can be used. For example, polyester resins such as aromatic polyester and aliphatic polyester; acrylic resins; polycarbonate resins; poly (meth) acrylimide resins; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; cellophane, triacetyl Cellulosic resins such as cellulose, diacetylcellulose, and acetylcellulose butyrate; polystyrene, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), styrene / ethylene / butadiene / styrene copolymer, and styrene / ethylene / butadiene / styrene Styrene resins such as copolymers; polyvinyl chloride resins; polyvinylidene chloride resins; fluorine-containing resins such as polyvinylidene fluoride; other, polyvinyl alcohol, ethyl It can be mentioned colored resin films and the like; vinyl alcohol, polyether ether ketone, nylon, polyamide, polyimide, polyurethane, polyether imide, polysulfone, polyether sulfone. These films include unstretched films, uniaxially stretched films, and biaxially stretched films. Moreover, the laminated film which laminated | stacked 2 or more of these 1 or more types is included.

Among these, a polyvinyl chloride resin film and a polyester resin film are preferable from the viewpoint of adhesion to a steel plate.

The thickness of the colored film is not particularly limited, but may be preferably 50 μm or more, more preferably 80 μm or more from the viewpoint of smoothing the decorative decorative surface by absorbing the unevenness of the metal plate. On the other hand, from the viewpoint of cost, it may be preferably 300 μm or less, more preferably 200 μm or less.

The decorative sheet of the present invention may further have a printed pattern layer between arbitrary layers in order to enhance the design feeling, if desired. The printed pattern layer can be formed by printing an arbitrary pattern on any layer directly or via an anchor coat using an arbitrary printing ink and an arbitrary printing machine. The printed pattern layer is not limited to one layer, and may be two or more layers.

The above patterns include metal-like patterns such as hairlines, wood grain patterns, stone patterns imitating the surface of rocks such as marble, fabric patterns imitating cloth or cloth-like patterns, tiled patterns, brickwork patterns, parquet patterns , And patchwork. As said printing ink, what mixed the pigment, the solvent, the stabilizer, the plasticizer, the catalyst, the hardening | curing agent, etc. in the binder suitably can be used. Examples of the binder include polyurethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, polyester resins, polyamides. Resins such as resin, butyral resin, polystyrene resin, nitrocellulose resin, and cellulose acetate resin, and these resin compositions can be used.

Moreover, in order to give a metallic design, aluminum, tin, titanium, indium and oxides thereof may be deposited by a known method.

When the printed pattern layer is formed between the layer (A) and the layer (B) or between the layer (B) and the layer (C), it has a glassy depth. In order not to impair the design feeling, it is preferable to provide the printing pattern partially or using a transparent printing ink.

The decorative sheet of the present invention may further have a transparent resin coating layer on the surface side of the layer (A).

The resin coating layer is a layer made of a coating for forming a resin coating such as a thermoplastic resin composition coating or an active energy ray curable resin composition, and can enhance the damage resistance of the decorative sheet.

The thermoplastic resin composition paint is a paint prepared by dissolving a thermoplastic resin in an organic solvent, and a resin coating film can be formed by coating and drying the paint.

Examples of the thermoplastic resin include urethane resins, polyester resins, acrylic resins, vinyl acetate resins, vinyl chloride resins, silicon resins, and fluorine resins. Among these, urethane resin, polyester resin, and acrylic resin are preferable. As a thermoplastic resin, these 1 type, or 2 or more types of mixtures can be used.

Examples of the organic solvent include 1-methoxy-2-propanol, ethyl acetate, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone. As an organic solvent, these 1 type, or 2 or more types of mixtures can be used.

If necessary, the thermoplastic resin composition paints include antistatic agents, surfactants, leveling agents, thixotropic agents, antifouling agents, printability improvers, antioxidants, weathering stabilizers, and light resistance. One kind or two or more kinds of additives such as a property stabilizer, an ultraviolet absorber, a heat stabilizer, a colorant and a filler may be contained.

The thermoplastic resin composition paint can be obtained by mixing and stirring these components.

The active energy ray-curable resin composition can be polymerized and cured by active energy rays such as ultraviolet rays and electron beams to form a hard coat. Examples of the composition include a compound having two or more isocyanate groups (—N═C═O) and / or a photopolymerization initiator.

Examples of the active energy ray-curable resin include polyurethane (meth) acrylate, polyester (meth) acrylate, polyacryl (meth) acrylate, epoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate, and polyether. (Meth) acryloyl group-containing prepolymer or oligomer such as (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Lauryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate Phenyl cellosolve (meth) acrylate, 2-methoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-acryloyloxyethyl hydrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl ( (Meth) acrylate and (meth) acryloyl group-containing monofunctional reactive monomers such as trimethylsiloxyethyl methacrylate; monofunctional reactive monomers such as N-vinylpyrrolidone and styrene; diethylene glycol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2,2′-bis (4- (meth) acrylo (Methoxy) acryloyl group-containing bifunctional reactive monomers such as 2,2′-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane; trimethylolpropane tri (meth) (Meth) acryloyl group-containing trifunctional reactive monomers such as acrylate and trimethylolethane tri (meth) acrylate; (meth) acryloyl group-containing tetrafunctional reactive monomers such as pentaerythritol tetra (meth) acrylate; and dipentaerythritol Examples of the resin include one or more selected from (meth) acryloyl group-containing hexafunctional reactive monomers such as hexaacrylate or the like, or one or more of the above as constituent monomers. As the active energy ray curable resin, one kind or a mixture of two or more kinds thereof can be used. In the present specification, (meth) acrylate means acrylate or methacrylate.

Examples of the compound having two or more isocyanate groups in one molecule include methylene bis-4-cyclohexyl isocyanate; trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylol of isophorone diisocyanate. Polyisocyanates such as propane adduct, isocyanurate of tolylene diisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, biuret of hexamethylene diisocyanate; and urethanes such as block isocyanates of the above polyisocyanates A crosslinking agent can be used. These can be used alone or in combination of two or more. Further, at the time of crosslinking, a catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be added as necessary.

Examples of the photopolymerization initiator include benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4′-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl. Benzophenone compounds such as -4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; benzoin, benzoin methyl ether, benzoin Benzoin compounds such as ethyl ether, benzoin isopropyl ether and benzyl methyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, etc. Acetophenone compounds; anthraquinone compounds such as methylanthraquinone, 2-ethylanthraquinone, 2-amylanthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; alkylphenones such as acetophenone dimethyl ketal Compounds; triazine compounds; biimidazole compounds; acyl phosphine oxide compounds; titanocene compounds; oxime ester compounds; oxime phenylacetate compounds; hydroxy ketone compounds; and aminobenzoate compounds. it can. These can be used alone or in combination of two or more.

In addition, the active energy ray-curable resin composition includes an antistatic agent, a surfactant, a leveling agent, a thixotropic agent, a stain prevention agent, a printability improving agent, an antioxidant, and a weather resistance stabilizer as necessary. In addition, one or more additives such as a light resistance stabilizer, an ultraviolet absorber, a heat stabilizer, a colorant, and a filler may be contained.

Moreover, since the said active energy ray curable resin composition is diluted to the density | concentration which is easy to apply, it may contain the solvent as needed. The solvent is not particularly limited as long as it does not react with the components of the curable resin composition and other optional components or does not catalyze (promote) the self-reaction (including deterioration reaction) of these components. Examples thereof include 1-methoxy-2-propanol, ethyl acetate, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone.

The active energy ray-curable resin composition can be obtained by mixing and stirring these components.

The method for forming the resin coating film using the resin coating film-forming coating material is not particularly limited, and a known web coating method can be used. Specifically, methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating can be used.

The thickness of the resin coating film is preferably 5 μm or more, more preferably 10 μm or more, from the viewpoint of obtaining the effect of improving the trauma resistance. On the other hand, the thickness of the resin coating film is preferably 100 μm or less, and more preferably 50 μm or less, from the viewpoint of web handling properties and workability of forming the resin coating film.

The lamination of the above layers is not particularly limited, and can be performed by any method. For example, methods such as thermal lamination and dry lamination can be used.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Measurement method (b) Deepness:
In a dark place, light from a 40 W white fluorescent lamp (300 lux) is perpendicularly incident from a position 50 cm away from the decorative sheet side surface of the decorative steel sheet, forming an angle of 45 ° with the decorative sheet surface, The decorative sheet was visually observed from a position separated by a distance of 30 cm and evaluated according to the following criteria. This was done for five panelists and their total score was determined.
2 points: Transparent and deep.
1 point: I feel a little deep.
0 points: No sense of depth.

(B) Boiling water test:
The decorative steel sheet is treated in boiling water at 100 ° C. for 3 hours, taken out and allowed to stand at room temperature for 30 minutes, then the surface is washed with distilled water and dried, and then the decorative sheet side surface of the decorative steel sheet is visually observed. Evaluated by criteria. This was repeated 5 times and the total score was determined.
2 points: No cloudiness or bubbles are observed.
1 point: Some cloudiness and bubbles are observed.
0 point: Cloudiness and bubbles are observed.

(C) Eriksen test:
Referring to JIS Z2247: 2006, from the surface of the decorative steel sheet on the surface side of the decorative steel sheet, the surface of the decorative steel sheet on the decorative sheet side is subjected to drawing with an indentation depth of 8 mm at a test speed of 10 mm / min. Were visually observed and evaluated according to the following criteria. This was repeated 5 times and the total score was determined.
2 points: No cracks or cracks are observed.
0 points: Cracks and cracks are observed.

(D) Smoothness:
In a dark place, light from a 40 W white fluorescent lamp (300 lux) is incident at an angle of 45 ° from a position 50 cm away from the decorative sheet side surface of the decorative steel sheet, and the decorative sheet side surface of the decorative steel sheet The face on the decorative sheet side of the decorative steel sheet was visually observed from a position at an angle of 45 ° and a distance of 30 cm, and evaluated according to the following criteria. This was done for five panelists and their total score was determined.
2 points: Smooth.
1 point: Some unevenness is recognized.
0 point: Unevenness is observed.

Raw material used (A) Biaxially stretched polyethylene terephthalate resin film:
(A-1) A biaxially stretched polyethylene terephthalate resin film having a thickness of 25 μm.

(B) Polyester copolymer:
(B1) Assuming that the total amount of monomers is 100 mol%, 50.0 mol% of structural units derived from terephthalic acid, 38.7 mol% of structural units derived from 1,4-cyclohexanedimethanol, 2,2,4, A polyester copolymer containing 11.3 mol% of a structural unit derived from 4, -tetramethyl-1,3-cyclobutanediol. Glass transition temperature 110 ° C., heat of fusion 0 J / g (no clear melting peak in DSC second melting curve).
(B2) Assuming that the total amount of monomers is 100 mol%, 49.9 mol% of structural units derived from terephthalic acid, 32.3 mol% of structural units derived from 1,4-cyclohexanedimethanol, 2,2,4, A polyester copolymer containing 18.0 mol% of a structural unit derived from 4, -tetramethyl-1,3-cyclobutanediol. Glass transition temperature 119 ° C., heat of fusion 0 J / g (no clear melting peak in DSC second melting curve).

(B ′) Comparative polyester resin:
(B′1) Eastman Chemical Company's amorphous aromatic polyester-based resin “KODAR PETG GS1 (trade name)”, glass transition temperature 81 ° C., heat of fusion 0 J / g (no clear melting peak in DSC second melting curve) ).
(B′2) “Toraycon 1200M (trade name)”, a polybutylene terephthalate resin by Toray Industries, Inc.
(B′3) Polytrimethylene terephthalate resin “Cortera CP509200 (trade name)” of Shell Chemicals Japan Co., Ltd., melting point 225 ° C.
(B′4) A mixture of 90 parts by mass of (b′1) and 10 parts by mass of (b′2).
(B′5) A mixture of 50 parts by mass of (b′1) and 50 parts by mass of (b′2).
(B′6) A mixture of 90 parts by mass of (b′1) and 10 parts by mass of (b′3).
(B′7) A mixture of 50 parts by mass of (b′1) and 50 parts by mass of (b′3).

(B) Transparent polyester resin film:
(B-1) Using (b1) above, a resin film having a thickness of 300 μm was obtained by a T-die extrusion film forming method under the condition of a T-die outlet resin temperature of 270 ° C.
(B-2) A resin film having a thickness of 300 μm was obtained in the same manner as in (B-1) except that (b2) was used instead of (b1).
(B-3) Using (b1) above, a resin film having a thickness of 600 μm was obtained by a T-die extrusion film forming method under the condition of a T-die outlet resin temperature of 270 ° C.

(B ′) Comparative transparent resin film:
(B′-1) A resin film having a thickness of 300 μm was obtained in the same manner as in (B-1) except that (b′1) was used instead of (b1).
(B′-2) A resin film having a thickness of 300 μm was obtained in the same manner as in (B-1) except that (b′2) was used instead of (b1).
(B′-3) A resin film having a thickness of 300 μm was obtained in the same manner as in (B-1) except that (b′3) was used instead of (b1).
(B′-4) A resin film having a thickness of 300 μm was obtained in the same manner as in (B-1) except that (b′4) was used instead of (b1).
(B′-5) A resin film having a thickness of 300 μm was obtained in the same manner as in (B-1) except that (b′5) was used instead of (b1).
(B′-6) A resin film having a thickness of 300 μm was obtained in the same manner as in (B-1) except that (b′6) was used instead of (b1).
(B′-7) A resin film having a thickness of 300 μm was obtained in the same manner as in (B-1) except that (b′7) was used instead of (b1).
(B′-8) A-PET (amorphous polyethylene terephthalate film) having a thickness of 300 μm.
(B′-9) A biaxially stretched polyethylene terephthalate resin film having a thickness of 300 μm.
(B′-10) A transparent polyvinyl chloride resin film having a thickness of 300 μm.

(C) Transparent resin containing high brightness pigment:
(C-1) A resin containing 100 parts by mass of a polyvinyl chloride resin having a degree of polymerization of 800, 20 parts by mass of a phthalate ester plasticizer (diisononyl phthalate), and 1 part by mass of a high-intensity pigment (aluminum scaly fine particles) A film having a thickness of 80 μm made of the composition.

(D) Colored resin film:
(D-1) A colored polyvinyl chloride resin film having a thickness of 100 μm and a black color (lightness 2.3 measured according to JISZ8721: 1993).

Example 1
The following component (c1-1) is applied to the above (A-1) using a knife coater so as to have a dry film thickness of 5 μm, and after drying, the above (B-1) is applied to the coated surface of the laminate roll. Was laminated under the condition of a surface temperature of 150 ° C. The following component (c1-1) is applied to the above (D-1) using a knife coater so as to have a dry film thickness of 5 μm, and after drying, the above (C-1) is applied to the coated surface of the laminate roll. Was laminated under the condition of a surface temperature of 150 ° C. Subsequently, the following component (c1-1) was applied to the surface of the (C-1) opposite to the (D-1) laminated surface using a knife coater so as to have a dry film thickness of 5 μm. After drying, the surface opposite to the (A-1) laminated surface of (B-1) was laminated on the coated surface under the condition that the surface temperature of the laminating roll was 150 ° C. to obtain a decorative sheet. . Subsequently, the decorative sheet obtained above was bonded to a steel plate having a thickness of 0.6 mm using an acrylic adhesive so that the surface on the (D-1) side was an adhesive surface, and a decorative steel plate was obtained. It was. The above tests (a) to (d) were conducted. The results are shown in Table 1.

Examples 2, 3 and Comparative Examples 1-10
All of the procedures were performed in the same manner as in Example 1 except that the materials shown in Table 1 or 2 were used as the layer (B) instead of (B-1). The results are shown in Table 1 or Table 2.

A decorative steel sheet using the decorative sheet of the present invention exhibits suitable physical properties and design properties.

(C) As a transparent resin layer containing a high-luminance pigment, (c1) 100 parts by mass of a transparent resin; and (c2) an average particle diameter of 10 to 250 μm, and the surface is made of titanium oxide, indium oxide, zinc oxide, and tin oxide. The case where a resin composition containing 0.01 to 10 parts by mass of glass particles coated with one or more selected from the group consisting of the following is described.

Measuring method (e) Luster (luminance):
In a dark place, light from a 40W white fluorescent lamp (300 lux) is perpendicularly incident from a position separated by a distance of 50 cm from the surface of the decorative sheet, forms an angle of 45 ° with the surface of the decorative sheet, and has a distance of 50 cm. The decorative sheet was visually observed from the separated position and evaluated according to the following criteria.
A: The glitter is very high.
○: High brightness.
Δ: Low glitter.
X: There is almost no glitter.

(F) Transparency (design effect by the color of the layer (D)):
In a dark place, the light of a 40 W white fluorescent lamp (300 lux) is irradiated in parallel so that the surface of the decorative sheet and the light beam of the fluorescent lamp are separated by a distance of 50 cm, and the surface of the decorative sheet on the light source side is 45 °. The decorative sheet was visually observed from positions separated by a distance of 50 cm and evaluated according to the following criteria.
(Double-circle): The design feeling by the color of a layer (D) is not impaired at all.
○: The design feeling by the color of the layer (D) is hardly impaired.
(Triangle | delta): The design feeling by the color of a layer (D) is impaired a little.
X: The design feeling by the color of a layer (D) is impaired greatly.

Raw material used (c1) transparent adhesive:
(C1-1) Vinyl chloride / vinyl acetate / acrylic copolymer adhesive “VTP-NT (trade name)” from DIC Graphics Co., Ltd., total light transmittance 92%.

(C2) Glass particles:
(C2-1) Titanium oxide coated glass particles “Metashine 1080RS (trade name)” manufactured by Nippon Sheet Glass Co., Ltd., particle size of 80 μm.
(C2-2) Titanium oxide-coated glass particles having a particle diameter of 20 μm.
(C2-3) Titanium oxide-coated glass particles having a particle diameter of 40 μm.
(C2-4) Titanium oxide-coated glass particles having a particle diameter of 120 μm.
(C2-5) Titanium oxide-coated glass particles having a particle diameter of 200 μm.

(C′2) Reference component:
(C′2-1) Titanium oxide-coated glass particles having a particle diameter of 5 μm.
(C′2-2) Titanium oxide-coated glass particles having a particle diameter of 300 μm.
(C′2-3) Silver-coated glass particles “Metashine 1080PS (trade name)” manufactured by Nippon Sheet Glass Co., Ltd., particle size of 80 μm.

Example 4
The component (c1-1) is applied to the above (A-1) using a knife coater so as to have a dry film thickness of 5 μm, and after drying, the above (B-1) is applied to the coated surface of the laminate roll. Was laminated under the condition of a surface temperature of 150 ° C. Subsequently, 100 parts by mass of the component (c1-1) and 0.5 parts by mass of the component (c2-1) are formed on the surface of the (B-1) opposite to the (A-1) laminated surface. Is applied using a knife coater so as to have a dry film thickness of 15 μm. After drying, the above (D-1) is laminated on the coated surface under the condition of a surface temperature of the laminating roll of 150 ° C. , Got a decorative sheet. The above (i) to (f) were evaluated. The results are shown in Table 3.

Examples 5-12, Reference Examples 1-5
The same procedure as in Example 4 was performed except that the raw materials to be used and the mixing ratio were changed as shown in Table 3 or Table 4. The results are shown in Table 3 or Table 4.

(C) As a transparent resin layer containing a high-luminance pigment, (c1) 100 parts by mass of a transparent resin; and (c2) an average particle diameter of 10 to 250 μm, and the surface is made of titanium oxide, indium oxide, zinc oxide, and tin oxide. By using a resin composition containing 0.01 to 10 parts by mass of glass particles coated with one or more selected from the group consisting of the following, the design properties were further improved.

It is a conceptual diagram which shows an example of the decorative sheet of this invention. It is a measurement example of ¹ H-NMR.

1: Biaxially stretched polyethylene terephthalate resin film layer 2: Transparent polyester resin film layer 3: Transparent resin layer containing high brightness pigment 4: Colored resin film layer 5: Print pattern layer

Claims (5)

(A) Biaxially stretched polyethylene terephthalate resin film layer having a thickness of 10 to 200 μm in order from the surface side;
(B) Constitution derived from terephthalic acid, 45 to 50 mol%, structural unit derived from isophthalic acid, 5 to 0 mol%, and 1,4-cyclohexanedimethanol A polyester copolymer comprising 25 to 45 mol% of units and 25 to 5 mol% of structural units derived from 2,2,4,4, -tetramethyl-1,3-cyclobutanediol, and having a thickness of 50 to 3000 μm A layer of transparent polyester resin film; and (D) a layer of colored resin film;
A decorative sheet having
(A) Biaxially stretched polyethylene terephthalate resin film layer having a thickness of 10 to 200 μm in order from the surface side;
(B) Constitution derived from terephthalic acid, 45 to 50 mol%, structural unit derived from isophthalic acid, 5 to 0 mol%, and 1,4-cyclohexanedimethanol A polyester copolymer comprising 25 to 45 mol% of units and 25 to 5 mol% of structural units derived from 2,2,4,4, -tetramethyl-1,3-cyclobutanediol, and having a thickness of 50 to 3000 μm A layer of transparent polyester resin film;
(C) a transparent resin layer containing a high brightness pigment; and (D) a layer of a colored resin film;
A decorative sheet having
The transparent resin layer containing the above (C) high brightness pigment,
(C1) 100 parts by mass of a transparent resin; and (c2) a glass having an average particle diameter of 10 to 250 μm and having a surface coated with one or more selected from the group consisting of titanium oxide, indium oxide, zinc oxide, and tin oxide The decorative sheet according to claim 2, comprising a resin composition containing 0.01 to 10 parts by mass of particles.
The metal plate containing the decorative sheet of any one of Claims 1-3.
An article comprising the metal plate according to claim 4.