JP2005081764A - Decorative sheet, decorative metal sheet, its fabricated article, and their manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative metal sheet which has excellent abrasion resistance, and shows good adhesion between the metal sheet and the decorative sheet and causes no whitening and cracking, during deep drawing, bending and roll forming, at a low temperature in particular, and to provide its fabricated article, a decorative sheet suitable for such a decorative metal sheet, and their manufacturing method. <P>SOLUTION: The decorative sheet has a 30 to 300 μm thick base layer 11 formed by hardening a radiation-curable coating containing 45 to 100 mass% of a polymerizable oligomer and 0 to 55 mass% of a polymerizable monomer. The decorative metal sheet 30 is obtained by laminating the decorative sheet on a metal sheet 31 via an adhesive agent. The fabricated article is obtained by subjecting the decorative metal sheet 30 to at least one of deep drawing, bending and roll forming. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a decorative sheet, a decorative metal plate, a processed product thereof, and methods for producing them.

Conventionally, a decorative metal plate obtained by bonding a decorative sheet on which a pattern, a pattern, or the like is printed to a metal plate such as a steel plate has been used for home appliances such as a refrigerator, a system kitchen, furniture, and building materials. Further, since the decorative metal plate can be made solvent-free, it is expected to be applied to the exterior of automobiles as a means to replace painting.
As a decorative metal plate, for example, a decorative steel plate in which a decorative material made of a transparent vinyl chloride sheet having a printed layer is laminated on a steel plate is known (see Patent Document 1).

  However, the use of decorative steel sheets using vinyl chloride sheets tends to be avoided due to the increasing interest in environmental problems in recent years. In addition, a decorative steel sheet using a vinyl chloride sheet has a problem that when a deep drawing process, a bending process, a roll forming process, or the like is performed in a low temperature environment such as a cold district or winter, a processed part is whitened.

  Further, in order to protect the surface of the vinyl chloride sheet, a hard protective layer made of a radiation curable resin is formed on the surface. The thickness of the protective layer is about 3 to 4 μm for the purpose of wear resistance. However, when a deep drawing process, a bending process, a roll forming process or the like is performed, the thin and hard protective layer cannot follow the deformation, and there is a problem that the processed part is whitened or cracked.

As a decorative sheet for decorative steel sheet that does not contain chlorine, a polyolefin-based decorative sheet has been proposed (for example, see Patent Document 2).
However, a decorative steel sheet in which a polyolefin-based decorative sheet is bonded to a steel sheet also has a problem that whitening and cracking occur in the processed portion when deep drawing, bending, roll forming, or the like is performed. In addition, the polyolefin-based decorative sheet has poor adhesion to the steel sheet, and the decorative sheet may peel from the steel sheet.
JP-A-8-142296 Japanese Patent Laid-Open No. 2003-19776

  Therefore, the object of the present invention is to provide excellent wear resistance and good adhesion between the metal plate and the decorative sheet, without whitening and cracking at the time of deep drawing, bending and roll forming, especially at low temperatures. The object is to provide a decorative metal plate, a processed product thereof, a decorative sheet suitable for such a decorative metal plate, and a method for producing the same.

That is, the decorative sheet of the present invention has a base layer having a thickness of 30 to 300 μm obtained by curing a radiation curable coating containing 45 to 100% by mass of a polymerizable oligomer and 0 to 55% by mass of a polymerizable monomer. It is a feature.
Moreover, it is desirable that the decorative sheet of the present invention further has a primer layer.
Here, the primer layer is preferably a dry paint film of a solvent-type paint containing a polymerizable oligomer and / or an acrylic polyol resin.

The decorative sheet of the present invention preferably further has a printed layer or a plated layer.
Moreover, the decorative sheet of the present invention may have a protective film for protecting the surface of the base material layer.
Moreover, the embossing may be given to the single side | surface of a base material layer.
In addition, the decorative sheet of the present invention preferably further includes an adhesive layer and a release sheet that covers the surface of the adhesive layer.

Moreover, the manufacturing method of the decorative sheet of the present invention forms a coating film by applying a radiation curable paint containing 45 to 100% by mass of a polymerizable oligomer and 0 to 55% by mass of a polymerizable monomer on the surface of a release substrate. A coating film forming step, a curing step of irradiating the coating film with radiation, curing the coating film to form a substrate layer having a thickness of 30 to 300 μm, and a peeling step of peeling the peeling substrate. And
In addition, the method for producing a decorative sheet according to the present invention includes a primer layer forming step of forming a primer layer by applying a primer to the surface of a release substrate and drying the coating film, and a polymerizable oligomer 45 on the primer layer. A coating film forming step of forming a coating film by applying a radiation curable coating containing ~ 100% by mass and 0 to 55% by mass of a polymerizable monomer, and irradiating the coating film with radiation to cure the coating film It has the hardening process which makes a 30-300 micrometer base material layer, and the peeling process which peels a peeling base material, It is characterized by the above-mentioned.

Moreover, the manufacturing method of the decorative sheet of this invention has a decoration process which gives printing or plating on a primer layer and forms a printing layer or a plating layer between a primer layer formation process and a coating-film formation process. Is desirable.
Moreover, as for the manufacturing method of the decorative sheet of this invention, it is desirable to have a coating process which coat | covers a coating film with a protective film between a coating-film formation process and a hardening process.
Here, the protective film is preferably an embossed film having irregularities on one side.
Moreover, it is desirable for the manufacturing method of the decorative sheet of this invention to have the adhesive bond layer formation process which provides an adhesive bond layer after a peeling process, and bonds a release paper on the adhesive bond surface.

Moreover, the decorative metal plate of the present invention is formed by bonding the decorative sheet of the present invention to a metal plate.
The method for producing a decorative metal plate of the present invention is characterized in that the decorative sheet of the present invention is bonded to a metal plate via an adhesive.
Moreover, the manufacturing method of the decorative metal plate of this invention peels a release sheet from the decorative sheet of this invention, and affixes the adhesive bond layer side of a decorative sheet on a metal plate.
The processed product of the present invention is obtained by subjecting the decorative metal plate of the present invention to at least one of deep drawing, bending, and roll forming.
The method for producing a processed product of the present invention is characterized in that at least one of deep drawing, bending, and roll forming is applied to the decorative metal plate of the present invention.

Since the decorative sheet of the present invention has a base material layer having a thickness of 30 to 300 μm obtained by curing a radiation curable coating containing 45 to 100% by mass of a polymerizable oligomer and 0 to 55% by mass of a polymerizable monomer, a metal plate The decorative metal plate to which this is bonded is not whitened or cracked during deep drawing, bending, or roll forming, especially at low temperatures.
Further, the decorative metal plate of the present invention is formed by laminating the decorative sheet of the present invention to the metal plate, so that whitening and cracking do not occur at the time of deep drawing, bending, roll forming, especially at low temperatures. Also, it has excellent wear resistance and good adhesion between the metal plate and the decorative sheet.
Further, the processed product of the present invention does not cause whitening or cracking in the processed part, has excellent wear resistance, and does not peel off the decorative sheet.

The present invention will be described in detail below.
<Coating sheet>
FIG. 1 is a cross-sectional view showing an example of the decorative sheet of the present invention. The decorative sheet 10 includes a base material layer 11, a printing layer 12 that contacts one side of the base material layer 11, a primer layer 13 that contacts the printing layer 12, an adhesive layer 14 that contacts the primer layer 13, and an adhesive layer 14. The release paper 15 that covers the surface of the substrate and the protective film 16 that protects the surface of the base material layer 11 are provided.

The base material layer 11 is a layer formed by curing a radiation curable paint. Here, “radiation” in the present invention means ultraviolet rays or electron beams.
As the radiation curable coating material, those containing a polymerizable oligomer and a polymerizable monomer are used because they are excellent in coating property when cured into a sheet, curing shrinkage, flexibility when formed into a sheet, and abrasion resistance.

  Examples of the polymerizable oligomer include acrylic oligomers such as urethane acrylate oligomers, polyester acrylate oligomers, epoxy acrylate oligomers, and acrylic resin acrylates; allyl ether oligomers, vinyl ether oligomers, and allyl urethane oligomers.

  Among these polymerizable oligomers, a urethane acrylate oligomer composed of a high molecular weight isocyanate and an acrylate having a hydroxyl group is preferred because of its low curing shrinkage. Examples of the high molecular weight isocyanate include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate; aliphatic and alicyclic isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate and hydrogenated xylene diisocyanate. Examples of the acrylate having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol acrylate, and the like. The mass average molecular weight of the urethane acrylate oligomer is usually preferably about 400 to 7000.

  Another preferable acrylic oligomer includes acrylic resin acrylate. Acrylic resin acrylate is a copolymer of (meth) acrylate monomers with functional groups such as carboxyl, epoxy, and hydroxyl in advance in an acrylic copolymer containing polymethyl methacrylate as the main component. In addition, a double bond is introduced by addition reaction with an acrylate monomer having a functional group that undergoes an addition reaction.

  Examples of polymerizable monomers include monofunctional acrylates such as hexyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, and isooctyl acrylate; bifunctional acrylates such as 1,6-hexanediol diacrylate and neopentyl glycol diacrylate; trimethylol Examples thereof include polyfunctional acrylates such as propane triacrylate and dipentaerythritol hexaacrylate.

  The content of the polymerizable oligomer in the radiation curable coating is in the range of 45 to 100% by mass, preferably in the range of 50 to 98% by mass, and more preferably 55 to 95% by mass. When the content of the polymerizable oligomer is less than 45% by mass, the curing shrinkage becomes large when forming into a sheet, and the flexibility when formed into a sheet is insufficient. Moreover, when the finally obtained decorative metal plate is processed, whitening and cracking are likely to occur in the processed portion.

  The content of the polymerizable monomer in the radiation curable coating is in the range of 0 to 55% by mass, preferably in the range of 2 to 50% by mass, and more preferably in the range of 5 to 45% by mass. When the content of the polymerizable oligomer exceeds 55% by mass, the strength is insufficient when forming into a sheet, and the flexibility when formed into a sheet is insufficient. Further, when the decorative metal plate finally obtained is processed, cracks are likely to occur in the processed portion.

When the radiation curable coating is an ultraviolet curable coating that is cured by ultraviolet rays, a photopolymerization initiator or the like is included. When the radiation curable coating is an electron beam curable coating that is cured by an electron beam, a photopolymerization initiator is not required.
The radiation curable paint is preferably a solventless radiation curable paint in that the problem of residual solvent does not occur. The radiation curable paint may contain a trace amount of solvent that does not cause the problem of residual solvent.

  The thickness of the base material layer 11 formed by curing such a radiation curable paint is 30 to 300 μm, and preferably 50 to 250 μm. If the thickness of the base material layer 11 is less than 30 μm, the strength of the decorative sheet 10 is insufficient, and when the decorative metal plate finally obtained is processed, cracks are likely to occur in the processed portion. On the other hand, when the thickness of the base material layer 11 exceeds 300 μm, the amount of paint used increases and the cost increases.

  Moreover, the surface of the base material layer 11 may be embossed. Embossed shapes include, for example, a copy of the uneven shape of natural products such as wood, stone, fabric, and sand, letters, symbols, lines, various abstract patterns, various matte surfaces, specular gloss, etc. Can be mentioned.

The printed layer 12 gives a pattern, a pattern, etc. to the decorative sheet 10. Examples of the pattern and pattern include wood grain, stone grain, cloth grain, grain grain, tiled pattern, brickwork pattern, leather pattern, geometric pattern, character, symbol, full-face solid, metallic and the like. These patterns are used singly or in combination of two or more according to the application.
Examples of the printing ink for forming the printing layer 12 include vehicles made of a binder resin and the like, colorants such as pigments and dyes, and various additives.

  Examples of the vehicle include acrylic resin, vinyl chloride-vinyl acetate copolymer, chlorinated polypropylene, polyester resin, cellulose resin, and urethane resin.

  Examples of the colorant include inorganic pigments such as titanium white, zinc white, carbon black, iron black, petal, chrome vermillion, cadmium red, ultramarine, cobalt blue, chrome lead, and titanium yellow, phthalocyanine blue, and indanthrene. Examples thereof include organic pigments such as blue, isoindolinone yellow, benzylgin yellow, quinacridone red, polyazo red, berylene red, and aniline black, and pearlescent pigments such as scaly foil powder such as aluminum and brass.

  Further, instead of the printing layer 12 or in combination with the printing layer 12, a plating layer may be provided. Examples of the plating layer include a metal vapor deposition layer.

  The primer layer 13 is a layer for improving the adhesiveness between the adhesive layer 14 and the printed layer 12 and / or the base material layer 11. As the primer layer 13, a dry paint film of a solvent-type paint containing a polymerizable oligomer and / or an acrylic polyol resin is used in terms of adhesion to the radiation curable paint of the base material layer 11 and the printing ink of the printing layer 12. preferable.

  Examples of solvent-based paints containing polymerizable oligomers include radiation curable resins containing acrylic oligomers. Preferred specific examples thereof include “CSEB5 medium” (urethane acrylate oligomer), “CSEB12” manufactured by Showa Ink Industries, Ltd. "Medium" (acrylic resin acrylate oligomer).

Specific examples of the solvent-type paint containing an acrylic polyol resin include “MKA Medium”, “CSEB2 Medium”, and “CSEB10 Medium” manufactured by Showa Ink Industries, Ltd.
These solvent-type paints may be used alone, or may be used by mixing a solvent-type paint containing a polymerizable oligomer and a solvent-type paint containing an acrylic polyol resin.

  The thickness of the primer layer 13 is not particularly limited, but is preferably in the range of 1 to 5 μm. If the thickness of the primer layer 13 is less than 1 μm, the adhesiveness between the adhesive layer 14 and the printed layer 12 and / or the substrate layer 11 may be insufficient. On the other hand, even if the thickness of the primer layer 13 is thicker than 5 μm, an improvement in adhesion to the printing layer 12 and / or the base material layer 11 cannot be expected so much, which is not economical.

As an adhesive for forming the adhesive layer 14, an adhesive for steel plates can be used.
As the steel plate adhesive, for example, an acrylic resin, a polyester resin, an epoxy resin, a urethane resin, or the like is used as a base, and a crosslinking agent such as melamine, amine, or isocyanate is added thereto.

  Although the thickness of the adhesive bond layer 14 is not specifically limited, The range of 5-50 micrometers is preferable. If the thickness of the adhesive layer 14 is less than 5 μm, the adhesion between the decorative sheet 10 and the metal plate may be insufficient. On the other hand, even if the thickness of the adhesive layer 14 is thicker than 50 μm, an improvement in adhesion between the decorative sheet 10 and the metal plate cannot be expected so much, which is not economical.

  The release sheet 15 can be peeled off from the adhesive layer 14 and protects the adhesive layer 14 until just before the decorative sheet 10 is bonded to a metal plate. Examples of the release sheet 15 include those in which a release agent that does not exhibit adhesiveness is applied to the adhesive layer 14 on one side of a base material such as paper or plastic film.

  The protective film 16 can be peeled from the base material layer 11 and protects the surface of the base material layer 11. Examples of the protective film 16 include a film made of a thermoplastic resin such as polyethylene terephthalate and polypropylene. Moreover, if the unevenness | corrugation is formed in the single side | surface of the protective film 16, depending on the manufacturing method of the decorative film 10, the base material layer 11 can be embossed.

Next, a method for manufacturing the decorative sheet 10 will be described.
First, a solvent-type paint containing a polymerizable oligomer and / or an acrylic polyol-based resin is continuously applied to the surface of an endless belt-like release substrate that moves in a certain direction, and the coating film is dried to obtain a primer layer 13. (Primer layer forming step). Next, printing (or plating) is performed on the primer layer 13 to form the printing layer 12 (or plating layer) (decoration process).

  Next, a radiation curable paint containing 45 to 100% by weight of polymerizable oligomer and 0 to 55% by weight of polymerizable monomer is continuously applied on the primer layer 13 through the printing layer 12 to form a coating film ( Coating film forming step). Next, the coating film is continuously coated with the protective film 16 (coating process), and the coating film is irradiated with radiation in a nitrogen gas atmosphere from the protective film 16 to cure the coating film to a thickness of 30 to 300 μm. The base material layer 11 is set (curing step). At this time, if an embossed film having unevenness on one side is used as the protective film 16, the surface of the base material layer 11 can be embossed simultaneously with curing.

  After the coating film is cured, the cured coating film is peeled off from the release substrate, an adhesive is applied on the primer layer 13 to provide an adhesive layer 14, and a release sheet 15 is bonded to the surface of the adhesive layer 14 ( Adhesive layer forming step), the decorative sheet 10 is obtained.

Here, as a peeling base material, peeling films, such as a polyethylene terephthalate (PET) film, a stainless steel belt, etc. can be used.
A die coating method, a knife coating method, a gravure coating method, or the like can be employed as a method for applying the paint to the release substrate. Among these, the die coating method is preferable because the dimensional accuracy of the resulting decorative sheet is good. The die coater used in this die coating method is "Super Precision Coating Die Coater" manufactured by Toshiba Machine Co., Ltd., "Slot Die Coater" manufactured by Yasui Seiki Co., Ltd., "Slit Die Coater" manufactured by Toray Engineering Co., Ltd. And the like.

As a method for curing the radiation curable coating, electron beam curing is preferable. By using electron beam curing, addition of an additive such as a photopolymerization initiator to the radiation curable coating can be omitted, so that there is no decrease in transparency due to a decomposed product of the additive. Moreover, productivity can be improved from the magnitude | size of the energy which an electron beam has.
Moreover, as a printing method of the printing layer 12, well-known printing methods, such as gravure printing, offset printing, and silk printing, are employable. Moreover, when providing a plating layer instead of the printing layer 12, metal vapor deposition etc. are employable.

In the decorative sheet 10 described above, the base material layer 11 is obtained by curing a radiation curable paint containing 45 to 100% by mass of a polymerizable oligomer and 0 to 55% by mass of a polymerizable monomer, Since thickness is 30-300 micrometers, it is excellent in a softness | flexibility although it is what hardened | cured the radiation curing coating material. Therefore, when the finally obtained decorative metal plate is deep-drawn, bent, or roll-formed, the decorative sheet 10 can follow the deformation of the metal plate, and whitening and cracking in the processed portion can be suppressed. . Further, compared to a decorative sheet using a thermoplastic resin as a base material, there is less change in flexibility due to temperature, and even when processed at low temperatures, the processed portion is less likely to be whitened or cracked.
In addition, since the base material layer 11 is obtained by curing a radiation curable coating containing 45 to 100% by mass of a polymerizable oligomer and 0 to 55% by mass of a polymerizable monomer, it is excellent in wear resistance, and further has a polyolefin makeup. Excellent adhesion to metal plates compared to sheets.

Note that the decorative sheet of the present invention is not limited to the decorative sheet 10 shown in FIG. 1, and may be, for example, a decorative sheet 20 without the print layer 12 as shown in FIG.
Further, the decorative sheet of the present invention is not limited to the printing layer 12 provided on the back surface side of the base material layer 11 as shown in FIG. 1, and the printing layer 12 is provided on the front surface side of the base material layer 11. It doesn't matter. However, in the case where the printed layer 12 is provided on the surface side of the base material layer 11, when the final decorative metal plate is deep-drawn, bent, or roll-formed, the printed layer 12 is replaced with the base material layer 11. Compared with what was provided in the back surface side of this, the elongation of the printed pattern in a process part becomes large, and an external appearance worsens. Therefore, it is desirable to provide the printing layer 12 on the back side of the base material layer 11.

  Further, the decorative sheet of the present invention is not limited to the illustrated example, and when the adhesive layer 14 and the printed layer 12 and / or the base material layer 11 have good adhesion, the primer layer 13 is not necessarily provided. There is no need to provide it. When obtaining a decorative metal plate, it is not always necessary to provide the adhesive layer 14 when an adhesive is applied to the metal plate side and a decorative sheet is bonded thereto. Further, another layer may be provided on the surface of the base material layer 11. Moreover, if it is not necessary to protect the surface of the base material layer 11, the protective film 16 does not necessarily need to be provided.

<Decorated metal plate>
FIG. 3 is a cross-sectional view showing an example of the decorative metal plate of the present invention. The decorative metal plate 30 includes a base material layer 11, a printed layer 12 in contact with one surface of the base material layer 11, a primer layer 13 in contact with the print layer 12, an adhesive layer 14 in contact with the primer layer 13, and a base material layer. The adhesive layer 14 side of a decorative sheet having a protective film 16 that protects the surface of 11 is attached to a metal plate 31.

  As the metal plate 31, a plated steel plate, a stainless steel plate, an aluminum plate, or the like can be applied. Among these, various steel plates suitable for deep drawing, bending, or roll forming are suitable. Examples of the plating applied to the metal plate include hot dip galvanizing, electrogalvanizing, Zn—Al plating, Ni—Zn alloy plating, and the like. As the base treatment of the metal plate, a phosphate base treatment or a chromate base treatment can be applied.

  The decorative metal plate 30 can be obtained by peeling the release sheet 15 from the decorative sheet 10 shown in FIG. 1 and attaching the adhesive layer 14 side of the decorative sheet 10 to the metal plate 31. Alternatively, an adhesive is applied to the surface of the metal plate 31, and the base material layer 11, the printing layer 12 in contact with one surface of the base material layer 11, the primer layer 13 in contact with the printing layer 12, and the base material layer 11. It can obtain by bonding together the decorative sheet which has the protective film 16 which protects the surface of this.

The decorative metal plate 30 can be made into various processed products by processing into a desired shape by a conventionally known processing method. In particular, the conventional decorative steel sheet is suitable for a processing method in which whitening or cracking is likely to occur in a processed portion, such as deep drawing processing, bending processing, and roll forming processing. The protective film 16 remains in the processed product thus obtained. This protective film 16 also serves as a protective film for the processed product.
Applications of processed products include housings for home appliances such as refrigerators, system kitchens, furniture, building interiors, building materials such as exterior walls, and the like. It is also suitable for automobile bodies because of its excellent wear resistance and the elimination of solvents.

In the decorative metal plate 30 described above, since the decorative sheet 10 described above is used, it is possible to wear resistance without whitening or cracking at the time of deep drawing, bending, roll forming, especially at low temperatures. The adhesion between the metal plate and the decorative sheet is also good.
In addition, the processed product of the decorative metal plate 30 does not cause whitening or cracking in the processed portion, is excellent in wear resistance, and does not peel off the decorative sheet.

[Example 1]
A primer of a solvent-type acrylic polyol resin (“KA-4b” manufactured by Showa Ink Industries Ltd., solid content: 40% by mass) is applied to a release film made of a smooth polyethylene terephthalate film with a coater and dried to a thickness of 2 μm. A primer layer was formed. Next, a wood grain pattern was printed on the primer layer by gravure printing. As the printing ink, KA-4b type added with a pigment was used. Next, a solvent-free radiation curable paint (“CTO-2b” manufactured by Showa Ink Industry Co., Ltd., urethane acrylate oligomer 90% by mass, polymerizable acrylate monomer 10% by mass) is applied on the printed layer by a die coating method. The coating film was coated with an embossed film made of a polyethylene terephthalate film having irregularities formed on the surface so that the irregular surface was on the paint side.

  Next, an electron beam was irradiated from above the embossed film in a nitrogen gas atmosphere under the conditions of an absorbed dose of 7 Mrad and a passing speed of 50 m / min to cure the radiation-cured coating material to form a transparent substrate layer having a thickness of 80 μm. . A sheet composed of an embossed film, a base material layer, a printing layer, and a primer layer is separated from the release film, and a two-component curable adhesive (“5250” manufactured by No Tape Kogyo Co., Ltd.) is applied on the primer layer to form an adhesive layer. did.

  This decorative sheet was bonded to a 500 μm thick galvanized steel sheet, and the decorative sheet was adhered to the steel sheet. The following evaluation was performed about the obtained decorative steel plate.

(Deep drawing workability)
Using a deep drawing processing tester (manufactured by Hitachi Zosen Co., Ltd., 500 Ton hydraulic press), a deep drawing with a diameter of 300 mm and a depth of 200 mm as shown in FIG. 4 is performed, and the state of the decorative sheet on the surface is visually confirmed. Evaluation was made according to the following evaluation criteria. The results are shown in Table 1.
○: Fully following deep drawing without whitening.
Δ: Following deep drawing, the decorative sheet is partially broken.
X: The decorative sheet does not follow the deep drawing and the decorative sheet is broken.

(Bending workability)
Using a bending machine (NC press brake “PH2253E” manufactured by Komatsu Industries Co., Ltd.), 90 ° and 180 ° bending bending is performed, and the condition of the decorative sheet on the surface is visually confirmed. evaluated. The results are shown in Table 1.
○: Whitening and cracking do not occur.
Δ: Whitening but no cracks occurred.
X: Whitening and cracking have occurred.

(Roll forming processability)
Using a roll forming machine (manufactured by Mori Machinery Co., Ltd.), roll forming as shown in FIG. 5 was performed, the state of the decorative sheet on the surface was visually confirmed, and the following evaluation criteria were evaluated. The results are shown in Table 1.
○: Whitening and cracking do not occur.
Δ: Whitening but no cracks occurred.
X: Whitening and cracking have occurred.

(Steel adhesion)
After the decorative steel sheet test piece was heated and stored at 80 ° C ± 3 ° C for 100 hours, the decorative sheet side of the decorative steel sheet was cut into a gobang (1 mm interval, 100 squares) with an NT cutter so that the cut reached the steel sheet. Then, cello tape (registered trademark) (manufactured by Nichiban Co., Ltd.) was pasted thereon and crimped by reciprocating a 2 kg roller. Immediately after the pressure bonding, the tape was peeled off, the state of the decorative sheet on the surface was visually confirmed, and the following evaluation criteria were evaluated. The results are shown in Table 1.
○: All of the mass remained on the steel plate.
(Triangle | delta): Although all the mass remained on the steel plate, damage is recognized by a decorative sheet.
X: Some squares were peeled off.

[Example 2]
A decorative sheet and a decorative steel sheet were obtained in the same manner as in Example 1 except that the thickness of the base material layer was changed to 150 μm. About the obtained decorative steel plate, evaluation similar to Example 1 was performed. The results are shown in Table 1.

[Example 3]
A decorative sheet and a decorative steel sheet were obtained in the same manner as in Example 1 except that the thickness of the base material layer was changed to 200 μm. About the obtained decorative steel plate, evaluation similar to Example 1 was performed. The results are shown in Table 1.

[Example 4]
Except for changing the solvent-free radiation curable paint used in Example 1 to “CTO2H-a” (80% by mass of urethane acrylate oligomer, 20% by mass of polymerizable acrylate monomer) manufactured by Showa Ink Industries, Ltd. A decorative sheet and a decorative steel sheet were obtained in the same manner as in Example 1. About the obtained decorative steel plate, evaluation similar to Example 1 was performed. The results are shown in Table 1.

[Example 5]
Except for changing the solvent-free radiation curable paint used in Example 1 to “CTO2E-a” (70% by mass of urethane acrylate oligomer, 30% by mass of polymerizable acrylate monomer) manufactured by Showa Ink Industries, Ltd. A decorative sheet and a decorative steel sheet were obtained in the same manner as in Example 1. About the obtained decorative steel plate, evaluation similar to Example 1 was performed. The results are shown in Table 1.

[Example 6]
Except for changing the solvent-free radiation curable coating used in Example 1 to “CTO2F-a” (50% by mass of urethane acrylate oligomer, 50% by mass of polymerizable acrylate monomer) manufactured by Showa Ink Industries, Ltd. A decorative sheet and a decorative steel sheet were obtained in the same manner as in Example 1. About the obtained decorative steel plate, evaluation similar to Example 1 was performed. The results are shown in Table 1.

[Example 7]
Except for changing the solvent-free radiation curable paint used in Example 1 to “CTO α-a” (80% by mass of polyester acrylate oligomer, 20% by mass of polymerizable acrylate monomer) manufactured by Showa Ink Industries, Ltd. A decorative sheet and a decorative steel sheet were obtained in the same manner as in Example 1. About the obtained decorative steel plate, evaluation similar to Example 1 was performed. The results are shown in Table 1.

[Comparative Example 1]
A decorative sheet having the same layer structure as that of Example 1 was prepared using a vinyl chloride resin sheet having a thickness of 150 μm as the base material layer. A decorative steel sheet was obtained in the same manner as in Example 1. About the obtained decorative steel plate, evaluation similar to Example 1 was performed. The results are shown in Table 1.

[Comparative Example 2]
A decorative sheet having the same layer structure as that of Example 1 was prepared using a 150 μm thick polyethylene terephthalate (PET) sheet as a base material layer. A decorative steel sheet was obtained in the same manner as in Example 1. About the obtained decorative steel plate, evaluation similar to Example 1 was performed. The results are shown in Table 1.

[Comparative Example 3]
Except that the solvent-free radiation curable paint used in Example 1 was changed to “CTO2M-a” (30% by mass of urethane acrylate oligomer, 70% by mass of polymerizable acrylate monomer) manufactured by Showa Ink Industries, Ltd. A decorative sheet and a decorative steel sheet were obtained in the same manner as in Example 1. About the obtained decorative steel plate, evaluation similar to Example 1 was performed. The results are shown in Table 1.

  The decorative sheet of the present invention realizes a decorative steel sheet that is optimal for deep drawing, bending, or roll forming, which has been difficult with conventional decorative steel sheets. In addition, the decorative metal plate of the present invention can be used in various applications such as housings for home appliances such as refrigerators, system kitchens, furniture, building interiors, building materials such as outer walls, and automobile bodies.

It is sectional drawing which shows an example of the decorative sheet of this invention. It is sectional drawing which shows the other example of the decorative sheet of this invention. It is sectional drawing which shows an example of the decorative metal plate of this invention. It is sectional drawing which shows the shape of the deep drawing process performed in the Example. It is sectional drawing which shows the shape of the roll forming process performed in the Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Decorative sheet 11 Base material layer 12 Print layer 13 Primer layer 14 Adhesive layer 15 Release sheet 16 Protective film 20 Decorative sheet 30 Decorative metal plate 31 Metal plate

Claims (18)

  A decorative sheet comprising a substrate layer having a thickness of 30 to 300 μm obtained by curing a radiation-curing paint containing 45 to 100% by mass of a polymerizable oligomer and 0 to 55% by mass of a polymerizable monomer.   The decorative sheet according to claim 1, further comprising a primer layer.   The decorative sheet according to claim 2, wherein the primer layer is a dry paint film of a solvent-type paint containing a polymerizable oligomer and / or an acrylic polyol resin.   The decorative sheet according to any one of claims 1 to 3, further comprising a printed layer or a plated layer.   The decorative sheet according to any one of claims 1 to 4, further comprising a protective film for protecting the surface of the base material layer.   The decorative sheet according to any one of claims 1 to 5, wherein one side of the base material layer is embossed.   The decorative sheet according to any one of claims 1 to 6, further comprising an adhesive layer and a release sheet that covers a surface of the adhesive layer. A coating film forming step of forming a coating film by applying a radiation curable coating containing 45 to 100% by mass of a polymerizable oligomer and 0 to 55% by mass of a polymerizable monomer on the surface of a release substrate;
A curing step of irradiating the coating film with radiation and curing the coating film to form a substrate layer having a thickness of 30 to 300 μm;
A method for producing a decorative sheet, comprising: a peeling step for peeling the peeling substrate. A primer layer forming step of applying a primer to the surface of the release substrate and drying the coating film to form a primer layer;
On the primer layer, a coating film forming step of forming a coating film by applying a radiation curable coating containing 45 to 100% by mass of a polymerizable oligomer and 0 to 55% by mass of a polymerizable monomer;
A curing step of irradiating the coating film with radiation and curing the coating film to form a substrate layer having a thickness of 30 to 300 μm;
A method for producing a decorative sheet, comprising: a peeling step for peeling the peeling substrate.   The decorative sheet according to claim 9, further comprising a decorating step of forming a printed layer or a plated layer by printing or plating on the primer layer between the primer layer forming step and the coating film forming step. Production method.   The method for producing a decorative sheet according to any one of claims 8 to 10, further comprising a coating step of coating the coating film with a protective film between the coating film forming step and the curing step.   The method for producing a decorative sheet according to claim 11, wherein the protective film is an embossed film having irregularities on one side.   The method for producing a decorative sheet according to any one of claims 8 to 12, further comprising an adhesive layer forming step in which an adhesive layer is provided after the peeling step and the release paper is bonded to the surface of the adhesive layer.   A decorative metal plate obtained by bonding the decorative sheet according to any one of claims 1 to 7 to a metal plate.   A method for producing a decorative metal plate, comprising bonding the decorative sheet according to any one of claims 1 to 6 to a metal plate via an adhesive. A release sheet is peeled from the decorative sheet according to claim 7,
A method for producing a decorative metal plate, comprising bonding an adhesive layer side of a decorative sheet to a metal plate.   A processed product obtained by subjecting the decorative metal sheet according to claim 14 to at least one of deep drawing, bending, and roll forming. A method for producing a processed product, wherein the decorative metal plate according to claim 14 is subjected to at least one of deep drawing, bending, and roll forming.

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