JP2005074735A - Metal panel decorating sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metal panel decorating sheet excellent in both of processability and weatherability. <P>SOLUTION: The metal panel decorating sheet is constituted by providing a pattern layer, a transparent resin layer and a transparent protective layer on a base material sheet and characterized in that the transparent protective layer is provided as the outermost surface layer. The transparent protective layer is formed from a material containing a polymer having an ultraviolet absorbing group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a metal sheet decorative sheet.

  In addition to exterior building materials such as entrance doors (including so-called semi-exterior building materials; the same shall apply hereinafter), various home appliances, office equipment, instruments, etc. are laminated with a decorative sheet on the surface of a metal plate such as a steel plate. Material is used. Such a material first manufactures a laminate in which a decorative sheet is laminated on a steel plate, and the laminate is subjected to processing such as bending (so-called post-processing) according to various product forms.

  For this reason, it is necessary for the decorative sheet not to be damaged by these processes. In particular, the transparent protective layer, which is the outermost layer of the decorative sheet, is subjected to great stress during processing, but has the flexibility to stretch and deform following the deformation of the steel sheet without causing voids during bending. Must. In addition, this characteristic is required to be maintained even at a low temperature (for example, 0 ° C.).

  On the other hand, when it is used for an exterior, it is necessary to have weather resistance in addition to the above processability. If the transparent protective layer that is the outermost layer of the decorative sheet is excellent in weather resistance, the appearance (designability) can be maintained over a long period of time.

  As the transparent protective layer having such characteristics, polyolefin resins such as polypropylene are mainly known (see Patent Document 1, Patent Document 2, etc.).

However, the polyolefin-based resin can be sufficiently used as a transparent protective layer of a decorative sheet for interior building materials (building materials for interiors), but is still sufficient particularly in terms of weather resistance for use as an exterior. I can not say.
JP 2000-326443 A JP-A-8-141499

  Accordingly, the main object of the present invention is to provide a sheet for decorative metal sheet which is excellent in workability and weather resistance.

  In light of the problems of the prior art, the present inventor has found that the above object can be achieved by employing a transparent protective layer having a specific configuration, and has completed the present invention.

  That is, the present invention relates to the following metal sheet decorative sheet.

1. A metal sheet decorative sheet having a pattern layer, a transparent resin layer and a transparent protective layer on a base sheet, the transparent protective layer being provided as an outermost surface layer,
The metal sheet decorative sheet, wherein the transparent protective layer is formed of a material containing a polymer having an ultraviolet absorbing group.

  2. Item 2. The metal sheet decorative sheet according to Item 1, wherein the material further contains an aliphatic diisocyanate polyisocyanate.

  3. Item 3. The metal sheet cosmetic sheet according to Item 2, wherein the aliphatic diisocyanate polyisocyanate is hexamethylene diisocyanate polyisocyanate.

  4). Item 4. The metal sheet decorative sheet according to Item 3, wherein the hexamethylene diisocyanate polyisocyanate is at least one of biuret polyisocyanate and isocyanurate polyisocyanate.

  5). Item 5. The metal sheet cosmetic sheet according to any one of Items 1 to 4, wherein the transparent resin layer is formed of a polyolefin resin.

  6). Item 6. The metal sheet decorative sheet according to any one of Items 1 to 5, wherein an adhesive layer is interposed between the pattern layer and the transparent resin layer.

  7). The decorative metal plate by which the said sheet | seat is laminated | stacked on a metal plate so that the transparency protective layer of the sheet for metal plate cosmetics in any one of said claim | item 1-6 may become an outermost surface layer.

  Since the metal sheet decorative sheet of the present invention has a specific laminated structure including a transparent protective layer, and the transparent protective layer is formed of a material containing a polymer having an ultraviolet absorbing group, It is possible to obtain a weather resistance superior to that of a conventional product while maintaining a bending characteristic or the like equivalent to that of the product.

  The decorative sheet of the present invention having such characteristics can be used as a decorative sheet for indoor building materials, exterior and semi-exterior building materials, and also for metal sheets constituting household appliances, office equipment, instruments, etc. It can be used widely as a sheet.

1. TECHNICAL FIELD The present invention relates to a metal plate having a pattern layer, a transparent resin layer, and a transparent protective layer on a base sheet, and the transparent protective layer is provided as the outermost surface layer (outermost layer). A cosmetic sheet,
The transparent protective layer is formed of a material containing a polymer having an ultraviolet absorbing group.

  The formation method of each layer is not particularly limited, for example, printing such as gravure printing, flexographic printing, silk screen printing, offset printing, transfer printing, etc .; application of spray, roller, brush, etc .; Any of these can be adopted. What is necessary is just to select combining suitably from these methods according to the characteristic, raw material, etc. of each layer.

  The thickness of each layer is not limited, and can be appropriately determined according to the use and characteristics of the final product. Usually, it can be in the range of about 0.1 to 500 μm.

Transparency protective layer In this invention, the transparency protection layer is provided as an outermost surface layer. The transparent protective layer may be colored as long as it is transparent. Further, it may be translucent as long as the pattern layer is visible.

  The transparent protective layer is formed of a material containing a polymer having an ultraviolet absorbing group (hereinafter referred to as “ultraviolet absorbing group-containing polymer”). The polymer having an ultraviolet absorbing group is not particularly limited as long as it has an ultraviolet absorbing group (that is, a radical generated by ultraviolet rays or a group that inactivates active oxygen). As such a polymer, a known polymer or a commercially available product can be used. For example, product names “PUVA-30M”, “PUVA-30S” (all manufactured by Otsuka Chemical), product names “Udouble E”, “Udouble S-2000”, “Udouble H-4000”, “Udouble S-5000”. "Udouble C" and "Udouble UV" (both made by Nippon Shokubai Co., Ltd.) can be used.

  In the present invention, it is preferable that an aliphatic diisocyanate-based polyisocyanate (hereinafter also referred to as “polyisocyanate”) is contained in the material. In the present invention, by using the polyisocyanate and the UV-absorbing group-containing polymer in combination, both of them act synergistically, and as a result, better weatherability can be exhibited along with good processability.

The aliphatic diisocyanate-based polyisocyanate is not particularly limited as long as it has a diisocyanate OCN-R-NCO part (where R represents an alkylene group). Among these, polyisocyanate used as a non-yellowing urethane resin curing agent is preferable. For example, hexamethylene diisocyanate polyisocyanate can be used. Hexamethylene diisocyanate-based polyisocyanate is a compound having an OCN— (CH ₂ ) ₆ —NCO moiety and is known per se. Hexamethylene diisocyanate-based polyisocyanates include biuret-based polyisocyanates, isocyanurate-based polyisocyanates, adduct-based polyisocyanates, bifunctional prepolymer systems, and the like, and commercially available products can also be used.

  In the present invention, it is particularly desirable to use at least one of biuret type polyisocyanate and isocyanurate type polyisocyanate.

  The biuret polyisocyanate has the following chemical structure:

(In the formula, R represents — (CH ₂ ) ₆ —). The polyisocyanate itself may be a known one or a commercially available product. For example, product names “Duranate 24A-100”, “Duranate 22A-75PX”, “Duranate 21S-75E”, “Duranate 18H-70B” (all manufactured by Asahi Kasei) and the like can be used.

  The above isocyanurate-based polyisocyanate has the following chemical structure:

(In the formula, R represents — (CH ₂ ) ₆ —). The polyisocyanate itself may be a known one or a commercially available product. For example, product names “Duranate TPA-100”, “Duranate THA-100”, “Duranate MFA-90X”, “Duranate TSA-100” (all manufactured by Asahi Kasei) and the like can be used.

  When polyisocyanate is used, the blending ratio of the polyisocyanate and the UV-absorbing group-containing polymer can be appropriately determined according to the type of polyisocyanate and UV-absorbing group-containing polymer used, the desired properties of the transparent protective layer, and the like. In general, it is desirable to use 1 to 50 parts by weight, particularly 5 to 20 parts by weight of polyisocyanate with respect to 100 parts by weight of the UV-absorbing group-containing polymer.

  In the present invention, the above material may contain other components. For example, additives such as a solvent, an ultraviolet absorber, an antioxidant, a dispersant, a light stabilizer, a gloss adjusting agent, an antiblocking agent, and a lubricant can be blended.

  Although the thickness of a transparent protective layer is not limited, Usually, it is desirable to set it as 0.1-50 micrometers, especially 1-20 micrometers.

  In the decorative sheet of the present invention, the configuration of a known decorative sheet can be appropriately adopted as the configuration other than the transparent protective layer. An example of a particularly preferred configuration is shown below.

The base sheet has a pattern layer or the like sequentially laminated on the front surface (front surface) and a metal plate laminated on the back surface.

  As a base material sheet, what was formed, for example with the thermoplastic resin can be used conveniently. Specifically, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer Polymers, ionomers, acrylic esters, methacrylic esters and the like can be mentioned.

  The base material sheet may be colored. In this case, a coloring material (pigment or dye) can be added to the above thermoplastic resin for coloring. As the colorant, for example, inorganic pigments such as titanium dioxide, carbon black and iron oxide, organic pigments such as phthalocyanine blue, and various dyes can be used. These can be selected from one or more known or commercially available ones. Further, the addition amount of the colorant may be appropriately set according to the desired color tone.

  The base sheet contains various additives such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, and light stabilizers as necessary. May be.

  Although the thickness of a base material sheet can be suitably set with the use of a final product, a usage method, etc., generally it is preferable to set it as 50-250 micrometers.

  In the base material sheet, if necessary, the surface (front surface) can be subjected to corona discharge treatment in order to strengthen the adhesion of the ink for providing the pattern layer. What is necessary is just to implement the method and conditions of a corona discharge process according to a well-known method.

  In addition, if necessary, a corona discharge treatment or a primer layer can be formed on the back surface of the base sheet for lamination with a metal plate. Examples of the material for forming the primer layer include polyester resins, polyurethane resins (particularly, two-part curable resins of polyacryl polyols, polyester polyols, polyether polyols, and the like and isocyanate compounds), acrylic resins, and polycarbonates. In addition, resins such as alkyl titanates and ethyleneimines can be used in addition to resins such as vinyl resins, vinyl chloride / vinyl acetate copolymers, polyvinyl butyral resins, and nitrocellulose resins. Using these as they are or in a state dissolved or dispersed in a solvent, a primer layer can be formed according to a known printing method, coating method or the like.

Picture layer The picture layer can represent not only patterns or patterns of natural materials such as wood grain and joints, but also letters and figures.

  The formation of the pattern layer is preferably carried out by a known printing method such as gravure printing, flexographic printing, silk screen printing, offset printing, etc., preferably using an ink excellent in adhesiveness with the colored thermoplastic resin layer. .

  As the ink, an ink containing a colorant and a binder can be generally used. The ink binder may be appropriately selected from known or commercially available products depending on the material of the base sheet. For example, chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester resins, urethane resins (preferably polyester urethane resins), acrylic resins, vinyl chloride / vinyl acetate copolymers, and cellulose resins are used. be able to. These can use 1 type (s) or 2 or more types. Moreover, a coloring material is not specifically limited, A well-known coloring material can be used. For example, titanium white, zinc white, petal, vermilion, ultramarine blue, cobalt blue, titanium yellow, carbon black and other inorganic pigments, isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, indanthrene blue RS, Examples include organic pigments (including dyes) such as annin phosphorus black, metal pigments such as aluminum and brass, pearlescent pigments made of foil powder such as titanium dioxide-coated mica and basic lead carbonate, and the like. These can be used alone or in combination of two or more.

Adhesive Layer In the present invention, an adhesive layer is preferably interposed between the pattern layer and the transparent resin layer. The adhesive used in the adhesive layer can be appropriately selected from known or commercially available adhesives according to the components constituting the pattern layer or the transparent resin layer. For example, various adhesives such as polyurethane resin, polyacrylic resin, polycarbonate resin, and epoxy resin can be used. In addition to the reactive curing type, any type of adhesive such as a hot melt type, an ionizing radiation curing type, and an ultraviolet curing type may be used.

  What is necessary is just to implement as an adhesion | attachment method according to a well-known method according to the kind etc. of adhesive agent to be used. For example, using a polyolefin resin such as polyethylene or polypropylene, a method of coating on a pattern layer by melt extrusion (extrusion coating method), a thermosetting resin such as a polyester resin, a polyurethane resin, or an epoxy resin, isocyanate, Apply an adhesive such as a crosslinking agent such as amine, a polymerization initiator such as methyl ethyl ketone peroxide, hydroperoxide, azabisisobutyronitrile, a polymerization accelerator such as cobalt naphthenate, dimethylaniline, etc. A dry laminating method can be employed. In the present invention, an adhesive capable of thermocompression bonding is used, and the pattern layer and the transparent resin layer can be laminated by thermocompression bonding.

  In the present invention, a known easy adhesion treatment such as a corona discharge treatment, a plasma treatment, a degreasing treatment, a surface roughening treatment or the like can be applied to the adhesion surface as necessary.

  The thickness of the adhesive layer varies depending on the transparent protective layer, the type of adhesive used, and the like, but generally may be about 0.1 to 30 μm.

Transparent resin layer The transparent resin layer may be colored as long as it is transparent. Moreover, it may be translucent as long as the pattern layer is visible.

  Examples of the resin include polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, ionomer, Examples thereof include polymethylpentene, acrylic acid ester, methacrylic acid ester, polycarbonate, and cellulose triacetate. The transparent resin layer is particularly preferably a polyolefin resin such as polypropylene. More preferably, it is a polyolefin resin having stereoregularity.

  In the transparent resin layer, a filler, a matting agent, a foaming agent, a flame retardant, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a radical scavenger, a soft component (for example, as necessary) Various additives such as rubber) may be included.

  The thickness of the transparent resin layer is not particularly limited, but generally may be about 10 to 150 μm.

The transparent resin layer can be provided with an uneven pattern as necessary. For example, it is possible to give a concavo-convex pattern by known embossing or the like. As a result, a three-dimensional appearance can be given to the cosmetic sheet.
2. Decorative metal plate The decorative metal plate of the present invention is obtained by laminating the metal decorative plate sheet of the present invention on a metal plate. More specifically, the sheet is laminated on the metal plate such that the transparent protective layer of the metal sheet decorative sheet is exposed as the outermost surface layer.

It does not specifically limit as a metal plate metal plate, It can select suitably from the metal or alloy currently used as a building material. In particular, aluminum, aluminum alloys (Al-Mg type, etc.), iron, steel, stainless steel, titanium, copper, brass and the like can be preferably used. In particular, aluminum or an aluminum alloy is preferable because it can be easily bent or drawn, and can be sawed to adjust the dimensions at the construction site, is lightweight, and has high heat diffusibility.

  For the purpose of improving adhesion and preventing corrosion, the metal plate can be subjected to oxidation treatment, or chromate treatment, phosphate treatment, etc., and can be plated with zinc, tin, chromium, etc. .

  The thickness of the metal plate can be appropriately determined according to its use, usage method, and the like. For example, when used as an entrance door or the like, it can be set within a range of about 0.1 to 10 mm.

The lamination of the laminated metal sheet decorative sheet on the metal plate to the metal sheet can be performed in the same manner as the lamination of a known decorative sheet. For example, it is possible to suitably laminate a decorative sheet on a metal plate using an adhesive.

  As the adhesive that can be used, any type of adhesive such as a thermoplastic resin, a thermosetting resin, and a rubber can be used. As this, a known product or a commercially available product can be used.

  As thermoplastic resin adhesives, polyvinyl acetate resin, polyvinyl alcohol, polyvinyl acetal (polyvinyl formal, polyvinyl butyral, etc.), cyanoacrylate, polyvinyl alkyl ether, polyvinyl chloride, polyamide, polymethyl methacrylate, nitrocellulose, acetic acid Examples include cellulose, thermoplastic epoxy, polystyrene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and the like.

  Thermosetting resin adhesives include urea resin, melamine resin, phenol resin, resorcinol resin, furan resin, epoxy resin, unsaturated polyester resin, polyurethane resin, polyimide, polyamideimide, polybenzimidazole, polybenzothiazole, etc. Illustrated.

  Rubber (elastomer) adhesives include natural rubber, recycled rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, polysulfide rubber, silicone rubber, polyurethane rubber, stereo rubber (synthetic natural rubber), ethylene propylene rubber And block copolymer rubber (SBS, SIS, SEBS, etc.).

  Examples and comparative examples are shown below to further clarify the features of the present invention. However, the scope of the present invention is not limited to the examples.

Example 1
A cosmetic sheet having the structure shown in FIG. 1 was prepared.

  A polypropylene resin film 1 (thickness 80 μm) colored by adding 10% by weight of a coloring material (titanium oxide) was prepared, and the front surface (front surface) and the back surface were subjected to corona discharge treatment. A colored ink using a two-component curable urethane resin as a binder was gravure printed on this surface (front surface), and a woodgrain pattern layer 2 was formed using an ink containing an acrylic resin as a binder. Moreover, the primer layer 6 which used urethane type resin as the binder was formed in the back surface by the gravure printing, and the printing sheet was obtained.

  Next, an adhesive layer 3 (not shown) made of a two-component curable urethane resin is formed with a thickness of 15 μm on the pattern layer 2 of the printed sheet, and then a transparent polypropylene resin film is formed on the coating film. 4 (thickness 80 μm) was laminated.

  Next, the laminate obtained by the above lamination is heated from the surface on the side of the transparent polypropylene resin film 4 with an infrared non-contact type heater to soften the transparent polypropylene resin film 4 and immediately applied to the surface under heating. The embossing was performed by pressing, and the concavo-convex pattern of the wood grain conduit groove pattern was shaped. After this surface is subjected to corona discharge treatment, 100 parts by weight of a polymer (trade name “PUVA-30M” manufactured by Nippon Shokubai Co., Ltd.) incorporating an ultraviolet absorbing group and biuret polyisocyanate (trade name “DURANATE 24A-100” are used. A transparent protective layer 5 (thickness: 4 μm) was formed on the concavo-convex pattern using a mixture with 10 parts by weight of Asahi Kasei.

Example 2
A transparent protective layer was formed in the same manner as in Example 1 except that isocyanurate-based polyisocyanate (trade name “Duranate TPA-100” manufactured by Asahi Kasei) was used instead of biuret-based polyisocyanate.

Example 3
A transparent protective layer was formed in the same manner as in Example 1 except that the polymer “PUVA-30S” was used instead of the polymer “PUVA-30M”.

Comparative Example 1
A transparent protective layer was formed in the same manner as in Example 1 except that instead of the polymer “PUVA-30M”, an ordinary two-component curable urethane-based resin having no ultraviolet absorbing group was used.

Comparative Example 2
A transparent protective layer was formed in the same manner as in Example 2 except that instead of the polymer “PUVA-30M”, a normal two-part curable acrylic urethane-based resin having no ultraviolet absorbing group was used.

Test example 1
A decorative metal plate was prepared by laminating a decorative sheet having a transparent protective layer obtained in Examples and Comparative Examples on a steel plate. The laminating method was implemented by sticking a decorative sheet on a steel plate using a polyurethane adhesive. Each decorative metal plate thus obtained was used as a test body, and a weather resistance test and a peel test were performed on each.
(1) Weather resistance test As for weather resistance, the sunshine weather meter and metal weather meter were used, respectively, and the test was conducted under the following conditions, respectively. Deterioration of the specimen surface after the test (whitening / cracking), designability Changes (whether there was fading or gloss change) were observed with the naked eye. The results are shown in Table 1.
1) Sunshine weather meter Equipment: Product name “WEL-300” manufactured by Suga Test Instruments)
Step 1: Irradiation for 102 minutes (black panel temperature 63 ° C, humidity 50% RH)
Step 2: Irradiation / rainfall for 18 minutes (40 ° C in the tank, 90% humidity)
Total test time 4000 hours 2) Metal weather meter Equipment used: Product name “KU-R4CI-A” manufactured by Daipura Wintes Step 1: Irradiation for 20 hours (black panel temperature 63 ° C., humidity 50% RH)
Step 2: Shower for 10 seconds Step 3: Condensation for 4 hours (Black panel temperature 30 ° C, humidity 98% RH)
Step 4: Shower for 10 seconds Total test time: 300 hours (2) Peel test Further, a peel test using cello tape (trade name, manufactured by Nichiban Co., Ltd.) was performed on the test specimen after the weather resistance test. The transparent protective layer was cut into 2 mm squares in a grid pattern (10 × 10 = 100 pieces), a cellophane tape was attached from above, and the number of peeled pieces when peeled vertically upward was measured. Five-stage evaluation was performed according to the number of peeled pieces. The results are shown in Table 1.

5: 0 peeling pieces 4: 1 to 10 peeling pieces 3: 11 to 50 peeling pieces 2: 51 to 100 peeling pieces 1: Surface layer deteriorated and peeled during the test

  As is apparent from the results in Table 1, it can be seen that the product of the present invention having a transparent protective layer formed using an ultraviolet absorbing group-containing polymer can exhibit excellent weather resistance.

FIG. 3 is a view showing a laminated structure of a cosmetic sheet produced in Example 1.

Explanation of symbols

1 Colored polypropylene resin film (base material sheet)
2 Picture layer 3 Adhesive layer 4 Transparent polypropylene resin film (transparent resin layer)
5 Transparency protective layer 6 Primer layer

Claims (7)

A metal sheet decorative sheet having a pattern layer, a transparent resin layer and a transparent protective layer on a base sheet, the transparent protective layer being provided as an outermost surface layer,
The metal sheet decorative sheet, wherein the transparent protective layer is formed of a material containing a polymer having an ultraviolet absorbing group. The metal sheet decorative sheet according to claim 1, wherein the material further contains an aliphatic diisocyanate polyisocyanate. The metal sheet cosmetic sheet according to claim 2, wherein the aliphatic diisocyanate polyisocyanate is hexamethylene diisocyanate polyisocyanate. The metal sheet cosmetic sheet according to claim 3, wherein the hexamethylene diisocyanate polyisocyanate is at least one of biuret polyisocyanate and isocyanurate polyisocyanate. The metal sheet decorative sheet according to any one of claims 1 to 4, wherein the transparent resin layer is formed of a polyolefin-based resin. The metal sheet decorative sheet according to any one of claims 1 to 5, wherein an adhesive layer is interposed between the pattern layer and the transparent resin layer. A decorative metal plate obtained by laminating the sheet on the metal plate such that the transparent protective layer of the metal plate decorative sheet according to claim 1 is an outermost surface layer.

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