JPH07112599A - Decorative panel - Google Patents

Abstract

PURPOSE:To provide a decorative panel having high-order design effect due to highly detailed patterns and high water resistance and weathering resistance. CONSTITUTION:A decorative panel is obtained by successively laminating a transfer base layer containing a solvent soluble fluorine copolymer having a fluoroolefin unit with fluorine content of 10wt.% or more and a hydroxyl group and a polyisocyanate compd. and colored by a coloring agent so as to have an arbitrary hue having concealability, a transfer printing layer containing fluorine ink whose binder is a solvent soluble fluorine copolymer and a topcoat layer containing a solvent soluble fluorine copolymer having a fluoroolefin unit with fluorine content of 10wt.% or more and a hydroxyl group and a polyisocyanate compd. on a base material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative plate having a high degree of design and weather resistance, which is used for outdoor walls, panel materials or outdoor decorations.

[0002]

2. Description of the Related Art Conventionally, as a panel material for indoor walls and ceilings, or a decorative plate used for interior decoration, for example,
Japanese Patent Publication No. 59-1111 and Japanese Patent Publication No. 60-58717 disclose a method for producing a decorative board by transfer using a polyol-cured polyurethane resin paint. According to such a technique, since a clear and delicate colored pattern pattern can be obtained as a decorative plate, it has a high decorative value. However, this product is useful as an interior product, but when used outdoors, its weather resistance is insufficient, so that it has the drawback of causing color fading and deterioration such as chalking due to long-term use. Also, Japanese Patent Publication No. 47-51734 and Japanese Patent Laid-Open No. 63-63
JP-A-16673 discloses a decorative glass plate which is transfer-printed with a transfer paper on which a pattern is formed by an ink containing a sublimable dye. This product has a high decorative value as a decorative plate for interior because a clear and delicate colored pattern can be obtained. However, when it is used outdoors, it has a drawback that it is markedly discolored over time because it is a sublimable dye. In addition to this, there is a coated plate coated with a fluororesin paint that has been put into practical use as an exterior. Since this uses a fluororesin paint, it has good weather resistance,
Since it was a plain paint, its design was low and its decorative value was not high.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the drawbacks of the conventional decorative plate as described above, and has a high degree of designability and performance for exterior use, which is excellent in weather resistance and rich in designability. It is intended to provide a decorative plate having.

[0004]

[Means for Solving the Problems] That is, the content of fluorine in a fluoroolefin unit in which a transparent or coloring material is blended on a substrate to give an arbitrary hue having a hiding property 1
In a fluoroolefin unit, a transfer base layer containing 0% by weight or more and a hydroxyl group-containing solvent-soluble fluorocopolymer and a polyisocyanate compound, a transfer printing layer containing a fluorine-based ink having a solvent-soluble fluorocopolymer as a binder, A solvent-soluble fluorine copolymer having a fluorine content of 10% by weight or more and having a hydroxyl group,
By sequentially laminating a top coat layer containing a polyisocyanate compound and a polyisocyanate compound, a decorative plate satisfying performances such as designability and weather resistance can be obtained. The outline of the present invention will be described with reference to the drawings.

FIG. 1 shows a cross-sectional view of a decorative plate manufactured according to the present invention. The decorative plate comprises a base material (1), a transfer base layer (2), a transfer printing layer (3) and a top coat layer (4).
Are sequentially laminated. As the base material (1),
Sandwich structure composite laminated board with polyethylene resin or polypropylene resin as core material and aluminum foil as surface material is lightweight and rigid as structural material, has good workability, water resistance, corrosion resistance, etc. It is preferably used due to its excellent resistance to various uses. In addition to this, plywood, metal plate, particle board, resin plate or film, gypsum board, slate plate, glass plate or their composite base material, thermosetting resin is used. It is also possible to use molded plates that have been used. The thickness of the base material is not particularly limited, but a thickness of 1 to 10 mm is preferably used in practice. These substrates can be coated with a primer or surface-treated as needed.

The transfer base layer (2) and the top coat layer (4) are for closely adhering to the substrate to fix the transfer printing layer, and to exhibit various performances including weather resistance. Fluorine content in unit of 10% by weight
The solvent-soluble fluorocopolymer having the above and having a hydroxyl group, and the polyisocyanate compound are mixed and used at the time of use. The polyisocyanate compound is preferably a non-yellowing type. When the fluorine content of the fluorinated copolymer is less than 10% by weight, the weather resistance is poor and the object of the present invention cannot be achieved. The fluorine content is usually selected from the range of 10 to 70% by weight, preferably 15 to 50% by weight. Even if the fluorine content is 10% by weight or more, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer, polychlorotrifluoroether, tetra Fluorine-containing copolymers that are insoluble in various solvents such as fluoroethylene-ethylene copolymers are not compatible with polyisocyanates and are not suitable for use. The solvent-soluble fluorine-containing copolymer having a fluorine content of 10% by weight or more in the fluoroolefin unit and a hydroxyl group used in the present invention has a hydroxyl value of the fluorine-containing copolymer of about 2 to 200, preferably 5 to 5. It is preferable to select it in the range of 150.
If the hydroxyl value is less than the lower limit of the above range, the crosslinking reaction will not proceed sufficiently and it will be difficult to form a tough coating film. When the amount exceeds the upper limit of the above range, the crosslink density becomes too large, so that the obtained coating film becomes brittle and the contraction stress accompanying the curing reaction also becomes large, resulting in a decrease in adhesion. As the fluorine-containing copolymer, polyvinylidene fluoride, tetrafluoroethylene-propylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene Examples thereof include copolymers of such fluoroolefins and ethylenically unsaturated compounds such as vinyl ether, vinyl ester, allyl ether, allyl ester, acryloyl compound, and methacryloyl compound. Particularly preferable examples include a fluoroolefin-vinyl ether copolymer and a fluoroolefin-vinyl ester copolymer. The polyisocyanate compound is preferably a non-yellowing type. As the non-yellowing polyisocyanate compound,
Generally, a compound using hexamethylene diisocyanate as a raw material is adopted. Preferred is an isocyanurate derivative using hexamethylene diisocyanate as a raw material, which is excellent in compatibility with the fluorinated copolymer. In addition, burette type polyisocyanate and adduct type polyisocyanate may be used. The ratio of isocyanate group / hydroxyl group is preferably 0.5 to 2.0 in terms of equivalent ratio. If the equivalent ratio is less than 0.5, unreacted hydroxyl groups remain after heat curing, and the adhesion and water resistance are reduced.
If it is greater than 2.0, unreacted isocyanate groups remain after heat curing, causing stickiness and deterioration of adhesion. When it is used for the transfer base layer, it is made into a paint by using a coloring material, a filler, a solvent, and other additives by a known means, and is made transparent or has a desired hue. These paints are coated by a known coating method such as curtain flow coater, roll coater, spraying, brush coating, dipping, etc., with the viscosity adjusted appropriately with a solvent. The thickness of the transfer base and top coat is 10-60
In micron, drying is preferably performed by heating and drying so that the solvent can be removed and cured in a short time.

In the transfer printing layer, a fluorine ink in which a solvent-soluble fluorine copolymer is used as a binder and a pigment is dispersed is used. Fluorine-containing copolymer, when used in combination with a curing agent isocyanate, will have poor adhesion to the surface of the transfer base layer during transfer, so isocyanate cannot be used in combination, but other resins within the range not departing from the object of the present invention, For example, a binder such as a vinyl resin, a thermoplastic acrylic resin, a thermoplastic polyester resin, an olefin resin, or the above-mentioned polyol resin can be used together. The transfer printing layer of the present invention is formed by transferring a print image in which an arbitrary pattern is previously formed on a base sheet such as a polyester film by a gravure printing method, a screen printing method, an offset printing method or the like to the surface of the transfer base layer.

[0008]

〔Base material〕

 Base material 1 Composite laminated board with sandwich structure in which the core material is polyethylene resin and aluminum foil is the surface material Thickness 6 mm Base material 2 Aluminum plate (alumite processed product) Thickness 2 mm

[Transfer base] Transfer base A % Remarks Titanium white 15.00 Solvent-soluble fluororesin 40.00 Asahi Glass Co., Ltd. Lumiflon LF-100 Hexamethylenediiso Sumitomo Bayer Urethane Co., Ltd. Cyanate 3.60 Sumidule N-3500 Xylene 23.40 Toluene 18.00 100.00 The main compound and the curing agent were mixed in the ratio of 8/1 to obtain the above composition. Equivalent ratio (isocyanate / hydroxyl group) = 1.0

Transfer base B % Remark Titanium White 15.70 Solvent-soluble fluororesin 41.86 Asahi Glass Co., Ltd. Lumiflon LF-100 Hexamethylenediiso Sumitomo Bayer Urethane Co., Ltd. Cyanate 2.26 Sumidule N-3500 Xylene 22.71 Toluene 17.47 100.00 The main compound and the curing agent were mixed at a ratio of 8 / 0.6 to obtain the above composition.
Equivalent ratio (isocyanate / hydroxyl group) = 0.6

Transfer base C % Remark Titanium White 13.78 Solvent-soluble fluororesin 36.74 Asahi Glass Co., Ltd. Lumiflon LF-100 Hexamethylenediiso Sumitomo Bayer Urethane Co., Ltd. Cyanate 5.95 Sumidule N-3500 Xylene 24.43 Toluene 19.10 100.00 The main compound and the curing agent were mixed at 8 / 1.8 to obtain the above composition. Equivalent ratio (isocyanate / hydroxyl group) = 1.8

Transfer base D % Remarks Titanium white 15.00 Acrylic polyol 40.00 Dainippon Ink and Chemicals, Inc. Acrydeck A-801 Hexamethylenediiso Asahi Kasei Co., Ltd. Cyanate 6.37 Duranate 24A-100 Butyl acetate 23.63 Toluene 15.00 100.00 The main component and the curing agent were mixed in a ratio of 6/1 to prepare the above composition. Equivalent ratio (isocyanate / hydroxyl group) = 1.0

[0013] [transfer film] Name Type Printing Pattern type ink film transfer film A polyethylene te solvent-soluble fluorine resin granite pattern terephthalate transfer film B polyethylene tape vinyl chloride acetate-based granite pattern terephthalate

[Top coat] Top coat A % Remarks Solvent-soluble fluororesin 50.00 Asahi Glass Co., Ltd. Lumiflon LF-302 Hexamethylenediiso Sumitomo Bayer Urethane Co., Ltd. Cyanate 4.16 Sumidule N-3500 Xylene 23.54 Toluene 12.30 Acetic acid Butyl 10.00 100.00 The main compound and the curing agent were mixed at a ratio of 10/1 to obtain the above-mentioned composition. Equivalent ratio (isocyanate / hydroxyl group) = 1.0

Topcoat B % Remark Acrylic polyol 50.00 Hitachi Chemical Co., Ltd. Hitaroid 3008 Hexamethylenediiso 11.34 Sumitomo Bayer Urethane Co., Ltd. Cyanate Sumijour N-75 Octix tin 0.10 Nippon Chemical Industry Co., Ltd. Manufactured methyl ethyl ketone 14.56 Toluene 14.00 Butyl acetate 10.00 100.00 The main ingredient and the curing agent were mixed at a ratio of 4/1 to obtain the above blending. Equivalent ratio (isocyanate / hydroxyl group) = 1.0

[Boiling Water Resistance Test] The test piece was immersed in boiling water for 8
After boiling for 1 hour, take it out, leave it at room temperature for 2 hours, and use a cutter knife to cut the cross-cut lines (1 mm square × 1 mm) on the surface coating film.
100 pieces), and then press the cellophane tape strongly.
After that, the cellophane tape was peeled off, and the number X of the remaining coating films was counted and set to X / 100. [Water resistance test] The test piece was immersed in warm water at 50 ° C for 10 days, taken out and allowed to stand at room temperature for 2 hours, and then a checkerboard-shaped cut line (1 mm square x 100 pieces) was put into the coating film with a cutter knife. After that, strongly press the cellophane tape. After that, the cellophane tape was peeled off, and the number X of the remaining coating films was counted and set to X / 100. [Weather resistance test] The fading of the transferred pattern after the test piece was irradiated with a sunshine weather meter for 4000 hours was visually determined. The case where a clear difference is recognized as compared with the unirradiated test piece is indicated by x, and the case where there is almost no difference is indicated by o.

Example 1 A vertical and horizontal 300 precoated with a polyester-based primer
A transfer base A is applied to a base material 1 (“ALPOLIC” manufactured by ALPOLIC Co., Ltd.) having a thickness of 300 mm and a thickness of 6 mm so that the dry coating film thickness is 20 to 30 μ, and hot air at 90 ° C. In air to form a white transfer base layer. After that, the base material is heated to 90 ° C., and then the transfer film A is pressure-bonded with a rubber roll having JIS hardness of 60 at a pressure bonding temperature of 85 ° C. and a pressure of 4 Kg / cm ² , and cooled to 40 ° C., and the polyethylene terephthalate film is peeled off. Then, the granite pattern was transferred onto the transfer base to form a transfer print layer. Further, the top coat A mixed with the main agent / curing agent = 10/1 is applied by air spraying so that the dry coating film has a thickness of 30 μ.
It was dried in hot air at ℃ for 40 minutes to form a top coat layer. The decorative plate thus produced had a granite pattern design clearly and neatly and had a high decorative value. The boiling water resistance, water resistance and weather resistance of this product were good.

Example 2 A decorative plate was produced in the same manner as in Example 1 except that the transfer base B was used instead of the transfer base A. This product had a clear and beautiful granite pattern and had a high decorative value. The boiling water resistance, water resistance and weather resistance of this product were good.

Example 3 A decorative board was produced in the same manner as in Example 1 except that the transfer base C was used instead of the transfer base A. This product had a clear and beautiful granite pattern and had a high decorative value. The boiling water resistance, water resistance and weather resistance of this product were good.

Example 4 A transfer base layer, a transfer printing layer, and a top coat layer were sequentially laminated on a base material 2 having a length and width of 300 × 300 mm and a thickness of 2 mm in the same manner as in Example 1 to prepare an exterior decorative plate. did. The decorative plate produced in this manner had good transferability, a granite pattern was finished clearly and neatly, and had a high decorative value. The weather resistance, water resistance and boiling water resistance of this product were good.

Comparative Example 1 A vertical and horizontal 300 precoated with a polyester-based primer
A transfer base D is coated on a base material 1 (“ALPOLIC” manufactured by ALPOLIC Co., Ltd.) having a thickness of 300 mm and a thickness of 6 mm by air spraying so that the dry coating film thickness is 20 to 30 μm, and hot air at 90 ° C. In air to form a white transfer base layer. After that, the base material is heated to 90 ° C., and then the transfer film B is pressure-bonded using a rubber roll of JIS hardness 60 at a pressure bonding temperature of 85 ° C. and a pressure of 4 Kg / cm ² , and cooled to 40 ° C., and the polyethylene terephthalate film is peeled off. Then, the granite pattern was transferred onto the transfer base to form a transfer print layer. Further, the top coat B mixed with the main agent / curing agent = 4/1 is applied by air spraying so that the dry coating film becomes 30 μ, and the temperature is 100 ° C.
Was dried in hot air for 40 minutes to form a top coat layer. The decorative plate thus produced had a granite pattern design clearly and neatly and had a high decorative value. Further, the boiling water resistance and water resistance of this product were good. However, in the weather resistance test, the pattern became unclear due to discoloration and choking occurred on the surface of the coating film, which was a practical problem.

Comparative Example 2 The same method as in Example 1 was used except that the transfer paper used for the transfer printing layer was changed from transfer paper A to transfer paper B on the base material 2 having a length and width of 300 × 300 mm and a thickness of 2 mm. A decorative plate was produced. The decorative plate produced in this way has good transferability,
The granite pattern was finished clearly and neatly, and had a high decorative value. However, the water resistance and boiling water resistance of this product are slightly inferior in adhesion, and in the weather resistance test, the pattern becomes unclear due to discoloration, and peeling occurs between the transfer printing layer and the top coat layer in 3000 hours. It was a problem in practice.

Table 1 shows the results of the boiling water resistance test, the water resistance test, and the weather resistance test for the decorative plates obtained in Examples 1 to 4 and Comparative Examples 1 and 2. The test results were all good in the examples and useful as a decorative plate for exterior, but in the comparative examples, they were not usable as decorative plates for exterior because of poor weather resistance.

[0024]

[0025]

Industrial Applicability According to the present invention, it is possible to provide a decorative plate having a high degree of designability, weather resistance, water resistance and the like, which is used for outdoor walls, panel materials or outdoor decorations.

[Brief description of drawings]

FIG. 1 shows a cross-sectional view of a decorative plate according to the present invention.

[Explanation of symbols]

 1 ... Base material 2 ... Transfer base layer 3 ... Transfer printing layer 4 ... Top coat layer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ankichi Ogasawara 2-33 Kyobashi, Chuo-ku, Tokyo Toyo Inki Manufacturing Co., Ltd.

Claims (2)

[Claims] 1. A solvent-soluble fluorocopolymer having a fluorine content of 10% by weight or more and a hydroxyl group in a fluoroolefin unit in which a transparent or coloring material is blended on a substrate to give an arbitrary hue having a hiding property. And a transfer base layer containing a polyisocyanate compound, a transfer printing layer containing a fluorine ink using a solvent-soluble fluorocopolymer as a binder, and a solvent-soluble fluorine having a fluorine content in a fluoroolefin unit of 10% by weight or more and having a hydroxyl group. A decorative plate obtained by sequentially laminating a top coat layer containing a copolymer and a polyisocyanate compound. 2. The decorative board according to claim 1, wherein a composite laminated board having a sandwich structure in which a polyolefin resin is a core material and an aluminum foil is a surface material is used as a base material.