WO1995005941A1

WO1995005941A1 - Decorative board

Info

Publication number: WO1995005941A1
Application number: PCT/JP1994/001414
Authority: WO
Inventors: Yoshio Takahashi; Hideaki Kondo; Keiji Sakamoto; Yasukichi Ogasawara
Original assignee: Toyo Inc Manufacturing Co., Ltd.
Priority date: 1993-08-27
Filing date: 1994-08-26
Publication date: 1995-03-02
Also published as: KR960705684A; JPH07112599A

Abstract

A decorative board having high decorativeness and performances, i.e., a highly brilliant pattern and good water and weathering resistances. The board comprises a base material and, stacked thereon, a transfer base layer containing a polyisocyanate compound and a solvent-soluble hydroxylated fluorocopolymer which has an arbitrary hue that has been rendered opacifying by using a stain and which has a fluorine content of at least 10 wt. % in the fluoroolefin units, a transfer printing layer containing a fluorine ink containing a solvent-soluble fluorocopolymer as the binder, and a topcoating layer containing a polyisocyanate compound and a solvent-soluble hydroxylated fluorocopolymer having a fluorine content of at least 10 wt. % in the fluoroolefin units.

Description

Specification

Decorative plate Technical field

The present invention relates to a decorative plate having a high degree of design and weatherability, which is used for outdoor walls, panel materials, outdoor decorations, and the like. Background art

Conventionally, as decorative materials used for panel materials such as indoor walls and ceilings or interior decoration, for example, JP-B-59-1111 and JP-B-60-58717 have a polyol-cured polyurethane resin paint. A method for producing a decorative board by transfer has been disclosed. According to such a technique, a clear and delicate colored pattern pattern can be obtained as a decorative plate, so that the decorative value is high. However, this is useful for interior use, but has the drawback that when used outdoors, it has poor weather resistance, causing color fading and deterioration of choking due to long-term use.

In addition, Japanese Patent Publication No. Sho 477-171634 and Japanese Patent Laid-Open Publication No. Sho 63-16673 describe decorative glass transferred and printed on transfer paper on which a pattern is formed with an ink containing a sublimable dye. A board is disclosed. This product has a high decorative value as an interior decorative plate, because it can provide clear and delicate colored patterns. However, when used outdoors, there is a drawback that remarkable fading occurs with time due to the sublimable dye.

In addition, there is a painted plate coated with fluororesin paint that has been put to practical use for exterior use. This has good weather resistance because it uses a fluororesin paint, but its plain design has low design properties and no decorative value.

The present invention solves such drawbacks of the conventional decorative plate, and has a high degree of design for exterior use, which has good weather resistance and rich design. An object of the present invention is to provide a decorative plate having both performances.

That is, a solvent-soluble fluorine-containing copolymer having a fluorine content of 10% by weight or more and a hydroxyl group in a fluorophore unit having an arbitrary hue having a hiding property by blending a transparent or coloring material on a substrate, And a transfer printing layer containing a solvent-soluble fluorine copolymer as a binder, a fluorine-containing transfer printing layer containing a solvent-soluble fluorine copolymer, and a fluorine-containing group having a fluorine content of 10% by weight or more in a fluoroolefin unit. By successively laminating a topcoat layer containing a solvent-soluble fluorine-containing copolymer having the above and a polyisocyanate compound, a decorative plate satisfying performances such as design property and weather resistance can be obtained. Disclosure of the invention

An outline of the present invention will be described based on the drawings.

FIG. 1 shows a sectional view of a decorative plate manufactured according to the present invention. The decorative plate has a configuration in which a transfer base layer (2), a transfer printing layer (3), and a top coat layer (4) are sequentially laminated on a base material (1).

As the base material (1), a sandwich laminate structure having a core material of a polyethylene resin or a polypropylene resin and an aluminum foil as a surface material is lightweight and rigid as a structural material, and has good workability. A force that is preferably used due to its excellent resistance to various properties such as water resistance and corrosion resistance. In addition, plywood, metal plates, particle boards, resin plates or films, gypsum boards, slate plates, glass plates For these, a composite substrate, a molded plate using a thermosetting resin, or the like can also be used. The thickness of the substrate is not particularly limited, but a thickness of 1 to 10 mm is preferably used in practical use. These substrates can be coated with a primer or surface treated as needed.

¾

The transfer base layer (2) and top coat layer (4) It is used to fix the transfer printing layer in close contact and to exhibit various performances including weather resistance.The fluorine content in fluorofluorin units

A solvent-soluble fluorine-containing copolymer having a hydroxyl group at 10% by weight or more and a polyisocyanate compound are mixed and used at the time of use. The polyisocyanate compound is preferably a non-yellowing type. If the fluorine content of the fluorine-containing copolymer is less than 10% by weight, the weather resistance becomes 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) ) Fluorine-containing copolymers that are insoluble in various solvents, such as copolymers, polychlorinated trifluoroethers, and tetrafluoroethylene-ethylene copolymers, are not suitable for use because they are not compatible with the polyisocyanate. . The solvent-soluble fluorinated copolymer having a fluorine content of 10% by weight or more and a hydroxyl group in the fluororefin unit used in the present invention has a hydroxyl value of 2 to 200. It is preferable to select the size so as to be in the range of 5 to 150. If the hydroxyl value is less than the lower limit of the above range, the crosslinking reaction does not proceed sufficiently, and it becomes difficult to form a tough coating film. If the upper limit of the above range is exceeded, the bridge density becomes too high, so that the obtained coating film becomes brittle, and the shrinkage stress accompanying the curing reaction also increases, causing a decrease in adhesion. Examples of the fluorine-containing copolymer include polyvinylidene fluoride, tetrafluoroethylene-propylene copolymer, vinylidene fluoride hexafluoropropylene-tetrafluoroethylene copolymer, tetrafluoroethylene, and cyclotrifluoroethylene, Co-polymerization of fluorinated olefins such as hexafluoropropylene with ethylenically unsaturated compounds such as vinyl ethers, vinyl esters, aryl ethers, aryl esters, acryloyl compounds, and methacryloyl compounds Coalescence and the like are exemplified. Particularly preferred examples include a fluororefin-vinyl ether copolymer and a fluororefin-vinyl ester copolymer. The polyisocyanate compound is preferably non-yellowing. As the non-yellowing type polyisocyanate compound, a compound using hexamethylene diisocyanate as a raw material is generally employed. Preferably, it is an isocyanurate derivative which is excellent in compatibility with the fluorinated copolymer and is made of hexane methylenedisocyanate as a raw material. In addition, a bullet-type polyisocyanate or an adduct-type polyisocyanate may be used. The ratio of the isocyanate group to the hydroxy group is preferably in the range of 0.5 to 2.0 in 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 larger than 2.0, unreacted isocyanate groups remain after heat curing, causing stickiness and reduced adhesion. When used for the transfer base layer, it is formed into a paint by using a coloring material, a filler, a solvent, and other additives according to a known means, and is used in a transparent or desired hue. These paints are applied by a known coating method, for example, Curtain Floco One Night, One Day Paint, Spraying, Brushing, Dubbing, etc., by adjusting the viscosity with a solvent as appropriate. The film thickness of the transfer base and the top coat is 10 to 60 microns, and drying is preferably performed by heating and drying in order to remove the solvent and cure in a short time.

For the transfer printing layer, a fluorine-based ink in which a solvent-soluble fluorocopolymer is used as a binder and a pigment is dispersed is used. When the fluorine-containing copolymer is used together with the curing agent isocyanate, the adhesiveness to the surface of the transfer base layer is deteriorated at the time of transfer.Therefore, the isocyanate cannot be used together, and other resins are used within the scope 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 may be used in combination. The transfer printing layer according to the present invention may be formed of a base sheet such as a polyester film in advance. This is a print image in which an arbitrary pattern is formed on a transfer base layer by a gravure printing method, a screen printing method, an offset printing method, or the like. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows a sectional view of a decorative plate according to the present invention. Reference numeral 1 is a base material, reference numeral 2 is a transfer base layer, reference numeral 3 is a transfer printing layer, and reference numeral 4 is a top coat layer. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described with reference to examples. The base film, transfer base, and transfer film and top coat used for the transfer printing layer used in the examples are shown below. In the examples, all “%” represent “% by weight”. Various tests performed in the examples were performed as follows.

〔Base material〕

Substrate 1 Composite laminate of sandwich structure with core material of polyethylene resin and aluminum foil as 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 Lumiflon LF-100 manufactured by Asahi Glass Co., Ltd. Sineto Sumitomo Bayer Urethane Co., Ltd. 3.60 Sumidur N—350 xylene 23.40

Toluene 18.00

100. 00

The main agent and the curing agent were mixed at 8 Z1 to obtain the above composition.

Equivalent ratio (Isocyanate Z hydroxy group) = 1.0 Transfer base B% Remarks

Titanium white 15.70

Solvent-soluble fluororesin 41. 86 Lumiflon LF-100 Hexamethylene diiso manufactured by Asahi Glass Co., Ltd. Cyanate 2.26 Sumidur N-350'xylene 22.71 manufactured by Sumitomo Bayer Urethane Co., Ltd.

Toluene 17.47

100. 00

The main agent and the curing agent were mixed at 80.6 to obtain the above composition.

Equivalent ratio (Isocyanate Z hydroxy group) 0.6 Transfer base C Remarks

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 Sumidur N—350 xylene 24.43

Toluene 19.10

100. 00

The main agent and the curing agent were mixed at 8 Z 1.8 to make the above composition.

Equivalent ratio (Isoocyanate Z hydroxy group) = 1.8 Transfer base D%

Titanium white 15.00

Acryl polyol 40.00 Acrydec A-801 manufactured by Dainippon Ink and Chemicals, Inc.

Hexamethylene diiso Asahi Kasei Kogyo Co., Ltd.

Cyanate 6.37 Duranate 24 A—100 Butyl acetate 23.63

Toluene 15.00

100. 00 The main agent and the curing agent were mixed at a ratio of 6/1 to obtain the above composition.

Equivalent ratio (Isocyanate Z hydroxy group) = 1.0 [Transfer film]

Name Film type Ink type Print pattern Transfer film A Polyethylene solvent-soluble fluoropolymer Granite pattern phthalate

Transfer film B Polyethylene te PVC-based granite pattern phthalate

[Top Coat]

Top coat A Remarks

Solvent soluble fluororesin 50.00 Asahi Glass Co., Ltd. Lumiflon LF-302 Hexamethylene diiso Sumitomo Bayer Urethane Co., Ltd. Cyanate 4.16 Sumijoule N-350 xylene 23.54

Toluene 12.30

Butyl acetate 10.00

100. 00

The main agent and the curing agent were mixed at 10 Z1 to obtain the above composition.

Equivalent ratio (isocyanate hydroxyl group) 1.0 Topcoat B% Remarks

Acrylic polyol 50.00 manufactured by Hitachi Chemical Co., Ltd.

Hitaroid 3 0 0 8

S 11.34 Sumitomo Bayer Urethane Co., Ltd.

Cyanate Sumijoule N— 7 5

Octin tin 0.10 Nippon Kagaku Sangyo Co., Ltd.

Methyl ethyl ketone 14.56

Toluene 14.00 Butyl acetate 10.

100.00

The main agent and the curing agent were mixed at a ratio of 4/1 to obtain the above composition.

Equivalent ratio (isocyanate / hydroxyl group) = 1.0 [boiling water resistance test]

The test piece was immersed in boiling water, boiled for 8 hours, taken out, left at room temperature for 2 hours, and cut into a grid pattern (1 mm square x 100 pieces) with a cutter knife on the surface coating. Press the cellotape hard. Thereafter, the cellophane tape was peeled off, and the number X of the remaining coats was counted to give XZ100.

(Water resistance test)

The test specimen was immersed in warm water at 50 ° C for 10 days, taken out, left at room temperature for 2 hours, and cut in a grid pattern (1 mm square x 100 pieces) with a cutter knife on the coating film. After inserting, press the cellophane tape firmly. Thereafter, the cellophane tape was peeled off, and the number X of the remaining coats was counted to give XZ100.

(Weather resistance test)

After irradiating the test piece with a sunshine weather meter for 400 hours, the fading of the transferred pattern was visually determined. X indicates that there is a clear difference compared to the unirradiated test piece, and 、 indicates that there is almost no difference.

Example 1

Transfer base A is applied to base material 1 (Alpolic Co., Ltd. “Alpolic”) with a length and width of 300 x 300 mm and a thickness of 6 mm, on which a polyester-based primer has been applied in advance. The coated film was dried so as to have a dry film thickness of 20 to 30 ° and dried in hot air at 90 ° C. for 10 minutes to form a white transfer base layer. After then heated pressurizing the substrate to 9 0 ° C, the transfer film A to be rubber roll ^ using the JIS hardness of 6 0, compression temperature 8 5 ° C, allowed pressed at a pressure 4 KgZcm ^2, 4 0 ° C or Then, the polyethylene terephthalate film was peeled off, and the granite pattern was transferred onto the transfer base to form a transfer print layer. In addition, Topcoat A mixed with the main agent Z curing agent = 10/1 was applied by air spray so that the dry coating film became 30 and was heated in hot air at 100 ° C for 40 minutes. After drying, a top coat layer was formed. The decorative plate produced in this way was finished with a fine and beautiful granite pattern, and was of high decorative value. The product had good boiling water resistance, water resistance, and weather resistance.

Example 2

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

Example 3

A decorative plate was manufactured in the same manner as in Example 1 except that the transfer base C was used instead of the transfer base A in Example 1. This one had a fine and beautiful finish with a granite pattern, and was of high decorative value. The product had good boiling water resistance, water resistance, and weather resistance.

Example 4

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

Comparative Example 1

3 0 0 X 3 0 0 Transfer base D to base material 1 (Alpolic Co., Ltd.) with a thickness of 6 mm and a thickness of 6 mm by air spray so that the dry coating thickness becomes 20 to 30 // And dried in hot air at 90 ° C. for 10 minutes to form a white transfer base layer. Then substrate from heated warm to 9 0 ° C, the transfer film B using a rubber roll of JIS hardness 6 0, compression temperature 8 5 ° C, allowed pressed at a pressure ^{4 K g / cm 2, 4} 0 ° C After cooling, the polyethylene terephthalate film was peeled off and the granite pattern was transferred onto the transfer base to form a transfer print layer. In addition, Topcoat B mixed with the base resin / hardener = 4 Z 1 was applied by air spraying so that the dried coating film became 30 and dried in hot air at 100 ° C for 40 minutes. A top coat layer was formed. The decorative plate produced in this way had a fine and beautiful granite pattern, and was of high decorative value. In addition, the boiling water resistance and the water resistance were good. However, in the weather resistance test, the pattern became unclear due to fading, and chalking occurred on the coating film surface, which was a practical problem.

Comparative Example 2

For the exterior in the same manner as in Example 1, except that the transfer paper used for the transfer print layer was changed from transfer paper A to transfer paper B on a base material 2 with a length and width of 300 x 300 mm and a thickness of 2 mm. A decorative plate was produced. The decorative plate produced in this manner had good transferability, and the granite pattern was finished clearly and neatly, and was of high decorative value. However, in the water resistance and boiling water resistance tests, the adhesion was slightly inferior.In the weather resistance test, the pattern became unclear due to fading, and separation occurred between the transfer printing layer and the top coat layer in 300 hours. Was a practical problem. Table 1 shows the results of the boiling water 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 panel for exterior use, but were not usable as a decorative panel for exterior use in the comparative example due to poor weather resistance. Was something.

table 1

* Bliss evening Industrial applicability

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

Claims

The scope of the claims

1. A solvent-soluble fluorine-containing copolymer having a fluorine content of 10% by weight or more and a hydroxyl group in a fluorofluorin unit having a desired hue having a hiding property by blending a transparent or coloring material on a substrate. A transfer base layer containing a polymer and a polyisocyanate compound, a transfer print layer containing a fluorine-containing ink having a solvent-soluble fluorine copolymer as a binder, and a fluorine content of at least 10% by weight in a fluoroolefin unit and A decorative plate obtained by sequentially laminating a top coat layer containing a solvent-soluble fluorine-containing copolymer having a hydroxyl group and a polyisocyanate compound.

2. The decorative plate according to claim 1, wherein a composite laminate having a sandwich structure using a polyolefin resin as a core material and an aluminum foil as a surface material is used as a base material.