JPH0428543A - Decorative sheet and its manufacture - Google Patents

Abstract

PURPOSE:To obtain a decorative sheet having beauty due to a gloss difference, a visual effect of interest induction, heat resistance, size stability, curl-proofing properties and contamination resistance by laminating a thermally curable synthetic resin layer with an uneven pattern on a base. CONSTITUTION:Polyester film is used as a base 1 and a urethane resin application liquid is applied to the surface of the film as a thermally curable synthetic resin 2. In this case, a gravure roll coater 3 is used and then the film is allowed to pass through a dryer 4 to laminate a thermally curable synthetic resin layer in a semi-cured state. On the other hand, a form-donative sheet 5 consists of a polyvinylchloride sheet having a fine embossed water drop pattern on the surface is fed. After this process, the sheet is pressed between a metal roll and a press roll 7 so that the embossed water drop pattern surface comes in contact with the semi-cured synthetic resin surface. Next, this sheet is taken up by a winding roll 8 in the form of one piece. The wound laminated product is peeled off the form-donative sheet after aging process.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a decorative sheet and a method for manufacturing the same, and more specifically, it has a visually beautiful effect due to differences in gloss at various stages, has excellent dimensional stability, The present invention relates to a decorative sheet that does not curl, protects its surface from dirt and damage, and maintains its beauty, and a method for producing the same.

[Conventional technology and problems]

Conventionally, this type of decorative sheet has either been printed or vapor-deposited on a base material such as paper, or a synthetic resin film with a flat surface is added as a protective layer on the surface of the printed or vapor-deposited layer. An integral configuration is common.

However, in the former case, it is inevitable that the printing or vapor deposition will be damaged, or the color will change or fade, while in the latter case, although these problems are solved, the film surface is flat and Because of this, the printing or vapor deposition seen through the film is literally flat, which is disappointing as it lacks visual beauty and interest. Even if it is used as a base material for gold and silver thread, it will inevitably give a mediocre impression.

Therefore, attempts have been made to use a thermoplastic synthetic resin and form an uneven pattern on its surface to provide a visual effect due to the difference in gloss. However, thermoplastic synthetic resins generally have low heat resistance and poor dimensional stability, and therefore tend to curl when subjected to heating steps in the manufacturing process and post-processing process.

If this is to be avoided, it is necessary to lower the drying temperature or change the processing conditions, which not only reduces productivity but also adversely affects the quality of the post-processed products. Further, if thermoplastic engineering plastics with high heat resistance are used, the problem of heat resistance can be solved, but the resin is expensive and has poor processability, so it is not suitable for practical use.

Furthermore, depending on the configuration or use, there is a drawback that the sheet surface is easily soiled.

[Means for solving problems]

In view of the above circumstances, an object of the present invention is to provide a cosmetic sheet that has visual effects such as beauty and interest due to difference in gloss, as well as heat resistance, dimensional stability, curl prevention, and stain resistance. shall be.

That is, the first aspect of the present invention is a decorative sheet formed by laminating a thermosetting synthetic resin layer having an uneven pattern on a base material, and the second aspect of the present invention is a decorative sheet formed by laminating a thermosetting synthetic resin layer having an uneven pattern on a base material. A third aspect of the present invention is a decorative sheet formed by laminating a thermosetting synthetic resin layer having an uneven pattern of 8j on the surface. A fourth aspect of the present invention provides a method for producing a decorative sheet, which comprises applying a resin and providing an uneven pattern on the surface of the thermosetting synthetic resin when the thermosetting synthetic resin is semi-cured. Each content is a method for producing a decorative sheet, which is characterized by laminating a base material or a printed and/or vapor-deposited base material and a thermosetting synthetic resin sheet having an uneven pattern on its surface. be.

Substrates used in the present invention include paper, coated paper, size press paper, supercalendered paper, functional paper, synthetic paper, nonwoven fabric, woven fabric, laminated paper, etc., as well as synthetic resin film, metal foil, and vapor-deposited paper. This includes films and laminates thereof. The selection of the base material is determined by the purpose and use of the base material.

There are no restrictions on printing or vapor deposition, and all known methods can be used.

A synthetic resin layer having an uneven pattern is laminated on the surface of a base material or a printed and/or vapor deposited layer of a base material that has been printed and/or vapor deposited.

Examples of the thermosetting synthetic resin layer having an uneven pattern include unsaturated polyester resin, epoxy resin, melamine resin, alkyd resin, diallyl phthalate resin, urethane resin, and acrylic resin. These resins are preferably transparent for beauty and visual effects.

By incorporating an antifouling substance into the thermosetting synthetic resin layer having an uneven pattern or the surface protective layer provided on the surface of the thermosetting synthetic resin layer, a cosmetic sheet that is even more resistant to staining can be obtained. Examples of antifouling substances include silicone compounds such as alkenes (C+. to C2°) of polymethylhydrodiene siloxane and propylene adducts, fluorine compounds such as block polymers containing fluorinated alkyl groups, and charged kneading types. These can be used alone or in combination. The amount of antifouling substance is 0.
It is preferably about 5 to 10% by weight.

In addition to antifouling substances, stabilizers and fillers (inorganic, organic, granular,
Fibrous) etc. can also be included as necessary.

The uneven pattern is not particularly limited and includes all patterns such as designs, single characters, symbols, attached plates, Japanese paper, leather, and textile patterns.

One method for laminating a thermosetting synthetic resin layer having an uneven pattern on the surface of a substrate or a printed and/or vapor-deposited substrate is to laminate a thermosetting synthetic resin layer on the substrate or printed and/or vapor-deposited surface. Alternatively, the thermosetting synthetic resin may be coated on the surface of a base material that has been vapor-deposited, and a pattern of projections and depressions may be formed on the surface of the thermosetting synthetic resin when it is semi-cured.

Furthermore, this method includes a shaped sheet (printed sheet, embossed sheet) method and an embossed roll method.

The shaping sheet method uses a shaping sheet with an uneven pattern,
The imprinting surface is pressed so that it is in contact with the thermosetting synthetic resin (semi-cured) surface, and after the resin is cured and cooled, the imprinting sheet is peeled off and the uneven pattern of the imprinting sheet is formed using the heat. This is a method of transferring onto a hardening synthetic resin surface.

In the embossing roll method, the embossing roll surface with an uneven pattern is placed so as to be in contact with the thermosetting synthetic resin (semi-cured) surface, and the embossing roll is pressed between the embossing roll and a press roll to remove the unevenness of the embossing roll. This is a method of transferring a pattern onto the surface of the thermosetting synthetic resin.

A molded sheet having an uneven pattern in advance is disclosed in Japanese Patent Application Laid-Open No. 62-11.
6197 etc., a printed sheet such as that disclosed in JP-A-1999-1
Embossed sheet as disclosed by No. 188399 etc.
Other sheets easily obtained by known methods may be used.

When laminating a base material or a printed and/or vapor-deposited base material with a thermosetting synthetic resin layer to which an uneven pattern is to be applied, the cough base material or printed and/or vapor-deposited base material is laminated to improve adhesion.
Alternatively, anchor treatment, corona treatment, flame treatment, etc. can be performed on the base material subjected to vapor deposition.

Another method for laminating a thermosetting synthetic resin layer having an uneven pattern on the surface of a base material or a printed and/or vapor-deposited substrate is to laminate a thermosetting synthetic resin sheet having an uneven pattern on the surface. Prepare $ and use this and the base material or printing and/or
Alternatively, a method of laminating a base material that has been subjected to vapor deposition may be mentioned.

The lamination method is not particularly limited, and examples include dry lamination, lamination, lamination, and methods using adhesives.

The surface of the cosmetic sheet thus obtained may be printed and/or vapor-deposited, and/or a surface protective layer may be provided. Moreover, a reinforcing layer and a backer layer can also be provided on the back surface of the base material layer.

〔Example〕

The present invention will be explained below with reference to Examples and Comparative Examples.
Of course, the present invention is not limited to these. still,
In the following, parts by weight and % by weight are respectively meant unless otherwise specified.

Reference example Polymethylhydrodiene siloxane (Pm2O3, M
W = 22000) 45.6 parts, α-olefin (Dialen-30J, manufactured by Mitsubishi Chemical Industries, MW = 650) 54
．． 4 parts, 0.1% H2PtCIb 6H20 in tetrahydrofuran? Charge 8 parts of fi into a reactor and heat at 80°C.
The reaction was carried out for an additional time of 130" C1B. The reaction was stopped when the viscosity of the reaction product reached about 10,000 cps.

The reaction product was washed three times with acetone to remove unreacted parts, and purified and dried. The silicone content of the resulting exfoliated lily was 45.6%.

Example 1 Base material (1) (!: Polyester film rE510
0J (manufactured by Toyobo, thickness 9 μm), and on the surface of this thermosetting synthetic resin (2) ester type urethane resin "Atocoat 806J (manufactured by Toyo Morton, solid content concentration 60%) and curing type "Atocoat RT-8J (manufactured by Toyo Morton, solid content concentration 75%) in a ratio of 10 = 1, and using a coating liquid with ethyl acetate with a solid content concentration of 27%, coated with gravure roll coater (3) at 15g/I (wet). After applying the base), pass it through the dryer (4) for 90 minutes.
A semi-cured thermosetting synthetic resin layer was laminated by drying at °C for 30 seconds and containing about 1 g/l of residual solvent.

On the other hand, there is a fine embossed polka dot pattern on the surface (depth 10-40μm).
, a patterned sheet (5) (thickness: 80 μm) made of a polyvinyl chloride sheet having a polka dot pattern of 200/1 nch parallel line set units arranged with adjacent units arranged in different directions. , the metal roll (6) is placed so that this embossed polka dot pattern surface and the semi-hardened synthetic resin surface are in contact with each other.
(surface temperature: 80° C.) and a press roll (7), and then wound up as one piece with a take-up roll (8). After aging the rolled-up laminate at 40° C. for 148 hours, the imprinting sheet was peeled off and a polyester laminate sheet having an embossed polka dot pattern on the thermosetting resin surface was obtained. This laminated sheet had good heat resistance and dimensional stability, and no curling was observed even at 150°C.

Next, gold-colored aluminum vapor deposition was performed on the embossed polka dot pattern surface of the laminated sheet by a conventional method to obtain a decorative sheet as a base material for gold thread.

Comparative Example 1 In Example 1, methacrylic resin "Acryvet VHJ" was used as a thermoplastic synthetic resin instead of the thermosetting synthetic resin.
A laminated sheet was obtained in the same manner as in Example 1, except for using a laminate (manufactured by Mitsubishi Rayon). This laminated sheet was unsatisfactory because the thermoplastic synthetic resin had poor heat resistance and dimensional stability, and curling of the laminated sheet occurred from 60°C.

Comparative Example 2 A polyester film "rE5100" (manufactured by Toyobo, thickness 12 μm) was used as a base material, and after anchor treatment was performed by a conventional method, a thermoplastic polyester resin "
Juranenx 600FPJ (manufactured by Polyplastics) was extrusion laminated using a T-die extruder (screw diameter: 40 mm, T-die temperature: 300°C). On the other hand, a grid pattern was printed on a polyester film rE5100J with a thickness of 50 μm that had not been anchored, and a molded sheet was placed so that the printed surface was in contact with the resin, and the extruded resin was sandwiched in the center. Then, it was pressed with a press roll, and polysane lamination was performed so that the extruded resin thickness was 20 μm. After cooling with a cooling roll, the laminate [printed notebook/polyester resin/
Anchor coat/base material (polyester film)] was wound up as one piece using a winding machine. When the imprinting sheet was peeled off and removed from the laminate, a laminate sheet in which the intended printing pattern was accurately copied onto the surface of the polyester resin was obtained. This laminated sheet began to curl at 50'C, which was unsatisfactory during the vapor deposition process.

Example 2 Coated paper (basis weight 85 g/rrf) was used as a base material, and 76% by weight of Alkit resin "Besokozuru ER-3400-60J (manufactured by Dainippon Ink and Chemicals) was applied as a thermosetting resin on the surface of the coated paper (basis weight 85 g/rrf) in terms of solid content. , curing agent "Super Beckamine G-821-60J (manufactured by Dainippon Ink & Chemicals) at a solid content of 20% by weight, curing accelerator valatoluenesulfonic acid at 1% by weight, and the modified silicone compound obtained in Reference Example 3% by weight. A thermosetting resin liquid consisting of A laminated sheet of motsu was obtained.On the other hand,
A molded sheet having a woodgrain uneven pattern on the surface of a 50 μm thick polyester sheet was prepared, and this uneven surface was superimposed on the semi-cured resin surface and heated at 120° under a load of 15 kg/cJ.
After heating for 160 seconds at C, aging was performed for 124 seconds at 40°C. Next, the shaped sheet was peeled off to obtain a laminated sheet having the uneven pattern on the surface of the thermosetting synthetic resin and having excellent gloss. This laminated sheet is not only beautiful and interesting, but also has good heat resistance and dimensional stability.
No curling occurred even after the heat treatment at 0°C.

Furthermore, it had excellent releasability and antifouling properties, and was able to withstand repeated use as a decorative sheet for urethane molding. Comparative Example 3 In Example 2, the thermosetting synthetic resin composition was coated with "Kozol ER-". 3400'-60J 78% by weight (solid content)
and “Super Beckamin G-82160J 20% by weight
(solid content) and 1% by weight of balatoluenesulfonic acid, but in the same manner as in Example 2, a laminated sheet having a wood grain pattern and excellent gloss was obtained. Although this laminated sheet had excellent cosmetic properties, heat resistance, dimensional stability, and curl resistance, it did not have antifouling properties and, for example, if it was left in a factory for a month, it would cause flaking, oil smoke, etc. It was very dirty.

[Action/Effect]

As mentioned above, the present invention has a visually beautiful effect due to the difference in gloss, has excellent dimensional stability, does not curl, protects the surface from staining, and maintains its beauty for a long time. A cosmetic sheet that can be used for cosmetic purposes is provided.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing the apparatus used in Example 1. ■... Base material, 2... Thermosetting synthetic resin 3... Gravure roll, 4... Dryer... Shaping sheet, 6... Metal roll 7... Press roll, 8...・Take-up roll

Claims (1)

[Claims] 1. A decorative sheet formed by laminating a thermosetting synthetic resin layer having an uneven pattern on a base material. 2. A decorative sheet formed by laminating a thermosetting synthetic resin layer having an uneven pattern on the surface of a printed and/or vapor-deposited base material. 3. The cosmetic sheet according to claim 1 or 2, wherein the surface of the thermosetting synthetic resin layer having an uneven pattern is printed and/or vapor-deposited. 4. The cosmetic sheet according to claim 1, 2 or 3, wherein a synthetic resin layer containing an antifouling substance is provided on the surface. 5. Coat a thermosetting synthetic resin on a substrate or a printed and/or vapor-deposited substrate, and create unevenness on the surface of the thermosetting synthetic resin when the thermosetting synthetic resin is semi-cured. A method for producing a decorative sheet characterized by providing a pattern. 6. After the molding surface of the molding sheet having an uneven pattern is brought into close contact with the thermosetting synthetic resin surface and the resin is cured,
6. The manufacturing method according to claim 5, wherein an uneven pattern is provided on the surface of the synthetic resin by peeling and removing the shaping sheet. 7. The manufacturing method according to claim 5, wherein an uneven pattern is provided on the surface of the thermosetting synthetic resin using an embossing roll. 8. A method for producing a decorative sheet, which comprises laminating a base material or a printed and/or vapor-deposited base material and a thermosetting synthetic resin sheet having an uneven pattern on its surface. 9. A method for producing a decorative sheet, which comprises printing and/or vapor deposition on a thermosetting synthetic resin layer having an uneven pattern. 10. The manufacturing method according to claims 5 to 9, wherein a synthetic resin layer containing an antifouling substance is provided on the surface.