JP2000071401A - Laminated decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a decorative laminated sheet with high surface hardness by providing an adhesive layer on the upper part of a completely amorphous polyester layer and also a crystalline polyester layer on the upper part of the adhesive layer as a non-vinyl chloride sheet which maintains the design properties of the decorative laminated sheet including a vinyl chloride sheet. SOLUTION: An adhesive of a two-pack curing type such as a polyester polyol and an isocyanate is applied to the upper part of a completely amorphous polyester layer which is composed mainly of terephthalic acid or dimethylterephthalic acid and 1,4-cyclohexadimethanol and ethylene glycol and obtained by a polycondensation reaction through an esterification reaction. In addition, the completely amorphous polyester layer does not give rise to the deterioration of physical properties by recrystallization, even when a reheating treatment is performed and in such case, is completely free from a crystalline component. Further, a crystalline biaxially oriented polyester resin sheet is formed on the upper part of the adhesive layer. Each of these layers is manufactured as a decorative sheet of a desired size and a desired thickness using a calender, a T-die extruder or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated decorative sheet in which a completely amorphous polyester layer and a crystalline polyester layer are laminated with an adhesive.
The present invention relates to a laminated decorative sheet that enhances commercial value by bonding an adhesive to a surface of a steel plate or a plywood in the furniture field and to a surface of a resin in the light electric field.

[0002]

2. Description of the Related Art Conventionally, this type of laminated decorative sheet has been printed between a transparent crystalline biaxially stretched polyester sheet and a vinyl chloride sheet due to adhesiveness, printability, transparency, mechanical strength, and workability. Generally, a layer provided with a layer is used (for example, JP-A-9-109329). Vinyl chloride sheet is not only excellent in adhesiveness and printability, but also
Since the coloring property is also good, the vinyl chloride sheet is colored,
By combining with a printing layer, it is possible to develop a product with high designability. The transparent crystalline biaxially stretched polyester sheet is the outermost sheet, so it can be used for protection, the printed pattern can be seen from the table, and the surface state of the polyester sheet is mirrored and grained In some cases, various patterns can be appropriately selected, so that it is possible to develop a product having a high design quality.

[0003]

However, the current market demands a replacement of vinyl chloride sheets with non-vinyl chloride sheets. Unless the surface hardness, which cannot be obtained with a vinyl chloride sheet, is further improved, and the scratching of the surface of the laminated decorative sheet is not further eliminated, the use of high value-added and highly designable architectural components, furniture, and weak electric components is a problem. was there. Accordingly, an object of the present invention is to maintain the design of a laminated decorative sheet including a conventional vinyl chloride sheet,
It is an object of the present invention to realize a non-vinyl chloride sheet, which is a demand from the market, and to provide a laminated decorative sheet having a high surface hardness, which cannot be achieved by the conventional technology.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the following means can be used to solve the problems, and have completed the present invention. The invention according to claim 1 is characterized in that (A) an adhesive layer is provided on top of the completely amorphous polyester layer;
A laminated decorative sheet comprising (C) a crystalline polyester layer provided on an adhesive layer. In the invention according to claim 2, the (C) crystalline polyester layer is transparent, and the printing layer is provided between the (C) crystalline polyester layer and the (B) adhesive layer. It is a laminated decorative sheet. The invention according to claim 3 is the laminated decorative sheet according to claim 1 or 2, wherein the (C) crystalline polyester layer is transparent, and the (C) crystalline polyester layer is provided with an anti-scratch coating on top of the crystalline polyester layer. It is. According to a fourth aspect of the present invention, an adhesive is applied to the lower surface of the (A) completely amorphous polyester layer of the laminated decorative sheet according to any one of the first to third aspects, and a surface of a steel plate, a plywood, and a resin molded product is applied. A composite product obtained by bonding to any of the above.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION (A) The completely amorphous polyester layer does not cause a decrease in physical properties due to recrystallization even if subjected to heat treatment again, and has no crystalline component. The crystallinity in the present invention means the crystallinity measured by the DSC method (JIS K7121). (A) The completely amorphous polyester layer is preferably produced by a polycondensation reaction through a esterification reaction using, for example, terephthalic acid or dimethyl terephthalic acid, and 1,4-cyclohexadimethanol and ethylene glycol as main components. used. For the completely amorphous polyester layer (A), a copolymer type completely amorphous polyester obtained by copolymerizing the third component can be used in addition to the above, and this type is preferable in the present invention. As the third component, 1,4-
Preferably, cyclohexadimethanol or isophthalic acid is used, and more preferably, the diol component is composed of two or more types. Most preferably, the carboxylic acid component is terephthalic acid, and the diol component is ethylene glycol. Those having 50 to 99 mol% and 1 to 50 mol% of 1,4-cyclohexadimethanol are preferred.
In particular, ethylene glycol 60-80 mol% and 1,
Those having 20 to 40 mol% of 4-cyclohexadimethanol are preferred. The method for producing a completely amorphous polyester resin is already widely known in the art, and is disclosed in, for example, US Pat. No. 5,340,907.
(A) The lower limit of the thickness of the completely amorphous polyester layer is 1
0 μm or more, preferably 20 μm or more, more preferably 50 μm or more, and the upper limit is 1000 μm or less, preferably 300 μm or less, more preferably 200 μm or less.
It is as follows. If the thickness is less than 10 μm, the layer is liable to be broken due to lack of strength.

For the crystalline polyester layer (C), for example, a sheet of a crystalline biaxially stretched polyester resin can be used. This sheet is manufactured by a sequential biaxial stretching method using a tenter method using a polyester resin obtained by condensation polymerization of terephthalic acid and ethylene glycol as a raw material. The characteristics of the polyester resin sheet are as follows: (1) excellent mechanical properties; (2) wide operating temperature range; (3) little change in dimensions and temperature and humidity; (4) high transparency; and (5) thin film film. Manufacture is possible; and so on. (C) The lower limit of the thickness of the crystalline polyester layer is 3
μm or more, preferably 10 μm or more, more preferably 20 μm or more, and the upper limit is 250 μm or less, preferably 100 μm or less, more preferably 50 μm or less. If it is thinner than 3 μm, it will not be strong and easily broken.
If it exceeds 0 μm, wrinkles are likely to occur when laminating, and workability is poor.

The adhesive layer (B) is provided for fixing the (A) completely amorphous polyester layer and the (C) crystalline polyester layer exposed on the surface. (B) The thickness of the adhesive layer has a lower limit of 1 μm or more, preferably 2 μm or more, and an upper limit of 100 μm or less, preferably 60 μm or less, and more preferably 30 μm or less. When the adhesive layer is thinner than 1 μm, the sheet is easily peeled. Also 100 μm
When it exceeds, the laminated decorative sheet may become uneven in the drying process. The adhesive used is a two-component curing type of polyester polyol and isocyanate, a two-component curing type of urethane polyol and isocyanate, a two-component curing type of polyamide polyol and isocyanate, and a one-component curing type of polyester polyol, urethane polyol and polyamide polyol. And the like. In addition,
Each sheet of the (A) completely amorphous polyester layer and the (C) crystalline polyester layer is subjected to a corona treatment, an ozone treatment, or the like to make the surface of the sheet active to improve the adhesiveness with the adhesive. It is good to keep.

Each of the above layers can be formed into a sheet having a desired size and thickness by using a calendering machine, a T-die extruder, or the like. The thickness of the resulting laminated decorative sheet has a lower limit of 14 μm or more, preferably 40 μm or more, more preferably 70 μm or more, and an upper limit of 1350.
μm or less, preferably 410 μm or less, and more preferably 280 μm or less. If the thickness is less than 14 μm, it is easy to cut, and if it exceeds 1350 μm, the laminated decorative sheet may be wrinkled.

Further, by making the (C) crystalline polyester layer transparent and providing a printed layer on the back surface thereof, it is possible to produce a laminated decorative sheet which is rich in change and excellent in design. As the printing ink, for example, urethane resin,
Printing using an acrylic resin, a polyester melamine resin, a vinyl chloride-vinyl acetate copolymer, or an ink using a blend of a vinyl chloride resin and a vinyl acetate resin, using a known printing technique. Can be.

Further, in order to increase the surface hardness of the laminated decorative sheet and further enhance the scratch resistance of the product, a coating for preventing scratching may be provided on the surface of the (C) crystalline polyester layer. This coating is preferably a coating obtained by coating a one-part or two-part curing type, preferably an ultraviolet curing type paint, and further irradiating with ultraviolet rays to cure the coating. The UV-curable paint is not particularly limited. For example, a monomer having a polyfunctional group
Parts by weight, 12 to 18 parts by weight of a monomer having a monofunctional group, 5 to 10 parts by weight of a photoinitiator, 0.1 of a silicone additive
Parts by weight and 100 to 200 parts by weight of a solvent. This coating is preferably applied and cured by a gravure method or the like so as to obtain a mirror-like finish. As a method other than the gravure method, there are a reverse coat, a Mayer bar, and a knife coater.

An adhesive is applied to the lower surface of (A) the completely amorphous polyester layer of the laminated decorative sheet, and the steel sheet, the plywood,
The composite product adhered to one of the surfaces of the resin molded product is useful as a product with high designability in various fields.

[0012]

The present invention will be further described below with reference to examples and comparative examples. (Example 1) A transparent crystalline biaxially stretched polyester sheet having a thickness of 25 µm (Toray Industries, Ltd .: S-50)
Solvent type two-part adhesive (Toyo Morton Co., Ltd. AD52)
7 / CATHY-92) was applied by a gravure coating method. After the application, the solvent was evaporated and scattered in a drying furnace to form an adhesive layer (thickness: 2.5 ± 0.5 μm). 7 drying ovens
The temperature was set at 5 ° C. to 85 ° C., and the sample passed through the floating drying zone for 18 to 22 seconds. After the adhesive layer is dried, the adhesive layer side of the crystalline biaxially stretched polyester sheet and a 100 μm-thick completely amorphous polyester sheet (SET286 F, manufactured by Riken Vinyl Industry Co., Ltd.)
Z13332, 0% crystalline component) and heat-sealed with a metal roll. Thereafter, the sheet was wound up and left at room temperature 40 ± 2 ° C. for 72 hours to cure the adhesive, thereby obtaining a product. (Note) Completely amorphous polyester sheet (RIKEN Vinyl Industrial Co., Ltd. SET286 FZ13332, crystalline component 0)
%) Is as follows. Composition: copolymer type Glycol component: 70 mol% of ethylene glycol and 30 mol% of 1,4-cyclohexanedimethanol Dicarboxylic acid component: terephthalic acid Crystal component: 0%

(Example 2) Transparent crystalline biaxially stretched polyester sheet having a thickness of 25 µm (Toray Co., Ltd .: S-50)
Was provided with a printing layer 1.5 ± 0.5 μm (Crystal Marble, Nippon Decor Co., Ltd.) on one side of the film and cured. Other than this, Example 1 was repeated.

Example 3 Transparent crystalline biaxially stretched polyester sheet having a thickness of 25 μm (Toray Co., Ltd .: S-50)
A UV-curable paint (Clear) (manufactured by Riken Vinyl Industry Co., Ltd.) having a thickness of 2 to 3 μm dry base) is applied to the surface of the substrate by a gravure coating method, and then the drying is performed in the same manner as in the drying of the adhesive in Example 1. After drying, a high-pressure mercury lamp (160 w) was fixed at a distance of 10 to 15 cm from this sheet, and irradiated with ultraviolet rays for 0.5 to 1.5 seconds to cure the coating. Other than this, Example 1 was repeated.

(Comparative Example 1) The completely amorphous polyester sheet used in Example 1 (SET2 manufactured by Riken Vinyl Industry Co., Ltd.)
86 FZ13332) instead of a 100 μm-thick polyvinyl chloride sheet (BS12, Riken Vinyl Industry Co., Ltd.)
Example 1 was repeated except that K) was used.

Comparative Example 2 A completely amorphous polyester sheet used in Example 2 (SET2 manufactured by Riken Vinyl Industry Co., Ltd.)
86 FZ13332) instead of a 100 μm-thick polyvinyl chloride sheet (BS12, Riken Vinyl Industry Co., Ltd.)
Example 2 was repeated except that K) was used.

(Comparative Example 3) The completely amorphous polyester sheet used in Example 3 (SET2 manufactured by Riken Vinyl Industry Co., Ltd.)
86 FZ13332) instead of a 100 μm-thick polyvinyl chloride sheet (BS12, Riken Vinyl Industry Co., Ltd.)
Example 3 was repeated except that K) was used.

(Comparative Example 4) The completely amorphous polyester sheet used in Example 1 (SET2 manufactured by Riken Vinyl Industry Co., Ltd.)
86 FZ13332) instead of a polypropylene sheet having a thickness of 100 μm (RIKEN Vinyl Industrial Co., Ltd. OST-
Example 1 was repeated except that 4, BE017) was used.

Various physical properties were tested on the laminated decorative sheets obtained in the above Examples and Comparative Examples by the methods shown in Tables 1 and 2 below. The obtained results are also shown.

[0020]

[Table 1]

[0021]

[Table 2]

[0022]

According to the present invention, it is possible to realize a non-vinyl chloride sheet, which is demanded from the market, while maintaining the design property of the laminated decorative sheet including the conventional vinyl chloride sheet, and it cannot be achieved by the conventional technology. A laminated decorative sheet having a high surface hardness can be provided.

Continued on the front page F-term (reference) 4F100 AB03D AK01D AK15 AK15J AK22 AK22J AK25 AK41A AK41B AK42 AK51 AK51G AP02D AR00C BA02 BA03 BA04 BA07 BA10A BA10C BA10D BA13 CB00 CC03 EH01 GB08 JB12BJJB08

Claims (4)

[Claims] (1) An adhesive layer (B) is provided on a completely amorphous polyester layer, and a crystalline polyester layer (C) is provided on the adhesive layer (B). And laminated decorative sheet. 2. The laminated makeup according to claim 1, wherein (C) the crystalline polyester layer is transparent, and a printing layer is provided between the (C) crystalline polyester layer and (B) the adhesive layer. Sheet. 3. The laminated decorative sheet according to claim 1, wherein (C) the crystalline polyester layer is transparent, and a coating for preventing scratching is provided on the (C) crystalline polyester layer. 4. An adhesive is applied to the lower surface of the (A) completely amorphous polyester layer of the laminated decorative sheet according to any one of claims 1 to 3, and an adhesive is applied to any of a steel plate, a plywood, and a resin molded product surface. A composite product obtained by bonding crab.