JPH0664109A - Decorative material and manufacture thereof - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a cosmetic material which is excellent in transparency, surface gloss, stain resistance and cold resistance, and which is free from bending whitening. Reliably prevent delamination. [Structure] An A-PET film-like material 1 and a PVC film-like material 2 are laminated via an adhesive layer 3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative material having a high-grade feeling and excellent moldability, and a method for producing the same.

[0002]

2. Description of the Related Art Generally, a decorative board used for construction or the like is constructed by laminating a decorative material on a base material composed of a plywood, a steel plate, an inorganic plate and the like. The decorative material constituting the surface layer of the decorative plate is a single layer of a general-purpose resin, for example, a polyvinyl chloride film, or in order to improve the designability, for example, a transparent polyvinyl chloride having a drawn pattern on the surface. It is a thermocompression laminated body obtained by laminating a film (top film) and a colored polyvinyl chloride film (base film) having a printed pattern on one surface.

[0003]

However, since a polyvinyl chloride film is generally inferior in transparency, when it is used as a top film of a decorative material composed of a laminate such as the latter, the printed pattern of the base film and the Inhibits the coloring effect of the base film.

In addition, a cosmetic material using a polyvinyl chloride film has poor surface gloss and poor stain resistance.
In order to improve this stain resistance, the amount of the plasticizer in the polyvinyl chloride film can be set to zero or can be eliminated by extremely reducing it, but in this case, it becomes a hard film, It becomes difficult to process a curved surface, and whitening by bending causes deterioration of moldability, and further, cold resistance becomes poor.

The present invention has been made in view of the above points, and an object thereof is to specify a film-like material used as a surface layer by using polyvinyl chloride, which is a general-purpose resin, as a base film and Another object of the present invention is to provide a cosmetic material which is excellent in transparency, surface gloss, stain resistance and cold resistance depending on the characteristics of the film-like material used for the surface layer, and which is free from folding whitening. Furthermore, it is to surely prevent delamination.

[0006]

In order to achieve the above object, the first means for solving the problems of the present invention is to provide a film-like material made of amorphous polyethylene terephthalate and a film-like material made of polyvinyl chloride as an adhesive. It is characterized in that they are laminated through layers.

A second solving means of the present invention is characterized in that, in the case of the first solving means, the adhesive layer is composed of a polyester urethane two-pack type adhesive.

A third means for solving the problems of the present invention is the same as the first means for solving the problems, wherein the film-like material made of polyvinyl chloride is contained in an amount of 20 parts by weight or less of a plasticizer per 100 parts by weight of polyvinyl chloride. It is characterized by

A fourth solution of the present invention is the same as the first solution, in which a film-like product made of amorphous polyethylene terephthalate is a copolymer of polyethylene terephthalate and isophthalic acid or polyethylene terephthalate and cyclohexanediol. It is characterized by being composed of a copolymer.

In a fifth means for solving the problems of the present invention, first, an adhesive is applied to a film material made of polyvinyl chloride. Next, the film-like material made of polyvinyl chloride coated with this adhesive is laminated at a temperature of 70 to 90 ° C. with a film-like material made of amorphous polyethylene terephthalate, and then rapidly cooled. To do.

In the sixth means for solving the problems of the present invention, first, a film-like material made of amorphous polyethylene terephthalate is coated with an adhesive composed of toluene or a mixed solvent of 50% by weight or less of ketone in toluene. Next, a film-like material made of amorphous polyethylene terephthalate coated with this adhesive is laminated at a temperature of 70 to 90 ° C. on a film-like material made of polyvinyl chloride, and then rapidly cooled. To do.

[0012]

With the above-mentioned structure, in the first to fourth means for solving the problems of the present invention, the film-like material made of amorphous polyethylene terephthalate and the film-like material made of polyvinyl chloride are laminated via the adhesive layer. Because
If a film-like material composed of the above-mentioned amorphous-polyethylene terephthalate is used as the surface layer, it will be excellent in transparency, surface gloss and stain resistance from its characteristics.
It gives a high-class feeling. Further, it has excellent cold resistance, does not fold and whiten, and facilitates curved surface processing. Further, the creep is large, and the shrinkage after stretching during curved surface processing is small, so that delamination does not occur.

In the fifth and sixth means for solving the problems of the present invention, when laminating a film-shaped material made of amorphous polyethylene terephthalate and a film-shaped material made of polyvinyl chloride, the adhesive is a film-shaped material made of polyvinyl chloride. Or a film-shaped product made of amorphous polyethylene terephthalate, and the film-shaped product coated with the adhesive is heated to 70 to 90 ° C., both are laminated and rapidly cooled. When the adhesive is applied to the film-like material made of amorphous polyethylene terephthalate, an adhesive made of toluene or a mixed solvent of 50% by weight or less of ketone in toluene is used. From this, it is possible to reliably prevent the film-like material made of amorphous polyethylene terephthalate from being crystallized, that is, whitened, by heating and the solvent in the adhesive.

[0014]

Embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 shows a decorative material A according to an embodiment of the present invention, in which 1 is a colorless transparent or colored transparent layer constituting the surface layer, having a thickness of 25 to 400 μm (preferably 100 to 400 μm).
m) a film-like material (hereinafter abbreviated as A-PET film-like material) made of amorphous-polyethylene terephthalate (hereinafter abbreviated as A-PET). The A
-PET film-like material 1 is an amorphous material that has not been biaxially stretched, and its properties are excellent in transparency, surface gloss and stain resistance, and also in cold resistance and when curved surface processing is performed. It also has the characteristic that it does not turn white. Further, since the A-PET film-like material 1 has a large creep, it has a characteristic that it does not shrink much even after being stretched during curved surface processing and does not cause delamination even when laminated on the other side. This A-PET film material 1
Is, for example, A-PET alone (homopolymer), A-PE
Uniaxial or biaxial extrusion of a copolymer obtained by copolymerizing 0 to 30 wt% of T and isophthalic acid or a copolymer obtained by copolymerizing 0 to 30 wt% of A-PET and cyclohexanediol. 230 from the machine T-die
Immediately after being extruded at 280 ° C. to form a film, the film was rapidly cooled to 50 ° C. or less with a cooling roll to be non-crystallized.

Reference numeral 2 denotes a film-like material (hereinafter referred to as PVC film-like material) made of colored polyvinyl chloride having a thickness of 30 to 1000 μm (preferably 50 to 800 μm). Is 3 to 30
It is laminated on the A-PET film-like material 1 with an adhesive layer 3 of μm (preferably 5 to 10 μm) interposed. The PVC film material 2 contains 20 parts by weight or less of a plasticizer such as DOP with respect to 100 parts by weight of polyvinyl chloride, thereby imparting flexibility to the PVC film material 2 and facilitating curved surface processing. At the same time, bending whitening is prevented to improve moldability and also cold resistance.

The adhesive constituting the adhesive layer 3 is, for example, a polyester urethane two-component adhesive or the like, at a temperature at which the A-PET film material 1 does not crystallize (for example, 70 to 90 ° C.). Select one that works in. For example, polyester polyol (PTMEG1000 manufactured by Hitachi Chemical Co., Ltd.) and polyisocyanate (MDI, TD)
I, IPDI) at a ratio of about 2: 1 by stirring and mixing to react with the main agent, polyisocyanate (toluene diisocyanate, trimethylolpropanate adduct body Sumidule L Sumitomo Bayer Urethane Co., Ltd.)
(Manufactured by Mitsui Chemicals Co., Ltd.) in a ratio of 15: 1, or polyethylene terephthalate as a main component in which an aliphatic divalent carboxylic acid such as sebacic acid or an aliphatic polyether is copolymerized in an amount of 20 to 30 wt% (Vylon 30SS.
Toyobo Co., Ltd.), using polyisocyanate (as listed above) as a curing agent, and the curing agent is 20: 1 with respect to the main agent.
It is a mixture of the ratios.

Therefore, in the decorative material A of the present invention, A-
By using the PET film material 1 as the surface layer, it is possible to impart physical properties excellent in transparency, surface gloss and stain resistance from its characteristics, and to give a high-grade feeling. Further, since it has excellent cold resistance and does not whiten by bending, curved surface processing can be easily performed. Furthermore, since the creep is large and the shrinkage after stretching is small during curved surface processing, delamination can be prevented.

The decorative material A having the above structure is
A polyester-based urethane two-component adhesive is applied to the A-PET film material 1, and then the A-PET film material 1 coated with the adhesive is heated to 70 to 90 ° C. to form a PVC film material. It is manufactured by stacking 2 and then quenching. At this time, the solvent of the adhesive used is
Other than the ester type (ethyl acetate etc.) and the ketone type (methyl ethyl ketone etc.) are preferable, and toluene is particularly preferable. When it is unavoidable to use ketones, 50% by weight
Below. This is because the A-PET film material 1 is crystallized and whitened by the solvent, and is for preventing this. However, if a method of applying an adhesive to the PVC film-like material 2 and laminating it with the A-PET film-like material 1 is adopted, even if an ester-based or ketone-based solvent is used, A-PET
The film-shaped material 1 does not crystallize. Also, PVC
The reason why the film material 2 is heated to 70 to 90 ° C. is that the A-PET film material 1 is crystallized (whitened) when heated to a temperature higher than this. The drying time after applying the adhesive is preferably about 30 seconds to 2 minutes.

Therefore, according to the manufacturing method of the present invention, it is possible to reliably prevent the A-PET film-like material 1 from being heated and crystallized by the solvent in the adhesive, that is, whitening during lamination.

Next, the data of the decorative materials of the present invention are shown in Tables 1 and 2 together with the comparative examples. The decorative materials of Examples of the present invention and Comparative Examples were manufactured in the following manner.

[Cosmetic materials in Table 1] <Invention Example 1> As an A-PET film, a homopolymer, Dyanite PA-500 (manufactured by Mitsubishi Rayon Co., Ltd.) was used, and this was used in a 90 mm twin-screw extruder. It was extruded with a T-die at a die temperature of 280 ° C. 50 this
It was cast on a cooling roll whose temperature was adjusted to ℃, and was pulled out and wound while cooling. The thickness was 80 μm. PVC film is plasticizer 5phr, thickness 100μm
It is a product of calender rolling. A-PE
A polyester two-component urethane adhesive (manufactured by KU2N Konishi Co., Ltd.) was used as an adhesive for bonding the T film and the PVC film together. This adhesive is applied to an A-PET film by a reverse coater with a thickness of 10 μm, dried, and then P
It was attached to a VC film. At the time of this bonding, P
While heating the VC film to 80 ° C., the temperature of the pressure bonding roll was also set to 80 ° C.

<Invention Example 2> The manufacturing method is the same as in Invention Example 1. PVC film has a plasticizer of 20 phr and a thickness of 10
The thickness of the A-PET sheet is 400 μm.

<Invention Example 3> The manufacturing method is the same as in Invention Example 1. PVC sheet plasticizer 5 phr, thickness 300μ
m, and the thickness of the A-PET sheet is 400 μm.

<Invention Example 4> In the manufacturing method, the die temperature is 250.
The same as Example 1 of the present invention except that the temperature was set to ° C. The plasticizer of PVC film is 5 phr and the thickness is 100 μm.
-PET film thickness is 80 μm. A-
Dyanite, which is a copolymer as a PET film
KR-4163 (manufactured by Mitsubishi Rayon Co., Ltd., isophthalic acid 10% copolymerization) was used.

Comparative Example 1 A PVC film and a PVC film were heat-laminated, and one PVC film surface was mirror-finished with a glazing roll. Both films have a plasticizer of 5 phr and a thickness of 100 μm.

<Comparative Example 2> A PVC film and a PVC film were heat-laminated, and one PVC film surface was mirror-finished with a glazing roll. Both films have a plasticizer of 20 phr and a thickness of 100 μm.

<Comparative Example 3> A modified PMMA (polymethylmethacrylate) film (Sanduren film manufactured by Kanegafuchi Chemical Co., Ltd.) and a PVC film were heat laminated, and the surface of the modified PMMA film was mirror-finished with a glazing roll. did. Modified PMMA film thickness is 75μm, PVC
The plasticizer of the film is 5 phr and the thickness is 100 μm.

<Comparative Example 4> Biaxially stretched PET film (Lumirror # 38F92 manufactured by Toray Industries, Inc., corona treated product)
And a PVC film were dry-laminated using a polyester two-component urethane adhesive in the same manner as in Inventive Example 1. The thickness of the biaxially stretched PET film is 75 μm, P
VC film plasticizer 5 phr, thickness 100 μm.

<Comparative Example 5> As an A-PET film, a homopolymer, Dyanite PA-500 (manufactured by Mitsubishi Rayon Co., Ltd.) was used, and this and a PVC film were combined with a one-component polyether adhesive (Chemit KS102 Toray ( (Manufactured by K.K.) was used for dry lamination in the same manner as in Inventive Example 1. A-PET film thickness is 80μ
m, PVC film plasticizer 5 phr, thickness 100 μm.

[Decorative Material of Table 2] <Invention Example 5> The manufacturing method is the same as in Invention Example 1. A-P
The thickness of the ET sheet (Homopolymer A-PET AVD Mineron Kasei Co., Ltd.) is 400 μm, the plasticizer of the PVC film is 5 phr, and the thickness is 200 μm.

<Invention Example 6> The manufacturing method is the same as in Invention Example 1. The thickness of the A-PET film (the same as in Inventive Example 5) is 200 μm, the plasticizer of the PVC sheet is 5 phr, and the thickness is 400 μm.

<Invention Example 7> The manufacturing method is the same as in Invention Example 1. The thickness of the A-PET film (the same as in Inventive Example 5) is 200 μm, the plasticizer of the PVC sheet is 5 phr, and the thickness is 600 μm.

<Invention Example 8> The manufacturing method is the same as in Invention Example 1. The thickness of the A-PET film (the same as that of Inventive Example 5) is 200 μm, the plasticizer of the PVC sheet is 5 phr, and the thickness is 800 μm.

<Invention Example 9> The manufacturing method is the same as in Invention Example 1. The thickness of the A-PET film (the same as that of Inventive Example 5) was 200 μm, and the plasticizer of the PVC film was 20 phr.
, And the thickness is 200 μm.

<Comparative Example 6> An acrylic film (Acryprene HBS manufactured by Mitsubishi Rayon Co., Ltd.) and a PVC sheet were heat laminated, and the surface of the acrylic film was mirror-finished with a glazing roll. Thickness of acrylic film is 75μm, plasticizer of PVC sheet is 5phr, thickness 600
μm.

<Comparative Example 7> Biaxially stretched PET film (Lumirror # 38F92 manufactured by Toray Industries, Inc., corona treated product)
And a PVC sheet were dry laminated using a polyester two-component urethane adhesive in the same manner as in Inventive Example 1. Biaxially stretched PET film has a thickness of 38 μm, PV
The C sheet has a plasticizer of 5 phr and a thickness of 600 μm.

<Comparative Example 8> Plasticizer 5 phr, thickness 200 μ
m PVC film, plasticizer 5 phr, thickness 400 μm
Was heat-laminated, and the surface of the PVC film was mirror-finished with a glazing roll.

[Vacuum Forming Method] As shown in FIGS. 2 and 3, the base material 5 coated with the adhesive 4 is set on the surface plate 7 via the jig 6, and the present invention example and The decorative material A of the comparative example is arranged, the decorative material A is pressed from above by the silicone rubber sheet 8 under the following vacuum press conditions, and the pressure is reduced through the pores 9, 9, ... Formed on the surface plate 7. By press forming.

<Vacuum press conditions> Molding machine: Vacuum press machine (made by SAVE Co., Ltd.) Adhesive: Urethane two-component water-based adhesive (CVC550 Konishi Co., Ltd.) Base material: MDF (R section shape 5R, 10R) ) Molding conditions Pressure: 3.0 kg / cm ² (Table 1) 3.5 kg / cm ² (Table 2) Press temperature: The temperature of the silicone rubber sheet was measured with a thermo label.

Press time: 150 seconds Preheating time: 10 seconds (Table 1) 20 seconds (Table 2) Pressure reduction: 760 mmHg [Evaluation of shrinkage after molding] Decorative material A by vacuum press molding
After the base material 5 and the base material 5 are attached to each other, as shown in FIG. 4, a cut is made in the decorative material A, and the material is left in a 60 ° C. oven for 48 hours, then taken out of the oven and marked with ◯ shown in FIG. The shrinkage amount of the surrounding edge portion and the opening amount of the corner portion surrounded by ◯ shown in FIG. 6 were measured based on the following formulas.

Shrinkage amount of edge portion = (A + B + C + D) / 4 Opening amount of corner portion = (E + F + G + H) / 4

As is clear from the data in Tables 1 and 2, the inventive examples are superior to the comparative examples in surface gloss, vacuum formability, gloss, bent whitening and cold resistance. I understand.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

As described above, according to the present invention according to claims 1 to 4, since the A-PET film-like material and the PVC film-like material are laminated via the adhesive layer, the A-P
Depending on the characteristics of the ET film material, the transparency, surface gloss and stain resistance can be made excellent, and a high-class feeling can be obtained. In addition, it is excellent in cold resistance, does not whiten by bending, and facilitates curved surface processing. Further, the creep is large, and the shrinkage after being stretched at the time of processing the curved surface can be reduced to prevent delamination.

In the method of the present invention according to claims 5 and 6, after the adhesive is applied to the PVC film or the A-PET film, the adhesive-coated film is heated to 70 to 90 ° C. In the heated state, both are laminated and then rapidly cooled. Then, as the adhesive agent applied to the A-PET film-like material, toluene or a mixed solvent of 50% by weight or less of ketone in toluene is used. Therefore, it is possible to reliably prevent heating of the A-PET film and crystallization due to the solvent in the adhesive, that is, whitening.

[Brief description of drawings]

FIG. 1 is a vertical sectional view of a decorative material.

FIG. 2 is a diagram illustrating a procedure of vacuum press molding.

FIG. 3 is a vertical cross-sectional view showing a state in which a decorative material is attached to a base material by vacuum press molding.

FIG. 4 is a view showing a cut portion in a decorative material after molding.

FIG. 5 is a diagram showing measurement points of an amount of shrinkage of an edge portion in a decorative material after molding.

FIG. 6 is a diagram showing measurement points of a corner portion opening amount in a molded material after molding.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 A-PET film-like material (film-like material made of amorphous polyethylene terephthalate) 2 PVC film-like material (film-like material made of polyvinyl chloride) 3 Adhesive layer A Decorative material

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location // C09J 175/06 JFB 8620-4J

Claims (6)

[Claims] 1. A cosmetic material comprising a film-like material made of amorphous polyethylene terephthalate and a film-like material made of polyvinyl chloride, which are laminated via an adhesive layer. 2. The decorative material according to claim 1, wherein the adhesive layer is composed of a polyester urethane two-component adhesive. 3. The cosmetic material according to claim 1, wherein the film-shaped material made of polyvinyl chloride contains 20 parts by weight or less of a plasticizer with respect to 100 parts by weight of polyvinyl chloride. 4. The film-like material made of amorphous polyethylene terephthalate is composed of a copolymer of polyethylene terephthalate and isophthalic acid or a copolymer of polyethylene terephthalate and cyclohexanediol. Cosmetic material. 5. Amorphous polyethylene is obtained by applying an adhesive to a film made of polyvinyl chloride and then heating the film made of polyvinyl chloride coated with the adhesive to 70 to 90 ° C. A method for producing a decorative material, which comprises rapidly laminating a film of terephthalate and then cooling it. 6. An amorphous-polyethylene terephthalate film-like material is coated with an adhesive consisting of toluene or a mixed solvent of 50 parts by weight or less of ketone in toluene, and then the amorphous-formation coated with this adhesive.
A film made of polyethylene terephthalate
A method for producing a decorative material, comprising laminating a film made of polyvinyl chloride in a state of being heated to 0 to 90 ° C. and then rapidly cooling.