JP2011104832A - Decorative sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative sheet using a polyolefin base material and transparent acrylic resin and capable of satisfying all of heat seal performance, weatherability and hot water whitening performance. <P>SOLUTION: The decorative sheet is constituted by laminating at least a picture ink layer 2 and a heat seal layer 3 in this order on the surface of a polyolefin base material sheet 1 and performing heat sealing of an transparent acrylic resin sheet 4 on the layer 3. The heat seal layer 3 is made of 50-70 pts.wt. of acrylic polyol and 30-50 pts.wt. of vinyl chloride-vinyl acetate copolymer, and a glass-transition temperature of the acrylic polyol is 80-100°C. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  INDUSTRIAL APPLICABILITY The present invention is used as an interior / exterior material for a building such as a house, a construction material such as a construction material, a joinery, a furniture fixture, an exterior material such as a household equipment or a home appliance, a vehicle interior / exterior material such as an automobile. In particular, the present invention relates to a decorative sheet that is used in a part that requires high weather resistance, such as an exterior material for a house.

  Conventionally, as a decorative sheet for such use, a sheet obtained by printing an appropriate pattern on a polyvinyl chloride resin film has been mainly used. In recent years, taking into account environmental issues, there has been a switch to decorative sheets that use non-chlorine resin films such as polyolefin resins that do not cause the generation of harmful substances such as hydrogen chloride or dioxin during combustion. Progressing.

  Furthermore, an attempt was made to improve weather resistance, surface hardness, contamination resistance, and design by bonding a transparent acrylic resin sheet to the outermost surface of the sheet.

  By the way, when laminating a transparent acrylic resin sheet / polyolefin base sheet with such a decorative sheet, dry lamination with a solvent-based adhesive is generally avoided due to the problem of solvent resistance of the transparent acrylic resin sheet. Bonding with a seal is the main.

  At that time, in order to improve the heat-sealability of the transparent acrylic resin sheet and the polyolefin-based substrate sheet, a heat sealant is applied in advance, but the commonly used vinyl chloride / vinyl acetate copolymer is Adhesiveness is good regardless of the type of sheet to be bonded, but the weather resistance is poor and causes problems such as yellowing. On the other hand, acrylic resin with good adhesiveness with transparent acrylic resin sheet is used with polyolefin base sheet. The heat sealability is poor and the hot water whitening property is a problem.

Japanese Patent Laid-Open No. 2002-370311

  The present invention has been made in order to solve such problems. That is, the subject is to use a polyolefin base material and a transparent acrylic resin, heat sealability, weather resistance, hot water whitening all It is to provide a decorative sheet that can satisfy the requirements.

  The present invention solves the above-mentioned problems, and the invention according to claim 1 is formed by laminating a pattern ink layer / heat seal layer at least in this order on the surface of a polyolefin-based substrate sheet, and further thereon. A decorative sheet formed by heat-sealing a transparent acrylic resin sheet, wherein the heat seal layer comprises 50 to 70 parts by weight of an acrylic polyol and 30 to 50 parts by weight of a vinyl chloride / vinyl acetate copolymer, and the acrylic polyol glass. A transition sheet has a transition point of 80 to 100 ° C.

  The decorative sheet of the present invention comprises a heat seal layer comprising 50 to 70 parts by weight of an acrylic polyol having a glass transition point of 80 to 100 ° C. and 30 to 50 parts by weight of a vinyl chloride / vinyl acetate copolymer. While maintaining the heat sealability of the polyolefin base sheet and transparent acrylic resin sheet, it has excellent weather resistance and can greatly improve the warm water whitening property, which is a weak point unique to acrylic resins. is there.

It is explanatory drawing which shows the structure of the cross section of one Example of the decorative sheet of this invention.

  Hereinafter, the present invention will be described in detail based on the drawings. FIG. 1 shows a cross-sectional structure of one embodiment of the decorative sheet of the present invention. A pattern ink layer 2, a heat seal layer 3, and a transparent resin sheet 4 are provided on a substrate sheet 1.

  As the base material sheet 1 in the present invention, one made of polyolefin resin is used. The polyolefin resin to be used is not particularly limited. For example, polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; polypropylene; ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate Examples thereof include ethylene copolymers such as copolymers and ethylene-α-olefin copolymers, and those obtained by mixing elastomers such as styrene resins with these olefin resins can also be used. Moreover, you may be comprised using the mixed resin which mixed multiple types of different olefin resin uniformly, and what laminated | stacked the sheet | seat which consists of a different olefin resin may be sufficient. The layer thickness is preferably about 50 to 150 μm.

  The base sheet 1 may contain a pigment or the like as a colorant and can be appropriately selected depending on the purpose. For example, azo, phthalocyanine, selenium, dye lake, quinacridone, Organic pigments such as dioxazines; various inorganic pigments such as oxides such as titanium oxide described above, chromic molybdates, sulfides / selenides, ferrocyanides, and calcium carbonate can be used as appropriate. By containing these pigments in the olefin-based resin base sheet, the color of the adherend can be concealed and the saturation of the colored coating layer can be improved. In this case, a white pigment is desirable for concealing the color of the adherend and improving the saturation of the colored coating layer, and titanium oxide is particularly preferably used.

  Furthermore, other additives may be added to the base sheet 1 as long as the sheet moldability and sheet physical properties are not impaired, and examples thereof include a light stabilizer, an ultraviolet absorber, and a heat stabilizer.

  The pattern ink layer 2 in the present invention is not particularly limited in the contents of the pattern ink layer, such as the pattern ink layer forming method, material, and pattern. The pattern ink layer is usually formed using ink by a conventionally known printing method such as gravure printing, silk screen printing, offset printing, gravure offset printing, and ink jet printing. The pattern is, for example, a wood grain pattern, a stone pattern, a grain pattern, a cloth pattern, a tile tone pattern, a brick tone pattern, a crest pattern, a character, a symbol, a geometric pattern, or a combination of two or more of these. . Moreover, you may give weatherproof prescriptions, such as a ultraviolet absorber and a light stabilizer.

  The heat sealant used for the heat seal layer 3 in the present invention comprises 50 to 70 parts by weight of an acrylic polyol having a glass transition point of 80 to 100 ° C. and 30 to 50 parts by weight of a vinyl chloride / vinyl acetate copolymer. To do. The heat seal agent enables adhesion between the polyolefin resin used for the base sheet 1 and the acrylic resin 5 used for the transparent resin sheet 4 described later by a heat laminating method. In this case, the heat-sealing property, weather resistance, and warm water whitening property are improved. If the glass transition point is lower than 80 ° C, warm water whitening is observed, and if the glass transition point is higher than 100 degrees, the heat sealability is deteriorated. Moreover, it can have a suitable weather resistance by containing 50-70 weight part of acrylic polyols.

  As the transparent resin sheet 4 in the present invention, one made of an acrylic resin is used. As the resin to be used, for example, an acrylic acid derivative such as any known acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, acrylic ester or methacrylic ester which has been conventionally used as a surface layer for a decorative sheet is mainly used. Examples of the component include various thermoplastic resins obtained by single or copolymerization. Among them, a resin mainly composed of a methacrylic acid ester such as methyl methacrylate, for example, a long-chain alkyl ester of methacrylic acid such as butyl methacrylate, an acrylic acid ester such as methyl acrylate, methacrylic acid or acrylic acid, etc. Add selected monomers as copolymer components or improve the flexibility and thermoformability by graft copolymerization, block copolymerization or blending of rubber components such as styrene-butadiene rubber or methyl methacrylate-butadiene rubber Thus, the resin etc. which are formed can be used conveniently.

  In addition, various additives such as fillers, weather resistant formulations (benzotriazole-based, benzophenone-based, triazine-based UV absorbers, hindered amine light stabilizers, hindered phenol-based antioxidants, etc. may be added as appropriate. The above resins can be used alone or in combination.

  Using a 70 μm-thick homopropylene resin colored sheet (manufactured by Riken Technos Co., Ltd .: “Rivestar TPO”) as a polyolefin base sheet, a pattern ink layer using a two-component urethane resin binder ink on a gravure printing machine, A mixture of an acrylic polyol having a glass transition point of 100 ° C. (“UC Sealer EXP90717HS-D” manufactured by DIC Corporation) and a vinyl chloride / vinyl acetate copolymer (“V424PCV primer” manufactured by Toyo Ink Manufacturing Co., Ltd.) A heat seal layer using a heat seal agent consisting of (weight ratio 7: 3) was applied. On top of this, a transparent acrylic film (Mitsubishi Rayon Co., Ltd .: “Acryprene 006”) having a thickness of 50 μm was used as a transparent acrylic resin sheet, and these were thermally laminated to prepare a decorative sheet of the present invention.

<Comparative Example 1>
A decorative sheet was obtained in the same manner as in Example 1 except that an acrylic polyol having a glass transition point of 50 ° C. (“UC Sealer EXP90717HS-B” manufactured by DIC Corporation) was used as the acrylic polyol in the heat seal layer. .

<Comparative example 2>
A decorative sheet was obtained in the same manner as in Example 1 except that an acrylic polyol having a glass transition point of 115 ° C. (“UC Sealer EXP90717HS-G” manufactured by DIC Corporation) was used as the acrylic polyol in the heat seal layer. .

<Comparative Example 3>
A decorative sheet was obtained in the same manner as in Example 1 except that the heat seal layer was made of only vinyl chloride / vinyl acetate copolymer.

  For the following three items, the decorative sheets prepared in Examples and Comparative Examples were used for the test.

<Heat sealability>
The prepared decorative sheet was cut out to a width of 1 inch and peeled off at the transparent acrylic resin sheet / polyolefin base sheet interface to confirm the ease of peeling. ○: No peeling or sheet material breakage, Δ: Considerable force required for peeling, ×: Easy peeling

<Hot water whitening>
The prepared decorative sheet was immersed in warm water at 80 ° C. for 24 hours, and the degree of whitening of the heat seal layer was visually confirmed. ○: Almost no whitening is observed, Δ: Whitening is confirmed, ×: Whitening is intense

<Weather resistance>
Metal weather (Daipura Wintes Co., Ltd.) is used. The prepared decorative sheet was subjected to an accelerated weathering test under the following conditions. Test conditions: Illuminance 65 mW / cm2, Light (53 ° C., 70% RH) 20 h, Dew (30 ° C., 95% RH) 4 h. 312h) Implementation. The sample after the test was visually confirmed by paying attention to the yellowing of the heat seal layer.
○: No yellowing, △: Some yellowing is observed, ×: Yellowing is severely yellow The above results are summarized in Table 1.

  The decorative sheet of the present invention can be used particularly for parts requiring high weather resistance such as exterior materials for houses and the like.

DESCRIPTION OF SYMBOLS 1 ... Base material sheet layer 2 ... Pattern ink layer 3 ... Heat seal layer 4 ... Transparent resin sheet

Claims (1)

  In a decorative sheet formed by laminating a pattern ink layer / heat seal layer at least in this order on the surface of a polyolefin base sheet, and further heat-sealing a transparent acrylic resin sheet thereon, the heat seal layer is acrylic. A decorative sheet comprising 50 to 70 parts by weight of a polyol and 30 to 50 parts by weight of a vinyl chloride / vinyl acetate copolymer, wherein the acrylic polyol has a glass transition point of 80 to 100 ° C.