JP2010076222A - Decorative sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative sheet excellent in a scratching resistance (particularly, resistance properties to a high load in a pencil hardness test or the like), and at the same time excellent also in lapping processing suitability. <P>SOLUTION: The decorative sheet comprises a bonding of an amorphous polyester resin layer on a thermoplastic resin substrate. A biaxially stretched polyethylene terephthalate sheet is bonded on the amorphous polyester resin layer. A picture design layer 2 is arbitrarily provided on the thermoplastic resin substrate 1, the amorphous polyester resin layer 3 is bonded on the biaxially stretched polyethylene terephthalate sheet 4, and a surface protective layer 5 is provided arbitrarily on the surface. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a decorative sheet that is used to improve the surface design of kitchen doors, bathroom interiors, and the like by bonding to a base such as a wood base, an inorganic base, a synthetic resin base, and a metal base.

  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, in addition to this, taking into account environmental issues, decorative sheets using 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. Has also been developed and is becoming widely used.

  By the way, the above-described uses such as kitchen doors and bathroom interiors are required to have remarkably superior high-definition properties compared to other ordinary uses. The above-described polyvinyl chloride resin films and polyolefin-based resin films are required. Can not cope. This is because the polyvinyl chloride resin film is soft and has poor thickness accuracy and surface smoothness, and the polyolefin resin has high surface haze due to its high crystallinity, and both are poor in scratch resistance. .

  Therefore, as a decorative sheet for uses requiring high definition, conventionally, a mirror-type decorative sheet having a configuration in which a polyester resin film having excellent transparency, surface smoothness, scratch resistance, and the like is arranged on the surface, It is mainly used. Specifically, a transparent polyester system in which an appropriate pattern is printed on the back surface in advance through an adhesive on the surface of a concealing base sheet made of a colored polyvinyl chloride resin film or a colored polyolefin resin film. A resin film is laminated.

Furthermore, an attempt was made to further improve the scratch resistance by laminating an ionizing radiation curable surface protective layer on the surface portion. Further, as the total thickness of the decorative sheet is increased, it is possible to prevent duck of the adhesive that occurs when the decorative sheet is bonded to the base material, and it is possible to further prevent high-load dents. However, as the total thickness of the sheet is thicker or the PET thickness is thicker, the bending elasticity of the sheet by the lapping process becomes stronger, and there is a problem that the R processing of the end portion becomes difficult.
JP 57-165259 A JP-A-4-238026 JP-A-10-258488

  The present invention solves the above-described problems, and provides a decorative sheet that has excellent scratch resistance (particularly resistance to high loads such as a pencil hardness test) and is also excellent in lapping processability.

  The present invention solves this problem. That is, the invention according to claim 1 is a decorative sheet obtained by laminating a non-crystalline polyester resin layer on a thermoplastic resin substrate. A decorative sheet characterized in that a biaxially stretched polyethylene terephthalate sheet is bonded onto a layer.

  According to the invention described in claim 1 of the present invention, by attaching two layers of an amorphous polyester resin layer and a biaxially stretched polyethylene terephthalate sheet on a thermoplastic resin substrate, scratch resistance (especially pencil hardness test etc. It is a decorative sheet that is excellent in resistance to high loads) and is also excellent in suitability for lapping.

  Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 shows the cross-sectional shape of one embodiment of the decorative sheet of the present invention. A pattern layer 2 is appropriately provided on the thermoplastic resin substrate 1, an amorphous polyester resin layer 3, a biaxially stretched polyethylene terephthalate sheet 4 are bonded together, and a surface protective layer 5 is appropriately provided on the surface.

  As the thermoplastic resin base material 1 in the present invention, a conventionally known polyvinyl chloride resin or polyolefin resin can be used, and is not particularly limited. It is preferable to use a polyolefin resin that does not cause generation of harmful substances such as hydrogen chloride or dioxin. The thickness of the thermoplastic resin substrate 1 is not particularly limited as long as the total thickness is in a range described later and is balanced with other layers, but is preferably about 80 to 120 μm.

  For the thermoplastic resin substrate 1, for example, a colorant, a filler, an antioxidant, a Shiga line-of-sight absorber, a light stabilizer, a heat stabilizer, a plasticizer, a lubricant, an antistatic agent, a flame retardant, an antibacterial agent, if necessary. One or more selected from various additives such as an agent and an antifungal agent can also be added. In particular, when the target decorative sheet is required to conceal the surface color or defects of the substrate to be adhered, for example, titanium oxide, zinc oxide, iron oxide, carbon black or the like is applied to the thermoplastic resin substrate 1. It is desirable that the thermoplastic resin substrate 1 be colored and concealed by adding a concealing color pigment.

  The pattern layer 2 provided as appropriate is provided by printing or the like for the purpose of providing a desired design pattern. There are no restrictions on the type, composition material, formation method, etc. of the pattern. In general, the pattern is, for example, a wood grain pattern, a stone pattern, a cloth pattern, an abstract pattern, a geometric pattern, a character or a symbol, or a combination thereof. Absent. As the constituent material, it is common to use printing ink or paint in which a colorant such as a dye or pigment is dispersed in a color extender such as a synthetic resin. It is necessary to have flexibility that can follow the elongation of the sheet at the time, for example, using printing ink or paint that uses urethane resin, acrylic resin, vinyl resin, fiber derivative etc. as color developing agent It is desirable to do.

  Examples of the method for forming the pattern layer 2 include known printing methods such as a gravure printing method, an offset printing method, a gravure offset printing method, a screen printing method, a flexographic printing method, a relief printing method, an ink jet printing method, and a transfer printing method. In the case of solid, for example, gravure coating method, micro gravure coating method, roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, dip coating method, flow coating method, spray A known coating method such as a coating method can be used.

  Further, by performing easy adhesion treatment such as corona discharge treatment, plasma treatment, flame treatment, ionizing radiation treatment, acid treatment, alkali treatment, anchor treatment or primer treatment on the printing surface before printing the pattern layer 2. Improvement of adhesiveness can also be carried out arbitrarily as required.

  The non-crystalline polyester resin used for the non-crystalline polyester resin layer 3 in the present invention is a polyester resin whose crystallization speed is slow to such an extent that it hardly crystallizes under normal molding conditions. For example, in a condensation polymerization reaction of an aromatic dicarboxylic acid or ester thereof such as terephthalic acid or naphthalenedicarboxylic acid and an aliphatic diol such as ethylene glycol or 1,4-butanediol, for example, sebacic acid or eicoic acid may be used as the dicarboxylic acid component. , Long chain aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid such as dodecanedioic acid, dimer acid, cyclohexanedicarboxylic acid, or both ends of polyethylene glycol, polytetramethylene glycol, cyclohexanedimethanol, etc. as diol components Having a hydroxyl group Produced by, for example or to introduce Le-based diol and / or alicyclic diol were there is a copolymerized polyester resin or the like.

  Among them, the most typical one is 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin, which is commercially available as PET-G. Specifically, for example, “NAGASEA” manufactured by Nagase Sangyo Co., Ltd. -PET ", Riken Technos Co., Ltd." RIVESTAR ", etc. can be mentioned. The thickness of the backer layer is not particularly limited as long as the total thickness is within a range described later and is balanced with other layers, but about 80 to 120 μm is preferable.

  As the biaxially stretched polyethylene terephthalate sheet 4 in the present invention, a commercially available biaxially stretched polyethylene terephthalate film can be used. An ultraviolet absorber, a light stabilizer, and a heat stabilizer may be added. A thickness of 25 to 190 μm is suitable for two-dimensional and three-dimensional formability.

  The material of the surface protective layer 5 provided as appropriate is not particularly limited in the present invention, but it is desirable to use a curable resin from the viewpoint of various surface properties. Specifically, for example, urethane resins, aminoalkyd resins, melamine resins, epoxy resins, unsaturated polyester resins, urea resins, phenol resins, and other thermosetting resins, unsaturated polyester resins, Ionizing radiation curable resins such as acrylate resins and methacrylate resins can be used. By providing the surface protective layer, it is possible to improve scratch resistance, to prevent generation of interference fringes due to interference of reflected light, and to provide a function of preventing contamination.

  Among them, a two-component curable urethane resin excellent in balance between surface physical properties such as surface hardness and wear resistance and flexibility suitable for bending processing and three-dimensional molding processing, that is, acrylic polyol or acrylic poly A thermosetting resin containing ether as a main component and adding an isocyanate curing agent to cross-link curing is most suitable for the purpose of the present invention. The thickness of the surface protective layer 5 is not particularly limited in the present invention, but it is usually appropriate to be about 3 to 20 μm from the viewpoint of physical properties and flexibility.

  For the surface protective layer 5, for example, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a gloss adjusting agent, a lubricant, an antistatic agent, an anti-condensation agent, an antibacterial agent, an antifungal agent, an antifriction agent, and coloring One or more selected from various additives such as an agent and a filler may be added. The surface protective layer 5 may be composed of two or more layers of the same type or different types. For example, the particles on the first layer containing high-hardness wear-resistant particles such as silica, alumina, silicon carbide and the like. By providing a second layer that does not contain a material, it is possible to achieve both wear resistance, scratch resistance, surface gloss and surface smoothness, or a glossy state on the first layer provided on the entire surface. It is also possible to apply different second layers in arbitrary patterns to express a visual three-dimensional effect due to gloss change.

  The total thickness of the decorative sheet of the present invention is 300 to 350 μm. By setting it as this range, it becomes possible to make it a high mirror surface and not to be affected by the adhesive duck. The thickness of each layer is not particularly limited, but it is preferable that each layer thickness of the thermoplastic resin substrate 1, the amorphous polyester resin layer 3, and the biaxially stretched polyethylene terephthalate sheet 4 is about 100 μm.

A random propylene resin colored sheet (“OW” manufactured by Riken Technos Co., Ltd.) having a thickness of 120 μm is used as the thermoplastic resin substrate 1, and printing is performed using a two-component urethane resin binder ink on a gravure printing machine. 2.
A 200-μm thick 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin sheet (“RIVESTAR” manufactured by Riken Technos Co., Ltd.) was laminated as an amorphous polyester resin layer 3 on the pattern layer 2 by a dry lamination method.
A 100 μm biaxially stretched polyethylene terephthalate sheet (“Lumirror T60” manufactured by Toray Industries, Inc.) that was previously corona-treated as a biaxially stretched polyethylene terephthalate sheet 4 was dry laminated on the amorphous polyester resin layer 3.
Furthermore, after diluting a silicone-modified UV curable resin (manufactured by Toyo Ink Manufacturing Co., Ltd.) as a surface protective layer 5 on this biaxially stretched polyethylene terephthalate sheet 4 to an appropriate viscosity with a diluent solvent, a direct reverse gravure method (circumferential speed) After coating so that the coating thickness after drying was 5 to 6 μm by coating at a ratio of 100%, ultraviolet rays were applied and cured using a high-intensity high-pressure mercury lamp to obtain a decorative sheet.

<Comparative Example 1>
A decorative sheet was obtained in the same manner as in Example 1 except that the amorphous polyester resin layer 3 was not provided on the thermoplastic resin substrate 1 and the biaxially stretched polyethylene terephthalate sheet 4 was directly dry laminated.

<Comparative example 2>
A decorative sheet was obtained in the same manner as in Example 1 except that the amorphous polyester resin layer 3 was not provided on the thermoplastic resin substrate 1, and a biaxially stretched polyethylene terephthalate sheet 4 having a thickness of 188 μm was dry laminated. It was.

<Physical property test>
As an evaluation test, a loop repulsion force test was performed by a pencil hardness test based on JIS K 5400 and the method described below. A test schematic is shown in FIG. A tensilon tensile test mode 10 kg load cell was used as a measuring device, and a “U” shaped jig as shown in FIG. 2 was attached to the tensilon. A sheet of 25 mm width and 50 mm length previously rolled into a ring shape is placed between the jigs, and the ring sheet is crushed to a point 4 mm before the jig contacts at a pulling speed of 10 mm / min. The drag force was measured. The sheet drag under each ambient temperature was measured by changing the ambient temperature of the measurement environment. The results are shown in Tables 1 and 2. From Tables 1 and 2, it can be said that the sheet of Example 1 is excellent in scratch resistance and has good bending workability at the temperature during lapping (80 ° C. or higher).

  The decorative sheet of the present invention can be used by being bonded to a base material such as a woody base material, an inorganic base material, a synthetic resin base material, and a metal base material.

It is explanatory drawing which shows the shape of the cross section of one Example of the decorative sheet in this invention. It is explanatory drawing which shows the outline of the test of the loop repulsion force test used by this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Thermoplastic resin base material 2 ... Pattern pattern layer 3 ... Amorphous polyester resin layer 4 ... Biaxially stretched polyethylene terephthalate sheet 5 ... Surface protective layer

Claims (1)

A decorative sheet obtained by bonding a non-crystalline polyester resin layer on a thermoplastic resin base material, wherein a biaxially stretched polyethylene terephthalate sheet is bonded on the non-crystalline polyester resin layer.