JP4487694B2 - Decorative sheet - Google Patents

Description

  The present invention relates to a decorative sheet to be bonded to a base material such as a woody base material, an inorganic base material, and a metal base material, and particularly relates to an olefin type decorative sheet.

  A decorative sheet using an olefin resin is used as an environmentally friendly non-vinyl chloride resin decorative sheet. The surface of this decorative sheet is generally provided with a surface protective layer to impart surface properties such as solvent resistance and weather resistance, but depending on the material of the surface protective layer, the adhesive strength between the layers becomes a problem. There was a thing.

  In order to impart surface properties such as solvent resistance and weather resistance, it is common to use a cured coating film made of ionizing radiation curable resin. There was a problem. There is also a problem that interference fringes are generated due to interference between reflected lights due to uneven coating thickness.

  On the other hand, the decorative sheet surface often requires embossing in order to give a three-dimensional appearance and texture, and therefore, after embossing a single-layer or multi-layer thermoplastic resin sheet, It may form surface protection. In most cases, the decorative sheet obtained by this method is flat-coated or lapped on a wooden base material such as MDF or particle board and used as a decorative plate, but it is extremely difficult to obtain a product having excellent scratch resistance. .

  The present invention is made in order to solve the above-mentioned problems, and the problem is that it is bonded to a base material such as a wood base material, an inorganic base material, a synthetic resin base material, and a metal base material. An object of the present invention is to provide a highly-designed decorative sheet that is excellent in scratch resistance, has good bending workability, is capable of surface embossing, and is an olefin-based decorative sheet.

The present invention is for solving such problems, and the invention according to claim 1 comprises an amorphous polyester resin or an amorphous crystalline polyester resin on an olefin-based decorative sheet substrate. It has a transparent resin layer , an adhesive layer containing acrylic polyol and hexamethylene diisocyanate (hereinafter referred to as HDI) based curing agent is provided on the transparent resin layer , and an ionizing radiation curable resin and heat are provided on the outermost surface. A decorative sheet characterized in that a surface protective layer obtained by mixing a curable resin in a ratio of 3: 7 to 1: 9 is provided , and the surface is embossed .

According to the second aspect of the present invention, a transparent resin layer made of an amorphous polyester resin or an amorphous crystalline polyester resin is provided on an olefin-based decorative sheet substrate, and an acrylic polyol is formed on the transparent resin layer. And an adhesive layer containing hexamethylene diisocyanate curing agent, and an ionizing radiation curable resin and a thermosetting resin were mixed at a ratio of 3: 7 to 1: 9 on the adhesive layer, and diluted appropriately. Applying resin, irradiating with ionizing radiation to cure the ionizing radiation curable resin, immediately curing the thermosetting resin while applying surface embossing by hot pressure embossing, and then heat drying It is the manufacturing method of the decorative sheet characterized.

  According to the invention described in claim 1, by mixing the ionizing radiation curable resin and the thermosetting resin and adjusting the ratio thereof, it is excellent in scratch resistance, has good bending workability, and can be embossed on the surface. It is possible to provide a highly decorative decorative sheet. Also, by providing an adhesive layer containing acrylic polyol and HDI-based curing agent, it becomes a thermosetting resin layer with good elongation, improves the adhesion of the surface protective layer, and protects the surface even when bending is performed. The layer will not peel off.

  According to the second aspect of the present invention, the adhesive layer is provided between the other layer and the surface protective layer, so that the interlaminar adhesion and the bending workability are good, and the ionizing radiation is irradiated to irradiate the ionizing radiation. By curing the resin and immediately curing the thermosetting resin while performing surface embossing with hot-pressure embossing, even if fine foreign substances adhere when coating the surface protective layer, the surface shape is not affected. In addition, it is possible to prevent generation of interference fringes due to interference between reflected lights due to uneven thickness, and it is easy to wipe off even if dirt is attached to a smooth portion.

  In FIG. 1, the structure of the cross section of one Example of the decorative sheet of this invention is shown. In the present embodiment, the decorative sheet is provided with a pattern layer 2 and a transparent resin layer 3 as appropriate on a decorative sheet substrate 1 made of an olefin resin, and an adhesive containing an acrylic polyol and an HDI curing agent. The layer 4 is provided with a surface protective layer 5 made of a mixed resin of an ionizing radiation curable resin and a thermosetting resin. An embossing 6 may be appropriately provided on this surface.

  As the decorative sheet substrate 1 in the present invention, a polyolefin-based resin is used, and specifically, a polyethylene resin and a polypropylene resin can be used. A highly crystalline homopolypropylene, a low crystalline homopolypropylene, a block polypropylene, a random polypropylene, Among these copolymers, it can be used by appropriately judging from transparency and processing suitability required for a decorative sheet substrate. Moreover, you may add 1 type (s) or 2 or more types of additives, such as an inorganic pigment, antioxidant, a light stabilizer, and an antiblocking agent, suitably from the physical property requested | required similarly.

  Examples of the pattern layer 2 in the present invention include a concealing layer and a pattern layer using printing ink. Gravure printing, intaglio printing, flexographic printing, silk printing, electrostatic printing, ink jet printing on the front and / or back of the decorative sheet substrate 1 as a method of forming the pattern layer 2 on the decorative sheet substrate 1 However, this is not necessarily the case. Ink used is also known, that is, a colorant such as a dye or pigment or an extender pigment is added to the vehicle, and further, a plasticizer, a stabilizer, a wax, a grease, a desiccant, a curing agent, a thickener, and a dispersant. The ink may be obtained by arbitrarily adding a filler or the like and sufficiently kneading with a solvent, a diluent or the like.

  Alternatively, a concealing layer and / or a pattern layer are formed on a completely different transfer base sheet by the above-described forming method, etc., and the above-described thermal laminating method, dry laminating method, wet laminating method, extrusion laminating method For example, a method of peeling the transfer base sheet and transferring the concealing layer and / or the pattern layer to the decorative sheet base material 1 after being attached to the decorative sheet base material 1 can be used. .

  As the transparent resin layer 3 in the present invention, a polyester-based transparent resin is preferably used from the viewpoint of interlayer adhesion with other layers, but is not particularly limited to this, and is used by appropriately judging from required physical properties and transparency. be able to. In particular, when surface embossing is performed by hot-pressure embossing, a crystalline polyester resin in an amorphous state or an amorphous state is suitable.

  As the adhesive layer 4 in the present invention, 10 parts by weight of HDI isocyanate is mixed with a mixed resin of an acrylic resin and a polyurethane polyol resin, diluted to an appropriate viscosity, and then applied by a direct natural gravure coating method. Provided.

  The surface protective layer 5 in the present invention is made of a mixed resin of an ionizing radiation curable resin and a thermosetting resin. This makes it possible to obtain surface resistance with an ionizing radiation curable resin, while providing bending workability with a thermosetting resin, and the resin is mixed in a ratio of 3: 7 to 1: 9. Thus, it is possible to obtain high scratch resistance while adapting to bending workability such as lapping.

  As the ionizing radiation curable resin, a composition in which a polymerizable unsaturated bond or a prepolymer having an epoxy group, an oligomer, and / or a monomer is appropriately mixed in the molecule is used. Examples of these resins include acrylates such as urethane acrylate, polyester acrylate, and epoxy acrylate, silicon resins such as siloxane, and known resins such as epoxy. Examples of the prepolymer and oligomer include unsaturated polyesters such as unsaturated dicarboxylic acid and polyhydric alcohol condensates, polyester methacrylates, polyether methacrylates, polyol methacrylates, methacrylates such as melamine methacrylates, polyester acrylates, epoxy acrylates, There are acrylates such as urethane acrylate, polyether acrylate, polyol acrylate and melamine acrylate. Examples of the monomer include styrene monomers such as styrene and α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, Acrylic esters such as methoxybutyl acrylate and phenyl acrylate, and methacrylic esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate and lauryl methacrylate , 2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-diethylamino) ethyl methacrylate, -2- (N, N-dibenzylamino) ethyl acrylate, -2-methacrylic acid-2- (N, N-dimethylamino) methyl, Substituted amino alcohol esters of unsaturated acids such as uric acid-2- (N, N-diethylamino) propyl, unsaturated carboxylic acid amides such as acrylamide and methacrylamide, ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol Polyfunctional compounds such as diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, and / or polythiol compounds having two or more thiol groups in the molecule, such as trimethylol Examples include propane-removing thioglycolate, trimethylolpropane trithiopropylate, and pentaerythritol tetrathiol glycol. The above compounds can be used alone or in combination of two or more as required.

  Examples of the thermosetting resin include phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation resin, silicon resin. Polysiloxane resins and the like, and those to which a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, an extender pigment, and the like are added as necessary. The curing agent is usually an unsaturated polyester resin, polyurethane resin, amine epoxy resin, peroxide such as methyl ethyl ketone peroxide, radical initiator such as azoisobutyl nitrile unsaturated polyester resin, etc. Often used. Further, as the isocyanate, a divalent or higher aliphatic isocyanate or aromatic isocyanate can be used, but an aliphatic isocyanate is desirable from the viewpoints of preventing thermal discoloration and weather resistance.

  An example of the manufacturing method of the decorative sheet in the present invention is as follows. First, the printing layer 2 is provided on the olefin-based decorative sheet substrate 1 by gravure printing. If it is a roll-like sheet, it may be wound up once. Subsequently, the adhesive layer 3 is provided thereon with a coating apparatus. On top of this, an ionizing radiation curable resin and a thermosetting resin are mixed at a ratio of 3: 7 to 1: 9 and coated with a suitably diluted resin, and the ionizing radiation is irradiated to cure the ionizing radiation curable resin. Immediately after that, the thermosetting resin is cured while performing surface embossing by hot-pressure embossing, and thereafter, it is warm-cured and finished. The surface protective layer becomes a semi-cured state by irradiation with ionizing radiation, and it becomes possible to form an emboss on the surface and completely cure by heating. By reducing the mixing ratio of ionizing radiation curable resin, semi-curing can be instantaneously performed by using ionizing radiation curing, and the heat of the subsequent hot press embossing can be used for curing the thermosetting resin. Since the ionizing radiation curable resin is cured before embossing, the curing shrinkage of the ionizing radiation curable resin does not affect the embossing.

(UV resin + urethane coat (3/7))
A polyolefin sheet (“Rivesta-TPO, 120 μm thickness” manufactured by Riken Technos Co., Ltd.) was used as a decorative sheet base material, and an abstract pattern was printed by gravure printing. A transparent polyester resin (Nagase Sangyo) “NAGASE A-PET, 200 μm thickness” manufactured by Co., Ltd. was bonded by dry lamination.
Next, 100 parts by weight of a mixed resin of acrylic resin and polyurethane polyol resin (“UV Clear” manufactured by Dainippon Ink & Chemicals, Inc.) and an HDI curing agent (produced by Dainippon Ink & Chemicals, Inc.) ) Mix 10 parts by weight, dilute with diluted solvent (butyl acetate) to a viscosity (Zahn cup # 3) 18 seconds, and apply the coating amount after drying by the direct natural gravure coating method to 2 g / m ² did.
Next, on this surface, 30 parts by weight of an ultraviolet curable resin (Dainippon Ink Chemical Co., Ltd.), 70 parts by weight of an acrylic polyol resin as a thermosetting resin, and an HDI curing agent (Dainippon Ink Chemical Co., Ltd.) Kogyo Co., Ltd.) was mixed with 5 parts by weight equivalent to the acrylic polyol resin, diluted with a diluent solvent (butyl acetate) to a viscosity (Zahn cup # 3) of 17 seconds, and then subjected to direct natural gravure coating. The coating amount after drying was applied so as to be 10 g / m ^2, and the surface was irradiated with ultraviolet rays by a high pressure mercury lamp at 240 W 1 lamp and a line speed of 20 m / min. Immediately after that, after preheating with a 120 ° C IR heater, the surface was embossed with an embossed plate at 60 ° C and completely cured by heat drying at 40 ° C to obtain a decorative sheet.

(UV resin + urethane coat (1/9))
A decorative sheet was obtained in the same manner as in Example 1 except that the proportion by weight of the ultraviolet curable resin and the thermosetting resin was 10 parts by weight and 90 parts by weight, respectively.

<Comparative Example 1>
(UV resin + urethane coat (5/5))
A decorative sheet was obtained in the same manner as in Example 1 except that the proportion by weight of the ultraviolet curable resin and the thermosetting resin was 50 parts by weight and 50 parts by weight, respectively.

The decorative sheet prepared as described above was bonded to a medium-sized fiberboard with an adhesive composed of an ethylene / vinyl acetate copolymer resin and an isocyanate curing agent, and then sufficiently pressed and evaluated. In addition, a double-sided tape was bonded to the back of the decorative sheet for processing and molding, and evaluation was performed by bonding to a medium-quality fiberboard having various R-shaped processes. The results are shown below.

  The present invention can be used as a decorative sheet to be bonded to a base material such as a wood base material, an inorganic base material, and a metal base material.

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

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Cosmetic sheet base material 2 ... Picture layer 3 ... Transparent resin layer 4 ... Adhesive layer 5 ... Surface protective layer 6 ... Embossing

Claims (2)

A transparent resin layer made of an amorphous polyester resin or an amorphous crystalline polyester resin is formed on an olefin-based decorative sheet substrate, and acrylic polyol and hexamethylene diisocyanate-based curing are formed on the transparent resin layer. An adhesive layer containing an agent is provided, and a surface protective layer obtained by mixing an ionizing radiation curable resin and a thermosetting resin in a ratio of 3: 7 to 1: 9 is provided on the outermost surface, and the surface is embossed. A decorative sheet characterized by having been subjected to . A transparent resin layer composed of an amorphous polyester resin or an amorphous crystalline polyester resin is provided on an olefin-based decorative sheet substrate, and an acrylic polyol and a hexamethylene diisocyanate curing agent are provided on the transparent resin layer. An ionizing radiation curable resin and a thermosetting resin are mixed at a ratio of 3: 7 to 1: 9 and coated with an appropriately diluted resin, and irradiated with ionizing radiation. A method for producing a decorative sheet, comprising: curing an ionizing radiation curable resin; immediately curing a thermosetting resin while performing surface embossing by hot-pressure embossing;

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