JPH08238739A - Decorative sheet - Google Patents

Abstract

PURPOSE: To obtain a decorative sheet having senses of depth and design by shaping a luster thermoplastic resin layer by heat pressing by using a sheet having an uneven pattern layer cured with curable resin on a mold release base material, simultaneously transferring the pattern layer, and then releasing to remove the base material. CONSTITUTION: A decorative sheet 10 is formed by forming a fine and sharp transparent uneven pattern layer 2 of an ionizing radiation curable resin on a transparent thermoplastic resin sheet 1 to become a releasing base material, superposing the pattern surface on a luster thermoplastic resin layer (luster sheet) 3 mixed with luster component, heating and press bonding it. At this time, since the layer 2 of the curable resin has high hardness, it is embedded in the layer 3, and formed as an interior uneven pattern layer. Instead of the sheet 3, a thin luster layer 3' and a design layer 3" may be provided on a suitably selected thermoplastic resin base material layer 4 by coating.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a decorative material for interior materials, furniture, cabinets, kitchens and the like.

[0002]

2. Description of the Related Art According to the invention described in Japanese Utility Model Laid-Open No. 5-35394, an opaque thermoplastic resin film having a glitter layer on the surface thereof is provided with a picture layer on the surface thereof, and a depth of 3 The interval between the protrusions of -30 μm and the protrusion is 1 to 1000 μm
m is a parallel curve group, or a pattern or a function curve in which a parallel curve group and a parallel straight line group are combined is selected from non-parallel curve groups in which the interval between the curves changes smoothly in the vertical direction by changing the parameters. There is a decorative material characterized in that a transparent resin layer thicker than the depth of the uneven pattern is provided on the surface of the uneven pattern after providing the uneven pattern composed of a line group pattern.

[0003]

However, in the above-mentioned decorative material, since the uneven pattern is completely embedded in the transparent resin layer and the unevenness is formed inside the transparent resin layer, the luster of the surface of the grain is reduced. Although there is an effect on the design properties such as expression and there is an advantage that unevenness is not crushed during the manufacturing process of the decorative material, the manufacturing process includes the formation of the uneven pattern and the formation of the transparent resin layer and the transparent resin layer. In order to obtain easy adhesion, it is necessary to separately form the recoat layer and the like, which is time-consuming, and there is a risk that the uneven pattern may disappear when the transparent resin layer is provided. There are drawbacks such as difficulty in maintaining the accuracy of surface smoothness.

[0004]

Therefore, the present invention made to solve such problems is the following two. That is, using a sheet having an uneven pattern layer obtained by curing a curable resin on a releasable substrate, the glittering thermoplastic resin layer is shaped by heating and pressing, and at the same time, the uneven pattern layer is transferred. A decorative sheet obtained by peeling and removing the releasable base material. The decorative sheet according to claim 1, wherein the curable resin layer is an ionizing radiation curable resin layer.

[0005]

In the decorative sheet of the present invention, the surface of the ionizing radiation-curable resin layer from which the mold-releasing base material has been peeled off is a mirror surface, imparts scratch resistance and a feeling of painting, and at the same time, has a good gloss against the ionizing radiation-curable resin layer. By heating and pressing the thermoplastic resin layer,
Glittering unevenness can be provided on the surface of the glittering thermoplastic resin layer, that is, inside the decorative sheet.

[0006]

The present invention will be described in detail below with reference to the drawings.
FIG. 1 is a schematic diagram showing a basic layer structure of a decorative sheet 10 according to the present invention. FIG. 1A shows an embodiment of a decorative sheet 10, in which a fine and sharp transparent concave-convex pattern layer 2 made of an ionizing radiation-curable resin is formed on a transparent thermoplastic resin sheet 1 serving as a releasable substrate, which will be described later. This is a case where it is formed by the method (DPS), and this concavo-convex pattern surface is overlaid on a separately prepared glittering thermoplastic resin layer (glare sheet) 3 into which a glittering component is mixed and heated and pressure-bonded. The concavo-convex pattern layer 2 made of an ionizing radiation curable resin has a high hardness and is embedded in the glittering thermoplastic resin layer 3 to be formed as an internal concavo-convex pattern layer. FIG. 1 (b) shows another embodiment, in which instead of the glittering sheet 3, a thermoplastic resin in which a thin glittering thermoplastic resin layer (glossy layer) 3'and a pattern layer 3 ^" are appropriately selected by coating. This is the case when it is provided on the base material layer 4.
The inner concavo-convex pattern layer 2 formed of the ionizing radiation curable resin may be colored, but needs to be transparent. The concavo-convex pattern layer 2 forms a sharp concavo-convex interface of fine edges with the glittering sheet 3 or the glittering layer 3 ', so that a three-dimensional pattern can be obtained.
Further, depending on the selection of the concavo-convex pattern, it is possible to bring about the effect of partially changing the gloss when viewed from various angles.

The lower thermoplastic resin layer 3 in contact with the concave / convex pattern layer 2 of the decorative sheet having the above-mentioned constitution in the present invention
If 1 to 30% by weight of an acrylic resin is mixed in, the adhesion with the concavo-convex pattern layer will be improved. Further, vinyl chloride is also used for the ionizing radiation curable resin that forms the uneven pattern layer 2.
It is preferable to mix a vinyl acetate copolymer and other vinyl chloride-based additives described below. Vinyl chloride resin is often used for the thermoplastic resin layers 1 and 3. The reason is that the moldability is improved and the adhesiveness to the uneven pattern layer containing the vinyl chloride-based additive is taken into consideration.

FIG. 2 is an explanatory view of a method of manufacturing the decorative sheet 10. A method of forming a fine concavo-convex pattern on the surface of the transparent thermoplastic resin sheet 1 serving as a releasable substrate is performed by a method called a drum printing system (hereinafter referred to as DPS) that applies a roll intaglio printing method.
FIG. 2A is an explanatory diagram of the principle of DPS. Normal DPS
Is used by appropriately selecting a resin from the ionizing radiation curable resins described below. First, the ionizing radiation curable resin liquid 2'is applied to the transparent thermoplastic resin sheet 1 supplied from the paper feed roll 5 by the coating device 6 using a gravure coating method, a roll coating method, a T-die nozzle coating method, or the like. After the solvent is dried by the drying oven 9, the transparent thermoplastic resin sheet 1 is formed on the plate surface of the roll intaglio 11 in which the recesses corresponding to the desired uneven pattern are engraved, via the ionizing radiation curable resin liquid 2 '. Is pressed by the nip roll 12 so that at least the concave portion of the roll intaglio 11 is filled,
While traveling at a traveling speed that is synchronized with the peripheral speed of the roll intaglio 11, before the next nip roll 13, ionizing radiation is irradiated from the back surface of the transparent thermoplastic resin sheet 1 by the ionizing radiation irradiating device 14 to cure the ionizing radiation. The resin liquid 2'is cured, and the cured ionizing radiation curable resin 2 is adhered to the transparent thermoplastic resin sheet 1 and released from the roll intaglio 11 by the feed roll 13, and the finished uneven sheet is discharged by the paper discharge roll 15. Roll up. DP explained above
According to S, the fine and sharp concave shape formed on the roll intaglio 11 can be faithfully reproduced on the transparent thermoplastic resin sheet 1.

Since the concavo-convex pattern formed on the decorative sheet 10 of the present invention faithfully reproduces the concavo-convex pattern engraved on the roll intaglio 11, an extremely wide range of concavo-convex pattern can be formed or used. For example, it is possible to apply an imitation shape of a natural material such as wood, stone, cloth, or sand, a letter symbol, a line pattern, various abstract patterns, various matte surfaces, and other irregular patterns. In addition, the above-mentioned roll intaglio 11
Is chrome-plated copper, metal such as iron, glass, quartz,
Using ceramics such as PLZT or a synthetic resin such as a silicon resin, the recess can be formed by a known method such as a photocorrosion method, an electroforming method, or a milling method.

FIG. 2 (b) is an illustration of thermal lamination. Concavo-convex sheet processed by DPS and glitter sheet 3
Alternatively, the thermoplastic resin sheet 4 having the glittering layer 3'on its surface is supplied from the paper feed rolls 16 and 17, respectively, and is heated by the heating device 19 while being laminated on the heat drum 18 to perform thermal lamination, and then the cooling roll. Two
After cooling at 0, the decorative sheet 10 is wound up by the paper discharge roll 21.

The ionizing radiation curable resin molded and cured by the recesses formed in the roll intaglio 11 is the uneven pattern layer 2
However, in order to sufficiently cure this, ionizing radiation may be further irradiated from an ionizing radiation irradiation device (not shown) installed separately from the ionizing radiation irradiation device 14.

Since a solvent is used in the method of forming the uneven pattern layer 2 described above, when the transparent thermoplastic resin sheet 1 is coated with the ionizing radiation curable resin liquid 2 ', the fluidity of the resin liquid 2'is controlled. In addition to facilitating the adjustment of coatability, the range of resins that can be used is widened.

Examples of the material of the releasable substrate of the present invention include polyester resin films such as polyethylene terephthalate, polybutylene terephthalate and ethylene terephthalate / isophthalate copolymers, polyrefin resin films such as polyethylene and polypropylene, polyvinyl chloride. A vinyl resin film, such as
Those having a thickness of about 200 μm can be used. Further, those formed with a release layer of silicone resin, fluororesin, melamine resin, polyolefin resin or the like on an ordinary base material such as plastic film or paper can be used.

As the curable resin of the present invention, a room temperature curable resin, a thermosetting resin, an ionizing radiation curable resin or the like can be used. The room temperature curable resin is a polyurethane resin composed of a polyol compound and a polyisocyanate compound, and the thermosetting resin is a phenol resin, a melamine resin,
One or a mixture of two or more of urea resins, guanamine resins, diallyl phthalate resins, unsaturated polyester resins, epoxy resins, aminoalkyd resins, silicone resins, furan resins, xylene resins and the like can be used.

The ionizing radiation curable resin of the present invention includes:
A polymer, a prepolymer, or a monomer that causes a cross-linking polymerization reaction by ionizing radiation to be solidified is used. Specifically, a radical polymerization system composed of a compound having a (meth) acryloyl group such as (meth) acrylamide, (meth) acrylonitrile, (meth) acrylic acid, (meth) acrylic acid ester (here, (meth)) Acryloyl means acryloyl or methacryloyl. The same shall apply hereinafter), epoxy, cyclic ether, cyclic acetal, lactone, vinyl monomer, cationic polymerization system composed of a combination of cyclic siloxane and aryldiazonium salt, diaryliodonium salt, thiol group. A compound having a compound such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, pentaerythritol tetrathioglycol and a polyene / thiol system composed of a polyene compound can be used.

Examples of the monofunctional monomer of the radical polymerization type (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, methoxyethyl (meth) acrylate and methoxybutyl (meth). ) Acrylate, butoxyethyl (meth) acrylate, 2 ethylhexyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) Acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dibenzylaminoethyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, ethylcarbitol (meth) acr Rate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, tetrahydroxyfurfuryl (meth) acrylate, methoxytripropylene glycol (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate , 2-
(Meth) acryloyloxypropyl hydrogen phthalate,

As the polyfunctional monomer of radical polymerization system, ethylene glycol di (meth) acrylate,
Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexyldiol di ( (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, triprolylene glycol di (meth) acrylate, bisphenol A-di (meth) acrylate
Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, glycerin polyethylene oxide tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, etc.

Alkyd (meta) as a prepolymer
There are (meth) acrylates such as acrylates, urethane (meth) acrylates, epoxy (meth) acrylates, polyester (meth) acrylates, polybutadiene (meth) acrylates, and unsaturated polyesters.

Among these compounds containing a (meth) acryloyl group, a compound containing an acryloyl group, that is, an acrylate, has a higher polymerization reaction rate. Therefore, when importance is attached to the production rate of coating and forming the ionizing radiation-curable resin layer, acrylate is more preferable than methacrylate.

The above compounds may be used alone or in admixture of two or more. Further, the total sum of (meth) acryloyl groups in the mixed composition is 0.2 to 12 mmol /
g, preferably 2 to 10 mmol / g.

Here, as a photopolymerization initiator for curing by ultraviolet irradiation, benzoin, benzoin methyl ether, acetophenone, benzophenone, Michler's ketone, diphenyl sulfide, dibenzyl disulfide, diethyl oxite, triphenyl biimidazole, isopropyl One or two or more kinds of —N, N-dimethylaminobenzoate and the like can be used by mixing 0.1 to 10 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin.

Here, ethyl acetate, butyl acetate, as a solvent for dissolving the ionizing radiation-curable resin in the composition containing the ionizing radiation-curable resin and adjusting its viscosity and the like to impart coating suitability, One or two or more of esters such as cellosolve acetate, ketones such as acetone, methyl ethyl ketone, ethyl isobutyl ketone, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, etc. can be used in an arbitrary mixture. .

Additives mixed in the ionizing radiation-curable resin include polyvinyl chloride, polyvinyl acetate, vinyltoluene, vinyl chloride, vinyl chloride-vinyl acetate copolymer, and other vinyl resins, ethyl cellulose, ethyl hydroxyethyl cellulose, and cellulose. Cellulose derivatives such as acetate propionate and cellulose acetate. Polystyrene, poly α-
Styrene resins such as methylstyrene, (meth) acrylic resins such as methyl (ethyl, butyl) poly (meth) acrylate, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, rosin ester resins such as polymerized rosins,
A coumarone resin, a polyester-based resin, a polyurethane-based resin, a butyral resin, or the like may be used alone or as a mixture of two or more thereof.

As the glittering thermoplastic resin layer of the present invention,
Glittering sheet is formed by kneading the glittering pigment into the thermoplastic film itself, or one is to form a glittering layer by coating on a base sheet with an ink in which the glittering pigment is dispersed using a thermoplastic resin as a vehicle. can do. Examples of the bright pigment used here include powder or foil pieces of metal such as aluminum, copper and brass, pigments having metallic luster such as metal flakes and fine fragments of metal vapor deposition synthetic resin film, titanium dioxide coated mica, fish scales. A pearlescent or interference luster pigment composed of foil or scale-shaped foil pieces such as bismuth acid chloride, or two or more kinds of resin layers having different refractive indexes, such as a polyester resin layer and an acrylic resin layer, for several μm or less. Pigments made of foil powder obtained by slicing a large number of films having a thickness of 1 to produce an iris color due to light interference. Examples of the vehicle include resins such as vinyl-based, acrylic-based, aminoalkyd-based, and butyral, and the printing method is a known means such as gravure, flexo, and silk screen. The thickness of the glitter layer may be appropriately set so that the desired glitter can be obtained, but it is usually preferable to form the glitter layer to a thickness of about 1 to 10 μm.

In the constitution of the present invention, the pattern layer may be provided on the glitter sheet 3 or on or below the glitter layer 3 '. The design of the design layer may be appropriately selected according to the use, purpose, etc. of the decorative material.For example, a cross-sectional pattern of a wood grain annual ring, various wood grain patterns such as color tone of wood grain, a copy of natural products such as stone and cloth, A layer formed by printing a pattern appropriately selected from figures, symbols, characters, ruled lines, whole surface solids, etc. of a vehicle used as an ink for forming the glitter layer as an ink for forming the pattern layer It may be appropriately selected from the above, and as the pigment, an inorganic or organic pigment can be used. As the printing method, the same means as for the glitter layer can be used.

In the constitution of the present invention, an adhesive can be provided on the uneven pattern layer obtained by curing the curable resin or on the pattern layer or the glittering thermoplastic resin layer. An adhesive or the like can be appropriately selected.

Example 1 A transparent polyvinyl chloride sheet having a thickness of 100 μm (BHS manufactured by Bando Kagaku Co., Ltd.) A urethane acrylate UV curable resin (XD manufactured by Dainichiseika Co., Ltd.) on the surface of a releasable substrate by the DPS method. An uneven sheet having an uneven pattern layer according to (808) was prepared. The roll intaglio used here was provided with an uneven pattern (depth 12 μm, convex portion width and concave portion width 35 μm) consisting of wavy curve groups by an etching method, and the line speed of the DPS method was 10 μm.
m / min, and an ozone high-pressure mercury lamp (manufactured by Nippon Battery Co., Ltd.) 160 W / 2 lamp was used for ultraviolet irradiation. On the other hand, a glittering polyvinyl chloride sheet (BHS manufactured by Bando Kagaku Co., Ltd.) having a thickness of 150 μm in which polymethyl methacrylate and a pearl pigment are mixed as an additive and the uneven surface of the uneven sheet are overlapped, and the drum temperature 16
0 ° C., speed 6 m / min. , Pressure 4kgf / cm ²
I did thermal lamination. After thermal lamination, the transparent polyvinyl chloride sheet releasable substrate was peeled off. The surface layer of the thus obtained decorative sheet was an ionizing radiation curable resin film having specular gloss, and the decorative sheet further had three-dimensional unevenness inside.

Example 2 Transparent polyvinyl chloride sheet having a thickness of 25 μm (Teijin Ltd.)
HP-7) manufactured by HP Co., Ltd. An uneven sheet having an uneven pattern layer made of a urethane acrylate ionizing radiation curable resin (XD-808 manufactured by Dainichiseika Co., Ltd.) was prepared on the surface of a releasable substrate by the DPS method. The roll intaglio used here has an uneven pattern (depth 12 μm, convex portion width and concave portion width 35 μm) each consisting of a group of wavy curves provided by an etching method, and the line speed of the DPS method is 6 m /
The ozone high pressure mercury lamp (manufactured by Nippon Battery Co., Ltd.) 160 W / 2 lamp was used for irradiation of ultraviolet rays. On the other hand, a gravure ink containing a pearl pigment (shown by Showa Ink Kogyo: Chemical X on a colored polyvinyl chloride sheet having a thickness of 150 μm in which polymethyl methacrylate is mixed as an additive).
Gravure printing on the entire surface with (Pearl), and then gravure printing a grain pattern with (Chemical X manufactured by Showa Ink Kogyo Co., Ltd.) to overlay the uneven surface of the uneven sheet and the printed surface of the glittering vinyl chloride sheet. Together, the drum temperature is 160 ℃,
Speed 6m / min. Thermal lamination was performed at a pressure of 4 kgf / cm ² . After thermal lamination, the transparent polyvinyl chloride sheet releasable substrate was peeled off. The surface layer of the thus obtained decorative sheet was an ionizing radiation curable resin film having specular gloss, and the decorative sheet further had three-dimensional unevenness inside.

[0029]

According to the decorative sheet of the present invention, the surface of the ionizing radiation curable resin layer from which the releasable substrate is peeled off is a mirror surface,
Scratch resistance and a coating feeling are imparted, and at the same time by heating and pressurizing the ionizing radiation curable resin layer and the glittering thermoplastic resin layer, the glittering thermoplastic resin layer surface, that is, the inner surface of the decorative sheet is glittered. The uneven shape can be imparted. As a result, it becomes possible to obtain a decorative sheet that has irregularities inside and has a deep design feeling.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing a basic layer structure of a decorative sheet according to the present invention.

FIG. 2 is an explanatory diagram of a method for manufacturing a decorative sheet according to the present invention (a) an explanatory diagram of the principle of DPS (b) an explanatory diagram of thermal lamination

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Releasable substrate 2 Uneven pattern layer obtained by curing a curable resin 3 Glittering thermoplastic resin layer (glossy sheet) 3'Glittering thermoplastic resin layer (glossy layer) 3 ^" Picture layer 4 Thermoplastic resin Sheet 5 Paper feed roll 6 Ionizing radiation curable resin liquid coating device 7 Coating roll 8 Backup roll 9 Drying oven 10 Decorative sheet according to the present invention 11 Roll unevenness 12 Nip roll 13 Feed roll 14 Ionizing radiation emitting device 15 Paper discharge roll 16 Supply Paper roll 17 Paper feed roll 18 Heat drum 19 Heating device 20 Cooling roll 21 Paper discharge roll

Claims (2)

[Claims] 1. A sheet having an uneven pattern layer obtained by curing a curable resin on a releasable substrate is used to shape the glittering thermoplastic resin layer by heating and pressing, and at the same time, the uneven pattern layer is formed. A decorative sheet obtained by transferring and releasing the releasable base material. 2. The decorative sheet according to claim 1, wherein the curable resin layer is an ionizing radiation curable resin layer.