JPH10230580A - Decorative sheet and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent air residue and return of a projection-recess pattern by forming of a laminate of a surface of a decorative design provided on a base material sheet made of polyolefin resin, ultraviolet curable resin layer and a transparent resin layer made of polyolefin resin executed by corona discharging on the melt extrusion film formed and shaped projection-recess pattern and non-shaped surface. SOLUTION: The decorative sheet 10 is obtained by laminating an ultraviolet curable resin layer 3 and a transparent resin layer 4 having a extrusion film formed and shaped projection-recess pattern 5 on a surface of a decorative design 2 made of a print layer 22 and design layer 21 provided as needed for a base material sheet 1 made of polyolefin resin. And, when the layer 4 is film formed, corona discharging is executed to perform an operation of adhesive on a non-shaped surface of the pattern. And, the layer 4 is constituted by polyolefin resin. When the pattern of a transparent resin layer is used by a method for directly press bonding molted polyolefin resin directly to a cooling roll at the time of forming a resin layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polychlorinated compound which imparts an uneven surface design to furniture, wall surfaces, home appliances, flooring materials and the like, has excellent surface protection performance, and generates hydrochloric acid and the like during incineration treatment. The present invention belongs to a plastic decorative sheet for lamination that does not use a vinyl sheet and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a decorative plastic sheet having excellent surface design and workability, a pattern layer is provided on a colored soft polyvinyl chloride sheet, and vinyl chloride / vinyl acetate which is a binder of the ink of the pattern layer is used. A decorative sheet was formed by doubling embossing, in which a transparent polyvinyl chloride or the like was heat-laminated at the same time as a transparent polyvinyl chloride, using a system copolymer as a heat-sensitive adhesive resin layer.

[0003] The plastic decorative sheet is laminated on a wood plywood, a metal plate or the like with an adhesive, and has been subjected to processing such as so-called V-cut. However, decorative sheets based on polyvinyl chloride contain chlorine in their constituents, and generate hydrogen chloride when burning their waste, causing pollution problems such as damage to incinerators and acid rain. In addition, there is a problem that human casualties occur in the event of a fire. There is a disadvantage that the surface is poor in stain resistance due to leaching of the plasticizer.

[0004] Attempts have been made to use polyolefin resins as resins in place of polyvinyl chloride. However, when attempting doubling embossing in the same manner as conventional polyvinyl chloride using a polyolefin-based resin, the work cannot proceed due to fusing of the film due to the high molding temperature of the uneven pattern, and when the processing temperature is lowered, There was a problem that air remained between the films, that is, bubbles were entrapped and the appearance was poor.

[0005] In addition, lamination by dry lamination using a reactive adhesive such as polyurethane has been attempted, as well as the non-imprinted surface of a transparent polyolefin film in which a concavo-convex pattern has been preliminarily formed as a protective layer and a printed polyolefin sheet. Since the film has an uneven pattern, there is a problem that both films cannot be uniformly adhered to each other and bubbles are trapped.

[0006]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems caused by chlorine, a polyolefin resin is printed on a base sheet made of a polyolefin resin and a protective layer by using an adhesive without a return of an uneven pattern. It is an object of the present invention to provide a decorative sheet having no air residue, in which a laminate of a sheet and a transparent polyolefin film having an embossed pattern is uniformly adhered, and a method for producing the same.

[0007]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides a decorative pattern provided on a base sheet made of a polyolefin resin, an ultraviolet-curable resin layer, and a melt-extruded film-forming material. It is composed of a laminate of a molded irregularity pattern and a transparent resin layer subjected to a corona discharge treatment on the non-imprinted surface (or both surfaces if necessary), and the surface of the transparent resin layer has a polyolefin resin irregularity pattern. It is a decorative sheet and its manufacturing method. Further, a transparent resin layer provided with a corona discharge treatment and an ultraviolet curable resin layer on a non-molded surface, and a surface of a decorative pattern provided on a base sheet made of a polyolefin-based resin and a melt-extruded film-formed embossed pattern. And a method of manufacturing the decorative sheet, wherein the transparent resin layer has a colored uneven pattern formed by wiping and / or a surface protective layer.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION As shown in FIG.
A UV-curable resin layer 3 on a surface of a decorative pattern 2 composed of a solid printed layer 22 and a pattern layer 21 provided on a base sheet 1 made of a polyolefin resin as required, and a pattern 5 formed by melt extrusion. And a transparent resin layer 4 having the following. The decorative sheet 10 is provided with a corona discharge treatment and an ultraviolet curable resin layer 3 provided on the non-imprinted surface of the transparent resin layer 4 and laminated, and a method of manufacturing the same. (Hereinafter, in the present specification, the transparent resin layer is described as including the ultraviolet-curable resin layer and the polyolefin-based resin layer.) As shown in FIG. A decorative sheet provided with a surface protection layer 7 on a wiping portion 6 as shown in FIG. 3, and a method for manufacturing the same.

The base sheet of the present invention is a polymer mainly composed of polyolefin, such as polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / butene-1 copolymer, propylene / butene-1 copolymer, and polyolefin. Stretched and unstretched thickness of methylpentene, olefin-based elastomer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ionomer, saponified ethylene-vinyl acetate copolymer Is a sheet of 50 to 500 μm.
In particular, an unstretched sheet that is easily stretched is preferably subjected to a bending process such as a V-cut process. When providing a decorative pattern, coloring corresponding to a solid print layer can be made high in density and high in hiding power (opaque).

[0010] Pigments used for coloring the base sheet include inorganic pigments such as titanium white, red iron oxide, carbon black, ultramarine and navy blue, quinacridone, isoindoline, phthalocyanine blue aniline black, aluminum powder, copper powder, and metal-deposited synthetic resin. Colorants such as organic pigments or dyes such as finely cut pieces of film, pearly luster such as titanium dioxide-coated mica, and fish scale foil can be used. In addition, fillers such as calcium carbonate, silica, alumina, and barium sulfate are added as necessary.

In order to make the base sheet flame-retardant,
The resin 100 may be made of magnesium hydroxide, aluminum hydroxide, antimony trioxide, etc., depending on the desired degree of flame retardancy.
It is added in the range of 10 to 100 parts by weight with respect to parts by weight in consideration of the suitability for post-processing such as film formation. (If the amount is too small, there is no effect, and if the amount is excessive, the workability deteriorates.) In addition, an ultraviolet absorber and / or a light stabilizer for improving light resistance may be added.

The base sheet is preferably subjected to a corona discharge treatment on both sides thereof.
Adhesive strength between the adhesive and the plywood or the like can be increased.

For the decorative pattern of the picture layer including the solid print layer, a usual printing method such as gravure printing, silk screen printing, letterpress printing or the like can be used. In addition, drawing and transfer printing can also be performed. In addition, the base sheet of polyolefin may cause unevenness in the adhesion of the ink depending on the coloring material contained in the ink. Therefore, providing a primer layer prior to printing the ink is advantageous for stabilizing the adhesion. .

For the primer layer, a varnish containing no particles such as pigments can be used. The primer layer is made of a thermoplastic resin such as linear polyester or urethane, and is reactive with polyol, isocyanate, polyester isocyanate, epoxy or acrylic. Can be selected from compositions having And when the primer layer and the solid printing layer are performed in the same process, immediately after coating, or even if the primer layer has some tackiness after the reaction,
Since blocking can be prevented by the solid printing layer, a material that remains sticky can be used.

The transparent resin layer of the present invention is a polymer mainly composed of polyolefin, such as polyethylene, polypropylene, ethylene / propylene copolymer, propylene / butene-1 copolymer, polymethylpentene, olefin-based elastomer, ethylene / propylene copolymer. Acrylic acid copolymers, ethylene / acrylic ester copolymers, ionomers, saponified ethylene / vinyl acetate copolymers, and the like can be selected from those capable of forming a melt-extruded film and forming an uneven pattern.

The polyolefin resin constituting the transparent resin layer may include an ultraviolet absorber and / or a light stabilizer in order to improve the light resistance of the decorative sheet (discoloration of the decorative pattern, prevention of deterioration of the transparent resin layer by light). Is added.

When forming the resin layer, the concave and convex pattern of the transparent resin layer is formed by pressing the melted polyolefin resin on a cooling roll having the concave and convex pattern with an air knife or a rubber roll, and cooling and peeling. In a separate step, the polyolefin sheet cooled by the above method can be formed by press-bonding and cooling-peeling to a cooling roll having an uneven pattern in a heated and molten state. Preferably, a method in which the molten resin is directly compression-molded on a cooling roll can preferably provide a shaped state.

When forming the transparent resin layer, a corona discharge treatment is performed on the non-shaped surface of the uneven pattern to exert the effect of the adhesive. It is preferable that the corona discharge treatment is performed on the sheet immediately after film formation, and the degree of the treatment is 40 to 50 according to a test method based on JIS K6768.
It is preferable to set the surface tension to be dyn / cm.

The ultraviolet curable resin used as an adhesive between the face of the decorative pattern of the substrate sheet and the transparent resin layer is a prepolymer, polymer and / or polymer having a polymerizable unsaturated bond or a cationically polymerizable functional group in the molecule. Alternatively, a composition which is appropriately mixed with a monomer and which can be cured by ultraviolet rays is preferably used. UV-curable resins have a (meth) acryloyl group in the molecule (in the present application,
An acryloy group and a methacryloy group are simply referred to as a (meth) acryloy group. ), A radical polymerizable unsaturated group such as a (meth) acryloyloxy group, a cationic polymerizable functional group such as an epoxy group, or a monomer, a prepolymer or a polymer having two or more thiol groups. These monomers, prepolymers or polymers are used alone or as a mixture of two or more.

Examples of the prepolymer having a radical polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and silicon (meth). Acrylate and the like can be used. Those having a molecular weight of 250 to 10,000 are used. As the polymer having a radically polymerizable unsaturated group, those having a degree of polymerization of about 1000 formed above are used.

Examples of the prepolymer having a cationically polymerizable functional group include prepolymers of epoxy resins such as bisphenol epoxy resins and novolak epoxy resins, and vinyl ether resins such as aliphatic vinyl ethers and aromatic vinyl ethers. Examples of the monomer having a radical polymerizable unsaturated group include methyl (meth) acrylate, monofunctional monomer of (meth) acrylate compound,
-Ethylhexyl (meth) acrylate, phenoxy (meth) acrylate and the like.

Examples of the polyfunctional monomer having a radical polymerizable unsaturated group include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane. Examples include ethylene oxide tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

As examples of the monomer having a cationically polymerizable functional group, the above-mentioned prepolymeric monomer having a cationically polymerizable functional group can be used. Examples of the monomer having a thiol group include trimethylolpropane trithioglycolate and dipentaerythritol tetraglycolate.

In order to cure the above composition with ultraviolet light or visible light, a photopolymerization initiator is added. As the photopolymerization initiator in the case of a resin composition having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, and the like can be used alone or in combination. Further, the photopolymerization initiator in the case of a composition having a cationically polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metallocene compound, a benzoin sulfonic acid ester or the like is used alone or as a mixture. be able to. If necessary for these UV-curable resins, thermoplastic resins such as vinyl chloride / vinyl acetate copolymers, polyvinyl acetate, acrylic resins, cellulose derivatives, etc. may be used as plasticizers or anti-adhesives, or calcium carbonate, sulfuric acid, etc. An extender made of fine powder such as barium, silica, and alumina, and a coloring agent such as a dye and a pigment can be used.

When the above-mentioned UV-curable resin is applied to a transparent resin layer, a gravure coat or a roll coat in which a normal coating pressure is uniformly applied because a concave-convex pattern is formed on the back surface, The coating amount is not uniform due to uneven pressure. In such a case, the coating is performed by a method such as reverse coating using a rubber roll, comma coating, bar coating, or flow coating. (In the present specification, coating weight solids, is described in g / m ^2.) Coating amount is 2 to 30 g / m ^2. High amounts not only waste resources, but also may cause cracks in the decorative sheet due to the cured adhesive layer. On the other hand, if the amount is less than 2 g / m ² , pressure cannot be applied uniformly during pressure bonding, and air residue may be generated.

Light sources for curing the ultraviolet-curable resin layer include:
Light sources such as ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, and metal halide lamps can be used.
Ultraviolet light, usually in the wavelength range of 1900 to 3800 °, is used. In addition, as long as the polyolefin-based resin does not deteriorate, curing can be performed by irradiation with a light electron beam.

In the wiping process, only the concave portion is colored by filling the concave portion with a coloring ink. The surface of the transparent resin layer on which the uneven pattern has been formed is subjected to an easy adhesion treatment such as a corona discharge treatment as necessary, and a paint using a urethane-based resin as a binder is applied to the entire surface. The image is formed by wiping with a doctor blade, an air knife or a roller having a sponge, a cloth, or the like as a surface, removing the paint on the convex portion, and coloring only the concave portion with the paint filled. If necessary, a small amount of paint other than the concave portions may be left to assist in coloring the surface. Further, a surface protective layer may be provided for the purpose of protecting the above colored layer and improving the scratch resistance of the transparent resin layer. The surface protective layer can be appropriately selected from conventionally known ones corresponding to the transparent resin layer. For example, a two-component curable polyurethane using a curing agent such as isocyanate or amine, polyester, urethane acrylate, or the like can be used.
For coating, conventionally known methods such as roll coating, gravure reverse coating, and spray coating can be used.

Next, the present invention will be described in more detail based on examples. (Example 1) As shown in FIG.
Thickness of linear polyethylene treated with double-sided corona discharge treatment with a density of 0.915 g / cm ³ and colored with a mixed pigment mainly composed of red iron oxide, carbon black and isoindolinone
On one side of a 50 μm base sheet, a solid printing layer 22 and a picture layer 2 with an ink using polyurethane as a binder.
1 was formed. On the other hand, a resin composition obtained by adding 0.5% by weight of bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebasate to a copolymer of propylene and α-olefin was used to form a wood pattern using a T-die film forming machine. The molten resin is pressed and cooled with an air knife to form a wood grain pattern (conduit part) on a cooling roll created by engraving the pattern, and a wood grain pattern (conduit part) is formed. A resin layer 4 was formed.
On the non-imprinting surface of the transparent resin layer 3, Three Bond 3000 (adhesive made of an ultraviolet curable resin) manufactured by Three Bond Co.,
5 g / m ² coating, decorative pattern 2 provided on base sheet 1
And crimped. Then, the decorative sheet 10 of the present invention was prepared by irradiating ultraviolet rays under the condition of 240 W / cm ² to cure the ultraviolet curable resin. The formed decorative sheet 10 did not have a heating history required for lamination and curing, and ultraviolet light did not have a strong action like an electron beam, so the sheet was not deteriorated and curing of the adhesive could be completed. .

(Example 2) The surface of the transparent resin layer of the decorative sheet 10 prepared in Example 1 was subjected to wiping processing to prepare a decorative sheet 11 of Example 2 shown in FIG.

(Example 3) On the surface of the transparent resin layer of the decorative sheet 11 prepared in Example 2, 5 ultraviolet curable resin was applied.
g / m ^{2 was} applied and irradiated with ultraviolet rays to provide the surface protective layer 7, thereby preparing the decorative sheet 12 of Example 3 shown in FIG.

(Comparative Example 1) A decorative pattern 2 of a base sheet 1 and a transparent resin layer 3 prepared in the same manner as in Example 1 and having the same resin composition as in Example 1 were prepared by ionizing radiation-curing type from which a photosensitizer was removed. The resin is irradiated with an electron beam of 250 KV, 6 Mrad,
The decorative sheet 10 of Comparative Example 1 was prepared by curing the ionizing radiation-curable resin.

Comparative Example 2 A 50 μm thick transparent resin layer 4 having a wood pattern of a concave portion was formed using a T-die with the same resin composition and film forming method as in Example 1. On the other hand, 5 g / m ² of a polyester isocyanate-based adhesive (corresponding to Example 3) was applied to the surface of the decorative pattern 2 provided on the base sheet 1 prepared in Example 1 by gravure coating, and the solvent was dried. The winding of the transparent resin layer 4 which was pressed against the non-shaped surface was aged at 40 ° C. for 72 hours to complete the curing of the adhesive layer. Thus, the decorative sheet 11 of Comparative Example 2 was produced.

(Comparative Example 3) The transparent resin layer of the decorative sheet 11 prepared in Example 2 was coated with a urethane resin at 5 g / m ² by isocyanate curing, and aged. The decorative sheet 12 of Comparative Example 3 similar to that of FIG. 3 was prepared.

(Comparative Example 4) The face of the decorative pattern of the base sheet 1 provided with the decorative pattern 2 prepared in Example 1 and the non-shaped face of the polypropylene sheet on which the wood pattern was formed were formed. The decorative sheet 10 of Comparative Example 4 was formed by bonding in the same manner as in Example 1.

(Comparative Example 5) The face of the decorative pattern of the base sheet 1 provided with the decorative pattern 2 prepared in Example 1 and a polypropylene sheet of a 100 μm-thick mirror formed by the T-die method were heated by a hot roll. The laminate was pressure-bonded and subjected to heat lamination to prepare a decorative sheet having no UV-curable resin.

The samples of Examples and Comparative Examples were evaluated for residual air, deterioration of the film, change in the shape of the concavo-convex pattern, and scratch resistance by the following evaluation methods. The results are shown in Tables 1 and 2. Air remaining: Evaluate visually. ○ No hug. △ There is a little hug. Film deterioration: 4 with sunshine fade meter
After irradiation for 00 hours, the sample is bent at 20 ° C., and the change in the bent surface is visually evaluated. ○ No change. Δ: Some cracks are observed. Change in unevenness pattern: After leaving in an oven at 100 ° C. for 1000 hours, the change in the unevenness pattern is visually evaluated. ○ No change. △ There is a slight return. Surface strength: The scratch resistance is evaluated by pencil hardness. ○ 2H or more. △ F or less. (Below)

[0037]

[Table 1]

[0038]

[Table 2]

As described in detail above, according to the present invention, since it is made of a material containing no chlorine, acid rain and generation of hydrogen chloride are observed as in the incineration of a decorative sheet made of polyvinyl chloride. There is no pollution from incineration.
Further, since the transparent resin layer is provided as an adhesive layer using an ultraviolet-curable resin, an effect of preventing remaining air, deterioration of the film, return of the uneven pattern, and the like, which are conventionally observed in the laminate of the polyolefin-based resin, can be obtained. And the thing by the wiping process which comprised the surface layer is excellent in abrasion resistance, and comprises a decorative sheet.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a decorative sheet of the present invention.

FIG. 2 is a schematic sectional view of a decorative sheet subjected to wiping processing according to the present invention.

FIG. 3 is a schematic cross-sectional view of a decorative sheet provided with a wiping process and a protective layer according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base sheet 2 Decorative pattern 21 Picture layer 22 Solid printing layer 3 UV curable resin layer 4 Transparent resin layer 5 Irregular pattern layer 6 Wiping processing part 7 Surface protective layer 10, 11, 12 Decorative sheet

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C08J 7/00 303 C08J 7/00 303 B29L 9:00

Claims (4)

[Claims] 1. A corona discharge treatment is applied to a surface of a decorative pattern provided on a base sheet made of a polyolefin resin, a UV-curable resin layer, and a non-molded surface formed by a melt-extruded film-formed embossed pattern. Made of a laminate with a transparent resin layer, and
A decorative sheet, wherein the transparent resin layer has an uneven pattern of a polyolefin-based resin layer. 2. The surface of a decorative pattern provided on a base sheet made of a polyolefin resin is subjected to a corona discharge treatment on an ultraviolet-curable resin layer, and a concavo-convex pattern formed by melt extrusion film formation and a non-molded surface. A decorative sheet comprising a laminate with a transparent resin layer, wherein the polyolefin resin on the surface of the transparent resin layer comprises a colored uneven pattern formed by wiping and / or a surface protective layer. 3. A corona coating is applied to a face of a decorative pattern provided on a base sheet made of a polyolefin resin and to a non-shaped face of a transparent polyolefin resin layer formed by forming a concavo-convex pattern simultaneously with melt extrusion film formation. 2. The makeup according to claim 1, wherein an electric discharge treatment is performed, an ultraviolet curing resin layer is further provided, and lamination and pressure bonding are performed. Then, ultraviolet light is irradiated from the transparent polyolefin resin layer side to cure the ultraviolet curing resin. Sheet manufacturing method. 4. A surface of a decorative pattern provided on a base sheet made of a polyolefin-based resin, and a non-shaped surface of a transparent polyolefin-based resin layer formed by shaping a concavo-convex pattern simultaneously with melt extrusion film formation. After performing corona discharge treatment, further providing an ultraviolet curing resin layer, laminating and pressing, irradiating ultraviolet rays from the transparent polyolefin resin layer side to cure the ultraviolet curing resin, and wiping processing on the surface side of the transparent polyolefin resin layer 3. The method for producing a decorative sheet according to claim 2, wherein a colored uneven pattern is provided by the method, and a protective layer is further formed as necessary.