JPH10211638A - Manufacture of decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To contrive to prevent the lowering of productivity and loss from developing even in small lot production, in manufacturing an embossed decorative sheet using olefin-based elastomer resin. SOLUTION: In order to manufacture this decorative sheet, a printed sheet is formed by providing a printing ink layer 2 on a base material sheet made of olefin-based thermoplastic elstomer. After that, a transparent olefin-based thermoplastic elastomer resin layer, which is made of two or more layers and the pasting side layer of which is made of easily bondable resin, is extruded under melted state from a multi-layer extruder onto the printed surface of the printed sheet for lamination in order to form a top sheet 3. After that, the top sheet 3 is subjected off-line to a thermal embossing work.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a decorative sheet having a high design used by being bonded to a surface of a wooden board / bar, a metal plate or the like.

[0002]

Heretofore, as a base sheet and a top sheet of a decorative sheet for building materials, a PVC resin such as a vinyl chloride sheet or a vinyl chloride-vinyl acetate copolymer sheet has been generally used. These sheets have advantages such as excellent workability, printability, and embossability, the hardness of which can be easily adjusted by the amount of plasticizer added, and the low cost. However, this type of decorative sheet has a drawback that the heat resistance is insufficient or the surface has poor stain resistance due to bleeding of the plasticizer.

[0003] In recent years, olefin resins and olefin elastomer resins have been used as resins in place of PVC resins,
A method has been proposed in which two or more layers of the resin (transparent) are simultaneously extruded and laminated in a molten state on a printed base sheet using a multilayer extruder, and simultaneously embossed. In this method, the embossed pattern is changed according to the pattern of the base material sheet, and when the production of the decorative sheet becomes small-lot and many kinds, it takes a long time to replace the embossed plate, and the extrusion conditions of the extruded resin are stabilized. The loss of printed sheet and extruded resin up to the point increases. In recent years, there has been a tendency for small lots of various kinds, and this problem cannot be ignored.

A method has also been proposed in which an olefin-based resin or an olefin-based elastomer resin is extruded and embossed simultaneously to form an embossed transparent sheet, and an adhesive is applied to the printed sheet in-line and dry-laminated. When the dry lamination is performed in-line in this manner, the productivity problems such as the replacement of the embossing plate are not solved, and the dry lamination has a problem that air enters at the time of lamination and a problem of high cost due to an adhesive.

The present invention has been made in view of the above problems, and has as its object to manufacture an embossed decorative sheet using an olefin-based thermoplastic elastomer resin that does not adversely affect the environment. In this regard, it is an object of the present invention to provide a method for manufacturing a decorative sheet that can reduce productivity and prevent loss even in a small lot.

[0006]

Means for Solving the Problems To achieve the above object, a method for producing a decorative sheet according to the present invention comprises providing a printing ink layer on a base sheet made of an olefin-based thermoplastic elastomer resin to form a printed sheet. After that, two or more transparent olefin-based thermoplastic elastomer resin layers whose bonding side is an easily adhesive resin are extruded and laminated on the printing surface of the printing sheet in a molten state by a multilayer extruder, and then offline. The heat embossing is performed.

[0007] A printing sheet may be formed by providing a printing ink layer and a heat-adhesive anchor layer on the base sheet. After the hot embossing, the wiping and the surface protection resin coating may be performed.

[0008] In the manufacturing method having the above-mentioned structure, no harmful gas is generated at the time of incineration because the olefin-based thermoplastic elastomer resin is used as the material of the decorative sheet. Also,
A transparent olefin-based thermoplastic elastomer resin consisting of two or more layers in a molten state was laminated on the print sheet by co-extrusion as a top sheet, and then hot-embossed off-line to reduce the production quantity per pattern. In this case, productivity reduction and loss in the extrusion resin laminating step are prevented, and the embossed decorative sheet can be manufactured inexpensively as a whole. In addition, since the thermocompression bonding is performed twice, ie, when laminating the top sheet and when performing the hot embossing, the adhesion between the base sheet and the top sheet is improved.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION There are six types of the following olefinic thermoplastic elastomers used for a substrate sheet.

A simple blend of (A) an olefin elastomer as a soft segment and (B) an olefin resin as a hard segment. Specifically, as the olefin resin, polyethylene, ethylene / propylene copolymer, ethylene / butene-1 copolymer, polypropylene, propylene / butene-1 copolymer, polybutene-1, butene-1 / propylene / ethylene A terpolymer, butene-1, hexene-1, octene-1, terpolymer, polymethylpentene, or a resin alone or a mixture of two or more resins. Examples of the olefin elastomer include various rubbers. Examples of the rubber include a diene rubber and a hydrogenated diene rubber, and among them, a hydrogenated diene rubber is preferable.

The hydrogenated diene rubber is obtained by adding a hydrogen atom to at least a part of the double bond of the diene rubber molecule, and suppresses crystallization of the polyolefin resin.
It plays a role in improving flexibility and transparency. Also, generally, when a diene rubber is added to a polyolefin resin, the double bond of the diene rubber causes the weather resistance and heat resistance to be lower than those of the polyolefin resin without the diene rubber.
In the present invention, since the double bond of the diene rubber is saturated with hydrogen, the polyolefin resin has good weather resistance and heat resistance without deterioration. Examples of the diene rubber include isoprene rubber, butadiene rubber, butyl rubber, propylene / butadiene rubber, acrylonitrile / butadiene rubber, acrylonitrile / isoprene rubber, and styrene / butadiene rubber. For the purpose of the present invention, styrene-butadiene rubber is particularly preferred.

The rubber is added in an amount of about 1 to 90 parts by weight based on 100 parts by weight of the olefin resin.
If the amount is less than 1 part by weight, the elasticity, elongation, and impact resistance due to the addition of rubber are insufficient, and cracks and cracks are likely to occur during bending such as V-cutting and drawing. On the other hand, if it exceeds 90 parts by weight, the elasticity and elongation become too large, and the registration during printing becomes poor, which is not preferable.

Further, as the olefin elastomer,
Olefin-based thermoplastic elastomers such as those described below may be used.

(A) The number average molecular weight Mn is 25,000 or more, and the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn as described in JP-B-6-23278.
From a mixture of 10 to 90% by weight of a boiling heptane-soluble polypropylene of ≦ 7 (soft segment) and (B) 90 to 10% by weight of a boiling heptane-insoluble polypropylene (hard segment) having a melt index of 0.1 to 4 g / 10 min. Becomes soft polypropylene.

As described in JP-B-53-21021, (A) an olefin polymer (crystalline polymer) such as polyethylene, polypropylene or polymethylpentene is used as a hard segment, and (B) a partially crosslinked ethylene / propylene is used. An olefin elastomer obtained by using a soft segment of a monoolefin copolymer rubber such as a copolymer rubber or an unsaturated ethylene / propylene non-conjugated diene terpolymer rubber as a soft segment, and uniformly mixing and mixing these. (B) / (A)
= 50/50 to 90/10 (weight ratio).

As described in JP-B-53-34210, (A) an uncrosslinked monoolefin copolymer rubber (soft segment), (B) an olefin copolymer (crystalline, hard segment) and a crosslinking agent are mixed. An olefin elastomer obtained by heating and applying a shear stress to dynamically partially crosslink. (A) / (B) = 60 / 40-80 / 20
(Weight ratio).

As described in JP-B-56-15575, etc., (A) mixed with a peroxide such as isotactic polypropylene, propylene / ethylene copolymer or propylene / butene-1 copolymer, and the molecular weight is reduced by heating. By mixing and heating a peroxide-decomposable olefin polymer (hard segment) that increases fluidity and a peroxide such as (B) ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene terpolymer rubber, Mixing with peroxides such as peroxide-crosslinked monoolefin copolymer rubber (soft segment) whose flowability is reduced by crosslinking, (C) polyisobutylene, butyl rubber, etc.
Peroxide non-crosslinked hydrocarbon rubber (soft segment and fluidity-modifying component) that does not crosslink even when heated and does not change its flowability, and (D) mineral oil softening such as paraffinic, naphthenic, aromatic, etc. An olefin-based elastomer obtained by mixing the agent and an agent and dynamically heat-treating the mixture in the presence of an organic peroxide. (A) is 90 to 40 parts by weight, (B) is 10 to 60 parts by weight, and (C) and (D) are 5 to 100 parts by weight.

An olefin elastomer comprising an ethylene / styrene / butylene copolymer as described in JP-A-2-139232.

These olefinic thermoplastic elastomers may optionally contain a coloring agent, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a flame retardant,
A foaming agent or the like is added.

Examples of the coloring agent include inorganic pigments such as titanium white, zinc white, red iron oxide, vermilion, ultramarine blue, cobalt blue, titanium yellow, carbon black, isoindoline, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue and the like. Organic pigments, dyes, metal pigments such as aluminum and brass, pearlescent pigments made of titanium dioxide-coated mica, and foil powders such as basic zinc carbonate. Also, an inorganic filler may be added as necessary,
Examples of the inorganic filler include powders such as calcium carbonate, barium sulfate, clay, talc, silica (silicon dioxide), and alumina (aluminum oxide). The base sheet is colored transparent or colored opaque depending on the application,
Generally, colored opaque is preferable because the surface of the adherend can be concealed.

The UV absorber and the light stabilizer are for imparting good weather resistance (light resistance) to the resin, and the amount of the UV absorber and the light stabilizer is usually 0.5 to 1
It is about 0% by weight. Generally, it is preferable to use an ultraviolet absorber and a light stabilizer in combination. As an ultraviolet absorber,
Organic substances such as benzotriazole, benzophenone, and salicylate, or inorganic substances such as zinc oxide, cerium oxide, and titanium oxide having a diameter of 0.2 μm or less can be used. As light stabilizers, bis- (2,2,
Radical scavengers such as hindered amine radical scavengers such as 6,6-tetramethyl-4-piperidinyl) sebacate and piperidine radical scavengers can be used.

Since the adhesive strength between the base sheet and the top sheet deteriorates with the lapse of time due to ultraviolet rays, it is not sufficient to secure the initial adhesive strength as a decorative sheet during production. (Plaque panel 63 ° C.) In order to provide sufficient adhesion strength as a decorative sheet even after irradiation, an ultraviolet absorber may be added to the top sheet. As a result of various studies, it is preferable to add a benzotriazole-based UV absorber at 0.1% by weight or more or a hindered amine-based UV absorber at 0.1% by weight or more as a result of various studies.

Known heat stabilizers such as phenol-based, sulfite-based, phenylalkane-based, phosphite-based, and amine-based stabilizers are used. These stabilizers are more effective in preventing deterioration such as thermal discoloration during thermal processing. Improve.

As the flame retardant, powders such as aluminum hydroxide and magnesium hydroxide are used, and these are added when it is necessary to impart flame retardancy.

Further, as a preferable base sheet for use in the present invention, a sheet comprising a high-density polyethylene resin, a thermoplastic elastomer, a colorant and an inorganic filler is exemplified. According to the sheet, the performance required as a decorative sheet, that is, thermoformability similar to polyvinyl chloride, creep deformation resistance, cold bending resistance, organic solvent resistance, elongation at break, impact strength, moderate A material that satisfies a high flexural modulus and easy adhesion is obtained.

As the high-density polyethylene, it is more preferable to use a polyethylene having a specific gravity of 0.94 to 0.96 and having a high degree of crystallinity obtained by a low-pressure method and having a small number of branched structures. . Examples of the thermoplastic elastomer include a diene rubber, a hydrogenated diene rubber, and an olefin elastomer. The amount of the thermoplastic elastomer added is 10 to 6 in the base sheet.
It is about 0% by weight, preferably about 30% by weight. If the amount is less than 10% by weight, the change in elongation at a constant load becomes too sharp, and the elongation at break and the impact resistance decrease. If the amount is more than 60% by weight, the transparency, weather resistance and creep resistance are reduced. A drop occurs. The same inorganic filler as described above is used as the inorganic filler, and is added to the base sheet in an amount of about 5 to 60% by weight, preferably about 30% by weight. 5 added
If the amount is less than 60% by weight, the creep deformation resistance and the easy adhesion decrease. If the amount is more than 60% by weight, the elongation at break and the impact resistance decrease. As the colorant, the same one as described above is used.

Preferred examples of the transparent olefin-based thermoplastic elastomer provided on the surface include those described in the description of the olefin-based thermoplastic elastomer above.
It is a sheet made of a colorless or colored transparent soft polypropylene-based resin having a composite three-dimensional structure, comprising a mixed system of isotactic polypropylene and atactic polypropylene. According to the sheet made of the soft polypropylene resin having the above composite three-dimensional structure, the performance required as a decorative sheet, namely, creep deformation resistance, organic solvent resistance, elongation at break, impact strength, moderate flexural modulus And good transparency and weather resistance (no whitening or turbidity due to recrystallization even when heating and cooling accompanying embossing or the like are applied). Specific examples of the soft polypropylene resin include (A) (a) a solid catalyst component containing magnesium, titanium, a halogen atom and an electron donor as essential components, (b) an organoaluminum compound, and (c) a general aluminum compound. Formula 1

Embedded image (Wherein R ¹ is an alkyl group having 1 to 20 carbon atoms, R ² is a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or a nitroso group, m
Is an integer of 1 to 6, and n is an integer of 0 or 1 to (6-m)), and is obtained by polymerizing propylene in the presence of a catalyst comprising a combination of alkoxy group-containing aromatic compounds. , The number average molecular weight (Mn) is 25,000
Boiling heptane-soluble polypropylene (atactic polypropylene) having a weight average molecular weight (Mw) of 0 or more and a ratio (Mw / Mn) of number average molecular weight (Mn) of 7 or less
10 to 90% by weight and (B) the melt index is 0.1%.
90 to 10% by weight of boiling heptane-insoluble polypropylene (isotactic polypropylene) of 1 to 4 g / 10 minutes
And a soft polypropylene resin composition comprising:

The above soft polypropylene resin composition has an elongation at break (T _b ) of 400% or more, preferably 500 to 7%.
Residual elongation (PS ₁₀₀ ) after 100% and 100% elongation is 80
%, Preferably 50 to 75%, and the stress at break (M
_B ) and the stress at yield (M _Y ) (M _B / M _Y ) are 1.
It is desirably in the range of 0 or more, preferably in the range of 1.5 to 3.5.

In the above soft polypropylene resin composition, the atactic polypropylene as the component (A) is soluble in boiling heptane and has a number average molecular weight (M
n) is 25,000 or more, preferably 30,000 to 6
Weight average molecular weight (Mw) in the range of 000
And a number average molecular weight (Mn) having a ratio Mw / Mn of 7 or less, preferably 2 to 6. This M
When n is less than 25,000 or when the Mw / Mn ratio exceeds 7, the effect of contributing to the mechanical properties of the atactic polypropylene in the obtained resin is not sufficiently exhibited, and the stress at break of the obtained resin ( The ratio of (M _B ) to the stress at yield (M _Y ) is less than 1.0, and the residual elongation (PS ₁₀₀ ) after 100% elongation exceeds 80%, which is not desirable.

The atactic polypropylene of the component (A) may be a homopolymer of propylene, or may contain propylene units and 40% by weight or less, preferably 30% by weight or less of other α-alkyl having 2 to 30 carbon atoms. It may be a propylene copolymer containing an olefin unit. Further, this atactic polypropylene may be used alone or in combination of two or more. The atactic polypropylene of the component (A) can be produced by a known method (Japanese Patent Publication No. 23278/1994).

In the above soft polypropylene resin composition, as the component (B), a melt index (MI)
However, boiling heptane-insoluble crystalline isotactic polypropylene of 0.1 to 4 g / 10 min is used. If the melt index is less than 0.1 g / 10 minutes, the melting properties are low, and sheet forming becomes difficult. If the melt index exceeds 4 g / 10 minutes, the mechanical strength becomes insufficient and V-cutting may not be performed well. There is. The isotactic polypropylene of the component (B) may be a propylene homopolymer having isotactic stereoregularity,
It may be a copolymer of propylene having the stereoregularity and another α-olefin. The α-olefin has 2 to 8 carbon atoms, such as ethylene and butene-1.
Pentene-1, heptene-1, octene-1 and the like are preferred, and among them, ethylene and butene-1 are preferred. As the copolymer, a block copolymer or a random copolymer containing the above-mentioned α-olefin unit in an amount of usually 40% by weight or less, preferably 30% by weight or less is used.

Preferred examples of the isotactic polypropylene as the component (B) include a propylene homopolymer and 1 to 30% by weight of ethylene units, preferably 3 to 30% by weight.
A random copolymer or block copolymer of propylene and ethylene containing 25% by weight is exemplified. The production of such isotactic polypropylene can be performed in the same manner as the production of conventional crystalline polypropylene.

In the above soft polypropylene resin composition, the isotactic polypropylene of the component (B) may be used alone or in combination of two or more. The atactic polypropylene of the component (A) and the isotactic polypropylene of the component (B) have a content of the component (A) of 10 to 90% by weight, preferably 25 to 80% by weight, and the component (B) Content of 90 to
It is used in such a proportion that it becomes 10% by weight, preferably 75 to 20% by weight. The content of the component (A) is 10% by weight.
If it is less than 1, the stress at yield (M _Y ) of the resin becomes too large, and the ratio M of stress at break (M _B ) to stress at yield (M _Y ) is M.
_{The B} / _MY ratio is less than 1.0, and the residual elongation (PS ₁₀₀ ) after 100% elongation is also larger than 80%. On the other hand, if the content exceeds 90% by weight, the stress at break (M
_B) is too small, the M _B / M _Y ratio is less than 1.0, and the mechanical strength there is a possibility to decrease. Also,
By increasing the ratio of the component (B), the Young's modulus of the obtained soft polypropylene increases. A particularly preferred ratio of the component (A) to the component (B) is 1: 1.

Further, the two-layer structure of the base material sheet and the surface resin layer to be laminated thereon is made of the above-mentioned base material sheet made of the above-described high-density polyethylene resin, thermoplastic elastomer, colorant, and inorganic filler. By forming the layer as a sheet made of a colorless or colored transparent soft polypropylene resin made of a mixed system of the above-mentioned isotactic polypropylene and atactic polypropylene, each sheet shares various conditions required for the decorative sheet described above. As a result, a highly practical decorative sheet of the present invention can be obtained.

The easy-adhesive transparent olefin-based thermoplastic elastomer is the same as the transparent olefin-based thermoplastic elastomer described above, except that olefin-based elastomer and olefin-based resin such as polyethylene, ethylene-α-olefin copolymer, polypropylene, polybutene, and polyisobutylene are used. And polydiolefins such as polybutadiene and polyisoprene or copolymers thereof, for example, carboxylic acids, carboxylate salts, carboxylic anhydrides, carboxylic acid esters, carboxylic acid amides to imides, aldehydes, ketones Ethylene such as a copolymer with one or more ethylenically unsaturated monomers having a carbonyl group based on the like alone or in combination with a cyano group, a hydroxy group, an ether group, an oxirane ring group, etc. With unsaturated monomers And copolymers. Generally, it is sufficient if the thickness is about 10 μm.

Examples of the ethylenically unsaturated monomer having a polar group include: Ethylenically unsaturated carboxylic acids: acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, 5-norbornene-2.3-dicarboxylic acid and the like. B. Ethylenically unsaturated carboxylic anhydride: maleic anhydride, citraconic anhydride, 5-norbornene-2.3-dicarboxylic anhydride, tetrahydrophthalic anhydride and the like. C. Ethylenically unsaturated esters: ethyl acrylate, methyl methacrylate, 2-ethylhexyl acrylate, mono or diethyl maleate, vinyl acetate, vinyl propionate, propyl γ-hydroxy methacrylate, β-
Ethyl hydroxyacrylate, glycidyl acrylate, glycidyl methacrylate, β-N-ethylaminoethyl acrylate, and the like. D. Ethylenically unsaturated amide to imide: acrylamide, methacrylamide, maleimide and the like. E. FIG. Ethylenically unsaturated aldehydes or ketones: acrolein, methacrolein, vinyl methyl ketone, vinyl butyl ketone and the like. Is mentioned.

Preferred as easily adhesive thermoplastic elastomers are homo-chlorine-modified polyolefins and random-polymerized non-chlorine polyolefins. The following metal ions are used as the carboxylate. Na ⁺ , K ⁺ , Li ⁺ , C as monovalent metal ions
There are s ⁺ , Ag ⁺ , Hg ⁺ , and Cu ⁺ , and as divalent metal ions, Be ⁺⁺ , Mg ⁺⁺ , Ca ⁺⁺ , Ba ⁺⁺ , Cu ⁺⁺ , C
d ⁺⁺ , Hg ⁺⁺ , Sn ⁺⁺ , Pb ⁺⁺ , Fe ⁺⁺ , Co ⁺⁺ , Ni
⁺⁺ , Zn ⁺⁺ , and trivalent metal ions include Al ⁺⁺⁺ , Sc
⁺⁺⁺ , Fe ⁺⁺⁺ , and Yt ⁺⁺⁺ . The degree of neutralization is determined by MI after neutralizing the copolymer carboxylic acid with metal ions.
Is in the range of about 2 to 20.

The heat-adhesive anchor layer is used to thermally bond the easily-adhesive olefin-based thermoplastic elastomer layer of the top sheet to the printing ink layer on the base sheet, and uses a reactive hot-melt adhesive. . Further, although the adhesion strength is lowered, an isocyanate-based anchor coating agent (for example, a compound such as tolylene diisocyanate, hexamethylene diisocyanate, etc.) can be used. Ordinary thermoplastic inks can also be used.

As the ink used for the printing ink layer, when the above-mentioned heat-adhesive anchor layer is used, chlorinated olefin-based inks such as chlorinated polyethylene and chlorinated polypropylene, amide-based inks, urethane-based inks, vinyl acetate, A general olefin ink such as a vinyl / vinyl acetate copolymer or a cellulose resin is used. When the heat-adhesive anchor layer is not used, a urethane-based high-temperature reaction type (150 to 250 ° C.) ink is preferable.

As the pattern of the printing ink layer, a wood grain pattern,
Stone patterns, cloth patterns, leather crests, geometric figures, characters, symbols, line drawings, various abstract patterns, and the like may be used.

By providing a primer layer between the substrate sheet and the printing ink layer for improving the ink adhesion, the range of choice of the printing ink vehicle is widened. The same can be said of between the printing ink layer and the thermal adhesive anchor layer or between the printing ink layer and the top sheet. However, since the number of steps increases, it is determined in consideration of the required adhesion strength. As the resin for the primer layer, acryl, vinyl chloride / vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, chlorinated polyethylene and the like are used, and polyurethane is particularly preferable.

FIG. 1 shows an example of hot embossing performed off-line. A in the figure shows a printing sheet in which a printing ink layer 2 or a printing ink layer 2 and a thermoadhesive anchor layer are provided on a base sheet 1 and a top sheet 3 made of two or more transparent olefin-based thermoplastic elastomer resins. It is a finished decorative sheet. In this example, first, the decorative sheet A is pre-heated to 120 to 130 ° C. while being pressure-bonded through the preheat roll 4 so that the base sheet 1 side faces, and then the surface of the embossed surface is further heated from the top sheet 3 side by the panel heater 5. Ignite so that the temperature becomes 180 ° C or higher,
The surface of the top sheet 3 is embossed by passing between the embossing roll 6 and the pressing roll 7 at a temperature set to 70 ° C. or lower. And after applying the hot embossing,
Wiping and surface protection resin coating are performed as necessary.

The embossing plate used for embossing is, for example, one obtained by copying the state of unevenness such as the surface of wood by electroforming to form an embossed pattern of a conduit, or photographing the state of unevenness such as the surface of wood. It is preferable that an embossed pattern of a conduit is formed by a photoetching method using an original prepared by copying by a plate making method. Further, for example, in the case of a stone pattern, the state of unevenness of the stone material surface including a crack or the like can be similarly copied. By using such an embossing plate, it is subjected to heat and pressure molding to form a concave pattern.

FIG. 2 shows one embodiment of the produced decorative sheet. This decorative sheet comprises a printing ink layer 1 on a base sheet 11 made of an olefin-based thermoplastic elastomer resin.
2, and a thermo-adhesive anchor layer 13 as required,
On top of this, a top sheet 16 composed of an easily adhesive transparent olefin-based thermoplastic elastomer resin layer 14 and a transparent olefin-based thermoplastic elastomer resin layer 15 is provided. Then, as shown in the drawing, the top sheet 16 may have a concave pattern by embossing,
Wiping ink 17 may be applied to the concave portion of the concave pattern, and a surface protective coat 18 may be further applied.

Examples of the coloring agent to be filled in the concave portions of the concave pattern on the surface of the top sheet include natural resins such as shellac, corval, dammar, rosin and rosin ester or modified resins thereof, nitrocellulose, acetylcellulose, ethylcellulose and the like. Cellulose derivatives such as benzyl cellulose, phenolic resin, urea resin, phthalic acid resin, maleic acid resin, melamine resin, polyvinyl acetate resin, polyvinyl chloride resin, acrylic resin, polyvinyl alcohol, polyvinyl Butyl, epoxy resin, silicone resin, polyester resin, polyamide resin, polyurethane resin, synthetic resin such as others, and other rubber derivatives such as chlorinated rubber, cyclized rubber, and synthetic rubber are used as vehicle constituent materials. Colorant inside, sedimentable sulfuric acid Extender pigments such as helium, paint or ink is used formed by adding a plasticizer. When an acrylic sheet is used as the transparent thermoplastic resin sheet, it is preferable to use an acrylic or urethane aqueous emulsion type transparent or opaque colored ink.

This colored paint or ink is coated on the concave portion of the sheet surface with a roll coat or knife coat, and then scraped off with a doctor blade or wiping paper to remove the colored paint or ink coated on the convex portion of the sheet. Then, only the concave portion is filled with the colored paint or ink. Here, the viscosity of the paint or the ink composition, the number of rotations of the roll, the angle of the blade of the doctor, the thickness, the sheet speed, the speed of the wiping paper, the hardness of the rubber roll, and the like are set so that the paint or the ink composition remains only in the concave portion. It is necessary to prepare. For example, the color tone of the colored paint or ink is preferably the same or similar to a conduit in the case of a wood pattern, and is preferably the same or similar to a crack in the case of a stone pattern.

Further, in order to impart abrasion resistance and chemical resistance of the decorative sheet and adjust the gloss of the surface, it is preferable to provide a surface protective resin coat layer. As the surface protective resin coat layer, a transparent or translucent resin such as an acrylic resin, a polyurethane resin, or an epoxy resin is used. When an acrylic resin is used on the surface side of the top sheet, an acrylic or urethane-based aqueous resin is used. It is preferable to use an emulsion type. Then, coating is performed by a gravure coat, a roll coat, a knife coat, an air knife, or the like.

[0048]

【Example】

(Example 1) An ink ("Showa Ink Co., Ltd.", "X") made of a vinyl chloride resin was applied to a 100 μm thick base sheet ("Soft Rex" manufactured by Nippon Petrochemical) made of an olefin-based thermoplastic elastomer resin. The pattern is printed using a straight-grain pattern, and an anchor coating agent made of vinyl chloride vinyl chloride / acrylic resin (“UNISTOL P-80” manufactured by Mitsui Petrochemical Co., Ltd.)
5 ") to form a printed sheet by applying a thermal adhesive anchor layer.

The transparent olefin-based thermoplastic elastomer in a molten state and the easily adhesive transparent olefin-based thermoplastic elastomer were simultaneously extruded and laminated on the printed surface of the above-mentioned printed sheet by a multilayer extruder. In this example,
"Tuffmer XR110T" manufactured by Mitsui Petrochemical Industries was used as the transparent olefin-based thermoplastic elastomer, and "Admer QF305" manufactured by Mitsui Petrochemical Industry was used as the easily adhesive transparent olefin-based thermoplastic elastomer. The thickness of the easily adhesive transparent olefin-based thermoplastic elastomer resin layer on the substrate sheet side was 20 μm, and the thickness of the transparent olefin-based thermoplastic elastomer resin layer on the surface side was 80 μm.

The thus obtained decorative sheet is pre-heated and rolled so that the base sheet faces the roll and preheated, and then heated from the top sheet side with a panel heater (180 ° C.), and then embossed. The surface of the top sheet was embossed by passing between a roll and a pressure roll. The obtained decorative sheet had sufficient adhesive strength between layers.

(Example 2) The embossed surface of the decorative sheet obtained in Example 1 was subjected to a corona treatment, and the embossed surface was coated with an acrylic urethane resin-based colored ink ("W-141" manufactured by Showa Ink Industries Co., Ltd.). ), And a urethane resin (“OP, No. 8 manufactured by Showa Ink Industries, Ltd.”).
0 ").

Example 3 Using the same printed sheet as in Example 1, a transparent olefin-based thermoplastic elastomer in a molten state and a transparent olefin-based thermoplastic having a high adhesion property were printed on a printing surface of the printed sheet by a multilayer extruder. The elastomer was extruded and laminated. In this embodiment, as the transparent olefin-based thermoplastic elastomer, a mixed polypropylene composed of isotactic polypropylene and atactic polypropylene (“E-2600” manufactured by Idemitsu Petrochemical)
A resin obtained by blending 0.1% by weight of a benzotriazole-based UV absorber and 0.1% by weight of a hindered amine-based light stabilizer is graft-polymerized with the above-mentioned mixed polypropylene and maleic anhydride as an easily adhesive transparent olefin-based thermoplastic elastomer. A resin made of polypropylene (“Polytac” manufactured by Idemitsu Petrochemical) was used. The thickness of the easily adhesive transparent olefin-based thermoplastic elastomer resin layer on the substrate sheet side was 20 μm, and the thickness of the transparent olefin-based thermoplastic elastomer resin layer on the surface side was 80 μm.

The thus obtained decorative sheet is pre-heated and rolled so that the base sheet faces the roll and preheated, and then heated from the top sheet side with a panel heater (180 ° C.), and then embossed. The surface of the top sheet was embossed by passing between a roll and a pressure roll. Further, the sheet was subjected to a wiping process and a surface protective resin coat to obtain an embossed decorative sheet. The obtained decorative sheet had sufficient adhesive strength between layers.

(Example 4) After the embossed surface of the decorative sheet obtained in Example 3 was subjected to corona treatment, the embossed surface was coated with an acrylic urethane resin-based colored ink ("W-141" manufactured by Showa Ink Industries Co., Ltd.). ), And a urethane resin (“OP, No. 8 manufactured by Showa Ink Industries, Ltd.”).
0 ").

[0055]

As described above, according to the present invention,
After extruding and laminating a transparent olefin-based thermoplastic elastomer consisting of two or more layers on the printed base sheet,
Embossing by heating again off-line minimizes the loss of the EC process, which usually takes a long time to set the conditions and the loss of the base sheet. Since the laminated top resin layer undergoes two thermocompression bonding steps of compression bonding during lamination and thermocompression bonding during embossing, the adhesion between the base sheet and the top sheet is high.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing an example of hot embossing performed off-line.

FIG. 2 is a cross-sectional view showing one embodiment of a decorative sheet manufactured by the present invention.

[Explanation of symbols]

A decorative sheet 1 base sheet 2 printing ink layer 3 top sheet 4 preheat roll 5 panel heater 6 emboss roll 7 pressure roll 11 base sheet 12 printing ink layer 13 heat-adhesive anchor layer 14 easy-adhesive transparent olefin-based thermoplastic elastomer Resin layer 15 Transparent olefin-based thermoplastic elastomer resin layer 16 Top sheet 17 Wiping ink 18 Surface protective coat

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // B29L 9:00

Claims (3)

[Claims] 1. A transparent olefin-based thermoplastic elastomer having two or more layers in which a printing ink layer is provided on a base sheet made of an olefin-based thermoplastic elastomer resin to form a printed sheet, and the bonding side is an easily adhesive resin. A method for manufacturing a decorative sheet, comprising: extruding a resin layer in a molten state by a multilayer extruder onto a printing surface of the printing sheet and laminating the resin layer, and then performing offline hot embossing. 2. The method for producing a decorative sheet according to claim 1, wherein a printing ink layer and a thermo-adhesive anchor layer are provided on the base sheet to form a printed sheet. 3. The method for producing a decorative sheet according to claim 1, wherein a wiping process and a surface protection resin coating are performed after the hot embossing process.