JPH10286928A - Decorative sheet and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet which is almost free from the deterioration of an initial interlayer adhesion strength immediately after manufacturing, and also, an interlayer adhesion strength due to ultraviolet rays or heat and has an adequate strength for use as a building material as well as a method for manufacturing the decorative sheet. SOLUTION: After forming a printing ink layer with an arbitrary pictorial pattern on a base material sheet A made up of an opaque olefin thermoplastic elastomer, a transparent olefin thermoplastic elastomer comprising two or more layers with an easily adhesive resin layer formed on the side to be fitted to a printing face, is extruded from a multilayer extruder and the extrusions are laminated on the printing face of the base material sheet A as a top sheet B. At the time of this lamination, the easily adhesive resin face in the molten transparent olefin thermoplastic elastomer extruded from the die of the extruder 10, is treated by spraying an air G containing an ozone at a high temperature to generate numerous polar functional groups. Thus the multilayer laminate is strongly bonded through a chemical reaction between the vehicle of a printing ink or a primer layer and the functional groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

In recent years, as a decorative sheet not using a PVC resin, a decorative sheet obtained by printing an olefin base sheet and laminating a top sheet made of a transparent olefin resin on the printed surface. However, this type of decorative sheet has a problem that it is difficult to obtain a sufficient adhesion strength between the base sheet and the top sheet (particularly deterioration with time due to ultraviolet rays) because the olefin resin has no polarity. Therefore, a two-layer extruded sheet with an easily adhesive resin is used for the top olefin resin,
A method using a top sheet in which the whole resin is made of an easily adhesive resin, a method in which the surface of a printed base sheet is subjected to ozone treatment, and the resin of the top sheet is extruded and laminated are proposed.

[0003] In the field of building materials, decorative sheets are used as construction materials and the like, and therefore it is required to maintain high quality for a long period of time. In particular, with respect to a decorative sheet having a two-layer structure of a printed base sheet and a transparent top sheet, Sunshine Carbon Arc W.C. O. M. 10
It is required to maintain sufficient adhesion strength even after irradiation for 00 hours, and there is also a demand for a higher level of adhesion. However, although each of the above methods is effective for obtaining the adhesion strength immediately after bonding, it is not always sufficient to reduce the interlayer adhesion over time due to long-term ultraviolet irradiation or heat. Also, a method of adding an ultraviolet absorber to the resin of the top sheet has been proposed,
This is not a fundamental solution.

The present invention has been made in view of the above-mentioned problems, and has as its object to reduce not only the initial interlayer adhesion strength immediately after production but also a decrease in interlayer adhesion strength due to ultraviolet rays or heat. An object of the present invention is to provide a decorative sheet having sufficient strength as a building material and a method for producing the same.

[0005]

Means for Solving the Problems To achieve the above object, the decorative sheet of the present invention is provided with a printing ink layer of an arbitrary pattern on a base sheet made of an opaque olefin-based thermoplastic elastomer, and a printing surface. In a decorative sheet in which a transparent olefin-based thermoplastic elastomer composed of two or more layers having an easily-adhesive resin layer on the side to be fitted is extruded by a multilayer extruder and laminated as a top sheet on a printing surface of a substrate sheet, The present invention is characterized in that air containing ozone is blown at a high temperature onto the easily adhesive resin surface of the transparent olefin-based thermoplastic elastomer in a molten state extruded from a die to generate many polar functional groups.

As described above, according to the present invention, by subjecting the easily adhesive resin surface of the top sheet to ozone treatment at a high temperature, more polar functional groups are generated, and the top sheet is laminated on the printed base sheet at a high temperature. Thus, a reaction occurs between the vehicle or the primer layer of the printing ink and the functional group so that the printing ink is firmly adhered.

[0007]

FIG. 1 is a sectional view showing one embodiment of a decorative sheet according to the present invention. This decorative sheet has two or more layers in which a printing ink layer 2 having an arbitrary pattern is provided on a base sheet 1 made of an opaque olefin-based thermoplastic elastomer, and an easily adhesive resin layer 3a is provided on a side corresponding to a printing surface. A transparent olefin-based thermoplastic elastomer composed of a transparent olefin-based thermoplastic elastomer extruded by a multilayer extruder and laminated as a top sheet 3 on the printing surface of the base sheet 1. Ozone-containing air is blown onto the adhesive resin surface at a high temperature to generate many polar functional groups. In the decorative sheet shown in FIG. 2, the primer layer 4 that reacts with the polar functional group formed on the easily adhesive resin surface of the extruded transparent olefin-based thermoplastic elastomer is placed on the printing ink layer 2 of the base sheet 1. Provided.

FIG. 3 is an explanatory view showing a method for manufacturing a decorative sheet according to the present invention. First, a printed base sheet A in which a printing ink layer of an arbitrary pattern and a primer layer as necessary are provided on a base sheet made of an opaque olefin-based thermoplastic elastomer is prepared. Then, when a transparent olefin-based thermoplastic elastomer composed of two or more layers having an easily adhesive resin layer on the side corresponding to the printing surface is extruded by the multilayer extruder 10 and laminated as a top sheet B on the printing surface of the base sheet. The air G containing ozone is blown at a high temperature, for example, by passing air G containing ozone through the heater 11 to the adhesive surface of the transparent olefin thermoplastic elastomer in the molten state extruded from the die of the extruder 10. Perform processing. As a result, many polar functional groups are generated on the easily adhesive resin surface of the top sheet B. By laminating the functional group on the printed base sheet A at a high temperature, the functional groups react with the vehicle or primer layer of the printing ink. And firmly adhere.

The olefin-based thermoplastic elastomers are the following three types of composite thermoplastic elastomers composed of an elastomer and an olefin-based resin. That is,
A simple blend of an elastomer as the soft segment and an olefin-based resin as the hard segment, a cross-linked type in which the elastomer and the olefin-based resin are partially cross-linked to form a complex, and an olefin-based resin that is cross-linked with the olefin-based elastomer And the following five types are specifically mentioned.

[0010] A simple blend of (A) an 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, terpolymers, butene-1, hexene-1, octene-1, terpolymers, and polymethylpentene resins alone or as a mixture of two or more resins. Can be Examples of the elastomer include various rubbers. Examples of the rubber include a diene rubber, a hydrogenated diene rubber, and an olefin elastomer. 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 olefin elastomer may be of two types or three types.
An elastic copolymer obtained by adding at least one kind of polyene copolymerizable with at least one kind of olefin. As the olefin, ethylene, propylene, α-olefin or the like is used. As the polyene, 1,4 hexadiene, cyclic diene , Norbornene and the like are used. Preferred olefin copolymer rubbers include, for example, elastic copolymers containing an olefin as a main component, such as ethylene-propylene copolymer rubber, ethylene-propylene non-conjugated diene rubber, and ethylene-butadiene copolymer rubber.

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, the elastomer will be described later.
And the like.

(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) partially crosslinked ethylene An olefin elastomer obtained by using a mono-olefin copolymer rubber such as a propylene copolymer rubber or an unsaturated ethylene / propylene non-conjugated diene terpolymer rubber as a soft segment, and uniformly blending 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.

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 ultraviolet absorber and the light stabilizer are for imparting good weather resistance (light resistance) to the resin, and the amount of the ultraviolet absorber and the light stabilizer is usually 0.01 to 0.01.
It is about 0.15% by weight. Generally, it is preferable to use an ultraviolet absorber and a light stabilizer in combination. As the ultraviolet absorber, an organic substance such as benzotriazole, benzophenone, and salicylate, or an inorganic substance such as zinc oxide, cerium oxide, and titanium oxide in the form of fine particles having a diameter of 0.2 μm or less can be used. As a light stabilizer, bis- (2,
Hindered amine radical scavengers such as (2,6,6-tetramethyl-4-piperidinyl) sebacate and radical scavengers such as piperidine radical scavengers can be used.

Known heat stabilizers such as phenol-based, sulfite-based, phenylalkane-based, phosphite-based, and amine-based heat stabilizers are used, and they 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, a preferable substrate sheet used in the present invention is a sheet comprising a high-density polyethylene resin, a thermoplastic elastomer, a coloring agent and an inorganic filler. 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, and the same as those described above are used. The addition amount of the thermoplastic elastomer is 10 to 60% by weight, preferably about 30% by weight in the base sheet. 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. As the inorganic filler, the same one as described above is used, and about 5 to 60% by weight, preferably 3 to
About 0% by weight is added. If the addition amount is less than 5% by weight, the creep deformation resistance and the easy adhesion decrease, and if it 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 as the transparent olefin-based thermoplastic elastomer provided on the surface are those mentioned in the description of the above-mentioned olefin-based thermoplastic elastomer.
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 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 have a propylene unit content of at most 40% by weight, preferably at most 30% by weight, and other α-olefins 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 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 sheet and the top sheet laminated thereon is such that the base sheet is a sheet comprising the above-mentioned high-density polyethylene resin, thermoplastic elastomer, coloring agent and inorganic filler, and the top sheet is By making a sheet made of a colorless or colored transparent soft polypropylene-based resin composed of a mixture of the above-mentioned isotactic polypropylene and atactic polypropylene, each sheet shares various conditions required for the decorative sheet described above. Thus, a highly practical decorative sheet of the present invention can be obtained.

The transparent olefin-based thermoplastic elastomer having good adhesion properties 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 the easily-adhesive thermoplastic elastomer 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 ozone treatment is performed by heating and blowing air containing ozone from a nozzle or a slit-shaped outlet toward the molten thin film. The amount of ozone in the air to be blown is preferably 5 g / m ³ or more and 0.2 l / min / cm or more. However, if the blown amount is too large, the molten thin film is pushed by the atmospheric pressure and the thickness becomes uneven. It is desirable that the air containing ozone be heated to 50 ° C. or higher so as not to lower the temperature of the molten thin film, since the adhesive force at the time of lamination increases.

Since the adhesion strength between the base sheet and the top sheet deteriorates with time due to ultraviolet rays, it is not sufficient to secure the initial adhesion strength as a decorative sheet during production. (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 the ultraviolet absorber, those which maintain the ultraviolet cut effect are preferable, and it is preferable to use a reactive ultraviolet absorber or a high molecular weight ultraviolet absorber. It is preferable to add 1% by weight or more, or add 0.1% by weight or more of a hindered amine radical ultraviolet absorber.

A heat bonding anchor layer may be provided for thermally bonding the easily adhesive olefin-based thermoplastic elastomer layer of the top sheet to the printing ink layer on the base sheet.
For this, a reactive hot melt adhesive is used. 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.

When the above-mentioned heat-adhesive anchor layer is used as the ink for the printing ink layer, 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 for the portion between the printing ink layer and the heat-bonding anchor layer. However, the number of steps is increased, so that it is determined in consideration of the required adhesion strength. As the resin for the primer layer,
Acrylic, vinyl chloride / vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, chlorinated polyethylene and the like are used, and polyurethane is particularly preferable.

The lamination of the base sheet and the top sheet is performed by doubling or doubling embossing. The embossing plate used for doubling embossing is, for example, one obtained by copying an uneven state such as a wood surface by an electroforming method to form an embossed pattern of a conduit, or, for example, forming an uneven state such as a wood surface by a photoengraving method. It is preferable that an embossed pattern of a conduit is formed by a photoetching method using an original prepared by copying. 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.

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, other synthetic resins, and other rubber derivatives such as chlorinated rubber, cyclized rubber, and synthetic rubber are used as vehicle constituent materials. Colorant, settling sulfate Extender pigments such as um, paint or ink is used formed by adding a plasticizer. And
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 a knife coat, and then scraped off with a doctor blade or wiping paper to remove the colored paint or the 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.

[0047]

【Example】

Example 1 A 100 μm-thick base sheet (“Soft Rex” manufactured by Nippon Petrochemical) made of an olefin-based thermoplastic elastomer was coated with a vinyl chloride resin ink (“X-X” manufactured by Showa Ink Industries, Ltd.). The printed sheet was formed by pattern printing.

The molten transparent olefin-based thermoplastic elastomer was extruded in two layers by an extruder from above the printing surface of the printing sheet, and laminated as a top sheet.
Here, "E-2600" manufactured by Idemitsu Petrochemical Co., Ltd.
And a layer on the printing surface side using "Polytack" manufactured by Idemitsu Petrochemical Co., Ltd., which has an easy adhesion of 80 μm and 20 μm, respectively.
Extruded at the thickness of. At this time, the surface of the easily adhesive resin in the transparent olefin-based thermoplastic elastomer in the molten state extruded from the die of the extruder was subjected to ozone treatment and then laminated. Specifically, air having an ozone concentration of 100 g / m ³ was heated to 80 ° C. by an electric heater, and this was heated to 2 Nm ^3.
/ H.

(Example 2) A two-component curable polyurethane resin ink ("ALFA" manufactured by Showa Ink Industries, Ltd.) was applied to the printing surface of the same printing sheet as in Example 1 to form a primer layer. A top sheet was laminated in the same manner as in No. 1.

For the decorative sheets obtained in Examples 1 and 2, the sunshine carbon arc W.P. O. M. At 100
When a peeling test was performed after irradiation for 0 hours, no decrease in interlayer strength was observed.

[0051]

As described above, according to the present invention,
The extruded topsheet's easily adhesive resin surface is subjected to ozone treatment at a high temperature to generate many polar functional groups, and laminated at a high temperature on a printed base sheet, so that a printing ink vehicle or primer layer and the Since the functional group reacts and adheres firmly, it is possible to obtain a decorative sheet having not only the initial interlayer adhesion strength immediately after production but also a sufficient strength as a building material application with little decrease in interlayer adhesion strength due to ultraviolet rays or heat. it can.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing one embodiment of a decorative sheet according to the present invention.

FIG. 2 is a cross-sectional view showing another form of the decorative sheet according to the present invention.

FIG. 3 is an explanatory view showing a method for producing a decorative sheet according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base sheet 2 Printing ink layer 3 Top sheet 3a Adhesive resin layer 4 Primer layer 10 Extruder 11 Heater A Printed base sheet B Top sheet G Air containing ozone

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[Procedure amendment]

[Submission date] May 19, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

The olefin-based thermoplastic elastomers are the following three types of composite thermoplastic elastomers composed of an elastomer and an olefin-based resin. That is,
Elastomer and simplicity blended type olefinic resin as a hard segment as a soft segment, elastomer and the olefin resin and partially to crosslink the in composite, crosslinked type, it by crosslinking the error elastomer olefin resin There are three types of dispersion, specifically, the following five types.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction contents]

The easy-adhesive transparent olefin-based thermoplastic elastomer, the at transparent olefin thermoplastic elastomer, if example embodiment, polyethylene, ethylene -α- olefin copolymer, polypropylene, polybutene, such as poly-α- olefin and polyisobutylene Polybutadiene, polydiolefins such as polyisoprene or copolymers thereof, for example, carboxylic acid, carboxylate,
Ethylenic unsaturated having a carbonyl group based on carboxylic acid anhydride, carboxylic acid ester, carboxylic acid amide to imide, aldehyde, ketone, etc. alone or in combination with cyano group, hydroxy group, ether group, oxirane ring group, etc. It is composed of a copolymer with an ethylenically unsaturated monomer , such as a copolymer with one or more kinds of monomers.
In general, it is sufficient if the thickness is about 10 μm.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction contents]

Extruder from above printing surface of substrate sheet
Melts transparent olefin-based thermoplastic elastomer
Embossing at the same time as putting out and laminating with the top sheet
It is carried out. The embossing plate used for the embossing process is, for example, one obtained by copying an uneven state such as a wood surface by an electroforming method to form an embossed pattern of a conduit, or, for example, a photoengraving method using an uneven state such as a wood surface. It is preferable that an embossed pattern of a conduit is formed by a photo-etching method using an original prepared by copying the above. 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.

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Claims (8)

[Claims] 1. A transparent ink comprising two or more layers having a printing ink layer of an arbitrary pattern provided on a base sheet made of an opaque olefin-based thermoplastic elastomer and having an easily adhesive resin layer on a side corresponding to a printing surface. In a decorative sheet in which an olefin-based thermoplastic elastomer is extruded by a multilayer extruder and laminated as a top sheet on a printing surface of a base sheet,
A decorative sheet characterized in that ozone-containing air is blown at a high temperature onto a surface of an easily-adhesive resin in a molten transparent olefin-based thermoplastic elastomer extruded from a die of an extruder to generate many polar functional groups. 2. The transparent olefin-based thermoplastic elastomer is a polypropylene-based thermoplastic elastomer having a hard segment of isotactic polypropylene and a soft segment of atactic polypropylene,
The decorative sheet according to claim 1, wherein the easily adhesive resin is obtained by graft-polymerizing maleic acid to the polypropylene to introduce a polar functional group. 3. The extruded transparent olefin-based thermoplastic elastomer, wherein a primer layer that reacts with a polar functional group formed on the easily adhesive resin surface of the thermoplastic olefin-based thermoplastic elastomer is provided on the printing ink layer of the substrate sheet. A decorative sheet according to claim 1. 4. The decorative sheet according to claim 1, wherein an ultraviolet absorbent is added to the transparent olefin-based thermoplastic elastomer. 5. After providing a printing ink layer of an arbitrary pattern on a base sheet made of an opaque olefin-based thermoplastic elastomer, two or more layers having an easily adhesive resin layer on the side corresponding to the printing surface are provided. In a method of manufacturing a decorative sheet in which a transparent olefin-based thermoplastic elastomer is extruded by a multilayer extruder and laminated as a top sheet on a printing surface of a base sheet, a transparent olefin-based thermoplastic elastomer in a molten state extruded from a die of an extruder is used. A method for producing a decorative sheet, characterized in that ozone-containing air is blown onto a surface of an easily-adhesive resin at a high temperature to perform a surface treatment to generate many polar functional groups. 6. The transparent olefin-based thermoplastic elastomer is a polypropylene-based thermoplastic elastomer having a hard segment of isotactic polypropylene and a soft segment of atactic polypropylene,
The method for producing a decorative sheet according to claim 6, wherein the easily adhesive resin is obtained by graft-polymerizing maleic acid to the polypropylene to introduce a polar functional group. 7. The primer sheet according to claim 5, wherein a primer layer that reacts with a polar functional group formed on the easily adhesive resin surface of the transparent olefin-based thermoplastic elastomer is provided on the printing ink layer of the base sheet. Method for producing a decorative sheet. 8. The method for producing a decorative sheet according to claim 5, wherein an ultraviolet absorber is added to the transparent olefin-based thermoplastic elastomer.