JPH10286930A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly weatherable decorative sheet which shows excellent working suitability which is well comparable with a decorative sheet using a vinyl chloride resin. SOLUTION: A first primer layer 2 is formed on a base material sheet 1 made up of an opaque olefin thermoplastic elastomer resin, then a printing ink layer 3 with an arbitrary pictorial pattern is formed on the first primer layer 2, and a second primer layer 4 is formed if necessary. After that, a transparent acrylic thermoplastic resin is extruded in a molten state over the printing face using an extruder so that the extrusions are laminated as a top sheet 5 and at the same time, are embossed.

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.

[0002]

Heretofore, a vinyl chloride resin such as a vinyl chloride sheet or a vinyl chloride-vinyl acetate copolymer sheet has been mainly used as a base sheet and a top sheet in this type of decorative sheet. . These sheets are excellent in printability and embossability, are easily processed into a decorative sheet, have excellent post-processability such as V-cut and wrapping, and have the advantage of being inexpensive.
However, this type of decorative sheet has a drawback that heat resistance is insufficient or that the surface has poor stain resistance due to bleeding of a plasticizer.

[0003] In recent years, styrene, olefin, urethane, polyamide and ester thermoplastic elastomer resins, EVA, PE
It has been proposed to use T, acrylic (polyacrylic acid, polymethacrylic acid and esters thereof). Of these, elastomeric resins have processing suitability comparable to that of vinyl chloride resins, but there is a high demand for weather resistance in the field of building materials and decorative materials, and for example, direct sunlight from windowsills, entrances, storefronts, etc. For a part to be subjected to, for example, a decorative sheet having further higher weather resistance than that using an elastomer resin is required.

[0004] The present invention has been made in view of the above-mentioned problems, and an object thereof is to provide an excellent processing suitability comparable to a decorative sheet using a PVC resin. Another object of the present invention is to provide a decorative sheet having high weather resistance.

[0005]

In order to achieve the above object, the decorative sheet of the present invention is provided with a first primer layer on a base sheet made of an opaque olefin-based thermoplastic elastomer resin, on which a first primer layer is provided. After providing a printing ink layer of an arbitrary pattern and further providing a second primer layer as needed, a transparent acrylic thermoplastic resin is melt-extruded from the printing surface using an extruder and laminated as a top sheet. And embossed at the same time.

[0006]

FIG. 1 shows one embodiment of a decorative sheet according to the present invention. In this decorative sheet, a first primer layer 2 is provided on a base sheet 1 made of an opaque olefin-based thermoplastic elastomer resin, a printing ink layer 3 having an arbitrary pattern is provided thereon, and a second primer layer is further provided. 4, the transparent acrylic thermoplastic resin is melt-extruded from the printing surface using an extruder, laminated as a top sheet 5, and simultaneously embossed.

FIG. 2 shows another form of the decorative sheet. In this decorative sheet, the second primer layer 4 in the layer structure of FIG. 1 is omitted.

The transparent acrylic thermoplastic resin is a random copolymer of ethylene and methacrylic acid, and is a resin in which carboxyl groups randomly present in the molecular chains are crosslinked between molecular chains by hydrogen bonding. Either a copolymer of methyl acid and ethylene or an ionomer resin is used. Further, acrylic rubber may be added to these transparent acrylic thermoplastic resins.

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, as the thermoplastic 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) 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.

The olefinic thermoplastic elastomer containing a coloring pigment or a coloring pigment and a filler is used as a base sheet. If desired, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a flame retardant, a foaming agent and the like are added.

The coloring pigment may be appropriately selected from known ones and used. Specifically, titanium white, zinc white, red petal,
Vermilion, ultramarine, cobalt blue, titanium yellow, inorganic pigments such as carbon black, isoindoline, Hansa Yellow A,
Organic pigments such as quinacridone, permanent red 4R, and phthalocyanine blue; metal pigments such as aluminum and brass; pearl luster pigments made of foil powder such as titanium dioxide-coated mica and basic zinc carbonate are used. As the filler, those generally used as plastic fillers, for example, calcium carbonate, calcium sulfate, talc, clay, diatomaceous earth, silica, titanium oxide and the like are used.

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.

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, 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.

The first primer layer is provided to improve the adhesion between the thermoplastic olefin elastomer resin of the base sheet and the pattern ink. As the resin of the primer layer, a two-component curable urethane resin is preferable, but an amide resin may be used. In addition, chlorinated polypropylene also shows good adhesion, but is not preferred because it contains chlorine atoms.

As the ink used for the printing ink layer, a urethane-based high-temperature reaction type (150 to 250 ° C.) ink is preferable. Examples of the pattern of the printing ink layer include a wood grain pattern, a stone grain pattern, a cloth grain pattern, a leather crest pattern, a geometric figure, a character, a symbol, a line drawing, various abstract patterns, and the like.

The second primer layer is provided in order to improve the adhesion between the printing ink layer and the transparent acrylic thermoplastic resin layer of the top sheet. However, the second primer layer is not necessarily provided because the adhesion of the resin is better than that of the olefin resin. No need to provide.
As the resin for the primer layer, an acrylic resin or a urethane resin may be used.

Examples of the acrylic rubber to be added to the transparent acrylic thermoplastic resin include a rubber-like elastic material obtained by polymerization of an acrylate ester or copolymerization based on this. Examples of the acrylate include ethyl acrylate and butyl acrylate, and the monomers to be copolymerized include 2-chloroethyl vinyl ether, methyl vinyl ketone, acrylic acid, acrylonitrile, and butadiene. An amine such as ethyltetramine and tetraethylenepentamine and sulfur are used for flowing the copolymer.

The top sheet needs to be thinner than the base sheet in consideration of V processing and lapping suitability.
The total thickness of the decorative sheet is preferably from 100 to 200 μm.
A method of attaching an acrylic film to the base sheet with doubling embossing is also conceivable, but the processing speed is low due to the problem of reproducibility of embossing, and the occurrence of curl is large, so the melt extrusion simultaneous embossing method of the present invention wins I have. The embossing plate to be used 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 the conduit, or by copying the state of unevenness such as the surface of wood by photoengraving. It is preferable to form an embossed pattern of a conduit by a photoetching method using the prepared master. 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.

A coloring agent may be filled in the concave portions of the recessed pattern on the surface of the top sheet. Examples of the coloring agent include natural resins such as shellac, cobal, dammar, rosin, rosin ester, and modified resins thereof, and nitro resins. Cellulose, acetyl cellulose, ethyl cellulose, 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 butyral, 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, and coloring agents, precipitated barium sulfate, etc. are contained in the vehicle. A paint or ink obtained by adding an extender, a plasticizer, or the like is used.

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 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.

The decorative sheet produced by the present invention can be used as a surface decoration material for various uses. For example, building interior materials such as walls, floors and ceilings, furniture such as partitions, furniture, vehicle interior materials such as cars and trains, kitchen equipment, bathtubs, and bathroom equipment such as bathrooms,
It is used by being laminated on the surface of a container such as a bag or box. Particularly, from the viewpoint of good weather resistance, it is suitable for use in a portion receiving direct sunlight, such as a window, an entrance, a storefront, and the like.

[0035]

【Example】

(Example 1) A two-component curable polyester resin ink ("AFS" manufactured by Showa Ink Kogyo Co., Ltd.) is applied to a base sheet ("Soft Rex" manufactured by Nippon Petrochemical) having a thickness of 100 µm made of an olefinic thermoplastic elastomer resin. First
Is formed, a two-component curable acrylic urethane resin ink ("UE" manufactured by Showa Ink Kogyo Co., Ltd., "UE") is applied on the primer layer, and then a vinyl chloride resin ink (Chemical X manufactured by Showa Ink Kogyo Co., Ltd.) )) To give a printed sheet.

On the printing surface of the printing sheet, a two-component curable polyurethane resin ink ("ALF" manufactured by Showa Ink Industries, Ltd.)
A)) was applied to form a second primer layer, from which a transparent acrylic thermoplastic resin was extruded with a T-die extruder, laminated as a top sheet, and simultaneously embossed. In this example, “Nucrel” manufactured by DuPont-Mitsui Polychemicals was used as a transparent acrylic thermoplastic resin, and extruded at a thickness of 80 μm.

Example 2 An embossed decorative sheet was obtained in the same manner as in Example 1 except that “HIMILAN” manufactured by DuPont-Mitsui was used as the transparent acrylic thermoplastic resin of the top sheet.

Example 3 CHEVRON CHEMICA was used as a transparent acrylic thermoplastic resin for the top sheet.
An embossed decorative sheet was obtained in the same manner as in Example 1 except that L EMAC was used.

Example 4 A first primer layer was formed on a substrate sheet in the same manner as in Example 1, and a colored solid was applied thereon. A two-component curable polyurethane resin ink ("ALFA" manufactured by Showa Ink Industries, Ltd.), which is a vehicle ink having good adhesion to the acrylic thermoplastic resin, was subjected to straight-grain pattern printing to obtain a print sheet.

Without providing a second primer layer on this printed sheet, the same transparent acrylic thermoplastic resin as in Example 1 was extruded directly from the printing ink layer with a T-die extruder and laminated as a top sheet. Embossing was performed at the same time.

Each of the decorative sheets obtained in Examples 1 to 4 was excellent in processability such as V-cutting and lapping. Sunshine carbon arc W.C. O.
M. No delamination or deterioration of the sheet was observed even after irradiation for 2000 hours.

[0042]

As described above, according to the present invention,
By using a thermoplastic olefin-based elastomer resin as the base sheet and a highly acrylic workable resin as the top sheet, V-cut processing that is comparable to a decorative sheet using a PVC-based resin, A highly weather-resistant decorative sheet having excellent post-processing properties such as lapping can be obtained. In addition, since the acrylic resin is laminated by extrusion melt coating and embossing is performed at the same time, the reproducibility of embossing is good, and the number of steps is reduced as compared with the case where the sheet is formed and then laminated, so that it can be manufactured at low cost.

[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 sectional view showing another embodiment of the decorative sheet according to the present invention.

[Explanation of symbols]

 Reference Signs List 1 base sheet 2 first primer layer 3 printing ink layer 4 second primer layer 5 top sheet

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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] 0014

[Correction method] Change

[Correction contents]

[0014] In addition, as an image elastomer, - (to be described later)
And the like.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction contents]

[0019] These olefin-based thermoplastic elastomer, optionally, coloring agents, UV absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, flame retardants,
A foaming agent or the like is added.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction contents]

As a coloring agent , titanium white, zinc white, red stalk,
Vermilion, ultramarine, cobalt blue, titanium yellow, inorganic pigments such as carbon black, isoindoline, Hansa Yellow A,
Organic pigments such as quinacridone, permanent red 4R, and phthalocyanine blue; metal pigments such as aluminum and brass; pearl luster pigments made of foil powder such as titanium dioxide-coated mica and basic zinc carbonate are used. As the filler, those generally used as plastic fillers, for example, calcium carbonate, calcium sulfate, talc, clay, diatomaceous earth, silica, titanium oxide and the like are used.

Claims (5)

[Claims] 1. A first primer layer is provided on a base sheet made of an opaque olefin-based thermoplastic elastomer resin, a printing ink layer having an arbitrary pattern is provided thereon, and a second primer is provided as necessary. A decorative sheet characterized in that a transparent acrylic thermoplastic resin is melt-extruded from the printing surface using an extruder after the layers are provided, laminated as a top sheet, and simultaneously embossed. 2. The transparent acrylic thermoplastic resin is a random copolymer of ethylene and methacrylic acid, and is a resin in which carboxyl groups randomly present in a molecular chain are cross-linked between molecular chains by a hydrogen bond. 2. The decorative sheet according to 1. 3. The decorative sheet according to claim 1, wherein the transparent acrylic thermoplastic resin is a copolymer of methyl acrylate and ethylene. 4. The decorative sheet according to claim 1, wherein the transparent acrylic thermoplastic resin is an ionomer resin. 5. The decorative sheet according to claim 1, wherein an acrylic rubber is added to the transparent acrylic thermoplastic resin.