JP2000167992A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet capable of solving an environmental problem at the time of incineration and capable of also satisfying various physical properties required in an easy adhesive layer such as deterioration-resistant characteristics with the elapse of time, blocking-resistant characteristics or adhesiveness. SOLUTION: An easy adhesive layer 2 compounded with two or more kinds of chlorine-free resins, for example, an acrylic resin, a urethane resin, polyester resin or a copolymer of them is formed on one surface of a chlorine-free polyolefinic resin sheet 1 subjected to decoration treatment by a pattern layer 3, a protective layer 4 or the like. As the polyolefinic resin sheet 1, both of a stretched sheet and an unstretched sheet can be used but, if necessary, various additives such as a filler, a foaming agent, a fire retardant, a lubricant, an oxidation inhibitor, an ultraviolet absorber or a light stabilizer are added to this sheet. The thickness of the resin sheet 1 is pref. about 20-300 μm according to a use.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet whose surface is subjected to a decorative treatment and which is used by being bonded to a base material of various goods such as furniture, building materials, and housing equipment. The present invention relates to a decorative sheet configured to be used.

[0002]

2. Description of the Related Art A decorative sheet to be bonded to a base material for a decorative board has one surface subjected to pattern printing or embossing as a decorative treatment, and is used as a surface decorative material for various furniture, building materials, housing equipment, and the like. Used as As a resin sheet used for such a decorative sheet, a vinyl chloride resin sheet is most common.

However, recently, environmental problems at the time of incineration have been gaining social importance, and in particular, there has been a demand for a tendency not to use a vinyl chloride resin sheet containing chlorine as a decorative sheet. As a substitute for such a vinyl chloride resin, for example, a resin containing no chlorine, such as polyethylene or polypropylene, has been studied, and attempts have been made to form a decorative sheet using a resin sheet containing no chlorine.

[0004] Decorative sheets are generally commercialized by being bonded to various substrates, but before the bonding, an easy-adhesion layer (primer) is attached to the bonding surface of the resin sheet in order to improve the bonding characteristics. Layer) is formed. This easy-adhesion layer is composed of, for example, a vinyl chloride-vinyl acetate copolymer-based resin layer or a chlorinated polypropylene-modified polyurethane-based resin layer so that it can be adhered to a substrate using a vinyl chloride resin adhesive.

[0005]

However, from the viewpoint of environmental protection, even when the resin sheet is made of a resin containing no chlorine, the easy-adhesion layer of the decorative sheet is formed by the above-mentioned vinyl chloride-vinyl acetate. In the case of a copolymer or a chlorinated polypropylene-modified polyurethane resin layer, these easy-adhesion layers themselves contain chlorine, which also causes a problem when the decorative sheet is incinerated.

In addition, when a simple resin containing no chlorine such as urethane resin, acrylic resin, polyester resin or the like is used, environmental problems due to chlorine can be solved. Various conditions such as deterioration characteristics, blocking resistance characteristics, and adhesiveness are not satisfied. In addition, these non-chlorine resins generally have poor compatibility with the polyvinyl chloride adhesive as compared with the case of using a polyvinyl chloride-based primer, and are likely to cause poor adhesion. For example, when the resin of the easy-adhesion layer is hardened and its anti-blocking property is improved, when subsequently embossed, the resin layer may be broken by pressure and heat by a hot roll,
The hard adhesive layer cannot follow the shrinkage of the resin sheet, resulting in poor adhesion.

[0007] Therefore, the present invention solves the environmental problem at the time of incineration, as well as the aging resistance, the blocking resistance, and the like.
An object of the present invention is to provide a decorative sheet that can satisfy various physical properties required for an easily adhesive layer such as adhesiveness.

[0008]

According to the present invention, there is provided (1) a chlorine-free resin sheet to be subjected to a decoration treatment, wherein an easy-adhesion layer containing a chlorine-free resin is formed on one surface of the resin sheet. A decorative sheet, characterized in that (2) the easy-adhesion layer is 2
(1) The decorative sheet according to (1), wherein the easy-adhesion layer comprises a copolymer of two or more types of chlorine-free resins. (4) The decorative sheet according to the above (1), wherein the easy-adhesion layer comprises a chlorine-free resin copolymer and a chlorine-free resin. The decorative sheet according to (1) above,
(5) The decorative sheet according to (1), wherein the easy-adhesion layer is mainly composed of a resin containing no chlorine, and is further blended with a vinyl chloride-vinyl acetate copolymer. (1) The decorative sheet as described in any one of (1) to (5) above, wherein the resin containing no chlorine is an acrylic resin or urethane. The decorative sheet according to any one of the above (1) to (6), which is appropriately selected from a series resin and a polyester resin.

[0009]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS As shown in FIG. 1, a decorative sheet according to one embodiment of the present invention comprises a resin sheet 1 made of a resin containing no chlorine and an easy-adhesion layer 2 formed on one surface thereof. Preferably, the picture layer 3 and the protective layer 4 are formed on the surface on which the easy adhesion layer 2 is not formed. As shown in FIG. 2, this decorative sheet is attached to the base material 5 or the like via the adhesive 6 on the easy-adhesion layer 2 side, and is used as a decorative material.

The resin sheet 1 is a colored sheet, a non-colored sheet, a transparent sheet, a translucent sheet, an opaque (concealing property).
Any of the sheets may be used, and is appropriately used according to the use of the decorative sheet. The resin sheet 1 may have a single layer as shown in the drawing, or may have a structure in which a plurality of layers are laminated. Picture layer 3
Is formed on the surface on which the easy-adhesion layer 2 is not formed as shown in the figure. However, when a transparent or translucent sheet is used, it may be formed on the side on which the easy-adhesion layer 2 is formed. When the resin sheet 1 is composed of a plurality of layers, the picture layer 3 may be formed inside the sheet.

In this embodiment, a polyolefin resin is used for the resin sheet 1 as a resin containing no chlorine. As the polyolefin resin, polyethylene (low density or high density), polypropylene (isotactic type, syndiotactic type, or a mixture thereof),
Highly crystalline non-elastomeric polyolefin resins such as polymethylpentene, polybutene, ethylene-propylene copolymer, and propylene butene copolymer, or various olefinic thermoplastic elastomers described below are used. The polyolefin resin sheet is a stretched sheet,
Any unstretched sheet can be used, but if necessary, various additives such as fillers, foaming agents, flame retardants, lubricants, antioxidants, ultraviolet absorbers, light stabilizers, etc. Is added. The thickness of the resin sheet 1 depends on the application and the like, but is preferably about 20 to 300 μm.

[0012] The olefinic thermoplastic elastomer is
The main raw material is made of either high-density polyethylene or polypropylene, which is a hard segment, to which an elastomer and an inorganic filler as a soft segment are added, and the hard segment described in JP-B-6-23278 is used. A mixture comprising a certain isotactic polypropylene and an atactic polypropylene as a soft segment;
JP, JP-A-5-77371, JP-A-7-31
Those comprising an ethylene-propylene butene copolymer described in No. 6358 and the like are typical. If necessary, additives such as a coloring agent are added to this and used. The details are described below.

The high-density polyethylene used in the present invention is preferably a polyethylene having a specific gravity of 0.94 to 0.96, and is a polymer having a high degree of crystallinity and a small number of branched structures obtained by a low-pressure method. High density polyethylene is used. Further, as the polypropylene, preferably, isotactic polypropylene is used.

As the elastomer in the present invention, a diene rubber, a hydrogenated diene rubber, an olefin elastomer or the like is used. 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 the crystallization of the polyolefin resin (high-density polyethylene or polypropylene in the present invention). Improve flexibility. 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. The olefin elastomer is an elastic copolymer to which at least one polyene copolymerizable with two or three or more olefins is added, and the olefin is ethylene, propylene, α
Monoolefins are used, and polyenes are 1,4
Hexadiene, cyclic diene, norbornene and the like are used. Preferred olefin copolymer rubbers include, for example, elastic copolymers containing olefin as a main component, such as ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene rubber, and ethylene butadiene copolymer rubber. In addition, these elastomers may be appropriately cross-linked by using a cross-linking agent such as an organic peroxide or sulfur, if necessary.

The amount of these elastomers added is 1
It is about 0 to 60% by weight, preferably about 30% by weight. 1
If it is lower than 0% by weight, the change in elongation at a constant load with respect to temperature becomes too steep, and the elongation at break, impact resistance and easy adhesion decrease, and if it is higher than 60% by weight, transparency and weather resistance And a decrease in creep resistance occurs.

As the inorganic filler in the present invention, powder having an average particle size of about 0.1 to 10 μm such as calcium carbonate, barium sulfate, clay, talc, etc. is used. The amount of addition is about 1 to 60% by weight, preferably about 5 to 30% by weight. If the amount is less than 1% 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, and the film formation becomes difficult.

[0017] Japanese Patent Publication No. Hei 6-23278 discloses
(A) As a soft segment, the number average molecular weight Mn is 2
(B) 10 to 90% by weight of atactic polypropylene soluble in boiling heptane having a ratio of weight average molecular weight Mw to number average molecular weight Mn of 5,000 or more, Mw / Mn ≦ 7;
As a hard segment, the melt index is 0.1
Soft polypropylene consisting of a mixture of ４4 g / 10 min boiling heptane-insoluble isotactic polypropylene 90-10 wt%. Among this kind of olefin-based thermoplastic elastomers, so-called "necking" is unlikely to occur, and as a material having good suitability for molding into various shapes using heat and pressure or embossing, isotactic polypropylene and It is made of a mixture with atactic polypropylene, and the weight ratio of the atactic polypropylene is 5% by weight or more and 50% by weight or less. The polypropylene-based olefin-based thermoplastic elastomer itself is already known, but when used in a conventionally known application such as a packaging container, the weight ratio of the atactic polypropylene as a soft segment is 5 to emphasize strength. Less than% by weight was exclusively used. However, when forming or embossing into a three-dimensional shape or uneven shape, necking occurs as described above, and good processing is impossible. On the other hand, contrary to the conventional composition design, embossing is performed by setting the weight ratio of the atactic polypropylene to 5% by weight or more in the polypropylene-based thermoplastic elastomer.
Deformation of a non-uniform sheet due to necking in molding into a three-dimensional or uneven article, and resulting defects such as wrinkles and pattern distortion can be eliminated. Particularly, the case where the weight ratio of the atactic polypropylene is 20% by weight or more is preferable. On the other hand, if the weight ratio of the atactic polypropylene is excessively increased, the sheet itself is deformed, a pattern is distorted, and in multicolor printing, defects such as a misregistration (register) are likely to occur. Further, it is not preferable because it is easily broken during molding. The upper limit of the weight ratio of atactic polypropylene is to print a pattern layer using a normal transfer printing machine such as rotogravure printing, and to emboss the sheet, vacuum forming, V-cut processing, and laminate simultaneously with injection molding. Is employed, the content is 50% by weight or less, more preferably 40% by weight or less.

A thermoplastic elastomer comprising an ethylene / propylene / butene copolymer resin. Here, as the butene, any of the three structural isomers of 1-butene, 2-butene and isobutylene can be used. The copolymer is a random copolymer and partially includes an amorphous portion. Preferred specific examples of the ethylene-propylene-butene copolymer include the following (i) to (iii).

(I) Those described in JP-A-9-111055. This is a random copolymer of a terpolymer of ethylene, propylene and butene. The weight ratio of the monomer components is 90% by weight or more of propylene. The melt flow rate is 1-509 / 230 ° C. and 2.16 kg.
Ten minutes is preferred. A transparent nucleating agent containing an aryl phosphate compound as a main component is used in an amount of 0.01 to 5 parts by weight per 100 parts by weight of such a tertiary random copolymer.
0 parts by weight, fatty acid amide having 12 to 22 carbon atoms 0.003
~ 0.3 parts by weight is melt-kneaded.

(Ii) Those described in JP-A-5-77371. This is made up of ethylene, propylene and 1-butene.
80 to 0% by weight of amorphous polypropylene is added to 20 to 100% by weight of an amorphous polymer having a propylene component content of 50% by weight or more.

(Iii) Those described in JP-A-7-316358. This is an ethylene / propylene / 1-butene terpolymer, in which the content of propylene and / or 1-butene is 50% by weight or more, and is a low-crystalline polymer 20 to 100.
5% by weight of an oil gelling agent such as N-acylamino acid amine salt or N-acylamino acid ester per 100 parts by weight of a composition mixed with 80 to 0% by weight of a crystalline polyolefin such as isotactic polypropylene based on 100% by weight %.

The ethylene / propylene / butene copolymer resin may be used alone, or may be used in the above (i) to (iii).
If necessary, another polyolefin resin may be mixed and used.

The resin sheet 1 may contain a coloring agent. The coloring agent is used to give the base sheet the necessary color as a decorative sheet, and is made of inorganic materials such as titanium white, zinc white, red iron oxide, vermilion, ultramarine, cobalt blue, titanium yellow, graphite, and carbon black. Pigment, isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R,
Organic pigments or dyes such as phthalocyanine blue, metal pigments made of foil powder such as aluminum and brass, mica coated with titanium dioxide, and pearlescent pigments made of foil powder such as basic zinc carbonate are used. The coloring may be transparent coloring or opaque (concealing) coloring.

Furthermore, if necessary, the resin sheet 1
Heat stabilizers, flame retardants, radical scavengers, etc. are added. The heat stabilizer is a known one such as a phenol type, a sulfite type, a phenylalkane type, a phosphite type, and an amine type, and is used for further improving the prevention of deterioration such as thermal discoloration during thermal processing. 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.

A resin sheet is obtained by blending these materials by a conventional method such as a calendering method. The thickness of the resin sheet is about 50 to 200 μm, preferably about 100 μm. In the case of forming a film by a melt extrusion method using a composition to which a coloring agent, an inorganic filler, or both are added as a resin sheet, if the film is formed into a thin film, the film forming aptitude decreases, and the surface of the resin sheet becomes smooth. Does not finish.
Generally, a colorant or the like is added in an amount of about 10 parts by weight or more,
This tendency is conspicuous when the film is formed to a thickness of 0 μm or less. Therefore, in such a case, it is advisable to co-extrude three layers, add a colorant only to the center layer, and add no pigment or the like to the outermost layers on the front and back sides.

The surface of the resin sheet 1 is preferably subjected to an easy adhesion treatment such as a corona discharge treatment, a plasma treatment and an ozone treatment. For these easy adhesion treatments, a method usually used for this type of sheet can be used.

By performing such an easy adhesion treatment,
Active hydrogen atom-containing functional groups such as a hydroxyl group and a carboxyl group can be formed on the surface of the resin sheet. When the base sheet is formed by a melt extrusion method, these polar functional groups are generated to some extent on the surface during the formation of the film. Therefore, if the polar functional groups generated at the time of film formation are sufficient, the easy adhesion treatment may be omitted.

Next, as the chlorine-free resin constituting the easy-adhesion layer 2, a polyester resin (or polyolefin resin), an acrylic resin, a urethane resin, or the like is used. In order to satisfy the required physical properties, two or more resins are blended. The resin blended here is a polyester-based resin (or polyolefin-based resin), two or more selected from acrylic resins and urethane-based resins, or a resin blended with two or more of these copolymers Further, a combination of a simple resin and a copolymer resin is used.

The required physical properties include anti-blocking properties and adhesion to the raw material, as well as aging and heat resistance. For example, when the urethane-based resin is used alone in the easy-adhesion layer 2, the adhesion to the raw material is excellent, but the anti-blocking property is lacking, and the acrylic resin is used alone in the easy-adhesion layer 2. In such a case, the blocking resistance is good, but the original film adhesion becomes a problem. Thus, as one example, a urethane-based resin and an acrylic-based resin are blended to make up for the disadvantages of both, thereby satisfying the required physical properties. Further, not only the combination of such simple resins but also the physical properties required by the copolymer may be satisfied. An example of a copolymer suitable for such physical properties is a urethane / acrylic copolymer as an example.

The polycarboxylic acids constituting the polyester resin include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6- Naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid, trimellitic acid, Examples include trimesic acid, trimellitic anhydride, phthalic anhydride, p-hydroxybenzoic acid, monopotassium trimellitate, and ester-forming derivatives thereof.

Examples of the polyvalent hydroxy compound constituting the polyester resin include ethylene glycol,
-Propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-
Pentanediol, neopentyl glycol, 1,4-
Cyclohexane dimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin,
Trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolpropionate and the like. The polyester resin can be synthesized by a conventional polycondensation reaction between the above-mentioned polyvalent carboxylic acid and polyvalent hydroxy compound. In addition, in addition to the above,
A composite polymer having a polyester component such as a so-called acrylic graft polyester described in Japanese Patent No. 65633 can also be used as the polyester resin.

The polyolefin resins other than the above polyester resins and copolymers thereof include polypropylene, polymethylpentene, ethylene / propylene copolymer, ethylene / butene-1 copolymer and propylene / butene-1 copolymer. Polymer, butene-1 / propylene / ethylene terpolymer, ethylene / vinyl alcohol copolymer,
Examples include an ethylene / vinyl acetate copolymer.

The acrylic resin for forming the easy-adhesion layer 2 and the copolymer thereof include poly (methyl meth) acrylate, poly (ethyl meth) acrylate, propyl poly (meth) acrylate, poly (meth) acrylate, and the like. (Meth) butyl acrylate, methyl (meth) acrylate / butyl (meth) acrylate, ethyl (meth) acrylate / butyl (meth) acrylate, ethylene / methyl (meth) acrylate An acrylic resin comprising a homopolymer or a copolymer containing a (meth) acrylate such as a styrene-methyl (meth) acrylate copolymer is exemplified.

Polyurethane is a composition containing a polyol (polyhydric alcohol) as a main component and an isocyanate compound as a crosslinking agent (curing agent). As a polyol,
It has two or more hydroxyl groups in the molecule, and basically includes monomeric diols, triols and the like, and polymer diols and triols containing a chain of alkylene repeating units mainly contributing to the molecular weight thereof. Typical polymer polyols consist essentially of either linear or branched chains of the above repeating units terminated with hydroxy groups, preferably monomeric polyols having 2, 3, 4 or more hydroxy groups including. For example, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, 1,2,6-hexanetriol, butenediol, sucrose, glucose, sorbitol, pentaerythritol, mannitol, triethanolamine, n-methyldimethanolamine, and Including cyclic aromatic and aliphatic and triols. Further, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol and the like are used.

On the other hand, as the isocyanate compound, a polyvalent isocyanate compound having two or more isocyanate groups in a molecule is used. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, crude MD
A polyphenylmethane polyisocyanate designated I,
Xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, aliphatic or alicyclic or aromatic di- or triisocyanate compounds such as triphenylmethane triisocyanate, hydrogenated tolylene diisocyanate, Isocyanate terminals obtained by reacting hydrogenated diphenylmethane diisocyanate or a polyisocyanate compound with a low molecular weight glycol or triol, for example, dipropylene glycol, 1,6-hexanediol, 1,2,6-hexanetriol, trimethylolpropane Low molecular weight adducts can be used

The easy-adhesion layer 2 is made of a resin containing no chlorine, such as the above-mentioned polyester resin (or polyolefin resin), acrylic resin, urethane resin, or a copolymer thereof, or a combination thereof. May be used as a main component, and further a vinyl chloride-vinyl acetate copolymer may be blended. Thus, vinyl chloride
By blending the vinyl acetate copolymer, it is possible to improve blocking resistance and heat resistance during embossing,
The familiarity with the adhesive 6 is also improved. When blending a vinyl chloride-vinyl acetate copolymer, 10-30 parts of the total resin
% Is preferably added.

Further, the easy-adhesion layer 2 can be filled with an extender pigment to further improve blocking resistance, heat resistance during embossing, and adhesion by an anchor effect. As the extender used in the present invention, conventionally known pigments can be used alone or in combination of two or more, and there is no particular limitation. For example, clay, talc, clay,
Diatomaceous earth, calcium carbonate, barium sulfate, titanium oxide, alumina white, silica, kaolin, mica, inorganic fine particles such as aluminum hydroxide, polyacrylate, polyurethane, polyester, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride,
Organic fine particles such as polystyrene, polysiloxane, phenol resin, epoxy resin, and benzoguanamine resin, or fine particles made of a copolymer thereof can be used.

The picture layer 3 can be made of a pattern layer such as a wood pattern, a stone pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, a line drawing, various abstract patterns, or a solid layer such as a solid printing. Become. The picture layer 3 may be either a pattern layer only, a solid layer only, or a two-layer structure of a pattern layer and a solid layer.

The picture layer 3 can be formed by printing and coating using a general picture printing ink. The ink is composed of a binder and a colorant. Examples of the binder include chlorinated polyethylene, chlorinated polyolefins such as chlorinated polypropylene, polyester, polyurethane (two-component curable urethane resin, or thermoplastic urethane resin), Acrylic, polyvinyl acetate, vinyl chloride
One or a mixture of two or more kinds of vinyl acetate copolymers and cellulose resins is used. As a coloring agent,
Bright pigments consisting of pigments or dyes such as titanium white, carbon black, red iron oxide, graphite, ultramarine, phthalocyanine blue, quinacridone, isoindolinone, metal foil powders such as aluminum and brass, and foil powders of titanium dioxide coated mica. Use one or more of them.

It is preferable to provide a protective layer 4 made of a transparent resin for improving the abrasion resistance and chemical resistance of the decorative sheet and for adjusting the surface color. The protective layer 4 can be formed by coating on the surface of the picture layer 3 as shown in FIG. 1 or by sticking (laminating) a sheet formed in advance to cover the picture layer 3. The protective layer 4 is made of a polyolefin-based resin (similar to those mentioned as a material of the base sheet), an acrylic resin, a polyurethane resin, an epoxy resin, or an unsaturated (meth) acrylate-based or epoxy-based ionizing radiation. A transparent or translucent resin such as a curable resin is used. When the protective layer 4 is formed by coating, a gravure roll coat, roll coat, curtain flow coat, comma coat / extrusion (melt extrusion) coat, or the like is used. It is formed by a method such as dry lamination using an adhesive such as a resin or fusion by a hot press.

The thickness of the protective layer 4 is 1 to 1 when dried.
Preferably, it is formed to have a thickness of about 00 μm. In the protective layer 4, various additives such as a matting agent (light diffusing agent) for matting, a lubricant, a weathering additive,
A lubricant or the like may be added. The matting agent is calcium carbonate,
Fine particles having a particle size of about 1 to 30 μm, such as silica, barium sulfate, urethane resin beads, and polycarbonate resin beads, are effective. As the lubricant, particles having a particle size of about 5 to 30 μm such as spherical α-alumina are used. The above-mentioned thing is used as a weather resistance additive. Wax or the like is used as the lubricant.

The decorative sheet of the present invention may be provided with decorations other than the picture layer in addition to the picture layer. For example, in addition to the method of adding a dye or a pigment to the above-described base sheet to perform transparent coloring or opaque coloring, a wood grain board conduit groove, a stone board surface unevenness (granite cleavage face, etc.), a cloth surface texture is provided on the surface of the protective layer 4. A,
A method of forming a concavo-convex pattern such as a satin finish, a grain, a hairline, a linear groove, or the like can be given. In order to form the concavo-convex pattern, for example, there are an embossing method by heating and pressing, a hairline processing method, and a shaping film method. The embossing method is a method in which the surface of the protective layer is heated and softened, and the surface is pressed with an embossing plate to shape the concavo-convex pattern of the embossing plate, and then fixed by cooling. An embossing machine or the like is used.

Further, a colored layer may be formed on the concave portion of the above-mentioned uneven pattern by a wiping method. As a wiping method, after applying the colorant ink to the entire surface including the concave portion by the doctor blade coating method or the knife coat method, the colorant ink is removed from the surface other than the concave portion, so that only the concave portion is colored. Form a layer. The colorant ink forming the colored layer is composed of a colorant such as a dye, a pigment, and a bright pigment as described above, a thermoplastic resin, a thermosetting resin, a binder resin such as an ionizing radiation-curable resin, and a vehicle. Inks and emulsion type water-based inks can be used.

In order to impart flame retardancy to the decorative sheet, a powder such as aluminum hydroxide or magnesium hydroxide may be added to the resin sheet 1 or the protective layer 4 as a flame retardant. In order to impart antibacterial properties to the decorative sheet, an antibacterial agent such as zeolite powder carrying silver ions or an antifungal agent such as 10,10′-oxybisphenoxyarsine is applied to the resin sheet 1 and the protective layer 4. It may be added.

The decorative sheet of the present invention can be laminated on various adherends, subjected to a predetermined forming process, and used for various decorative purposes. For example, interior decoration of buildings such as walls, ceilings and floors, surface decoration of fittings such as window frames, doors, handrails, furniture such as wardrobes or surface decoration of cabinets for light electric / OA equipment such as television receivers, automobiles, trains Applications include vehicle interiors such as ships, aircraft interiors, and window glass for cosmetics.

As the material of the substrate 5 to which the decorative sheet of the present invention is bonded, paper, plastic, metal foil, plate, or the like is used. Alternatively, any of plate-like materials such as a metal plate, a wooden plate, and a plastic plate can be used. When a sheet-shaped substrate is used, a substrate having a thickness of 5 to 200 μm is preferably used. Further, as the base material 5, a material having irregularities on the surface, a material having a three-dimensional shape, or the like can be used.

Specific examples of the paper used as the base material 5 include thin paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, and so-called vinyl wallpaper in which polyvinyl chloride resin is sol-coated or dry-laminated on paper. Raw paper, high quality paper,
Examples include coated paper, art paper, sulfuric acid paper, glassine paper, parchment paper, paraffin paper, Japanese paper, and the like. Further, a paper-like sheet can also be used as the base material. The above-mentioned paper-like sheet includes glass fiber, asbestos, potassium titanate fiber,
Inorganic fiber such as alumina fiber, silica fiber, carbon fiber,
A woven or non-woven fabric using an organic resin such as polyester or vinylon is exemplified.

The plastic sheet used as the base material 5 includes polyolefin resins such as polyethylene, polypropylene, and polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, and ethylene-vinyl acetate copolymer. Coal, ethylene-vinyl alcohol copolymer, vinyl resin such as vinylon, polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate-isophthalate copolymer, polymethyl methacrylate, polyethyl methacrylate, poly Acrylic resins such as ethyl acrylate and polybutyl acrylate; polyamides such as nylon 6 and nylon 66; cellulose resins such as cellulose triacetate and cellophane; polystyrene; Sulfonates, polyarylate, synthetic resin films such as polyimide, or a single layer body or a laminated body of the sheets. Examples of the metal used as the metal foil include aluminum, stainless steel, iron, and copper.

The board used as the base material 5 may be wood veneer, wood plywood, particle board, wood board such as MDF (medium density fiber board), gypsum board, gypsum board such as gypsum slag board, calcium silicate board. Cement board such as asbestos slate board, lightweight foam concrete board, hollow extruded cement board, etc., fiber cement board such as pulp cement board, asbestos cement board, wood chip cement board, pottery, porcelain, stoneware, earthenware, glass, enamel etc. Ceramic plate, iron plate, galvanized steel plate, polyvinyl chloride sol coated steel plate, aluminum plate, metal plate such as copper plate, polyolefin resin plate, acrylic resin plate, ABS
Thermosetting resin plates such as thermoplastic resin plates such as plates, polycarbonate plates, phenol resin plates, urea resin plates, unsaturated polyester resin plates, polyurethane resin plates, epoxy resin plates, melamine resin plates, phenolic resins, urea resins, Unsaturated polyester resin, polyurethane resin, epoxy resin,
A resin plate such as a so-called FRP plate or the like obtained by impregnating and curing a resin such as a melamine resin or a diallyl phthalate resin into a glass fiber nonwoven fabric, a cloth, paper or other various fibrous base materials to form a double impregnation.

The substrate 5 may be a composite substrate obtained by laminating two or more of the above-mentioned various substrates by a known means such as an adhesive or heat fusion.

An arbitrary adhesive 6 can be used for bonding the decorative sheet of the present invention and the substrate 5. Examples of the adhesive 6 include a urea resin adhesive, a melamine resin adhesive, a phenol resin adhesive, an α-olefin resin adhesive, an adhesive made of a mixture of an aqueous polymer and an isocyanate, an epoxy adhesive, and a solution. Vinyl acetate resin adhesive, emulsion vinyl acetate resin adhesive, acrylic emulsion adhesive, hot melt adhesive, cyanoacrylate adhesive, polyurethane adhesive, chloroprene rubber adhesive, nitrile rubber adhesive , SBR
Adhesives, modified rubber emulsion adhesives, ethylene copolymer resin adhesives, resorcinol adhesives, natural rubber adhesives, cellulose adhesives, starch pastes, dextrins and the like.

When the substrate 5 is wood, a urea resin adhesive, a melamine resin adhesive, an α-olefin resin adhesive, an adhesive made of a mixture of an aqueous polymer and an isocyanate, an emulsion type vinyl acetate resin adhesive An acrylic emulsion adhesive, a chloroprene rubber adhesive, a modified rubber emulsion adhesive, and a cellulose adhesive are mainly used.

[0053]

EXAMPLES Examples 1 to 7 and Comparative Examples 1 to 3 The decorative sheet of the present invention will be described from concrete examples based on experiments. In the experiment, a resin sheet made of polypropylene resin was used as the resin containing no chlorine, and the easy-adhesion layer coated on the resin sheet was changed for each example, and the adhesive force to the base material in normal conditions, blocking, and initial adhesion of the raw material were used. , Heat resistance, moisture resistance, and heat resistance of embossing were examined.

The structure of the easily adhesive layer (primer layer)
Example 1 in which an acrylic resin and a urethane resin were blended, Example 2 in which a urethane / acrylic copolymer was blended with an acrylic resin, and an acrylic resin was blended in a urethane / acrylic copolymer and further chlorided Example 3 was obtained by adding 10% of a vinyl-vinyl acetate copolymer, and Example 4 was obtained by adding an acrylic resin to a urethane / acrylic copolymer and further adding 20% of a vinyl chloride-vinyl acetate copolymer. Example 5 was obtained by blending an acrylic resin with a urethane / acrylic copolymer and further adding 30% of a vinyl chloride-vinyl acetate copolymer, and blending an acrylic resin and a urethane resin with silica as an extender. Example 6 was prepared by adding 7% by weight of styrene to an urethane / acrylic copolymer, and 7% by weight of silica was further added as an extender. It was 7. The composition of the easy-adhesion layer was Comparative Example 1 using only the vinyl chloride-vinyl acetate copolymer, Comparative Example 2 using only the acrylic resin, and precipitated barium sulfate was added to the vinyl chloride-vinyl acetate copolymer. Comparative Example 3 was 25% by weight. As the acrylic resin, urethane resin, urethane / acrylic copolymer, and vinyl chloride-vinyl acetate copolymer, those used in general building material inks were used. Table 1 shows the experimental results. The test method is as follows.

[Normal substrate adhesive strength] A wooden substrate is coated with an emulsion adhesive at about 8 g / m ² (including a solvent), and after overlaying a decorative sheet, it is fully cured, and the decorative sheet is oriented 180 °. The material was forcibly peeled off, and the state of material destruction of the substrate was confirmed. [Blocking resistance] A urethane-based ink and a primer are coated on a colored polypropylene film, and the coated surfaces are put together into a blocking tester, and a pressure of 3 kgf is applied.
/ Cm ² and left at 40 ° C. for 2 days to observe the condition after curing. [Initial Adhesion of Raw Material] Immediately after the primer coating, a cellophane tape adhesion test was performed. Immediately after, the time taken for the material to come off or the time required for the material to become hard to come off was observed. [Heat resistance] After the decorative sheet was cured at 80 ° C. for 200 hours, it was flat-attached with an emulsion adhesive, and a substrate adhesion test was performed. [Moisture Resistance] After the decorative sheet was cured at 40 ° C. and 90% RH for 200 hours, it was flat-attached with an emulsion adhesive and subjected to a substrate adhesion test. [Emboss Heat Resistance] An olefin-based decorative sheet pre-coated with a primer was heated to a molten state and hot-embossed, and a base material adhesion test was performed on the sheet. [Scratch property] A primer was applied to a polypropylene film, and immediately thereafter, it was scratched with a nail to confirm the degree of ink peeling. This test is a check of scratch resistance against rubbing with a guide roller in a printing press.

[0056]

[Table 1] ◎: extremely good, ○: good, Δ: slightly poor, ×: poor, XX: extremely poor

As is clear from Table 1 above, in the easy-adhesion layers of Examples 1 to 7, almost satisfactory values were obtained for the required physical properties. And sufficient usefulness is recognized.

[0058]

The decorative sheet of the present invention can satisfy various physical properties such as adhesiveness, anti-blocking property and heat resistance during embossing required for the easy-adhesion layer by compensating for disadvantages of a single resin. In addition, because it does not contain chlorine, it can solve environmental problems such as incineration. At the same time, the blocking resistance and the heat resistance during embossing are improved. Further, a material obtained by adding a small amount of a vinyl chloride-vinyl acetate copolymer to the easy-adhesion layer has good compatibility with the adhesive. Also,
Similarly, even if an extender such as silica is added to the easy-adhesion layer, the blocking resistance and the heat resistance during embossing are improved, and the compatibility with the adhesive is also improved.

[Brief description of the drawings]

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

FIG. 2 is a schematic sectional view illustrating an example of a decorative material using the decorative sheet of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Resin sheet 2 Easy adhesion layer 3 Picture layer 4 Protective layer

 ──────────────────────────────────────────────────の Continuing on the front page F term (reference) 4F100 AA07 AA20 AK01A AK01B AK07 AK15B AK15J AK22B AK22J AK25A AK25B AK25J AK41A AK41B AK51A AK51B AK51J AL01B AL05B AR00B BA02 CA13B00 GB08GB

Claims (7)

[Claims] 1. A decorative sheet, characterized in that an easy-adhesion layer containing a chlorine-free resin is formed on one surface of a chlorine-free resin sheet to be decorated. 2. The decorative sheet according to claim 1, wherein the easy-adhesion layer contains two or more kinds of chlorine-free resins. 3. The decorative sheet according to claim 1, wherein said easy-adhesion layer comprises a copolymer of two or more kinds of resins containing no chlorine. 4. The decorative sheet according to claim 1, wherein the easy-adhesion layer is a mixture of a chlorine-free resin copolymer and a chlorine-free resin. 5. The decorative sheet according to claim 1, wherein the easy-adhesion layer is mainly composed of a resin containing no chlorine, and is further blended with a vinyl chloride-vinyl acetate copolymer. 6. The decorative sheet according to claim 1, wherein an extender pigment is compounded in the easy-adhesion layer. 7. The cosmetic according to claim 1, wherein the resin containing no chlorine is appropriately selected from an acrylic resin, a urethane resin, and a polyester resin. Sheet.