JP2000094608A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve a scuff resistance and a scratch resistance of a surface and to provide excellent adhesive properties of a transparent protective layer with a resin layer by forming a transparent resin layer by adding a specific amount of olefin resin fine particles having a specific article size on an olefin transparent resin layer laminated on a base material sheet. SOLUTION: In order to gloss regulate a surface by giving a wear resistance and a chemical resistance to the decorative sheet 1 obtained by laminating a decorative layer 3 and an olefin transparent resin layer 4 on a base material sheet 2, a transparent protective layer 5 is formed on the uppermost surface, and in order to improve adhesive properties of the layer 4 with the layer 5, 0.5 to 5 pts.wt. of fine particles obtained by granulating the olefin resin to 0.3 to 10 μm of a particle size is contained in the layer 5. As the olefin resin to be granulated to the particles, a high-density polyethylene, a straight chain low-density polyethylene or the like is used. As the layer 5, an uppermost surface of the sheet 1 is coated with a resin composition obtained by adding the particles to a transparent or translucent resin such as an acrylic resin, a polyurethane resin or the like and formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet used for interior decoration of buildings, surface decoration of fittings, vehicle interior decoration, and the like.

[0002]

2. Description of the Related Art A decorative sheet in which a transparent resin layer made of a thermoplastic resin is provided on the surface of a base sheet has been known. A vinyl chloride resin has been generally used as a thermoplastic resin.

[0003] However, since vinyl chloride resin generates chlorine gas during incineration and its effect on the environment cannot be ignored, in recent years, from the viewpoint of environmental protection, a decorative sheet using no vinyl chloride resin has been strongly demanded.

Therefore, in recent years, various decorative sheets have been proposed in which an olefin-based transparent resin layer is formed by using a polyolefin-based resin instead of vinyl chloride (for example, Japanese Patent Application Laid-Open No. Hei 6-79830). Gazette,
JP-A-79850), and a decorative sheet provided with a transparent protective layer on the outermost surface of the decorative sheet in order to improve the scratch resistance and scratch resistance of the decorative sheet surface is also known.

However, the olefin-based transparent resin layer has poor abrasion resistance and scratch resistance and thus requires a surface protective layer. However, the olefin-based transparent resin layer has poor adhesion to other layers and is easily peeled off therefrom. was there.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks of the prior art, and is a decorative sheet comprising a base sheet and at least a decorative layer and an olefin-based transparent resin layer laminated thereon. And a transparent protective layer formed by adding 0.5 to 5 parts by weight of olefin resin fine particles having a particle size of 0.3 to 10 μm on the olefin transparent resin layer. Is the gist.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to the drawings. As shown in FIG. 1, in the decorative sheet 1 of the present invention, a decorative layer 3, an olefin-based transparent resin layer 4, and a transparent protective layer 5 are sequentially formed on a base sheet 2.

In the present invention, a transparent protective layer 5 is formed on the outermost surface of the decorative sheet 1 in order to impart abrasion resistance and chemical resistance to the decorative sheet 1 and adjust the gloss of the surface.

In the present invention, in order to improve the surface physical properties of the decorative sheet 1 such as scratch resistance and scratch resistance, and to improve the adhesion between the olefin-based transparent resin layer 4 and the transparent protective layer 5. , Olefin resin with particle size 0.3
The transparent protective layer 5 contains fine particles granulated to a size of 10 to 10 μm, preferably 0.3 to 0.5 μm in a ratio of 0.5 to 5 parts by weight, preferably 1 to 4 parts by weight.

If the particle size of the olefin-based resin fine particles is less than the above range, the effect of the present invention cannot be obtained. If the particle size exceeds the above range, the printability when forming the protective layer 5 deteriorates.
If the amount of the fine particles is less than the above range, the effect of the present invention cannot be sufficiently obtained. If the amount exceeds the above range, transparency and smoothness are not preferable.

The olefin resin used to granulate the fine particles includes high-density polyethylene, linear low-density polyethylene, low-density polyethylene, polypropylene and the like.

The transparent protective layer 5 is made of a resin composition obtained by adding the above-mentioned fine particles to a transparent or translucent resin such as an acrylic resin, a polyurethane resin, an epoxy resin, etc., using a gravure coat, a roll coat, a knife coat, an air knife or the like. The coating is formed on the outermost surface of the decorative sheet 1 by a method.

In the present invention, in the decorative sheet 1 having the olefin resin layer 4, the outermost surface of the decorative sheet 1
It is particularly important that the transparent protective layer 5 is formed as described above, whereby the scratch resistance and the scratch resistance of the surface of the decorative sheet 1 are improved, and the gap between the transparent protective layer 5 and the olefin-based resin layer 4 is improved. Of the decorative sheet 1 can also be improved, and the slipperiness of the surface of the decorative sheet 1 can be improved.

Next, another configuration of the decorative sheet 1 of the present invention, that is, the decorative layer 3 and the olefin-based transparent resin layer 4 on the base sheet 2 will be described.

[Base Sheet] The base sheet 2 is composed of (a) an olefin-based resin film or sheet (hereinafter referred to as a sheet in the present invention including a film), or (b)
A fibrous sheet or the like is used.

(A) A sheet preferably comprising a high-density polyethylene resin, a thermoplastic elastomer, a colorant, and an inorganic filler is preferably used for the olefin resin sheet. According to the sheet, the performance required as a decorative sheet, that is, thermoformability comparable to polyvinyl chloride, creep deformation resistance, cold bending strength, organic solvent resistance, elongation at break, impact strength, moderate Those satisfying the flexural modulus and easy adhesion can be 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 few branched structures.

Examples of the thermoplastic elastomer include diene rubber, hydrogenated diene rubber, and olefin elastomer. The addition amount of the thermoplastic elastomer is 10 to 60% by weight, preferably about 30% by weight in the base sheet. If it is lower than 10% by weight, the change in elongation at a constant load becomes too steep, and the elongation at break and impact resistance decrease. If it exceeds 60%, the transparency, weather resistance and creep resistance decrease. Occurs. By the addition of the thermoplastic elastomer, the flexibility, impact resistance, easy adhesion and the like when formed as a base sheet can be improved.

Specifically, examples of the olefin resin include highly crystalline non-crystalline resins such as polyethylene (low density or high density), polypropylene, polymethylpentene, polybutene, ethylene / propylene copolymer, and propylene / butene copolymer. Elastomeric polyolefin resins or various olefinic thermoplastic elastomers are used. As the olefin-based thermoplastic elastomer, for example, the following can be used.

[0020] Japanese Patent Publication No. Hei 6-23278 describes,
(A) As a soft segment, the number average molecular weight Mn is 2
5,000 or more, 10 to 90% by weight of a boiling heptane-soluble atactic polypropylene having a ratio Mw / Mn ≦ 7 of the weight average molecular weight Mw to the number average molecular weight Mn, and (B) a melt index of 0 as a hard segment. .1 to
And 10 to 10% by weight of a heptane-insoluble isotactic polypropylene boiling at 4 g / 10 min.

Among the olefinic thermoplastic elastomers of this type, those which are less likely to cause so-called "necking" and have good suitability for forming into various shapes by applying heat and pressure and embossing include isotactic elastomers. It is composed of a mixture of an atactic polypropylene and an 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, in order to emphasize the strength, the atactic polypropylene which is a soft segment is used. Those having a weight ratio of less than 5% by weight were exclusively used. However, when this is applied to a novel use such as forming into a three-dimensional shape or an uneven shape or embossing as intended in the present invention, necking occurs as described above and good processing cannot be performed. Met.

Accordingly, the present inventors have conducted various studies and found that, contrary to the conventional design of the composition, the weight ratio of the atactic polypropylene is set to 5% by weight or more in the polypropylene-based thermoplastic elastomer. It has been found that unevenness of the sheet due to necking when embossing or molding into a three-dimensional or irregularly shaped article, and the resulting defects such as wrinkles and pattern distortion are solved. 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 increases too much, the sheet itself tends to be deformed, and when the sheet is passed through a printing machine, the sheet is deformed, and the pattern is distorted or the pattern is multicolored. Failures such as (Register) mismatch are likely to occur. Also, it is not preferable because it is easily broken during molding. As for the upper limit of the weight ratio of atactic polypropylene, the pattern layer is printed using a normal rotary printing machine such as rotogravure printing, and embossing of the sheet, vacuum forming, V-cut processing, simultaneous lamination of injection molding, etc. are employed. In this case, the content is 50% by weight or less, more preferably 40% by weight or less.

A thermoplastic elastomer composed of an ethylene-propylene-butene copolymer resin, wherein any one of three structural isomers of butene, 1-butene, 2-butene and isobutylene can be used. The above ethylene
Preferred specific examples of the propylene / butene copolymer include the following (i) to (iii) which are random copolymers and partially include an amorphous portion.

(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 set to 90% by weight or more of propylene. The melt flow rate is 1 to 50 g / 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 0.03 to
0.3 parts by weight is melt-kneaded.

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

(Iii) Those described in JP-A-7-316358. This is ethylene, propylene, butene 3
80 to 0% by weight of a crystalline polyolefin such as isotactic polypropylene with respect to 20 to 100% by weight of a low-crystalline polymer having a propylene and / or 1-butene content of 50% by weight or more. Composition 1 containing
An oil gelling agent such as an N-acylamino acid amine salt or an N-acylamino acid ester is added in an amount of 0.5% by weight to 00 parts by weight.

The ethylene / propylene / butene copolymer resin may be used alone, or may be used by mixing other polyolefin resins as required in the above (i) to (iii).

As described in JP-B-53-21021, (A) an olefin polymer (crystalline polymer) such as polyethylene, polypropylene or polymethylpentene is used as a hard segment, and (B) a partially crosslinked ethylene- Monoolefin copolymer rubber such as propylene copolymer rubber or unsaturated ethylene / propylene / non-conjugated diene terpolymer rubber is used as a soft segment, and these are uniformly blended and mixed. In addition, monoolefin rubber / olefin polymer = 50 / 50-9
Mix at a ratio of 0/10 (weight ratio).

As described in JP-B-53-34210 and the like, (B) uncrosslinked monoolefin copolymer rubber (soft segment) and (A) olefin copolymer (crystalline, hard segment) are crosslinked. An olefin-based elastomer obtained by mixing with an agent, heating and applying a shearing force to dynamically partially cross-link. (B) Monoolefin rubber /
(A) Olefin-based copolymer = 60/40 to 80/20
(Weight ratio).

As described in JP-B-56-15741, (A) mixing with a peroxide such as isotactic polypropylene, propylene-ethylene copolymer or propylene-butene-1 copolymer and heating reduces the molecular weight and increases the fluidity. By mixing and heating the peroxide-decomposing type olefin polymer (hard segment) which increases and the peroxide such as (B) ethylene-propylene copolymer rubber and ethylene-propylene-non-conjugated diene terpolymer rubber,
Peroxide non-crosslinked peroxide-crosslinkable monoolefin copolymer rubber (soft segment) whose crosslinkability is reduced, and (C) non-crosslinked peroxide that does not crosslink even when mixed and heated with peroxides such as polyisobutylene and butyl rubber Type hydrocarbon rubber (soft segment and fluidity modifying component),
And (D) a mineral oil-based softener such as a paraffin-based, naphthenic-based or aromatic-based softener, and dynamically heat-treated in the presence of an organic peroxide. (A) is 90 to 40 parts by weight, (B) is 10 to 60 parts by weight, and (A) + (B) = 100 parts by weight.
(C) and / or (D) have a compounding ratio of 5 to 100 parts by weight.

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

The above-mentioned olefin-based thermoplastic elastomer having a hydroxyl group and / or a carboxyl group as a polar group. For example, an olefin-based thermoplastic elastomer in which a hydroxyl group is introduced by graft polymerization of an ethylene / vinyl alcohol copolymer or the like and a carboxyl group is introduced by a copolymer of maleic acid, fumaric acid, itaconic acid or the like is used. Either one or both of the hydroxyl group and the carboxyl group may be used in combination, and these polar groups have an effect of improving the adhesiveness to other layers such as a printing ink layer and an adhesive layer.

The above polyolefin resin sheet can be formed into a sheet by a film forming method such as a calendering method, an inflation method, and a T-die extrusion method. The thickness of the sheet to be used depends on the use and the like, but is 20 to 20.
It is about 300 μm.

As these polyolefin resin sheets, any of a stretched sheet and an unstretched sheet can be used.
An unstretched sheet has better formability such as cutting. Various additives such as a filler, a foaming agent, a flame retardant, a lubricant, an antioxidant, an ultraviolet absorber, and a light stabilizer are added to the sheet as needed.

[Base Sheet] The base sheet 2 is preferably colored by adding a colorant comprising a pigment or a dye.
The coloring is colored transparent or opaque (concealing) coloring depending on the application. The color of the base sheet 2 is generally opaque because it can cover the surface of the adherend.

Examples of the coloring agent include inorganic pigments such as titanium white, zinc white, red iron oxide, vermilion, ultramarine, cobalt blue, titanium yellow, carbon black, and the like; Organic pigments or dyes, metal pigments such as aluminum and pearls, mica coated with titanium dioxide, pearlescent pigments made of foil powder such as basic zinc carbonate and the like are used.

An inorganic filler may be added to the base sheet 2 if necessary. As the inorganic filler, powders such as calcium carbonate, barium sulfate, clay, and talc are contained in the base sheet in an amount of about 5 to 60% by weight, preferably 30% by weight.
To some extent. If the amount is less than 5% by weight, the creep deformation resistance and the adhesion will be reduced. If it is more than 60% by weight, the elongation at break and the impact resistance will be reduced.

Further, if necessary, 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 to the base sheet 2.

The ultraviolet absorber and the light stabilizer are for imparting better weather resistance (light resistance) to the resin, and the amount of the ultraviolet absorber and the light stabilizer is usually 0.5 to 1 for both the ultraviolet absorber and the light stabilizer.
It is about 0% by weight. Generally, it is preferable to use an ultraviolet absorber and a light stabilizer in combination.

Organic substances such as benzotriazole, benzophenone, salicylate, etc.
Alternatively, inorganic substances such as zinc oxide, cerium oxide, and titanium oxide having a diameter of 0.2 μm or less can be used.

As a light stabilizer, bis- (2,2,6,
Hindered amine radical scavengers such as 6-tetramethyl-4-piperidinyl) sebacate and radical scavengers such as piperidine radical scavengers can be used.

The heat stabilizer is a known heat stabilizer such as a phenol type, a sulfite type, a phenylalkane type, a phosphite type, and an amine type, and is used in order to further improve the prevention of deterioration such as thermal discoloration during thermal processing. Used.

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

The olefin resin sheet used for the base sheet 2 is obtained by forming a blend of the above materials into a sheet by a conventional method such as a calendering method.

When an olefin resin sheet is used as the base sheet 2, its thickness is about 40 to 150 μm, more preferably about 50 to 120 μm. Further, as the olefin-based resin sheet, any of a stretched sheet and an unstretched sheet can be used, but the unstretched sheet has good formability such as V-cut processing.

The (b) fibrous sheet used for the base sheet 2 may be a sheet made of paper, woven fabric or non-woven fabric having a basis weight of about 50 to 150 g / m ² . Its thickness can be selected from the range of about 50 to 300 μm.

The fibrous material constituting the fibrous sheet is an organic synthetic fiber such as cellulose pulp, hemp, cotton, nylon or the like, or an artificial fiber such as asbestos, glass, quartz, carbon, potassium titanate or the like. Is mentioned. The fibrous material can be subjected to flame retardant treatment by mixing a flame retardant such as a phosphoric acid compound such as aziridinyl phosphine oxide. Incidentally, the fibrous base material sheet using cellulose pulp fiber is a so-called "paper", specifically,
Fine paper, kraft paper, Japanese paper and the like can be mentioned.

[Decoration Layer] The decoration layer 3 is formed on the surface of the base sheet 2 by pattern printing, coloring printing, or the like. Decorative layer 3
Is specifically a colored (transparent or opaque) pattern or solid printing by adding a pigment, using a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, or the like. It is formed of a paint (hereinafter simply referred to as ink).

The pattern of the decorative layer 3 includes a wood grain pattern, a stone grain pattern, a cloth grain pattern, a squeezed pattern, a geometric figure, characters, symbols, and the like. The decoration layer 3 may be provided on the entire surface of the surface of the base sheet 2 or may be provided partially.

As the ink used for the decorative layer 3, as a binder, chlorinated polyolefin such as chlorinated polyethylene, chlorinated polypropylene, polyester, polyurethane, acryl, vinyl acetate, vinyl chloride / vinyl acetate copolymer, cellulose resin, etc. And one obtained by mixing one or more kinds thereof and adding a known pigment as described above to the mixture. When printing directly on an olefin-based resin sheet, it is preferable to use chlorinated polyolefin, polyurethane, or the like as a binder in terms of adhesiveness, but the olefin-based resin sheet is subjected to an easy adhesion treatment such as a corona discharge treatment or a plasma discharge treatment. Alternatively, if a layer is formed by appropriately selecting an easy-adhesion primer, the decorative layer 3 can be provided on the base sheet 2 with sufficient adhesiveness even if other binders are used. The easy-adhesion primer is selected from acrylic, vinyl chloride / vinyl acetate copolymer, polyester, urethane, chlorinated polypropylene, chlorinated polyethylene and the like. The ink used for the decoration layer 3 is preferably a urethane-based high-temperature reaction type (150 to 250 ° C.), and the use of such an ink makes it unnecessary to apply an adhesive described later.

[Olefin-Based Transparent Resin Layer] The olefin-based transparent resin layer 4 contains an olefin-based resin as a main component, and the olefin-based resin used in the base sheet described above can be used. Further, the olefinic thermoplastic elastomers or the like exemplified as the material of the base sheet 2 can be used. These resins may be used alone or in combination of two or more.

In the present invention, preferably used are
It is a colorless or colored transparent soft polypropylene-based resin having a complex three-dimensional structure and comprising a mixed system of isotactic polypropylene and atactic polypropylene, which is mentioned in the description of the olefin-based thermoplastic elastomer. If a soft polypropylene resin having the above composite three-dimensional structure is used, the performance required as a decorative sheet,
That is, creep deformation resistance, organic solvent resistance, elongation at break,
Good impact strength, moderate flexural modulus, good transparency,
Further, even if heating and cooling accompanying embossing or the like are applied, whitening and turbidity due to recrystallization do not occur, and a material having satisfactory weather resistance can be obtained.

The olefin resin may be mixed with an ethylene / methyl methacrylate copolymer or an ethylene / vinyl acetate copolymer in order to improve the adhesiveness of the polyolefin transparent resin layer 4 to other layers. it can.

The ethylene / methyl methacrylate copolymer is obtained by copolymerizing ethylene and methyl methacrylate.

When the ethylene / vinyl acetate copolymer is blended, the blending amount is preferably 5 to 20% by weight.
If the amount of the ethylene / vinyl acetate copolymer is less than 5% by weight, the adhesion cannot be sufficiently improved. On the other hand, if it exceeds 20% by weight, the initial adhesion is good, but the adhesion decreases with time, resulting in poor weather resistance. Also, if a large amount of the ethylene / vinyl acetate copolymer exceeds 20% by weight, the acetic acid odor may be generated by the deacetic acid reaction, and the heat resistance of the olefin-based transparent resin layer 4 may be significantly reduced.

The ethylene / vinyl acetate copolymer is obtained by copolymerizing ethylene and vinyl acetate.

By blending the olefin-based transparent resin layer 4 with an ethylene / methyl methacrylate copolymer or an ethylene / vinyl acetate copolymer, the adhesion to other layers of the olefin-based transparent resin layer 4 is improved. However, the blending of these copolymers tends to lower the inherent heat resistance of the olefin resin. Such a tendency is remarkable as the thickness of the olefin-based transparent resin layer 4 is required and the amount of the copolymer used is increased, and furthermore, a large amount of an expensive ethylene-methyl methacrylate copolymer is used. This is disadvantageous in terms of cost, and when a large amount of ethylene-vinyl acetate copolymer is used, there is a possibility that acetic acid odor is generated due to a deacetic acid reaction.

For this reason, when an ethylene-methyl methacrylate copolymer or an ethylene-vinyl acetate copolymer is blended with the olefin resin, the olefin resin layer 4 is coated with the olefin resin as shown in FIG. (A)
It is preferable to form a two-layer structure including a layer (layer 4) and a layer (layer B) 4b that is not blended, and to blend only the above-mentioned layer A 4a located on the decorative layer 3 side in the above-described ratio.

The effect of blending these copolymers is that even if the A layer 4a is thinned, at least the decorative layer 3
If the copolymer is present on the side surface, it can be obtained sufficiently. For this reason, the above-mentioned A layer 4a is made as thin as possible to reduce the amount of the ethylene-methyl methacrylate copolymer or the ethylene-vinyl acetate copolymer to avoid the adverse effects caused by the blending of these copolymers. Can be.

In order to form the olefin transparent resin layer 4 into the two-layer structure as described above, for example, in the case of extrusion coating, (a) an olefin resin mixed with the above copolymer is added to the surface of the decorative layer 3. , (B) and an olefin-based resin not blended with the copolymer may be laminated by co-extrusion so that (a) is on the decorative layer 3 side. In the case of laminating a sheet formed in advance into a sheet shape by dry lamination, heat lamination, or the like, the two-layered sheet is formed by co-extrusion, and the side where the copolymer is blended is the decorative layer 3. It suffices to stick them together so as to be on the side.

Further, various additives such as an ultraviolet absorber, a light stabilizer, a filler, a flame retardant, and a foaming agent as described in the description of the base sheet 2 are added to the olefin resin as required. be able to.

The adhesion between the decorative layer 3 and the olefin-based transparent resin layer 4 is prevented from deteriorating with the lapse of time due to ultraviolet rays.
Even after irradiation for 2000 hours (black panel 63 ° C.), in order to provide sufficient adhesion strength as a decorative sheet and to further improve weather resistance, an ultraviolet absorber, a light-stable It is advisable to add an agent. As a result of various studies, it is preferable to add 0.1% by weight or more of a benzotriazole-based ultraviolet absorber or 0.1% by weight or more of a hindered amine-based radical scavenger.

The olefin-based transparent resin layer 4 is formed, for example, by blending the above-mentioned olefin-based resin with an ethylene / methyl methacrylate copolymer, melt-kneading the resin, and applying the molten resin to the surface of the decorative layer 3 by extrusion coating. Laminate or
Alternatively, the decorative layer 3 is formed on the decorative layer 3 by a method such as dry lamination using an adhesive such as a two-component curable polyurethane or polyester resin, or heat lamination by fusing with a hot press. Laminated. The thickness of the olefin-based transparent resin layer 4 is 1 to 100 μm.
m. When the olefin-based transparent resin layer 4 is used by laminating a sheet that has been previously formed into a sheet shape, the sheet can be either a stretched sheet or an unstretched sheet. An unstretched sheet is preferable because of good formability such as processing.

In laminating the olefin-based transparent resin layer 4 on the decorative layer 3, an adhesive can be applied to the surface of the decorative layer 3.

As the adhesive, an acrylic polyol-based adhesive,
An adhesive such as a polyester polyol is used.
If a binder having the same composition as the above-mentioned adhesive is used as the binder of the ink for forming the decorative layer 3, application of the adhesive is not particularly necessary.

In the decorative sheet 1 of the present invention, although not particularly shown, an uneven pattern may be formed on the surface of the olefin-based transparent resin layer 4 by embossing, hairline processing or the like.

In the embossing, the olefin-based transparent resin layer 4 is heated and softened, and is pressed and shaped with an embossing plate.
A known sheet-fed or rotary embossing machine is used for cooling and fixing. As the embossed uneven shape,
Wood channel grooves, stone plate surface irregularities (granite cleavage planes, etc.), fabric surface texture, pears, sand, hairlines, and alley grooves.

The concave portions of the concavo-convex pattern can be filled with a coloring ink or a paint (hereinafter simply referred to as a coloring ink) by a known wiping method (see Japanese Patent Publication No. 58-14312), if necessary.

The coloring inks include, for example, shellac,
Natural resins such as Koval, dammar, rosin, rosin ester or modified resins thereof, cellulose derivatives such as nitrocellulose, acetylcellulose, ethylcellulose, benzylcellulose, phenolic resins, urea resins, phthalic resins, maleic resins, melamine Resin, polyvinyl acetate resin, polyvinyl chloride resin, acrylic resin, polyvinyl alcohol, polyvinyl butyral,
Epoxy resins, silicone resins, polyester resins, polyamide resins, polyurethane resins or other synthetic resins, rubber derivatives such as chlorinated rubber, synthetic rubber, etc. are used as vehicle components, and colorants and sediments are settled in the vehicle. An ink obtained by adding an extender such as neutral barium sulfate, a plasticizer, or the like is used.

The coloring ink is coated on the concave portion of the sheet surface with a roll coat or a knife coat, and then the colored ink coated on the convex portion of the sheet is removed by scraping off with a doctor blade or wiping paper, and only the concave portion is colored. The viscosity of the ink composition, the number of rotations of the roll, the blade angle of the doctor, the thickness, the sheet speed,
It is necessary to adjust the speed of the wiping paper, the hardness of the rubber roll, and the like. For example, the area of the colored ink is preferably the same as or similar to a conduit in the case of a grain pattern, and is preferably the same or similar to a crack in the case of a stone pattern.

The decorative sheet 1 of the present invention can be used for interior decoration of buildings such as walls, ceilings and floors, surface decoration of fittings such as window frames, doors and handrails, furniture and cabinets for light electric / OA equipment. Surface makeup, vehicle interiors such as automobiles and trains, aircraft interiors, window glass makeup, and the like.

When the decorative sheet 1 is used for interior and exterior of a building, surface decoration of fittings and furniture, interior of a vehicle, and the like, it is more preferable to have the following functions (1) to (9).

(1) Thermoformability comparable to polyvinyl chloride. In particular, it must have the characteristic that the change in elongation at constant load due to temperature changes is as slow and continuous as that of polyvinyl chloride. In addition, deterioration of material mechanical properties such as strength reduction does not occur with heating or cooling. (2) Good creep resistance. Exterior and interior materials are often subjected to a constant load by fittings and furniture for long periods of time, and when creep deformation occurs, the loaded parts are turned up or peeled off. Therefore, it is preferable that the material does not cause creep deformation as much as possible. (3) Good cold bending strength. When bending such as V-cutting is performed in cold weather, if stress relaxation is insufficient, whitening, cracking, breakage, and the like are likely to occur in the bent portion. (4) Good organic solvent resistance. The decorative sheet can be prevented from swelling and deforming due to the solvent in the adhesive for bonding the decorative sheet and the adherend. The same applies when a decorative sheet having a multilayer structure is obtained. (5) High elongation at break and high impact strength. This is a characteristic for preventing a crack at a bent portion during V-cut processing. (6) Having an appropriate bending elastic modulus. The followability of the decorative sheet in the bending portion is sufficient. (7) Good transparency. (8) Whitening and turbidity due to recrystallization do not occur even when heating and cooling accompanying embossing or the like are applied. (9) Be superior in weather resistance.

The base sheet 2 is made of a high-density polyethylene, a thermoplastic elastomer, a coloring agent, and an inorganic filler, and the olefin-based transparent resin layer 4 is made of a mixture of isotactic polypropylene and actatic polypropylene. By providing a colorless or colored transparent soft polypropylene resin as a main component, various conditions required for the decorative sheet described above can be shared, and a highly practical decorative sheet can be obtained.

[0077]

EXAMPLES Example 1 As a base material, "Tuffer" 100 μm manufactured by Tatsuno Chemical Co., Ltd. was used.
m, gravure printing is performed on the surface of the base sheet with a urethane-based ink (“PPGR” manufactured by Showa Ink Co., Ltd.) to form a decoration layer, and then a urethane-based adhesive [Dainichiseika Co., Ltd.) was applied.

Next, a layer formed by extruding random polypropylene (“Noblen” manufactured by Sumitomo Chemical Co., Ltd.) at 240 ° C. from an extruder is 70 μm, 70% by weight of random polypropylene (“Noblen” manufactured by Sumitomo Chemical Co., Ltd.) and ethylene / methacrylic acid. A resin obtained by melt-kneading 30% by weight of a methyl copolymer (“Aklift WH303” manufactured by Sumitomo Chemical Co., Ltd.) is coextruded by a feed block method so that a layer formed by extruding the melted resin has a thickness of 10 μm. Extruded with a thickness of 80 μm onto the adhesive-coated surface of the substrate,
Lamination was performed while nipping between a cooling roll and a pressure roll to provide an olefin-based transparent resin layer.

Then, on the olefin-based transparent resin layer, 1 weight of fine particles obtained by granulating a random polypropylene (“Mitsui High Wax NP105” manufactured by Mitsui Petrochemical Industries, Ltd.) to a particle size of 1 μm as a urethane resin was used. The resin composition thus added was applied by a gravure coater to form a transparent protective layer.

The obtained decorative sheet was subjected to JIS K
The interlayer adhesion between the olefin-based transparent resin layer and the transparent protective layer was measured by a crosscut tape method of No. 5400. As a result, even if the adhesive tape was repeatedly attached and peeled 10 times, no interlayer peeling occurred.

An accelerated test was conducted for one week at a temperature of 70 ° C., but no shrinkage of the olefin-based transparent resin layer and no decrease in interlayer adhesion were observed.

Further, when a postcard made by government was overlaid on the obtained decorative sheet and reciprocated twice with a load of 250 g / cm ^2, no visible scratch was found on the surface of the decorative sheet.

[0083]

[Comparative Example] "Tough Bar" 10 manufactured by Tatsuno Chemical Co., Ltd.
Using 0 μm, the surface of the base sheet is gravure-printed with a urethane-based ink (“PPGR” manufactured by Showa Ink Co., Ltd.) to provide a decoration layer, and then a urethane-based adhesive (Dainichi Seika) Co., Ltd.) was applied.

Then, a layer formed by extruding random polypropylene (“Noblen” manufactured by Sumitomo Chemical Co., Ltd.) at 240 ° C. from an extruder was 70 μm, 70% by weight of random polypropylene (“Noblen” manufactured by Sumitomo Chemical Co., Ltd.) and ethylene methacryl were added. A resin in a molten state is co-extruded by a feed block method so that a layer obtained by extruding a mixture obtained by melting and kneading 30% by weight of an acid methyl copolymer (“Acryft WH303” manufactured by Sumitomo Chemical Co., Ltd.) becomes 10 μm. 8 in total
It was extruded at a thickness of 0 μm onto the adhesive-coated surface of the base material, and was laminated while being nipped between a cooling roll and a pressure roll to provide an olefin-based transparent resin layer.

Next, on the olefin-based transparent resin,
A urethane-based resin transparent protective layer was formed.

The obtained decorative sheet was subjected to JIS K
When the interlayer adhesion between the olefin-based transparent resin and the transparent protective layer was measured by a crosscut tape method of 5400, adhesion and peeling of the adhesive tape were peeled off three times.

An accelerated test for one week was conducted at a temperature of 70 ° C., but no shrinkage of the olefin-based transparent resin layer or a decrease in interlayer adhesion was observed.

Further, when a postcard made by government was overlaid on the obtained decorative sheet and reciprocated twice with a load of 250 g / cm ^2, a visible scratch was generated on the surface of the decorative sheet.

[0089]

As described above, according to the decorative sheet of the present invention, the transparent protective layer formed on the olefin-based transparent resin layer contains 0.5 to 5% by weight of olefin-based resin particles having a particle size of 0.3 to 10 μm. By adding a part, the scratch resistance and scratch resistance of the surface of the decorative sheet are improved, and the interlayer adhesion between the transparent protective layer and the olefin resin layer is also excellent.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view showing one example of the decorative sheet of the present invention.

FIG. 2 is a longitudinal sectional view showing another example of the decorative sheet of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Base sheet 3 Decorative layer 4 Olefin transparent resin layer

 ──────────────────────────────────────────────────の Continued on the front page F term (reference) 4F100 AK03C AK03D AK03H AK07 AK51 AK71 AR00D AT00A BA04 BA07 BA10A BA10D CA23D DE01D DE01H EH20 GB08 GB31 GB33 HB00B JK16 JK20 JN01C JN01D YY00D YY00H

Claims (1)

[Claims] 1. A decorative sheet comprising a base sheet and at least a decorative layer and an olefin-based transparent resin layer laminated thereon, wherein the olefin-based transparent resin layer has a particle size of 0.3 to 10%.
A decorative sheet comprising a transparent protective layer formed by adding 0.5 to 5 parts by weight of a fine olefin resin particle of 0.5 μm.