JP2001277447A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet, in which the generation of environmentally unfriendly gas or substance such as hydrogen chloride gas and a polycyclic organic chlorine compound or the like is prevented at time of incineration and also adhesion in the case of being stuck to the other member is high and adhesive properties to the member are good and a change in the lapse of time is not caused. SOLUTION: The decorative sheet 1 is constituted of laminating a thermoplastic resin sheet 5 having >=35 mN/m wetting index on the rear side (opposite face of a printed layer 3) of a printed polyolefin sheet 4, in which the printed layer 3 is provided on the surface of a polyolefinic resin sheet 2.

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 by being bonded to various materials such as wood and plastic products.

[0002]

2. Description of the Related Art As a conventional decorative sheet, a sheet obtained by laminating a polyvinyl chloride sheet on a polyvinyl chloride sheet having a pattern or the like printed on its surface has been used. In recent years, products using a vinyl chloride resin do not use a polyvinyl chloride sheet because they generate environmentally undesirable gases or substances such as hydrogen chloride gas and polycyclic organic chlorine compounds during combustion such as incineration. A product is desired.

[0003]

Attempts have been made to use a polyolefin resin as a decorative sheet instead of a polyvinyl chloride sheet. By using a polyolefin resin sheet, it is possible to prevent the generation of environmentally undesirable gases or substances such as hydrogen chloride gas and polycyclic organic chlorine compounds such as dioxin, but when attaching a decorative sheet to another member Has low adhesion and tends to peel off from a member bonded to another member.
Therefore, in Japanese Patent Application Laid-Open No. 50-91672, it is possible to impart a corona discharge treatment to a polyolefin resin sheet to generate a polar functional group such as a hydroxyl group or a carboxyl group on the sheet surface, thereby imparting easy adhesion. was suggested. However, there has been a problem that the effect of improving the adhesion by the corona discharge treatment is lost over time and is not stable.

The present invention has been made to solve the above-mentioned drawbacks of the prior art, and prevents the generation of environmentally unfriendly gases and substances such as hydrogen chloride gas and polycyclic organochlorine compounds during incineration, and prevents other gases from being generated. An object of the present invention is to provide a decorative sheet that has high adhesion when bonded to a member, has good adhesion to the member, and does not change with time.

[0005]

According to the present invention, there is provided (1) a wettability index of 35 m on a back surface of a polyolefin resin sheet having at least one of a front surface and a back surface printed thereon.
(2) The decorative sheet according to (1), wherein a thermoplastic resin sheet having a thickness of at least N / m is laminated, (2) a decorative protective sheet is provided on the surface of the polyolefin-based resin sheet. Sheet, (3) a wetting index of 35 mN /
m or more, wherein the thermoplastic resin sheet is an ABS resin sheet, the decorative sheet according to the above (1) or (2),
The above (1), wherein the transparent protective layer is a transparent acrylic resin sheet
(5) The decorative sheet according to any one of (1) to (3), and (5) the decorative sheet (6) according to (4) above, wherein a transparent protective coat layer is formed on the transparent acrylic resin sheet. Polyolefin sheet or wetting index 35 mN / m
The decorative sheet according to any one of the above (1) to (6), wherein a primer layer is provided on the back surface side of the thermoplastic resin sheet described above.

[0006]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to the drawings. FIG. 1 shows an embodiment of the present invention. As shown in FIG. 1, a decorative sheet 1 of the present invention is a printed polyolefin sheet in which a printed layer 3 such as a pattern is provided on the surface of a polyolefin-based resin sheet 2. A thermoplastic resin sheet 5 having a specific wetting index is laminated on the back surface side of 4 (the opposite side of the printing layer 3). In FIG. 1, reference numeral 6 denotes an easy-adhesion layer provided on the back surface side of the polyolefin-based resin sheet 2, and reference numeral 7 denotes a transparent protection provided on the printing layer 3 for protecting the surface of the decorative sheet. Reference numeral 8 denotes a dry laminating adhesive for laminating the thermoplastic resin sheet 5.

In the present invention, the thermoplastic resin sheet 5 has a wetting index of 35 mN / m or more, preferably 38 mN / m.
mN / m or more. The upper limit of the wetting index is not particularly limited, but there is no thermoplastic resin sheet having an unlimitedly high wetting index. Therefore, the upper limit of the actually available thermoplastic resin sheet naturally determines the upper limit of the wetting index. Usually 5
It is about 6 mN / m or less. In the present invention, the wetting index was determined to be such that a series of standard liquids (usually a mixture of formamide and ethylene glycol monoethyl ether) having different surface tensions were applied to the sheet surface, and the sheet surface was just wetted. It is defined as the numerical value of the surface tension (mN / m) of the standard liquid. The measuring method of the wetting index is based on JIS
As specified in K6768.

[0008] In the decorative sheet of the present invention, the thermoplastic resin sheet 5 is for backing (backing) a printing sheet made of a so-called polyolefin resin sheet to improve the adhesion (adhesion) to other members. Since the thermoplastic resin sheet has a wetting index greater than or equal to the specific value described above, the adhesiveness to other members is superior to the printed polyolefin sheet 4. Therefore, the adhesive force when the decorative sheet is bonded to another member is increased, and the bonding process can be easily performed. Then, by forming the sheet from a thermoplastic resin, it is possible to satisfactorily mold into various desired shapes by heating and softening during molding such as insert molding described below.
In addition, the effect of improving the adhesive strength is maintained for a long time. On the other hand, in the conventional method of simply giving a polar functional group to the surface of a polyolefin-based resin sheet by corona discharge treatment, the effect of improving the adhesive strength is unstable and tends to change over time (the effect is lost). Also, by laminating this thermoplastic resin sheet, compared to the sheet before lamination, the thickness of the entire decorative sheet can be formed thicker, so that the flatness is improved. There is an advantage that the mirror surface is also improved.

As the thermoplastic resin sheet 5, various kinds of thermoplastic resin sheets having the above specific wettability are used, but from the viewpoint of cost, an ABS (acrylonitrile-butadiene-styrene copolymer) resin sheet is used. It is preferably used. There are two types of ABS resins: a styrene-acrylonitrile copolymer, a polymer blend type with NBR, and a graft type obtained by graft copolymerizing styrene and acrylonitrile in the presence of BR or SBR latex. Either can be used.

In addition, the thermoplastic resin sheet 5 includes:
The following resin sheets can also be used. For example, acrylic resin, polystyrene, acrylonitrile-styrene copolymer and the like can be mentioned.

The thickness of the thermoplastic resin sheet 5 can be appropriately selected according to the use of the decorative sheet, and is not particularly limited.
μm is preferred.

The printed polyolefin sheet 4 is disclosed in, for example, JP-A-10-109387 and JP-A-8-11856.
No. 5, a sheet having a polyolefin resin sheet as a base sheet, a decoration such as a picture, and a protective layer laminated on the surface can be used. Specifically, a decorative sheet formed by laminating a transparent protective layer made of a protective sheet of an acrylic resin on a sheet substrate made of an olefin resin in which a thermoplastic resin elastomer and an inorganic filler are blended with high-density polyethylene, polyethylene and A pattern printing layer is provided on a polyolefin resin sheet made of a mixed resin of two or more polyolefins having different melting points, such as polypropylene, and a transparent protection made of an acrylic resin sheet such as a methyl methacrylate resin is provided thereon. It is a decorative sheet or the like formed by laminating layers. Hereinafter, a polyolefin-based resin (base material) sheet, a transparent protective layer, a printed layer, and the like used for the printed polyolefin sheet will be described.

As the base resin of the polyolefin resin sheet 2, a polyolefin resin is used, and specifically, polyethylene (low density or high density), polypropylene (isotactic type, syndiotactic type, High-crystalline non-elastomeric polyolefin resin such as polymethylpentene, polybutene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, propylene-butene copolymer, or various olefins described below And the like.

The olefin-based thermoplastic elastomer is
(A) The main raw material is made of either high-density polyethylene or polypropylene which is a hard segment, and an elastomer and an inorganic filler as a soft segment are added thereto, and (A) JP-B-6-23278 describes Comprising a mixture of isotactic polypropylene as a hard segment and atactic polypropylene as a soft segment;
JP-A-1111055, JP-A-5-77371,
Examples thereof include those comprising an ethylene-propylene-butene copolymer described in JP-A-7-316358.

The above-mentioned high-density polyethylene is a polyethylene having a specific gravity of 0.94 to 0.96, a high crystallinity obtained by a low-pressure method, and a polyethylene having a small number of branched structures. The amount of the high-density polyethylene is 30% by weight or more based on the olefin resin obtained by mixing the thermoplastic elastomer and the inorganic filler with the high-density polyethylene.
It is preferably at most 5% by weight.

As the above-mentioned thermoplastic elastomer, for example, those exemplified in the following (1) to (5) are used. (1) Number average molecular weight: Mn is 25,000 or more, and the ratio of weight average molecular weight: Mw to number average molecular weight: Mn is Mw /
Boiling heptane-soluble polypropylene with Mn ≦ 7
90% by weight and a melt index of 0.1 to 4 g / 1
A mixture with 90 to 10% by weight of a 0 minute boiling heptane-insoluble polypropylene (soft polypropylene described in Japanese Patent Publication No. 23278/1994), (2) olefin polymers such as polyethylene, polypropylene and polymethylpentene (highly crystalline) Molecule) as a hard segment, and a monoolefin copolymer rubber such as an ethylene-propylene-non-conjugated diene terpolymer rubber partially crosslinked as a soft segment, and these are represented by a weight ratio of soft segment / hard segment = 50. Olefin elastomer (olefin elastomer described in JP-B-53-21021), which is uniformly blended and mixed at a ratio of / 50 to 90/10, and (3) uncrosslinked monoolefin copolymer rubber (soft segment ) And an olefin copolymer (crystalline hard segment) An olefinic elastomer obtained by mixing a soft segment / hard segment in a weight ratio of 60/40 to 80/20 in a weight ratio, mixing a crosslinking agent, heating, and dynamically partially cross-linking while applying shear stress ( The molecular weight is obtained by mixing and heating with a peroxide such as an olefin-based elastomer described in JP-B-53-34210, (4) isotactic polypropylene, propylene-ethylene copolymer, propylene-butene-1 copolymer and the like. Peroxide-decomposable olefin polymer (hard segment) with characteristics of decreasing and increasing fluidity
Peroxide-crosslinked monoolefin whose flowability is reduced by mixing and heating with a peroxide, such as 90 to 40 parts by mass, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene terpolymer rubber, etc. Peroxide non-crosslinked hydrocarbon rubber (10% to 60 parts by mass of copolymer rubber (soft segment) and polyisobutylene, butyl rubber, etc., which does not crosslink even when heated and mixed with peroxide and has constant fluidity (soft segment and fluidity) Reforming component)
5 to 100 parts by mass, and paraffinic, naphthenic, aromatic mineral softening agent mixed with 5 to 100 parts by mass,
Olefin elastomers dynamically treated in the presence of an organic peroxide (olefin elastomers described in JP-B-56-15741), and (5) olefin elastomers composed of an ethylene-styrene-butylene copolymer ( Olefin-based elastomer described in JP-A-2-139232).

Further, as the elastomer to be the soft segment, a diene rubber, a hydrogenated diene rubber or the like can be used, and among them, a hydrogenated diene rubber is preferable. 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 high-density polyethylene.
It plays a role in improving flexibility and transparency. In general, when a diene rubber is added to a polyolefin resin, weather resistance and heat resistance are lower than those of a polyolefin resin without a diene rubber due to a double bond of the diene rubber. By saturating the polyolefin resin, there is no fear that the weather resistance and the heat resistance of the polyolefin resin are reduced.

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.

As the inorganic filler to be added to the polyolefin resin sheet, powders such as calcium carbonate, barium sulfate, clay and talc are used. The olefin-based resin constituting the sheet substrate 2 contains the thermoplastic elastomer in a proportion of 10 to 60% by weight and the inorganic filler in a proportion of 5 to 60% by weight, and the total content of both is 70% by weight. The following is preferred. When the content of the thermoplastic elastomer is less than 10% by weight or the content of the inorganic filler is less than 5% by weight, the elasticity, elongation, and impact resistance of the polyolefin-based resin sheet are insufficient, and the decorative sheet is used. When a bending process such as a V-cut process or a drawing process is performed on a member on which is laminated, cracks and cracks are easily generated. If the content of the thermoplastic elastomer exceeds 60% by weight or the content of the inorganic filler exceeds 60% by weight, the elasticity and elongation of the polyolefin-based resin sheet 2 become too large, and printing is performed. When the layer 3 is formed by printing or the like, there is a possibility that problems such as difficulty in alignment may occur.

The polyolefin-based resin sheet can be obtained by blending the above materials and forming a film by a conventional method such as a calendering method or a melt extrusion method. When a film is formed by a melt extrusion method using a composition to which a coloring agent, an inorganic filler, or both are added as a polyolefin resin, the film forming aptitude decreases when the film is formed into a thin film, and the surface is smoothed. Absent. Generally, when a colorant or the like is added in a total amount of about 10 parts by mass or more to form a film having a thickness of 80 μm or less, this tendency is conspicuous. 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 polyolefin-based resin sheet may be any of a stretched sheet and an unstretched sheet. The sheet may contain a filler, a foaming agent, a flame retardant,
Various additives such as a lubricant, an antioxidant, an ultraviolet absorber, and a light stabilizer are added. The thickness of the polyolefin-based resin sheet depends on the application and the like, but is preferably about 20 to 300 μm.

As the flame retardant, powders such as aluminum hydroxide and magnesium hydroxide are used. The addition amount of the flame retardant is preferably about 10 to 150 parts by mass based on 100 parts by mass of the total amount of the high-density polyethylene and the thermoplastic elastomer.

As the ultraviolet absorber, the following (1)-
Something like (5) can be used. (1) Benzophenone type: 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid . (2) benzotriazole type; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-
(2'-hydroxy-3-, 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-
Hydroxy-3 ', 5'-dicumylphenyl) phenylbenzotriazole, 2- (2, -hydroxy-3'-
Dodecyl-5-methylphenyl) benzotriazole,
2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-
2-yl) phenol]. (3) acrylate type; ethyl-2-cyano-3,3 '
-Diphenyl acrylate, 2-ethylhexyl-2-
Cyano-3,3'-diphenyl acrylate. (4) salicylate; phenyl salicylate, 4-t
-Butylphenyl salicylate. (5) oxanilides; 2-ethoxy-2'-ethyloxalic acid bisanilide, 2-ethoxyxin-5
t-Butyl-2'-ethyloxalic acid bisanilide. The amount of these UV absorbers added is preferably in the range of 0.1 to 2% by weight based on the resin content. If it is less than 0.1% by weight, the effect of addition is poor, and if it exceeds 2% by weight, no improvement in the effect is observed.

As the light stabilizer, the following compounds, commonly called HALS, which take the initial of English name of hindered amine light stabilizer (Hindered Amine Light Stabilizer), can be used. Bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis- (N-methyl, 2,2.6,
6, -tetramethyl-4-piperidinyl) sebacate,
[Dimethyl succinate-1- (2-hydroxyethyl)-
4-hydroxy-2,2,6,6-tetramethylpiperidine] condensate, poly {[6- (1,1,3,3-tetramethylbutyl) imino] -1,3,5-triazine-
2,4-diyl [(2,2,6,6-tetramethyl-4
-Piperidyl) imino] hexamethylene [(2,2,
6,6-tetramethyl-4-piperidyl) iminol]}. The ratio of adding these light stabilizers is preferably in the range of 0.1 to 2% by weight based on the resin content of the layer to be added. If it is less than 0.1% by weight, the effect of addition is poor, and if it exceeds 2% by weight, no improvement in the effect is observed.

Although the ultraviolet absorber and the light stabilizer are effective even when used alone, it is not clear why they are used in combination, but the effects are synergistically improved. Things are desirable. In addition, if the ultraviolet absorber and the light stabilizer are simply mixed, bleeding during use is inevitable. Therefore, instead of the above hindered amine light stabilizer, 4- (meth) acryloyloxy-2,2 is used. ,
6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyloxy-1-propyl-2,2,6,6- Tetramethylbiperidine or 4- (meth) acryloyloxy-1-butyl 2,2
Compounds having a (meth) acryloyloxy group such as 2,6,6-tetramethylpiperidine, or 4-crotonoyloxy-2,2,6.8-tetramethylpiperidine, or 4-crotonoyloxy-1-propyl −
It is desirable to prevent bleeding by using a resin obtained by graft copolymerizing a compound having a crotonoyloxy group such as 2,2,6,6-tetramethylpiperidine.

As the polyolefin resin sheet 2, a cellular (sponge-like) foam may be used. In this case, a foaming agent is added to the resin constituting the sheet, and the foamed agent is fired by heating. . Examples of the foaming agent include azodicarbonamide, azobisisobutyronitrile, N-N'-dinitrosopentamethylenetetramine, oxybisbenzenesulfonylhydrazide, sodium hydrogencarbonate, potassium hydrogencarbonate, and the like, or acrylonitrile. A microcapsule type in which a heat-expandable gas such as hexane or isobutane is sealed in a resin spherical shell such as The addition amount of the foaming agent is 1 to 10 parts by mass based on 100 parts by mass of the base resin (the total amount of the high-density polyethylene and the thermoplastic elastomer) constituting the sheet base.

The surface of the polyolefin-based resin sheet (the front side, the back side, or both sides) can be subjected to an easy adhesion treatment such as a corona discharge treatment, a plasma treatment, and an ozone treatment. For this easy adhesion treatment, 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 polyolefin resin sheet. When a polyolefin resin sheet is formed by a melt extrusion method, these polar functional groups are generated to some extent on the surface during the film formation. Therefore, if the polar functional groups generated at the time of film formation are sufficient, the easy adhesion treatment may be omitted. However, these easy adhesion treatments lose their effects over time, so as soon as possible after treatment,
It is preferable to laminate a thermoplastic resin sheet having a wetting index of 35 mN / m or more and a printing layer.

The printing layer 3 is formed by printing and forming patterns of a wood grain pattern, a stone grain pattern, a cloth grain pattern, a leather crest pattern, a geometric figure, characters, symbols, line drawings, and various abstract patterns. Further, the printing layer 3 may be formed by solid printing with a colored ink having concealing properties. The print layer 3 may be composed of only a pattern print, may be composed of only a solid print, or may be composed of both a pattern and a solid. Also,
The printing layer 3 may be partial or whole.

The printing layer 3 can be formed by printing or coating using a general printing ink. As the ink, there can be used a composition mainly composed of a binder resin and a coloring agent, and if necessary, an extender pigment, a curing agent, an additive, a solvent and the like are added thereto. Examples of the binder resin include chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester resins, polyurethane resins (two-component curable urethane resins or thermoplastic urethane resins), acrylic resins, polyvinyl acetate, and vinyl chloride. One or a mixture of two or more kinds of vinyl acetate copolymers and cellulose resins is used. When printing directly on the polyolefin-based resin sheet 2, it is preferable to use chlorinated polyolefin, polyurethane or the like as a binder resin from the viewpoint of adhesiveness. However, if the easy-adhesion layer 6 is appropriately selected, other binder resins may be used. Even if used, sufficient adhesiveness can be obtained.

Examples of the coloring agent include titanium white, carbon black, red iron oxide, graphite, ultramarine, phthalocyanine blue,
Examples include pigments or dyes such as quinacridone red and isoindolinone yellow, metallic foil powders such as aluminum and brass, and glittering pigments composed of foil powders such as titanium dioxide-coated mica.

The printing method of the printing layer 3 may be a printing method such as gravure printing, intaglio printing, offset printing, letterpress printing, flexographic printing, silk screen printing, electrostatic printing, ink jet printing or the like, or once on a release sheet. A transfer sheet is formed by forming a picture pattern and a transfer printing method using the obtained transfer sheet.

The printing layer 3 can be formed of a metal thin film other than the above-described printing with the ink. In this case, a method of laminating the metal thin film on the entire surface or partially in a pattern is exemplified. The metal thin film is formed by using a metal such as aluminum, chromium, gold, silver, or copper by a method such as vacuum evaporation or sputtering, and is formed into a metal thin film having a partial pattern by an etching method or the like.

The printing layer 3 is provided on the front side of the polyolefin resin sheet 2 (between the polyolefin resin sheet and the transparent protective layer 7 in FIG. 1) as shown in FIG. And polyolefin resin sheet 2
May be provided on the back side of the polyolefin-based resin sheet (in the example shown in FIG. 1, between the easy-adhesion layer 6 and the polyolefin-based resin sheet 2). Alternatively, the print layer 3 may be formed on both the front side and the back side. When the polyolefin-based resin sheet is composed of two or more olefin-based resin sheets, a print layer may be formed between these sheets.

On the surface of the printed polyolefin sheet, a transparent protective layer 7 can be provided to protect the surface of the decorative sheet and to give the decorative sheet a paint-like appearance. The transparent protective layer is formed by laminating a transparent resin layer. The transparent resin layer is formed by laminating thermoplastic resin sheets or applying a resin solution. The transparency of the transparent protective layer may be any of colorless and transparent and colored and transparent, and the transparency may be transparent as long as the design information of the lower printed layer can be confirmed from the outermost surface, and includes translucent.

When the transparent protective layer 7 is formed by laminating thermoplastic resin sheets, an acrylic resin sheet is preferably used. Specific examples of the acrylic resin sheet include polymethyl (meth) acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate, butyl poly (meth) acrylate, and methyl (meth) acrylate- ( Homo- or copolymers containing (meth) acrylic ester of (meth) butyl acrylate copolymer, ethylene-methyl (meth) acrylate copolymer, styrene-methyl (meth) acrylate copolymer (here, And (meth) acryl means acryl or methacryl, and the same applies to the following.).
The thickness of this acrylic resin sheet is 20 to 100 μm
The degree is preferred.

The transparent protective layer 7 may contain an ultraviolet absorber, a light stabilizer and the like exemplified in the description of the polyolefin resin.

The transparent protective layer 7 may have an uneven pattern on the surface. In order to form the concavo-convex pattern, for example, there is an embossing method by heating and pressing, and in this embossing method, the surface of the transparent protective layer is softened by heating, and the surface is pressed with an embossing plate to form the concavo-convex pattern on the embossing plate. It is shaped, cooled and fixed, and a known single-wafer or rotary embossing machine can be used. Also, an uneven pattern can be formed by hairline processing. Examples of the concavo-convex pattern include a wood-grain board conduit groove, a stone board surface unevenness (granite cleavage plane or the like), a cloth surface texture, a satin finish, a grain, a hairline, a linear groove, and the like.

Further, a colored layer may be formed on the concave portion of the above-mentioned uneven pattern by a wiping method. As the wiping method, the entire surface including the concave portion is colored by a doctor blade coating method or a knife coating method. After applying the agent ink, a method of forming a coloring layer only on the recessed portion by removing the colorant ink from the surface other than the recessed portion can be used. As a colorant ink for forming a colored layer, an organic pigment, an inorganic pigment, a color pigment such as a bright pigment, and a thermoplastic resin, a thermosetting resin, a binder resin such as an ionizing radiation-curable resin and the like. Ink (or paint) is used. As ink, besides organic solvent solution type ink,
Emulsion type water-based ink can be used.

The appearance of the transparent protective layer 7 can be made matt or mirror-finished. To form a matte surface of the transparent protective layer 7, a matting agent (light diffusing agent) is added to the transparent protective layer. Examples of the matting agent include calcium carbonate, silica, alumina, barium sulfate, urethane resin beads, and polycarbonate resin beads.
Fine particles of about μm are effective. The thickness of the transparent protective layer 7 is preferably about 50 to 200 μm. In order to form the surface of the transparent protective layer 7 into a mirror surface, for example, when a resin sheet forming the transparent protective layer 7 is attached to a printed polyolefin sheet, a method in which a mirror plate is set on the resin sheet and pressed is used. Can be

As a method of laminating the polyolefin resin sheet 2 and the sheet of the transparent protective layer 7 (for example, an acrylic resin sheet), there are melt extrusion coating (extrusion coating), fusion by hot pressing, or two-liquid curing type. Dry lamination using an adhesive such as a polyurethane resin or a polyester resin is exemplified.

As shown in FIG. 1, a transparent protective coating layer 10 can be further provided on the surface of the transparent protective layer 7. The transparent protective coating layer 10 further enhances the surface protective effect of the transparent protective layer (particularly, abrasion resistance, chemical resistance,
It is formed in order to improve the stain resistance) or to adjust the gloss of the surface. As the material of the transparent protective coating layer, a two-component curable urethane resin, a polyfunctional (meth) acrylate prepolymer, or an ultraviolet or electron beam curable resin composed of a monomer is used. As described above, a matting agent may be added for the purpose of adjusting gloss (reducing gloss) and imparting scratch resistance. The thickness of the transparent coat layer is about 1 to 10 μm.

The printed polyolefin sheet 4 can be provided with an easy-adhesion layer 6 by applying a solution in which a binder resin or the like is dissolved in order to improve the adhesiveness with the thermoplastic resin sheet 5. Preferably, a resin having a wetting index of 35 mN / m or more is used as the binder resin of the easy-adhesion layer 6.
Specifically, acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester resin, epoxy resin, polyurethane resin, chlorinated polypropylene, chlorinated polyethylene and the like are used, and chlorinated polypropylene is particularly desirable. The thickness of the easy adhesion layer 6 is preferably 1 to 5 μm. Incidentally, the adhesive layer 6 is a layer for strengthening the adhesiveness between the two layers when the thermoplastic resin sheet 5 is laminated on the polyolefin resin sheet 2. When the easily adhesive layer 6 is made of a thermoplastic resin in particular, the easily adhesive layer 6 can be regarded as the first layer of the thermoplastic resin layer 5 formed as a two-layer laminate.

The acrylic resin for forming the easy-adhesion layer 6 includes poly (methyl meth) acrylate, poly (ethyl meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, Methyl (meth) acrylate-butyl (meth) acrylate copolymer, ethyl (meth) acrylate-butyl (meth) acrylate copolymer, ethylene-methyl (meth) acrylate copolymer,
Acrylic resins comprising a homo- or copolymer containing a (meth) acrylate such as a styrene-methyl (meth) acrylate copolymer are exemplified.

The polyurethane resin is a composition containing a polyol (polyhydric alcohol) as a main component and an isocyanate compound as a crosslinking agent (curing agent). As the polyol, those having two or more hydroxyl groups in the molecule, basically, a monomer diol, a triol or the like, and a polymer diol containing a chain of alkylene repeating units mainly contributing to the molecular weight thereof, Contains triol. 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 and the like can be used.

In order to manufacture the decorative sheet of the present invention, for example, a printed polyolefin resin sheet, a transparent protective layer and the like are laminated on a thermoplastic resin sheet, and if necessary, a dry laminating adhesive or the like is used. It is obtained by heating and pressurizing to integrate.

As the adhesive used for laminating the polyolefin resin sheet 2 and the thermoplastic resin sheet 5, a dry laminate adhesive such as a two-component curing type polyurethane resin or polyester resin is preferably used. In addition to the above method, the resin constituting the thermoplastic resin sheet 5 is melt-extruded on the surface of the easily adhesive layer of the polyolefin resin sheet 2 without using an adhesive (extrusion coating).
Then, a method of laminating at the same time as forming a sheet may be used.

As shown in FIG. 2, a back primer layer 9 can be further provided on the back surface of the decorative sheet 1 (the surface on the thermoplastic resin sheet 5 side). The back primer layer 9 is provided to further improve the adhesion when the decorative sheet is pasted to another member. The back primer layer 9 is made of a vinyl chloride-vinyl acetate copolymer, an ethylene-vinyl acetate copolymer, an acrylic resin, a polyurethane (two-component curing type comprising an isocyanate curing agent and various polyols), or the like. The thickness of the primer layer 9 is preferably 1 μm to 5 μm.

In order to impart antibacterial properties to the decorative sheet 1, a polyolefin resin sheet, a thermoplastic resin sheet, a transparent protective layer or another layer may be coated with an antibacterial agent such as zeolite carrying silver ions or the like. A fungicide such as' -oxybisphenoxyarsine may be added.

The decorative sheet of the present invention is used for decorating various members by attaching it to wood, plastic, and other members. For example, a mirror surface sheet used on the surface of a door member for building materials, a kiguchi sheet stuck on a kiguchi surface, a sheet decorating the surface of a plastic molded product, and the like can be given. In order to laminate the decorative sheet to the plastic molded product, for example, vacuum press molding, injection molding simultaneous painting (lamination) method, or the like is used. As a simultaneous painting method for injection molding, a decorative sheet preformed in the form of a molded product in a vacuum molding die different from the injection molding die disclosed in Japanese Patent Publication No. 61-17255 is used as a female mold for injection molding. In-molding, in which an unformed sheet is inserted between the male and female molds of injection molding disclosed in Japanese Patent Publication No. 43-27488, etc., and the sheet is molded into a molded product by the heat and pressure of the injection resin. For example, a method disclosed in Japanese Patent Publication No. 50-19132, in which a sheet is preliminarily formed into a formed product shape on a female mold of injection molding can be used.

[0050]

EXAMPLES Example 1 (1) Printed polyolefin sheet Both sides of a polyolefin resin sheet having a thickness of 100 μm and comprising 60 parts by mass of high-density polyethylene, 30 parts by mass of hydrogenated styrene-butadiene rubber, and 10 parts by mass of calcium carbonate powder. Immediately after corona discharge treatment, the entire surface of the sheet is gravure coated with an ink using a two-part curable urethane resin comprising 100 parts by mass of polyester polyol and 10 parts by mass of 1,6-hexamethylene diisocyanate as a binder. The mixture is further gravure printed with a mixture of a polyurethane resin and an acrylic resin as a binder, quinacridone red, isoindolinone yellow, and an ink obtained by adding a pigment consisting of phthalocyanine blue. With a thickness of 30 μm Rayon Co. acrylic resin sheet (Akuripuren HBS-027) to obtain a printed polyolefin sheet by heat lamination. (2) Decorative sheet On the opposite side (back side) of the printed surface of the printed polyolefin sheet of (1) above, a 300 μm thick ABS resin sheet (manufactured by Sanbo Resin; wetting index: 40 mN / m) is dry-laminated (adhesive: large). A decorative sheet was obtained by applying a two-component curable polyurethane resin-based adhesive manufactured by Nissei Chemical Co., Ltd. on a dry mass of 12 g / m ² . This sheet could be favorably used as a wood door tape for kitchen doors, fittings and the like.

Comparative Example 1 The printed polyolefin sheet described in (1) of Example 1 was used as the sheet of Comparative Example 1.

Example 2 A polyurethane resin-based primer (manufactured by The Inktech: P) was provided on the back side of the ABS resin sheet of the decorative sheet of Example 1.
UC) was applied to a thickness of 2 μm (when dried) to obtain a decorative sheet of Example 2.

Example 3 (1) Printed polyolefin sheet A corona discharge treatment was applied to the front and back surfaces of a polypropylene-based thermoplastic elastomer resin film (manufactured by Mitsubishi Chemical MKV) having a thickness of 100 μm, and immediately thereafter, one side (front side) of the sheet The grain pattern was printed by gravure printing in the same manner as in Example 1. A polyurethane resin primer (manufactured by Showa Ink: AFS) is applied to a thickness of 1 μm (when dried) on the surface opposite to the printing surface of this film, and a vinyl chloride-vinyl acetate copolymer primer (Showa Ink Co., Ltd.) was applied to a thickness of 2 μm (when dried) to form a printed polyolefin sheet. (2) Decorative sheet A 100 μm thick transparent acrylic resin sheet (manufactured by Mitsubishi Rayon: HBS-006) is overlaid on the printed surface of the printed polyolefin sheet of (1) above, and 300 μm thick on the opposite side.
ABS resin sheet (manufactured by Sanbo resin: wetting index 40 mN /
m) were laminated, and the three layers were laminated by hot-press lamination. At the time of bonding, a mirror-finished plate was pressed against the acrylic resin sheet side to obtain a decorative sheet having a mirror-finished surface. This sheet was successfully used for a mirror-finished sheet such as a storage door. By using the ABS resin as the backing sheet in this way, the overall thickness of the sheet is increased, and the mirror finish when the door is formed is improved.

Comparative Example 2 A transparent acrylic resin sheet (HBS-006, manufactured by Mitsubishi Rayon Co., Ltd.) having a thickness of 100 μm was laminated on the printed surface of the same printed polyolefin sheet as in Example 3, and the two layers were laminated by hot-pressure lamination ( The lamination of the ABS resin sheet was omitted). At the time of bonding, a mirror-surface plate was pressed against the acrylic resin sheet side to obtain a sheet of Comparative Example 2 whose surface was mirror-finished.

[0055]

As described above, the decorative sheet of the present invention employs a structure in which a thermoplastic resin sheet having a wetting index of 35 mN / m or more is laminated on the back surface of a polyolefin resin sheet. This prevents the generation of environmentally undesirable gases and substances such as hydrogen chloride gas and polycyclic organochlorine compounds during incineration, and has high adhesion when bonded to other members, and has good adhesiveness with members. A decorative sheet is obtained.

[Brief description of the drawings]

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

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

FIG. 3 is a sectional view showing an example of the decorative sheet of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Polyolefin resin sheet 3 Printing layer 4 Printing polyolefin sheet 5 Thermoplastic resin sheet 6 Easy adhesion layer 7 Transparent protective layer 8 Dry laminating adhesive 9 Back primer layer 10 Transparent protective coat layer

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4F100 AA08H AK01D AK03A AK04 AK07 AK25E AK73 AK74 AL06 AL09 AS00E BA03 BA04 BA05 BA07 BA10B BA10D BA10E EC03 EC032 EJ55 EJ551 GB08 HB01 HB31 HB31JHD01B

Claims (6)

[Claims] 1. A thermoplastic resin sheet having a wetting index of 35 mN / m or more is laminated on a back surface of a polyolefin resin sheet on which at least one of a front surface and a back surface is printed. And decorative sheet. 2. The decorative sheet according to claim 1, wherein a transparent protective layer is provided on the surface of the polyolefin resin sheet. 3. The decorative sheet according to claim 1, wherein the thermoplastic resin sheet having a wetting index of 35 mN / m or more is an ABS resin sheet. 4. The decorative sheet according to claim 1, wherein the transparent protective layer is a transparent acrylic resin sheet. 5. The decorative sheet according to claim 4, wherein a transparent protective coat layer is formed on the transparent acrylic resin sheet. 6. A primer layer is provided on the back side of a printed polyolefin sheet or a thermoplastic resin sheet having a wettability index of 35 mN / m or more.
The decorative sheet according to any one of Items 1 to 6,