JP2000198168A - Makeup sheet - Google Patents

Abstract

(57) [Problem] To provide a decorative sheet which has good adhesion and weather resistance of a pattern layer and good heat resistance to embossing even when a pattern layer is directly provided on a base sheet of a polyolefin resin. . SOLUTION: A resin system constituting a picture layer 2 formed so as to be in contact with a base sheet 1 of a polyolefin resin is a mixed resin system of an acrylic resin and a urethane resin.

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 exterior decoration, interior decoration, fittings, furniture, vehicle interior decoration and the like of a building. In particular, it relates to a non-PVC-based decorative sheet that does not use a vinyl chloride resin as a base sheet.

[0002]

2. Description of the Related Art A conventional decorative sheet is a PVC-based decorative sheet using a vinyl chloride resin film as a base material sheet and decorated by printing, embossing or the like (Japanese Patent Publication No.
5036, and Japanese Patent Publication No. 58-14312). However, since vinyl chloride resin generates hydrochloric acid gas when burned at the time of disposal, a decorative sheet using another resin not containing chlorine has been desired from the viewpoint of global environmental problems. Therefore, as a substitute for a PVC-based decorative sheet, a decorative sheet using a polyolefin-based resin sheet such as polyethylene, polypropylene, or olefin-based thermoplastic elastomer as a base sheet (Japanese Patent Application Laid-Open No. 54-62255, Japanese Patent Application Laid-Open No. 2108
08, JP-A-4-504384, JP-A-7
-26038).

[0003]

However, when the substrate sheet is a polyolefin resin, the adhesion is generally poor even when the pattern layer is directly printed on the substrate sheet. It was necessary to provide a resin-based primer layer. However, the primer layer is not directly related to the pattern expression, and also requires an extra printing unit, leading to an increase in the cost of the decorative sheet. In addition, the urethane resin-based primer layer generally had poor initial adhesion and poor weather resistance. In addition, because of poor heat resistance, it was not possible to form an uneven pattern by embossing.

Accordingly, an object of the present invention is to provide a non-PVC-based decorative sheet as a base sheet of a polyolefin resin.
An object of the present invention is to provide a decorative sheet having a good design layer with good adhesion and weather resistance, and good heat resistance to embossing even in a configuration in which a picture layer is directly provided without a primer layer.

[0005]

Means for Solving the Problems In order to solve the above problems, in the decorative sheet of the present invention, a decorative sheet provided with a pattern is formed on a base sheet made of a polyolefin resin so as to be in contact with the base sheet. The resin system forming the patterned picture layer is made of a mixed resin system of an acrylic resin and a urethane resin. In this way, even in the case of a base sheet of a polyolefin-based resin, a pattern layer can be formed with good adhesion without a primer layer on the base sheet by configuring with a specific resin combination. Has good initial adhesion and weather resistance adhesion. In addition, the lack of heat resistance to embossing due to the urethane resin-based primer layer is also eliminated, and a decorative sheet having a concavo-convex pattern by embossing is also possible.

[0006] Further, the decorative sheet of the present invention further has a configuration in which a polar functional group containing active hydrogen is provided on the surface of the substrate sheet on the picture layer side. In this case, the adhesion of the pattern layer to the base sheet is further improved by the polar functional group. Further, in the decorative sheet of the present invention, with respect to the above configuration, the resin system of the pattern layer contains an isocyanate compound, and the polar functional group on the surface of the base sheet and the resin system of the pattern layer have a urethane bond. Configuration. As a result, since the base sheet and the picture layer are chemically bonded by urethane bonds, strong adhesion can be obtained.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the decorative sheet of the present invention will be described with reference to the drawings. FIG. 1 and FIG. 2 are cross-sectional views illustrating some of the various possible forms of the decorative sheet of the present invention. FIG.
Is a single-layered base material sheet, and the decorative sheet of FIG. 2 is a multi-layered (two-layered) base material sheet.

[Summary] The decorative sheet of the present invention includes, for example,
Like a decorative sheet S shown in FIGS. 1A and 1B, a pattern layer 2 is formed on one side of a base sheet 1 made of a polyolefin resin so as to be in contact with the base sheet 1 and a pattern layer is formed. Is a decorative sheet composed of a resin mixture of an acrylic resin and a urethane resin. FIG. 1A shows an example in which a coloring layer 3 is contained in a base sheet 1 and a pattern layer is provided on the front side of a colored and opaque base sheet.
(B) is an example having a picture layer on the back side of the transparent base material sheet 1. More preferably, the base sheet 1 is a sheet having a polar functional group containing active hydrogen on the surface on the picture layer side. Further, in this case, it is preferable that the resin system of the picture layer contains an isocyanate compound, and the polar functional group on the surface of the base sheet and the resin system of the picture layer have a urethane bond.

Hereinafter, the base sheet, the picture layer and its resin system will be described in more detail.

[Base Sheet] As the base sheet 1, a resin sheet made of a polyolefin resin is used. Polyolefin resins include polyethylene (low density or high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-
Highly crystalline non-elastomeric polyolefin resin such as butene copolymer or various olefin thermoplastic elastomers are used. As the olefin-based thermoplastic elastomer, for example, the following can be used.

[0011] Japanese Patent Publication No. Hei 6-23278,
(A) As a soft segment, the number average molecular weight Mn is 2
An atactic polypropylene soluble in boiling heptane having a weight average molecular weight Mw of not less than 5,000 and a ratio of weight average molecular weight Mw to number average molecular weight Mn of 7 to 10 to 90% by weight;
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 the olefinic thermoplastic elastomers of this type, isotactic polypropylene which is less likely to cause so-called "necking" and has good suitability for forming into various shapes or embossing by heating and pressurizing is exemplified by isotactic polypropylene. The mixing ratio with the atactic polypropylene is 5% by weight or more and 50% by weight or less by weight ratio of the atactic polypropylene. 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 soft segment atactic polypropylene is 5 to emphasize strength. Less than% by weight was exclusively used. However, when this is applied to an application for forming into a three-dimensional shape or a concavo-convex shape or embossing, necking occurs as described above, and good processing is impossible. Therefore, 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 olefin-based thermoplastic elastomer. It is possible to eliminate non-uniform sheet deformation due to necking when forming the article surface shape, and resulting defects such as wrinkles and picture distortions. 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 deform, and the sheet deforms when the sheet is passed through a printing machine,
Defects such as distorted pictures and misregistration in multicolor printing are likely to occur. Further, it is not preferable because it is easily broken during molding. As the upper limit of the weight ratio of atactic polypropylene, the pattern layer is printed using a normal rotary printing machine such as rotary gravure printing, and embossing of the sheet, vacuum forming, V-cut processing, simultaneous lamination of injection molding, etc. When employed, it is at most 50% by weight, more preferably at most 40% by weight.

A thermoplastic elastomer comprising an ethylene-propylene-butene copolymer resin. Here, as the butene, 1-butene, 2-butene and isobutylene are used.
Any of the structural isomers can be used. Preferred specific examples of the ethylene-propylene-butene copolymer, which is a random copolymer and partially includes an amorphous portion, include the following (i) to (iii). (i) Those described in JP-A-9-111055. It 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 preferably 1 to 50 g / 10 minutes at 230 ° C. and 2.16 kg. And, for 100 parts by weight of such a ternary random copolymer, 0.01 to 50 parts by weight of a transparent nucleating agent containing a phosphate aryl ester compound as a main component,
It is obtained by melting and kneading 0.003 to 0.3 parts by weight of a fatty acid amide having 12 to 22 carbon atoms. (ii) Those described in JP-A-5-77371. this is,
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, which is a terpolymer of ethylene, propylene and 1-butene. It is. (iii) Those described in JP-A-7-316358. This is a terpolymer of ethylene, propylene, and 1-butene, and the content of propylene and / or 1-butene is 50% by weight or more and 20 to 100% by weight of the low crystalline polymer. 0.5% by weight of an oil gelling agent such as N-acylamino acid amine salt or N-acylamino acid ester is added to a composition containing 80 to 0% by weight of a crystalline polyolefin such as isotactic polypropylene. It becomes.

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

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- Propylene copolymer rubber, unsaturated ethylene-propylene-
An olefin-based elastomer obtained by using a monoolefin copolymer rubber such as a non-conjugated diene terpolymer rubber as a soft segment, and uniformly mixing and mixing these. Incidentally, monoolefin rubber / olefin polymer = 50/50 to 90
/ 10 (weight ratio).

The substrate sheet made of these polyolefin resins is usually formed by extrusion molding, calender molding or the like so as to have a thickness of about 50 to 200 μm. As the base sheet, any of a stretched sheet and an unstretched sheet can be used, but the unstretched sheet has better formability such as V-cut processing.

The base sheet is preferably a sheet having at least a polar functional group containing active hydrogen on the surface of the picture layer side, since the adhesion to the picture layer is further improved.
In order to have the polar functional group on the surface of the base sheet, for example, a resin having a polar functional group on the polyolefin resin itself constituting the base sheet itself may be used. Specifically, as the polar functional group having active hydrogen, for example, a hydroxyl group and / or a carboxyl group are provided.
And the like. For example, an olefin-based thermoplastic elastomer having a hydroxyl group introduced by graft polymerization of an ethylene-vinyl alcohol copolymer or the like and a carboxyl group introduced by a copolymer of maleic acid, fumaric acid, itaconic acid or the like is used. Either one or both of these hydroxyl groups and carboxyl groups may be used in combination.

Although the decorative sheet of the present invention does not include an easy-adhesion layer such as a primer layer between the base sheet and the picture layer, the face of the base sheet in contact with another layer such as the picture layer is
Known easy adhesion treatments such as corona discharge treatment, plasma treatment, and ozone treatment may be performed. In addition, a polar functional group containing active hydrogen can be provided on the surface of the base sheet by such an easy adhesion treatment.

The base sheet may be optionally provided
Various additives such as filler, flame retardant, antioxidant, foaming agent, lubricant, ultraviolet absorber, and light stabilizer are added. When the base sheet is colored, a known colorant, such as those listed in a picture layer described later, may be kneaded into the resin. Coloring includes transparent coloring and opaque (concealing) coloring. However, needless to say, in a configuration having a pattern layer on the back side of the base sheet (back printing specification), the coloring is transparent.

The following compounds can be used as the ultraviolet absorber. For example, 2- (2'-hydroxy-
3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-
3'-tert-butyl-5'-methylphenyl) -5
-Chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-methyl Phenyl)
-5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl)-
2'-hydroxyphenyl-5-chlorobenzotriazole based ultraviolet absorbers such as 5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-te
rt-butylphenyl) benzotriazole, 2-
Benzotriazole-based ultraviolet absorbers such as 2'-hydroxyphenylbenzotriazole-based ultraviolet absorbers such as (2'-hydroxy-5'-methylphenyl) benzotriazole; and 2,2'-dihydroxy-4-methoxybenzophenone , 2,2'-dihydroxy-4,4'-
2,2'-dihydroxybenzophenone-based ultraviolet absorbers such as dimethoxybenzophenone and 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone; Benzophenone-based ultraviolet absorbers such as 2-hydroxybenzophenone-based ultraviolet absorbers, phenyl salicylate, 4-tert-butyl-phenyl-
And salicylic acid ester-based ultraviolet absorbers such as salicylate. In addition, a reactive ultraviolet absorber having an acryloyl group or a methacryloyl group introduced into a benzotriazole skeleton may be used. In addition, the addition amount of these ultraviolet absorbers is usually about 0.1 to 5% by weight based on the resin component.

In order to further prevent the deterioration of each layer of the decorative sheet due to ultraviolet rays and to improve the weather resistance, it is preferable to add a radical scavenger as a light stabilizer. Examples of the radical scavenger include bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis- (N-
Methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and others, for example, Japanese Patent Publication No. 4-8262.
Hindered amine radical scavengers, piperidyl radical scavengers, and the like, such as the compounds disclosed in Japanese Patent Publication No. 5 are used. The addition amount of these radical scavengers is usually about 0.1 to 5% by weight based on the resin content.

The base sheet is used in a single layer as shown in each decorative sheet shown in FIG. 1, and is used in a multilayer (two layers in this figure) as each decorative sheet shown in FIG. In some cases.

[Pattern Layer] The pattern layer is made of a resin based on a mixture of an acrylic resin and a urethane resin. The picture layer is formed by printing (or coating) using an ink (or coating liquid) using the mixed resin system as a binder resin. The ink appropriately contains a solvent, an extender, a coloring agent, various additives, and the like, in addition to the resin of the specific material. All solid layers of the picture layer can be formed by coating.

Examples of the acrylic resin include poly (meth) acrylate, poly (ethyl) acrylate, poly (meth) acrylate, and poly (meth) acrylate.
Butyl acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, ethyl (meth) acrylate-butyl (meth) acrylate copolymer, ethylene-
An acrylic resin or the like made of a homo- or copolymer containing a (meth) acrylate such as a methyl (meth) acrylate copolymer or a styrene-methyl (meth) acrylate copolymer is used. In addition, (meth) acryl means acryl or methacryl. The acrylic resin used is 1
Seeds may be used, but two or more kinds may be used.

As the urethane resin, a curable resin having a polyol (polyhydric alcohol) as a main component and an isocyanate as a crosslinking agent (curing agent) is basically used. The polyol has two or more hydroxyl groups in the molecule, and examples thereof include polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, and polycarbonate polyol. As the isocyanate, a polyisocyanate having two or more isocyanate groups in a molecule is used. For example, 2,4-tolylene diisocyanate, xylene diisocyanate, 4,
Aromatic (or alicyclic) isocyanates such as aromatic isocyanates such as 4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are used. Alternatively, adducts or multimers of the above various isocyanates can also be used. For example, there are an adduct of tolylene diisocyanate and a trimer of tolylene diisocyanate.

Among these urethane resins, acrylic polyol is preferred as the polyol in terms of adhesion to the polyolefin resin and weather resistance. Particularly, methyl (meth) acrylate and (meth)
Preference is given to binary copolymers with 2-hydroxyethyl acrylate and ternary copolymers of octyl (meth) acrylate, cyclohexyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate. . The average molecular weight of these copolymers is about 5,000 to 15,000, and the hydroxyl value is about 40 to 50. These binary copolymers and 3
The mixing ratio with the terpolymer is usually about a binary copolymer: terpolymer = 2: 8 to 8: 2 (weight ratio). On the other hand, as the isocyanate, the above-mentioned aliphatic or alicyclic isocyanate is preferable.

The mixing ratio of the acrylic resin and the urethane resin is as follows: acrylic resin: urethane resin = 8: 2
It is preferable to select within a range of 5: 5 (weight ratio) according to required physical properties and the like. The greater the proportion of the acrylic resin, the better the weather resistance (weather resistance), but the lower the initial adhesion. On the other hand, as the proportion of the urethane resin increases, the initial adhesion and the pigment dispersibility in the ink are excellent, but the weather resistance adhesion decreases. The ideal mixture ratio of acrylic resin and urethane resin is about 7: 3. The mixing ratio is appropriately adjusted in consideration of the ink dispersibility of the color pigment. For example, the solid ink used for forming the entire solid layer is acrylic resin: urethane resin = 5:
For example, about 5.

In the case where the substrate sheet has a polar functional group containing active hydrogen on the surface of the pattern layer side, the resin system of the pattern layer contains an isocyanate compound, and And the resin of the picture layer has a urethane bond. As a result, since the base sheet and the picture layer are chemically bonded by urethane bonds, strong adhesion can be obtained. The isocyanate compound is, for example, the various isocyanates described above. If a urethane resin of an ink (or coating liquid) used for forming a picture layer is used as a two-component curable urethane resin, a urethane bond can be generated.

As the urethane resin to be mixed with the acrylic resin, a two-component curable urethane resin is basically used. In addition, a thermoplastic urethane resin, that is,
For example, a resin composed of linear molecules after reacting a diol or the like with a diisocyanate can be used. The diol is, for example, a diol of the various polyols described above,
The diisocyanates are, for example, the various diisocyanates described above. However, the handling of ink etc. is easy because the thermoplastic urethane resin does not cure, but the resin system of the picture layer and the base sheet cannot be urethane-bonded as described above.
Adhesion decreases accordingly.

The ink (or coating liquid) for forming the picture layer contains a pigment or dye as a coloring agent in a vehicle composed of a mixed resin of the above-mentioned specific resins. For example, inorganic pigments such as titanium white, zinc white, red flower, vermilion, ultramarine, cobalt blue, titanium yellow, graphite, carbon black, isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue,
Organic pigments (or dyes) such as Indus Limbly RS and aniline black; metal pigments such as aluminum and brass; pearlescent pigments made of foil powder such as titanium dioxide-coated mica and basic lead carbonate. is there.

The picture layer is formed by a printing method, hand-drawing, or the like. As a printing method, a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, or the like is used, and ink is used (or a coating liquid).

Further, the pattern of the picture layer includes a wood grain pattern,
There are a stone pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and a solid surface. The picture layer is formed on the front side (see FIGS. 1 (A), (D) and (E)), the back side (see FIGS. 1 (B) to (E)), the front and back sides (FIG. 1 (D)) of the base sheet. In the case where a plurality of base sheets are used, they may be provided between layers (see FIGS. 2A to 2C). The lamination of the base sheet is performed by known dry lamination, melt extrusion coating, or the like.

The picture layer is often used in combination of a pattern layer having a pattern and a solid layer having no pattern. In this case, when the pattern layer is formed after the formation of all solid layers, the urethane resin in the pattern layer is not a two-part curable urethane resin to which an isocyanate compound is added, but a thermoplastic urethane resin. A two-part curable urethane resin in which an isocyanate compound is added to the urethane resin may be used. And
The thermoplastic urethane resin in the pattern layer is a urethane resin having a hydroxyl group, and is an isocyanate compound of the two-component curable urethane resin (uncured product) in all the solid layers, even when the thermoplastic urethane resin is cured. good. This is because the entire solid layer is in contact with the base material sheet and is not a pattern layer, so that even in this case, the adhesion between the base material sheet and the pattern layer can be improved and satisfied. . The urethane resin of the pattern layer is also of a two-part curable type as a result, but contains an isocyanate compound, so that ink reusability (utilization of remaining ink) and productivity (when printing for a long time, This is advantageous in that the ink does not increase in viscosity and clogging of the plate does not occur), and the ink can be easily handled.

In the decorative sheet of the present invention, the pattern layer is formed so as to be in contact with the substrate sheet, and the resin layer of the layer is made of the above-mentioned specific mixed resin system. If it does not touch the sheet (or even if it touches the sheet, the area is small), it does not limit the use of another resin-based pattern layer or metal thin film layer as the pattern layer. For example, the formation of a metal thin film consists of aluminum, chromium, gold,
A film is formed by a method such as vacuum evaporation and sputtering using a metal such as silver or copper. Alternatively, a combination of these may be used.
The metal thin film may be provided on the entire surface or partially in a pattern.

[Decoration process other than the pattern layer] In the decorative sheet of the present invention, the above-mentioned pattern layer is formed for the purpose of decoration or the like. Processing may be performed. As such a decoration process, as in the decorative sheet S shown in FIG.
Coloring (transparent coloring or opaque coloring) by adding a coloring agent 3 such as a pigment to the base sheet 1 itself, FIG. 1 (D) and FIG.
It is shaping of the uneven pattern 5 like the decorative sheet S shown in (A). Alternatively, as in the decorative sheet S shown in FIGS. 1C to 1E, there is the formation of the overcoat layer 4 for glossiness adjustment and for imparting a design property such as a painted feeling. These decoration processes are used in appropriate combination.

When a coloring agent such as a pigment is added to the base sheet,
Various colorants as listed in the picture layer are kneaded into the resin of the base sheet. Needless to say, when the base sheet is made opaque, the picture layer is formed on the front side surface of the base sheet. For example, the decorative sheet S in FIGS. 2A and 2B
The structure has a pattern layer between the two base sheets 1 and 1a. Here, the base sheet 1a on the back side is colored by adding a coloring agent to form an opaque (concealed) colored sheet, and the base sheet 1 on the front side is An uncolored transparent sheet.

As the uneven pattern 5, there are a wood grain board conduit groove, a stone board surface unevenness (granite cleavage face etc.), a cloth surface texture, a satin finish, a grain, a hairline, a linear groove, and the like. The uneven pattern is formed by a known shaping method such as embossing and hairline processing. The surface on which the concavo-convex pattern is provided is arbitrary such as the front side surface, the back side surface, and the front and back side surfaces.

Further, if necessary, the colored portions 6 can be formed by filling the concave portions of the concave and convex pattern with a colored ink by a known wiping method (see Japanese Patent Publication No. 58-14312, etc.) [FIG. D)]. The coloring ink can be the same as the picture layer. However, from the viewpoint of abrasion resistance, the urethane resin of the binder is preferably a two-component curing type urethane resin.

The overcoat layer 4 is usually formed on the front and side surfaces by a known coating method, printing method, or the like, as a process after the above-described pattern layer and the above-described various decoration processes are performed. However, FIG.
As shown in (D), there is also a configuration in which a picture layer 2a is further formed on the overcoat layer 4 (the resin system of the picture layer in this case is:
Since it is a layer that does not come into contact with the base sheet, for example, a two-component curable urethane resin may be selected in consideration of the resin system and surface properties of the overcoat layer). The overcoat layer is also formed for imparting surface properties such as scratch resistance and chemical resistance. As the resin of the overcoat layer, for example, a two-component curable urethane resin, an ionizing radiation-curable resin made of various acrylates and the like, which is cured by ultraviolet rays or electron beams, is used. Fillers, flame retardants, ultraviolet absorbers, light stabilizers, and the like are appropriately added to the resin as needed.

[Adhesive Layer] Although not shown, an adhesive layer may be provided on the back surface of the decorative sheet if necessary. For the adhesive layer, for example, a conventionally known adhesive such as a heat-fusible adhesive made of a thermoplastic resin or the like, a curable adhesive made of a two-component curable urethane resin, or a pressure-sensitive adhesive is used. Used accordingly.

[Use of decorative sheet] The use of the decorative sheet of the present invention is not particularly limited, and the decorative sheet is laminated on the surface of various adherends and used for decorative purposes. The adherend is a plate material such as a flat plate or a curved plate of various materials, a three-dimensional article, a sheet (or film), or the like. For example, wood veneer, wood plywood,
Particleboard, wood board such as wood fiber board such as MDF (medium density fiber board), wood board material used as three-dimensional article, plate material such as iron and aluminum, metal material used as three-dimensional article or sheet, glass , Ceramics such as ceramics, non-cement ceramic materials such as gypsum, A
Non-porcelain ceramic materials such as LC (lightweight cellular concrete) plates, ceramic materials used as three-dimensional articles, etc., acrylic resins, polyester resins, polyolefin resins, polyolefin resins such as polypropylene, ABS
(Acrylonitrile-butadiene-styrene copolymer)
Resins, phenolic resins, vinyl chloride resins, cellulosic resins, rubber and other plate materials, resin materials used as three-dimensional articles or sheets, or high-quality paper used exclusively as sheets, paper such as Japanese paper, carbon, asbestos, glass And non-woven fabrics or woven fabrics made of fibers such as synthetic resins.
The laminate of decorative sheets is used as a decorative plate when the adherend is a plate material, and the laminate itself may be used as a decorative sheet when the adherend is a sheet.

As a method of laminating a decorative sheet on these various adherends, for example, a method of laminating a plate-like substrate by pressing with a pressure roller via an adhesive, Japanese Patent Publication No.
As described in JP-A-19132, JP-B-43-27488, etc., after a decorative sheet is placed between both male and female molds for injection molding, a molten resin is injected and filled into the mold to form a resin molded product. At the same time, a so-called injection molding simultaneous lamination method in which a decorative sheet is adhesively laminated on the surface,
No. 45768, Japanese Patent Publication No. 60-58014, etc., a decorative sheet is opposed to or placed on the surface of a three-dimensional article such as a molded article with an adhesive therebetween, and the three-dimensional article side So-called vacuum press lamination method in which a decorative sheet is laminated on the surface of a three-dimensional article by a pressure difference due to vacuum suction from the Japanese Patent Publication No. 61-5895, Japanese Patent Publication No. Hei 3-26.
No. 66, etc., while supplying a decorative sheet via an adhesive in the longitudinal direction of a columnar substrate such as a cylinder or a polygonal column, a plurality of rollers having different orientations are used. There is a so-called lapping method in which decorative sheets are sequentially pressure-bonded and laminated on a plurality of side surfaces constituting a material. Further, so-called V-cut or U-cut processing may be performed as post-processing after lamination.

The decorative sheet of the present invention is laminated on various adherends, subjected to predetermined molding processing as required, and used for various purposes. For example, interior decoration of buildings such as walls, ceilings and floors, surface decoration of fittings such as window frames, doors, handrails, furniture or light electricity / OA.
Surface makeup of equipment cabinets, interior decoration of vehicles such as automobiles, trains, aircraft, ships, etc., makeup of window glass, etc.

[0044]

EXAMPLES The decorative sheet of the present invention will be further described below with reference to examples and comparative examples.

A decorative sheet S as shown in FIG. 1E was prepared as follows. As the base sheet 1, a mixture of 75 parts by weight of a hard segment made of isotactic polypropylene and 25 parts by weight of a soft segment made of atactic polypropylene, 8000 ppm of a benzotriazole-based ultraviolet absorber and a hindered amine radical scavenger Thickness 1 made by adding 4000 ppm
A 20 μm transparent polypropylene resin sheet was used.

A corona discharge treatment was applied to both surfaces of the base sheet, and a pattern layer 2 composed of a mixed resin of an acrylic resin and a two-component curable urethane resin was formed on the back surface. As a picture layer, after forming a multicolor printing pattern layer having a wood grain pattern, all solid layers were further formed. Further, the resin system of the binder of the ink having the pattern layer formed thereon includes (A) methyl methacrylate and 2-methacrylic acid 2-methyl methacrylate.
(C) 50 parts by weight of an acrylic polyol consisting of a copolymer of hydroxyethyl, (B) 50 parts by weight of an acrylic polyol consisting of a copolymer of octyl acrylate, cyclohexyl acrylate, and 2-hydroxyethyl methacrylate; A mixed resin system comprising a two-part curable urethane resin composed of 8 parts by weight of hexamethylene diisocyanate (uncured product: 108 parts by weight) and 108 parts by weight of an acrylic resin composed of (D) polymethyl methacrylate was used. In addition,
The ratio between the acrylic resin and the urethane resin is 5: 5. In addition, a mixture of titanium color, red iron oxide, and isoindolinone was used as the coloring agent for the mixed resin system.

Next, after embossing by heat and pressure on the front surface of the base sheet, the uneven pattern 5 of the wood channel is formed, and then the topcoat layer 4 is applied over the entire surface to form the decorative sheet S. And The overcoat layer comprises (A) 50 parts by weight of an acrylic polyol composed of a copolymer of methyl methacrylate and 2-hydroxyethyl methacrylate, and (B) a mixture of (B) octyl acrylate, cyclohexyl acrylate, and 2-hydroxyethyl methacrylate. Two-part curable urethane resin (108 parts by weight) composed of 50 parts by weight of an acrylic polyol composed of a copolymer, 8 parts by weight of (C) hexamethylene diisocyanate, and 252 parts by weight of an acrylic resin composed of (D) polymethyl methacrylate And a mixed resin-based coating liquid.

Then, the decorative sheet was laminated on a Lauan plywood as an adherend using a two-part curable urethane resin-based emulsion adhesive to prepare a decorative sheet.
The pattern layer was laminated on the back side of the substrate sheet, and the uneven pattern was laminated on the Lauan plywood in a direction facing the front side of the substrate sheet.

[Evaluation of Performance] The decorative board was evaluated for initial adhesion and weather resistance in the following manner. as a result,
Both initial adhesion and weather resistance were good. In addition,
The initial adhesion was 3.53 kgf / 25 mm and the Lauan plywood was broken, and the weather resistance adhesion was 1.38 kgf / 25 mm and peeling between the Lauan plywood and the decorative sheet. Table 1 shows the results together with comparative examples. In addition, it had good water resistance and moisture resistance, and could be used sufficiently for building materials. In addition, since there was no primer layer, the problem of insufficient heat resistance during embossing caused by the primer layer did not occur.

Initial adhesion: 25 m wide on the surface of the decorative board
After making a cut into a parallel Lauan plywood at m with a cutter, the adhesive strength when peeling the decorative sheet with a width of 25 mm along the cut was evaluated by the initial adhesive strength before the accelerated weather resistance test described below. Weathering adhesion: The decorative plate was subjected to an accelerated weathering test for 200 hours with a sunshine weatherometer (carbon arc lamp type, black panel temperature 63 ° C., rainfall time 18 minutes out of 180 minutes), and then subjected to the method described above. Was used to measure the adhesion.

Comparative Example In the example, a pattern layer was formed after a primer layer having a thickness of 2 μm was formed on a substrate sheet. For the formation of the primer layer, an acrylic urethane primer (an acrylic polyol 1 comprising a copolymer of methyl methacrylate and 2-hydroxyethyl methacrylate) is used.
A two-part curable urethane resin of 00 parts by weight and 8 parts by weight of hexamethylene diisocyanate) was used. In addition, the resin system of the picture layer is a two-liquid composition comprising (A) 100 parts by weight of an acrylic polyol composed of a copolymer of methyl methacrylate and 2-hydroxyethyl methacrylate, and (C) 8 parts by weight of hexamethylene diisocyanate. A single type of curable urethane resin was used. Other than that, under the same conditions as in the example,
A decorative sheet was produced. Then, a decorative plate was prepared using the decorative sheet, and the performance was evaluated. As a result, the initial adhesion was good, but the weather resistance was poor. Incidentally, the initial adhesion was 2.99 kgf / 25 mm, the Rawan plywood was broken, and the weather resistance was 0.65 kgf / 25 mm, which was peeling between the Rawan plywood and the decorative sheet. In addition, the results of these adhesions were also affected by insufficient heat resistance during embossing due to the primer layer. However, the main cause of the decrease in the adhesion performance is the deterioration in the weather resistance of the primer. In addition,
Water resistance and moisture resistance were good.

[0052]

[Table 1]

[0053]

According to the decorative sheet of the present invention, even if the base sheet is made of a polyolefin resin, the resin layer of the picture layer is composed of a specific resin in combination, so that the primer sheet is formed on the base sheet. Without this, the pattern layer can be formed with good adhesion, and the initial adhesion and the weather resistance between the pattern layer and the base sheet are improved. In addition, the lack of heat resistance to embossing due to the urethane resin-based primer layer is also eliminated, and a decorative sheet having a concavo-convex pattern by embossing is also possible.
In addition, if a structure having a polar functional group containing active hydrogen is provided on the surface of the base material sheet on the side of the picture layer, a decorative sheet in which the adhesion of the picture layer to the base sheet is further improved. Furthermore,
If the resin system of the picture layer contains an isocyanate compound, and the polar functional groups on the surface of the base sheet and the resin system of the picture layer have a urethane bond, stronger adhesion can be obtained.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating various examples of the decorative sheet of the present invention (single-layer specifications of a base sheet).

FIG. 2 is a cross-sectional view illustrating another example of various forms of the decorative sheet of the present invention (two-layered base sheet specification).

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1, 1a Base sheet 2, 2a Picture layer 3 Colorant 4 Overcoat layer 5 Concavo-convex pattern 6 Colored part S Decorative sheet

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AK03A AK07 AK25B AK25H AK51B AK51H AK54H AL05B AP02 BA02 BA03 CA05 CA07 CA13 CB02 CC00 DD01 DD07 EJ551 GB07 GB08 GB33 HB00B HB01 HB21 JK06 JL12

Claims (3)

[Claims] 1. A decorative sheet in which a pattern is applied to a base sheet made of a polyolefin resin, wherein a resin system constituting a pattern layer formed so as to be in contact with the base sheet is a mixture of an acrylic resin and a urethane resin. A decorative sheet made of resin. 2. The decorative sheet according to claim 1, wherein the decorative sheet has a polar functional group containing active hydrogen on the surface of the base sheet on the picture layer side. 3. The decorative sheet according to claim 2, wherein the resin system of the picture layer contains an isocyanate compound, and the polar functional group on the surface of the base sheet and the resin system of the picture layer have a urethane bond.