JP2873964B1 - Decorative sheet - Google Patents

Abstract

An easy-adhesion primer layer provided on an olefin decorative sheet for adhesion to an adherend satisfies all of adhesiveness, anti-blocking property, and printability. SOLUTION: As an outermost layer in contact with a decorated polyolefin-based resin sheet 1, an extender pigment containing a vinyl chloride-vinyl acetate copolymer having a polar functional group having active hydrogen in the molecule and an isocyanate compound as a binder is used. An easy-adhesion primer layer 2 is formed, and the extender is a combination of silica and precipitated barium sulfate or silica and calcium carbonate. The isocyanate group of the isocyanate compound in the easy-adhesion primer layer and vinyl chloride-vinyl acetate A sheet S with a polar functional group having active hydrogen of the copolymer is bonded by a urethane bond. The decoration treatment includes addition of the pigment 3, formation of the decoration layer 4, and shaping of the uneven pattern 5.

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 primer technique for bonding an olefin-based decorative sheet to an adherend.

[0002]

2. Description of the Related Art Conventionally, as a decorative sheet used for the above-mentioned applications, a decorative sheet obtained by using a polyvinyl chloride sheet as a base sheet and decorating it by printing, embossing or the like. No. 28-5036, No. 5
No. 8-14312). However, since a decorative sheet using a vinyl chloride resin sheet generates hydrochloric acid gas when burned at the time of disposal, a decorative sheet using another resin containing no chlorine is desired from the viewpoint of global environmental problems. became. Therefore, in recent years, as an alternative to such a PVC-based decorative sheet, an olefin-based decorative sheet using a polyolefin-based resin sheet such as polyethylene, polypropylene, or an olefin-based thermoplastic elastomer (JP-A-54-62255; Kaihei 6-210808, Tokuhyo Hei 4-504384,
Japanese Patent Application Laid-Open No. 7-26038) has appeared.

[0003]

However, when a polyolefin resin sheet is used, when a decorative sheet is adhered to an adherend such as wood plywood, a conventional vinyl chloride resin such as an aqueous dispersion of a vinyl acetate resin is used. Adhesion for resin is difficult to adhere. Therefore, on the back surface of the decorative sheet, an attempt was made to provide an easy-adhesion primer layer composed of a vinyl chloride-vinyl acetate copolymer after corona discharge treatment, but the adhesion with the vinyl chloride resin adhesive was good. However, the adhesion to the polyolefin-based resin sheet was low, and as a result, sufficient adhesion to the adherend could not be obtained. Moreover,
There was a problem that the printed and wound decorative sheet was easily blocked. For this reason, for the purpose of preventing blocking, when an extender pigment is added to the easy-adhesion primer layer, silica is most effective.However, if a large amount is added due to its large particle size, print coating suitability becomes poor, Also, the interlayer strength, that is, the adhesive strength is reduced. However, if the addition amount is small, sufficient blocking resistance cannot be obtained. Therefore, when sedimentable barium sulfate or calcium carbonate is used as a substitute for silica, sedimentable barium sulfate or calcium carbonate has a small effect of improving blocking resistance because the particle size is smaller than silica. In addition, if a large amount is added in order to solve this, a problem has arisen that poor adhesion still occurs. As described above, when a polyolefin resin sheet is used for the decorative sheet, it is preferable that the easy-adhesion primer layer is formed on the back surface because the adhesion is poor. It was difficult to meet all. Therefore, an object of the present invention is to provide a non-vinyl chloride-based olefin-based decorative sheet using a polyolefin-based resin sheet without using a vinyl chloride resin, and to satisfy all of these characteristics in the easy-adhesion primer layer.

[0004]

Means for Solving the Problems In order to solve the above problems, in the decorative sheet of the present invention, a polyolefin resin sheet is a decorative sheet which has been subjected to a decoration treatment, and the outermost layer in contact with the resin sheet has a molecular structure as an outermost layer. In a decorative sheet in which a vinyl chloride-vinyl acetate copolymer having a polar functional group having active hydrogen and an isocyanate compound as a binder and an easy-adhesion primer layer containing an extender pigment are formed, the extender pigment is precipitated with silica. Barium sulfate, or a combination of silica and calcium carbonate, and a polar functional group having an isocyanate group of an isocyanate compound and an active hydrogen of the vinyl chloride-vinyl acetate copolymer in the easy-adhesion primer layer Are connected by a urethane bond. By making the extender pigment contained in the easy-adhesion primer layer composed of a binder of a specific material a combination of such two specific extender pigments, adhesion of the decorative sheet to the adherend and blocking resistance of the decorative sheet are prevented. A decorative sheet that satisfies all the properties and suitability for printing and coating during the production of the decorative sheet can be obtained.

[0005]

Embodiments of the present invention will be described below with reference to the drawings.

[Summary] First, the cross-sectional views of FIGS.
It is the figure which illustrated some from various forms which the decorative sheet S of the present invention can take. FIG. 1 shows an example in which the polyolefin-based resin sheet 1 has a single-layer configuration, and FIG. 2 shows an example in which the substrate has a two-layer configuration or the like and a multi-layer configuration using the polyolefin-based resin sheet 1 or the like. The cross-sectional view of FIG. 3 shows an example in which the decorative sheet S is adhered to a flat plate and a three-dimensional article as the adherend B.

In the decorative sheet S of the present invention, FIGS.
In the decorative sheet in which the polyolefin-based resin sheet 1 is subjected to some decorative treatment, the easily-adhesive primer layer 2 which is laminated as the outermost layer in contact with the polyolefin-based resin sheet 1 includes a resin of the binder and The extender comprises a layer having the above specific composition. The decoration treatment will be described in detail later. For example, as shown in FIG. 1A, a coloring treatment by adding a pigment 3 to the polyolefin resin sheet 1, and as shown in FIG.
The process includes forming the decorative layer 4 by printing a pattern on the polyolefin resin sheet 1 as shown in FIG.

As shown in FIG. 1 (B), the easy-adhesion primer layer 2 in the decorative sheet of the present invention comprises a decorative layer 4 formed on the polyolefin resin sheet 1 by printing or the like. Even when molded on the same side, the decorative layer 4 does not cover the entire surface of the polyolefin resin sheet 1,
Easy adhesion primer layer 2 is polyolefin resin sheet 1
This is the layer formed as the outermost layer of the decorative sheet so that there is a portion in contact with the decorative sheet. This is because the specific resin as the binder of the easy-adhesion primer layer 2 in the present invention is designed in consideration of the adhesiveness particularly in the case of a polyolefin-based resin (for example, on the decorative layer printed and molded over the entire surface). If the decoration layer is a layer made of a urethane resin-based binder, the adhesion layer to the urethane resin may be considered. Of course, the easy-adhesion primer layer of the specific composition in the present invention has good adhesion only to the polyolefin-based resin, and does not have poor adhesion to all other resins.

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

[0010] Japanese Patent Publication No. Hei 6-23278 discloses
(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 olefin thermoplastic elastomers of this type, those that are less likely to cause so-called "necking" and have good suitability for molding or embossing by heating and pressing are isotactic polypropylene and atactic polypropylene. And the mixture ratio of the isotactic polypropylene and the atactic polypropylene is 5% by weight or more and 50% by weight or less by weight of the atactic polypropylene.

[0011] The polypropylene-based thermoplastic elastomer itself is already known, but when it is used in a conventionally known application such as a packaging container, the weight of the atactic polypropylene as a soft segment is important in order to emphasize strength. Those with a 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 a concavo-convex shape or embossing, necking occurs as described above, and good processing cannot be performed. 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. The upper limit of the weight ratio of the atactic polypropylene is to print a decorative layer or the like using a normal rotary printing machine such as rotary gravure printing, and to emboss the sheet, vacuum forming, V-cut processing, and laminate simultaneously with injection molding. Is employed, the content is 50% by weight or less, more preferably 40% by weight or less.

A thermoplastic elastomer comprising an ethylene-propylene-butene copolymer resin. Here, as the butene, 1-butene, 2-butene and isobutylene are used.
Any of the structural isomers can be used. The copolymer is a random copolymer and partially includes an amorphous portion. Preferred specific examples of the ethylene-propylene-butene copolymer include the following (i) to (iii). (i) Those described in JP-A-9-111055. 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. It is preferable that the meter flow rate is 230 ° C. and 2.16 kg for 1 to 50 g / 10 minutes. 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. 0.5% by weight of an oil gelling agent such as an N-acylamino acid amine salt or an 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).

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 shear stress to dynamically partially cross-link. (B) Monoolefin rubber / (A)
Olefin 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. Mixing and heating with a peroxide-decomposable olefin polymer (hard segment) that increases fluidity and (B) a peroxide such as ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene terpolymer rubber, etc. Mixes with peroxides such as peroxide-crosslinked monoolefin copolymer rubber (soft segment), which crosslinks and reduces fluidity, (C) polyisobutylene, butyl rubber, etc.
Peroxide non-crosslinked hydrocarbon rubber (soft segment and fluidity-modifying component) that does not crosslink even when heated and does not change fluidity, and (D) mineral oils such as paraffinic, naphthenic, and aromatic An olefin-based elastomer obtained by mixing a softener and dynamically heat-treating the mixture in the presence of an organic peroxide. (A) is 90 to 40 parts by weight, (B) is 10 to 60 parts by weight.
(A) + (B) = 100 parts by weight,
(C) and / or (D) have a compounding ratio of 5 to 100 parts by weight.

An olefin-based 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 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 of these hydroxyl groups and carboxyl groups,
Alternatively, these polar groups 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 such as a decorative layer and an adhesive layer.

The above polyolefin resin can be formed into a sheet (film) 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 application and the like, but is about 20 to 300 μm. These polyolefin-based resin sheets can be used as either a stretched sheet or an unstretched sheet, but the unstretched sheet is more suitable for molding such as V-cut processing. 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. Further, one or both surfaces of these polyolefin resin sheets are preferably subjected to a corona discharge treatment, a plasma treatment, an ozone treatment, or the like, so that the surface of the polyolefin resin sheet has a hydroxyl group, a carboxyl group, or the like. By imparting a polar functional group having active hydrogen, it is preferable to improve the adhesion to the easily-adhesive primer layer or another layer. In particular, since the easy-adhesion primer layer contains an isocyanate group, in such a configuration, the isocyanate group in the easy-adhesion primer layer and the active hydrogen of the polar functional group on the surface of the polyolefin resin sheet are bonded by a urethane bond. I do.

[Easy-adhesive primer layer] As the easy-adhesive primer layer constituting the outermost layer of the decorative sheet, the decorative sheet of the present invention contains an extender pigment containing a vinyl chloride-vinyl acetate copolymer as a binder resin, In addition, the extender is a layer composed of any combination of silica and precipitated barium sulfate or silica and calcium carbonate. The vinyl chloride-vinyl acetate copolymer is used as the binder for the easy-adhesion primer layer because the usual adhesive used for bonding the decorative sheet to the adherend is a vinyl acetate resin, a polyamide resin, and one liquid. Or, it is made of a two-part curable urethane resin, and is a resin suitable in terms of adhesiveness with such a generally widely used adhesive. And the vinyl chloride-vinyl acetate copolymer,
In addition to vinyl chloride and vinyl acetate, maleic acid, fumaric acid, vinyl alcohol, etc. are further copolymerized to give vinyl chloride
A polar functional group having an active hydrogen such as a hydroxyl group or a carboxyl group is provided in the vinyl acetate copolymer. The copolymerization ratio of the vinyl chloride-vinyl acetate copolymer used was vinyl chloride /
Vinyl acetate is selected from the range of 1/9 to 9/1 (molar ratio) according to the use and the like. Further, a monomer serving as a polar functional group such as maleic acid is copolymerized, and at least 2 monomers per molecule of the vinyl chloride-vinyl acetate copolymer are copolymerized.
A polar functional group having active hydrogen is provided in a proportion of at least one. An isocyanate compound is added to the vinyl chloride-vinyl acetate copolymer. Isocyanate groups in the isocyanate compound are cross-linked by urethane bonds with the polar functional groups in the vinyl chloride-vinyl acetate copolymer to improve the cohesive failure strength of the easy-adhesion primer layer itself,
Prevents peeling from the sheet or adhesive layer due to creep deformation during heating. Further, the isocyanate group also forms a urethane bond with a polar functional group on the surface of the polyolefin resin sheet, thereby improving the strength between the sheet and the easily-adhesive primer layer. The isocyanate compound is selected from the same compounds as those listed below for the anchor agent layer. Among them, aliphatic (or alicyclic) compounds are preferable from the viewpoint of heat resistance and weather resistance.

Further, silica is more effective in blocking resistance than the other extender pigment to be combined, but the content of silica is in the range of 5 to 80 parts by weight based on 100 parts by weight of the resin component. preferable. If the amount is more than 80 parts by weight, the suitability for printing, coating, and adhesion is poor. If the amount is less than 5 parts by weight, the effect of blocking resistance cannot be sufficiently obtained even if a large amount of the other extender is added. The silica content of 5 to 80 parts by weight corresponds to 0.03 to 0.51 in terms of volume ratio according to Table 1 described below. Then, at least one of the extender pigments is silica, and the other extender pigment is a combination of two types of extender pigments using precipitated barium sulfate or calcium carbonate.
The total amount of the specific two types of extender pigments contained is the volume ratio of the vinyl chloride-vinyl acetate copolymer to the polymer when the volume of the copolymer is 1 (total extender pigment / vinyl chloride-vinyl acetate copolymer). 0.50 to 1.00 is preferred. However,
When importance is placed on the anti-blocking property, the above-mentioned volume ratio is set to 0.1.
75-1.00 is preferred. When importance is attached to adhesion, the volume ratio is preferably 0.50 to 0.75. When the total amount of the extender pigments exceeds these ranges, the adhesion decreases, and when the total amount is less than these ranges, the blocking resistance deteriorates.

Table 1 below shows the physical property values of each material used for the easy-adhesion primer layer. Basically, when silica having a particle size larger than that of precipitated barium sulfate or calcium carbonate is used, good results such as blocking resistance can be obtained.

[0023]

[Table 1]

The easy-adhesion primer layer may be formed by a known printing method such as gravure printing or silk screen printing, or a known coating method such as gravure coating. Further, more preferably, the surface of the polyolefin-based resin sheet is subjected to an easy-adhesion treatment such as a corona discharge treatment, a plasma treatment, and an ozone treatment, and then an easy-adhesion primer layer is formed. Adhesion with the adhesive primer layer is improved. The thickness of the easy-adhesion primer layer is usually about 1 to 10 μm. In addition, the easy-adhesion primer layer is usually on one side of the decorative sheet, usually also on the back side, but the present invention does not exclude the constitution of the easy-adhesion primer layer on both sides of the decorative sheet. This is a case where at least one of the adherends to which the decorative sheet is attached is transparent.

In the present invention, the anti-blocking property is improved by forming the easy-adhesion primer layer as described above.
In addition, the adhesion to the adherend is improved, and the printing suitability of the ink and the coating suitability of the coating liquid during printing or coating for forming the easy-adhesion primer layer can be favorably maintained. In addition, the above-mentioned easy-adhesion primer layer also has heat resistance such that it does not deteriorate even after undergoing an embossing step at the time of shaping the concavo-convex pattern. Therefore, an easy-adhesion primer layer can be formed on the polyolefin-based resin sheet in a separate step before the decorative layer or the like is formed by printing or the like. As a result, the decorative layer can be formed only on the non-defective sheet on which the easy-adhesion primer layer is formed, and a cost reduction effect by reducing sheet loss can be obtained. Also,
When forming an easy-adhesion primer layer after performing a corona discharge treatment on a polyolefin-based resin sheet in advance, after performing these in one step, decoration processing by lamination or printing with another base material can be performed in another step, The corona discharge treatment effect can also be prevented from decreasing over time. Further, as described above, the decorative sheet also has heat resistance to embossing, so that the decorative sheet can improve productivity by increasing the embossing speed.

[Decoration treatment] As the decoration treatment for the polyolefin resin sheet, the decorative sheet S shown in FIG.
, A coloring layer (transparent or opaque coloring) by adding a pigment 3 to the resin sheet 1 itself, a decorative layer 4 by printing or the like expressing a pattern or the like as shown by a decorative sheet S in FIG.
, Embossing (heating press) as shown in FIG. For example, as shown in FIG. 2, in the case of a decorative sheet having a multilayer structure in which a plurality of base sheets are laminated, the decorative treatment on the polyolefin resin sheet is defined as the polyolefin resin sheet in contact with the specific easy-adhesion primer layer. After decorating another layer (for example, a base sheet) other than the resin sheet, the other layer is laminated, or another layer is laminated on the polyolefin resin sheet and then decorated. As a result, the polyolefin-based resin sheet may be subjected to decorative treatment. Thus, the decoration process may be any of various conventionally known decoration processes for decorative sheets. Various decoration processes may be used in combination as appropriate depending on the application.

(Pigment addition) Inorganic pigments such as titanium white, zinc white, red iron oxide, vermilion, ultramarine blue, cobalt blue, titanium yellow, graphite and carbon black, isoindolinone, Hansa Yellow A, quinacridone Organic pigments (or dyes) such as Permanent Red 4R, Phthalocyanine Blue, Indaslen Buri RS, and aniline black; metal pigments such as aluminum and brass; titanium dioxide-coated mica; and foil powder such as basic lead carbonate. Pearlescent (pearl) pigments and the like. These are added and dispersed as powder or flaky foil pieces. The coloring by the pigment may be transparent coloring or opaque (concealing) coloring.

(Applying a decorative layer) The decorative layer is formed by a known printing method (or coating method) such as gravure printing, offset printing, silk screen printing, and transfer printing from a transfer sheet.
And formed with ink (or paint). Examples of the pattern of the decorative layer include a wood grain pattern, a stone grain pattern, a cloth grain pattern, a leather pattern, a geometric figure, a character, a symbol, and a solid surface. The pattern is the front and back of the polyolefin resin sheet,
It may be provided on both front and back surfaces or between the layers when the decorative sheet is a multilayer substrate. As ink (or) paint, chlorinated polyolefin such as chlorinated polyethylene, chlorinated polypropylene, polyester, urethane resin, acrylic resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, cellulose resin, etc. And used alone or in combination of two or more. A material obtained by adding known pigments and the like as described above to this is used.

When printing directly on a polyolefin resin sheet, chlorinated polyolefin, urethane resin or the like is preferable as a binder in terms of adhesiveness. However, if an anchor agent layer is formed on the printing surface side, other binders may be used. Provides sufficient adhesion even when used. Incidentally, as the anchor agent layer, acrylic resin, vinyl chloride-vinyl acetate copolymer,
Polyester resin, urethane resin, chlorinated polypropylene, chlorinated polyethylene and the like are used. Alternatively, a material similar to the above-mentioned easy adhesion primer layer may be used. In addition, corona discharge treatment, easy adhesion treatment such as plasma treatment, or more preferably, after performing these easy adhesion treatment,
The above-mentioned anchor agent layer may be formed.

Examples of the acrylic resin include poly (methyl meth) acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate, butyl poly (meth) acrylate, and methyl (meth) acrylate- (meth) acrylate. Such as butyl acrylate copolymer, ethyl (meth) acrylate-butyl (meth) acrylate copolymer, ethylene-methyl (meth) acrylate copolymer, and styrene-methyl (meth) acrylate copolymer; An acrylic resin comprising a homo- or copolymer containing (meth) acrylic acid ester (here, (meth) acryl means acryl or methacryl, and the same hereinafter).

The urethane resin is mainly composed of polyol (polyhydric alcohol) and isocyanate as a crosslinking agent (curing agent).
Polyurethane. 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 polyvalent isocyanate having two or more isocyanate groups in a molecule is used. For example, aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, and 4,4'-diphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; hydrogenated tolylene diisocyanate; An alicyclic) isocyanate, an isocyanate adduct such as an adduct of tolylene diisocyanate, or an isocyanate polymer such as a trimer of tolylene diisocyanate is used.

The decorative layer may be a metal thin film layer. The metal thin film is formed using a metal such as aluminum, chromium, gold, silver, and copper by a method such as vacuum deposition and sputtering. Alternatively, a combination of these may be used. The metal thin film may be provided on the entire surface or partially in a pattern.

(Emboss processing) As the emboss processing for forming an emboss pattern, a base material such as a polyolefin resin sheet is heated and softened, pressed and shaped with an emboss plate, and cooled and fixed to form. A known single-wafer or rotary embossing machine is used. Examples of the uneven pattern include a wood grain board conduit groove, a stone board surface unevenness (granite cleavage plane, etc.), a cloth surface texture, a satin finish, a grain, a hairline, a linear groove, and the like. As shown in the decorative sheet S of FIG. 1D, if necessary, a known wiping method (Japanese Patent Publication No. 58-1)
4312) can be filled with the coloring ink 6. The same thing as the above can be used for the coloring ink. However, from the viewpoint of abrasion resistance, a material using a two-component curable urethane resin as a binder is preferable. The uneven pattern is usually on the front side, but may be on the interlayer or the back side.

(Other Decoration Processing) The decoration processing includes forming an overcoat layer for imparting design properties such as gloss adjustment and painting feeling. For example, in the decorative sheet S shown in FIGS. 2A and 2B, the base material 7 laminated on the surface of the polyolefin-based resin sheet 1 opposite to the surface on which the easy-adhesion primer layer 2 is formed serves as an overcoat layer. .

[Cosmetic Sheet of Multi-Layer Structure] In the decorative sheet of the present invention, as shown in FIG. 1, the polyolefin resin sheet may be used as a single-layer base sheet. As illustrated, there may be a multilayer structure in which a plurality of base materials such as a base material sheet are laminated. Although FIG. 2 has a two-layer structure, a three or more layer structure may be used (not shown). For example, in the case of a multi-layer substrate such as being composed of a plurality of substrate sheets,
The base sheet in contact with the easy-adhesion primer layer having the specific composition as the outermost layer is made of the polyolefin-based resin sheet 1, but the other base materials 7 not in contact with the easy-adhesion primer layer are made of the same or different polyolefin-based resin sheets. Good, and a resin sheet other than the polyolefin resin may be used.
However, a chlorine-free resin sheet is preferred for the purpose of the present invention.

By way of explanation, the decorative sheet illustrated in FIG. 2 will be described. The decorative sheet S in FIG. 2A is composed of a polyolefin resin sheet 1 which is a base material in contact with the easy-adhesion primer layer 2 and a polyolefin resin sheet or This is a configuration in which a transparent substrate 7 made of another resin sheet or the like is laminated with the decoration layer 4 interposed therebetween. As described above, in the case of such a multilayer base material, the base material 7 on the side to be laminated on the polyolefin-based resin sheet 1 is subjected to a decoration process, and as a result, the polyolefin-based resin sheet is decorated. It can also be used as a decorative sheet. That is, the decorative layer 4 may be formed directly on the polyolefin-based resin sheet 1, but may be formed in advance on the base material 7 side such as a polyolefin-based resin sheet or another resin sheet by printing or the like. In some cases, the polyolefin resin sheet 1 is subjected to a decoration treatment by being laminated with the resin sheet 1.

Further, the decorative sheet S of FIG.
In the decorative sheet having the configuration of (A), the polyolefin resin sheet 1 which is a layer in contact with the easy-adhesion primer layer 2 is further subjected to a decoration treatment by adding a pigment 3. Further, the decorative sheet S of FIG. 2C has a configuration in which the uneven pattern 5 is formed on the surface of the base material 7 laminated on the polyolefin resin sheet 1 with respect to the decorative sheet of the configuration of FIG. It is.

When a chlorine-free resin sheet other than the polyolefin resin sheet is used as the base material 7, a resin sheet (film) made of the following resin can be used. For example, acrylic resin, ethylene-vinyl alcohol copolymer resin, thermoplastic polyester resin, etc.

Here, the acrylic resin includes poly (methyl meth) acrylate, poly (ethyl meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, and methyl (meth) acrylate.
(Meth) butyl acrylate copolymer, ethyl (meth) acrylate-butyl (meth) acrylate copolymer, ethylene-methyl (meth) acrylate copolymer, styrene-
Acrylic resin consisting of a homo- or copolymer containing a (meth) acrylate such as a methyl (meth) acrylate copolymer. The thickness of this acrylic resin sheet is
It is about 20 to 100 μm.

The ethylene-vinyl alcohol copolymer layer is formed by lamination by hot-melt or by an adhesive such as two-component curable urethane resin or melt-extrusion-coated polyethylene. It is formed by laminating a united sheet on a resin layer serving as a base material, and has a thickness of preferably 10 to 100 μm, more preferably 12 to 25 μm. As the sheet, a sheet obtained by molding a random copolymer of ethylene and vinyl alcohol into a sheet is generally used.

The ethylene-vinyl alcohol copolymer-based resin sheet may be a stretched sheet or an unstretched sheet, but the unstretched sheet is suitable in terms of sheet flexibility, bending workability, embossability and the like. It is preferably used.

The ethylene-vinyl alcohol copolymer sheet is prepared by changing the ratio of the copolymer components to obtain the thermoplasticity and water resistance of ethylene and the rigidity, oil resistance, solvent resistance, and non-chargeability of vinyl alcohol. Although the magnitude of the performance can be arbitrarily adjusted, it is preferable that the ethylene component is 30 to 45 mol% in order to obtain a sheet having both characteristics as much as possible and having excellent workability. If it is less than 30 mol%, the thermoplasticity, heat processing suitability and water resistance are poor.
If it exceeds 5%, the rigidity, oil resistance, solvent resistance, and non-charging property will be poor, which is not preferable.

The thermoplastic polyester resin is represented by polyethylene terephthalate, polybutylene terephthalate, ethylene-terephthalate-isophthalate copolymer and the like, and the acid component is terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or the like. It is a copolymer obtained as an ester of both an aromatic dicarboxylic acid and an aliphatic diol such as ethylene glycol, diethylene glycol, butanediol and hexanediol as alcohol components. Both stretched and unstretched sheets can be used, but unstretched sheets are more preferable in view of suitability for embossing and forming such as V-cutting.

As a method of further laminating a resin sheet of an acrylic resin, an ethylene-vinyl alcohol copolymer resin, a thermoplastic polyester resin, etc. on a polyolefin resin sheet, there are melt extrusion coating (extrusion coating), hot pressing, and the like. Or dry lamination using an adhesive such as a two-component curable polyurethane resin or polyester resin. In these resins, like the polyolefin resin sheet, if necessary,
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.

[Applied Body of Decorative Sheet] The application 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 application of the surface. The adherend is a plate material such as a flat plate or a curved surface plate of various materials (see FIG. 3A), a three-dimensional article (see FIG. 3B), a sheet (or film).
And so on. For example, wood veneer, wood plywood, particle board, wood material such as wood fiber board such as MDF (medium density fiber board) and wood board material used as a three-dimensional article, iron,
Plate materials such as aluminum, metal materials used as three-dimensional shaped articles or sheets, ceramics such as glass and ceramics, non-cement ceramic materials such as gypsum, and non-ceramic ceramic materials such as ALC (lightweight cellular concrete) plates Materials such as acrylic resin, polyester resin, polystyrene resin, polyolefin resin such as polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenol resin, vinyl chloride resin, and cellulose resin Resin material used as plate material such as resin and rubber, three-dimensionally shaped article or sheet, or paper such as high quality paper and Japanese paper used exclusively as sheet, non-woven fabric or woven fabric made of fiber such as carbon, asbestos, glass and synthetic resin Cloth.

FIG. 3 will be described here.
(A) shows a decorative sheet S on an adherend B via an adhesive layer A.
Are laminated articles. Here, the decorative sheet S has a two-layer base material configuration similar to that of FIG. 2C described above, and the base material of each of the two layers is made of the polyolefin resin sheet 1. FIG. 3B is a sectional view conceptually showing a case where the adherend B on which the decorative sheet S is laminated is a three-dimensional article. Here, the illustration of the easy-adhesion primer layer on the decorative sheet S side is shown. Omitted. Although the illustration of the adhesive layer is omitted, it is unnecessary when the adherend B has adhesiveness.

[Laminating method of decorative sheet on adherend] As a method of laminating the decorative sheet on these various adherends, for example, pressure is applied to a plate-like base material with a pressure roller via an adhesive. As described in Japanese Patent Publication No. 50-19132, Japanese Patent Publication No. 43-27488, etc., after the decorative sheet is placed between the male and female molds for injection molding, the molten resin is placed in the mold. A so-called simultaneous injection molding lamination method in which injection molding is performed and a decorative sheet is adhered and laminated on the surface of the resin molded article simultaneously with the molding thereof, as described in JP-B-56-45768 and JP-B-60-58014. , 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 decorative sheet is laminated on the surface of the three-dimensional article by a pressure difference due to vacuum suction from the three-dimensional article side. So-called vacuum Laminating method, as described in JP-B-61-5895, JP-B-3-2666, etc., an adhesive is provided between a decorative sheet and a columnar substrate such as a column or a polygonal column in the long axis direction. While feeding through
There is a so-called lapping method in which decorative sheets are successively pressed and laminated on a plurality of side surfaces constituting a columnar substrate by a plurality of rollers having different directions.

As a further processing method for a decorative sheet obtained by laminating decorative sheets, Japanese Utility Model 15-311
No. 22, JP-A-48-47972, a decorative sheet is first laminated on a plate-like base material with an adhesive therebetween to form a decorative sheet, and the surface opposite to the decorative sheet is used. To
Cut a V-shaped or U-shaped groove reaching the interface between the decorative sheet and the plate-shaped substrate, and then apply an adhesive in the groove and bend the groove to form a box or column. Is a so-called V-cut or U-cut processing method.

In particular, as the method of finally bonding the decorative sheet of the present invention to a three-dimensional object having irregularities, of the above methods, and the V-cut processing method are preferable.

[Use of decorative sheet and laminate thereof] 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, surface decoration of furniture or cabinets of light electric / OA equipment, vehicle interiors such as cars and trains, aircraft interiors, ship interiors, Window glass makeup. In addition, if the decorative sheet is laminated on the adherend and the surface of the article is the final product, it may be the final product. In some cases, an article obtained by laminating adherends is used as an intermediate product, which is then laminated on another adherend, or an assembled article becomes the final product. For example, when the adherend is a plate material, it is used as a decorative board, and when the adherend is a sheet, an intermediate product is also used as a decorative sheet.

[0051]

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

[Examples and Comparative Examples] 8 to 2 of isotactic polypropylene and atactic polypropylene
A sheet having a thickness of 100 μm in which 0.2% by weight of a benzotriazole-based ultraviolet absorber was added to a polyolefin-based resin comprising a mixture in a weight ratio was prepared as a polyolefin-based resin sheet. After one surface of the resin sheet is subjected to corona discharge treatment so as to have a critical surface tension of 38 [dyne / cm], a vinyl chloride-vinyl acetate copolymer obtained by copolymerizing maleic acid and hexamethylene diisocyanate are used. A 2 μm-thick, easy-to-adhere primer layer containing silica, sedimentable barium sulfate, and calcium carbonate as binders in various formulations shown in Table 2 was formed by gravure roll coating to prepare respective intermediate sheets. did. The average particle size of each extender used was
3.5μm silica, 0.5μ precipitated barium sulfate
m, calcium carbonate is 0.07 μm.

Next, the other surface of the intermediate sheet on which the easy-adhesion primer layer is formed is subjected to a corona discharge treatment, and then a two-component curable urethane resin is used as a binder, and a coloring ink is used as a petal or the like. , Wood grain pattern decoration layer,
Furthermore, a transparent 3 μm thick overcoat layer of a two-component curable urethane resin is formed on the entire surface by gravure printing in order,
The decorative sheets of the example and the comparative example were obtained. These decorative sheets have a layer configuration in which the base material 7 is an overcoat layer in the decorative sheet S of FIG. 2A. In addition,
As the two-component curable urethane resin used for the decorative layer and the overcoat layer, a 100: 8 weight ratio mixture of acrylic polyol and hexamethylene diisocyanate was used. In Examples 1 to 5, the composition of the easy-adhesion primer layer was prepared by adding hexamethylene diisocyanate and mixing the filler with two kinds of silica and precipitated barium sulfate or silica and calcium carbonate. did. As Comparative Examples 1 to 4, the composition of the easy-adhesion primer layer was obtained by adding hexamethylene diisocyanate. However, as an extender, only one of silica, precipitated barium sulfate, and calcium carbonate was used. Created. As Comparative Examples 5 and 6, the composition of the easy-adhesion primer layer is that the extender is a mixture of two kinds of silica and precipitated barium sulfate, but hexamethylene diisocyanate is added in Comparative Example 5 and not added in Comparative Example 6. Created things.

(Evaluation of Performance) With respect to each of the decorative sheets of the above Examples and Comparative Examples, blocking resistance and adhesion were evaluated as follows. Blocking resistance: Applying a load of 5 kg / cm ² to 40 from the top of a plurality of decorative sheets stacked in the same direction on a horizontal table
After adding at 48 ° C. for 48 hours, when the laminated decorative sheet was peeled off, it was evaluated whether or not the easily-adhesive primer layer was transferred to the adjacent decorative sheet surface.も の indicates no transfer, Δ indicates slight transfer, and × indicates the entire transfer. Adhesion: A decorative sheet is adhered to the surface of the 3 mm-thick Rawan plywood coated with a vinyl acetate resin-based emulsion adhesive at 40 g / m ² (when dried) on the side of the easy-adhesion primer layer. Was subjected to a tensile test of 180 ° peeling, and the tensile strength was evaluated. Tensile strength [kg / 25m
When the [m width] is less than 1, it was evaluated as x, and when it was 1 or more and less than 2, it was evaluated as Δ.

[0055]

[Table 2]

In Table 2, "precipitated burrs" represent precipitated barium sulfate, and "charcoal" represents calcium carbonate. The amount (parts by weight) of each extender is expressed as parts by weight based on 100 parts by weight of the vinyl chloride-vinyl acetate copolymer. The volume ratio represents the volume ratio of the total amount of the extender pigment of silica and precipitated barium sulfate, and silica and calcium carbonate, when the vinyl chloride-vinyl acetate copolymer is set to 1.

As shown in Table 2, when the extender pigment of the easy-adhesion primer layer is a combination of silica and precipitated barium sulfate or silica and calcium carbonate, a decorative sheet having both blocking resistance and adhesion can be obtained. Was. However, it was not compatible with only one of silica, precipitated barium sulfate, and calcium carbonate. And, if the isocyanate compound was not present in the easy-adhesion primer layer, the adhesion was insufficient. Further, in the examples, the suitability for printing and coating during production of the decorative sheet was also good.

[0058]

According to the decorative sheet of the present invention, a resin of a specific material is used for the binder as the outermost easy-adhesion primer layer, and the extender pigment to be contained is a combination of two specific extender pigments. As a result, a decorative sheet that satisfies all of the adhesiveness of the decorative sheet to the adherend, the blocking resistance of the decorative sheet, and the suitability for printing and coating during the production of the decorative sheet can be obtained. In addition, since the easy-adhesion primer layer also has heat resistance such that it does not deteriorate even after undergoing an embossing process at the time of embossing of a concavo-convex pattern, the easy-adhesion primer layer is applied to the polyolefin resin sheet before forming the decorative layer etc. by printing or the like. It can be formed in another process. As a result, the decorative layer can be formed only on the non-defective sheet on which the easy-adhesion primer layer is formed, and the cost of the decorative sheet can be reduced by reducing the occurrence of sheet loss. In addition, when embossing is performed due to the heat resistance of the easy-adhesion primer layer, the productivity can be improved by increasing the processing speed, so that the cost of the decorative sheet can be similarly reduced. Further, when forming an easy-adhesion primer layer after pre-corona discharge treatment on the polyolefin resin sheet,
After these are performed in one step, decoration processing by lamination or printing with another substrate can be performed in another step, so that the corona discharge treatment effect can be prevented from decreasing over time, and the adhesion performance of the easy-adhesion primer layer can be prevented. Becomes stable. In addition, since the easy-adhesion primer layer itself is cross-linked by urethane bonds and also urethane-bonded to a polyolefin resin sheet, heat-resistant creep deformation of the easy-adhesion primer layer does not occur, and stress is applied for a long time especially at high temperatures. In this case, the adhesive strength between the decorative sheet and the adherend is also improved.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating some of the various forms (single-layer substrates) of the decorative sheet of the present invention.

FIG. 2 is a cross-sectional view illustrating some of the various forms (multilayer base materials) of the decorative sheet of the present invention.

FIG. 3 is a cross-sectional view illustrating a case where the decorative sheet of the present invention is attached to an adherend.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Polyolefin resin sheet 2 Easy-adhesion primer layer 3 Pigment 4 Decorative layer 5 Uneven pattern 6 Colored ink 7 Base material B Adherend A Adhesive layer S Decorative sheet

Claims (1)

(57) [Claims] 1. A decorative sheet in which a polyolefin-based resin sheet has been subjected to a decoration treatment, wherein a vinyl chloride-vinyl acetate copolymer having a polar functional group having active hydrogen in a molecule as an outermost layer in contact with the resin sheet. In a decorative sheet having an easy-adhesion primer layer containing an extender pigment containing an isocyanate compound and a binder, the extender pigment is a combination of silica and precipitated barium sulfate, or silica and calcium carbonate, and A decorative sheet comprising an isocyanate group of an isocyanate compound in the easy-adhesion primer layer and a polar functional group having active hydrogen of the vinyl chloride-vinyl acetate copolymer bonded by a urethane bond.