JPH10157018A - Decorative sheet - Google Patents

Abstract

(57) [Summary] [PROBLEMS] A conventional decorative sheet made by decorating a polyvinyl chloride or polyolefin sheet has a problem in weather resistance and flexibility, or is used for bending a decorative material laminated with a decorative sheet. When you make a V-cut and fold the cosmetic material,
There were problems such as cracks in the decorative sheet. Also, a decorative sheet in which a surface layer of an acrylic resin is laminated on the surface of a polyolefin sheet, when the decorative material is subjected to V-cut or the like and the decorative material is bent, cracks or whitening occur in the surface layer of the acrylic resin. There was a problem. In addition, there is a problem in lapping suitability, and when the decorative sheet is wrapped on a substrate having an irregular cross section, there is a problem in that the decorative sheet is cracked. SOLUTION: The decorative sheet 1 of the present invention is a decorative sheet obtained by laminating a protective sheet of an acrylic resin on a sheet substrate of an olefin resin, wherein the protective sheet has a temperature of 25 ° C.
Tensile elongation at 100% or more, preferably 130%
The above-mentioned acrylic thermoplastic elastomer sheet is used.

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 the purpose of giving a design to a surface used for interior decoration of a building, surface decoration of a fitting, interior decoration of a vehicle, or protecting the surface.

[0002]

2. Description of the Related Art Conventionally, the following three types of decorative sheets have been known as decorative sheets used for such purposes.

(1) A polyvinyl chloride sheet decorated with printing or embossing (Japanese Patent Publication No. 28-5036)
No., JP-B-58-14312). (2) A sheet using an olefin sheet such as polyethylene or polypropylene instead of polyvinyl chloride (JP-A-54-62255).

(3) An olefin-based thermoplastic elastomer is mixed with an olefin-based resin obtained by graft-polymerizing a polar functional group (Japanese Unexamined Patent Publication No. 6-210808, Japanese Unexamined Patent Publication No.
No. 04384), a polyurethane resin is mixed with an olefin resin using a compatibilizer (Japanese Patent Laid-Open No. 7-260).
No. 38) to solve the drawback of the decorative sheet of (1) and the following drawbacks of the decorative sheet of (2). And so on.

[0005]

In the decorative sheet using a polyvinyl chloride sheet as described in (1), the heat resistance is insufficient, or the bleeding of the plasticizer causes the surface to be stain resistant. There was a problem that was bad.

In the case of the conventional decorative sheet as described in (2), the disadvantage of the decorative sheet using polyvinyl chloride can be improved, but transparency is insufficient. Insufficient heat resistance. Poor weather resistance. Inflexible. Insufficient adhesion to ink, adhesive, etc. during printing and lamination. After forming a V-shaped or U-shaped groove on the back surface of a decorative material with a decorative sheet laminated on the front surface, the decorative material is bent (V-shaped or U-shaped). The process of forming the groove and bending the decorative material is hereinafter simply referred to as a V-cut process.) The decorative sheet cracks and breaks. In particular, the heat history at the time of embossing from heating softening to embossing plate pressing to cooling causes crystallization to progress and the sheet becomes brittle, and this tendency is strengthened. In addition, embossing conditions are very narrow because of high crystallinity. And so on. Furthermore, when wrapping a decorative sheet on a substrate having an irregular cross-section, there was a problem that the decorative sheet was cracked (low lapping suitability). Further, even with the decorative sheet as in (3), it was still difficult to say that the disadvantage of the sheet in (2) has been solved.

Further, the present inventors have studied a decorative sheet having a structure in which a protective sheet made of an acrylic resin is laminated on a sheet base made of an olefin resin. However, a decorative sheet having an acrylic resin protective sheet has a problem that when a V-cut process is performed on a decorative material in which the sheet is laminated, the acrylic resin protective sheet is cracked or the protective sheet is whitened. was there.

The decorative sheet of the present invention is a decorative sheet having a structure in which a protective sheet made of an acrylic resin is laminated on the surface of an olefin resin sheet substrate by using a specific acrylic resin constituting the protective sheet. It has been found that the above-mentioned disadvantages can be solved, and the present invention has been completed.

[0009]

That is, the decorative sheet of the present invention is a decorative sheet obtained by laminating a protective sheet of an acrylic resin on a sheet substrate of an olefin resin, wherein the protective sheet has a breaking point at 25 ° C. It is a sheet of an acrylic thermoplastic elastomer having an elongation of 100% or more, preferably 130% or more.

[0010]

Embodiments of the present invention will be described below in detail with reference to the drawings. FIG. 1 shows an embodiment of a decorative sheet 1 of the present invention. In the figure, reference numeral 2 denotes a sheet base material of an olefin resin, and reference numeral 3 denotes a protective sheet.

In the decorative sheet 1 of the present invention, the sheet base 2 is made of an olefin resin. Examples of the olefin resin include polyethylene, ethylene / propylene copolymer, ethylene / butene-1 copolymer, polypropylene, propylene / butene-1 copolymer, and polybutene-
1, butene-1 / propylene / ethylene terpolymer,
Butene-1 / hexene-1 / octene-1 terpolymer, polymethylpentene, ethylene / vinyl alcohol copolymer, ethylene / vinyl acetate copolymer and the like. Also, JP-A-6-16832, Japanese Patent Publication No. 6-2
No. 3278, JP-B-53-21021, JP-B-53-34210, JP-B-56-15741, JP-A-2-139232 and the like. What mixed the plastic elastomer with the above-mentioned polyolefin resin can also be used. Especially, what mixed the said thermoplastic elastomer with high density polyethylene is preferable. High density polyethylene has a specific gravity of 0.94 to 0.9
Polyethylene No. 6 which is obtained by a low-pressure method and has a high degree of crystallinity and a low molecular branch structure.

As the thermoplastic elastomer, diene rubbers, hydrogenated diene rubbers and the like can be used, and among them, hydrogenated diene rubbers are preferred. The hydrogenated diene rubber is obtained by adding a hydrogen atom to at least a part of the double bond of the diene rubber molecule,
It plays a role in suppressing crystallization of high-density polyethylene and improving flexibility and transparency. Generally, when a diene rubber is added to an olefin resin, the double bond of the diene rubber is caused.
Weather resistance and heat resistance are lower than those of olefin resins without the addition of diene rubber.However, by saturating the double bond of diene rubber with hydrogen, the weather resistance and heat resistance of olefin resin may be reduced. Disappears.

Examples of the diene rubber include isoprene rubber, butadiene rubber, butyl rubber, propylene / butadiene rubber, acrylonitrile / butadiene rubber, acrylonitrile / isoprene rubber, and styrene / butadiene rubber. For the purpose of the present invention, styrene-butadiene rubber is particularly preferred.

The amount of the thermoplastic elastomer is preferably about 1 to 90 parts by weight based on 100 parts by weight of the polyolefin resin. If the amount is less than 1 part by weight, the elasticity, elongation, and impact resistance of the sheet base material 2 are insufficient, and when the decorative material is subjected to a bending process such as a V-cut process or a drawing process, the protective sheet 3 may be cracked. There is a risk of cracking. On the other hand, if it exceeds 90 parts by weight, the elasticity and elongation of the sheet base material 2 become too large, and when the decorative layer 4 is formed on the sheet base material 2 by printing or the like, the position of the position where the pattern layer 4 is formed. It is not preferable because alignment becomes difficult. In particular, when the sheet substrate 2 is made of an olefin resin containing a high-density polyethylene, a thermoplastic elastomer, and an inorganic filler, the content of the thermoplastic elastomer in the mixture of the high-density polyethylene, the thermoplastic elastomer, and the inorganic filler is as follows: 10-60% by weight
The degree is preferred.

[0015] There is a correlation between the thermal dimensional shrinkage of the sheet base material 2 and the crack and rupture resistance of the decorative sheet 1 during V-cut processing of the decorative material. The dimensional shrinkage rate after heating (based on before heating) is the longitudinal direction of the sheet (longitudinal direction of a long extruded sheet)
Is preferably in the range of -2 to + 7% in the sheet width direction (direction perpendicular to the longitudinal direction). If the dimensional shrinkage ratio deviates from this range, cracks are likely to occur during V-cut processing. The reason why the allowable value of the heating dimensional shrinkage ratio is different in the sheet longitudinal direction and the sheet width direction is that the material mechanical history of the sheet at the time of sheet production and the manner of applying the impact force at the time of sheet processing are determined by the longitudinal direction And in the width direction. The dimensional shrinkage upon heating largely correlates mainly with the stretching of the sheet substrate 2. If it is not stretched, the dimensional heat shrinkage of the sheet substrate 2 falls within the above range, and if it is stretched three times or more, it generally falls outside the above range. Therefore, in the case of stretching, it is preferable to suppress the stretching ratio so that the heating dimensional shrinkage falls within the above range.

Further, in order to improve the crack resistance and rupture resistance of the decorative sheet 1 at the time of V-cut processing, it is preferable that the resin constituting the sheet substrate 2 contains a filler. Fillers include calcium carbonate, barium sulfate,
Powders such as clay and talc are used. In particular, when the sheet base 2 is made of a high-density polyethylene, a thermoplastic elastomer, and an inorganic filler, the filler is based on a mixture of the high-density polyethylene, the thermoplastic elastomer, and the inorganic filler.
5 to 60% by weight, particularly about 30% by weight is preferred. It is preferable that the total amount of the thermoplastic elastomer and the filler is 70% by weight or less.

The protective sheet 3 in the decorative sheet 1 of the present invention is a sheet made of an acrylic thermoplastic elastomer having an elongation at break at 25 ° C. of 100% or more. If the tensile elongation at 25 ° C. of the protective sheet 3 is less than 100%, the protective sheet 3 is cracked or whitened by V-cutting. The elongation at break is especially 130
% Or more, and when the elongation at break of a sheet made of an acrylic thermoplastic elastomer is 130% or more, there is an effect that lapping suitability is improved. still,
The elongation at break is measured according to the JIS K6734 method. Protective sheet 3 with tensile elongation of 100% or more
Examples of the acrylic thermoplastic elastomer capable of forming a copolymer include a graft copolymer of butyl acrylate and / or butyl methacrylate with methyl acrylate and / or methyl methacrylate, and a graft copolymer of butyl acrylate and methyl methacrylate. Coalescence is more preferred. This acrylic thermoplastic elastomer is considered to have a soft soft segment portion having rubber elasticity or amorphousness and a hard hard segment portion having crystalline or thermoplasticity.
An acrylic thermoplastic elastomer capable of forming the protective sheet 3 having an elongation at break of 130% or more can be obtained by lowering the glass transition point (Tg) of the soft segment portion forming the matrix. If the temperature is too low, blocking occurs. Therefore, the temperature is preferably lowered to around 60 ° C.

When the acrylic thermoplastic elastomer is a graft copolymer of butyl acrylate and / or butyl methacrylate and methyl acrylate and / or methyl methacrylate, the butyl acrylate and / or butyl methacrylate having a high copolymerization ratio It is considered that the aggregation region, the aggregation region of molecules having a large number of side chains or the aggregation region of molecules having a high molecular weight, or butyl acrylate and / or butyl methacrylate forms a soft segment portion. On the other hand, an aggregation region of a molecule having a high copolymerization ratio of methyl acrylate and / or methyl methacrylate, an aggregation region of a molecule having a small number of side chains or an aggregation region of a molecule having a low molecular weight, or methyl acrylate and / or methyl methacrylate. The portions are considered to form hard segment portions.

The acrylic thermoplastic elastomer is considered to have a structure in which the soft segment portions serve as a matrix, and the hard segment portions are dispersed like islands in the matrix. When the acrylic thermoplastic elastomer is a graft copolymer of butyl acrylate and / or butyl methacrylate and methyl acrylate and / or methyl methacrylate, the copolymerization ratio is butyl acrylate and / or butyl methacrylate: methyl acrylate by weight ratio. And / or methyl methacrylate = 10: 90 to 90:10, more preferably 50:50 to 90:10. In order to further enhance the intended effect of the present invention, generally, the hard segments dispersed in the soft segment matrix preferably have a smaller particle size, and the glass transition point (Tg) of the soft segment portion forming the matrix is preferably smaller. ) Is lower the more effective.

It is more effective to add a plasticizer to the acrylic thermoplastic elastomer. As a plasticizer,
High molecular weight polyethylene glycol and the like can be mentioned. The protective sheet 3 made of an acrylic thermoplastic elastomer is
Generally, a thicker film is preferable, but the thickness is preferably about 25 to 100 μm in consideration of abrasion, flexibility of the decorative sheet 1, cost, and the like.

In the present invention, the protective sheet 3 preferably has a 60 ° specular gloss of 80 or less. The 60 ° specular gloss is a gloss measured according to JIS Z-8741. The surface of the protective sheet 3 has a 60 ° specular gloss of 8
As a method for reducing the particle size to 0 or less, an inorganic matting agent such as silica or an organic matting agent such as plastic beads is added to the protective sheet 3 or the flow of the acrylic thermoplastic elastomer constituting the protective sheet 3 is reduced. When a sheet is formed by adding a substance that inhibits the properties, a method of causing surface roughness may be used. The matting effect due to the addition of the matting agent or the substance that inhibits flowability differs depending on the difference in compatibility with the acrylic thermoplastic elastomer, the difference in flowability of the acrylic thermoplastic elastomer, and the like. It is necessary to consider the amount of the substance that inhibits the fluidity in accordance with the type of these substances, the fluidity of the elastomer, and the like. The reason why the 60 ° specular glossiness of the protective sheet 3 is preferably 85 or less is that when the protective sheet 3 is used as a decorative sheet having an embossed surface, the embossed decorative sheet is heated and softened. When the protective sheet 3 is placed in an atmosphere at a temperature higher than the temperature, the unevenness of the emboss may be lost (returned).
Setting the number to 5 or less has the effect of preventing such return.

As a method of laminating the sheet base material 2 and the protective sheet 3, melt extrusion coating (extrusion coating), fusion by hot pressing, or an adhesive such as a two-component curable polyurethane resin or polyester resin is used. The used dry laminating etc. are mentioned.

It is possible to directly print a decorative pattern or the like as described later on the surface of the sheet substrate 2 or directly apply an adhesive for bonding the protective sheet 3 to the sheet base. When it is necessary to make the adhesive strength with the material 2 stronger, the surface of the sheet substrate 2 may be subjected to an easy-adhesion treatment such as a corona discharge treatment or a plasma treatment, or an easy-adhesion layer (primer layer or (Also referred to as an anchor layer). 1 to 3 show an example in which an easy-adhesion layer 5 is provided on the back surface side of the sheet substrate 2.

For the formation of the easy-adhesion layer 5, acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester,
Polyurethane, chlorinated polypropylene, chlorinated polyethylene and the like are used, and chlorinated polypropylene is particularly desirable.

Acrylic resins for forming the easy-adhesion layer 5 include poly (methyl meth) acrylate, ethyl poly (meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, and the like. Methyl (meth) acrylate / butyl (meth) acrylate copolymer, ethyl (meth) acrylate / butyl (meth) acrylate copolymer, ethylene / methyl (meth) acrylate copolymer,
An acrylic resin containing a homo- or copolymer containing a (meth) acrylic ester such as a styrene-methyl (meth) acrylate copolymer (here, (meth)
Acrylic means acrylic or methacrylic. ).

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

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

As a method of decorating the decorative sheet 1 of the present invention, there is a method of adding a dye or a pigment to the sheet base 2 to give a transparent or opaque color. Examples of pigments to be added include inorganic pigments such as titanium white, zinc white, red iron oxide, vermilion, ultramarine blue, cobalt blue, titanium yellow, graphite, carbon black, isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, and phthalocyanine. Organic pigments (or dyes) such as Blue, Indaslen Blue 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 And the like. These can be added and dispersed in the resin constituting the sheet base material 2 as powder or scaly foil pieces.

As another method of decorating the decorative sheet 1 of the present invention, there is a method of providing a decorative layer 4 between the sheet substrate 2 and the protective sheet 3 as shown in FIG. The decorative layer 4 can be formed by printing or laminating a metal thin film. As a printing method, gravure printing, intaglio printing, offset printing, letterpress printing, flexographic printing, silk screen printing, electrostatic printing, inkjet printing, etc., or separately forming a pattern on a release sheet once And a transfer printing method using the obtained transfer sheet.

When the decorative layer 4 is formed by printing, various printing inks can be used, and a composition comprising a colorant, an extender pigment, a binder, a curing agent, an additive, a solvent, and the like. Can be used. There is no particular limitation on the binder, and chlorinated polyethylene, chlorinated polypropylene, vinyl acetate, a vinyl chloride-vinyl acetate copolymer, a thermoplastic resin such as a cellulosic resin, a normal temperature such as polyurethane, etc. A usual resin such as a curable resin or an ionizing radiation curable resin such as an acrylic resin can be used. In the case of printing directly on the sheet substrate 2, it is preferable to use chlorinated polyolefin polyurethane or the like as a binder from the viewpoint of adhesiveness.
If an appropriate binder is selected, sufficient adhesiveness can be obtained even if another binder is used.

When the decorative layer 4 is formed of a metal thin film, a method of laminating the metal thin film on the entire surface or partially in a pattern may be used. This metal thin film can be formed by using a metal such as aluminum, chromium, gold, silver, or copper by a method such as vacuum evaporation or sputtering, and can be formed into a partially patterned metal thin film by an etching method or the like.

The patterns of the decorative layer 4 include a wood pattern, a stone pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol,
Examples include line drawings and various abstract patterns, but decorations such as solid printing on the entire surface may also be used. The decorative layer 4 is not limited to the case provided between the sheet base 2 and the protective sheet 3 as shown in FIG. 1, and the back side of the sheet base 2 (see FIG. In the example shown, it can be provided on the upper surface of the easy adhesion layer 5). As shown in FIG. 2, the sheet base 2 may be composed of two (or more) olefin-based resin sheets 2a, 2b, and the decorative layer 4 may be provided between the sheets 2a, 2b.

As still another method of decorating the decorative sheet 1 of the present invention, there is a method of forming an uneven pattern 6 on the surface of the protective sheet 3 as shown in FIG. In order to form the concavo-convex pattern 6, for example, there is an embossing method by heating and pressing. In this embossing method, the surface of the protective sheet 3 is heated and softened, and the surface is pressed with an embossing plate to form the concavo-convex pattern on the embossing plate. Is formed, cooled, and fixed, and a known single-wafer or rotary embossing machine can be used. Also, the uneven pattern 6 can be formed by hairline processing.

Examples of the concavo-convex pattern 6 include a wood-grain board conduit groove, a stone board surface concavo-convex (granite cleavage plane, etc.), a cloth surface texture, a satin finish, a grain, a hairline, a linear groove, and the like.

Further, the coloring layer 7 may be formed on the recessed portion of the above-mentioned concavo-convex pattern 6 by a wiping method. As the wiping method, the entire surface including the recessed portion may be formed by a doctor blade coating method or a knife coating method. After applying the colorant ink to the surface, the colorant ink is removed from the surface other than the recessed portion, so that the coloring layer 7 can be formed only in the recessed portion. Examples of the colorant ink for forming the color layer 7 include color pigments such as organic pigments, inorganic pigments, and brilliant pigments, and binder resins such as thermoplastic resins, thermosetting resins, and ionizing radiation-curable resins. , A vehicle, and an emulsion-type water-based ink.

The surface of the protective sheet 3 on which the irregular pattern 6 has been formed can be covered with a surface protective layer 8 if necessary. The surface protective layer 8 is preferably formed of a chlorinated polyolefin, a two-component curable polyurethane, or an ionizing radiation curable resin.

The ionizing radiation-curable resin is specifically curable by ionizing radiation by appropriately mixing a prepolymer, polymer and / or monomer having a polymerizable unsaturated bond or a cationically polymerizable functional group in a molecule. A suitable composition is preferably used. Here, the ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually an ultraviolet ray (UV) or an electron beam (EB) is used.

The ionizing radiation-curable resin forming the cured coating film is more specifically a (meth) acryloyl group in the molecule.
It comprises a radically polymerizable unsaturated group such as (meth) acryloyloxy, a cationic polymerizable functional group such as an epoxy group, or a monomer having two or more thiol groups, a prepolymer or a polymer. These monomers, prepolymers or polymers may be used alone or as a mixture of two or more. Here, for example, a (meth) acryloyl group is used to mean an acryloyl group or a methacryloyl group.

Examples of the prepolymer having a radical polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth)
Acrylate, melamine (meth) acrylate, triazine (meth) acrylate and the like can be used, and those having a molecular weight of about 250 to 10,000 are usually used. As the polymer having a radical polymerizable unsaturated group, a polymer having a degree of polymerization of the above prepolymer of about 10,000 or more is used.

Examples of the prepolymer having a cationically polymerizable functional group include prepolymers such as epoxy resins such as bisphenol type epoxy resin and novolak type epoxy resin, and vinyl ether resins such as aliphatic vinyl ether and aromatic vinyl ether. Is mentioned.

Examples of the monomer having a radical polymerizable unsaturated group include monofunctional monomers such as (meth) acrylate compounds, for example, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenoxyethyl (meth) acrylate. ) Acrylates and polyfunctional monomers such as diethylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

As the group monomer having a cationically polymerizable function, the above-mentioned prepolymeric monomer having a cationically polymerizable functional group can be used. Examples of the monomer having a thiol group include trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate.

When curing with ultraviolet light or visible light, a photopolymerization initiator is added to the ionizing radiation-curable resin. In the case of a resin system having a radical polymerizable unsaturated group,
As the photopolymerization initiator, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether and the like can be used alone or as a mixture. In the case of a resin system having a cationically polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metaceron compound, a benzoin sulfonic acid ester, or the like is used alone or as a mixture as a photopolymerization initiator. be able to. The addition amount of these photopolymerization initiators is about 0.1 to 10 parts by weight based on 100 parts by weight of the ionizing radiation-curable resin.

When the surface protective layer 8 is matted, a matting agent (light diffusing agent) is added. As a matting agent,
Calcium carbonate, silica, alumina, barium sulfate, urethane resin beads, polycarbonate resin beads, etc.
Fine particles having a particle size of about 1 to 30 μm are effective. The thickness of the surface protective layer 8 is preferably about 1 to 100 μm.

In the present invention, each of the above-described decorating methods can be employed not only in one kind but also in an appropriate combination of two or more kinds.

In the decorative sheet 1 of the present invention, in order to impart better weather resistance (light) to the resin, if necessary, an ultraviolet absorber and a light stabilizer may be added to the sheet substrate 2 and the protective sheet 3. Can be added.

Organic substances such as benzotriazole, benzophenone, salicylic acid ester and the like,
Alternatively, inorganic substances such as zinc oxide, cerium oxide, and titanium oxide having a diameter of 0.2 μm or less can be used.
As a light stabilizer, bis- (2,2,6,6-tetramethyl-4-
Hindered amine radical scavengers such as piperidinyl) sebacate and radical scavengers such as piperidine radical scavengers can be used. Both the ultraviolet absorber and the light stabilizer are usually added so as to be about 0.5 to 10% by weight, but it is generally preferable to use the ultraviolet absorber and the light stabilizer together.

In order to impart flame retardancy to the decorative sheet 1, a flame retardant can be added to the sheet substrate 2 or the protective sheet 3. Powders such as aluminum hydroxide and magnesium hydroxide are used as the flame retardant. The addition amount of the flame retardant is 1 to 100 parts by weight of the olefin resin.
About 0 to 150 parts by weight is preferable.

Further, a cellular (sponge-like) foam may be used as the sheet substrate 2. In this case, a foaming agent is added to the resin constituting the sheet substrate 2 and heated to form the foaming agent. Foam. Examples of the foaming agent include azodicarbonamide, azobisisobutyronitrile, N-N'-dinitrosopentamethylenetetramine, oxybisbenzenesulfonylhydrazide, sodium hydrogencarbonate, potassium hydrogencarbonate, and the like, or acrylonitrile. A microcapsule type in which a heat-expandable gas such as hexane or isobutane is sealed in a resin spherical shell such as The addition amount of the foaming agent is about 1 to 10 parts by weight based on 100 parts by weight of the base resin constituting the sheet base 2.

The decorative sheet 1 of the present invention can be used by being laminated on another adherend (backing material). FIG. 4 shows a case where the adherend is a three-dimensional article 9, and FIG. 5 shows a case where the adherend is a flat or curved plate 10. The lamination of the decorative sheet 1 and the adherend can be performed without using an adhesive if the decorative sheet 1 itself can be bonded to the adherend (by heat fusion or the like). If does not adhere to the adherend,
Laminate using a suitable adhesive. The decorative sheet 1 of the present invention
May be used to obtain a final product such as a decorative material by laminating on an adherend, or may be laminated on an adherend in order to reinforce the mechanical strength of the decorative sheet 1 or to provide concealment. is there.

The object to be adhered is a molded article having a three-dimensional shape as shown in FIG. 4, a plate material having a flat or curved shape as shown in FIG. 5, or an article having various shapes such as a sheet (or film). Become. Materials used for any of plate materials, three-dimensionally shaped articles, and sheets (films) include wood veneers,
Wood plywood, particle board, medium density fiberboard (MD
F) or other wood board, wood fiber board such as wood fiber board, metal such as iron or aluminum, acrylic, polyester, polystyrene, polyolefin, ABS, phenol resin, polyvinyl chloride, cellulose resin, rubber or other resin, exclusively board material Materials used as three-dimensional articles include ceramics such as glass and ceramics, non-cement ceramic materials such as gypsum, and materials exclusively used as sheets (or films) include paper such as high-quality paper and Japanese paper. And nonwoven fabrics or woven fabrics made of fibers of carbon, asbestos, potassium titanate, glass, synthetic resin and the like.

The method of laminating these various adherends is as follows.
For example, as described in Japanese Patent Publication No. 50-19132, Japanese Patent Publication No. 43-27488, and the like, a method of laminating a plate-like base material by pressing with a pressure roller with an adhesive therebetween, Insert between the male and female molds of injection molding,
Close both molds, inject and inject molten resin from the male mold gate, cool, and simultaneously mold and mold a resin molded product. No. 45768, Japanese Patent Publication No. 60-
As described in Japanese Patent No. 58014, etc., a decorative sheet is opposed to or placed on the surface of a molded article with an adhesive therebetween.
A so-called vacuum press lamination method in which a decorative sheet is laminated on the surface of a molded product by a pressure difference caused by vacuum suction from the molded product side,
As described in JP-B-61-5895, JP-B-3-2666, etc., a decorative sheet is supplied in the longitudinal direction of a columnar substrate such as a column or a polygonal column via an adhesive layer therebetween. In addition, a so-called lapping method or the like is used in which decorative sheets are successively pressed and laminated on a plurality of side surfaces constituting a columnar body by a plurality of rollers having different directions. In order to obtain a three-dimensional article having the decorative sheet 1 of the present invention as a surface decorative layer, the above-mentioned lapping method, simultaneous injection molding laminating method, vacuum forming simultaneous laminating method and the like are preferable.

Further, the decorative sheet 1 is laminated on the plate material 10 via an adhesive, and then on the surface of the plate material 10 opposite to the surface on which the decorative sheet 1 is laminated, on the interface between the decorative sheet 1 and the plate-like base material. After arriving, cutting the groove 11 having a V-shaped or U-shaped cross section, and then applying an adhesive layer in the groove 11,
As shown in FIG. 6, an uneven three-dimensional article having the decorative sheet 1 of the present invention as a surface decorative layer can also be obtained by a so-called V-cut processing method or the like in which the decorative sheet is bent in the groove 11 to form a box or a column. . In the decorative sheet 1 of the present invention, even when the V-cut processing as shown in FIG. 6 is performed, there is no fear that the protective sheet 3 is cracked or whitened.

The decorative sheet 1 of the present invention can be laminated on various adherends, subjected to a predetermined molding process and the like, and used for various decorative purposes. For example, interior decoration of buildings such as walls, ceilings and floors, surface decoration of fittings such as window frames, doors, handrails, surface decoration of cabinets of furniture or light electric / OA equipment, vehicle interiors of automobiles and trains, aircraft interiors, windows Uses such as glass cosmetics can be mentioned.

[0055]

Embodiments of the present invention will be described below in detail.

Example 1 60 parts by weight of high-density polyethylene, 30 parts by weight of a thermoplastic elastomer (styrene-butadiene rubber), 10 parts by weight of an inorganic filler (calcium carbonate), and trace amounts of a coloring pigment, a heat stabilizer and a light stabilizer were added. The blended composition was formed into a film by a calendar method to obtain a sheet substrate having a thickness of 100 μm. After performing corona treatment on the front and back surfaces of the sheet substrate, an easy-adhesion layer is formed on the front surface side with a urethane-based primer (AFS, manufactured by Showa Ink), and a grain pattern print (manufactured by Showa Ink:
X ink). On the other hand, an easy-adhesion layer was formed on the back surface of the sheet substrate using a urethane-based primer (AFS, manufactured by Showa Ink).

On the other hand, 100 parts by weight of a graft copolymer of methyl methacrylate and butyl acrylate was added to a matting agent 1
A transparent matte acrylic resin sheet having a thickness of 50 μm was obtained by a T-die method using a mixture containing 0 parts by weight, polyethylene glycol parts by weight, a processing aid, and a trace amount of a light absorber. This sheet has a breaking elongation at 25 ° C. of 150%.
And the 60 ° specular gloss was 20.

The transparent matte acrylic resin sheet is heat-laminated as a protective sheet on the printed surface of the sheet substrate on which the wood pattern is printed, and the protective sheet surface is further embossed to form an uneven pattern of the wood conduit. did. In addition, wiping ink (manufactured by Showa Ink: PW-1)
After filling 2), a matte overcoat (OP-A12 made by Showa Ink) was applied on the uneven pattern to obtain a decorative sheet.

The sheet base side (back side) of this decorative sheet
Is bonded and laminated on a plywood having a thickness of 10 mm using an adhesive of an ethylene / vinyl acetate copolymer emulsion, and a cross section reaching the interface between the plywood and the decorative sheet on the surface of the plywood opposite to the decorative sheet side. A V-shaped groove was cut, an adhesive of an ethylene / vinyl acetate copolymer emulsion was applied to the groove, and the plywood was bent so as to close the groove (V-cut processing). The ambient temperature during processing was 10 ° C. No cracks, breaks, or whitening were observed in the decorative sheet after the V-cut processing. In addition, using an ethylene-vinyl acetate copolymer emulsion adhesive, lapping is performed by a normal lapping laminating machine so that the base sheet side of the decorative sheet and the R surface and the L90 surface of the irregular cross-section are bonded together. When the lapping suitability was tested, there was no problem at all.

Comparative Example 1 Instead of the acrylic resin emulsion sheet in Example 1, a polymethyl methacrylate sheet (2
A decorative sheet was obtained by performing the same processing as in Example 1 except that a breaking elongation at 5 ° C. of 90%) was used as a protective sheet. When a V-cut processing test similar to that of Example 1 was performed using the obtained decorative sheet, cracks and breaks were found in the decorative sheet at the bent portions. When the lapping suitability was tested in the same manner as in Example 1, cracks occurred in the sheet.

Example 2 Corona discharge treatment is applied to the front side and primer treatment is applied to the back side. The thickness is 100 μt (a polyethylene sheet substrate manufactured by Tatsuno Chemical: TKPS ADIS).
After solid pattern printing on the surface side of
An acrylic resin film (HBE-028, manufactured by Mitsubishi Rayon Co., Ltd., HBE-028, elongation at break at 25 ° C .: 130%) having a thickness of 75 μm on the printing surface was embossed at a pressure of 20 kg / cm.
^2. Laminated at a drum temperature of 120 ° C. and embossed to obtain a decorative sheet. When the same V-cut processing test as in Example 1 was performed using this decorative sheet,
After the V-cut processing, the decorative sheet has cracks and breaks,
No whitening was observed. Further, when a test for suitability for wrapping of this decorative sheet was performed, no problem was found.

Comparative Example 2 A decorative sheet was obtained in the same manner as in Example 2 except that an acrylic resin film having an elongation at break of 90% (manufactured by Mitsubishi Rayon: HBS-027, thickness 75 μm) was used. When a V-cut processing test similar to that of Example 1 was performed using this decorative sheet, cracks and breaks were found in the decorative sheet at the bent portions. Further, when a lapping suitability test was performed, a crack was generated in the sheet.

[0063]

As described above, the decorative sheet of the present invention is a protective sheet comprising an acrylic thermoplastic elastomer sheet having an elongation at break at 25 ° C. of 100% or more on an olefin resin sheet substrate. According to the decorative sheet of the present invention, the disadvantages of the conventional decorative sheet can be eliminated, and even if the decorative material on which the decorative sheet is laminated is subjected to V-cut processing, cracks and breaks are generated in the protective sheet. It has excellent characteristics that there is no risk of occurrence or whitening. When the elongation at break at 25 ° C. of the protective sheet made of an acrylic thermoplastic elastomer sheet is 130% or more, the lapping suitability is further improved.

[Brief description of the drawings]

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

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

FIG. 3 is a longitudinal sectional view of still another embodiment of the decorative sheet of the present invention.

FIG. 4 is a longitudinal sectional view of a three-dimensional article in which the decorative sheet of the present invention is laminated on an adherend.

FIG. 5 is a longitudinal sectional view of a plate-like body in which the decorative sheet of the present invention is laminated on an adherend.

6 is a longitudinal sectional view showing a state where the plate-shaped body of FIG. 5 is bent.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Sheet base material 3 Protective sheet 4 Decorative layer 5 Easy adhesion layer 6 Uneven pattern 7 Coloring layer 8 Surface protective layer

Claims (11)

[Claims] 1. A decorative sheet comprising an acrylic resin protective sheet laminated on an olefin resin sheet substrate, wherein the protective sheet has an elongation at break at 25 ° C. of 1
A sheet of acrylic thermoplastic elastomer with a tensile elongation of more than 00% (in the earlier application, the tensile elongation was used, but the elongation at break was set to match claim 2. Is the tensile elongation equal to the elongation at break?) A decorative sheet, characterized in that: 2. The decorative sheet according to claim 1, wherein the acrylic thermoplastic elastomer sheet has an elongation at break at 25 ° C. of 130% or more. 3. The acrylic thermoplastic elastomer constituting the protective sheet is a graft copolymer of butyl acrylate and / or butyl methacrylate and methyl acrylate and / or methyl methacrylate. 2. The decorative sheet according to 2. 4. The ratio of butyl acrylate and / or butyl methacrylate to methyl acrylate and / or methyl methacrylate in the graft copolymer is as follows:
Butyl acrylate and / or butyl methacrylate 1
The decorative sheet according to claim 3, wherein the content is 0 to 90 parts by weight, and 90 to 10 parts by weight of methyl acrylate and / or methyl methacrylate. 5. The decorative sheet according to claim 1, wherein the protective sheet has a 60 ° specular gloss of 85 or less. 6. The decorative sheet according to claim 1, wherein the sheet base comprises an olefin resin sheet containing high-density polyethylene, a thermoplastic elastomer, and an inorganic filler. 7. The decorative sheet according to claim 1, wherein a printed layer is formed on the sheet base material, and a protective sheet is laminated on the printed layer forming surface of the sheet base material. 8. The decorative sheet according to claim 1, wherein an easy adhesion treatment is applied to the back surface of the sheet substrate. 9. The decorative sheet according to claim 1, wherein the surface of the protective sheet is embossed. 10. The decorative sheet according to claim 1, wherein a colored layer is provided in the embossed concave portion. 11. The decorative sheet according to claim 1, wherein a surface protective layer is provided on the surface of the protective sheet.