JPH1045926A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a decorative sheet which has weather resistance, heat resistance and transparency equivalent to those of a decorative sheet made of PVC through it is made of an olefin resin by forming a specified resin layer on a specified colored base sheet. SOLUTION: Desirably, an electron-beam-curing resin layer, more desirably an ionizing-radiation-curing resin layer 3 (e.g. a resin layer made from a mixture of a monofunctional monomer of urethane acrylate with an acrylic copolymer) containing an ultraviolet absorber (e.g. benzotriazole ultraviolet absorber) and desirably having a thickness of 10-100μm is formed directly or through another layer (e.g. pattern layer 2) on a colored base sheet 1 made from a material mainly consisting of high-density PE desirably having a specific gravity of 0.94-0.95, a thermoplastic elastomer (e.g. styrene/butadiene rubber), a colorant (e.g. red iron oxide and carbon black) and an inorganic filler (e.g. CaCO3 ) and desirably having a thickness of 50-300μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet, and more particularly, to a decorative sheet suitable for use in interiors of buildings, surface decoration of fittings, interior of axles, and the like.

[0002]

2. Description of the Related Art Conventionally, as a decorative sheet used for the above-mentioned applications, a polyvinyl chloride film is used, and decorative sheets formed by printing, embossing or the like (Japanese Patent Publication No. 28-5036, Japanese Patent Publication No. 58-14312) has been used. In recent years, as an alternative to this, a decorative sheet using the following resin has been proposed.

(I) A decorative sheet using a polyolefin film such as polyethylene or polypropylene (see Japanese Patent Application Laid-Open No. 54-62255).

(II) As an improved specification of the above (I), a polyolefin resin having a polar functional group graft-polymerized is
A mixture of an olefin-based thermoplastic elastomer (Japanese Unexamined Patent Publication (Kokai) No. Hei 6-21080, Japanese Unexamined Patent Publication No. Hei 4-50438)
No. 4) or a decorative sheet using a mixture of a polyolefin resin and a polyurethane resin using a compatibilizer (Japanese Patent Application Laid-Open No. 7-26038).

[0005]

However, the decorative sheets using the above-mentioned polyolefin-based resins which have been conventionally proposed are not always satisfactory for the following reasons. That is, for interior and exterior of buildings, fittings, for surface decoration of furniture, etc., surface decorative sheet used for vehicle interior, etc.,
Usually, the following functions (1) to (10) are required, and the conventionally proposed ones do not always satisfy these requirements.

(1) Thermoformability comparable to polyvinyl chloride: It is required that deterioration of mechanical properties such as a decrease in strength does not occur with heating → cooling.

(2) Creep Deformability: In many cases, a constant load is applied to exterior and interior materials by fittings and furniture for a long time. When creep deformation occurs, the loaded portion is turned up or peeled off. Therefore, it is required that the material does not cause creep deformation as much as possible.

(3) Cold bending strength: When bending such as V-cutting is performed in cold weather, if stress relaxation is insufficient, whitening, cracking, breakage, etc. are likely to occur in the bent portion. Desired.

(4) Organic solvent resistance: It is required to prevent the decorative sheet from swelling and deforming due to a solvent in an adhesive for bonding the decorative sheet and the adherend. The same applies when a decorative sheet having a multilayer structure is obtained.

(5) Elongation at break and impact strength: These characteristics are required to prevent cracks in the bent portion during V-cut processing.

(6) Suitability for bending: Having an appropriate bending elastic modulus. This is required to ensure that the decorative sheet can follow the bent portion sufficiently.

(7) Transparency: In the case of a decorative sheet comprising a top film / pattern / base film, transparency is required for the top film.

(8) Suitability for embossing: It is required that whitening and turbidity due to recrystallization do not occur even when heating and cooling accompanying embossing and the like are applied.

(9) Easy adhesion: excellent adhesion is required.

(10) Weather resistance: It is required to have excellent weather resistance.

The conventional decorative sheet of the above specification (I) is as follows:
The mass production is difficult industrially, and the polyolefin resin has a high degree of crystallinity. For example, the conditions (1) and (5) to (10) are sufficiently satisfied. I haven't. In addition, since the conventional type (II) has a mixture of an olefin-based thermoplastic elastomer,
The conditions (1), (5), and (6) are improved, and thermoformability, embossability, etc. are improved, but heat resistance, weather resistance,
And the transparency is insufficient.

An object of the present invention is to solve the above-mentioned disadvantages of the conventional decorative sheet using an olefin resin, and specifically, to use a polyvinyl chloride resin while using the olefin resin. An object of the present invention is to provide a decorative sheet having the same heat resistance, weather resistance, and transparency as the decorative sheet used.

[0018]

In order to solve the above-mentioned problems, the decorative sheet of the present invention comprises a main material composed of a material containing high-density polyethylene, a thermoplastic elastomer, a colorant, and an inorganic filler. On the colored base sheet, an ionizing radiation-curable resin layer is formed directly or via another layer,
If necessary, a pattern layer is provided on the colored base sheet and / or the ionizing radiation-curable resin layer.

In the base sheet used in the decorative sheet of the present invention, the polyolefin as a compounding base is
High density polyethylene (H
DPE). Table 1 below shows the degree of satisfaction of the high-density polyethylene under the conditions (1) to (10) required for the decorative sheet.

[0020]

[Table 1] * 1: During embossing, due to crystallization improvement by cooling,
Elongation decrease. * 2: High yield point stress. * 3: The curvature modulus is too high. * 4: White turbidity due to fine crystal grains.

Therefore, by adding a thermoplastic elastomer, crystallization was inhibited and stress was absorbed and relaxed. The results are shown in Table 2 below.

[0022]

[Table 2]

As shown in Table 2, it can be seen that each condition has changed. As a result, the conditions (1), (5), and (6) were satisfied, but the creep resistance of the item (2) was somewhat reduced. In order to improve the creep resistance, an inorganic fine particle extender was further added. The results are shown in Table 3 below.

[0024]

[Table 3]

As shown in Table 3, it can be seen that each condition has changed. As a result, it was confirmed that the creep deformation resistance was also good, and that a material satisfying the performances (1) to (6) and (9) as the substrate sheet was obtained (for (7),
It is not required for colored substrate sheets. ).

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is based on the above experimental results. Basically, the decorative sheet according to the present invention comprises a high-density polyethylene, a thermoplastic elastomer, a coloring agent, and an inorganic filler as main ingredients. An ionizing radiation-curable resin layer is formed directly or via another layer on a colored substrate sheet manufactured using the material containing the ion-exchange radiation-curable resin layer. It is provided with a pattern layer.

Colored base sheet : The high-density polyethylene contained in the colored base sheet of the decorative sheet of the present invention includes:
Preferably, a polyethylene having a specific gravity of 0.94 to 0.95, a high crystallinity obtained by a low-pressure method, and a high-density polyethylene which is a polymer having a small number of branched structures is used.

As the thermoplastic elastomer in the present invention, diene rubber, hydrogenated diene rubber, olefin elastomer and the like are used. The hydrogenated diene-based rubber is obtained by adding a hydrogen atom to at least a part of the double bond of the diene-based rubber molecule, and suppresses the crystallization of the polyolefin-based resin (high-density polyethylene in the present invention). Up. 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. The olefin elastomer is an elastic copolymer obtained by adding at least one kind of polyene copolymerizable with two or more kinds of olefins. As the olefin, ethylene, propylene, α-olefin, or the like is used. 1,4 hexadiene, cyclic dienes, norbornene and the like are used. Preferred olefin copolymer rubbers include, for example, elastic copolymers containing an olefin as a main component, such as ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene rubber, and ethylene-butadiene copolymer rubber.

In addition, EPDM is used for polyolefin resin.
(Ethylene propylene diene methylene linkage) crosslinked and polymerized: polyolefin resin mixed with EPR (ethylene propylene rubber) and polymerized: amorphous polyolefin resin:

The addition amount of the thermoplastic elastomer is as follows:
It is 10 to 60% by weight, preferably about 30% by weight in the base sheet. If it is less than 10% by weight, the change in elongation at a constant load becomes too steep, and the elongation at break and impact resistance decrease. If it is more than 60% by weight, transparency, weather resistance and creep resistance are increased. A drop occurs.

As the inorganic filler in the present invention, powders such as calcium carbonate, barium sulfate, clay and talc are used. The addition amount is 5 to 60 in the base sheet.
%, Preferably about 30% by weight. If the amount is less than 5% by weight, the creep deformation resistance and the easy adhesion decrease, and if it is more than 60% by weight, the elongation at break and the impact resistance decrease.

The coloring agent in the present invention is for giving the base sheet the necessary color as a decorative sheet,
Titanium white, zinc indigo, red pattern, vermilion, ultramarine, cobalt blue,
Inorganic pigments such as titanium yellow and carbon black, organic pigments such as isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R and phthalocyanine blue, or dyes, metal pigments such as aluminum and brass, titanium dioxide-coated mica, basic carbonate Pearlescent pigments made of foil powder such as zinc are used. The coloring may be either transparent coloring or opaque (concealing) coloring, but opaque coloring is generally preferred in order to cover the adherend.

Further, if necessary, a heat stabilizer, a flame retardant, a radical scavenger and the like are added. The heat stabilizer is a known one such as a phenol type, a sulfite type, a phenylalkane type, a phosphite type, and an amine type, and is used for further improving the prevention of deterioration such as thermal discoloration during thermal processing.

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

A blend of these materials is formed into a film by a conventional method such as a calendering method to obtain an opaque colored base sheet. As described above, the obtained base sheet is required for the base sheet of the decorative sheet according to the above (1) to (10).
The conditions of (6), (9) and (10) are satisfied. The thickness of the base sheet is about 50 to 300 μm, preferably 100 μm.
m.

Easy adhesion layer : The surface of the base sheet is preferably subjected to an easy adhesion treatment such as application of an easy adhesion resin, corona discharge treatment, plasma treatment and the like. In this specification,
The term "easy adhesion" includes not only the application of an easily adhesive resin but also the case where an easily adhesive surface obtained by various surface treatments such as corona discharge treatment, plasma treatment, and solvent treatment is applied.

Acrylic, vinyl chloride-vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, chlorinated polyethylene and the like can be used as the easy-adhesion layer (also referred to as a primer layer or an anchor layer). desirable.

Acrylics that can be used for the easily adhesive layer include:
Methyl poly (meth) acrylate, ethyl poly (meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, methyl (meth) acrylate
(Meth) butyl acrylate copolymer, ethyl (meth) acrylate / butyl (meth) acrylate copolymer, ethylene / methyl (meth) acrylate copolymer, styrene
Acrylic resin composed of a homo- or copolymer containing (meth) acrylate such as (meth) methyl acrylate copolymer (however, (meth) acryl means acryl or methacryl) is used. Can be

Examples of the polyurethane that can be used for the easy-adhesion layer include a polyurethane having a polyol (polyhydric alcohol) as a main component and an isocyanate as a cross-linking agent (curing agent). Those having the above hydroxyl groups include, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol and the like. Further, as the isocyanate,
Polyvalent isocyanate having two or more isocyanate groups in the molecule, aromatic isocyanate such as 4,4-diphenylmethane diisocyanate, or aliphatic (such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate) Or alicyclic) isocyanate.

Ionizing radiation-curable resin layer : The ionizing radiation-curable resin is provided for imparting stain resistance and scratch resistance, or for imparting embossability, heat resistance and thermoplasticity. The resin usable for the ionizing radiation-curable resin is specifically curable by ionizing radiation obtained by appropriately mixing a prepolymer, a polymer and / or a monomer having a polymerizable unsaturated condensation or a cationic polymerizable functional group in a molecule. A 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 thickness of the ionizing radiation-curable resin layer is 10 μm.
１００100 μm is preferred. Further, a UV absorber may be added for imparting weather resistance to the ionizing radiation-curable resin layer. If a UV absorber has been added, it is cured by irradiation with an electron beam.

The ionizing radiation-curable resin forming the hard coating is, specifically, a (meth) acryloyl group in the molecule.
Examples include a monomer, a prepolymer, or a polymer having two or more radically polymerizable unsaturated groups such as a (meth) acryloyloxy group, a cationically polymerizable functional group such as an epoxy group, or a thiol. These monomers, prepolymers or polymers can be used alone or as a mixture of two or more. Here, for example, the (meth) acryloyl group is used in the meaning of an acryloyl group or a methacryloyl group.

A monofunctional monomer of urethane acrylate is used to impart embossing property to the ionizing radiation-curable resin layer, and an acrylic copolymer is mixed to impart thermoplasticity. The mixing ratio of the urethane acrylate and the acrylic copolymer is preferably from 2: 8 to 8: 2. However, the urethane acrylate ratio is preferably 4 or more in consideration of bending resistance, and is preferably 6 or less in consideration of stain resistance. In this case, it is desirable that the molecular weight of the urethane acrylate is 100 to 300, and the molecular weight of the acrylic copolymer is 10,000 to 30,000.

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. A molecular weight of about 250 to 10,000 is usually used. As the polymer having a radical polymerizable unsaturated group, a polymer having a degree of polymerization of about 10,000 or more is used.

Examples of the prepolymer having a cationically polymerizable functional group include prepolymers of epoxy resins such as bisphenol type epoxy resins and novolak type epoxy resins, and vinyl ether resins such as aliphatic vinyl ethers and aromatic vinyl ethers. No.

Examples of the monomer having a radical polymerizable unsaturated group include monofunctional monomers of a (meth) acrylate compound, for example, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl ( (Meth) acrylate and the like.

Examples of the polyfunctional monomer having a radical polymerizable unsaturated group include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane ethylene oxide. Tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

As examples of the monomer having a cationically polymerizable functional group, 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, dipentaerythritol tetrathioglycolate, and the like.

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 in combination.
In the case of a resin having a cationically polymerizable functional group,
As the photopolymerization initiator, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metaceron compound, a benzoinsulfonic acid ester, or the like can be used alone or as a mixture.

The addition amount of these photopolymerization initiators is based on 100% by weight of the ionizing radiation-curable resin.
It is about 0.1 to 10% by weight.

Spherical particles may be mixed and dispersed in the ionizing radiation-curable resin for the purpose of further imparting scratch resistance. The material of the spherical particles only needs to be higher in hardness than the cross-linkable curable resin, and any of inorganic particles and organic resin particles can be used. In terms of abrasion resistance and hardness, inorganic particles are recommended. The difference in hardness between the spherical particles and the crosslinkable resin is measured by a method such as Mohs hardness or Vickers hardness,
For example, when expressed in Mohs hardness, 1 or more is preferable.

Specific examples of the material of the spherical particles include inorganic particles such as α-alumina, silica, chromium oxide, iron oxide, diamond, and graphite, and organic resin particles such as synthetic resin beads such as cross-linked acryl. . Particularly preferred granular particles include spherical α-alumina because they have very high hardness and a large effect on wear resistance, and spherical particles are relatively easily obtained.

The spherical particles need only be surrounded by a smooth curved surface such as a true sphere, a spheroid obtained by flattening a sphere, and a shape close to the true sphere or spheroid. The spherical particles preferably have no projections, corners, valleys, or depressions on the particle surface, and have no so-called cutting edge. Spherical particles greatly improve the abrasion resistance of the surface resin layer itself as compared with amorphous particles of the same material, and do not wear the coating device and other objects that come into contact with the coated film after curing. Is not worn, and the transparency of the coating film is also increased. When there is no cutting edge, the effect is particularly large.

The following method can be used for embossing and wiping the ionizing radiation-curable resin layer.
Filling at least the concave portion of the roll intaglio with the ionizing radiation-curable resin and contacting the resin with a substrate sheet, and irradiating the resin with ionizing radiation while being held between the substrate sheet and the roll intaglio. The resin is cured to form a base sheet having an uneven pattern, and the base sheet is wiped to fill the concave portions of the uneven pattern with a coloring ink.

In still another embossing process and a wiping process, an ionizing radiation-curable resin is filled into at least the concave portion of the roll intaglio, and the resin is brought into contact with the base sheet so that the resin is placed between the base sheet and the roll intaglio. Irradiating ionizing radiation in a state where it is held to form a sheet having a concave and convex pattern by semi-curing the resin, filling the concave portion of the concave and convex pattern with colored ink by wiping the sheet,
There is a method of completely irradiating the ionizing radiation-curable resin by irradiating the semi-cured uneven pattern with ionizing radiation again.

Pattern layer : The pattern layer can be formed on one or both of the substrate sheet and the ionizing radiation-curable resin layer. Pattern printing includes pattern printing,
An embossing process (heating press), an embossing process by a hairline process, or the like may be used. Further, the concave portion of the embossing process may be filled with a coloring ink by a known wiping method.

As the pattern printing, a pattern can be formed by ink or paint using a known printing method such as gravure printing, offset printing, silk screen printing, and transfer printing from a transfer sheet. As the pattern, wood grain pattern,
Stone patterns, cloth patterns, squeezed patterns, geometric figures, characters, symbols, or solids on the entire surface.

In the ink or paint, chlorinated polyolefin such as chlorinated polyethylene, chlorinated polypropylene, polyester, polyurethane,
Acrylic, vinyl acetate, vinyl chloride / vinyl acetate copolymer, cellulosic resin, or the like is used, and one kind or a mixture of two or more kinds is used. A material obtained by adding known pigments such as those listed above to this is used.

When printing directly on a substrate sheet, chlorinated polyolefin, polyurethane or the like is preferable as a binder resin in terms of adhesiveness. However, if an easy-adhesion primer is appropriately selected and a layer is formed, other binder resins can be used. Provides sufficient adhesion even when used.

As the embossing, the base sheet is heated and softened, pressurized and shaped with an embossing plate, and fixed by cooling. A known sheet-fed or rotary embossing machine is used. Examples of the uneven shape include a wood grain board conduit groove, a stone board surface unevenness (granite cleavage face, etc.), a cloth surface texture, a matte finish, a grain, a hairline, a linear groove, and the like. Further, the same coloring ink as described above can be used for the coloring ink which may be a mirror flat surface. However, from the viewpoint of abrasion resistance, it is preferable to use a two-component curable urethane resin as the binder resin.

Further, a metal thin film may be formed as a pattern layer by using a metal such as aluminum, chromium, gold, silver, copper or the like, and forming the metal thin film by a method such as vacuum deposition or 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.

Application of decorative sheet : FIG. 1 is a representative illustration of one embodiment of the layer structure of the decorative sheet 10 of the present invention described above, and is printed on the colored base film 1 as necessary. Is formed, and an ionizing radiation-curable resin layer 3 is formed thereon. Further, an uneven pattern 4 is formed on the ionizing radiation-curable resin layer 3 as necessary. May be.

FIG. 2 shows the decorative sheet 1 of the present invention shown in FIG.
0 shows a state where it is adhered to an adherend (backing material) 20. When the decorative sheet 10 itself does not adhere to the adherend 20, the decorative sheet 10 is laminated via a suitable easy-adhesion layer or an adhesive layer 5. When the decorative sheet 10 itself can be adhered to the adherend 20 (by heat fusion or the like), the easy-adhesion layer or the adhesive layer 5 may be omitted.

Examples of the adherend include flat materials of various materials, plate materials such as curved plates, sheets (or films), and various three-dimensional articles (molded products). For example, as shown in FIG.
The decorative sheet of the present invention comprising the ionizing radiation-curable resin layer 3 formed on the colored base film 1 and the pattern layer 2 formed on the ionizing radiation-curable resin layer 3 can be bonded.

As a material to be used as a plate material or a sheet (film) as an adherend, a single wood plate,
Wood plywood, particle board, medium density fiberboard (MD
F) such as wood board, wood fiber board and other water board, iron, aluminum and other metals, acrylic, polycarbonate, ethylene, vinyl acetate copolymer, ethylene vinyl acetate,
Polyester, polystyrene, polyolefin / AB
Resins such as S, phenolic resin, polyvinyl chloride, cellulosic resin, and rubber.

Materials used exclusively as plates or three-dimensional articles as adherends include ceramics such as glass and porcelain, cement such as ALC (foamed lightweight concrete), cement-based ceramic materials such as calcium silicate and gypsum. Is mentioned.

Materials used exclusively as sheets (or films) as adherends include paper such as high-quality paper and Japanese paper, non-woven fabric or woven fabric made of fibers such as carbon, asbestos, potassium titanate, glass and synthetic resin. Is mentioned.

As a method of laminating these various adherends,
For example, the following methods can be mentioned. That is, a method of laminating a plate-like substrate by pressing with a pressure roller via an adhesive layer therebetween, Japanese Patent Publication No. 50-19132, Japanese Patent Publication No. 43-27
No. 488, etc., a decorative sheet is inserted between the male and female molds for injection molding, the molds are closed, the molten resin is injected and filled from the male gate, and then cooled and the resin is cooled. A so-called simultaneous injection molding laminating method in which a decorative sheet is adhered and laminated on the surface of a molded article at the same time as molding, Japanese Patent Publication No. 56-45768, Japanese Patent Publication No. 60-58.
No. 014, etc., a decorative sheet is placed on the surface of a molded article facing or opposite to the molded article via an adhesive, and the decorative sheet is placed on the surface of the molded article by a pressure difference due to vacuum suction from the molded article side. Lamination, so-called vacuum press lamination method, JP-B-61-5895, JP-B-3-2666
As described in Japanese Patent Application Publication No. 2000-205, the columnar base material such as a cylinder, a polygonal column, and the like, while supplying a decorative sheet through an adhesive layer between the column, a plurality of rollers having different directions, the columnar body. A so-called lapping method in which decorative sheets are sequentially adhered to a plurality of side surfaces constituting the sheet by laminating under pressure, a so-called lapping method, Japanese Utility Model Publication No. 15-31122,
No. 972, etc., a decorative sheet is first laminated on a plate-like base material via an adhesive layer, and then the decorative sheet and the plate-like material are placed on the surface of the plate-like base material opposite to the decorative sheet. Cut a V-shaped or U-shaped groove reaching the interface with the base material, then apply an adhesive in the groove, and then bend the groove to form a box or columnar body A so-called V-cut or U-cut processing method may be used.

FIGS. 4 and 5 are explanatory diagrams showing the application of the decorative sheet of the present invention to an adherend to be subjected to the V-cut processing method. FIG. 4 shows that the decorative sheet 10 is attached to the adherend 22 via the adhesive layer 5.
2 shows a cross-sectional view of the adherend 22 in which the V-shaped groove 6 is cut in the adherend 22. FIG. FIG.
4 shows a state in which the bonded body of FIG. 4 is bent in the V-shaped groove of the adherend 22.

The decorative sheet of the present invention can be used for various applications by laminating on various adherends and subjecting it to a predetermined molding process. For example, interior decoration of buildings such as walls, ceilings and floors, surface decoration of fittings such as window frames, doors, and handrails, furniture or light electricity / O
It can be used for surface decoration of cabinets of equipment A, interior of vehicles such as automobiles and trains, interior of aircraft, makeup of window glass, and the like.

[0071]

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

Example 1 Based on 60% by weight of high-density polyethylene, 30% by weight of styrene-butadiene rubber as a thermoplastic elastomer, 10% by weight of calcium carbonate as an inorganic additive, and reddish and carbon as coloring pigments A film obtained by adding 5% by weight of black and blending 5% by weight of a heat stabilizer and a hindered amine radical scavenger was formed into a film having a thickness of 100 μm by a calendering method to produce an opaque colored base sheet.

The colored base sheet produced in the above process was subjected to corona discharge treatment for easy adhesion treatment, and an abstract pattern was printed thereon. Next, on the printing surface, 100 parts by weight of an electron beam-curable resin (manufactured by Dainippon Ink and Chemicals, Unidick S6-340) having a mixing ratio of a monofunctional monomer of urethane acrylate and an acrylic copolymer of 3: 2. Against
A mixture obtained by adding 3 parts by weight of a hindered amine radical scavenger and 2 parts by weight of a benzotriazole ultraviolet absorber was applied by a comma coat method at 50 μm and cured. Next, the electron beam-curable resin-coated surface was mirror-finished by hot embossing with a mirror roll.

The obtained decorative sheet of Example 1 was examined for bending resistance, stain resistance, and embossability (texture transferability, embossing fastness). The results are shown in Table 4 below.
Regarding the bending resistance, the presence or absence of cracks and breaks in the sheet at the time of V-cut was examined.

Comparative Example 1 A 100-μm-thick biaxially stretched isotactic polypropylene sheet having a draw ratio of 3 was used as the colored base sheet of Example 1 except that
An easy-to-adhesive treatment was performed in the same manner as in Example 1 to print an abstract pattern. A 100-μm-thick sheet of biaxially stretched isotactic polypropylene having a draw ratio of 3 times was subjected to corona treatment on the back side of the printed surface, and then laminated with an adhesive. Then, the back surface was mirror-finished by hot embossing with a mirror roll in the same manner as in Example 1;
Was manufactured. The obtained decorative sheet of Comparative Example 1 was examined for bending resistance, stain resistance, and embossability (texture transferability, embossing fastness). The results are shown in Table 4 below.

[0076]

[Table 4]

[Performance Evaluation Test] Example 1 and Comparative Example 1
Table 5 below shows the results of comparison of various physical properties of each decorative sheet based on the test methods described below.

1. Transparency The haze value is measured with a direct-reading haze meter manufactured by Toyo Seiki Co., Ltd. The measurement is performed on a single layer of the polyolefin resin sheet layer without decoration treatment.

2. Weather resistance Carbon arc light type sunshine weather meter up to 3
Irradiation up to 000 hours (water spray: 12 minutes / 1 hour)
It stops when the appearance change such as cracks, whitening, discoloration, etc. becomes significant (visual measurement). The sample after irradiation at a black panel temperature of 63 ° C. is visually evaluated.

3. Heat resistance Heat in an 80 ° C. atmosphere for 3 minutes, and visually check the discolored state before and after the heating.

4. Sheet crack / rupture during V-cut The base sheet side of the decorative sheet is bonded and laminated to a 10 mm thick Rawan plywood using an adhesive of ethylene-vinyl acetate copolymer emulsion, and the decorative sheet side of the plywood is On the opposite side, cut a V-shaped groove reaching the interface between the plywood and the adhesive layer, apply an ethylene-vinyl acetate copolymer emulsion adhesive in the groove, and close the groove. Then, the plywood is bent to be L-shaped (cross-section).
The ambient temperature during processing is 10 ° C.

5. Heated dimensional shrinkage rate The decorative sheet is heated in an atmosphere of 100 ° C. for 30 minutes, and the heated dimensional shrinkage rate (%) represented by the following formula (1) is measured in each of the longitudinal direction (MD) and the width direction (TD). I do.

[0083]

(Equation 1)

6. Adhesive force In order to measure the adhesive force of the decorative sheet, a tensile test is performed by a peeling test at 180 degrees. Specifically, width 10m
A sample of the decorative sheet cut to m is pulled in a direction perpendicular to the width direction and at a tensile speed of 50 mm / min at an ambient temperature of 20 ° C. so that the tensile direction of each layer is 180 °. Measure the tension.

7. Scratch resistance Rub back and forth on the surface of the sample 10 times with $ 0000 steel wool.

[0086]

[Table 5]

According to Table 5, the ionizing radiation curable resin layer in the decorative sheet of the present invention is excellent in transparency and weather resistance, and is also excellent in heat moldability such as heat resistance and heat dimensional shrinkage. Furthermore, there is no cracking or breaking of the sheet at the time of V-cut, and it is possible to faithfully reproduce the concavo-convex pattern by the embossing plate on the entire surface, and it is excellent in the adhesive strength between layers and scratch resistance.

[0088]

The decorative sheet of the present invention is excellent in thermoformability and weather resistance in addition to the properties of the decorative sheet using the conventional polyolefin resin, and the ionizing radiation-curable resin layer is the top of the conventional decorative sheet. Excellent transparency compared to film. Also, the adhesiveness between the ionizing radiation-curable resin layer and the substrate sheet is excellent, and the scratch resistance is excellent.

[Brief description of the drawings]

FIG. 1 shows one embodiment of a layer configuration of a decorative sheet of the present invention.

FIG. 2 shows a state where the decorative sheet of the present invention shown in FIG. 1 is adhered to an adherend (backing material).

FIG. 3 shows a state in which the decorative sheet of the present invention is adhered to a three-dimensional object having irregularities.

FIG. 4 is an explanatory view showing the application of the decorative sheet of the present invention to an adherend on which a V-cut processing method is performed; A cross-sectional view of the combination is shown.

FIG. 5 is an explanatory view of applying the decorative sheet of the present invention to an adherend on which a V-cut processing method is performed, and shows a state where the decorative sheet is bent in a V-shaped groove.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Colored base film 2 Pattern layer 3 Ionizing radiation-curable resin layer 4 Irregular pattern 5 Adhesive layer 6 V-shaped groove 10 Decorative sheet 20, 22 Adherend 21 Irregular three-dimensional object

Claims (6)

[Claims] 1. An ionizing radiation-curable resin, directly or via another layer, on a colored base sheet whose main raw material is composed of a material containing high-density polyethylene, a thermoplastic elastomer, a colorant, and an inorganic filler. A decorative sheet having a layer formed thereon. 2. The decorative sheet according to claim 1, wherein the ionizing radiation-curable resin layer is an electron beam-curable resin layer. 3. The ionizing radiation-curable resin layer has a thickness of 1
The decorative sheet according to claim 1, which has a thickness of 0 to 100 μm. 4. The thickness of the colored base sheet is 50 to 30.
The decorative sheet according to claim 1, 2 or 3, which has a thickness of 0 µm. 5. The decorative sheet according to claim 1, wherein a UV absorber is added to the ionizing radiation-curable resin layer. 6. The decorative sheet according to claim 1, wherein a pattern layer is provided on the colored base sheet and / or the ionizing radiation-curable resin layer.