JP2000108293A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a stabilized bonding force and permit the solidification of an adhesive layer within a short period of time, and a deep-drawing embossing process under a softened condition of the adhesive layer by a method wherein the adhesive layer is formed of a hot-melt type ionized radiation curing resin. SOLUTION: In a decorative sheet 1 in which a printing layer 3 is formed on the surface of a substrate sheet 2, and an adhesive layer 4 and a protecting layer 5 are laminated thereon, the adhesive layer 4 is formed of a hot-melt type ionized radiation curing resin. The ionized radiation or ultraviolet ray curing resin is preferably the copolymerized type of the trunk polymer of the ionized radiation curing resin and a photo-initiated polymerization initiating agent since the contamination of an adhered body or the stimulation of skin due to the eluation of the photo-initiated polymerization initiating agent can be avoided. The forming method of the adhesive layer 4 is a direct coating method, in which a coating composition is coated directly on the substrate sheet 2, on which the printing layer 3 is formed, or the protecting layer 5, a transfer coating method, in which coating is formed previously on the surface of a separating substrate and, thereafter, the coating is transferred onto the substrate sheet 2 or the protecting layer 5, on which the printing layer is formed, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet having excellent decorativeness which can be used as a decorative face sheet used for interior decoration of buildings, surface decoration of fittings, vehicle interior decoration and the like.

[0002]

2. Description of the Related Art Conventionally, decorative sheets used in such applications include those obtained by decorating a polyvinyl chloride sheet by printing or embossing (Japanese Patent Publication Nos. 28-5036 and 58-14312), A sheet using a polyolefin sheet such as polyethylene or polypropylene instead of vinyl chloride (JP-A-54-62255) is known.

Further, as a means for enhancing the adhesive strength of the base sheet, the printed layer and the protective layer of the decorative sheet, a method of dry lamination using a solvent-based adhesive as the adhesive layer has hitherto been most commonly used. In addition, a method using a reactive hot melt resin as an adhesive layer has been proposed.

[0004]

However, the method of dry lamination using a solvent-based adhesive has a problem that the designed adhesive strength cannot be obtained due to the influence of the residual solvent, and the sheet tends to swell due to the residual solvent. was there. In addition, a large drying step is required to evaporate the solvent after laminating the decorative sheet, and it is inconvenient to handle due to problems such as the need to consider measures to ensure the safety of the solvent to the human body. Met. On the other hand, if a reactive hot melt adhesive is used for the adhesive layer, stable adhesive strength can be obtained, and since no solvent is used, the swelling of the sheet can be solved, and a drying step is not required, and safety is considered. Therefore, the disadvantage of the method of dry lamination using a solvent-based adhesive can be solved. However, the reactive hot melt adhesive requires a long time of 3 to 4 days to complete the reaction, so that the productivity is poor and the adhesive layer has poor appearance (unevenness due to embossing. Is different.) It is not easy to finish the surface of the decorative sheet beautifully. or,
The reactive hot-melt adhesive is difficult to handle because the reaction starts from the time of application, and for example, a phenomenon such as clogging of the adhesive inside an apparatus used for application occurs, so that workability is poor. Further, the reactive hot melt adhesive has a problem that embossing cannot be performed until the reaction is completely completed and the adhesive layer is solidified. This is because, since the reaction is gradually progressing from the time of application, if the embossing is performed in a partially solidified state, the adhesive layer may have irregularities. If the adhesive layer is completely solidified, embossing can be performed stably. However, since the adhesive layer is hardened, the elongation is poor, and a new problem that deep drawing embossing cannot be performed occurs. I do.

The present inventors have conducted intensive studies to solve the above-mentioned disadvantages of the prior art, and as a result, completed the present invention. That is, the present invention can obtain a stable interlayer adhesion,
It is an object of the present invention to provide a decorative sheet which is excellent in workability, solidifies the adhesive layer in a short time, and further enables deep drawing embossing in a state where the adhesive layer is softened.

[0006]

Means for Solving the Problems The decorative sheet of the present invention comprises:
In a decorative sheet in which a printed layer is formed on the surface of a base sheet and an adhesive layer and a protective layer are laminated on the printed layer, the adhesive layer is made of a hot-melt ionizing radiation-curable resin. And

In the decorative sheet of the present invention, the base sheet is preferably made of a fibrous sheet or a polyolefin resin sheet, and the protective layer is preferably made of a transparent or translucent olefin resin.

In the decorative sheet of the present invention, it is preferable to emboss the surface of the protective layer, and it is more preferable to provide a colored layer in the embossed concave portion formed by the embossing. It is more preferable to provide Further, in the present invention, it is preferable to perform an easy adhesion treatment on the back surface of the base material sheet.

[0009]

Embodiments of the present invention will be described below in detail with reference to the drawings. FIG. 1 is a longitudinal sectional view showing a basic configuration of the decorative sheet 1 of the present invention. In FIG. 1, 2 is a base sheet, 3 is a printing layer, 4 is an adhesive layer, and 5 is a protective layer.

The material constituting the base sheet 2 includes:
(A) Fibrous sheets made of paper, woven fabric or nonwoven fabric having a basis weight of about 50 to 150 g / m ² , and (B) thermoplastic resins such as olefin resins and vinyl chloride resins.

(A) When the base sheet 2 is made of a fibrous sheet made of paper, woven fabric or non-woven fabric, its thickness can be selected from a range of about 50 to 300 μm. Examples of the fibrous material forming the fibrous sheet include organic synthetic or artificial fibers such as cellulose pulp, hemp, cotton, and nylon, and inorganic fibers such as asbestos, glass, quartz, carbon, and potassium titanate. . The fibrous base material sheet using cellulose pulp fibers is so-called "paper", and specific examples include high quality paper, kraft paper, and Japanese paper.

The above fibrous sheet can be subjected to a flame retarding treatment by, for example, mixing a flame retardant such as aluminum hydroxide powder or a phosphoric acid compound such as aziridinyl phosphine oxide.

(B) When the base sheet is made of a thermoplastic resin, a vinyl chloride resin can be used, but a polyolefin resin is preferable. Examples of the polyolefin-based resin include a mixture in which a main raw material is made of either high-density polyethylene or polypropylene as a hard segment, and an elastomer and an inorganic filler as a soft segment are added thereto. or,
JP-A-9-111055, JP-A-5-7737
No. 1, JP-A-7-316358 and the like can be used for the base sheet 2, and isotactic as a hard segment described in JP-B-6-23278 can be used. A mixture of polypropylene and atactic polypropylene as a soft segment can be used for the base sheet 2. Coloring agents are added to these as needed.

The high-density polyethylene as a hard segment in the olefin resin is preferably a polyethylene having a specific gravity of 0.94 to 0.96, which has a high degree of crystallinity obtained by a low-pressure method, and High-density polyethylene, which is a polymer having a small number of branched structures, is used. As the polypropylene as the hard segment, preferably, isotactic polypropylene is used.

As the elastomer as the soft segment, diene rubber, hydrogenated diene rubber, olefin elastomer and the like are used. 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, and suppresses crystallization of the polyolefin resin to improve its flexibility. As the diene rubber, isoprene rubber, butadiene rubber, butyl rubber, propylene / butadiene rubber,
There are acrylonitrile-butadiene rubber, acrylonitrile-isoprene rubber, styrene-butadiene rubber and the like.
As the olefin elastomer, at least one polyene copolymerizable with two or three or more olefins is used.
Elastic copolymers are added, and ethylene, propylene, α-olefin and the like are used as the olefin, and 1,4 hexadiene, cyclic diene, norbornene and the like are used as the polyene. Preferred olefin elastomers 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, these elastomers may be excessively cross-linked by using a cross-linking agent such as an organic peroxide and sulfur as needed.

The amount of these elastomers added is 1
It is about 0 to 60% by weight, preferably about 30% by weight. 1
The change in elongation at a constant load of less than 0% by weight becomes too steep, and the elongation at break, impact resistance and easy adhesion decrease, and when it exceeds 60% by weight, transparency, weather resistance and creep resistance are reduced. The property is reduced.

As the inorganic filler, powder having an average particle size of about 0.1 to 10 microns such as calcium carbonate, barium sulfate, clay and talc is used. The amount of addition is about 1 to 60% by weight, preferably about 5 to 30% by weight. If the amount is less than 1% by weight, the creep deformation resistance and the easy adhesion decrease, and if it exceeds 60% by weight, the elongation at break and the impact resistance decrease.

As the olefin resin, a thermoplastic elastomer comprising an ethylene / propylene / butene copolymer resin is used. Here, as butene, any of three structural isomers of 1-butene, 2-butene and isobutylene can be used. The copolymer is a random copolymer and partially includes an amorphous portion.

Preferred specific examples of the ethylene / propylene / butene copolymer resin include the following (i) to (iii):
Is mentioned. (I) A random copolymer based on a terpolymer of ethylene, propylene and butene described in JP-A-9-111055. The weight ratio of the monomer components was 9 for propylene.
0% by weight or more. Melt flow rate is 230 °
C, it is preferably 1 to 50 g / 10 minutes under the condition of 2.16 kg. Such a ternary random copolymer 10
With respect to 0 parts by weight, the above random copolymer contains 0.0% of a transparent nucleating agent containing a phosphoric acid aryl ester compound as a main component.
1 to 50 parts by weight and 0.003 to 0.3 parts by weight of a fatty acid amide having 12 to 22 carbon atoms are melt-kneaded.

(Ii) A ternary copolymer of ethylene, propylene and butene described in JP-A-5-77371, wherein the propylene weight ratio is 50 to 100% by weight, and the amorphous polymer is 20 to 100% by weight. % Of an ethylene-propylene-butene copolymer obtained by adding 80 to 0% by weight of crystalline polypropylene.

(Iii) A terpolymer of ethylene, propylene and 1-butene described in JP-A-7-316358, wherein the content of propylene and / or 1-butene is 5
0% by weight or more of low crystalline polymer 20 to 100% by weight,
Ethylene propylene obtained by adding 0.5% by weight of an oil gelling agent such as N-acylamino acid amine salt or N-acylamino acid ester to a composition obtained by mixing 80 to 0% by weight of a crystalline polyolefin such as isotactic polypropylene. -Butene copolymer.

The above ethylene-propylene-butene copolymer resin (i) to (iii) may be used alone or, if necessary, may further contain another polyolefin. You may mix and use resin.

As the olefin resin, (A) a soft segment having a number average molecular weight Mn of 25,000 or more and a ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn described in JP-B-6-23278. ≦ 7
Atactic polypropylene 1 soluble in boiling heptane
0 to 90% by weight, and (B) a boiling heptane-insoluble isotactic polypropylene 90-1 having a melt index as a hard segment of 0.1 to 4 g / 10 min.
Soft polypropylene consisting of a mixture with 0% by weight.

Among the above-mentioned olefin-based thermoplastic elastomers, those comprising a mixture of isotactic polypropylene and atactic polypropylene and having a weight ratio of atactic polypropylene of 5 to 50% by weight are preferable, and a weight ratio of atactic polypropylene is preferred. Is particularly preferably 20 to 40% by weight. When the weight ratio of the atactic polypropylene is less than 5% by weight, uneven sheet deformation due to necking when embossing or forming into an article having a three-dimensional shape or unevenness, resulting in wrinkles and patterns. Distortion or the like occurs. On the other hand, if the weight ratio of the atactic polypropylene exceeds 50% by weight, the sheet itself tends to be deformed, the sheet is deformed when the sheet is passed through a printing machine, the pattern of the printed layer is distorted, and the register is multicolored. Failures such as incompatibility are likely to occur, and the sheet is likely to tear during molding.

If necessary, a colorant, a heat stabilizer, a flame retardant, an ultraviolet absorber, a radical scavenger, etc. are added to the olefin resin of the base sheet 2. Examples of coloring agents include inorganic pigments such as titanium white, zinc white, red iron, vermilion, ultramarine, cobalt blue, titanium yellow, graphite, carbon black, isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, and the like. Organic pigments or dyes, metal pigments composed of foil powder such as aluminum and brass, mica coated with titanium dioxide, pearlescent pigments composed of foil powder such as basic zinc carbonate and the like are used. The coloring agent is added to give the base sheet the necessary color as a decorative sheet, and may be either transparent coloring or opaque (concealing) coloring, but is generally opaque for covering the adherend. Coloring is preferred.

Known heat stabilizers such as phenol, sulfite, phenylalkane, physphite and amine can be used to improve the prevention of deterioration such as thermal discoloration during thermal processing. Used when planning. The flame retardant is added when imparting flame retardancy, and powder such as aluminum hydroxide and magnesium hydroxide is used.

The ultraviolet absorber is for imparting good weather resistance (light resistance) to the resin, and is an organic substance such as benzotriazole, benzophenone, salicylate, or a fine particle having a diameter of 0.2 μm or less. Inorganic substances such as zinc oxide, cerium oxide, and titanium oxide are used. In addition, a reactive ultraviolet absorber having an acryloyl group or a methacryloyl group introduced into a benzotriazole skeleton is also used. The amount of these UV absorbers is usually 0.1.
About 5 to 10% by weight

In order to further prevent deterioration due to ultraviolet rays and improve weather resistance, it is preferable to add a radical scavenger. As a radical scavenger, bis- (2,2,
6,6-tetramethyl-4-biperidinyl) sebacate, bis- (N-methyl-2,2,6,6-tetramethyl-4-biperidinyl) sebacate and others disclosed in, for example, Japanese Patent Publication No. 4-82625. Hindered radical scavengers, biperidinyl radical scavengers, and the like, for example, are used.

The base sheet 2 can be obtained by blending these materials to form a film by a conventional method such as calendering. The thickness of the base sheet is 50 to 2
It is about 00 μm, preferably about 100 μm.

The surface of the base sheet 2 is preferably subjected to an easy-adhesion treatment such as application of an easy-adhesion layer, corona discharge treatment, plasma treatment, and ozone treatment. An acrylic resin, a vinyl chloride-vinyl acetate copolymer, a polyester resin, a urethane resin, a chlorinated polypropylene, and a polyethylene chloride can be used as the easily adhesive layer (also referred to as a primer layer or an anchor layer).

The printing layer 3 is formed by pattern printing, coloring printing, or the like. The printing layer 3 is specifically made of a colored (transparent or opaque) pattern or solid printing by adding a pigment,
It is 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. The pattern of the print layer 3 includes a wood pattern, a stone pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and the like. The printing layer 3 may be provided on the entire surface of the substrate sheet 2 or on a part thereof. As shown in FIG. 1, the printing layer 3 may be composed of a solid printing layer 31 provided on the entire surface of the base sheet 2 and a pattern printing layer 32 provided partially on the surface of the printing layer. Good.

The ink or paint used for the printing layer 3 may be a chlorinated polyolefin such as chlorinated polyethylene or chlorinated polypropylene, polyester, polyurethane, acryl, vinyl acetate, a vinyl chloride / vinyl acetate copolymer, or a cellulose-based binder. Using resin, etc.,
Seeds or a mixture of two or more kinds are used. Further, the above-mentioned pigments and the like may be added thereto.

A metal film can be formed as the printing layer 3. For example, a metal such as aluminum, chromium, gold, silver, or copper can be formed as a metal thin film by a method such as vacuum evaporation or sputtering, or a combination thereof. The metal film can also be provided over the entire surface or partially.

The adhesive layer 4 is made of a hot melt type ionizing radiation curable resin. 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 ultraviolet (UV) or electron beam (EB) can be used.

The hot-melt type ultraviolet curable resin may be of a type obtained by mixing a photopolymerization initiator as a monomer with an ionizing radiation curable resin, or a photopolymerization initiator may be used as a base polymer of the ionizing radiation curable resin. There are polymerized types. In the present invention, either type can be used, but a type obtained by copolymerizing a photopolymerization initiator with a backbone polymer of an ionizing radiation-curable resin,
This is preferable because problems such as contamination of the adherend and irritation of the skin due to elution of the photopolymerization initiator can be avoided.

As the main polymer of the hot melt type ionizing radiation curable resin, an acrylic resin is preferable, but polyvinyl acetate, polyvinyl chloride, polyvinyl acetate / vinyl chloride copolymer, and ethylene / vinyl alcohol copolymer are preferable. Copolymer, ethylene / vinyl acetate copolymer, polyvinyl alcohol, vinyl copolymer such as polybutyl butyral, polyethylene, polyolefin resin such as polyethylene, cellulose nitrate, cellulose acetate, polyamide, ionomer or other, for example, nylon / epoxy A thermoplastic resin such as a copolymer can also be used.

Examples of the acrylic resin include polymers and copolymers of acrylic acid, acrylic acid ester, acrylamide, acrylonitrile, methacrylic acid, methacrylic acid ester and the like. Specifically, poly (meth) acrylic Methyl acrylate, poly (ethyl meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, methyl (meth) acrylate / (meth) acrylate
Such as butyl acrylate copolymer, ethyl (meth) acrylate / butyl (meth) acrylate, ethylene / methyl (meth) acrylate, and styrene / methyl (meth) acrylate A homo- or copolymer containing a (meth) acrylic acid ester is exemplified. Here, (meth) acryl means acryl or methacryl.

When the backbone polymer is a resin having a radical polymerizable unsaturated group such as an acrylic resin, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, etc. may be used alone or as the photopolymerization initiator. They can be used in combination. Further, when the trunk polymer is a resin having a cationically polymerizable functional group, as a photopolymerization initiator, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a methaserone compound, a benzoinsulfonic acid ester or the like alone or They can be used in combination. These photopolymerization initiators can be blended as monomers as described above, but it is preferable to copolymerize them with the backbone polymer of the ionizing radiation-curable resin because handling becomes convenient.

The thickness of the adhesive layer 4 made of a hot-melt type ionizing radiation curable resin in the present invention is 5 to 10 mm.
0 μm is preferred. When the thickness of the adhesive layer 4 is less than 5 μm, the interlayer adhesion strength between the adhesive layer 4 and the printing layer 3 or the protective layer 5 becomes weak. When the thickness of the adhesive layer 4 exceeds 100 μm, when the ionizing radiation is an electron beam, the electron beam does not reach the lowermost portion of the adhesive layer 4, so that the lowermost portion of the adhesive layer 4 may have poor curing. , If the ionizing radiation is ultraviolet,
There is a possibility that the adhesive layer 4 may undergo cohesive failure due to cracks generated during curing, and the adhesive strength may be weakened.

The resin forming the protective layer 5 is not limited.
It is preferable to use an olefin resin, and the same olefin resin as that used for the sheet base 2 can be used. When ultraviolet rays are used as ionizing radiation, the protective layer made of the olefin resin is preferably transparent or translucent. If the protective layer is not transparent or translucent, the adhesive layer made of the ionizing radiation-curable resin may not be cured even when irradiated with ultraviolet rays. When such a protective layer is not transparent or translucent, it is preferable to cure it using an electron beam.

The thickness of the protective layer 5 is 10 to 500 μm, preferably 50 to 100 μm. The thickness of the protective layer 5 is 1
If it is less than 0 μm, it is too thin to function as a protective layer. On the other hand, when the thickness of the protective layer 5 exceeds 500 μm, when the ionizing radiation is an electron beam, the electron beam does not reach the lowermost portion of the protective layer 5, and the lowermost portion of the protective layer 5 may have poor curing, If the ionizing radiation is ultraviolet,
There is a possibility that the protective layer 5 may not function as a protective layer due to a cohesive failure of the protective layer 5 due to a crack generated during curing.

As a method for forming the adhesive layer 4 made of a hot-melt type ionizing radiation-curable resin, there is a direct method in which a coating composition is directly applied to the base sheet 2 or the protective layer 5 on which the printed layer is formed. Coating method, base sheet 2 on which a printed layer is formed after being formed in advance on a releasable base material surface
Alternatively, a transfer coating method or the like for transferring to the protective layer 5 is used.

Which of the above or any of the above is adopted depends on whether
The basis is whether or not the coating composition permeates the base sheet. When the coating composition does not penetrate the base sheet, any of the above or any of the above may be used. However, the direct coating method is not an appropriate method when the coating composition soaks into the base sheet. However, since a layer made of an ionizing radiation-curable resin or the like can be directly formed on the surface of the base material, there is an advantage that the production is easy. On the other hand, the above-described transfer coating method does not cause a problem that the coating composition penetrates, and thus is an appropriate method when paper or the like that penetrates the coating composition is used as the base sheet 2. Also, when there is unevenness on the surface of the base sheet, when uniformity of the coating thickness is obtained, and when it is desired to form a uniform layer of ionizing radiation curable resin by making the intensity of ionizing radiation uniform, The coating method is an appropriate method because the problem of resin infiltration does not occur. However, the transfer coating method has a drawback that the number of steps in manufacturing is increased. In addition, if paper is used as the base sheet and the coating composition is composed of an ionizing radiation-curable resin composition or the like, the coating composition may soak into the base sheet, Direct coating is not an appropriate method. However, in this case, the solid print layer 3
By forming 1, the solid printing layer 31 effectively prevents the ionizing radiation curable resin or the like from impregnating the paper as the base sheet, so that the hot melt type film having a uniform and uniform film thickness can be obtained. An adhesive layer made of an ionizing radiation curable resin can be formed.

The above direct coating method includes gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, wheeler coat, dip coat, solid coat by silk screen, wire bar coat, flow coat , A comma coat, a pouring coat, a brush coat, a spray coat and the like can be used, and a gravure coat is preferable.

When an ionizing radiation irradiator used for curing an ionizing radiation-curable resin is irradiated with ultraviolet light, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp, a metal halide lamp or the like is used. Used, and when irradiating with an electron beam,
Various electron beam accelerators such as a Cockloft-Walton type, a Vandegraf type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type and a high frequency type are used.

The irradiation amount of the electron beam is usually 100 to 1000.
Electrons having an energy of keV, preferably 100 to 300 keV, are irradiated at a dose of about 0.1 to 30 Mrad. When the irradiation amount is less than 0.1 Mrad, curing may be insufficient, and when the irradiation amount exceeds 30 Mrad, the cured coating film or the base material may be damaged. In addition, the irradiation amount when curing with ultraviolet light is
Preferably it is 50 to 1000 mJ / cm ² . If the irradiation amount of ultraviolet rays is less than 50 mJ / cm ² , the curing may be insufficient, and if the irradiation amount exceeds 1000 mJ / cm ² , the cured coating film may turn yellow.

In the present invention, as described above, the adhesive layer 4 made of a hot-melt type ionizing radiation-curable resin is used.
Can be directly formed on the surface of the base sheet 2 provided with the print layer 3, whereby the base sheet 2, the print layer 3, the adhesive layer 4, and the protective layer 5 can be sequentially laminated. The respective layers can also be laminated by the method described above. FIG. 2 is a process diagram illustrating an example of a method of laminating the base sheet 2, the printing layer 3, the adhesive layer 4, and the protective layer 5 on the decorative sheet 1 of the present invention. Hereinafter, an example of a method of laminating each of the above layers of the decorative sheet 1 of the present invention will be described with reference to FIG. A base sheet layer 2 made of a fibrous sheet or a polyolefin resin sheet or the like is prepared, and a sheet 9 provided with a print layer 3 by sequentially forming a solid print layer 31 and a picture print layer 32 on the surface of the base sheet 2 is prepared. To manufacture. On the other hand, a hot-melt type ionizing radiation-curable resin is applied to a separately prepared protective layer 5 made of a polyolefin resin sheet or the like, and an adhesive layer 4 is formed.
The sheet 10 provided with is manufactured. Next, the surface of the sheet 9 on which the printed layer 3 is provided and the surface of the sheet 10 coated with the hot-melt ionizing radiation-curable resin are bonded using a roll press or the like to produce a laminated sheet. Next, as described above, ionizing radiation is irradiated from the protective layer 5 side of the laminated sheet to cure the ionizing radiation-curable resin, thereby forming the adhesive layer 4.
To form a decorative sheet 1.

FIG. 3 is a longitudinal sectional view showing a specific configuration example of the present invention. 3, reference numeral 6 denotes an uneven pattern formed on the surface of the protective layer 5, reference numeral 7 denotes a colored layer formed in a concave portion of the uneven pattern 6, reference numeral 8 denotes a surface protective layer formed on the surface of the protective layer 5, and reference numeral 11 denotes a base sheet. 2 is an easy-adhesion layer provided on the back side.

The concavo-convex pattern 6 may be provided so as to correspond to, for example, the portion where the print layer 3 is provided, or may be provided on the entire surface of the portion where the print layer 3 is provided. The pattern of the concavo-convex pattern 6 is, for example, a copy of a concavo-convex shape of a natural product such as a grain of wood, a stone, a grain of sand, a character symbol, a line, various abstract patterns,
Various matte surfaces, specular gloss, and the like.

In order to form the concavo-convex pattern 6 on the surface of the protective layer 5, for example, there is embossing by heating and pressing. This embossing process is to soften the surface of the protective layer 5 by heating, press the surface with an embossing plate to shape the embossed pattern of the embossing plate, and cool and fix it. A rotary embossing machine can be used. Also, the concavo-convex pattern 6 can be formed by using a flat plate press or the like, or by hairline processing. In the present invention,
Since a hot-melt ionizing radiation-curable resin is used as the adhesive layer, the concavo-convex pattern is formed in an uncured state, that is, in a softened state, immediately after the protective layer 5 is applied. As a result, it is possible to form an irregular pattern of deep drawing. This is different from the case where a reactive hot melt adhesive that can be shaped only after the curing is completed is used.

The colored layer 7 formed in the concave portion of the uneven pattern 6 can be formed by a wiping method. The wiping method is to apply a colorant ink to the entire surface including the concave portion, and then remove the colorant ink from the surface other than the concave portion by a doctor blade coating method or a knife coat method, so that the coloring layer is applied only to the concave portion. 7 is formed. Examples of the colorant ink for forming the color layer 7 include color pigments such as organic pigments, inorganic pigments, and brilliant pigments; binder resins such as thermoplastic resins, thermosetting resins, and ionizing radiation-curable resins; And an emulsion type water-based ink.

The surface protective layer 8 is coated to protect the surface of the protective layer 5 on which the uneven pattern 6 is formed. The surface protective layer 8 is preferably formed of a chlorinated polyolefin, a two-component curable polyurethane, or an ionizing radiation curable resin.

In the present invention, an appropriate amount of a matting agent (light diffusing agent) can be added to the surface protective layer 8 if necessary. As the matting agent, fine particles having a particle size of about 1 to 30 μm, such as calcium carbonate, silica, alumina, barium sulfate, urethane resin beads and polycarbonate resin beads, are effective. The thickness of the surface protective layer 8 is preferably about 1 to 100 μm.

In the decorative sheet 1 of the present invention, in order to impart better weather resistance (light) to the resin, the protective sheet 5 and the surface protective layer 8 may be provided with the base sheet if necessary. Similarly, an ultraviolet absorber and a light stabilizer can be added. However, when an ultraviolet absorber or the like is added, it is preferable to cure the adhesive layer 4 using an electron beam. Further, a flame retardant can be added to the protective layer 5 and the surface protective layer 8 as in the case of the base sheet 2.

In the decorative sheet 1, a flame retardant can be added to the protective layer 4 and the surface protective layer 8 in addition to the base sheet 2 in order to impart flame retardancy. Powders such as aluminum hydroxide and magnesium hydroxide are used as the flame retardant. The total amount of the high-density polyethylene and the thermoplastic elastomer is 100
It is preferably about 10 to 150 parts by weight based on parts by weight.

The easy-adhesion layer 11 is formed by laminating the decorative sheet 1 of the present invention on various adherends, performing a predetermined forming process, etc., and facilitating use of the substrate sheet for various decorative purposes. 2 is formed on the back side. Acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, chlorinated polyethylene, and the like are used for forming the easy-adhesion layer 11, and chlorinated polypropylene is particularly desirable.

The decorative sheet 1 of the present invention can be used by being laminated on another adherend (backing material). 4 shows a case where the adherend is a three-dimensional article 21, and FIG. 5 shows a case where the adherend is a plate member 22 having a flat or curved shape. When the decorative sheet 1 and the adherend are laminated, the decorative sheet 1 itself is attached to the adherend (by heat fusion or the like).
When it can be bonded, it can be performed without using an adhesive, but when the decorative sheet 1 itself does not adhere to the adherend,
Laminate using a suitable adhesive. The decorative sheet 1 of the present invention
May be a final product such as a decorative material by being laminated on an adherend, or may be laminated on an adherend in order to reinforce the mechanical strength of the decorative sheet 1 or to impart concealment. .

The adhesive may be any adhesive as long as the decorative sheet 1 and the adherend can be adhered, and examples thereof include vinyl acetate and urea.

The object to be adhered is a three-dimensional molded article as shown in FIG. 4, a flat or curved plate material as shown in FIG. 5, or an article of 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 porcelain, 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 carbon And nonwoven fabric or woven fabric made of fibers such as asbestos, potassium titanate, glass, and synthetic resin.

As a method of laminating these various adherends,
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.

The various adherends on which the decorative sheet 1 is laminated can be used as various decorative materials by subjecting them 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, 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.

[0062]

The present invention will be described below in more detail with reference to specific examples. Example 1 Impregnated paper NFP50 (thickness 50 to 5) manufactured by Sanko Paper Industries Co., Ltd.
(5 μm) as a substrate sheet, and gravure printing of a wood grain pattern was performed to form a print layer. On the other hand, a translucent polypropylene film manufactured by Mitsubishi Chemical MKV Co., Ltd.
m) as a protective layer, and an adhesive “UV Cure Hot Melt” manufactured by Mitsubishi Chemical BASF Co., Ltd.
Was extruded with a pump and uniformly applied to a thickness of 40 μm using a backside applicator to form an adhesive layer. Next, the base sheet on which the printed layer was formed and the protective layer to which the adhesive was applied were bonded together using a roll press to prepare a multilayer sheet. Next, the multilayer sheet was irradiated with an ultraviolet irradiation device (mercury lamp, 8
0W) at 5 m / min, and the adhesive was cured by irradiating ultraviolet rays from the protective layer side. still,
The curing of the adhesive by irradiation with ultraviolet rays was continuously performed in a series of steps after the production of the multilayer sheet, and was not left for a long time unlike the case of using a reactive hot melt resin. After embossing the formed multilayer sheet to form an uneven pattern, applying color to the embossed recesses of the embossed sheet and performing wiping treatment, a surface protective layer manufactured by Showa Ink Kogyo Co., Ltd. An acrylic resin "OPA-4" was gravure coated to obtain a decorative sheet.

Example 2 In the same manner as in Example 1, a base sheet on which a printed layer was formed and a protective layer coated with an adhesive were laminated to form a multilayer sheet. Embossing is performed on the sheet thus produced before irradiation with ultraviolet rays, and after forming a deeper uneven pattern than in Example 1,
The adhesive was cured by irradiating ultraviolet rays in the same manner as in Example 1. Next, in the same manner as in Example 1, coloring of the embossed concave portion, wiping treatment, and formation of a surface protective layer were performed to obtain a decorative sheet. Irradiation with ultraviolet rays was performed continuously in a series of steps for manufacturing a decorative sheet.

Example 3 A decorative sheet was produced in the same manner as in Example 1 except that a polypropylene film (thickness: 80 μm) manufactured by Mitsubishi Chemical MKV Co., Ltd. was used as a base sheet.

Comparative Example 1 A decorative sheet was obtained in the same manner as in Example 1 except that a colored and opaque polypropylene film (80 μm thick) manufactured by Mitsubishi Chemical MKV Co., Ltd. was used as a protective layer.

Comparative Example 2 A multi-layer sheet was prepared in the same manner as in Example 1 except that a reactive hot melt resin “170-7310” manufactured by NSC was used as an adhesive. After leaving the multilayer sheet at room temperature for 4 days to allow the adhesive to sufficiently react and solidify, embossing, coloring of the embossed concave portion, wiping treatment, and formation of a surface protective layer are performed in the same manner as in Example 1. A sheet was prepared. That is, a concave / convex pattern was formed in a state where the adhesive layer was cured to obtain a decorative sheet.

Comparative Example 3 A solvent-based adhesive containing "E-295L" manufactured by Dainichi Seika Co., Ltd. as a main agent and "C75N" manufactured by Dainichi Seika Co., Ltd. as a curing agent was applied by a gravure coating method. A decorative sheet was prepared in the same manner as in Example 1 except that hot air drying was performed at ° C.

The decorative sheets obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were evaluated for the degree of surface finish, the depth of embossed irregularities, and the interlayer adhesion by measuring the peeling strength. .

The evaluation criteria for the finished condition of the decorative sheet surface are as follows. ◎: extremely good ○: good △: bad ×: extremely bad

The evaluation criteria for the depth of the embossed irregularities on the surface of the decorative sheet are as follows. ◎: deep ○: normal ×: shallow

The peeling strength was measured according to JIS K685.
The peeling strength was calculated according to JIS K68 according to the T-type peeling test of No. 4 at a peeling speed of 50 mm / min.
The measurement was performed according to the area method described in the item “Processing of Measurement Results of Peeling Load” of No. 54.

The results of the above tests are shown in Table 1 together with the evaluation of the transparency of the protective layer and the easiness of the operation at the time of applying the adhesive. The evaluation criteria for the ease of work at the time of applying the adhesive are as follows. : Good △: inconvenient ×: extremely bad

[0073]

[Table 1]

[0074]

As described above, the present invention employs a layer structure in which a printing layer, an adhesive layer made of a hot-melt type ionizing radiation curable resin, and a protective layer are laminated on the surface of a base sheet. By doing so, the interlayer adhesive strength is excellent and the workability is excellent, and the adhesive layer can be solidified in a short time after the application of the adhesive. A possible decorative sheet can be provided.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view showing a basic configuration of a decorative sheet of the present invention.

FIG. 2 is a process chart showing an example of a method for producing a decorative sheet of the present invention.

FIG. 3 is a longitudinal sectional view showing a specific configuration 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.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Base sheet 3 Printing layer 4 Adhesive layer 5 Protective layer 6 Concavo-convex pattern 7 Colored layer 8 Surface protective layer 11 Easy adhesion layer

 ──────────────────────────────────────────────────の Continued on the front page F term (reference) 4F100 AK01B AK01G AK03A AK03C AK07 AK25 AR00E AS00C AS00D AT00A BA03 BA04 BA05 BA07 BA31 CB03B DG00A EJ40C EJ91C EJ91D GB08 GB33 HB31 HB31JJ14G14 JB14L JB10L

Claims (7)

[Claims] 1. A decorative sheet having a printed layer formed on the surface of a substrate sheet and an adhesive layer and a protective layer laminated on the printed layer, wherein the adhesive layer is a hot melt type ionizing radiation curable resin. A decorative sheet comprising: 2. The decorative sheet according to claim 1, wherein the base sheet comprises a fibrous sheet or a polyolefin resin sheet. 3. The decorative sheet according to claim 1, wherein the protective layer is made of a transparent or translucent olefin resin. 4. The decorative sheet according to claim 1, wherein the surface of the protective layer is embossed. 5. The decorative sheet according to claim 4, wherein a colored layer is provided in the embossed concave portion. 6. The decorative sheet according to claim 1, wherein a surface protective layer is provided on the surface of the protective layer. 7. The decorative sheet according to claim 1, wherein an easy adhesion treatment is applied to the back surface of the base sheet.