JP2000326451A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the generation of defective laminate of sheets such as the breakage, elongation, deformation, deterioration or others by laminating a surface resin layer on a base sheet through a heat bonding resin layer composed of an acryl-polyester-vinyl acetate resin. SOLUTION: A pattern layer 2 with a proper pattern to be printed as desired is formed on the surface of a base sheet 1 composed of a thermoplastic resin using a polyethylene, a polypropylene, a polybutene or a polymethylpentene. A surface layer 4 composed of a transparent thermoplastic resin is laminated on the pattern layer 2 through a heat bonding resin layer 3 composed of a polyester resin-vinyl acetate resin using a homopolymer such as an acrylic resin-polyethylene terephthalate composed of an acrylic derivative like an acrylonitril or an acrylic acid as a main component, or such as a polyethylene naphthalate and integrated thereon.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to interior and exterior materials for buildings such as houses, construction materials, building materials such as fittings, furniture and fixtures, and the like.
It relates to a decorative sheet for use in vehicle interiors, surface decoration of housing equipment and home appliances, etc., particularly for surface decoration of architectural members where weather resistance and heat resistance such as entrance doors are required. It relates to a suitable decorative sheet.

[0002]

2. Description of the Related Art A decorative sheet made of polyvinyl chloride resin, which is inexpensive and excellent in workability, has been most commonly used as a decorative sheet for use in various applications as described above. The decorative sheet has a single-layer decorative sheet formed by printing an appropriate desired pattern such as wood grain on the front or back surface of a base sheet made of polyvinyl chloride resin, and is made of polyvinyl chloride resin. Print a pattern on the surface of the base sheet,
There is a decorative sheet having a multilayer structure in which a surface resin layer made of a transparent polyvinyl chloride resin is laminated on the printing surface.
Among them, the latter multi-layered decorative sheet, the pattern printing is protected by the polyvinyl chloride resin layer from both the front and back sides, which is advantageous in terms of processing and durability, and coloring of the base sheet It has been widely used more widely than a decorative sheet having a single-layer structure, for example, because it is easy to achieve high concealment.

[0003] In addition to the above, there is also a decorative sheet made of a combination of a polyvinyl chloride resin and another thermoplastic resin. For example, some quasi-exterior applications where weather resistance is required include those using an acrylic resin with excellent weather resistance for the surface resin layer, and applications where high sharpness is required such as for steel sheets. In some cases, a polyester resin having excellent transparency and surface smoothness is used for the surface resin layer. And, as described above, the decorative sheet composed of a combination of polyvinyl chloride resins or a combination of polyvinyl chloride resin and another thermoplastic resin is formed by utilizing the excellent thermal adhesiveness of the polyvinyl chloride resin. It was most commonly manufactured by a laminating method.

In recent years, however, it has been pointed out that polyvinyl chloride resin generates a large amount of chlorine gas, hydrogen chloride gas and the like at the time of combustion, which directly or indirectly causes the generation of toxic dioxin. From the viewpoint of environmental protection, the development of a decorative sheet using a material replacing polyvinyl chloride resin has been demanded. In response to such demands, for example, a decorative sheet using a chlorine-free thermoplastic resin other than polyvinyl chloride, such as a polyolefin resin, an acrylic resin, or a polyester resin, has already been developed and put into practical use. Replacement of decorative sheets made of vinyl chloride resin is gradually progressing.

[0005] However, these alternative resins are all inferior in thermal adhesiveness to polyvinyl chloride resin. Therefore, as in the case of a decorative sheet using a conventional polyvinyl chloride resin, thermal lamination is performed. When producing a decorative sheet by the method, there is a problem that it is difficult to obtain a necessary adhesive strength. In particular, when a polyolefin-based resin is used, the range of temperature conditions at which heat bonding can be performed is extremely narrow, and the temperature is too high, so that lamination failure such as breakage, elongation, deformation, and deterioration of the sheet occurs.
Further, even if the thermal lamination is performed in a low temperature range where these inconveniences do not occur, the laminate strength is extremely low, and a very practical decorative sheet cannot be obtained.

To cope with such a problem, there has been proposed a method of providing a heat-adhesive resin layer made of vinyl chloride-vinyl acetate-acrylic resin between a substrate sheet and a surface resin layer (Japanese Patent Application Laid-Open No. H9-1997). -30059 publication etc.). According to this method, lamination is performed by interposing a heat-adhesive resin layer that is sufficiently heat-activated and develops adhesiveness in a low-temperature region where sheet breakage, elongation, deformation, deterioration, and the like do not occur. There is an advantage that sufficient lamination strength can be achieved without causing defects.

However, since the above-mentioned heat-adhesive resin layer is essentially made of a resin having poor heat resistance, the obtained decorative sheet has poor heat resistance. When heated by sunlight, there is a problem that the heat-adhesive resin layer is softened by the heat and the surface resin layer is peeled off from the substrate sheet. This problem would theoretically be improved by using a heat-adhesive resin having a high heat-softening temperature, but this would inevitably require an increase in the lamination temperature, and as a result, the sheet This results in lamination failure such as breakage, elongation, deformation, deterioration, etc., and the intended purpose cannot be achieved.

Therefore, a crosslinking agent such as an isocyanate compound is blended in the heat-adhesive resin, and the heat is applied during laminating to develop the adhesiveness to bond the base sheet and the surface resin layer. It is also conceivable to improve the heat resistance after lamination by causing a cross-linking reaction inside the conductive resin. However, according to such a method, after applying the heat-adhesive resin to the base material sheet, if a time is left before the heat lamination, the crosslinking reaction proceeds during the time, so that the heat adhesion is no longer exhibited during the heat lamination. It is necessary to immediately perform thermal lamination because it is lost. Therefore, it is difficult to manage the progress of the decorative sheet manufacturing process, and it is not possible to keep a large number of printed base material sheets coated with a thermo-adhesive resin. Are also very difficult.

[0009] In addition, there are proposals such as a dry lamination method and a melt extrusion lamination method as an alternative to the heat lamination method, but these require large-scale and expensive production equipment, and are suitable for multi-product small-quantity production and short delivery time. However, the melt extrusion lamination method has problems such as limitations on the types of resins that can be used, so that the heat lamination method cannot be completely substituted.

[0010]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems in the prior art, the present inventors have conducted intensive studies and as a result, have found that a specific resin composition is used as a heat-adhesive resin. Break, stretch, deform,
The present inventors have found that a decorative sheet that can be stably heat-laminated without causing lamination failures such as deterioration and that can obtain a decorative sheet excellent in adhesive strength, heat resistance, and weather resistance can be obtained. It is.

[0011]

Means for Solving the Problems The decorative sheet of the present invention comprises:
In a decorative sheet in which a surface resin layer made of a thermoplastic resin is laminated on a base sheet made of a thermoplastic resin via a heat-adhesive resin layer, the heat-adhesive resin layer is made of an acrylic-polyester-vinyl chloride-based It is characterized by being made of resin.

Further, the decorative sheet of the present invention is a decorative sheet according to the above, wherein the base sheet is laminated with a plurality of thermoplastic resin layers via a thermo-adhesive resin layer composed of an acrylic-polyester-vinyl chloride-based resin. It is characterized by being a laminate of layers.

Further, the decorative sheet of the present invention is the decorative sheet described above, wherein the surface resin layer has a plurality of layers of thermoplastic resin laminated via a heat-adhesive resin layer composed of an acrylic-polyester-vinyl chloride-based resin. It is characterized by being a laminate of layers.

In the decorative sheet according to the present invention, the base sheet and the surface resin layer are made of a thermoplastic resin selected from a polyolefin resin, an acrylic resin and a polyester resin. It is a feature.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the decorative sheet of the present invention will be described below in detail with reference to the drawings. 1 to 3 are side sectional views each showing an embodiment of the decorative sheet of the present invention.

In the decorative sheet of the present invention, as shown in FIG. 1, for example, a pattern layer 2 formed by printing an appropriate pattern as desired is provided on the surface of a base sheet 1 made of a thermoplastic resin. Is provided with a surface resin layer 4 made of a transparent thermoplastic resin via a heat-adhesive resin layer 3, wherein the heat-adhesive resin layer 3 is made of an acrylic-polyester-vinyl chloride It is characterized by being made of resin.

The type of the thermoplastic resin constituting the base sheet 1 and the surface resin layer 4 is not particularly limited. For example, a known base material for a decorative sheet or a known material used for a surface resin layer is used. Any thermoplastic resin can be used. Specifically, for example, polyolefin resins such as polyethylene, polypropylene, polybutene and polymethylpentene; ethylene-vinyl acetate copolymers or saponified products thereof; and polyolefin resins such as ethylene- (meth) acrylic acid (ester) copolymers Polyester resins such as copolymers, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, and polycarbonate; acrylic resins such as polymethyl methacrylate; 6-nylon, 6,6-nylon, 6,10-nylon Such as polyamide resins, styrene resins such as polystyrene resins, AS resins and ABS resins; cellulose derivatives such as cellulose acetate and nitrocellulose; chlorine resins such as polyvinyl chloride and polyvinylidene chloride; polyvinyl fluoride; Vinylidene reduction,
Polytetrafluoroethylene, fluorine-based resin such as ethylene-tetrafluoroethylene copolymer, or two or three or more copolymers or mixtures, composites selected therefrom,
A laminate or the like can be used.

However, in view of adaptation to environmental problems which are becoming social problems in recent years, the use of the above-mentioned chlorine-based resins and fluorine-based resins is not very preferable. It is preferable to use a resin not containing, that is, a non-halogen resin. Among them, including the ease of market price, distribution volume, and procurement, the balance of moderate flexibility and strength as a base sheet for decorative sheets, processing suitability such as bending, cutting, and cutting, abrasion resistance, From various aspects such as surface physical properties such as solvent resistance and weather resistance,
It is most preferable to use a thermoplastic resin selected from a polyolefin resin, an acrylic resin, and a polyester resin.

As the polyolefin-based resin, various homopolymers and copolymers including the above-mentioned ones are known. Among them, the most preferred material for the base sheet for decorative sheet is polypropylene-based resin, that is, polypropylene. The main component is a homopolymer or a copolymer, specifically, for example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, and having a polypropylene crystal part, and having 2 to 20 carbon atoms other than propylene α Olefins, preferably propylene-α-olefin copolymers containing at least 15 mol% of a comonomer of ethylene, butene-1, 4-methylpentene-1, hexene-1 or octene-1. . It is also possible to add modifiers such as ethylene-α-olefin copolymer, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer rubber which are usually used for softening a polypropylene resin. .

Examples of the acrylic resin include various acrylic resins such as acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, and the like. Thermoplastic resins can be mentioned. Among them, a resin mainly containing a methacrylic acid ester such as methyl methacrylate, for example, a long-chain alkyl ester of methacrylic acid such as butyl methacrylate,
Acrylic esters such as methyl acrylate, or a monomer selected from methacrylic acid or acrylic acid is added as a copolymer component, or a rubber component such as styrene-butadiene rubber or methyl methacrylate-butadiene rubber is graft-copolymerized, A resin obtained by improving flexibility and thermoformability by block copolymerization or blending can be suitably used.

Examples of the polyester resin include, in addition to the above-mentioned homopolymers such as polyethylene terephthalate and polyethylene naphthalate, aromatic dicarboxylic acids or dicarboxylic acid esters such as terephthalic acid and naphthalenedicarboxylic acid, ethylene glycol and 1,4. -In the condensation polymerization reaction with an aliphatic diol such as butanediol,
As a dicarboxylic acid component, for example, sebacic acid, eicoic acid,
A long-chain aliphatic dicarboxylic acid and / or an alicyclic dicarboxylic acid such as dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid are introduced, and / or both ends of polyethylene glycol, polytetramethylene glycol, and the like as a diol component. By introducing a polyether-based diol having a hydroxyl group, a resin or the like having improved flexibility and thermoformability can be suitably used.

The thermoplastic resin constituting the base sheet 1 and the thermoplastic resin constituting the surface resin layer 4 may be the same or different. For example, while the base sheet 1 is made of a relatively inexpensive polyolefin resin having good workability, the surface resin layer 4 is made of an acrylic resin to provide weather resistance, or the surface resin layer 4 is made of a polyester resin. To provide high definition. Further, the base sheet 1 and / or the surface resin layer 4 may be formed of a laminate of a plurality of layers made of the same or different thermoplastic resins.

In general, a decorative sheet such as the present invention often requires concealment of colors and defects on the surface of a substrate to be adhered. Therefore, in order to impart sufficient concealing properties to the intended decorative sheet, the concealing pigment can be added to the thermoplastic resin constituting the base sheet 1 to make the base sheet 1 concealing. Instead of making the base sheet 1 concealable, a concealed solid printing layer of a printing ink composition containing a concealing pigment may be provided on the front or back surface of the base sheet 1, or both may be used in combination. Of course, it is possible.

As the concealing pigment, it is desirable to use an inorganic pigment having a high refractive index and excellent concealing properties. Specifically, for example, graphite, yellow iron oxide, cadmium yellow,
Titanium yellow, barium yellow, quinacridone, aureoline, molybdate orange, cadmium red, red stalk, lead red, cinnabar, mars violet, manganese violet, cobalt violet, cobalt blue, cerulean blue, ultramarine, navy blue, emerald green, chrome vermilion , Chromium oxide, viridian, iron black, carbon black, and other colored pigments, such as titanium oxide (titanium white, titanium white), zinc oxide (zinc white), basic lead carbonate (lead white), basic lead sulfate, and sulfurized White pigments such as zinc, lithopone, titanox and the like can be used.

Among them, pigments which are excellent in concealing properties and light fastness and which are suitable for decorative sheets in terms of color tone in terms of design, and iron oxide pigments such as red iron oxide, yellow iron oxide and iron black, and white pigments as colored pigments It is most preferable to use a titanium oxide pigment. Of course, other hiding or non-hiding inorganic pigments or organic pigments can be used in combination for the purpose of adjusting the color tone, etc., in which case, if the inorganic pigment is an inorganic pigment such as cobalt blue, carbon black, etc. If it is a pigment, it is preferable to use a pigment excellent in weather resistance, such as a phthalocyanine-based pigment such as phthalocyanine blue. In addition, extenders such as silica, calcium carbonate, barium sulfate and the like can be used in combination as needed.

In addition, the thermoplastic resin constituting the base sheet 1 and the surface resin layer 4 may include, for example, an antioxidant, an ultraviolet absorber, a light stabilizer, Stabilizers, plasticizers, lubricants, antistatic agents,
One or more kinds of conventionally known various additives such as a flame retardant and a filler may be added.

As the antioxidant, for example, a phenol type,
For example, benzophenone, benzotriazole, salicylate, etc.
Cyanoacrylates, formamidines, oxanilides, etc., as light stabilizers, for example, hindered amines,
For example, a hindered phenol type, a sulfur type, a hydrazine type, etc. as a heat stabilizer, a phthalate ester type, a phosphate ester type, a fatty acid ester type, a fat, etc. Group A dibasic acid ester type, oxybenzoic acid ester type, epoxy type, polyester type, etc. Examples of the lubricant include fatty acid ester type, fatty acid type, metal soap type, fatty acid amide type, higher alcohol type, paraffin type, etc. As, for example, cationic, anionic, nonionic, zwitterionic, etc.
Examples of the flame retardant include bromine, phosphorus, chlorine, nitrogen, aluminum, antimony, magnesium,
As a filler such as a boron-based or zirconium-based filler, for example, one or a mixture of two or more selected from calcium carbonate, barium sulfate, talc, rubble, kaolin, and the like is used.

When a picture layer 2 to be described later is provided between the base sheet 1 and the surface resin layer 4, the surface resin layer 4 has transparency at least so that the picture layer 2 thereunder can be seen through. It is most preferable that the material is colorless and transparent, but it may be colored and transparent or translucent. To that extent, the surface resin layer 4 may contain a coloring agent or a filler.

The thicknesses of the base sheet 1 and the surface resin layer 4 are not particularly limited, and may be, for example, the same as those of conventional general decorative sheets. In particular,
In general, the thickness of the base sheet 1 is about 20 to 300 μm, more preferably about 50 to 200 μm, and the thickness of the surface resin layer 4 is 1 to 3 depending on the use of the decorative sheet and the type of resin.
About 0 to 200 μm, more preferably 10 to 100 μm
It is better to be within the range.

The method of forming the base sheet 1 and the surface resin layer 4 is not particularly limited. For example, a film is formed by any conventionally known forming method such as an extrusion molding method, an inflation molding method, a calendar molding method, and a cast molding method. Films or sheets prepared can be used.

The design layer 2 is provided for the purpose of imparting any desired design to the intended decorative sheet. Therefore, for example, when the surface coloring or color adjustment can be sufficiently achieved by coloring the base sheet 1 or forming a concealed solid printing layer, such as a plain decorative sheet only for the purpose of simple surface coloring or color adjustment. The pattern layer 2 may not be particularly provided when the base sheet 1 itself is provided with a pattern by kneading a pigment or transferring a sublimable or melt-transferable dye. However, in general, a pattern layer 2 having an appropriate pattern is often provided on the front surface of the base sheet 1 or the back surface of the front resin layer 4 by a printing method or the like.

When the base sheet 1 and / or the surface resin layer 4 comprises a plurality of layers, the picture layer 2 is provided between any of the layers constituting the base sheet 1 and / or the surface resin layer 4. It is also possible (provided that all resin layers on the surface side from the relevant portion have transparency). In addition, by providing the pattern layer 2 at a plurality of locations selected from these layers and the layer between the base sheet 1 and the surface resin layer 4, the decorative sheet is imparted with an excellent design with a deep feeling and a three-dimensional effect. You can also.

The constituent material and the forming method of the picture layer 2 are not limited at all, and any image forming material or image forming method conventionally applied to the picture layer of the decorative sheet according to the related art can be appropriately applied. Specifically, for example, a printing ink or a coating agent obtained by dissolving or dispersing a colorant such as a dye or a pigment in a suitable solvent together with a suitable binder resin can be used.

Examples of the colorant include inorganic pigments such as carbon black, titanium white, zinc white, red iron oxide, navy blue and cadmium red, azo pigments, lake pigments, anthraquinone pigments, phthalocyanine pigments, quinacridone pigments, and isoindolinones. Pigments, organic pigments such as dioxazine pigments,
Metal powder pigments such as gold powder, silver powder, copper powder, aluminum powder, bronze powder, fish scale powder, basic lead carbonate, bismuth oxychloride,
Pearlescent pigments such as mica coated with titanium oxide, fluorescent pigments, luminous pigments, and the like, or a mixture of two or more kinds selected therefrom can be used.

Further, as the binder resin, for example,
Acrylic resin, styrene resin, polyester resin, urethane resin, polyvinyl resin, alkyd resin, petroleum resin, ketone resin, epoxy resin, melamine resin, fluorine resin, silicone resin, cellulose derivative , Various synthetic resins such as rubber-based resins, or their 2
Mixtures of more than one species, copolymers and the like can be used.

Examples of the solvent include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane, ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-methoxyethyl acetate. Ethyl organic solvents such as ethoxyethyl, alcoholic organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol and propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone Organic solvents, diethyl ether, dioxane, ether organic solvents such as tetrahydrofuran,
Various organic solvents such as chlorinated organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene and tetrachloroethylene, inorganic solvents such as water, or a mixed solvent of two or more thereof can be used.

In addition, various types of additives such as extenders, plasticizers, dispersants, surfactants, tackifiers, adhesion aids, desiccants, stabilizers, curing agents, curing accelerators and curing retarders, if necessary. Can be appropriately added.

In order to make the intended decorative sheet have excellent interlayer adhesion, it is preferable to use a resin having strong adhesiveness and cohesive force as the binder resin of the picture layer 2, and from that viewpoint, it is preferable to use a resin having a high thermal conductivity. It is preferable to use a cross-linkable curable resin such as a curable resin or an ionizing radiation-curable resin. Among them, it has a moderate flexibility and flexibility while having a high cohesive force after crosslinking and curing, and also exhibits excellent adhesiveness to an inert thermoplastic resin such as a polyolefin resin, In the present invention, it is most preferable to use a two-component curable urethane resin in that it has excellent adhesion to the acrylic-polyester-vinyl chloride-vinyl acetate resin used for the heat-adhesive resin layer 3. Specifically, after printing a printing ink composition obtained by adding 3 to 10 parts by weight of an isocyanate compound such as xylene diisocyanate or hexamethylene diisocyanate to 100 parts by weight of a main agent mainly composed of a polyester polyol-based resin, It is most desirable to form the picture layer 2 by crosslinking and curing under heating.

The method of forming the picture layer 2 is not particularly limited.
For example, conventionally known various printing methods such as a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an inkjet printing method can be used. In addition, for example, when the entire surface is solid, in addition to the various printing methods described above, for example, a roll coating method, a knife coating method, an air knife coating method, a die coating method, a lip coating method, a comma coating method, a kiss coating method, a flow coating method And various coating methods such as a dip coating method. In addition, for example, the hand-drawing method,
Of course, it is also possible to perform a photographic method, a laser beam or electron beam drawing method, a partial vapor deposition method of metal or the like, an etching method, or the like, or a combination of a plurality of these methods.

Prior to the formation of the picture layer 2, if necessary, the surface of the base sheet 1 may be subjected to, for example, corona treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, or the like.
By performing a surface treatment such as an anchor or primer treatment, the adhesiveness between the base sheet 1 and the picture layer 2 can be improved.

There are no particular restrictions on the types of pictures that the picture layer 2 comprises, and for example, wood patterns, stone patterns, cloth patterns, abstract patterns, and geometric patterns widely used in the field of decorative sheets according to the related art. In the case of a study pattern or the like, or simple coloring or color adjustment, a single-color solid color may be used. In short, any desired pattern can be adopted according to the intended use of the decorative sheet.

The heat-adhesive resin layer 3 is provided for the purpose of enabling adhesion between the base material sheet 1 and the surface resin layer 4 by a heat laminating method and exhibiting an adhesive strength between the two layers. In the present invention, particularly acrylic-polyester-
A thermo-adhesive resin made of polyvinyl chloride-based resin is used. This heat-adhesive resin, while taking advantage of the advantages of acrylic resins and vinyl chloride vinyl chloride resins that easily melt by heating and exhibit adhesiveness,
It takes into account the properties of the polyester-based resin that causes little decrease in cohesive force even under heating, and has a relatively low temperature that does not adversely affect the base sheet 1 or the surface resin layer 4 such as breakage, elongation, deformation, and deterioration. Under the conditions, it can exhibit sufficient adhesiveness and can be subjected to thermal lamination, and at the same time, has the property of maintaining sufficient peeling resistance without losing adhesive strength even under high temperature use conditions such as quasi-exterior use. .

The mixing ratio of acrylic resin, polyester resin and polyvinyl chloride resin in the acrylic-polyester-vinyl chloride resin is 10 to 60% by weight of acrylic resin, 10 to 60% by weight of polyester resin, and polyvinyl chloride resin. 10-6
It is preferably in the range of 0% by weight, in particular, an acrylic resin of 20 to 50% by weight and a polyester resin of 20 to 50%
% By weight, and most preferably in the range of 20 to 50% by weight.

In laminating the base sheet 1 and the surface resin layer 4 via the heat-adhesive resin layer 3, the heat-adhesive resin layer 3
May be formed in advance on the base sheet 1 side,
A coating may be formed on the surface resin layer 4 side. When a film-like heat-adhesive resin layer 3 is available, it can be laminated by sandwiching it between the base sheet 1 and the surface resin layer 4 to perform heat lamination. However, in general, since the thermo-adhesive resin layer 3 tends to have excellent adhesiveness with the surface of the thermoplastic resin layer formed by coating, the thermo-adhesive resin layer 3 is applied to both surfaces of the two thermoplastic resin layers to be bonded. When the heat-adhesive resin layer 3 is formed in advance by coating, the most excellent adhesive strength by the heat lamination method can be obtained.

The base sheet 1 may be composed of a laminate of a plurality of layers made of the same or different kinds of thermoplastic resins, for example, two layers of a lower resin layer 11 and an upper resin layer 13 (FIG. 2), and / or When the surface resin layer 4 is composed of a laminate of a plurality of layers made of the same or different thermoplastic resins, for example, a laminate of two layers of a lower surface resin layer 41 and an upper surface resin layer 43 (FIG. 3). The heat-adhesive resin layers 12 and 42 made of the above-described resin composition may be provided between the layers.
Such a decorative sheet is formed into a film shape or a sheet shape in advance, and three or more thermoplastic resin layers in which the thermoadhesive resin layers 12, 3, and 42 are formed on the lamination surface are laminated simultaneously and thermally laminated. It can be manufactured efficiently.

The surface of the surface resin layer 4 may be provided with an embossment having a desired and appropriate pattern as required, as is conventionally known. There are no particular restrictions on the type of embossed pattern. For example, the embossed pattern may be of various patterns such as woodgrain (especially conduit pattern), stonegrain, cloth, Japanese paper, geometrical pattern, or the like. It may be a simple matte, grain, hairline, suede, or the like. Further, the design can be further improved by synchronizing these embossed patterns with the design of the design layer 2. However, if it is not necessary, the design may be out of synchronization. It is also possible to provide a pattern emboss including both a pattern synchronized with the pattern and a pattern not synchronized with the pattern.

The method of forming the emboss is not particularly limited, but a mechanical embossing method using a metal embossing plate is most common. There is no particular limitation on the timing of forming the emboss, and any timing can be selected from before, simultaneously with or after lamination of the surface resin layer 4 with the base sheet 1. The embossing of the same or a different pattern can be performed a plurality of times at a plurality of times selected from. In particular, according to the method of embossing simultaneously with the lamination of the base material sheet 1 and the surface resin layer 4 by the thermal lamination method, the lamination and the embossing can be performed in one step, so that the thermal energy is also reduced in terms of production efficiency. It is also advantageous in terms of efficiency.

The concave portion of the emboss may be filled with a coloring agent by a technique such as a wiping method as necessary.
Thereby, it is possible to obtain a decorative sheet excellent in design property having a color pattern synchronized with the uneven pattern on the surface.

Further, a top coat layer 5 may be further provided on the surface of the surface resin layer 4 for the purpose of imparting more excellent surface physical properties to the surface of the decorative sheet. As a constituent material of the top coat layer 5, any material selected from various known top coat agents conventionally used as a constituent material of the top coat layer of the decorative sheet according to the related art can be used. In general, it is necessary to have at least transparency so that the base can be seen through, and to have surface properties such as abrasion resistance, abrasion resistance, solvent resistance, and stain resistance required by the use of the decorative sheet. For this purpose, it is preferable to use a material containing a curable resin as a main component.

Specific examples of the constituent material of the top coat layer 5 include melamine resins, phenol resins,
Urea resin, epoxy resin, aminoalkyd resin,
A thermosetting resin such as a urethane resin, a polyester resin, or a silicone resin, or an ionizing radiation-curable resin such as an acrylic resin can be suitably used. If necessary, various additives such as a gloss adjusting agent, a lubricant, an antistatic agent, an anti-condensation agent, an antibacterial agent and an antifungal agent can be appropriately added. Moreover, by using two or more kinds of resin compositions having different gloss states, and forming a part or all of the resin composition into an arbitrary pattern, a highly decorative decorative sheet having a visual three-dimensional effect due to a change in gloss. You can also get

The method of forming the top coat layer 5 is not particularly limited. If the entire surface is solid, for example, the gravure coating method,
Roll coating, dip coating, air knife coating, knife coating, comma coating, die coating, lip coating, kiss coating, rod coating,
A conventionally known arbitrary coating method such as a spray coating method and a flow coating method can be appropriately applied. In the case of providing in a pattern, it can be provided by any printing method such as a gravure printing method, an offset printing method, a screen printing method, and a flexographic printing method.

If the adhesion between the surface resin layer 4 and the top coat layer 5 is insufficient, the surface of the surface resin layer 4 is subjected to, for example, corona treatment, ozone treatment before the top coat layer 5 is formed. By performing a surface treatment such as a treatment, a plasma treatment, an ionizing radiation treatment, a dichromic acid treatment, an anchor or a primer treatment, the adhesion between the surface resin layer 4 and the top coat layer 5 can be improved.

The decorative sheet of the present invention is used by attaching (laminating) it to the surface of various base materials such as a wooden base material and an inorganic base material, like the conventional decorative sheet. At the time of the application, an appropriate adhesive such as a urethane-based or vinyl acetate-based adhesive is used. However, depending on the type of the adhesive, the adhesiveness to the thermoplastic resin constituting the base sheet 1 is not sufficient. Can be enough. In preparation for such a case, it is preferable to provide a primer layer 6 made of a resin having excellent adhesion to the laminating adhesive on the back surface of the base sheet 1.

As the primer layer 6, various primers such as urethane, acrylic, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer and the like are known. The material selected according to the thermoplastic resin constituting 1 is used. When a powder such as silica, alumina, calcium carbonate, barium sulfate or the like is added to the primer layer 6, the surface of the primer layer 6 is roughened, so that blocking during winding and storage of the decorative sheet can be prevented. At the same time, it is possible to improve the adhesion to the laminating adhesive by the anchor effect.

[0055]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to specific examples and comparative examples of the decorative sheet of the present invention.

Example 1 A two-part curable urethane resin ink (3% by weight of a polyester polyol-based vehicle and an isocyanate curing agent) was blended on the surface of a colored polyethylene resin film (manufactured by Bando Chemical Co., Ltd.) having a thickness of 90 μm. A pattern is printed by a gravure printing method using Toyo Ink Mfg. Co., Ltd., and an acrylic-polyester-vinyl chloride-vinyl acetate-based heat-adhesive resin (acrylic / polyester / vinyl chloride = 1/1) is further printed on the printed surface. 1/1) was applied by a gravure coating method to a coating amount after drying of 5 g / m ² to form a heat-adhesive resin layer. Thereafter, a 50 μm-thick transparent acrylic resin film (manufactured by Mitsubishi Rayon Co., Ltd.) was thermally laminated on the surface of the heat-adhesive resin layer at a film surface temperature of 120 ° C. to produce a decorative sheet of the present invention.

Example 2 In Example 1 described above, acrylic / acrylic was used as the heat-adhesive resin.
A decorative sheet of the present invention was prepared under the same conditions as in Example 1 except that a resin having a composition of polyester / vinyl chloride = 4/4/2 was used.

Example 3 In Example 1 described above, acrylic resin was used as the heat-adhesive resin.
A decorative sheet of the present invention was produced under the same conditions as in Example 1 except that a resin having a composition of polyester / vinyl chloride = 4/2/4 was used.

Comparative Example 1 In the above-mentioned Example 1, acrylic / acrylic resin was used as the heat-adhesive resin.
A decorative sheet was produced under the same conditions as in Example 1 except that a resin having a composition of polyester = 1/1 was used.

Comparative Example 2 In the above-mentioned Example 1, acrylic / acrylic resin was used as the heat-adhesive resin.
A decorative sheet was produced under the same conditions as in Example 1 except that a resin having a composition of polyester = 7/3 was used.

Comparative Example 3 In the above-mentioned Example 1, acrylic / acrylic resin was used as the heat-adhesive resin.
A decorative sheet was produced under the same conditions as in Example 1 except that a resin having a composition of polyester = 3/7 was used.

Comparative Example 4 In Example 1 described above, acrylic / acrylic was used as the heat-adhesive resin.
A decorative sheet was produced under the same conditions as in Example 1 except that a resin having a composition of polyvinyl chloride = 6/4 was used.

Adhesion Performance Test The decorative sheets of Examples 1 to 3 and Comparative Examples 1 to 4 were each subjected to an immersion peeling test under the conditions of boiling for 2 hours and hot water of 48 ° C. at 80 ° C. to obtain a colored polyethylene resin film. The state of adhesion to the transparent acrylic resin film was evaluated. The results were as shown in the following table.

[0064]

Example 4 A gravure printing method was used on a surface of a colored polypropylene resin film having a thickness of 90 μm, using a two-part curable urethane resin-based ink obtained by blending 3% by weight of an isocyanate curing agent with a polyester polyol-based vehicle. A picture is printed, and an acrylic-polyester-vinyl chloride / vinyl chloride-based thermo-adhesive resin (acrylic / polyester / vinyl chloride / vinyl chloride = 1/1/1) is coated by a gravure coating method to a coating amount of 5 g / m ² after drying. Thus, a heat-adhesive resin layer was formed. Thereafter, a transparent polypropylene resin film having a thickness of 50 μm was overlaid on the surface of the heat-adhesive resin layer, and heat-laminated at a film surface temperature of 120 ° C. to prepare a decorative sheet of the present invention.

Example 5 A two-part curable urethane resin-based ink comprising a polyester polyol-based vehicle and 3% by weight of an isocyanate-curing agent was mixed on the surface of a 90-μm-thick colored polypropylene resin film by gravure printing. A picture is printed, and an acrylic-polyester-vinyl chloride / vinyl chloride-based thermo-adhesive resin (acrylic / polyester / vinyl chloride / vinyl chloride = 1/1/1) is coated by a gravure coating method to a coating amount of 5 g / m ² after drying. Thus, a heat-adhesive resin layer was formed. Thereafter, a transparent amorphous polyester resin film having a thickness of 50 μm was overlaid on the surface of the heat-adhesive resin layer, and heat-laminated at a film surface temperature of 120 ° C. to prepare a decorative sheet of the present invention.

Example 6 Surface of a 90 μm-thick colored polypropylene resin film
And isocyanate to polyester polyol vehicle
-Curable urethane tree containing 3% by weight of a curing agent
Print patterns by gravure printing method using oil-based ink
And an acrylic-polyester-salt vinegar on the printing surface.
Bi-based thermal adhesive resin (acrylic / polyester / vinyl chloride =
4/4/2) was applied by gravure coating after drying.
5g / m ^TwoTo form a heat-adhesive resin layer. one
On the other hand, 50μm thick transparent polypropylene resin film
Acrylic-polyester-vinyl chloride-based thermal adhesive tree on the surface
Fat (acryl / polyester / vinyl chloride = 4/4/2)
Coating amount after drying 5 g / m^TwoAnd apply a heat-adhesive resin layer
Formed. After that, colored polypropylene resin film
Transparent polypropylene resin film on the surface of the heat-adhesive resin layer
Layer on the side on which the heat-adhesive resin layer is not
And a heat-adhesive resin for the transparent polypropylene resin film.
25 μm thick transparent biaxially stretched polyethylene tereph
When the tarate resin film is overlaid, the film surface temperature 12
Laminating under the condition of 0 ° C. to give the decorative sheet of the present invention
Produced.

Example 7 A two-component curable urethane resin-based ink comprising a polyester polyol-based vehicle and 3% by weight of an isocyanate-curing agent was coated on the surface of a colored polypropylene resin film having a thickness of 50 μm by a gravure printing method. A picture is printed, and on the other side, an acrylic-polyester-vinyl chloride-based thermal adhesive resin (acrylic / polyester / vinyl chloride = 1/1)
/ 1) was applied by a gravure coating method after drying 5 g /
m ² to form a heat-adhesive resin layer. On the other hand, on the back of a 50 μm thick transparent polypropylene resin film,
Acrylic-polyester-vinyl chloride-based thermal adhesive resin (acrylic / polyester / vinyl chloride = 1/1/1) is applied by a gravure coating method to a coating amount of 5 g / m ² after drying, and the thermal adhesive resin is applied. A layer was formed. Thereafter, a thickness of 80 μm was formed on the surface of the heat-adhesive resin layer of the colored polypropylene resin film.
The colored acrylic resin film was laminated on the printing surface with the heat-adhesive resin layer surface of the transparent polypropylene resin film, respectively, and thermally laminated at a film surface temperature of 120 ° C. to produce a decorative sheet of the present invention.

[0069]

As described in detail above, the decorative sheet of the present invention is obtained by laminating a surface resin layer made of a thermoplastic resin on a base sheet made of a thermoplastic resin via a heat-adhesive resin layer. In the decorative sheet, the heat-adhesive resin layer is made of an acrylic-polyester-vinyl chloride-based resin, so that it can be easily manufactured by a heat lamination method, but has excellent adhesive strength, heat resistance, and weather resistance. Yes,
A decorative sheet that can be used sufficiently for semi-exterior use can be obtained.

Further, even when the base sheet and / or the surface resin layer is a laminate of a plurality of layers made of the same or different thermoplastic resins, the above-mentioned heat-adhesive resin layer is provided between the respective layers. With the interposition, a decorative sheet excellent in heat resistance, weather resistance, and adhesive strength can be easily obtained by a heat lamination method. The method of the present invention is particularly useful when the base sheet and the surface resin layer are composed of a thermoplastic resin selected from a polyolefin resin, an acrylic resin, and a polyester resin. The advantage is that a decorative sheet having the same or better performance as the decorative sheet of the system can be easily manufactured by the same heat lamination method as that of the conventional decorative sheet of the polyvinyl chloride resin. Have

[Brief description of the drawings]

FIG. 1 is a side sectional view showing an embodiment of a decorative sheet of the present invention.

FIG. 2 is a side sectional view showing an embodiment of the decorative sheet of the present invention.

FIG. 3 is a side sectional view showing an embodiment of the decorative sheet of the present invention.

[Explanation of symbols]

 Reference Signs List 1 base material sheet 11 lower resin layer 12 thermal adhesive resin layer 13 upper resin layer 2 picture layer 3 thermal adhesive resin layer 4 surface resin layer 41 lower surface Resin layer 42 ‥‥ Heat-adhesive resin layer 43 ‥‥ Upper layer surface resin layer 5 ‥‥ Top coat layer 6 ‥‥ Primer layer

 ──────────────────────────────────────────────────の Continued on the front page F term (reference) 4F100 AK01A AK01B AK03A AK03B AK15G AK15J AK22G AK22J AK25A AK25B AK25G AK25J AK41A AK41B AK41G AK41J AK51H AK51H AL01G BA02B06 J08 BA10B BA10BBAJB01

Claims (4)

[Claims] 1. A decorative sheet in which a surface resin layer made of a thermoplastic resin is laminated on a base sheet made of a thermoplastic resin via a heat-adhesive resin layer, wherein the heat-adhesive resin layer is made of acryl-polyester. -A decorative sheet comprising a polyvinyl chloride-based resin. 2. The method according to claim 1, wherein the base sheet is a laminate of a plurality of thermoplastic resin layers laminated via a thermo-adhesive resin layer made of an acrylic-polyester-vinyl chloride-vinyl acetate resin. The decorative sheet according to claim 1. 3. The method according to claim 1, wherein the surface resin layer is a laminate of a plurality of thermoplastic resin layers laminated via a thermo-adhesive resin layer made of an acrylic-polyester-vinyl chloride-based resin. The decorative sheet according to claim 1. 4. The method according to claim 1, wherein the base sheet and the surface resin layer are made of a thermoplastic resin selected from a polyolefin resin, an acrylic resin and a polyester resin. A decorative sheet according to claim 1.