JP2000326450A - 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 forming a heat bonding resin layer formed on a base sheet and composed of a vinyl-acetate urethane resin cured by the crosslinking reaction with a block isocyanate compound. 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 polyolefin resin such as a polyethylene, a polypropylene, a polybutaine or a polymethylpentane. A surface layer 4 composed of a transparent thermoplastic resin is formed on the pattern layer 2 through a thermoadhesive resin layer 3 composed of a vinyl-acetate urethane resin cured by the crosslinking reaction with a block isocyanate compound. The heat laminating can be carried out stably without generating defective laminate of the sheets such as the breakage, elongation, deformation, deterioration or others by the arrangement.

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 crosslinked with a blocked isocyanate compound. It is characterized by comprising a cured salted vinegar bi-urethane resin.

In the decorative sheet according to the present invention, in the decorative sheet described above, the base sheet is provided via a heat-adhesive resin layer made of a vinyl chloride-vinyl-urethane-based resin cured by a crosslinking reaction with a blocked isocyanate compound. It is a laminate of a plurality of laminated thermoplastic resin layers.

[0013] In the decorative sheet of the present invention, in the decorative sheet, the surface resin layer is formed via a heat-adhesive resin layer made of a vinyl chloride-vinyl-urethane-based resin cured by a crosslinking reaction with a blocked isocyanate compound. It is a laminate of a plurality of laminated thermoplastic resin 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 crosslinked with a blocked isocyanate compound. It is characterized by comprising a cured salted vinegar bi-urethane 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 desirable to use a two-component curable urethane resin in that the adhesiveness to the vinyl chloride-vinyl-urethane resin used for the heat-adhesive resin layer 3 is excellent. Specifically, an isocyanate compound such as xylene diisocyanate or hexamethylene diisocyanate is used in an amount of 3 to 100 parts by weight of a main component mainly composed of a polyester polyol resin.
After printing the printing ink composition added with 10 parts by weight, it is most desirable to form the picture layer 2 by crosslinking and curing at room temperature or 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 particular, the present invention, as this heat-adhesive resin layer,
It employs a vinyl chloride-vinegar-urethane resin cured by a crosslinking reaction with a blocked isocyanate compound.

This heat-adhesive resin is a resin composition obtained by blending a blocked isocyanate compound with a vinyl chloride-vinyl-polyol resin, and before curing, the vinyl chloride-vinyl-polyol resin as a main resin is in an uncrosslinked state. Therefore, it is easily melted by heating and exhibits excellent adhesiveness. The blocking agent of the blocked isocyanate is dissociated by heating during or after the heat lamination, and the liberated active isocyanate group undergoes a cross-linking reaction with the polyvinyl chloride-polyol-based resin to be cured, whereby the vinyl acetate-urethane-based resin is cured. It produces resin and exhibits excellent cohesive strength and heat resistance due to the intermolecular cross-linking structure.

In this way, the heat-laminating process is performed by sufficiently developing adhesiveness even at a relatively low temperature without adversely affecting the base sheet 1 and the surface resin layer 4 such as breakage, elongation, deformation and deterioration. At the same time, it has the property of maintaining sufficient peeling resistance without losing adhesive strength even under high-temperature use conditions such as semi-exterior applications after curing.

The vinyl chloride-vinegar-polyol resin includes
A resin obtained by introducing a hydroxyl group capable of undergoing a cross-linking reaction with an isocyanate group into a polyvinyl chloride resin molecule may be used, or a polyvinyl chloride resin containing no hydroxyl group in the molecule and a polyol containing a hydroxyl group in the molecule It may be a mixture with a system resin.
Of course, a polyvinyl chloride-based resin having a hydroxyl group introduced into the molecule and a polyol-based resin can be used in combination.

Examples of the vinyl chloride-based resin having a hydroxyl group introduced into the molecule include α, β-unsaturated carboxylic acids such as (meth) acrylic acid and maleic acid, hydroxyalkyl (meth) acrylate, and hydroxyalkyl vinyl ether. Examples of the resin include a resin obtained by copolymerizing a monomer containing a hydroxyl group with vinyl chloride and vinyl acetate, and a resin obtained by saponifying a part of a vinyl acetate component of a vinyl chloride resin to introduce a hydroxyl group. On the other hand, as the polyol-based resin, for example, polyester polyol-based resin, polyether polyol-based resin, polyurethane polyol-based resin,
An acrylic polyol-based resin can be used.

Examples of the blocked isocyanate added as a curing agent to these main resins include isocyanate compounds such as tolylene diisocyanate, xylene diisocyanate, mesitylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate, or burettes thereof. Adducts, free isocyanate groups contained in isocyanurates and the like, for example, phenol-based blocking agents such as phenol and cresol, oxime-based blocking agents such as methyl ethyl ketone oxime and acetone oxime, ε-caprolactam, γ-butyrolactam and the like Lactam blocking agent, ethyl acetoacetate,
Active methylene blocking agents such as acetylacetone and ethyl malonate, alcohol blocking agents such as methanol and ethanol, amine blocking agents, imine blocking agents, imide blocking agents, imidazole blocking agents,
A compound blocked with a blocking agent such as a mercaptan-based blocking agent can be used.

If the dissociation temperature of the blocked isocyanate is too low, the crosslinking reaction proceeds during the application of the heat-adhesive resin to the base sheet 1 or the surface resin layer 4 or during storage at room temperature, resulting in thermal lamination. If it is too high, the base sheet 1 and the surface resin layer 4 may be excessively softened.
Since the crosslinking reaction can not be sufficiently cured in a temperature range where the deformation is not caused, it is necessary to select a dissociation temperature range in consideration of these. In particular, it is most preferable to select a material that sufficiently dissociates at the temperature of the heat lamination between the base sheet 1 and the surface resin layer 4 because the cross-linking reaction and curing can be performed simultaneously with the heat lamination. In particular,
It is most desirable to employ a blocked isocyanate having a dissociation temperature in the range of about 60 to 120 ° C.

The mixing ratio of the blocked isocyanate to the vinyl chloride-vinyl-polyol-based main resin is not particularly limited, but the amount of the blocked isocyanate to be added may be equivalent or slightly excessive to the amount of the hydroxyl group contained in the main resin. Is good. Generally, it is preferable to add about 3 to 15 parts by weight of a blocked isocyanate to 100 parts by weight of the main resin.

When applying the above-mentioned heat-adhesive resin to the surface of the base sheet 1 or the surface resin layer 4, hot-melt coating may be carried out in a low temperature range where the added blocked isocyanate compound is not dissociated, or What is necessary is just to apply | coat and dry what melt | dissolved or disperse | distributed resin and block isocyanate in suitable solvent in the low temperature range which a block isocyanate compound does not dissociate.

In laminating the base sheet 1 and the surface resin layer 4 via 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. This method is particularly effective as a method for improving interlayer adhesion when bonding resin layers having poor thermal adhesion, such as a polyolefin resin, for example.

The base sheet 1 may be composed of a laminate of a plurality of layers made of the same or different 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 very simply and efficiently.

The surface of the surface resin layer 4 may be provided with an embossment having a desired and appropriate pattern, if necessary, 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 can be further provided on the surface of the surface resin layer 4 for the purpose of imparting more excellent surface 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, a 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.

[0062]

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 surface of a colored polypropylene film having a thickness of 90 μm was subjected to corona discharge treatment, and then gravure was performed using a two-part curable urethane resin ink obtained by mixing 3% by weight of an isocyanate curing agent with a polyester polyol vehicle. A wood grain pattern is formed by printing using a printing method, and a heat-adhesive resin (mixture of a polyvinyl chloride-based resin and a polyester polyol-based resin) containing 5% by weight of a blocked isocyanate is dried thereon, and the coated amount after drying is 5 g / m. ² to form a heat-adhesive resin layer, and after a corona discharge treatment on the back surface, a gravure coating of a urethane-based primer resin mixed with silica powder to a coating amount of 1 g / m ² after drying, A lower printed polypropylene single layer film was obtained. On the other hand, after applying a corona discharge treatment to the back surface of a transparent polypropylene film having a thickness of 70 μm, the same heat-adhesive resin as described above was applied to a coating amount of 5 g / m ² after drying to form a heat-adhesive resin layer. A transparent polypropylene single layer film was obtained.

When the lower printed polypropylene single-layer film and the upper transparent polypropylene single-layer film are polymerized with their heat-adhesive resin layers facing each other and subjected to heat lamination at a sheet surface temperature of 120 ° C. At the same time, the surface of the upper transparent polypropylene single-layer film is embossed with a conduit pattern, the recessed portion of the emboss is subjected to wiping treatment, filled with coloring ink, and the entire surface is coated with a two-component urethane top coat resin after drying. 6g / m
² to give a decorative sheet of the present invention.

Comparative Example 1 A decorative sheet was prepared under the same conditions as in Example 1 above, except that a vinyl chloride / vinyl-acrylic resin containing no blocked isocyanate was used as the thermal adhesive resin.

Performance Comparison Using the decorative sheets of Example 1 and Comparative Example 1, 8
When the immersion peel test was performed for 48 hours at 0 ° C. in hot water, no abnormality was found in the decorative sheet of Example 1, whereas
In the decorative sheet of Comparative Example 1, it was confirmed that the peeling-off occurred partially at the interface between the lower printed polypropylene single-layer film and the upper transparent polypropylene single-layer film.

Example 2 A transparent acrylic resin film having a thickness of 50 μm was laminated on the surface of the heat-adhesive resin layer of the lower-layer printed polypropylene single-layer film in Example 1 above. The embossed portion was filled with a coloring agent by wiping, and a two-component urethane resin-based top coat (coating amount after drying was 6 g / m ² ) was applied to prepare a decorative sheet of the present invention. .

Example 3 A transparent amorphous polyester resin film having a thickness of 50 μm was placed on the surface of the heat-adhesive resin layer of the lower-layer printed polypropylene single-layer film in Example 1 above.
At the same time as the heat lamination under the condition of 20 ° C., the embossing of the conduit pattern is performed, and further, the coloring agent is filled into the embossed concave portion by the wiping method, and the two-component urethane resin-based top coat (coating amount after drying 6 g / m ² ) Thus, the decorative sheet of the present invention was produced.

Example 4 On the surface of a colored acrylic resin film having a thickness of 80 μm,
A wood grain pattern is formed by gravure printing using a two-component curable urethane resin-based ink containing 3% by weight of an isocyanate curing agent mixed with a polyester polyol-based vehicle. 5% by weight of a thermo-adhesive resin (mixture of polyvinyl chloride-based resin and polyester polyol-based resin) is applied after drying.
g / m ² to form a heat-adhesive resin layer, and a 70 μm-thick transparent amorphous polyester resin film is superimposed on the heat-adhesive resin layer, and heated at a film surface temperature of 120 ° C. Simultaneously with laminating, embossing of a conduit pattern was performed, and further, a coloring agent was filled into the embossed concave portion by a wiping method, and a two-liquid urethane resin-based top coat (coating amount after drying was 6 g / m ² ) was applied. A decorative sheet was produced.

Example 5 After a corona discharge treatment was applied to the front and back surfaces of a colored polypropylene film having a thickness of 50 μm, a two-component curable urethane resin ink obtained by mixing 3% by weight of an isocyanate curing agent with a polyester polyol vehicle was used. After a wood grain pattern is formed by printing using a gravure printing method, a heat-adhesive resin (mixture of a polyvinyl chloride resin and a polyester polyol resin) containing 5% by weight of a blocked isocyanate on the printed surface and the back surface is dried. The coating was applied at an application amount of 5 g / m ² to form a heat-adhesive resin layer, thereby obtaining a printed polypropylene single-layer film. On the other hand, the back surface of the transparent polypropylene film having a thickness of 50 μm was subjected to corona discharge treatment, and then the same heat-adhesive resin as described above was applied to a dry coating amount of 5 g / m ² to form a heat-adhesive resin layer. A transparent polypropylene single layer film was obtained.

An 80 μm-thick colored acrylic resin film is polymerized on the back side of the printed polypropylene single-layer film, and the upper transparent polypropylene single-layer film is placed on the front side with the heat-adhesive resin layers facing each other. Polymerization and heat lamination at a sheet surface temperature of 120 ° C., and at the same time, embossing of the conduit pattern on the surface of the upper layer transparent polypropylene single-layer film, followed by wiping the embossed recesses and coloring The ink was filled, and a two-component urethane-based top coat resin was applied on the entire surface to a coating amount of 6 g / m ² after drying to obtain a decorative sheet of the present invention.

Example 6 A heat-adhesive resin prepared by mixing 5% by weight of a blocked isocyanate after corona treatment on both surfaces in advance on the surface of the heat-adhesive resin layer of the lower-layer printed polypropylene single-layer film in Example 1 described above. Polyester polyol-based resin) is applied to a dry coating amount of 5 g / m ² to form a heat-adhesive resin layer, and a 50 μm-thick transparent polypropylene single-layer film is laminated thereon. A 25 μm-thick transparent biaxially stretched polyethylene terephthalate resin film coated at a coating amount of 5 g / m ² after drying was thermally laminated at a film surface temperature of 120 ° C. A two-component urethane-based top coat resin is applied to the surface to a coating amount of 6 g / m ² after drying,
A decorative sheet of the present invention was produced.

[0073]

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 composed of a vinyl chloride-vinyl-urethane-based resin cured by a crosslinking reaction with a blocked isocyanate compound. It is possible to obtain a decorative sheet which is excellent in heat resistance and weather resistance and can be sufficiently used for semi-exterior use.

In the case where 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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09J 131/04 C09J 131/04 Z 175/04 175/04 // C09J 7/02 7/02 Z (72 ) Inventor Tsutomu Saito 1-5-1, Taito, Taito-ku, Tokyo Inside Toppan Printing Co., Ltd. (72) Inventor Yumiko Tsuruta 1-1-1, Taito 1-5-1, Taito-ku, Tokyo Toppan Printing Co., Ltd. ) 4F100 AK01A AK01B AK01C AK03A AK03B AK03C AK07A AK07B AK15G AK15J AK22G AK22J AK25A AK25B AK25C AK41A AK41B AK41C AK51C AK51G AL05G BA03 BA07 BA10A BA10C BA15 GB07 GB08 GB31 GB33 GB43 GB81 GB90 HB00 HB01A JB13G JB16A JB16B JB16C JJ03 JK06 JL02 JL09 JL12G JN01B 4J004 AA07 AA09 AA14 CA03 CA05 CC02 CC03 CD01 CE01 FA01 4J040 DC051 DD051 DE021 DF061 EF111 EF112 EF131 EF132 EF181 EF182 EF331 EF332 GA05 HC16 JA02 JA03 JA08 JB02 KA 16 LA06 LA07 LA08 MA10 MA11 MB03 NA08 NA12

Claims (4)

[Claims] 1. A decorative sheet having a surface resin layer made of a thermoplastic resin laminated on a base sheet made of a thermoplastic resin via a heat adhesive resin layer, wherein the heat adhesive resin layer is a blocked isocyanate compound. A decorative sheet comprising a vinyl chloride-vinegar-urethane resin cured by a crosslinking reaction with 2. The method according to claim 1, wherein the base sheet is formed of a plurality of thermoplastic resin layers laminated via a thermo-adhesive resin layer made of a vinyl chloride-vinyl-urethane-based resin cured by a crosslinking reaction with a blocked isocyanate compound. The decorative sheet according to claim 1, which is a laminate. 3. A thermoplastic resin layer comprising a plurality of thermoplastic resin layers laminated via a thermoadhesive resin layer made of a vinyl chloride-vinyl-urethane-based resin cured by a crosslinking reaction with a blocked isocyanate compound. The decorative sheet according to claim 1, wherein the decorative sheet is a laminate. 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.