JP2000301672A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet excellent not only in vacuum moldability but also in various surface physical properties such as surface hardness, abrasion resistance, solvent resistance or the like. SOLUTION: A decorative sheet is constituted by providing an intermediate resin layer 2 comprising a thermoplastic olefinic resin and a transparent resin layer 3 comprising a thermoplastic olefinic resin on a substrate sheet comprising an amorphous polyester resin. The glass transition temp. of the amorphous polyester resin is desirably 60-85 deg.C and the cold crystallizing temp. thereof is desirably 120 deg.C or higher.

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.
The present invention relates to a decorative sheet for use in surface makeup of household equipment and home electric appliances. More specifically, it is possible not only to attach to a substrate on a flat surface, but also to perform three-dimensional molding such as V-cut processing, lapping on an uneven substrate, vacuum molding, etc., and does not generate harmful substances such as hydrogen chloride gas during combustion. It is related to an environmentally friendly decorative sheet.

[0002]

2. Description of the Related Art In recent years, with the sophistication and diversification of consumer preferences, demands for various complicated three-dimensional decorative members have been increasing. As such a three-dimensional decorative member, for example, plywood, particle board, medium density fiberboard (MD
F) and other various types of base materials such as woody base materials, inorganic base materials such as calcium silicate plate, slate plate and wood wool cement plate, and synthetic resin base materials such as fiber reinforced plastic (FRP). , A decorative sheet obtained by sticking an appropriate decorative sheet
Some have been subjected to bending processing such as cutting. In addition, along the surface of the columnar substrate having an irregular shape on the surface,
There is also a wrapping process in which a decorative sheet is wound and attached.

However, according to these techniques, the range of the three-dimensional shape that can be manufactured is limited to a shape that can be developed in a plane, and it is not possible to cope with a more complicated three-dimensional shape. Therefore, a decorative sheet made of thermoplastic resin is applied on the surface of various base materials that have been formed into a complicated three-dimensional three-dimensional shape in advance.
A technique of performing three-dimensional molding by a vacuum forming method (including a pressurized air forming method and a vacuum pressurized air forming method) and simultaneously attaching the three-dimensionally formed one has already been widely adopted. And, with the further sophistication and diversification of consumer preferences in recent years, the demand for more and more complex three-dimensional three-dimensional decorative members has been increasing.
There is an increasing demand for the development of decorative sheets that can withstand more severe molding conditions.

Heretofore, as a thermal composition resin constituting a general decorative sheet made of a thermoplastic resin, a polyvinyl chloride resin which is inexpensive and excellent in processability and various physical properties has been most often used. However, in recent years, in response to growing public interest in environmental issues, polyvinyl chloride resins that may generate harmful substances such as hydrogen chloride gas and dioxin during combustion have been shunned. There is a strong demand for a decorative sheet using a non-chlorine-based resin that has little adverse effect on the environment. In response to this, decorative sheets using, for example, a thermoplastic olefin resin have been developed as a substitute material for the polyvinyl chloride resin and have been put into practical use (Japanese Patent Laid-Open No. 6-16832).
No.).

However, a decorative sheet using, for example, a general-purpose polypropylene resin as a thermoplastic olefin-based resin has insufficient flexibility, so that when subjected to bending or vacuum forming, whitening, cracking, or the like occurs. There was a problem that breakage, necking, and the like were easily generated. Therefore, for the purpose of solving such problems, a decorative sheet using a so-called soft olefin resin in which flexibility is imparted to a resin such as polypropylene by means of copolymerization with a soft monomer or blending of a soft component such as an elastomer. Also, various proposals have been made (JP-A-9-300554, JP-A-9-328).
562, JP-A-10-17679, etc.).

[0006] However, the decorative sheet made of a soft olefin-based resin imparted with flexibility as described above can solve the above-mentioned problems, but the sheet is essentially flexible and has low stiffness and heat resistance. Due to chemical weakness, wrinkles at the time of sticking to the substrate, poor appearance to pick up irregularities on the surface of the substrate, drawdown and uneven molding due to excessive softening of the sheet due to heating during vacuum forming However, there are problems such as poor appearance and the like, and poor surface properties such as surface hardness, abrasion resistance and solvent resistance.

[0007]

SUMMARY OF THE INVENTION The present invention has been made for the purpose of solving the above-mentioned problems in the prior art, and is excellent in vacuum forming suitability, surface hardness, abrasion resistance, and the like. An object of the present invention is to provide a decorative sheet having excellent surface properties such as solvent resistance.

[0008]

According to the present invention, an intermediate resin layer made of a thermoplastic olefin resin and a transparent resin layer made of a thermoplastic olefin resin are formed on a base sheet made of an amorphous polyester resin. Are sequentially provided.

In the present invention, the amorphous polyester resin preferably has a glass transition temperature of 60 ° C. or more and 85 ° C. or less,
A decorative sheet having a cold crystallization temperature of 120 ° C. or higher.

[0010]

Embodiments of the present invention will be described below in detail with reference to the drawings. FIG. 1 is a side sectional view showing an embodiment of the decorative sheet of the present invention.

[0011] The decorative sheet of the present invention, as shown in FIG.
On a base sheet 1 made of an amorphous polyester resin,
An intermediate resin layer 2 made of a thermoplastic olefin resin and a transparent resin layer 3 made of a thermoplastic olefin resin are at least sequentially laminated. In the decorative sheet of the present invention, “transparent” of the transparent resin layer 3 is not necessarily limited to colorless and transparent, but also includes translucent and colored transparent.

The kind of the amorphous polyester resin constituting the base sheet 1 is not particularly limited, but a typical one is commercially available as a so-called A-PET sheet, which is a general-purpose thermoplastic resin. It is formed by extruding a polyethylene terephthalate resin as a polyester resin into a sheet under molding conditions that do not cause crystallization.

More specifically, for example, "Teijin Tetron Sheet (A-PET)" manufactured by Teijin Limited, "Toyobo PETMAX Sheet A Series" manufactured by Toyobo Co., Ltd., and "Kanebo A-PET Sheet" manufactured by Kanebo Co., Ltd. Commercially available ones can be mentioned. These are already widely used for applications such as transparent containers.

As the amorphous polyester resin, in addition to the above-mentioned molding conditions, various copolymerization components for suppressing crystallization while using a general-purpose thermoplastic polyester resin such as a polyethylene terephthalate resin as a basic skeleton are used. The used copolyester resin can also be used.

For example, in a condensation polymerization reaction of an aromatic dicarboxylic acid or dicarboxylic acid ester such as terephthalic acid or naphthalenedicarboxylic acid with an aliphatic diol such as ethylene glycol or 1,4-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. Examples include those into which a polyether diol having a hydroxyl group is introduced. Specifically, for example, it is commercially available as "Spectar" manufactured by Eastman Kodak Company.

In the present invention, in addition to the above, a sheet made of an arbitrary resin selected from various amorphous polyester resins can be used as the base sheet. Of course, a laminate of a plurality of layers made of the same or different amorphous polyester-based resin may be used.

Since the amorphous polyester resin does not use a polyvinyl chloride resin, there is very little danger of generating harmful chemical substances such as hydrogen chloride gas and dioxin even when incinerated. Since it has a higher melting point than vinyl chloride resin, it has excellent heat resistance (break resistance upon heating), and also has excellent solvent resistance, so that a wide selection range of printing inks and adhesives is wide. In addition, in comparison with the polyolefin resin, the amorphous polyester resin has extremely uniform moldability due to the absence of the sea-island structure of the crystalline phase and the non-crystalline phase, such as necking, pattern distortion, and whitening. No molding failure occurs.

The thickness of the base sheet 1 is not particularly limited.
A sheet having a thickness similar to that of a base sheet of a conventional decorative sheet can be used. However, if it is too thin, it is easily broken at the time of vacuum forming. On the other hand, if it is too thick, it is inferior in moldability and uneconomical.
It is better to be within the range. Above all, 50-150 μm
A range of degrees is most recommended.

In order to conform to the molding conditions of a conventional vacuum molding machine for cosmetics, the amorphous polyester resin constituting the base sheet 1 must have a glass transition temperature. It is desirable to employ a resin having a (Tg) of 60 ° C. or more and 85 ° C. or less and a cold crystallization temperature (Tc) of 120 ° C. or more.

If the glass transition temperature exceeds 85 ° C., it is necessary to set the heating temperature during vacuum forming higher than usual.
It is disadvantageous in terms of thermal energy efficiency and molding cycle time, and disadvantageous in terms of moldability because the resin becomes hard. On the other hand, if the temperature is lower than 60 ° C., the sheet is inferior in heat resistance, so that molding defects such as drawdown are likely to occur, and the produced decorative material is disadvantageous in terms of heat resistance and durability. If the cold crystallization temperature is less than 120 ° C., the crystallization of the resin proceeds by heating during vacuum forming, the resin loses flexibility and the moldability is reduced, and the sea-island between the crystalline phase and the amorphous phase is reduced. Structure appears,
This is because molding defects such as necking and pattern distortion due to a difference in deformation characteristics between the two and whitening due to a difference in refractive index between the two tend to occur.

The glass transition temperature and the cold crystallization temperature depend not only on the composition and molecular weight of the resin but also on the molding conditions at the time of molding the resin sheet. What is necessary is just to appropriately select a material that meets the conditions, or to set the sheet forming conditions so as to be in a suitable range.

Other properties of the amorphous polyester resin constituting the base sheet 1 include a tensile modulus of 100%.
kgf / mm ² or more 300 kgf / mm ² or less it is desirable. If the tensile modulus is less than 100 kgf / mm ² , the resin is too soft and easily damaged and the waist is weak, and wrinkles and scratches at the time of lamination, drawdown, and poor molding for picking up irregularities on the surface of the base material, etc. On the other hand, 300
If the weight exceeds kgf / mm ² , the flexibility of the resin is insufficient and the processability is poor, and the molding cannot be completely followed in the three-dimensional three-dimensional shape of the base material. This is because they tend to cause temporal separation or the like due to the applied stress.

If necessary, the amorphous polyester resin constituting the base sheet 1 may be, for example, a coloring agent, a filler, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, or a lubricant. One or more of various additives such as an antistatic agent and a flame retardant can be added.

In particular, when the intended decorative sheet is required to have a concealing property with respect to the surface of the base material to be adhered, a coloring agent is added to the amorphous polyester resin constituting the base sheet 1 for coloring. However, by setting the concealing property, a sufficiently excellent concealing property can be obtained. As the colorant, for example, organic or inorganic dyes or pigments may be mentioned, but it is preferable to use at least a opaque pigment having a high refractive index from the viewpoint of concealing power. It is desirable to use.

Specifically, for example, white inorganic pigments such as titanium oxide, zinc oxide and basic lead carbonate;
Colored inorganic pigments such as yellow iron oxide and iron black), chromium oxide, cobalt blue and carbon black; metal powder pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride. Can be.
Needless to say, for the purpose of adjusting the color, an organic pigment having excellent weather resistance such as a phthalocyanine pigment may be used in combination. If necessary, extender pigments such as silicon oxide, calcium carbonate, barium sulfate and the like can be used in combination.

Other additives include, for example, phenol-based, sulfur-based, and phosphorus-based antioxidants, and benzophenone-based, benzotriazole-based, salicylate-based, cyanoacrylate-based, formamidine-based, and oxanilide-based ultraviolet absorbers. Such as hindered amine type, nickel complex type, etc., as the light stabilizer, hindered phenol type, sulfur type, hydrazine type, etc., as the heat stabilizer, and phthalic acid ester type as the plasticizer,
Phosphate ester type, fatty acid ester type, aliphatic dibasic acid ester type, oxybenzoic acid ester type, epoxy type,
For example, polyester-based lubricants such as fatty acid ester-based, fatty acid-based, metal soap-based, aliphatic amide-based, higher alcohol-based, paraffin-based, and silicone-based anti-static agents, such as cationic, anionic, and nonionic,
Examples of flame retardants such as zwitterionics are bromine-based, phosphorus-based,
Chlorine-based, nitrogen-based, aluminum-based, antimony-based, magnesium-based, boron-based, and zirconium-based fillers such as calcium carbonate, barium sulfate, talc, rubble,
It is used in one kind or a mixture of two or more kinds selected from kaolin and the like.

The type of the thermoplastic olefin resin constituting the intermediate resin layer 2 and the transparent resin layer 3 is not particularly limited.
For example, any thermoplastic olefin resin conventionally used as a constituent material of a decorative sheet can be used. Specifically, for example, various homopolymers such as polyethylene resin, polypropylene resin, polybutene-1 resin, poly-4-methylpentene-1 resin,
Olefin copolymer resins such as ethylene-α olefin copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene- (meth) acrylic acid (ester) copolymer resin, ethylene-vinyl alcohol copolymer resin, etc. Can be mentioned.

Among them, the most suitable for the purpose of the present invention is a polypropylene resin, that is, a homopolymer or a copolymer containing polypropylene as a main component.
Block polypropylene resin, and having a polypropylene crystal part, and having 2 to 20 carbon atoms other than propylene α
Olefins, preferably ethylene, butene-1,4-
Methylpentene-1, hexene-1 or octene-1,
Containing at least 15 mol% of a comonomer of
Olefin copolymers and the like can be exemplified. It is also possible to add modifiers such as ethylene-α-olefin copolymer, ethylene-propylene copolymer rubber, and ethylene-propylene-non-conjugated diene copolymer rubber which are usually used for softening polypropylene-based resin. it can.

Of course, the kind of the thermoplastic olefin resin constituting the intermediate layer 2 and the transparent resin layer 3 is not limited to these. Further, a laminate of a plurality of layers made of the same or different thermoplastic olefin-based resins may be used.

The above-mentioned thermoplastic olefin resin may contain, if necessary, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, a lubricant, an antistatic agent depending on the intended use of the decorative sheet. One or more kinds of conventionally known various additives such as an agent, a flame retardant, and a filler may be added. Specifically, for example, those exemplified as the additives to be added to the amorphous polyester resin constituting the base sheet 1 can be used.

In particular, when the picture layer 4 is provided between the intermediate resin layer 2 and the transparent resin layer 3, if the intermediate resin layer 2 is formed of a concealable resin film or sheet, it is sufficiently excellent as a decorative sheet. In addition, the concealing property can be easily provided. Specifically, a hiding pigment is added to the thermoplastic olefin resin constituting the intermediate resin layer 2. As the concealing pigment, those already mentioned as those which can be added to the amorphous polyester resin constituting the base sheet 1 can be used. When sufficient hiding power can be ensured by the hiding intermediate resin layer 2, the base sheet 1 does not necessarily need to have hiding power.

As described above, when the picture layer 4 is provided between the intermediate resin layer 2 and the transparent resin layer 3, a layer made of an olefin resin having better solvent resistance than an amorphous polyester resin is used. Since the picture layer 4 is formed by printing, there is also an advantage that the range of selection of printing ink used for forming the picture layer 4 is expanded.

The thicknesses of the intermediate resin layer 2 and the transparent resin layer 3 made of a thermoplastic olefin resin are not particularly limited, and surface physical properties such as abrasion resistance and solvent resistance, weather resistance, painting feeling and depth feeling are provided. The balance of various characteristics is comprehensively taken into consideration, such as the design properties such as emboss depth, flexibility and flexibility as a decorative sheet, and the ability to follow the three-dimensional shape of the substrate surface during vacuum forming. The range of thickness that can be taken is selected. Specifically, the intermediate resin layer 2 and the transparent resin layer 3 are generally selected from a range of about 20 to 200 μm, depending on the use of the decorative sheet, the required quality corresponding thereto, the type of the thermoplastic olefin resin to be used, and the like. The particularly preferred range is about 50 to 150 μm.

The method for laminating the base sheet 1, the intermediate resin layer 2, and the transparent resin layer 3 is not particularly limited, and any conventionally known laminating method can be appropriately employed. The order of the laminating step is not particularly limited, and the intermediate resin layer 2 may be first laminated on the base sheet 1 and then the transparent resin layer 3 may be laminated. 3 may be laminated on the back surface of the intermediate resin layer 2. Of course, three layers can be simultaneously laminated and integrated.

As a method of laminating each layer, for example, a dry lamination method, a wet lamination method, a heat lamination method,
It can be appropriately selected from conventionally known various laminating methods such as an ultrasonic laminating method, a high-frequency laminating method, an extrusion laminating method, and a sand laminating method. Of course, a combination of a plurality of laminating methods may be used.

In the extrusion lamination method, that is, a method in which another resin is melted and extruded on the surface of a resin layer formed into a sheet shape, and then molded into a sheet shape and laminated at the same time, the bonding between two layers to be laminated is performed. If the property is inferior, as is well known, a heat-sensitive adhesive anchor layer 5 is provided on the surface of the molded resin layer in advance,
And / or by co-extruding and laminating the melt-extruded resin and the separately-easy heat-adhesive resin and sandwiching the adhesive resin layer 6 between the layers, the adhesiveness can be improved.

As described above, the decorative sheet of the present invention has
It is customary to provide a picture layer 4 for the purpose of imparting a design with a desired picture such as wood grain. The position of the picture layer 4 is not particularly limited as long as it can be seen through from the surface of the decorative sheet. For example, when all of the base sheet 1, the intermediate resin layer 2, and the transparent resin layer 3 are transparent, the back surface of the base sheet 1, the interlayer between the base sheet 1 and the intermediate resin layer 2, the intermediate resin layer 2 And the transparent resin layer 3 and at an arbitrary position selected from the surface of the transparent resin layer 3. Also, it may be provided at a plurality of locations selected from these.

Among them, the most recommended is a structure in which a picture layer 4 is provided between the opaque intermediate resin layer 2 and the transparent resin layer 3. That is, a pattern layer 4 is formed by printing on the surface of a film or sheet made of a concealable thermoplastic olefin-based resin to be the intermediate resin layer 2, and a transparent olefin-based resin to be the transparent resin layer 3 is formed thereon. First, a laminated sheet is prepared by laminating a film or sheet by an appropriate method such as a dry lamination method, a heat lamination method, or an extrusion lamination method, and thereafter, a film or a film made of an amorphous polyester resin to be the base sheet 1 An adhesive 7 is attached to the back surface of the intermediate resin layer 2 of the laminated sheet.
With or without intermediary, lamination may be performed by an appropriate method such as a dry lamination method, a heat lamination method, or an extrusion lamination method.

There are no particular restrictions on the type of pattern in the pattern layer 4, for example, wood grain patterns, stone patterns, cloth patterns, abstract patterns, geometric patterns, etc., which have been widely used in the field of decorative sheets according to the prior art. Or, for the purpose of simple coloring or color adjustment, a single-color solid color may be used.
Any desired pattern can be adopted according to the intended use of the decorative sheet.

There is no particular limitation on the constituent material and the forming method of the picture layer 4, and any image forming material or image forming method which has been conventionally applied to the picture layer of the decorative sheet can be appropriately employed. 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. However, it is necessary to select a material having flexibility that can follow vacuum forming into a three-dimensional three-dimensional shape.

Examples of the coloring agent 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, quinacridone pigments, phthalocyanine pigments, and isoindolinones. Pigments, organic pigments such as dioxazine pigments,
Metal powder pigments such as aluminum powders and bronze powders, mica coated with titanium oxide, pearlescent pigments such as bismuth oxychloride, fluorescent pigments, luminous pigments, and the like, or a mixture of two or more selected from these can be used.

Examples of the binder resin include acrylic resins, styrene resins, polyester resins,
Urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum resin, ketone resin, epoxy resin, melamine resin, fluorine resin, silicone resin And various synthetic resins such as cellulose derivatives, rubber resins, or a mixture of two or more thereof.

Examples of the solvent include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane and methylcyclohexane, and ethyl acetate, butyl acetate and acetic acid-2.
-Ethyl organic solvents such as -methoxyethyl, acetic acid-2-ethoxyethyl, etc., alcoholic organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol, acetone, methyl ethyl ketone, methyl Ketone organic solvents such as isobutyl ketone and cyclohexanone; ether organic solvents such as diethyl ether, dioxane and tetrahydrofuran; various organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene and other organic solvents; and inorganic materials such as water. A solvent or a mixture 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 or retarders, if necessary. Can be appropriately added.

The method for forming the picture layer 4 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 carry out the method by a photographic method, a transfer method, a laser beam or electron beam drawing method, a partial vapor deposition method of metal or the like, an etching method, or a combination of two or more selected from these various methods.

Prior to the formation of the picture layer 4, if necessary, the printing surface is subjected to a surface treatment such as a corona treatment, an ozone treatment, a plasma treatment, an ionizing radiation treatment, a dichromic acid treatment, an anchor or a primer treatment. Thereby, the adhesion of the picture layer 3 to the surface to be printed can be improved.

When the intended decorative sheet requires concealing properties, and when the base sheet 1 or the intermediate resin layer 2 is transparent or lacks concealing properties, the concealing layer is used together with the picture layer 4. Can also be provided. The material and method for forming the concealing layer are the same as those for the above-described pattern layer 4, but in order to obtain good concealing properties, at least a concealing inorganic pigment such as a titanium oxide pigment or an iron oxide pigment is used. Is preferred. In addition, by coloring in an appropriate color, the function as the background color of the picture layer 4 can also be achieved.

The concealing layer may be formed on the back side of the pattern layer 4. For example, when the pattern layer 4 is provided between the intermediate resin layer 2 and the transparent resin layer 3, the base sheet may be used. 1, a back side, an interlayer between the base sheet 1 and the intermediate resin layer 2,
Alternatively, it can be provided at any position between the intermediate resin layer 2 and the picture layer 4.

On the surface of the transparent resin layer 3, an emboss 8 having a desired and appropriate pattern can be provided as required, as is conventionally known. There is no particular limitation on the type of the embossing 8, and various types of patterns such as woodgrain (especially, pipe pattern), stone, cloth, Japanese paper, and geometric patterns may be used. It may be a matte shape such as a tone, a hairline shape, a suede tone, or the like. The design of these patterns can be further improved by synchronizing the patterns of the embossing 8 with the patterns of the pattern layer 4. A pattern emboss 8 including both a pattern synchronized with a picture and a pattern not synchronized can be provided.

The method of forming the emboss 8 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 embossing 8, and any timing can be selected before, simultaneously with or after lamination of the transparent resin layer 3 with the intermediate resin layer 2. Further, the embossing 8 having the same or different pattern can be applied a plurality of times at a plurality of times selected from these. The concave portion of the embossing 8 may be filled with a coloring agent by a technique such as a wiping method as necessary, whereby a decorative sheet having a color pattern synchronized with the unevenness of the surface and having an excellent design can be obtained. Obtainable.

Further, a top coat layer 9 may be provided on the surface of the transparent resin layer 2 for the purpose of imparting more excellent surface physical properties to the surface of the decorative sheet. As the constituent material of the top coat layer 9, any material selected from various known top coat agents conventionally used as the 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 9 include melamine resins, phenol resins,
Urea resin, epoxy resin, aminoalkyd resin,
Thermosetting resins such as urethane resins, polyester resins, and silicone resins, and ionizing radiation-curable resins such as (meth) acrylate resins 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 a fungicide can be appropriately added.

The method of forming the top coat layer 9 is not particularly limited. For example, gravure coating, roll coating, dip coating, air knife coating, knife coating, comma coating, die coating, lip coating,
A conventionally known arbitrary coating method such as a kiss coating method, a rod coating method, a spray coating method, a flow coating method and the like can be appropriately applied.

If the adhesion between the transparent resin layer 3 and the top coat layer 9 is insufficient, the surface of the transparent resin layer 3 may be subjected to, for example, corona treatment, ozone treatment before the top coat layer 9 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 transparent resin layer 3 and the top coat layer 9 can be improved.

As described above, 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. Generally, an appropriate adhesive such as a urethane-based or vinyl acetate-based adhesive is used for the attachment. However, depending on the type of the adhesive, the adhesiveness with the amorphous polyester resin constituting the base sheet 1 may be insufficient. In preparation for such a case, if a primer layer made of a resin having excellent adhesiveness with a general-purpose laminating adhesive is provided on the back surface of the substrate sheet 1, sufficient adhesiveness can be obtained when laminating to various substrates. It can also be secured.

Various primers such as urethane, acrylic, ethylene-vinyl acetate copolymer and vinyl chloride-vinyl acetate copolymer are known as the primer layer. Select and use the one according to 1. In addition, for example, if a powder of silica, alumina, calcium carbonate, barium sulfate, or the like is added to the primer layer, the surface of the primer layer can be roughened to prevent blocking during winding and preservation of the decorative sheet. The adhesion to the laminating adhesive can be improved by the anchoring effect.

[0057]

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

Example 1 A pattern was printed on the surface of a 90 μm thick opaque colored olefin-based resin film with a urethane resin-based gravure printing ink for building materials, and a urethane resin-based thermoadhesive anchor layer was formed on the printed surface. After coating, an ethylene-ethyl acrylate adhesive resin layer having a thickness of 20 μm, a light stabilizer of 0.2 wt% and a UV absorber of 0.3 wt% were added to a thickness of 90 μm.
m and a transparent random-polymerized polypropylene resin layer are sequentially laminated by a co-extrusion laminating method, and a two-component curable urethane resin-based top coating agent is further coated on the surface by a gravure coating method to a coating amount of 4 g / m ² after drying. After coating, an amorphous polyester resin film having a thickness of 100 μm is coated on the back surface of the opaque colored olefin resin film via a polyester resin adhesive having a coating amount of 6 g / m ² after drying. The decorative sheet of the present invention was prepared by laminating by a dry lamination method.

The above-mentioned decorative sheet was previously coated on the surface with an aqueous two-liquid urethane resin-based adhesive at a coating amount of 10 g / m ² after drying, and dried. The wood base having a three-dimensional three-dimensional shape with a radius of curvature of 5R was obtained. Sheet temperature 60 with vacuum forming machine on the surface of the material
When three-dimensionally formed and laminated under the conditions of ° C., a good laminated product free from molding defects such as necking, whitening, and pattern elongation could be obtained. In addition, surface hardness and scratch resistance,
The surface properties, such as solvent resistance, were also practically acceptable.

Example 2 A 90 μm-thick transparent olefin resin film was coated on the surface with a urethane resin-based ink containing a pigment composition mainly composed of a hiding inorganic pigment (titanium oxide and iron oxide). Print the concealing layer by gravure printing,
Next, a pattern is printed with a urethane resin-based gravure printing ink for building materials, and the coated amount after drying is 6 g / m ² on the printing surface.
Thickness of 90 μm with 0.2% by weight of a light stabilizer and 0.3% by weight of an ultraviolet absorber added through a polyester-based adhesive
m, a transparent random-polymerized polypropylene resin layer is laminated by a dry lamination method, and a two-component curable urethane resin-based top coat agent is coated on the surface thereof by a gravure coating method to a coating amount of 4 g / m ² after drying. Thereafter, a coating amount of 6 g / m ² was applied on the back surface of the transparent olefin resin film.
100μm thick via polyester resin adhesive
Was bonded by a dry lamination method to produce a decorative sheet of the present invention.

The obtained decorative sheet was previously coated with an aqueous 2
Coating amount of liquid urethane resin adhesive after drying 10 g / m ²
3D molding and lamination at a sheet temperature of 60 ° C. using a vacuum forming machine on the surface of a wooden substrate having a three-dimensional three-dimensional shape with a radius of curvature of 5R, which was coated and dried, was necked, whitened, and patterned. A good laminated product free from molding defects such as elongation could be obtained. Further, the surface physical properties such as surface hardness, scratch resistance, and solvent resistance were all practically acceptable.

[0062]

As described in detail above, the decorative sheet of the present invention uses a base sheet made of an amorphous polyester resin to cause molding defects such as necking, whitening, and pattern elongation during vacuum forming. It is possible to mold uniformly without performing, and furthermore, by providing an intermediate resin layer made of a thermoplastic olefin resin and a transparent resin layer made of a thermoplastic olefin resin on the base sheet, the surface hardness is improved. The present invention has an excellent effect that a decorative sheet excellent in various surface properties such as scratch resistance, abrasion resistance and solvent resistance can be easily realized.

[Brief description of the drawings]

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

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base material sheet 2 Intermediate resin layer 3 Transparent resin layer 4 Picture layer 5 Anchor layer 6 Adhesive resin layer 7 Adhesive 8 Emboss 9 Top coat layer

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2E110 AA47 AA48 AB22 AB23 BA05 BB02 BB23 4F100 AK03B AK03C AK07 AK41A AK41G AK51G AK71G BA03 BA07 BA10A BA10C BA15 CB00 GB08 GB48 GB81 HB00 JA05JJBJJBJ JBJJBJ

Claims (2)

[Claims] (1) An intermediate resin layer made of a thermoplastic olefin resin and a transparent resin layer made of a thermoplastic olefin resin are sequentially provided on a base sheet made of an amorphous polyester resin. Makeup sheet. 2. The decorative sheet according to claim 1, wherein the amorphous polyester resin has a glass transition temperature of 60 to 85 ° C. and a cold crystallization temperature of 120 ° C. or more.