JP2000085066A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a decorative sheet which is free from necking, whitening and others during three-dimensional molding such as vacuum forming and excellent in surface physical properties such as solvent resistance by forming a transparent resin layer of a thermoplastic olefin resin on the surface of a base material sheet of a thermoplastic acrylic resin. SOLUTION: A transparent resin layer 2 of a thermoplastic polyolefin resin is formed on the surface of a base material sheet 1 of a thermoplastic acrylic resin through a pattern layer 3. When the adhesion between the sheet 1 and the layer 2 is poor, a thermosensible anchor layer 4 is formed in advance on the sheet 1, or an adhesive resin layer 5 is held between the sheet 1 and the layer 2. A coloring agent 7 is packed in the defective part of an embossment 6 formed on the surface of the layer 2, and a decorative sheet having a colored pattern in accordance with an uneven pattern on the surface can be obtained. A top coat layer 8 is formed on the surface of the resin layer 2 to give improved surface physical properties.

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 decoration of household equipment, home appliances, and the like, and in particular, for the surface decoration of fittings such as interior doors, kitchen doors, and storage doors, for example, by a vacuum molding method or a vacuum pressure method. The present invention relates to a decorative sheet suitable for use by being formed into a three-dimensional shape by a forming method or the like.

[0002]

2. Description of the Related Art Conventionally, decorative sheets used for the purpose of forming into a three-dimensional shape as described above have a unique excellent thermoformability, and furthermore, such as surface hardness, abrasion resistance and chemical resistance. A decorative sheet made of polyvinyl chloride resin with a wide range of well-balanced properties in various surface physical properties, weather resistance, secondary workability, etc.
Most widely used. However, in recent years, it has been pointed out that polyvinyl chloride resin may generate toxic gases such as hydrogen chloride and highly toxic substances such as dioxin during combustion. However, there is a strong demand from society.

To meet such demands, for example, a decorative sheet using a thermoplastic polyolefin resin has already been proposed (see Japanese Patent Application Laid-Open No. 6-16832), and replacement with a decorative sheet made of polyvinyl chloride resin is gradually progressing. I am doing it. The decorative sheet made of this polyolefin-based resin has been shown to have excellent performance for the most common decorative sheet use, such as for a flat decorative board, for V-cut processing, for lapping, and the like. It is regarded as the most promising alternative to decorative sheets made of polyvinyl chloride resin.

However, polyolefin resin is essentially a crystalline polymer, which also has a structure in which crystallized portions are scattered in an amorphous matrix. It is non-uniform when viewed, and local non-uniform deformation is likely to occur even during plastic deformation. Due to this principle, there is a problem that in the case of an application for molding into a three-dimensional shape as described above, molding defects such as necking are likely to occur, and it cannot be used for applications with large three-dimensional irregularities. there were.

In order to solve this problem, it is considered preferable to use a resin having a uniform structure which is unlikely to cause uneven deformation, for example, an essentially amorphous resin. For example, a thermoplastic acrylic resin may be considered as a candidate. Various decorative sheets using a thermoplastic acrylic resin have already been proposed. Specifically, for example, a decorative sheet in which an acrylic resin surface protection sheet is laminated on the surface of an olefin resin base sheet (Japanese Patent Application Laid-Open No.
No. 0-157018) or a decorative sheet in which an acrylic resin surface protection sheet is laminated on the surface of an acrylic resin base sheet (see JP-A-8-48014).
There are proposals such as.

However, in reality, these decorative sheets cannot always be said to be suitable for three-dimensional molding. This is because acrylic resins such as polymethyl methacrylate are inherently hard and brittle resins, and when used in applications such as decorative sheets, the flexibility and flexibility required for their processing and handling are required. Generally, a soft component, a rubber component, or the like is added to provide the composition. As a result, whitening is likely to occur during deformation such as stretching, the surface hardness is reduced, and the solvent resistance, stain resistance, and the like are also deteriorated. This can be said of a decorative sheet for general use, especially in an application requiring a high degree of flexibility and thermoformability, such as for three-dimensional moldability.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a non-toxic material which does not generate toxic substances such as chlorine gas during combustion. To provide a decorative sheet using a halogen-based resin, which does not cause problems such as necking and whitening during three-dimensional forming such as vacuum forming and has excellent surface physical properties such as solvent resistance. is there.

[0008]

Means for Solving the Problems The present invention is a decorative sheet characterized in that a transparent resin layer made of a thermoplastic olefin resin is provided on the surface of a base material sheet made of a thermoplastic acrylic resin.

Further, the present invention provides the above decorative sheet,
The decorative sheet is characterized in that the base sheet is a concealable base sheet containing a concealing pigment.

[0010] The present invention also relates to the above decorative sheet,
A decorative sheet comprising at least an inorganic pigment as the opaque pigment.

Further, the present invention provides the above decorative sheet,
A decorative sheet comprising at least one selected from a titanium oxide pigment and an iron oxide pigment as the inorganic pigment.

[0012]

FIG. 1 is a schematic sectional view of an example of a decorative sheet according to the present invention. The decorative sheet of the present invention is configured such that a transparent resin layer 2 made of a thermoplastic polyolefin-based resin is provided on a surface of a base sheet 1 made of a thermoplastic acrylic-based resin via a picture layer 3 appropriately provided. Things.

The thermoplastic acrylic resin constituting the base sheet 1 is, for example, homopolymerized or copolymerized with an acrylic acid derivative such as acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, acrylate or methacrylate as a main component. This is a thermoplastic resin obtained by the following method. Particularly preferred is a resin containing a methacrylic ester such as methyl methacrylate as a main component. For the purpose of improving flexibility and thermoformability, for example, a long-chain alkyl ester of methacrylic acid such as butyl methacrylate or methyl acrylate A monomer selected from acrylates, methacrylic acid, acrylic acid, etc., is added as a copolymer component to prepare a film having desired appropriate physical properties. Of course, other suitable copolymer components, additives and the like may be used in combination for the purpose of further improving the physical properties.

In order to achieve good thermoformability, the thermoplastic acrylic resin constituting the base sheet 1 is
Dynamic elastic modulus at a frequency of 10 Hz in a temperature range of 50 ° C. to 90 ° C. is 4.0 × 10 ⁸ Pa or more and 1.0 × 10 ¹⁰
Pa, and the dynamic loss is desirably 6.0 × 10 ⁷ Pa or more and 6.0 × 10 ⁸ Pa or less. If the dynamic elastic modulus exceeds 1.0 × 10 ¹⁰ Pa, the deformation responsiveness at the time of thermoforming becomes insufficient, which causes cracks, whitening, and molding failure. On the other hand, if the dynamic elastic modulus is less than 4.0 × 10 ⁸ Pa, It becomes too soft during thermoforming, causing drawdown and pattern flow.
On the other hand, if the dynamic loss exceeds 6.0 × 10 ⁸ Pa, the resin is inherently easily plastically deformed with high stress relaxation, and this also causes drawdown and pattern flow.
If the pressure is less than × 10 ⁷ Pa, stress relaxation is too slow, and it is difficult to follow the molding speed at the time of thermoforming, which results in poor molding and residual internal stress.

The thermoplastic acrylic resin constituting the base sheet 1 is preferably added with a concealing pigment for imparting concealing properties. As a method for imparting hiding properties to a decorative sheet, in addition to a method of adding a hiding pigment to the base sheet 1, for example, a printing ink or a coating agent containing the hiding pigment on the front or back surface of the base sheet 1 is used. There are also a method of providing a concealed solid layer, a method of applying a metal deposition layer on the front surface or the back surface of the base sheet 1, and the like. However,
In the case of three-dimensional molding applications, such as a concealed solid layer or a metal vapor deposited layer, while these concealed layers are thinned or cracked by stretching during three-dimensional molding, the concealability tends to be insufficient, If the concealing pigment is added to the base sheet 1 having a sufficient thickness compared to these, there is no such fear.
Even if a phenomenon (for example, a fine crack inside the resin or a change in the arrangement state of the resin molecules) that may cause whitening occurs in the base sheet 1 during molding, the base sheet 1 may As a result of being concealed by the concealing pigment contained therein, the design is not substantially affected as whitening.

As described above, the concealing pigment is a fine powdery pigment having a refraction index significantly higher than that of a resin serving as a dispersion medium, and reflects or refracts light at an interface due to a difference in the refractive index. The direct light transmission between the front and back surfaces of the sheet is prevented by the light scattering effect of the sheet, and the concealing property is developed. Since the refractive index of a resin such as a thermoplastic acrylic resin is about 1.5, a pigment having a refractive index of about 2.0 or more is generally selected as a concealing pigment, and a light (visible) In general, a particle having a particle size in the range of about 0.1 to 1 μm is used from the viewpoint of the ability to scatter light (light). In addition,
The addition amount of the concealing pigment is preferably as large as possible from the viewpoint of the concealing property. However, if the amount is too large, the resin may be embrittled and the thermoformability may be impaired. It is preferred to be within.

Among such concealing pigments, pigments having a high light-absorbing property are referred to as coloring pigments because they exhibit a coloring effect by absorbing a part of the incident light. ,
It is referred to as a white pigment because it exhibits the effect of reflecting most of the incident light in the incident direction by the light scattering effect to make the color tone bright (white). Then, by selecting a pigment having a good balance between the light absorption coefficient and the refractive index, or by mixing and using the above-described color pigment and white pigment in an appropriate ratio, it is possible to obtain an arbitrary desired color tone. Can be done.

As the concealing pigment, various organic and inorganic pigments are known. In general, an inorganic pigment has a higher refractive index and a higher concealing property than an organic pigment. It is preferable to use an inorganic pigment also from the viewpoint of durability and fastness because it is excellent in discoloration) and chemical resistance. Particularly in the case of a decorative sheet for three-dimensional molding, when the resin is stretched by three-dimensional molding, micro-peeling occurs between the resin and the inorganic pigment, thereby absorbing internal stress, resulting in excellent moldability. Which is not seen when an organic pigment is used.

Among the inorganic pigments, coloring pigments include, for example, graphite, yellow iron oxide, cadmium yellow, titanium yellow, barium yellow, aureoline, molybdate orange, cadmium red, red stalk, leadtan, cinnabar, mars violet, Manganese violet, cobalt violet, cobalt blue, cerulean blue, ultramarine,
Navy blue, emerald green, chrome vermillion, chromium oxide, viridian, iron black, carbon black, etc. Examples of white pigments include titanium oxide (titanium white, titanium white), zinc oxide (zinc white), and basic lead carbonate (lead white). ), Basic lead sulfate, zinc sulfide, lithopone, titanox and the like.

Among them, pigments which are excellent in concealing property 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 coloring pigments It is preferable to use a titanium oxide pigment.

Of the above-mentioned acid iron-based pigments, the petiole is ferric oxide F
a red pigment consisting of e ₂ O ₃ (also called hematite),
Those having an average particle size of about 0.2 to 0.6 μm are used. For example, Anchor FR-110G manufactured by Toho Pigment Co., Ltd.
D, Ferro Color NF-150-P, manufactured by Nippon Fellow, Tetsuhara
NAT, Tone Sangyo SR-580, Toda Kogyo Toda Color 12
0ED, commercially available as Morishita Red Cloisonne, manufactured by Morishita Benara.

The yellow iron oxide is iron oxide hydroxide γ-FeO (O
H) A yellow pigment composed of (also known as leucite) or a hydrate thereof, and having an average particle size of about 0.3 to 0.8 μm, for example, Anchor FY-766 manufactured by Toho Pigment Co., Morishita dialect Morishita Yellow MTY-10 manufactured by Pattern Company, NYB-40 manufactured by Nippon Benza Pattern Company,
Toda Industry's Toda Color Y-1, Tone Sangyo's YP-100SB,
Toyo Shigyo Co., Ltd., Toshiki Synthetic Iron Yellow, BASF Sicotrans Ye
Commercially available as llow L 1916 and the like.

Iron black is a black pigment made of triiron tetroxide Fe ₃ O ₄ (also called magnetite), and has an average particle size of about 0.5 μm. For example, Morishita Bl.
ackMTB-10, Tone Sangyo's TB-50SB, Toda Kogyo's Toda
Color KN-320, commercially available as Toyo Synthetic Iron Black manufactured by Toyo Pigment Co., Ltd. By appropriately combining and using these iron oxide pigments, a wide range of color tones from yellow to ocher, brown, and black can be obtained.

The titanium oxide pigment is titanium dioxide TiO.
_{It is} a white pigment consisting of _{2, two} types of anatase type (also known as anatase) and rutile type (also called kinkoishi),
The refractive indices are 2.45 to 2.55 and 2.61 to 2.61, respectively.
It is 2.90, and the rutile type is preferable because it has excellent concealing properties due to the higher refractive index and also has excellent chemical stability and light resistance. Those having an average particle size of about 0.1 to 0.5 μm are used. For example, KR-310 manufactured by Titanium Industry Co., Ltd.
Commercially available as JR, Furukawa Mining Co., Ltd. FR-41, Ishihara Sangyo Co., Ltd. CR-50.

In addition to the iron oxide pigments and titanium oxide pigments described in detail above, it is possible to use a small amount of other concealable or non-concealable inorganic or organic pigments for the purpose of adjusting the color tone. Absent. However, it is imperative that iron oxide pigments and titanium oxide pigments be mainly used,
The amount of other pigments used is preferably about 20% by weight or less as a percentage of the total pigment. It is preferable to select a pigment having high light resistance as the pigment used in combination, and it is preferable to use a phthalocyanine pigment such as cobalt blue or carbon black among inorganic pigments and a phthalocyanine pigment such as phthalocyanine blue among organic pigments. In addition, extenders such as silica, calcium carbonate, barium sulfate and the like can be used in combination as needed.

In addition, the thermoplastic acrylic resin constituting the base sheet 1 may be, for example, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, etc., depending on the intended use of the decorative sheet. One or more kinds of conventionally known various additives such as an agent, a lubricant, an antistatic agent, 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.

The thickness of the base sheet 1 is not particularly limited.
A sheet having the same thickness as a base sheet of a conventional general decorative sheet can be used. Specifically, although it depends on the use of the decorative sheet and the type of resin, it is generally 20 to 200 μm.
Range, and a particularly preferred range is 50 to 10
It is about 0 μm. The method of forming the base sheet 1 is not particularly limited, and the base sheet 1 formed by any conventionally known forming method such as an extrusion forming method, an inflation forming method, a calendar forming method, and a cast forming method is used. can do.

The pattern layer 3 is provided for the purpose of imparting any desired design to the intended decorative sheet. Therefore, for example, when the surface coloring and color adjustment can be sufficiently achieved by coloring the base sheet 1 or forming a concealed solid layer, such as a plain decorative sheet for the purpose of merely surface coloring or color adjustment, In the case where a pattern is formed on the base sheet 1 itself by kneading a pigment or transferring a sublimable or melt-transferable dye, the pattern layer 3 may not be particularly provided. However, in general, the base sheet 1
In many cases, an appropriate pattern layer 3 is provided on the front surface of the transparent resin layer 2 or on the back surface of the transparent resin layer 2 by a printing method or the like.

The constituent material and the forming method of the picture layer 3 are not limited at all, 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 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 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, phthalocyanine pigments, isoindolinone pigments, dioxazines and the like. Organic pigments such as pigments, metal powder pigments such as gold powder, silver powder, copper powder, aluminum powder, bronze powder, fish scale powder, pearlescent pigments such as basic lead carbonate, bismuth oxide chloride, titanium oxide coated mica, 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, and ethyl acetate, butyl acetate and acetic acid-2.
Ester 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 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, drying agents, stabilizers, curing agents, curing accelerators or curing retarders, if necessary. Can be appropriately added.

The method for forming the picture layer 3 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, and a flow coating method And various coating methods such as a dip coating method. In addition, for example, the hand-drawing method, the sumi-shi 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.

The pattern layer 3 may be provided on the base sheet 1 before the base sheet 1 and the transparent resin layer 2 are laminated, or may be provided on the transparent resin layer 2 side. . Prior to the formation of the picture layer 3, if necessary, the printing surface of the base sheet 1 or the transparent resin layer 2 may be subjected to, for example, corona treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment,
By performing a surface treatment such as an anchor or primer treatment, the adhesion between the base material sheet 1 or the transparent resin layer 2 and the picture layer 3 can be improved.

There is no particular limitation on the type of pattern constituted by the pattern layer 3 described above. For example, a wood pattern, a stone pattern, an abstract pattern, etc., which are widely used in the field of decorative sheets according to the prior art, or a simple coloring. For the purpose of adjusting color or color, 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 transparent resin layer 2 made of a thermoplastic olefin resin is provided for the purpose of protecting the base sheet 1 and the picture layer 3 on the surface thereof from the outside. From the viewpoints of whitening properties and solvent resistance,
Particularly, a thermoplastic olefin resin is employed.
Here, “transparent” of the transparent resin layer 2 preferably has high transparency, but it is sufficient that the transparent resin layer 2 has at least transparency enough to see through the picture layer 3.
As far as it is concerned, it may be translucent or colored and transparent.

The thermoplastic olefin resin includes:
For example, various homopolymers and copolymers including polyethylene resin, polypropylene resin, polybutene-1 resin, poly-4-methylpentene-1 resin and the like are known, and among them, polypropylene is most preferable for the purpose of the present invention. A series resin, that is, a homopolymer or a copolymer mainly composed of polypropylene, specifically, for example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, and a polypropylene crystal part, and carbon other than propylene. Α-olefins of numbers 2 to 20, preferably ethylene, butene-1,4-methylpentene-
1, a co-monomer of hexene-1 or octene-1
A propylene-α-olefin copolymer containing 5 mol% or more can be exemplified. 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. .

The above-mentioned thermoplastic olefin resin may be used, if necessary, depending on the intended use of the decorative sheet, for example, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, a lubricant, an antistatic agent. 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 thermoplastic acrylic resin constituting the base sheet 1 can be used as these additives.

The thickness of the transparent resin layer 2 made of a thermoplastic olefin resin is not particularly limited, and can be, for example, the same as the thickness of the transparent resin layer in a conventional general multi-layer decorative sheet. In general, thicker sheets are more advantageous in terms of surface properties such as abrasion resistance and solvent resistance, weather resistance, design feeling such as painting feeling, depth feeling, emboss depth, etc. This is disadvantageous in terms of flexibility, conformability to the surface shape of the substrate during thermoforming, and the like, so that a thickness range that balances both is selected. Specifically, it is generally selected from the range of about 20 to 200 μm, and particularly preferably about 50 to 100 μm, although it depends on the use of the decorative sheet and the required quality corresponding thereto, the kind of the thermoplastic olefin resin used, and the like. It is.

The method for forming the transparent resin layer 2 is not particularly limited, and any conventionally known method can be appropriately applied. Specifically, for example, the transparent resin layer 2 previously formed into a film shape or a sheet shape is formed via a suitable adhesive such as a dry laminating adhesive, a heat-sensitive adhesive, a pressure-sensitive adhesive, or an ionizing radiation-curable adhesive. A method of bonding, a method of directly bonding by means of thermocompression bonding or ultrasonic welding without using an adhesive, or a method of heating and melting a thermoplastic olefin resin to form the transparent resin layer 2 and extruding the film or sheet. A method suitable for the characteristics of the resin can be appropriately selected from various conventionally known methods, such as a method of laminating and bonding on the surface of the base material sheet 1 at the same time as molding, and can be used.

If the adhesiveness between the substrate sheet 1 and the transparent resin layer 2 is poor in the latter method (extrusion laminating method), it is also known that the heat-sensitive adhesive Or an adhesive resin between the base sheet 1 and the transparent resin layer 2 is formed by co-extruding and laminating the constituent resin of the transparent resin layer 2 and a separately prepared thermal adhesive resin. By sandwiching the layer 5, the adhesiveness can be improved. Of course, both may be used in combination as needed.

On the surface of the transparent resin layer 2, an emboss 6 having a desired and appropriate pattern can be provided as necessary, as is conventionally known. There is no particular limitation on the type of the pattern of the emboss 6, and for example, various patterns such as a woodgrain (particularly a conduit pattern), a stonegrain, a Japanese paper, a cloth, a geometric pattern, or the like may be used. For example, it may be a simple matte, grain, hairline, suede, or the like. Further, the design of the embossment 6 can be synchronized with the pattern of the pattern layer 3 to further improve the design, but if it is not necessary, the pattern may be out of synchronization. It is also possible to provide a pattern emboss 6 including both a pattern synchronized with the picture and a pattern not synchronized with the picture.

The method of forming the emboss 6 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 embossment 6, and any timing can be selected before, simultaneously with or after lamination of the transparent resin layer 2 with the base sheet 1. The embossing 6 having the same or different pattern can be applied a plurality of times at a plurality of times selected from the following. The concave portion of the embossment 6 may be filled with a coloring agent 7 by a technique such as a wiping method as necessary, so that a decorative sheet having a color pattern synchronized with the surface irregularity pattern and having excellent design properties. Can be obtained.

Further, a top coat layer 8 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 8, any material selected from various known top coat agents conventionally used as constituent materials 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 8 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.

The method of forming the top coat layer 8 is not particularly limited. For example, a gravure coating method, a roll coating method, a dip coating method, an air knife coating method, a knife coating method, a comma coating method, a die coating method, a lip coating method,
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 2 and the top coat layer 8 is insufficient, the surface of the transparent resin layer 2 may be subjected to corona treatment, ozone By performing a surface treatment such as treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, anchor or primer treatment, the adhesion between the transparent resin layer 2 and the top coat layer 8 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. In general, an appropriate adhesive such as a urethane-based or vinyl acetate-based adhesive is used at the time of the attachment, but depending on the kind of the adhesive, the thermoplastic acrylic constituting the base sheet 1 may be used. In some cases, the adhesion to the system resin is insufficient. In preparation for such a case, on the back surface of the base material sheet 1,
It is preferable to provide a primer layer 9 made of a resin having excellent adhesion to the laminating adhesive.

As the primer layer 9, various primers such as urethane type, acrylic type, ethylene-vinyl acetate copolymer type and vinyl chloride-vinyl acetate copolymer type are known. A material that matches the base sheet 1 is selected and used. In addition, for example, silica, alumina, calcium carbonate,
If a powder such as barium sulfate is added, the surface of the primer layer 9 is roughened, so that the decorative sheet can be prevented from blocking during winding and preservation. Can also be improved.

[0052]

EXAMPLE The thickness of a pigment mainly composed of an inorganic pigment (iron oxide tea, iron oxide loess, titanium oxide white) and containing a small amount of carbon black black and cobalt blue (or phthalocyanine blue) in an amount of 5% by weight. 200 μm colored acrylic resin film manufactured by Kyowa Leather Industry Co., Ltd. (dynamic elastic modulus 1.0
× 10 ⁹ Pa, dynamic loss 8.0 × 10 ⁷ Pa), corona treatment on both sides to adjust the surface wetting index to 38 dyn / cm or more, and apply wood grain pattern on the surface with urethane gravure printing ink for building materials Is printed, and a thickness of 20 μm is printed on the printing surface.
m of an ethylene-ethyl acrylate adhesive resin layer,
A 90 μm thick transparent resin layer of a random polymerization polypropylene resin to which 0.2% by weight of a light stabilizer and 0.3% by weight of an ultraviolet absorber are added is sequentially laminated by a co-extrusion lamination method. A two-component curable urethane resin-based surface protective layer was formed on the surface of the film by a gravure coating method so as to have an applied amount of 4 g / m ² after drying, thereby producing 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
The surface of a wooden substrate having a surface irregularity with a radius of curvature of 0.5, which is obtained by coating and drying, is coated with a sheet temperature of 7 using a vacuum forming machine.
When three-dimensionally molded and laminated at 0 ° C., it sufficiently follows the molding speed and the residual of internal stress is small, molding defects such as necking and pattern flow, and design problems due to whitening of the transparent resin layer on the surface, etc. None, and a good laminated product could be obtained. Further, the surface physical properties such as surface hardness, scratch resistance, and solvent resistance were all practically acceptable.

[0054]

The decorative sheet of the present invention uses a non-halogen resin because a transparent resin layer made of a thermoplastic olefin resin is provided on the surface of a base sheet made of a thermoplastic acrylic resin. Not only does it not generate toxic substances such as chlorine gas during combustion, it does not cause problems such as necking and whitening during three-dimensional molding such as vacuum molding, and it also has excellent surface properties such as solvent resistance. It has advantages.

In particular, since the base sheet is a concealing base sheet containing a concealing pigment, even if the decorative sheet may be partially stretched by three-dimensional molding, the stretched portion may be used. In addition to a small decrease in the concealing property, even if a phenomenon that should cause whitening may occur in the resin constituting the base sheet, the opaque pigment is concealed. Has an excellent advantage that it does not affect the

Particularly, by containing at least an inorganic pigment such as a titanium oxide pigment or an iron oxide pigment as the concealing pigment, not only the concealing property is excellent, but also when the resin is stretched during three-dimensional molding. In addition, there is an excellent advantage that micro exfoliation occurs between the resin and the inorganic pigment and internal stress is absorbed, thereby exhibiting excellent moldability.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a laminated structure of an example of a decorative sheet of the present invention.

[Explanation of symbols]

 1 Base material sheet 2 Transparent resin layer 3 Picture layer 4 Anchor layer 5 Adhesive resin layer 6 Emboss 7 Colorant 8 Top coat layer 9 Primer layer

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Takashi Tominaga 1-5-1, Taito, Taito-ku, Tokyo Toppan Printing Co., Ltd. F-term (reference) 4F100 AA01B AA21B AA23B AA37 AK03B AK07 AK25A AK51 AK51G AK71G AP00 BA02 BA16 CA13A CB00 EJ91 GB07 GB08 HB00 HB01 HB31 JB07 JB16A JB16B JL01 JN01B JN30A

Claims (4)

[Claims] 1. A decorative sheet comprising a substrate sheet made of a thermoplastic acrylic resin and a transparent resin layer made of a thermoplastic olefin resin on a surface thereof. 2. The decorative sheet according to claim 1, wherein the base sheet is a concealable base sheet containing a concealing pigment. 3. The decorative sheet according to claim 2, wherein the hiding pigment contains at least an inorganic pigment. 4. The decorative sheet according to claim 3, wherein the inorganic pigment contains at least one selected from a titanium oxide pigment and an iron oxide pigment.