JPH11240123A - Decorative sheet and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To decrease a coefficient of friction with the resin layer of a sheet material and prevent the sweep irregularities of a colored ink from occurring by adding a thixotropic properties-imparting agent to the colored ink. SOLUTION: A thixotropic properties-imparting agent is added to a colored ink 2, and the decorative sheet comprises a layer consisting of a base sheet 1 and a layer 3 made of an olefin resin. The recessed part of the olefin resin layer 3 is filled with the colored ink 2. The olefin resin layer 3 is composed of an olefin thermoplastic elastomer of a blend of an isotactic polypropylene (hard segment) and an atactic polypropylene (soft segment) or composed of this elastomer, to which a chemical compound having a polar functional group is graft-polymerized. Or the olefin resin layer 3 is composed of the thermoplastic elastomer of an ethylene/propylene/butene copolymer. In addition to this resin layer 3, a pictorial pattern-printed layer 4 is formed. The base sheet 1 is made of an olefin resin, an acrylic resin, a polyester resin, a fluororesin or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a building material such as furniture and fittings, and a surface decoration material such as an automobile, a vehicle and an aircraft, in which a concave portion of a sheet surface having irregularities is filled with a coloring ink by wiping or the like. The present invention relates to a useful decorative sheet and a method for producing the same.

[0002]

2. Description of the Related Art A conventional decorative sheet has a picture layer and a transparent vinyl chloride resin layer on a vinyl chloride resin sheet.
It has been known that the transparent vinyl chloride-based resin layer has irregularities and the concave portions are filled with a coloring ink. As a typical production method for producing such a decorative sheet, as described in JP-B-58-14312, a transparent vinyl chloride resin surface is first embossed, and then a transparent vinyl chloride resin layer is formed. It is obtained by applying a coloring ink on the entire surface, then scraping the coloring ink on the surface with a doctor or the like, leaving the ink only in the embossed concave portions (so-called wiping process), and further providing a top coat layer as needed. It has been conventionally performed to perform a wiping process to obtain a high-quality decorative sheet with improved design.

[0003] However, since the decorative sheet using the vinyl chloride resin uses a vinyl chloride resin as a material, toxic chlorinated substances are generated at the time of disposal and combustion, so that there is a problem in terms of environmental pollution. For this reason, a decorative sheet using an olefin resin which is a non-vinyl chloride resin has been proposed. For example, JP-A-6-79850 discloses that an arbitrary pattern layer is provided on a base sheet made of a polyolefin-based resin (= olefin-based resin) having a masking property and containing a filler and a color pigment, and a transparent olefin is provided. 2. Description of the Related Art A decorative sheet subjected to a wiping process is known in which a resin layer is laminated, an embossed recess is provided at the same time, and the embossed recess is filled with a coloring ink.

In the wiping process of the decorative sheet, an embossed concave portion is provided on the surface of the olefin-based resin layer, an ordinary colored ink is applied, and the surface is immediately scraped off with a doctor blade, a rubber roll, or the like to remove excess ink. The wiping portion is formed by leaving the coloring ink only in the embossed concave portion.

[0005]

However, in the conventional wiping process as described above, a coloring ink having no thixotropic property (not considered) is used. There is a problem that the coefficient of friction is large, and when the colored ink is applied and scraped off with a doctor blade, unevenness of the colored ink is easily generated.

[0006] When such uneven coloring of the colored ink occurs, the ink remains on the surface of the olefin resin, so that an extra wiping operation of the surface of the decorative sheet is required, and the formation of the next top coat layer is also hindered. Will occur.

In view of such circumstances, the present invention provides a decorative sheet having a sheet surface subjected to wiping processing, which has a low coefficient of friction with a resin as a sheet material, particularly an olefin-based resin layer. It is an object of the present invention to provide a decorative sheet subjected to a wiping process using a colorless ink and a method for producing the same.

[0008]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides a decorative sheet in which a concave portion of a sheet surface having irregularities is filled with a coloring ink containing a thixotropic agent.

The decorative sheet of the present invention is preferably a decorative sheet having a TI value of 2.5 to 4 and having been subjected to wiping with a thixotropic colored ink.

[0010] The decorative sheet of the present invention preferably has a layer composed of a base material sheet and a layer composed of an olefin resin. More preferably, the olefin-based resin is an olefin-based thermoplastic elastomer composed of a blend of isotactic polypropylene (hard segment) and atactic polypropylene (soft segment), isotactic polypropylene (hard segment) and atactic polypropylene ( And a thermoplastic elastomer of an ethylene-propylene-butene copolymer, which is obtained by graft-polymerizing a compound having a polar functional group to the blend with the soft segment).

The present invention also provides a step of applying a coloring ink containing a thixotropy-imparting agent to the entire surface of a sheet having an uneven surface, and thereafter, scraping off only the ink on the convex portion and applying the coloring ink only on the concave portion. And a method of filling the decorative sheet.

According to the decorative sheet of the present invention and the method of manufacturing the same, the uneven coloring of the coloring ink, which has been a problem in the past, does not occur, and an extra work of wiping the surface of the decorative sheet is not required. It is possible to obtain an excellent decorative sheet having an arbitrary pattern.

Hereinafter, the present invention will be described in detail. Examples of the material of the base sheet used in the decorative sheet and the method of manufacturing the same according to the present invention include olefin-based resins, acrylic resins, polyester resins, fluororesins, polystyrene-based resins, polycarbonate resins, and the like. A layer or a laminate of two or more layers can be used.

As the olefin resin, for example,
There are olefinic thermoplastic elastomers and non-elastomeric olefinic resins. Specifically, polyethylene, polypropylene, polymethylpentene, ethylene
Propylene copolymers, ethylene-propylene-butene copolymers, crystalline non-elastomeric olefin resins such as ionomers, or olefin-based thermoplastic elastomers are used, but from the viewpoint of suitability for forming a decorative sheet, Olefinic thermoplastic elastomers are preferred.

The olefin-based thermoplastic elastomer resin is a thermoplastic elastomer elastomer of a composite material comprising an olefin-based elastomer and a non-elastomeric olefin-based resin.

(1) Simple blend of amorphous olefin-based elastomer as soft segment and crystalline non-elastomeric olefin resin as hard segment (2) Olefin-based elastomer and non-elastomeric olefin-based resin (3) A type in which an olefin-based elastomer is crosslinked and dispersed in a non-elastomeric olefin-based resin (4) Two or more olefins having different structures A type in which monomers are copolymerized to reduce the crystallization rate of the polymer

Examples of the olefin-based elastomer include ethylene rubbers represented by EPDM and the like, and examples of the non-elastomeric olefin-based resin include crystalline polymers such as polyethylene and polypropylene. In addition, additives such as a flame retardant and an antioxidant, which are used in ordinary olefin-based resins, can be appropriately added to the composition, if necessary. When these are used for the base sheet, pigments, extenders and the like can be added as appropriate.

As the type (1), for example, as described in JP-B-6-23278, isotactic polypropylene is used as a hard segment, atactic polypropylene is used as a soft segment, and both are used. (Hard segment / Soft segment) =
What mixed at 10 / 90-90 / 10 weight ratio is mentioned. Alternatively, a monomer having a polar functional group such as a carboxyl group such as maleic acid, fumaric acid or itaconic acid may be further added to this type of olefinic thermoplastic elastomer.
Those obtained by graft copolymerization of 0 ^-4 to 10% by weight are exemplified.

As the type (2), for example,
B) JP-B-53-21021, JP-B-53-34
No. 210, etc., b) Japanese Patent Publication No. 56
And those described in US Pat.

More specifically, for example, the above (a) includes 60 to 80 parts by weight of a monoolefin copolymerized elastomer (A), 40 to 20 parts by weight of a non-elastomeric polyolefin-based plastic (B), And those curing agents which are mixed and partially cured at the curing temperature to such an extent that they do not become insoluble in the usual solvents of the uncured blend during mastication. Examples of the olefin-based copolymer elastomer include an elastic copolymer obtained by adding at least one polyene copolymerizable with two or more olefins.

As the olefin, ethylene, propylene, α-olefin and the like are used, and as the polyene, 1,4-hexadiene, cyclic diene, norbonene and the like are used. Preferred olefin copolymer rubbers include, for example, elastic copolymers containing an olefin as a main component such as ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene rubber, and ethylene-propylene-butadiene copolymer rubber. No.

The non-elastomeric olefin plastic (B) is a crystalline thermoplastic resin obtained by polymerizing olefins such as ethylene, propylene, butene-1, pentene-1, and 4-methylpentene in a conventional manner. Yes, including polyethylene and polypropylene modified with higher α-olefins.

As the curing agent, peroxide,
Azide type, aldehyde-amine reaction products, substituted ureas, xanthates, dithiocarbamates, imidazoles, sulfonamides, thiuram disulfites, paraquinone dioxime, dibenzoparaquinone dioxime, sulfur and the like. it can.

The above composition is masticated on an open roll or heated to 150 ° C. in an internal mixer such as a Banbury mixer, an extrusion mixer or a transfer mixer.
Partial crosslinking can be performed by masticating at 280 ° C for 1-20 minutes.

The above (b) includes olefin copolymer rubbers such as ethylene / propylene copolymer rubber, ethylene / propylene non-conjugated diene rubber, ethylene / butadiene copolymer rubber, and propylene / ethylene copolymer. , Propylene-1-copolymer, propylene / 1-hexene copolymer, propylene / 4-methyl-1-pentene copolymer, etc., with high boiling point petroleum fraction, paraffinic, naphthenic, or aromatic A partially crosslinked olefinic thermoplastic elastomer can be obtained by melt-kneading with an organic peroxide together with a mineral oil-based softening agent such as the above.
These can be produced in the same manner as in the above method a).

The type (4) is described in
Examples thereof include ethylene-propylene-butene copolymers described in JP-A-77371, JP-A-7-316358, and JP-A-9-111055. As butene, any of 1-butene, 2-butene and isobutylene can be used, but 1-butene is more preferred. As the copolymer, a random copolymer is preferable, and the content of the propylene component is preferably 50% by weight or more. As needed,
0.01 to 50 parts by weight of a transparent nucleating agent mainly composed of an aryl phosphate compound, 0.03 to 0.3 parts by weight of a fatty acid amide having 12 to 22 carbon atoms, and an oil gel such as an N-acylamino acid amine salt About 0.5% by weight of an agent is added.

The olefin resin used in the present invention comprises:
Although it can be used alone, flexibility to the olefin resin,
In order to impart impact resistance and easy adhesion, various rubbers can be preferably added.

The rubbers to be added include diene rubbers,
There are a hydrogenated diene rubber, an olefin elastomer and the like, and among them, a hydrogenated diene rubber is preferable.
The hydrogenated diene rubber is obtained by adding a hydrogen atom to at least a part of the double bond of the diene rubber molecule. In the present invention, crystallization of the olefin resin is suppressed, and flexibility and transparency are improved. Has a role. Also,
Generally, when a diene rubber is added to an olefin resin, due to the double bond of the diene rubber, the weather resistance and heat resistance are lower than those of the polyolefin resin without the diene rubber.
In the present invention, since the double bond of the diene rubber is saturated with hydrogen, the olefin resin has good weather resistance and heat resistance without deterioration.

As the diene rubber, isoprene rubber,
Butadiene rubber, butyl rubber, propylene / butadiene rubber, acrylonitrile / butadiene rubber, acrylonitrile / isoprene rubber, styrene / butadiene rubber, and the like. For the purpose of the present invention, styrene-butadiene rubber is particularly preferred.

The amount of rubber added is 100
It is preferably about 1 to 90 parts by weight based on parts by weight. If the amount is less than 1 part by weight, the elasticity, elongation, and impact strength due to the addition of rubber are insufficient, and cracks and cracks are likely to occur during bending such as V-cutting and drawing. On the other hand, when the amount is 90 parts by weight or more, the elasticity and the elongation percentage become too large, and the registration of printing or the like becomes unfavorable.

Further, other fillers, foaming agents, flame retardants, ultraviolet absorbers and the like can be added to the olefin resin as required. The filler is added for the purpose of improving the physical properties such as the strength and appearance of the molded product,
For example, there are carbon black, calcium carbonate, calcium silicate, titanium white, white carbon, lignin, asbestos, mica, quartz powder, slate powder, glass sphere, glass fiber, wood powder and the like. The foaming agent is added to produce a porous molded article of plastics, and examples thereof include an azonitrile compound, a benzenesulfohydrazine compound, and a diazoamide compound.

Flame retardants are added to impart flame resistance to plastics materials, and include, for example, paraffin chloride, tricresyl phosphate, chlorinated oil, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, Examples include tetrabromobisphenol A, dibromopropyl phosphate, tri (2,3-dibromopropyl) phosphate, antimony oxide, hydrated alumina, and barium borate. The ultraviolet absorber is added to suppress oxidative decomposition of plastics, and examples thereof include alkylphenols, amines, and quinones.

The thermoplastic polyester resin contains aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid as acid components, and aliphatic diols such as ethylene glycol, diethylene glycol, butanediol and hexanediol as alcohol components. And a copolymer which can be obtained as an ester of both, such as polyethylene terephthalate, polybutylene terephthalate, and ethylene / terephthalate / isophthalate copolymer.

Examples of the fluororesin include polyvinyl fluoride, polyvinylidene fluoride, ethylene tetrafluoroethylene copolymer and the like. Examples of the polystyrene-based resin include polystyrene, acrylic styrene, and ABS.

Polycarbonate has --O--R-- in its main chain.
It is a linear polymer having O-CO- and can be produced by, for example, reacting glycol with a dihydric phenol and phosgene, or reacting with a carbonate ester.
Bisphenol A and the like can be mentioned.

Of the above-mentioned materials, it is particularly preferable to use, as the base sheet material, a material obtained by adding an inorganic filler such as rubber and calcium carbonate to high-density polyethylene, and an ethylene / propylene / butene copolymer. it can.

The base sheet is subjected to a decoration treatment as desired. For the decoration treatment, for example, a method of coloring a base sheet by adding a pigment, a method of laminating a transparent thermoplastic sheet by a known method on a pattern provided on a base sheet colored by the addition of a pigment, There are a method of printing a pattern such as a pattern on the thermoplastic sheet with ink, paint, or the like, and a method of embossing (hot pressing), hairline processing, or the like on the thermoplastic sheet to form an uneven pattern.

Examples of the pigments to be added include inorganic pigments such as titanium white, zinc white, red iron oxide, vermilion, ultramarine blue, cobalt blue, titanium yellow, carbon black, isoindolinone, Hansa Yellow A, quinacridone, and permanent red 4.
R, phthalocyanine blue, indaslen blue RS,
Organic pigments (including dyes) such as annin phosphorus black; metal pigments such as aluminum and brass; mica coated with titanium dioxide; and pearlescent (pearl) pigments made of foil powder such as basic lead carbonate. The coloring by the addition of the pigment may be a transparent job or an opaque (concealing) coloring. They are,
It is added and dispersed as powder or scaly foil.

As the pattern printing, a pattern can be formed with ink (or paint) using a known printing method such as gravure printing, offset printing, silk screen printing, and transfer printing from a transfer sheet.

Examples of the pattern include a wood grain pattern, a stone grain pattern, a cloth grain pattern, a leather pattern, a geometric figure, a character, a symbol, and a solid image on the entire surface. The pattern can be provided on the front, back, front and back, or between layers of the decorative sheet.

As the ink or paint, chlorinated polyolefin such as chlorinated polyethylene, chlorinated polypropylene, polyester resin, polyurethane resin, acrylic resin, vinyl chloride resin, vinyl chloride.
A vinyl acetate copolymer, a cellulosic resin, or the like can be used, and one or more of these may be used in combination. For this, those to which the above-listed pigments are added are used.

In the case of printing directly on an olefin resin, chlorinated polyolefin, polyurethane resin and the like are preferable as a binder in terms of adhesiveness. However, if a layer is formed by appropriately selecting an easy-adhesion primer, other binders may be used. However, sufficient adhesiveness can be imparted even by using.

The embossing is carried out by heating and softening an olefin resin, pressurizing and shaping with an embossed plate, cooling and fixing, and a known single-wafer or rotary embossing machine is used. As the uneven shape, there are a wood channel groove, a stone plate surface unevenness (granite cleavage surface or the like), a cloth surface texture, a matte finish, a grain, a hairline, a linear groove, and the like. Further, upon request, the concave portion of the uneven pattern may be filled with a coloring ink by a known wiping method (see Japanese Patent Publication No. 58-14312). The same thing as the above can be used for the coloring ink. However, from the viewpoint of abrasion resistance, a material using a two-component curable urethane resin as a binder is preferable.

As the olefin resin used for the surface sheet of the decorative sheet of the present invention, the same olefin resin as used for the above-listed base sheets can be appropriately selected and used. Of those listed above, olefin-based thermoplastic elastomers are preferred from the viewpoints of bending processability, interlayer adhesion, transparency, and the like of the decorative sheet. Preferable examples include a blend of isotactic polypropylene (hard segment) and atactic polypropylene (soft segment) or a blend of isotactic polypropylene (hard segment) and atactic polypropylene (soft segment), and a polar functional group. And an olefin-based thermoplastic elastomer composed of an ethylene-propylene-butene copolymer. The thickness of the topsheet is usually about 30 to 500 μm.

The decorative sheet of the present invention has an adhesive layer between the base sheet and the transparent olefin-based thermoplastic resin layer in order to improve the adhesion between the printed base sheet and the transparent olefin-based thermoplastic resin. May be.

Examples of the resin that can be used as the adhesive include urethane resins, polyester resins,
Resins such as polyamide resin, vinyl acetate-acrylate resin, carboxyl-containing acrylic resin, vinyl acetate-ethylene resin, and polyvinyl ether can be used. Of these, urethane-based resin adhesives are particularly preferable in consideration of the adhesion (including weather resistance) to the base sheet.

As the urethane resin adhesive, it is preferable to use a two-component curable urethane resin. For example, it is a resin having a polyol as a main component and an isocyanate as a cross-linking agent (curing agent).

The polyol has two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol,
Polyester polyol, polyether polyol, polycarbonate polyol and the like are used. As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in a molecule is used.

For example, aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, and 4,4-diphenylmethane diisocyanate, or fats such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate Group (or alicyclic) isocyanates are used. Alternatively, adducts or multimers of the above various isocyanates can also be used. For example, there are an adduct of tolylene diisocyanate, a trimer of tolylene diisocyanate, and the like.

Further, the adhesive layer or the olefin resin layer of the decorative sheet according to the production method of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, those which can absorb ultraviolet light in the 280 to 450 nm region which causes deterioration of polyolefin can be arbitrarily selected from known ones.

Examples of the ultraviolet absorber include benzophenone-based, salicylate-based, benzotriazole-based, and acrylonitrile-based ultraviolet absorbers. For example, an organic compound having an OH group in the molecule can be used, and 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-
Chlorobenzotriazole, 2- (2'-hydroxy-
3'-tert-butyl-5'-methylphenyl) -5
-Chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-methyl Phenyl)
-5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl)-
2′-hydroxyphenyl-5-chlorobenzotriazole-based ultraviolet absorbers such as 5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-ter)
t-butylphenyl) benzotriazole, 2- (2 ′
Benzotriazole-based UV absorbers such as 2'-hydroxyphenylbenzotriazole-based UV absorbers such as -hydroxy-5'-methylphenyl) benzotriazole; and 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ' 2-hydroxybenzophenones such as -dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxy-4,4'-tetrahydroxybenzophenone ultraviolet absorbers, and 2,4-dihydroxybenzophenone Benzophenone UV absorbers such as UV absorbers, phenyl salicylate,
A salicylic acid ester based ultraviolet absorber such as -tert-butylphenyl salicylate is used.

In addition, a reactive ultraviolet absorber having an acryloyl group or a methacryloyl group introduced into a benzotriazole skeleton can be used. Among these, a benzotriazole-based ultraviolet absorber is particularly preferred in consideration of the problems of absorption wavelength and coloring property. Furthermore, in the decorative sheet according to the production method of the present invention, the olefin-based resin layer has various amine-based radicals for imparting weather resistance, that is, for preventing discoloration, cracking, whitening, and strength deterioration due to sunlight. A scavenger can also be added.

As the radical scavenger, bis-
(2,2,6,6-tetramethyl-4-piperidinyl)
Sebacate and others, for example, hindered amine radical scavengers such as compounds disclosed in Japanese Patent Publication No. 4-82625, piperidyl radical scavengers and the like are used.

When a light stabilizer comprising a hindered amine radical scavenger is added to the polyolefin, not only the olefin resin but also a layer such as an ink layer and an adhesive layer adjacent to the olefin resin sheet may be made of polyurethane. Use of a resin containing no chlorine atom in the molecule, such as a resin, an olefin-based resin, or a polyamide resin, is advantageous in terms of improving weather resistance.

Further, in the present invention, a primer layer can be provided on the base sheet in order to improve the adhesion between the base sheet and the printing ink layer. The primer layer is usually provided to improve the adhesion between the base sheet and the pattern ink by reacting with a functional group present on the surface since the base sheet has been subjected to corona discharge treatment.

It is preferable to use a two-component curable urethane resin as the primer layer. When hexamethylene diisocyanate (HMDI) is used as the isocyanate and acrylic polyol is used as the polyol, it is particularly preferably used because of its good light adhesion.

In the decorative sheet according to the production method of the present invention, a solid ink layer is further formed on the primer layer in order to improve the adhesion between the base sheet and the pattern printing layer. Can be provided.

Titanium oxide and carbon can be added to the solid ink layer, and by increasing the content thereof, ultraviolet rays can be cut to prevent deterioration of the lower layer. The solid ink layer is provided as a concealing layer on the entire surface in order to adjust the color of the base, and when the color of the sheet is desired, the medium is colored with a transparent ink to decorate the sheet with a large difference in color tone from the sheet. Is preferably colored with white ink.

The outermost surface of the decorative sheet of the present invention is embossed, and the embossed concave portions are filled with a coloring ink. As a filling method, wiping processing or the like is employed. The embossing is performed to impart a desired texture such as a wood surface to the decorative sheet. For example, embossing heats and softens an olefin resin on a heating drum, further heats it to 160 to 180 ° C. with an infrared radiation heater, and pressurizes with an embossed plate provided with a desired shape of a concavo-convex pattern.
It is formed by shaping, cooling and fixing, and a known single-wafer or rotary embossing machine is used. As the concavo-convex pattern, a wood grain conduit groove, a grain of sand, a satin finish, a hairline, a cleaved surface irregularity of granite, or the like is used.

The wiping process refers to a process in which the surface is made uneven by embossing, colored ink is applied to the entire surface, and the concave portion is filled with the colored ink while scraping the surface with a doctor blade or the like. This is a typical method of filling the concave portions of the surface of the decorative sheet with the coloring ink.

The method for producing a decorative sheet according to the present invention is characterized in that wiping is performed with a coloring ink containing a thixotropic agent. In the present invention, the thixotropy-imparting agent is added to the coloring ink to give the coloring ink a thixotropy, that is,
An agent that imparts the property of forming a sol by simply stirring or shaking the ink at a constant temperature, and returning to a gel state when left alone.

Here, the TI value is an abbreviation of Thixotropy Index, and is a value that is an index of the thixotropic property of a substance.
The TI value can be measured by a rotational viscometer and is a value represented by a ratio of a torque at a low rotation speed (6 rpm) to a torque at a high rotation speed (60 rpm).

In the present invention, the TI value of the colored ink is preferably 2.5 to 4.0. When the TI value is less than 2.5, the scraping of the coloring ink, that is, the viscosity at the time of high shear becomes high, so that the scraping of the coloring ink on the convex portion becomes insufficient. On the other hand, when the TI value exceeds 4.0, the viscosity becomes high in a state where no shear is applied, and it becomes difficult to handle as a colored ink, apply to a decorative sheet and supply, and properly adjust the viscosity at low shear. If it is lowered, the viscosity at the time of high shear becomes too low, and there is a possibility that the coloring ink may be scratched unevenly.

Examples of the thixotropic agent which can be used in the present invention include various fillers such as silica and organic bentonite. The amount of the thixotropic agent is usually 1 g to 100 g of the ink.
5 g is preferred. By setting the amount of addition as described above, the TI value (6 rpm / 60 rpm) of the coloring ink can be adjusted to 2.4 to 4.0.

The thixotropic property is affected by the interaction acting between the particles, and thus is affected not only by the type of the particles but also by the particle size of the particles. In general, the smaller the particle size of the thixotropy-imparting agent, the larger the TI value becomes, and the more thixotropic the agent becomes. Further, since the gloss of the coloring ink may be reduced by the addition of the thixotropic agent, the particle size of the thixotropic agent (filler) is preferably smaller from the viewpoint of gloss of the coloring ink, About 0.4 μm is more preferable. By setting the particle size of the thixotropic agent to such a range,
Suitable thixotropic properties can be imparted to the colored ink while maintaining the desired glossing effect on the decorative sheet surface. That is, the particle size of the thixotropy-imparting agent is determined by the above-mentioned TI.
The type of the thixotropy-imparting agent is set so that the value is 2.5 to 4.0 and the gloss of the ink is not impaired.
The particle size and the amount added can be appropriately selected.

In the present invention, as the coloring ink, those obtained by adding a coloring agent such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent and the like to a binder can be used.

The binder can be appropriately selected from thermoplastic resins, thermosetting resins, ionizing radiation-curable resins and the like according to the use, required physical properties, and printability. As the thermoplastic resin, for example, ethyl cellulose, cellulose nitrate, cellulose acetate, ethyl hydroxyethyl cellulose, cellulose derivatives such as cellulose acetate propionate, polystyrene, styrene resin such as poly α-methylstyrene or styrene copolymer, polymethyl methacrylate , Acrylic resins such as polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate,

Vinyl chloride such as polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, rosin, rosin-modified maleic resin,
Rosin ester resins such as rosin-modified phenolic resins and polymerized rosins; chroman resins; vinyl ketone resins; and natural or synthetic resins such as polyamide resins.

As the thermosetting resin, a phenol resin,
There are urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation resin, silicon resin, polysiloxane resin and the like.

If necessary, a crosslinking agent, a curing agent such as a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, an extender and the like are added.

Usually, an isocyanate is an unsaturated polyester resin or a polyurethane resin, an amine is an epoxy resin, a peroxide such as methyl ethyl ketone peroxide, or a radical initiator such as azobisisobutyronitrile is an unsaturated polyester resin. Used as a curing agent in system resins.

As the isocyanate, as described above, 2
Although an aliphatic (or alicyclic) or aromatic isocyanate having a valency or higher can be used, an aliphatic isocyanate is desirable from the viewpoint of preventing thermal discoloration and weather resistance. Specific examples include hexamethylene diisocyanate, isophorone isocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like.

In order to accelerate the curing reaction, if necessary, heating may be performed after coating. For example, in the case of an isocyanate-cured urethane-curable unsaturated polyester-based resin or polyurethane-based resin, it is usually 1 to 5 at 40 to 60 ° C.
About a day, and in the case of polysiloxane resin,
It is about 1 to 300 minutes at 80 to 150 ° C.

As the ionizing radiation-curable resin,
A composition obtained by appropriately mixing a prepolymer, an oligomer, and / or a monomer having a polymerizable unsaturated bond such as a (meth) acryloyl group or a cationic polymerizable functional group such as an epoxy group is used. Examples of the prepolymer and oligomer having a polymerizable unsaturated bond include unsaturated polyesters such as a condensate of an unsaturated carboxylic acid and a polyhydric alcohol, polyester (meth) acrylate, polyether (meth) acrylate, and polyol (meth). There are (meth) acrylates such as acrylate and melamine (meth) acrylate. Here, the notation of (meth) acrylate is used in the meaning of acrylate or methacrylate.

Examples of the monomer include styrene monomers such as styrene and α-methylstyrene, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and (meth) acrylic acid. (Meth) acrylates such as methoxyethyl, butoxyethyl (meth) acrylate, butyl (meth) acrylate, methoxybutyl (meth) acrylate, and phenyl (meth) acrylate;

2- (N, N-diethylamino) ethyl (meth) acrylate, 2- (N, N-diethylamino) acrylate
N-dibenzylamino) methyl, (meth) acrylic acid-
Substituted amino alcohol esters of unsaturated acids such as 2- (N, N-diethylamino) propyl,

Unsaturated carboxylic acid amides such as (meth) acrylamide, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6
Compounds such as hexanediol di (meth) acrylate, triethylene glycol (meth) acrylate,

Polyfunctional compounds such as dipropylene glycol di (meth) acrylate, ethylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate, and / or polythiol compounds having a divalent or higher thiol group in the molecule; For example, there are trimethylolpropane trithioglycolate, trimethylolpropane trithiopropiolate, pentaneerythritol tetrathioglycol and the like.

Examples of the prepolymer having a cationically polymerizable unsaturated group include epoxy resins such as bisphenol epoxy resins and novolak epoxy resins, and prepolymers such as vinyl ether resins such as aliphatic vinyl ethers and aromatic vinyl ethers. There is.

If necessary, one or two of the above compounds may be used.
The prepolymer or oligomer is used in an amount of 5% by weight or more and the monomer and / or polythiol is used in an amount of 9% or more in order to impart ordinary coating suitability to the resin composition.
It is preferable that the content be 5% by weight or less.

In selecting a monomer, if flexibility of the cured product is required, the amount of the monomer may be reduced or monofunctional or bifunctional (as long as the suitability for coating is not impaired). Meta)
An acrylate monomer is used to provide a structure having a relatively low crosslink density. When the heat resistance, hardness, and solvent resistance of the cured product are required, the amount of the monomer may be increased as long as the coating suitability is not impaired, or a trifunctional or higher functional (meth) acrylate-based monomer may be used. It is also possible to adjust the coating suitability and the physical properties of the cured product by mixing the monomers.

Examples of the above-mentioned monofunctional (meth) acrylate monomers include 2-hydroxy (meth) acrylate, 1,6-hexanediol di (meth) acrylate and the like. Examples of the system monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

In order to adjust physical properties such as flexibility and surface hardness of the cured product, at least one of the above prepolymers, oligomers and monomers is used in the following ionizing radiation non-curable resin. 1 to 70% by weight, preferably 5 to 50%
% By weight, and can be used as a mixture.

As the ionizing radiation non-curable resin, thermoplastic resins such as urethane, cellulose, polyester, acrylic, butyral, polyvinyl chloride, and polyvinyl acetate can be used. In view of this, fibrous, urethane and butyral are preferred.

In particular, in the case of curing with ultraviolet rays, in the case of a resin system having a radical polymerizable unsaturated bond as a photopolymerization initiator in the ionizing radiation-curable resin composition, acetophenones, benzophenones, Michler benzoyl Benzoate, α-amyloxime ester, tetramethylmeuram monosulfide, thioxanthone, in the case of a resin having a cationically polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metallocene compound, benzoin Sulfonates and the like and / or n-butylamine, triethylamine, tri-n-butylphosphine and the like as a photosensitizer can be mixed and used.

As the pigment to be added to the coloring ink, commonly used organic or inorganic pigments can be used. As the yellow pigment, azo pigments such as monoazo, bisazo and polyazo, organic pigments such as isoindoline, inorganic pigments such as graphite, yellow iron oxide, cadmium yellow, titanium yellow and antimony can be used. As the red pigment, azo pigments such as monoazo, bisazo, and polyazo, organic pigments such as quinacdrine, and inorganic pigments such as red iron oxide, vermilion, cadmium red, and chromium vermillion can be used. As the blue pigment, organic pigments such as phthalocyanine blue and indathrene blue, and inorganic pigments such as navy blue and cobalt blue can be used. As the black pigment, an organic pigment such as aniline black and an inorganic pigment such as carbon black can be used. As the white pigment, inorganic pigments such as titanium dioxide, zinc white and antimony trioxide can be used.

Examples of the brilliant pigments include metal powders such as aluminum powder, copper powder, and brass powder, pigments having a metallic luster such as metal flakes and cut pieces of metal-deposited synthetic resin films, titanium dioxide-coated mica, fish scale foil, and tertiary pigment. Pigments having pearl luster or interference luster such as bismuth chloride, for example, as a polyester resin layer and an acrylic resin layer, two or more types of resin layers having different refractive indices are multilayer-laminated with a thickness of about several μm or less, Pigments made of foil powder obtained by cutting a film that has produced an iris color due to light interference can be used.

The matting pigments include, for example, those having a particle size of 0.1.
Fine powders of about 1 to 10 μm such as calcium carbonate, barium sulfate, silica, alumina, glass balloon, polyethylene and the like are used.

As the bead pigment, there is a pigment comprising spherical fine particles of a resin and containing a coloring agent such as a pigment or a dye therein as required. Particularly, those having excellent matting effect and abrasion resistance include Fe ₂ O ₃ , TiO ₂ , and CaCO ₃ .
₃ 、 Use common pigment fine powder such as quinacridone with elastic resin such as polyurethane, epoxy, acrylic, polyester, nylon, fluororesin, vinyl chloride-vinyl acetate copolymer, and further, if necessary, plasticizer and stabilizer. And particles dispersed in a composition to which a surfactant or the like is added, or coated with the composition to form spheres or sphere-like particles.

The particle size of the pigment has a distribution range of 5 to 80 μm,
In addition, those having a local maximum value in the range of 10 to 35 μm give a particularly good matting effect. If necessary, a colorant-free additive or a mixture of two or more bead pigments can be used. The bead pigment is particularly suitable for expressing a suede matte.

Examples of the weather-resistant pigments include yellow pigments such as organic pigments such as isoindolinone, sllen yellow G and permanent yellow HR, and inorganic pigments such as yellow iron oxide and nickel titanium yellow.

Further, quinacridone red, permanent red FGR and permanent F4 are used as red pigments.
Organic pigments such as RH, inorganic pigments such as red iron oxide and mercury cadmium sulfide, as blue pigments, organic pigments such as phthalocyanine blue and indathrene blue RS, inorganic pigments such as navy blue and ultramarine blue, and black pigments such as carbon black and white Examples of the pigment include titanium dioxide and antimony trioxide.

The particle size of the pigment depends on the intended use and required physical properties, but is usually preferably about 0.1 to 100 μm.

The ink solvent has the ability to dissolve and disperse colorants such as binder resins and pigments, and other additives.
A liquid having a suitable drying property can be selected. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ketones such as isophorone, pentane, hexane, heptane, gasoline, mineral spirits, aliphatic hydrocarbons such as petroleum benzine, benzene, toluene, aromatic hydrocarbons such as xylene, From among halogenated hydrocarbons such as trichloroethylene, perchlorethylene and carbon tetrachloride, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, ethylene glycol and glycerin, and ethers such as ethyl ether and methyl ether. 1
A species or a mixture of two or more species can be appropriately selected and used.

The decorative sheet of the present invention may further have a top coat layer on the outermost surface. The top coat layer covers the fragility of the decorative sheet surface,
It is provided to improve the scratch resistance. As the resin used for the top coat layer, for example, a two-component curable urethane resin can be used. The two-component curable urethane resin refers to a urethane resin containing polyol as a main component and isocyanate as a crosslinking agent (curing agent).

Polyols having two or more hydroxyl groups in the molecule include, for example, polyethylene glycol, polypropylene glycol, acrylic polyol,
Polyester polyol, polyether polyol, polycarbonate polyol and the like are used. As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in a molecule is used. For example, aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, and 4,4'-diphenylmethane diisocyanate; or aliphatic isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; Is used. Alternatively, adducts or multimers of the above-mentioned various isocyanates can also be used. For example, there are an adduct of tolylene diisocyanate, a trimer of tolylene diisocyanate, and the like.

The decorative sheet of the present invention can be laminated on another adherend. In the case of lamination, the adhesive layer can be omitted when the decorative sheet itself can be bonded to the adherend (by heat fusion or the like). If the decorative sheet itself does not adhere to the adherend, it can be laminated with an appropriate adhesive. The adherend is the final product, and in some cases a decorative sheet is laminated for surface cosmetics, and if necessary, to enhance the mechanical strength of the decorative sheet or to provide concealment, An adherend may be laminated.

[0098] The adherend may be a plate material such as a flat plate or a curved plate of various materials, a three-dimensional article, or a sheet (or film). Wood material such as medium density fiberboard (MDF), metals such as iron and aluminum, acrylic resin, polycarbonate, ethylene / vinyl acetate copolymer, ethylene vinyl acetate copolymer, polyester, polystyrene, olefin resin, ABS resin, Phenolic resin, polyvinyl chloride, cellulosic resin, resin such as rubber, etc., as a material exclusively used as a plate material or three-dimensional article, glass, ceramics such as ceramics, ALC
Non-cement ceramics materials such as cement (foamed lightweight concrete), calcium silicate, gypsum, etc. Materials used exclusively as sheets (or films) include high quality paper,
Examples include paper such as Japanese paper, or nonwoven fabric or woven fabric made of fibers such as carbon, asbestos, potassium titanate, glass, and synthetic resin.

As a method for laminating these various adherends,
For example, as described in Japanese Patent Publication No. 50-19132, Japanese Patent Publication No. 43-27488, etc., a decorative sheet is a method of laminating a plate-like substrate by pressing with a pressure roller via an adhesive. Into the injection-molded male and female molds,
Close both molds, inject and inject molten resin from the male mold gate, then cool and simultaneously mold the resin molded product and attach a decorative sheet to its surface. As described in JP-A-45768, JP-B-60-58014, etc., a decorative sheet is opposed to or placed on the surface of a molded product via an adhesive layer therebetween, and is subjected to vacuum suction from the molded product. A so-called vacuum press laminating method in which a decorative sheet is laminated on the surface of a molded product by a pressure difference, Japanese Patent Publication No. 61-5895, Japanese Patent Publication No. 3-2
As described in JP-A-666, etc., in the major axis direction of a columnar substrate such as a cylinder and a polygonal pillar, while supplying a decorative sheet via an adhesive layer therebetween, by a plurality of rollers having different directions,
A decorative sheet is sequentially pressure-adhered and laminated on a plurality of side faces constituting a columnar body, and is described in a so-called lapping method, Japanese Utility Model Publication No. 15-31122, JP-A-48-47972, and the like. As described above, the decorative sheet is first laminated on the plate-shaped substrate via the adhesive layer, and then reaches the interface between the decorative sheet and the plate-shaped substrate on the surface of the plate-shaped substrate opposite to the decorative sheet. . A so-called V-cut or U-cut in which a groove having a V-shaped or U-shaped cross section is cut, and then an adhesive is applied in the groove, and then the groove is bent to form a box or a column. There are processing methods and the like.

The decorative sheet of the present invention can be used for various purposes by laminating on various adherends and subjecting it to a predetermined molding process. As applications, for example, interior decoration of buildings such as walls, ceilings, floors, window frames, doors, surface decoration of fittings such as handrails,
Furniture or weak electricity, surface decoration of cabinets such as OA equipment,
There are vehicle interiors such as automobiles and trains, aircraft interiors, window glass makeup, and the like.

[0101]

Next, the decorative sheet of the present invention and the method for producing the same will be described in more detail with reference to the embodiments of the present invention.

First Embodiment FIG. 1 shows a decorative sheet according to a first embodiment of the present invention.
In the figure, reference numeral 1 denotes a base sheet, and 2 denotes a colored ink filled in a recess formed by wiping with a colored ink containing a thixotropic agent. Since the surface of the decorative sheet of the present embodiment has been subjected to wiping with a colored ink having thixotropic properties,
After coating with the coloring ink, it has less scratching unevenness.

Second Embodiment FIG. 2 shows a decorative sheet according to a second embodiment of the present invention.
In the figure, 1 is a base sheet, 2 is a wiping process using a coloring ink containing a thixotropic agent, and 3 is an olefin-based heat composed of a blend of isotactic polypropylene (hard segment) and atactic polypropylene (soft segment). Either a plastic elastomer, a blend of isotactic polypropylene (hard segment) and atactic polypropylene (soft segment), and a compound having a polar functional group graft-polymerized, or an ethylene-propylene-butene copolymer An olefin-based resin layer made of a thermoplastic elastomer and 4 represent a pattern printed layer on which pattern printing has been performed.

Since the surface of the decorative sheet of the present embodiment has been subjected to wiping with a colored ink having thixotropic properties, there is little scratching unevenness after the colored ink is applied.

Further, since the base sheet is made of high-density polyethylene, rubber and an inorganic filler, or an ethylene / propylene / butene copolymer, it has particularly excellent interlayer adhesion with the olefin resin layer. Also, when the decorative sheet is bent, uneven and insufficient elongation (so-called necking) does not occur, and no stress is locally concentrated on the bent portion to cause whitening or cracking.

Third Embodiment FIG. 3 shows a decorative sheet according to a third embodiment of the present invention.
In the figure, 1 is a substrate sheet containing pigment 5, 2 is a wiping process using a coloring ink containing a thixotropic agent, 3 is a mixture of isotactic polypropylene (hard segment) and atactic polypropylene (soft segment). A blend of olefinic thermoplastic elastomer, isotactic polypropylene (hard segment) and atactic polypropylene (soft segment) blended with a compound having a polar functional group, or a mixture of ethylene, propylene and butene An olefin-based resin layer 4 made of any thermoplastic elastomer of a polymer represents a printed layer on which a pattern is printed. Further, the decorative sheet of the present embodiment has a top coat layer 6 made of a two-component curable urethane resin on the outermost surface.

Since the surface of the decorative sheet of this embodiment has been subjected to wiping with a colored ink having thixotropic properties, scratching after coating with the colored ink is small.

Further, since the base sheet is made of high-density polyethylene, rubber and an inorganic filler, or an ethylene / propylene / butene copolymer, it has particularly excellent interlayer adhesion with the olefin resin layer. Also, when the decorative sheet is bent, uneven and insufficient elongation (so-called necking) does not occur, and no stress is locally concentrated on the bent portion to cause whitening or cracking.

Further, since it has a top coat layer on the outermost surface, it is a decorative sheet excellent in surface protection and design effects.

[0110]

EXAMPLE 1 An example of the production of a decorative sheet according to the present invention will now be described. First, FIG.
As shown in (1), a base sheet (thickness: 50 to 200 μm) was prepared by sequentially providing a pattern layer 9 made of a transparent ink on a polyethylene sheet 7 containing a coloring pigment 8 having a thickness of 0.1 mm.

Next, a two-part curable adhesive was applied to the surface of the base sheet by a gravure reverse method at 15 g / m ² (d
ry) (the adhesive layer 10). Next, the polypropylene resin sheet 11 was extruded and laminated with a T-die, and at the same time, the surface of the polypropylene resin sheet 11 was embossed with wood grain. On the other hand, the particle size is 0.1 to 0.2.
1.6% by weight of silica particles of μm was added to a coloring ink composed of a urethane elastomer (using methyl ethyl ketone, isopropyl alcohol, polyethylene glycol monomethyl ether, isobutanol, methyl isobutyl ketone, etc. as a solvent), and Colored inks whose values were adjusted to 2.9 to 3.0 were prepared.

Next, the prepared coloring ink was applied on the entire surface of the sheet at a processing speed of 15 to 45 m / min, and after the coating, the coloring ink on the embossed convex portion was scraped off with a doctor blade to obtain an embossed ink. Only the concave portions were filled with the coloring ink 12 to produce the decorative sheet of the present invention. In the step of scraping the colored ink, no unevenness in the scraping of the colored ink occurred.

Comparative Example 1 A decorative sheet (not shown) was produced in the same manner as in Example 1 except that a colored ink having a TI value of 1.5 to 1.8 (no thixotropic property) was used. In the step of scraping the colored ink in the production of the decorative sheet of Comparative Example 1, uneven coloring of the colored ink occurred, and an extra wiping operation was required.

[0114]

As described above, the method for producing a decorative sheet according to the present invention involves wiping using a colored ink having thixotropic properties. Therefore,
The coefficient of friction between the colored ink and the olefin resin is small,
After applying the coloring ink, when scraping with a doctor,
There is no scratching of colored ink. Further, the ink does not remain on the surface of the olefin-based resin, no extra wiping work on the surface of the decorative sheet is required, and there is no problem in forming the next top coat layer.

Further, when a topcoat layer is provided on the outermost surface of the decorative sheet, a decorative sheet particularly excellent in surface protection can be obtained.

Further, since the decorative sheet of the present invention mainly uses an olefin resin in place of the conventional vinyl chloride resin, the generation of toxic chlorinated products when discarded or burned is extremely small. It is preferable in environmental hygiene.

In particular, as the olefin-based resin, an olefin-based thermoplastic elastomer composed of a blend of isotactic polypropylene (hard segment) and atactic polypropylene (soft segment), isotactic polypropylene (hard segment) and atactic polypropylene ( Soft segment), blended with a compound having a polar functional group by graft polymerization, or ethylene / propylene / butene copolymer, when composed of any of thermoplastic elastomers, especially with the base sheet A decorative sheet having excellent interlayer adhesion can be obtained. In addition, when the decorative sheet is bent, uneven and insufficient elongation (so-called necking) does not occur, and no stress is locally concentrated on the bent portion to cause whitening or cracking. Therefore, the decorative sheet of the present invention can be used for various applications after being laminated on various adherends and subjected to a predetermined forming process.

[Brief description of the drawings]

FIG. 1 is a sectional view of a decorative sheet of the present invention.

FIG. 2 is a sectional view of the decorative sheet of the present invention.

FIG. 3 is a cross-sectional view of the decorative sheet of the present invention.

FIG. 4 is a cross-sectional view of the decorative sheet manufactured in Example 1.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Base sheet, 2,12 ... Colored ink, 3 ... Layer made of olefin resin, 4,9 ... Picture printing layer, 5,8 ... Colored pigment, 6 ... Top coat layer, 7 ... Base made of polyethylene Sheet, 10: adhesive layer, 11: layer made of polypropylene

Claims (5)

[Claims] 1. A decorative sheet having irregularities on its surface and filling said concave portions with a coloring ink, wherein said coloring ink contains a thixotropic agent. 2. The decorative sheet according to claim 1, wherein the coloring ink containing the thixotropic agent is a coloring ink having a TI value of 2.5 to 4. 3. The decorative sheet according to claim 1, comprising a layer composed of a base sheet and a layer composed of an olefin resin. 4. An olefin-based thermoplastic elastomer comprising a blend of isotactic polypropylene (hard segment) and atactic polypropylene (soft segment), isotactic polypropylene (hard segment) and atactic polypropylene. The decorative sheet according to claim 3, which is a thermoplastic elastomer of any one obtained by graft-polymerizing a compound having a polar functional group into a blend with (soft segment), or an ethylene-propylene-butene copolymer. 5. A step of applying a coloring ink containing a thixotropy-imparting agent to the entire surface of the sheet having an uneven surface, and thereafter, a step of scraping off only the ink of the projections and filling only the recesses with the coloring ink. A method for producing a decorative sheet, comprising: