JP2000343649A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet excellent in interlaminar adhesion strength while having sufficient concealability capable of corresponding to a base material of every kind for a decorative material, capable of being inexpensively produced for a short time and easily corresponding to multikind and small-quantity production. SOLUTION: A concealing solid printing layer 2 is provided on a colored substrate sheet 1 and, pref., a pattern printing layer 3 and a transparent resin layer 4 are further provided on the printing layer 2. The substrate sheet 1 may be constituted by providing a colorless surface layer 11 and/or a rear surface layer 13 on the upper surface and/or rear surface of a colored resin layer 12. The compounding ratio of concealable pigment to the colored resin layer 12 is pref. 1-20 pts.wt. per 100 pts.wt. of a resin and the thickness of the concealing solid printing layer 2 is desirably 20 μm or less.

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 such as walls and floors of buildings such as houses, construction materials, building materials such as fittings, furniture and fixtures, vehicle interiors, housing equipment and home appliances. And the like.

[0002]

2. Description of the Related Art Conventionally, as a decorative sheet used in such a field, there has been a paper-based decorative sheet obtained by printing an appropriate desired pattern such as wood grain on the surface of paper, for example. The use of paper with low strength, both chemically and chemically, results in poor surface physical properties such as surface hardness, abrasion resistance, water resistance and solvent resistance, and is essentially porous and rough. Since printing is performed on the surface of certain paper, the sharpness of the printed pattern is low and the design is inferior, so the usable applications are limited or not suitable for applications requiring a sense of luxury And so on.

On the other hand, there is also a thermoplastic resin-based decorative sheet in which a film or sheet made of a thermoplastic resin is printed with an appropriate desired pattern such as wood grain instead of paper. This is a decorative sheet that solves the problems of physical properties and design in the paper-based decorative sheet described above, and has been used in a wide range of applications, including applications that require strict physical properties and applications that require a luxurious feel. .

[0004] Such thermoplastic resin-based decorative sheets are roughly classified into single-layer decorative sheets and multi-layer decorative sheets. The single-layer type decorative sheet is obtained by printing a pattern on one surface of a film or sheet made of a thermoplastic resin as a base sheet, and further printing the pattern on the front side of the base sheet. And a back-printing mold in which a pattern is printed on the back side of the base sheet. On the other hand, the multi-layer type decorative sheet has a printed pattern,
It is sandwiched between a base sheet on the back side and a transparent resin layer made of a transparent thermoplastic resin layer on the front side.

[0005] The thermoplastic resin constituting the base sheet and the transparent resin layer of these thermoplastic resin-based decorative sheets includes:
In the past, polyvinyl chloride resin, which is inexpensive and excellent in processability and physical properties, has been used most often, but in recent years, due to the growing public interest in environmental issues, polyvinyl chloride resin with less adverse effect on the environment A decorative sheet using a resin other than the above, for example, a polyolefin resin has also been developed and put into practical use (see Japanese Patent Application Laid-Open No. 6-166159).

By the way, such decorative sheets are originally adhered to the surface of various base materials such as a wood board such as a plywood or a particle board, and an inorganic board such as a slate board or a wood wool cement board. Since it is used as a decorative material having a desired excellent design property on the surface of the base material, in order to maintain the stability of the design quality of the decorative material, the decorative sheet to be attached includes a base material It is required to have a sufficient concealing property to conceal undesired colors and variations thereof, defects such as knots and scratches, and to maintain a certain color and design.

As a means for imparting hiding properties to the decorative sheet, a method of using an opaque hiding base sheet obtained by forming a film of a thermoplastic resin composition to which a hiding pigment is added is used. General. The reason is that the base sheet usually has a thickness of about 50 to 100 μm, so that it is easy to impart concealing properties by adding a coloring pigment, or the base sheet is previously colored with the background color of the pattern. By doing so, color matching at the time of printing a pattern becomes easy. This method cannot be adopted in the case of the above-described single-layer type back-printing type, but is currently most commonly adopted for the single-layer type front-printing type and the multi-layer type decorative sheet. Method.

However, according to the above-described means of coloring the base sheet, it is necessary to prepare a colored base sheet having a color tone corresponding to the background color of the desired pattern before printing. In that case, it is difficult to respond in a short delivery time because the colored base sheet is manufactured after the adoption of the pattern is decided, and the company that handles many types of patterns requires the number of types of colored substrates Since it is necessary to prepare sheets and switch for each product type, inventory management of materials and work management of the manufacturing process are complicated. The production of colored base sheets of many kinds and small lots causes many problems, such as a decrease in equipment operation rate and an increase in material loss, resulting in a delay in delivery and an increase in product prices. It is actually holding It is. Also, from the viewpoint of the performance of the decorative sheet itself, since the pattern is printed on the surface of the colored base sheet, which is essentially concealable, the pattern has a poor sense of depth and is not necessarily satisfactory in design. There were problems such as not being able to do so.

Therefore, instead of using a colored base sheet as described above, a concealed solid printing layer using a concealable ink or paint containing a concealable pigment while using a non-colored non-concealable base sheet. It is also conceivable to provide concealing properties by providing. However, according to this method, there is a problem that it is difficult to obtain a sufficient concealing property because the concealed solid printing layer is much thinner than the base sheet. Because, theoretically, it is possible to improve the concealability of the concealed solid print layer by increasing the amount of the concealing pigment added or increasing the thickness of the concealed solid print layer. However, when any of these measures is taken, a decrease in the cohesive force of the concealed solid print layer or a bad effect such as a decrease in the adhesion strength with the base material sheet or the like occurs.
There is a limit to the thickness of the opaque pigment and the opaque solid printing layer,
Therefore, the concealing ability of a practical concealed solid printing layer is naturally limited.

[0010] Under such circumstances, some decorative sheets of the conventional configuration have sufficient concealing properties that can be applied to all types of decorative material base materials, have excellent interlayer adhesion strength, and are capable of producing a wide variety of products in small quantities and have a short delivery time. There is a problem that a decorative sheet that can easily cope with is not obtained.

[0011]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the prior art, and it is an object of the present invention to cope with all kinds of base materials for decorative materials. It is an object of the present invention to provide a decorative sheet which has sufficient concealing properties, has excellent interlayer adhesion strength, can be manufactured at low cost with a short delivery time, and can easily cope with small-lot production of many kinds.

[0012]

The present invention is characterized in that a concealed solid printing layer is provided on the surface of a base sheet including at least a colored resin layer made of a thermoplastic resin containing a concealing pigment. It is a decorative sheet.

[0013] The present invention is also a decorative sheet comprising a pattern printing layer and a transparent resin layer sequentially laminated on the concealed solid printing layer.

The present invention is also a decorative sheet, characterized in that the base sheet is formed by laminating a surface layer made of a thermoplastic resin containing no opaque pigment on the surface of the colored resin layer. .

[0015] The present invention is also a decorative sheet characterized in that the base sheet is formed by laminating a back layer made of a thermoplastic resin containing no opaque pigment on the back side of the colored resin layer. .

Further, according to the present invention, the base sheet is formed by laminating a surface layer and a back layer made of a thermoplastic resin containing no opaque pigment on the front side and the back side of the colored resin layer, A decorative sheet, wherein the thermoplastic resin forming the colored resin layer is softer than the thermoplastic resin forming the front surface layer and the back surface layer.

Further, the present invention is the decorative sheet, wherein the compounding ratio of the opaque pigment in the colored resin layer is from 1 part by weight to 20 parts by weight per 100 parts by weight of the thermoplastic resin.

Further, the present invention is the decorative sheet, wherein the thickness of the concealed solid printing layer is 20 μm or less.

[0019]

Embodiments of the present invention will be described below in detail with reference to the drawings. 1 to 5 are side sectional views each showing an embodiment of the decorative sheet of the present invention.

The decorative sheet of the present invention has a structure in which at least a concealed solid printing layer 2 is provided on a base sheet 1, and the base sheet 1 is a thermoplastic resin containing a concealing pigment. Characterized by comprising at least a colored resin layer 12 made of Preferably, on the concealed solid printing layer 2, further, a pattern printing layer 3,
A transparent resin layer 4 is provided (FIG. 1). The base sheet 1 may be composed of only the colored resin layer 12, or the surface layer 11 and / or the back layer 1 made of a thermoplastic resin containing no opaque pigment on the surface and / or the back surface.
3 may be provided (FIGS. 2 to 4).

The decorative sheet of the present invention is constructed as described above. As a result, the colored resin layer 12 made of a thermoplastic resin containing a concealing pigment and the concealed solid printing layer 2 complement the concealing property. High concealing properties can be obtained as compared with the case where only the resin layer 12 or only the concealed solid printing layer 2 is provided. Conversely, the colored resin layer 12 and the concealed solid printing layer 2 do not necessarily require high concealing properties as required when each is provided alone.

Therefore, since the concealing property of the concealed solid printing layer 2 itself is not required to be so strict, the thickness of the concealed solid printing layer 2 and the concealing pigment can be maintained while maintaining the concealing property of the decorative sheet as a whole at a sufficient level. The compounding ratio can be designed conservatively to ensure sufficient interlayer adhesion.
In addition, since the concealed solid printing layer 2 is provided on the surface side of the base sheet 1 and the base sheet 1 is added, the base sheet 1 itself is colored in a color tone that matches the background color of the desired pattern. You don't have to. Therefore, it is possible to manufacture decorative sheets having patterns of different colors using the base sheet 1 having the same color tone. Specifically, for example, the base sheet 1 may be a translucent sheet such as milky white.

As described above, since the base sheet 1 used in the decorative sheet of the present invention is highly versatile and can be used in common for many types of patterns, the desired individual patterns It is not necessary to reset the compounding ratio of various pigments to the raw resin according to the color tone of the raw material, and strict control of the color tone in the process can be omitted, so that production can be performed in a short delivery time, and general-purpose Because of its high possibility, large-scale ordering is possible, so that procurement can be performed at low cost. Also, depending on the conditions, it is possible to use a commercially available general-purpose colored resin film or sheet that is not dedicated to a decorative sheet as the base sheet 1, and it can respond to immediate delivery by inventory and further reduction in unit price. The delivery time of the manufactured decorative sheet can be shortened, and the manufacturing cost can be reduced.

In particular, when the base sheet 1 is configured such that the surface layer 11 made of a thermoplastic resin containing no opaque pigment is provided on the colored resin layer 12, the concealed solid printing layer is directly formed on the colored resin layer 12. 2, the concealing property is further improved. This is because the colored resin layer 12 and the concealed solid printing layer 2
Between the two layers colored by the opaque pigment, a surface layer 11, which is transparent because it does not contain the opaque pigment, has a refractive index (a complex refractive index) of a colored layer and a transparent layer. It is considered that the interfaces between the layers markedly different from each other) exist doubly, and the light reflection and refraction effects at these interfaces hinder straight traveling of light and amplify the concealment.

Therefore, utilizing this principle, the thickness of the concealed solid print layer 2 and the compounding ratio of the concealable pigment are further reduced to further improve the interlayer adhesion strength of the decorative sheet, and to improve the color resin layer 1
By further reducing the thickness of 2 and the compounding ratio of the opaque pigment, the production cost of the base sheet 1 can be reduced, and the suitability for molding and the molding speed can be improved. Or, conversely, if the thickness of the concealed solid printing layer 2 and the colored resin layer 12 and the blending ratio of the opaque pigment are the same, the color tone of the pattern of the decorative sheet that can be manufactured using the base sheet 1 having the same color tone You can also expand the range of choices.

In particular, the base material sheet 1 is
In the case of a three-layer structure in which the front layer 11 and the back layer 13 made of a thermoplastic resin containing no opaque pigment are provided on the front and back sides, the thermoplastic resin constituting the front layer 11 and the back layer 13 is Colored resin layer 1 made of soft thermoplastic resin
It is preferable that the second member be constituted. That is, the more flexible the resin, the less the heat fluidity is reduced by the addition of the concealing pigment, and it is possible to suppress the occurrence of molding defects such as uneven streaks and fish eyes during sheet molding by extrusion molding or the like. On the other hand, even if the flexible resin according to the colored resin layer 12 is used, the front and back surfaces are protected by the harder surface layer 11 and the rear surface layer 13 and at the same time, the strength is given. Sufficient abrasion resistance, solvent resistance, tensile strength and stiffness can be provided in a printing step or a processing step such as lamination. In particular, in a decorative sheet for use in bending or curved surface processing such as V-cut processing, lapping lamination processing, and vacuum lamination processing, the colored resin layer 12 made of a flexible resin has a role like a cushion. And there is also an advantage that a decorative sheet excellent in workability can be obtained.

In the decorative sheet of the present invention, the type of the thermoplastic resin constituting the base sheet 1, ie, the colored resin layer 12, the surface layer 11 and / or the back layer 13, is not particularly limited, and is generally more conventional. Any known thermoplastic resin used as a material of a base sheet for a decorative sheet can be employed. Specifically, for example, polyolefin resins such as polyethylene, polypropylene, polybutene and polymethylpentene; ethylene-vinyl acetate copolymers or saponified products thereof; and polyolefin resins such as ethylene- (meth) acrylic acid (ester) copolymers Copolymer,
Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate and polycarbonate; acrylic resins such as polymethyl methacrylate; 6-nylon;
-Polyamide resins such as nylon and 6,10-nylon; styrene resins such as polystyrene resin, AS resin and ABS resin; cellulose derivatives such as cellulose acetate and nitrocellulose; and chlorine resins such as polyvinyl chloride and polyvinylidene chloride. Resin, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, fluorine-based resin such as ethylene-tetrafluoroethylene copolymer, or two or three or more copolymers or mixtures selected from these,
Composites, laminates and the like can be used.

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

As the olefin-based resin, various homopolymers and copolymers including the above-mentioned ones are known. Among them, the most preferred material for the base sheet for decorative sheet is polypropylene-based resin, that is, polypropylene. It is a homo- or copolymer having a main component, specifically, for example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, and a polypropylene crystal part, and having 2 to 20 carbon atoms other than propylene
Α-olefin, preferably ethylene, butene-1,
4-methylpentene-1, hexene-1 or octene-
A propylene-α-olefin copolymer containing 15 mol% or more of the comonomer (1) 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. .

Acrylic resins and polyester resins can be exemplified as suitable resins other than the olefin resins. As the acrylic resin, for example, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, various thermoplastic resins obtained by homopolymerizing or copolymerizing an acrylic acid derivative such as an acrylate or a methacrylate as a main component. be able to.
Among them, a resin containing methacrylic acid ester such as methyl methacrylate as a main component, for example, a long-chain alkyl ester of methacrylic acid such as butyl methacrylate, an acrylate ester such as methyl acrylate, methacrylic acid or acrylic acid Improve flexibility and thermoformability by adding selected monomers as copolymerization components or graft copolymerizing, block copolymerizing or blending rubber components such as styrene-butadiene rubber or methyl methacrylate-butadiene rubber. It is possible to suitably use the resulting resin or the like.

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

The concealing pigment to be contained in the thermoplastic resin constituting the colored resin layer 12 is, as is well known, a fine powdery pigment having an extremely high refractive index as compared with the thermoplastic resin as a dispersion medium. Thus, the light scattering effect due to the reflection or refraction of light at the interface due to the difference in refractive index from the resin prevents direct transmission of light between the front and back surfaces of the colored resin layer 12, thereby exhibiting concealment. Since the refractive index of a general thermoplastic resin is approximately 1.5, it is general that a pigment having a refractive index of approximately 2.0 or more is selected as the opaque pigment,
Further, from the viewpoint of scattering ability with respect to light (visible light), those having a particle size of about 0.1 to 1 μm are usually used.

Among such concealing pigments, pigments having a high light-absorbing property are referred to as colored pigments because they absorb a part of the incident light and exhibit a chromatic coloring effect. Non-existing pigments are called white pigments because they exhibit 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-mentioned colored pigment and white pigment in an appropriate ratio, it is possible to obtain any desired color tone. Can be done.

In the decorative sheet of the present invention, the colored resin layer 12 does not necessarily have to be colored in a color to be a background of a picture, and it is sufficient if it has an appropriate hiding property. Should be added,
It is not always necessary to add a colored pigment. However, when dealing with a large number of types of color patterns having a high background color density, a base sheet which is slightly lightly colored by adding a colored pigment more sparingly than when the concealed solid print layer 2 is not provided. When 1 is prepared, variation in color tone due to variation in printing is suppressed, and there is an advantage that a product with stable color tone can be easily obtained.

Various organic and inorganic pigments are known as the concealing pigment. In general, an inorganic pigment has a higher refractive index and an excellent concealing property than an organic pigment. In order to give the sheet excellent concealment,
It is preferred to use inorganic pigments. Inorganic pigments are excellent in light resistance (fading resistance) and chemical resistance in addition to the above-described hiding properties, and are therefore very suitable from the viewpoint of durability and fastness.

Among the inorganic pigments, white pigments include, for example, titanium oxide (titanium white, titanium white), zinc oxide (zinc white), basic lead carbonate (lead white), basic lead sulfate, zinc sulfide, lithopone, Colored pigments such as titanox, for example, graphite, yellow iron oxide, cadmium yellow,
Titanium yellow, barium yellow, aureoline, quinacridone, molybdate orange, cadmium red, red stalk, lead red, cinnabar, mars violet, manganese violet, cobalt violet, cobalt blue, cerulean blue, ultramarine, navy blue, emerald green, chrome vermilion , Chromium oxide, viridian, iron black, carbon black and the like can be used.

Among them, pigments which are excellent in concealing properties and light resistance and which are suitable for decorative sheets in terms of color tone in terms of design, titanium oxide pigments as white pigments, red iron oxide, yellow iron oxide, iron black as colored pigments It is most preferable to use an iron oxide pigment such as

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.

The petiole is a red pigment composed of ferric oxide Fe ₂ O ₃ (also called hematite), and has an average particle size of 0.2 to 0.6.
Those having a size of about μm are used. Yellow iron oxide is a yellow pigment composed of iron hydroxide oxide γ-FeO (OH) (also known as leucite) or a hydrate thereof, and has an average particle diameter of 0.3 to 0.8 μm.
The degree is used. Iron black is ferrous tetroxide Fe ₃ O
_{4 A} black pigment composed of (also called magnetite) having an average particle size of about 0.5 μm is used. 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.

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 concealing or non-concealing inorganic or organic pigments for the purpose of adjusting the color tone. Absent. However, it is preferable to use a titanium oxide-based pigment and an iron oxide-based pigment as a main component, and it is preferable to use other pigments in an amount of about 20% by weight or less based on the entire 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.

The mixing ratio of the above opaque pigment to the thermoplastic resin constituting the colored resin layer 2 is not particularly limited, but if it is too small, sufficient concealment properties cannot be obtained, while if it is too large, the resin becomes brittle. Generally, 1 part by weight or more per 100 parts by weight of the thermoplastic resin, because the adhesion between layers is impaired, or the thermoformability is reduced, which causes poor molding such as uneven streaks or fish eyes at the time of forming the sheet. It is preferable that the content be in the range of 20 parts by weight or less.

In addition to the various pigments described above, the thermoplastic resin constituting the base sheet 1 may optionally include an antioxidant, an ultraviolet absorber, and the like, depending on the intended use of the decorative sheet.
One or more types of conventionally known various additives such as a light stabilizer, a heat stabilizer, a plasticizer, a lubricant, an antistatic agent, a flame retardant, and a filler may be added.

As the antioxidant, for example, a phenol compound,
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, talc, rubble, kaolin and the like is used.

The thickness of the base sheet 1 is not particularly limited, and a sheet having the same thickness as that of a conventional general decorative sheet can be used. Specifically, although it depends on the use of the decorative sheet and the type of the thermoplastic resin to be used, it is generally 2
It is selected from a range of about 0 to 200 μm, and a particularly preferred range is about 50 to 100 μm.

When the base sheet 1 is composed of two or three layers in which the surface layer 11 and / or the back layer 13 are added to the colored resin layer 12, the composition ratio of the thickness of each layer is not particularly limited. The sum of the thickness of the surface layer 11 and / or the back layer 13 is
It is desirable not to exceed the thickness of the colored resin layer 12. The thickness of the front surface layer 11 and the back surface layer 13 is usually designed within a range of about 1 to 20 μm. The method for laminating the colored resin layer 12 and the surface layer 11 and / or the back layer 13 is not particularly limited. For example, a wet lamination method or a dry lamination method using an adhesive, a heat lamination method, a resin solution or an uncured state Extrusion lamination method or sand lamination method, in which the resin that has been heated and melted is extruded into a sheet and simultaneously laminated, and a plurality of resin compositions are heated and melted simultaneously to form a sheet. Conventionally known arbitrary methods such as a co-extrusion method of extruding and laminating the layers can be applied. Among them, the co-extrusion method is most desirable from the viewpoint of productivity, interlayer adhesion and the like.

The concealed solid print layer 2 is sufficient to cover the concealability of the base sheet 1 and to conceal defects such as undesired colors and scratches on the surface of various base materials to which the decorative sheet is to be attached. It is provided for the purpose of imparting an excellent concealing property to a decorative sheet, and a printing ink or a coating agent having a concealing property is printed or coated in a solid form on the entire surface of the base sheet 1 as conventionally known. It is provided by the thing.

The concealable printing ink or coating agent is a mixture of a concealable pigment and an appropriate binder resin, and if necessary, an appropriate solvent such as a solvent or a dispersion medium is added thereto to prepare a printing or coating agent. It is a fluid composition adjusted to an appropriate viscosity according to the method, and a film in which a concealing pigment is dispersed in a binder resin obtained as a result of printing or coating is required as a concealed solid printing layer. It must be designed to have the required concealment. As the hiding pigment, the base sheet 1
The same pigments as those exemplified as the concealing pigment to be added to the colored resin layer 12 can be used. Further, for the purpose of adjusting the color or adjusting the flow characteristics, a non-concealing pigment or extender may be used in combination.

The amount of the inorganic pigment to be concealed added to the concealed solid printing layer 2 is not particularly limited, and the greater the amount, the more advantageous in terms of concealment. However, the cohesive strength is reduced and the interlayer adhesion of the decorative sheet is reduced. In order to achieve a balance between the two, the content is preferably in the range of about 100 to 1,000 parts by weight per 100 parts by weight of the binder resin, and most preferably about 300 to 700 parts by weight. In addition, the thickness of the concealed solid printing layer 2 is not particularly limited.
On the other hand, the cohesive force is reduced, which causes a decrease in the interlayer adhesion of the decorative sheet. Therefore, it is preferable to set the range not to exceed 20 μm, and most preferable to set the range to about 5 to 15 μm.

As the binder resin as a dispersion medium of the above-mentioned various pigments, any known resin conventionally used as a binder resin for a printing ink or a coating agent can be used. Specifically, 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 Various synthetic resins such as a series resin, a cellulose derivative, a rubber resin, or a mixture of two or more kinds thereof, a copolymer, and the like can be used.

Examples of the solvent for dissolving or dispersing the various pigments and the binder resin include hexane, heptane, octane, toluene, xylene, ethylbenzene, and the like.
Petroleum organic solvents such as cyclohexane and methylcyclohexane, and ester organic solvents such as ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate; methyl alcohol, ethyl alcohol, normal propyl alcohol, and isopropyl alcohol Alcohol-based organic solvents such as isobutyl alcohol, ethylene glycol and propylene glycol; ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ether-based organic solvents such as diethyl ether, dioxane and tetrahydrofuran; dichloromethane; carbon tetrachloride It is possible to use various organic solvents such as chlorinated organic solvents such as trichloroethylene and tetrachloroethylene, inorganic solvents such as water, or a mixed solvent of two or more thereof. Kill.

In addition, if necessary, various additives such as a dispersant, a plasticizer, a surfactant, a tackifier, an adhesion aid, a drying agent, a curing agent, a curing accelerator or a curing retarder are appropriately added. You can also.

Examples of the method of forming the concealed solid printing layer 2 include gravure printing, offset printing, screen printing, letterpress printing, flexographic printing, electrostatic printing, ink jet printing, electrophotography, and the like. Various printing methods, such as gravure coating, roll coating, dip coating, air knife coating, knife coating, comma coating, die coating, lip coating, kiss coating, rod coating, spray coating, flow coating Any conventionally known printing method or coating method such as various coating methods such as a coating method can be appropriately selected and implemented.

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

A pattern printing layer 3 is usually provided between the concealed solid printing layer 2 and a transparent resin layer 4 described later for the purpose of imparting a desired decorative design to a desired decorative sheet. It is common. However, for example, in the case of a plain decorative sheet only for the purpose of simple surface coloring or color adjustment, and the surface coloring or color adjustment can be sufficiently achieved only by the concealed solid printing layer 2, the pattern printing layer 3 is provided. Not always.

The constituent material and the forming method of the pattern printing layer 3 are not limited at all, and any image forming material or image forming method that has been conventionally applied to the pattern layer of the decorative sheet can be appropriately applied. Specifically, for example, various printing inks and printing methods similar to those of the concealed solid printing layer 2 described above can be applied.

However, if the base sheet 1 and the concealed solid printing layer 2 ensure sufficient concealing properties, the printing ink constituting the picture printing layer 3 is not required to have any particular concealing properties. For example, a colored transparent printing ink may be used. Accordingly, the pigment to be used is not particularly limited to inorganic pigments, and organic pigments can be sufficiently used as long as they have requirements such as sufficient light resistance and durability for decorative sheets. Specifically, for example, azo pigments, lake pigments, quinacridone pigments, anthraquinone pigments, phthalocyanine pigments, isoindolinone pigments, dioxazine pigments, or a combination of two or more of these organic pigments and the various inorganic pigments described above. Can be used.

The pattern printing layer 3 is formed by the above-described printing method, for example, a hand-drawing method, a sinking method, 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. Can be performed in combination.

The type of the pattern constituted by the pattern printing layer 3 is not particularly limited. For example, a wood pattern, a stone pattern, a cloth pattern, an abstract pattern, and a geometric pattern widely used in the field of decorative sheets according to the related art. Etc., or for the purpose of simple coloring or color adjustment, a single-color solid color may be used.
Any desired pattern can be adopted according to the intended use of the decorative sheet.

A transparent resin layer 4 is provided on the pattern printing layer 3 for the purpose of protecting the pattern printing layer 3 and imparting good surface properties such as abrasion resistance and solvent resistance to the decorative sheet. Is common. The transparent resin layer 4 is a material and preferably has high transparency.
It is only necessary that the film has transparency enough to be able to be seen through, and as long as it is transparent, it may be translucent or colored and transparent.

As the resin constituting the transparent resin layer 4, the same kind of resin as the resin used as the transparent resin layer on the front side in the conventional decorative sheet having a multilayer structure can be appropriately used. In the decorative sheet of the present invention, the same or different thermoplastic resin as the resin used as the constituent material of the base sheet 1 may be used, or a curable resin such as a thermosetting resin or an ionizing radiation-curable resin. May be. However, in consideration of the above-mentioned environmental problems and the like, it is preferable to use a non-halogen resin, that is, a polyolefin resin, an acrylic resin, a polyester resin, or the like, as in the case of the base sheet 1. Also, the transparent resin layer 4
May be composed of a multilayer laminate in which a plurality of layers made of the same or different transparent resins are laminated.

When the transparent resin layer 4 is formed of a multilayer laminate, the pattern printing layer 3 is provided between the concealed solid printing layer 2 and the transparent resin layer 4 instead of the multilayer printed layer constituting the transparent resin layer 4. It can also be provided between any layers of the body. Further, the same type or different types of patterns may be provided at a plurality of positions selected from between the concealed solid printing layer 2 and the transparent resin layer 4 and between the respective layers of the multilayer laminate constituting the transparent resin layer 4. With this configuration, it is possible to obtain a decorative sheet having high design and excellent depth and three-dimensional appearance.

When the transparent resin layer 4 is formed from a curable resin, the curable resin may be, for example, a melamine resin, a phenol resin, a urea resin, an epoxy resin,
Thermosetting resins such as unsaturated polyester resin, diallyl phthalate resin, urethane resin, aminoalkyd resin, and ultraviolet or electron such as acrylate resin, urethane acrylate resin, ester acrylate resin, epoxy acrylate resin, etc. An ionizing radiation curable resin or the like that is cured by irradiation with a line or the like can be used.

Generally, the thickness of the transparent resin layer 4 is more advantageous in terms of surface physical properties such as abrasion resistance and solvent resistance, weather resistance, design feeling such as painting feeling, depth feeling, emboss depth and the like. However, it is disadvantageous in terms of flexibility and flexibility as a decorative sheet, bending workability such as V-cut, and the like, and therefore a thickness range that balances both is selected. Specifically, when a curable resin is used, it is generally limited to 20 μm or less from the viewpoint of flexibility, and preferably ranges from about 3 to 10 μm.
When a thermoplastic resin is used, it can be provided thicker than this, and is generally about 20 to 200 μm, especially about 50 μm.
It is selected from a range of about 120 μm. Therefore, a thermoplastic resin is advantageous in terms of abrasion resistance, design properties, and the like, and is also advantageous in terms of a manufacturing process in which a curing treatment is unnecessary and quality is easily stabilized.

The method for forming the transparent resin layer 4 is not particularly limited, and any conventionally known method can be appropriately applied. Specifically, for example, a method of applying a coating agent obtained by dissolving or dispersing a resin to constitute the transparent resin layer 4 in an appropriate solvent and drying and solidifying the same, and a method of forming a resin to constitute the transparent resin layer 4 after curing. A method of applying a cured resin composition and then cross-linking and curing the same, and a method of forming a transparent resin layer 4 previously formed into a film or a sheet into a dry laminating adhesive, a heat-sensitive adhesive, a pressure-sensitive adhesive, or an ionizing radiation-curable adhesive. A method of bonding via an appropriate adhesive, or a method of directly bonding by means of thermocompression bonding or ultrasonic welding without using an adhesive, and in particular, the resin for forming the transparent resin layer 4 is a thermoplastic resin. In some cases, conventional methods such as extruding a heat-melted resin into a film or a sheet on a surface of a base sheet 1 on which a concealed solid printing layer 2 or a pattern printing layer 3 or the like are provided in advance, and simultaneously bonding the resin and the like. Public knowledge From various methods, a method that matches the characteristics of the resin for constituting a transparent resin layer 4 appropriately selected and can be used.

In the case where the latter method (extrusion laminating method) is adopted, if the adhesion between the pattern printing layer 3 and the transparent resin layer 4 is poor, this is also known in the art. Is provided with a heat-sensitive adhesive layer 5 in advance, or the constituent resin of the transparent resin layer 4 and a separately prepared heat-adhesive resin are co-extruded and laminated, so that the pattern printing layer 3 and the transparent resin layer 4 By sandwiching the adhesive resin layer 6 between them, the adhesiveness can be improved (FIG. 5). Of course, both may be used in combination as needed.

On the surface of the transparent resin layer 4, an emboss 7 having a desired and appropriate pattern can be provided as necessary, as is conventionally known. The type of the pattern of the emboss 7 is not particularly limited, and may be various patterns such as a woodgrain (particularly a conduit pattern), a stonegrain, a Japanese paper, a cloth, a geometric pattern, or the like. It may be a simple matte, grain, hairline, suede, or the like. Further, the design of the embossed pattern 7 can be synchronized with the pattern of the pattern printing layer 3 to further improve the design. However, if it is not necessary, the pattern may be out of synchronization. It is also possible to provide an embossed pattern 7 including both a pattern synchronized with the pattern 3 and a pattern not synchronized.

The method of forming the embossing 7 is not particularly limited, but a mechanical embossing method using a metal embossing plate is most common. Also, the timing of forming the emboss 7 is not particularly limited, and an arbitrary timing can be selected from before, simultaneously with or after lamination of the transparent resin layer 4 with the base sheet 1, and from among these, The embossing 7 having the same or different pattern can be applied a plurality of times at a plurality of selected times. The concave portion of the emboss 7 may be filled with a coloring agent by a method such as a wiping method as necessary.
Thereby, it is possible to obtain a decorative sheet excellent in design property having a color pattern synchronized with the uneven pattern on the surface.

Further, a top coat layer 8 can be provided on the surface of the transparent resin layer 4 for the purpose of imparting more excellent surface 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. In particular, the transparent resin layer 4
Is preferably made of a thermoplastic resin, it is preferable to apply a top coat layer 8 made of a curable resin.

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. In particular, by making the top coat layer 8 contain at least a substance having a low surface tension such as a silicone compound or a fluorine compound, the surface of the decorative sheet can have excellent stain resistance. Also, by using a plurality of types of resin compositions having different gloss on the surface and applying a part or all of the composition to a desired appropriate pattern, a design having a visual three-dimensional effect due to a change in gloss is provided. You can also.

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, and a die coating method as long as the entire surface is solid. ,
A lip coating method, a kiss coating method, a rod coating method, a spray coating method, a flow coating method, and the like, and when applied in a pattern, for example, a gravure printing method, an offset printing method, a screen printing method, a flexo printing method, or any other conventionally known arbitrary method. The coating method and the printing method can be appropriately applied.

If the adhesion between the transparent resin layer 4 and the top coat layer 8 is insufficient, the surface of the transparent resin layer 4 may be subjected to, for example, corona treatment, ozone By performing a surface treatment such as a treatment, a plasma treatment, an ionizing radiation treatment, a dichromic acid treatment, an anchor or a primer treatment, the adhesion between the transparent resin layer 4 and the top coat layer 8 can be improved.

As described above, the decorative sheet of the present invention is used by attaching it to the surface of various base materials such as a wooden base material and an inorganic base material, like the conventional decorative sheet. Generally, an appropriate adhesive such as a urethane-based or vinyl acetate-based adhesive is used at the time of the application, but depending on the type of the resin constituting the base sheet 1, such an adhesive for general-purpose lamination may be used. May not have sufficient adhesiveness. In preparation for such a case, it is preferable to provide an easy-adhesion primer layer 9 made of a resin having excellent adhesion to the above-mentioned general-purpose adhesive on the back surface of the base sheet 1.

Various primers such as urethane, acrylic, ethylene-vinyl acetate copolymer and vinyl chloride-vinyl acetate copolymer are known as the easy-adhesion primer layer 9. Material sheet 1
Select and use the ones that match. In addition, for example, silica, alumina, calcium carbonate,
By adding a powder such as barium sulfate, the surface of the easy-adhesion primer layer 9 is roughened to prevent blocking during winding and preservation of the decorative sheet. Adhesion can also be improved.

[0074]

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

Example 1 A 12 μm thick surface layer made of a transparent hard polyolefin resin containing no pigment was formed on the front and back of a 36 μm thick colored resin layer made of a soft polyolefin resin containing 6% of a titanium oxide pigment. A three-layered polyolefin resin sheet having a backside layer and a backside layer is prepared by a co-extrusion method to form a base sheet. First, the backside is subjected to a corona discharge treatment to adjust the critical surface tension to 38 dyne / cm or more. A thermoplastic urethane resin-based primer containing powder was applied to a dried film thickness of 1 μm to form an easily adhesive primer layer.

Next, the surface of the base sheet is subjected to a corona discharge treatment to adjust the critical surface tension thereof to 40 dyne / cm or more, and then a two-part curable urethane resin containing a concealing pigment containing an inorganic pigment as a main component. 8μm thick opaque ink (Toyo Ink Co., Ltd.) after drying by gravure printing
m to form a concealed solid printing layer. Next, a wood-grained pattern printing layer is formed on the concealed solid printing layer by a gravure printing method using a urethane resin-based printing ink, and a two-component curable urethane resin-based heat-adhesive anchor layer is further formed. Was coated and formed to a thickness of 1 μm after drying.

Next, a 20 μm thick maleic acid-modified olefin adhesive resin layer and a 70 μm thick transparent benzotriazole ultraviolet absorber and a hindered amine light stabilizer were added on the heat adhesive anchor layer. A transparent resin layer was formed by simultaneously extruding a transparent polyolefin resin layer into a sheet shape by a co-extrusion method to form a transparent resin layer, and at the same time, embossing a wood grain conduit pattern on the surface. Thereafter, on the surface of the transparent resin layer, a two-part curable urethane resin-based top coat layer to which a benzotriazole-based ultraviolet absorber and a hindered amine-based light stabilizer have been added is coated and formed to a thickness of 5 μm after drying, The decorative sheet of the present invention was obtained.

When the laminate strength (180 ° peel strength) between the base sheet and the transparent resin layer of the decorative sheet was measured, it was 2.0 kgf / inch or more, which was sufficient for this type of decorative sheet. It was confirmed to have. In addition, in order to check the concealment property, the lightness difference (ΔL ^* ) between the standard white board and the standard blackboard was measured using a colorimeter.
Was measured, the difference in lightness was 2.0, and it was confirmed that this type of decorative sheet had sufficient hiding properties. In addition, no significant change was observed visually after 1000 hours from the sunshine weather meter weathering test (black panel 63 ° C, with rainfall), and the result of no pattern removal in abrasion B test (Japanese Agricultural Standard Special Plywood) 1000 times And
It was confirmed that the decorative sheet was sufficiently excellent in terms of weather resistance and abrasion resistance.

Comparative Example 1 In the above-mentioned Example 1, the concealing property equivalent to that of the decorative sheet of Example 1 can be achieved by increasing the thickness of the concealed solid printed layer without adding any pigment to the base sheet. When the conditions were examined, the thickness of the concealed solid printing layer was required to be 25 μm. When the laminate strength of the decorative sheet thus obtained was measured in the same manner as in Example 1, it was 0.5 kgf
/ Inch or less (cohesive failure of the concealed solid print layer)
The value was insufficient for this type of decorative sheet.

Comparative Example 2 In the above-mentioned Example 1, the concealing property equivalent to that of the decorative sheet of Example 1 can be achieved by increasing the mixing ratio of the titanium oxide pigment to the colored resin layer without providing the opaque solid printing layer. Examination of the conditions revealed that it was necessary to add 30 parts by weight of a titanium oxide pigment per 100 parts by weight of the resin to the colored resin layer. When a resin sheet having this composition was used to produce a base sheet under the same processing conditions as in Example 1, a large number of molding defects such as streaks and fish eyes were visually confirmed on the sheet surface. The decorative sheet used was not satisfactory in design.

[0081]

As described above in detail, the decorative sheet of the present invention comprises a concealed solid printing layer provided on the surface of a base sheet including at least a colored resin layer made of a thermoplastic resin containing a concealing pigment. By the configuration, first, the concealed solid printing layer, the concealing property is supplemented by the colored base sheet, the concealing solid printing layer alone is not so strictly required for the concealing property, so the thickness of the concealed solid printing layer and Even if the compounding ratio of the opaque pigment is suppressed to such an extent that the interlayer adhesion is not deteriorated, a sufficient concealment property can be secured for the decorative sheet as a whole. On the other hand, since the base sheet is later colored by the concealed solid printing layer, it is not always necessary to prepare a base sheet in advance in accordance with the background color of the desired pattern, and a small number of types of base sheets are required. Since many kinds of patterns can be handled with the sheet, the thermoplastic resin film or sheet as the base sheet can be easily procured at a low cost and in a short delivery time, and material loss and the complexity of inventory management and process management are reduced. In addition, it has an excellent advantage that it can be adapted to low-cost, short-term delivery even in high-mix low-volume production.

In particular, when a base sheet having a structure in which a surface layer made of a thermoplastic resin containing no opaque pigment is laminated on the surface of the colored resin layer is used as the base sheet, the opaque pigment is contained. A layer having a remarkably different refractive index, that is, a surface layer containing no concealing pigment, is sandwiched between the concealed solid printing layer and the colored resin layer. The concealing property is further amplified as compared with the case where the printing layer is provided, and the influence of the color of the colored resin layer or the back side thereof on the front side of the concealed solid printing layer is reduced, so that the concealed solid printing layer or the pattern printing layer is reduced. This improves the design effect. Conversely, the concealing property of the concealed solid printing layer required to achieve the same design effect can be reduced, so the thickness of the concealed solid printing layer and the compounding ratio of the concealing pigment are reduced, and the interlayer adhesion is more excellent. It has an excellent advantage that it is also possible to obtain a decorative sheet.

Particularly, the base sheet has a structure in which a surface layer and a back layer made of a thermoplastic resin containing no opaque pigment are laminated on the front side and the back side of the colored resin layer. When the resin layer is made of a thermoplastic resin that is softer than the thermoplastic resin constituting the front surface layer and the back surface layer, sufficient tensile strength, waist, solvent resistance, scratch resistance, etc. as a base sheet for a decorative sheet can be obtained. It is possible to have sufficient flexibility and thermoformability to withstand bending and vacuum forming while holding the opaque pigment, and since the concealing pigment is added to the soft thermoplastic resin,
It has an excellent advantage that there is no possibility of adversely affecting the formability, flexibility, thermoformability and the like of the base sheet by the extrusion method or the like.

[Brief description of the drawings]

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

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

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

FIG. 4 is a side sectional view showing an embodiment of the decorative sheet of the present invention.

FIG. 5 is a side sectional view showing an embodiment of the decorative sheet of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base material sheet 11 Surface layer 12 Colored resin layer 13 Back surface layer 2 Concealed solid printing layer 3 Picture printing layer 4 Transparent resin layer 5 Anchor layer 6 Adhesive resin layer 7 Emboss 8 Top coat layer 9 Easy adhesion primer layer

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takeshi Kojima 1-5-1, Taito, Taito-ku, Tokyo Toppan Printing Co., Ltd. F-term (reference) 4F100 AA21H AH03H AK01A AK01D AK01E AK03 AK51 BA02 BA04 BA05 BA07 BA10A BA10D BA10E BA26 CA05 CA07 CA13 CA13A CB00 EH23 EJ38 EJ55 GB07 GB08 GB33 GB48 GB81 HB00C HB01 HB31B HB31C JB16A JB16E JK06 JK09 JK13E JL09 JL10A JN01D JN01E JN02A JN02Y YB02Y

Claims (7)

[Claims] Claims: 1. A surface of a base sheet including at least a colored resin layer made of a thermoplastic resin containing a masking pigment,
A decorative sheet comprising a concealed solid printing layer. 2. The decorative sheet according to claim 1, wherein a picture printing layer and a transparent resin layer are sequentially laminated on the concealed solid printing layer. 3. The substrate sheet according to claim 1, wherein a surface layer made of a thermoplastic resin containing no opaque pigment is laminated on the surface of the colored resin layer.
A decorative sheet according to claim 1. 4. The substrate sheet according to claim 1, wherein a back layer made of a thermoplastic resin containing no opaque pigment is laminated on the back side of the colored resin layer. A decorative sheet according to claim 1. 5. The base sheet is formed by laminating a surface layer and a back layer made of a thermoplastic resin containing no opaque pigment on the front side and the back side of the colored resin layer. The decorative sheet according to claim 1, wherein the thermoplastic resin forming the layer is softer than the thermoplastic resin forming the front surface layer and the back surface layer. 4. 6. The compounding ratio of the opaque pigment of the colored resin layer is as follows:
The decorative sheet according to any one of claims 1 to 5, wherein the amount is 1 part by weight or more and 20 parts by weight or less per 100 parts by weight of the thermoplastic resin. 7. The decorative sheet according to claim 1, wherein the thickness of the concealed solid printing layer is 20 μm or less.