JP2021030447A - Decorative sheet - Google Patents

Abstract

To provide a decorative sheet which can impart scratch resistance and abrasion resistance equivalent to a melamine planet even in a decorative sheet having no melamine plate, and is excellent in workability and productivity.SOLUTION: A decorative sheet 10 has a pattern layer 5, a transparent thermoplastic resin layer 6 and a surface protective layer 7 in this order on a base material layer 1, in which the base material layer 1 includes at least a first raw fabric layer 2 that is uniaxially drawn and a second raw fabric layer 3 that is formed on the first raw fabric layer 2 and is uniaxially drawn, the first raw fabric layer 2 and the second raw fabric layer 3 each includes a thermoplastic resin 4b and an inorganic material 4a, a content of the inorganic material 4a is within a range of 15 mass% or more and 90 mass% or less with respect to the masses of each of the raw fabric layers, and an extension direction of the first raw fabric layer 2 and an extension direction of the second raw fabric layer 3 cross each other.SELECTED DRAWING: Figure 1

Description

The present invention relates to a decorative sheet.

As a member having scratch resistance and abrasion resistance, for example, there is a member provided with the melamine plate described in Patent Document 1. Since the size of this melamine plate is regulated to some extent, there are many parts where the melamine plate is cut and discarded during product processing, which may reduce productivity. Further, when a melamine plate is used, the work efficiency is low because the laminating process is performed on a single leaf, and the workability may be poor due to its weight.

Japanese Unexamined Patent Publication No. 2014-188941

The present invention has been made to solve such a problem, and an object of the present invention is to provide scratch resistance and abrasion resistance equivalent to those of a melamine plate even if the decorative sheet does not have a melamine plate. It is to provide a decorative sheet which can be imparted and has excellent processability and productivity.

In order to solve the above problems, in the decorative sheet according to one aspect of the present invention, a pattern layer, a transparent thermoplastic resin layer, and a surface protective layer are laminated in this order on the base material layer, and the base material layer is formed. A uniaxially stretched first raw fabric layer and a uniaxially stretched second raw fabric layer formed on the first raw fabric layer and uniaxially stretched are provided at least, and the first raw fabric layer and the first raw fabric layer are provided. The raw fabric layer 2 contains a thermoplastic resin 4b and an inorganic material, respectively, and the content of the inorganic material is within the range of 15% by mass or more and 90% by mass or less with respect to the mass of each raw fabric layer. Yes, the stretching direction of the first raw fabric layer and the stretching direction of the second raw fabric layer intersect with each other.

The decorative sheet according to one aspect of the present invention can provide a decorative sheet having scratch resistance and abrasion resistance equivalent to those of a decorative sheet provided with a melamine plate, and having excellent processability and productivity. It becomes.

It is sectional drawing which shows the structure of the decorative sheet which concerns on embodiment of this invention.

Embodiments of the present invention will be described below with reference to the drawings. However, it should be noted that the drawings are schematic, and the relationship between the thickness and the plane dimension, the ratio of the thickness of each layer, etc. are different from the actual ones. Therefore, the specific thickness and dimensions should be determined in consideration of the following explanation.
Further, the embodiments shown below exemplify a configuration for embodying the technical idea of the present invention, and the technical idea of the present invention describes the materials of the constituent parts, their shapes, structures, and the like. The arrangement etc. is not specified as the following. The technical idea of the present invention can be modified in various ways within the technical scope specified by the claims stated in the claims.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
(Structure of decorative sheet 10)
An example of the structure of the decorative sheet 10 of the present embodiment is shown in FIG. The decorative sheet 10 is a decorative sheet to be attached to a base material such as a wood-based base material, an inorganic-based base material, a synthetic resin base material, a metal-based base material, etc. It is a decorative sheet used. Hereinafter, the configuration of the decorative sheet 10 will be specifically described.

In the decorative sheet 10, a base material layer 1, a pattern layer 5, a transparent thermoplastic resin layer 6, and a surface protective layer 7 are laminated in this order. Further, the base material layer 1 includes at least a uniaxially stretched first raw fabric layer 2 and a uniaxially stretched second raw fabric layer 3 formed on the first raw fabric layer 2. .. The first raw fabric layer 2 and the second raw fabric layer 3 contain an inorganic material 4a and a thermoplastic resin 4b, respectively, and the content of the inorganic material 4a is the content of each raw fabric layer (first raw fabric layer (first). It is in the range of 15% by mass or more and 90% by mass or less with respect to the mass of the original fabric layer 2 and the second original fabric layer 3). Further, the stretching direction of the first raw fabric layer 2 and the stretching direction of the second raw fabric layer 3 intersect each other in a plan view.
In addition, in FIG. 1, a void portion 4c is formed around the inorganic material 4a, which is a void portion generated when each raw fabric layer is stretched.
The details of each of the above layers will be described below.

[Base material layer 1]
The base material layer 1 is a layer that serves as a base material for the decorative sheet 10, and is a laminated body in which a plurality of raw fabric layers are laminated. FIG. 1 illustrates a base material layer 1 in which a first raw fabric layer 2 and a second raw fabric layer 3 are laminated via an adhesive resin layer 8. The first raw fabric layer 2 and the second raw fabric layer 3 are uniaxially stretched raw fabric layers, and their stretching directions intersect each other in a plan view. The first raw fabric layer 2 and the second raw fabric layer 3 are layers containing the thermoplastic resin 4b and the inorganic material 4a, respectively.
In addition, in each raw fabric layer shown in FIG.

<Inorganic material>
The content of the inorganic material 4a of the present embodiment is within the range of 15% by mass or more and 90% by mass or less with respect to the mass of each raw fabric layer of the first raw fabric layer 2 and the second raw fabric layer 3. It may be sufficient, and it is more preferably in the range of 20% by mass or more and 80% by mass or less, and further preferably in the range of 60% by mass or more and 80% by mass or less. If the content of the inorganic material 4a is less than 15% by mass with respect to the mass of each raw fabric layer, the proportion of the thermoplastic resin 4b is relatively large, so a Hoffman scratch tester is used on the surface of each raw fabric layer. When scratched by using it, it may be scratched to the extent that it can be visually recognized, that is, sufficient surface hardness may not be obtained. On the other hand, when the content of the inorganic material 4a exceeds 90% by mass with respect to the mass of each raw fabric layer, the proportion of the thermoplastic resin 4b becomes relatively small. For this reason, so-called "powder blowing" may occur on the surface of each raw fabric layer when an anchor layer is applied or printed on the surface of each raw fabric layer. Here, "powder blowing" means that the inorganic material 4a contained in each raw fabric layer emerges on the surface of each raw fabric layer. Further, when the pattern layer 5 is formed, the inorganic material 4a that emerges from the second raw fabric layer 3 may make it difficult for the ink to be laminated, that is, the printability may be lowered. Further, of the front surface anchor layer (first anchor layer) 2a, 3a, the back surface anchor layer (second anchor layer) 2b, 3b, the pattern layer 5, the transparent thermoplastic resin layer 6, and the surface protection layer 7, which will be described later. When laminating at least one member to a wood-based base material and a stone-based base material in the form of rolls or single leaves, it tends to be difficult to laminate, that is, the laminating suitability tends to decrease. Further, when a member forming at least one of the front surface anchor layers 2a and 3a, the back surface anchor layers 2b and 3b, the pattern layer 5, the transparent thermoplastic resin layer 6, and the surface protection layer 7 is bent and reopened, Cracks may occur from the bent portion, or the inorganic material 4a may fall off. Further, after the cellophane tape is pressure-bonded to the surface of the member on which the pattern pattern layer 5 is formed, the cellophane tape is strongly peeled off, and peeling occurs in the pattern pattern layer 5 or between the base material layer 1 and the pattern layer 5, that is, ink adhesion. Sex may be reduced.

As described above, the content of the inorganic material 4a of the present embodiment is 15% by mass or more and 90% by mass or less, preferably 20% by mass or more and 80% by mass or less, and more preferably 60% by mass with respect to the mass of each raw fabric layer. When it is in the range of% or more and 80% by mass or less, the occurrence of powder blowing can be reduced, the printability can be improved, the laminate suitability can be improved, and the occurrence of cracks at the bent portion of the sheet can be reduced. Sufficient surface hardness can be obtained, and ink adhesion can be improved.

Further, the inorganic material 4a of the present embodiment is preferably in a powder shape (powder shape), and the average particle diameter thereof is in the range of 1 μm or more and 3 μm or less, and the maximum particle diameter is 50 μm or less. preferable. When the average particle size and the maximum particle size of the inorganic material 4a are within the above numerical ranges, the flatness of the surface of each raw material layer can be maintained while improving the dispersibility of the inorganic material 4a with respect to the thermoplastic resin 4b. .. If the average particle size of the inorganic material 4a is less than 1 μm, the cohesive force between the inorganic materials 4a may increase, and the dispersibility in the thermoplastic resin 4b, which will be described later, may decrease. Further, when the average particle size of the inorganic material 4a exceeds 3 μm, the flatness of the surface of each raw fabric layer is lowered, and the thickness of the front surface anchor layers 2a and 3a or the back surface anchor layers 2b and 3b becomes uneven or uneven. Or chips may occur. Further, when the maximum particle size of the inorganic material 4a exceeds 50 μm, the flatness of the surface of each raw fabric layer is lowered, and the thickness of the front surface anchor layers 2a and 3a or the back surface anchor layers 2b and 3b becomes uneven or uneven. Or chips may occur. In the present embodiment, the "average particle diameter" means the mode diameter.

The inorganic material 4a is, for example, a powder containing at least one of calcium carbonate and calcium carbonate salt. The powder containing at least one of calcium carbonate and calcium carbonate salt preferably contains calcium carbonate or the like in the range of 50% by mass or more and 100% by mass or less. That is, the purity of the powder containing at least one of calcium carbonate and calcium carbonate salt is preferably in the range of 50% by mass or more and 100% by mass or less of calcium carbonate or the like. If the powder has a content of calcium carbonate or the like of 50% by mass or more, sufficient nonflammability or sufficient flame retardancy can be imparted to each raw fabric layer, and sufficient mechanical strength can be imparted. can do.

In addition to the powder containing at least one of calcium carbonate and calcium carbonate, the inorganic material 4a includes, for example, silica (particularly hollow silica), alumina, antimony trioxide, antimony soda, zircon silicate, and zircon oxide. Antimony trioxide complex with silica, trioxide, such as zirconium compounds, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borosand, zinc borate, molybdenum trioxide or antimony dimolybate complex with aluminum hydroxide At least one such as a complex of antimony and zinc white, silicic acid of zirconium, a complex of zirconium compound and antimony trioxide, and salts thereof can be mentioned. In particular, calcium carbonate and calcium carbonate salt are easy to control the particle size and compatibility with the thermoplastic resin 4b by the manufacturing method, and the material cost is low, so from the viewpoint of reducing the cost of the decorative sheet. Is also suitable.

Further, the inorganic material 4a may be a powder material having crystallinity, so-called crystalline powder, or a powder material having no crystallinity, so-called amorphous type powder material. If the inorganic material 4a is a crystalline powder material, the powder itself is homogeneous and has isotropic properties, so that the mechanical strength of the powder itself is improved, and the scratch resistance and durability of the decorative sheet 10 tend to be improved. is there. Further, if the inorganic material 4a is an amorphous type powder material, the electrical conductivity and thermal conductivity of the powder itself, as well as the light transmittance and light absorption rate can be appropriately adjusted, so that the tactile sensation and luster can be adjusted. It is possible to give a wide variety of designs.

In an inorganic material 4a such as calcium carbonate whose surface is not coated, the fluidity of the powder is generally low and the alkali resistance is not high, so that the hue tends to change easily.
On the other hand, when the pretreated, that is, the surface-treated inorganic material 4a such as calcium carbonate is used, the fluidity of the powder is generally improved, and the alkali resistance and the hue tend to be improved. In addition, the weather resistance can be improved by selecting an appropriate treatment agent for the pretreatment.
Therefore, in the present embodiment, with respect to the inorganic material 4a such as calcium carbonate, various surface treatments are performed as necessary for the purpose of improving the fluidity of the powder, alkali resistance, hue improvement, and other characteristics of the calcium carbonate filler. Surface treatment (coating) may be performed with an agent. This point will be described below.

The surface of the inorganic material 4a of the present embodiment is treated with at least one of an organic phosphorus-based surface treatment agent, an inorganic phosphoric acid-based surface treatment agent, a polycarboxylic acid-based surface treatment agent, and a coupling agent-based surface treatment agent. It may be a product. In addition, in this embodiment, "surface treatment" means that the surface is covered with a surface treatment agent, that is, the surface is covered.

Examples of the organic phosphorus-based surface treatment agent that can be used for the surface treatment of the inorganic material 4a include 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilotrismethylenephosphonic acid, trimethyl phosphate, triethyl phosphate, and tributyl phosphate. , Organic phosphoric acid systems such as triphenyl phosphate, methyl phosphate, ethyl phosphate and the like, and salts thereof.
Examples of the inorganic phosphoric acid-based surface treatment agent that can be used for the surface treatment of the inorganic material 4a include pyrophosphoric acid, polyphosphoric acids, condensed phosphoric acid typified by hexametaphosphoric acid, and salts thereof.
These surface treatment agents can be used alone or in combination of two or more as required.

Examples of the polycarboxylic acid-based surface treatment agent that can be used for the surface treatment of the inorganic material 4a include monocarboxylic acids such as polyacrylic acid, methacrylic acid, and crotonic acid, and itaconic acid, maleic acid, and fumaric acid. Dicarboxylic acid can be mentioned. These are used alone or in combination of two or more. Further, a copolymer with a compound having a functional group such as polypropylene glycol (PPG) or polyethylene glycol (PEG) can be used without any problem.

Further, examples of the coupling agent-based surface treatment agent that can be used for the surface treatment of the inorganic material 4a include silane-based cups such as vinyltrimethoxysilane and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane. Examples thereof include a ring agent, a titanate-based coupling agent typified by isopropyltriisostearoyl titanate, and a silicone-based oil typified by methylhydrogen. These are used alone or in combination of two or more.

Among these surface treatment agents, trimethyl phosphate (TMP) and triethyl phosphate (TEP) are considered from the viewpoints of compatibility with resin, heat resistance, inactivation of inorganic material 4a such as calcium carbonate, and dehydration / deaeration. ), Condensed phosphoric acid, silicone-based treatment is preferable. In particular, in the case of a polyester resin having an ester bond, a surface treatment agent is suitable because it has low alkali resistance.

The amount of the surface treatment agent used varies depending on the specific surface area of the inorganic material 4a such as calcium carbonate, the compound conditions, and the like, so it is difficult to unconditionally specify it. However, from the intended use of the present embodiment, calcium carbonate or the like is usually used. It is preferably in the range of 0.01% by mass or more and 5% by mass or less with respect to the inorganic material 4a. If the amount used is less than 0.01% by mass, it is difficult to obtain a sufficient surface treatment effect, while if it is added in excess of 5% by mass, the surface treatment agent decomposes and volatilizes during resin kneading, causing the hue of the resin to change yellow. Since problems such as the above may occur, it is more preferably in the range of 0.05% by mass or more and 3% by mass or less, and further preferably in the range of 0.1% by mass or more and 1.5% by mass or less.

As a surface treatment method for the inorganic material 4a such as calcium carbonate, for example, a mixer such as a super mixer, a Henschel mixer, a tumbler mixer, a kneader mixer, or a Banbury mixer is used, and a surface treatment agent is directly applied to the powder of the inorganic material 4a such as calcium carbonate. A dry treatment method in which the surface is treated by mixing and heating as necessary, or a surface treatment agent is dissolved in an aqueous solvent or the like and heated in a suspension of an inorganic material 4a such as calcium carbonate as necessary to surface the surface. After the treatment, a wet treatment method of dehydrating and drying, or a combination of both may be used to surface-treat a cake obtained by dehydrating a suspension of an inorganic material 4a such as calcium carbonate.
In addition, as long as the efficacy of each raw fabric layer is not impaired, for example, a lubricant, an antioxidant, a fluorescent whitening agent, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a neutralizing agent, and an antifogging agent. , Anti-blocking agent, antistatic agent, slip agent, colorant and the like may be blended.

<Thermoplastic resin>
The thermoplastic resin 4b of the present embodiment is preferably at least one of vinyl chloride, polyethylene terephthalate, polypropylene, polyethylene and polyester, and more preferably polypropylene. By using at least one of vinyl chloride, polyethylene terephthalate, polypropylene, polyethylene and polyester as the thermoplastic resin 4b, the dispersibility of the inorganic material 4a is improved. Further, by using polypropylene as the thermoplastic resin 4b, the dispersibility of the inorganic material 4a is further improved.

Further, the total content of the thermoplastic resin 4b and the inorganic material 4a is preferably in the range of 90% by mass or more and 100% by mass or less with respect to the mass of each raw fabric layer. When the total content of the thermoplastic resin 4b and the inorganic material 4a is within the above numerical range, sufficient surface strength is obtained, printability and laminating suitability are improved, and cracks generated in the bent portion of the sheet are reduced. can do. If the total content of the thermoplastic resin 4b and the inorganic material 4a is less than 90% by mass with respect to the mass of each raw fabric layer, sufficient surface strength may not be obtained. In addition, printability and laminating suitability may be reduced, and cracks may occur in the bent portion of the sheet.

When the total content of the thermoplastic resin 4b and the inorganic material 4a is 100% by mass with respect to the mass of each raw fabric layer, the content of the thermoplastic resin 4b is 10% by mass or more and 85% by mass. It is preferable that the content is in the range of% or less and the content of the inorganic material 4a is in the range of 15% by mass or more and 90% by mass or less. Further, it is more preferable that the content of the thermoplastic resin 4b is in the range of 20% by mass or more and 80% by mass or less, and the content of the inorganic material 4a is in the range of 20% by mass or more and 80% by mass or less. Further, it is more preferable that the content of the thermoplastic resin 4b is in the range of 20% by mass or more and 40% by mass or less, and the content of the inorganic material 4a is in the range of 60% by mass or more and 80% by mass or less. When the total content of the thermoplastic resin 4b and the inorganic material 4a is within the above numerical range, sufficient surface strength is surely obtained, printability and laminating suitability are surely improved, and it occurs at the bent portion of the sheet. Cracks can be reliably reduced.

The thickness of each raw fabric layer is preferably in the range of 50 μm or more and 250 μm or less, and more preferably in the range of 70 μm or more and 200 μm or less. When the thickness of each raw fabric layer is within the above numerical range, the mechanical strength of the entire sheet can be improved and cracks generated in the bent portion of the sheet can be reduced. If the thickness of each raw fabric layer is less than 50 μm, the laminating suitability tends to decrease. Further, if the thickness of each raw fabric layer exceeds 250 μm, cracks may occur in the bent portion of the sheet.

In addition, on at least one of the front surface (the surface on the pattern layer 5 side) and the back surface (the surface on the side opposite to the pattern layer 5 side) of each original fabric layer, for example, the front surface anchor layers 2a and 3a and the back surface anchor layer 2b. Before forming 3b, it is preferable to perform surface treatment such as corona treatment and plasma treatment. By applying surface treatment such as corona treatment or plasma treatment to at least one of the front surface and the back surface of each raw fabric layer, the adhesiveness between the front surface anchor layers 2a and 3a and the back surface anchor layers 2b and 3b and each raw fabric layer. (Adhesion) is improved.
Further, before forming the front surface anchor layers 2a and 3a and the back surface anchor layers 2b and 3b, for example, at least one of the front surface and the back surface of each raw material layer is brushed and powdered inorganic material 4a, for example, calcium carbonate and The powder containing at least one of the calcium carbonate salts may be removed in advance.

[Modification example of base material layer 1]
FIG. 1 shows a form in which two layers, a first raw fabric layer 2 and a second raw fabric layer 3, are laminated as the base material layer 1, but the present invention is not limited thereto. Absent. The base material layer 1 may be, for example, a laminated body in which three or more raw fabric layers are laminated. By laminating three or more layers of raw fabric, the mechanical strength of the decorative sheet 10 can be further improved.
Further, as described above, the stretching direction of the first raw fabric layer 2 and the stretching direction of the second raw fabric layer 3 may intersect with each other, but the crossing angle is preferably 30 ° C. or higher. It is in the range of 90 ° or less, and more preferably in the range of 80 ° C. or more and 90 ° or less.

[Surface anchor layer]
The surface anchor layers 2a and 3a are layers formed so as to cover the entire surface of each raw fabric layer, and are layers for preventing powder falling off of the inorganic material 4a contained in each raw fabric layer. If the inorganic material 4a contained in each raw fabric layer during printing or resin coating falls off in the printing system, specifically, in the printing apparatus, the inside of the printing system may be contaminated. Further, if the inorganic material 4a contained in each raw fabric layer is powdered off, problems such as ink loss may occur. Here, "ink missing" means that the ink is not partially printed.

Further, the surface anchor layer 2a also has a function for improving the adhesion between the first raw fabric layer 2 and the adhesive resin layer 8. If the surface anchor layer 2a is not provided, the second raw fabric layer 3 (adhesive resin layer 8) may peel off without being in close contact with the first raw fabric layer 2.
Further, the surface anchor layer 3a also has a function of improving the adhesion between the second raw fabric layer 3 and the ink forming the pattern pattern layer 5. If the surface anchor layer 3a is not provided, the ink forming the pattern layer 5 may peel off without adhering to the second raw fabric layer 3.

The surface anchor layers 2a and 3a preferably contain a urethane resin containing vinyl acetate or an acrylic resin containing vinyl acetate. Here, "salt vinegar bi" means a copolymer of vinyl chloride and vinyl acetate. The "urethane resin containing salt vinegar" is a composition containing salt vinegar and urethane resin, and the ratio of the content of salt vinegar to the content of urethane resin (salt vinegar). The bi content (mass) / urethane resin content (mass)) may be in the range of 80/20 to 1/99, preferably in the range of 50/50 to 5/95, and is preferably 20. It is more preferable if it is in the range of / 80 to 10/90.

Further, the "urethane-based resin containing vinyl acetate" may contain a curing agent in addition to the above-mentioned vinyl acetate and urethane-based resin. This curing agent is added to reliably cure the urethane-based resin containing vinyl acetate, and its content is not particularly limited. For example, the ratio of the content of the urethane resin containing salt and vinegar to the content of the curing agent (content of urethane resin containing salt and vinegar (mass) / content of curing agent (mass)) is 99. It may be in the range of / 1 to 1/99, preferably in the range of 99/1 to 50/50, and more preferably in the range of 95/5 to 90/10.

The content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the surface anchor layers 2a and 3a is 15% by mass or more and 100% by mass or less with respect to the mass of the surface anchor layers 2a and 3a. The range of 80% by mass or more and 100% by mass or less is more preferable, and the range of 85% by mass or more and 95% by mass or less is further preferable.
If the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the surface anchor layer 2a is within the above numerical range, the interlayer strength between the surface anchor layer 2a and the adhesive resin layer 8 is high. The surface anchor layer 2a can be formed uniformly and without unevenness or chipping. When the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the surface anchor layer 2a is less than 15% by mass with respect to the mass of the surface anchor layer 2a, the surface anchor layer 2a and The interlayer strength with the adhesive resin layer 8 may be insufficient.
Further, if the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the surface anchor layer 2a is less than 80% by mass with respect to the mass of the surface anchor layer 2a, there is no problem in use. Although there is no problem, the ratio of the surface anchor layer 2a to the first raw fabric layer 2 is lowered, and the interlayer strength between the surface anchor layer 2a and the first raw fabric layer 2 is slightly lowered.

If the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the surface anchor layer 3a is within the above numerical range, the interlayer strength between the surface anchor layer 3a and the pattern layer 5 is increased. It is possible to form a uniform surface anchor layer 3a without unevenness or chipping while making it sufficient. When the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the surface anchor layer 3a is less than 15% by mass with respect to the mass of the surface anchor layer 3a, the surface anchor layer 3a and the surface anchor layer 3a The interlayer strength with the pattern layer 5 may be insufficient. Further, if the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the surface anchor layer 3a is less than 80% by mass with respect to the mass of the surface anchor layer 3a, there is no problem in use. Although there is no problem, the ratio of the surface anchor layer 3a to the second raw fabric layer 3 is lowered, and the interlayer strength between the surface anchor layer 3a and the second raw fabric layer 3 is slightly lowered.

If the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the surface anchor layers 2a and 3a is 100% by mass or less with respect to the mass of the surface anchor layers 2a and 3a. There is no problem in use, but if it exceeds 95% by mass, or more accurately 98% by mass, the surface anchor layers 2a and 3a may be chipped due to insufficient curing, or the surface anchor layer 2a and the adhesive resin layer 8 or the adhesive resin layer 8 may be chipped. The interlayer strength between the surface anchor layer 3a and the pattern layer 5 may decrease.

The content of the urethane resin containing salt and vinegar in the front surface anchor layers 2a and 3a or the acrylic resin containing salt and vinegar is the urethane resin or salt containing salt and vinegar in the back surface anchor layers 2b and 3b. It may be the same as the content of the acrylic resin containing vinegar. That is, the content of the urethane resin containing salt and vinegar in the front surface anchor layers 2a and 3a or the acrylic resin containing salt and vinegar is the urethane resin or salt containing salt and vinegar in the back surface anchor layers 2b and 3b. It may be 1.0 times (within the range of 0.95 times or more and 1.04 times or less) the content of the acrylic resin containing vinegar. The content of the urethane resin containing salt and vinegar in the front anchor layers 2a and 3a or the acrylic resin containing salt and vinegar is the urethane resin or salt and vinegar containing salt and vinegar in the back surface anchor layers 2b and 3b. When the content of the acrylic resin containing the above is the same, the physical properties of the front surface anchor layers 2a and 3a and the physical properties of the back surface anchor layers 2b and 3b are almost the same. In the state where the front surface anchor layer 2a and the back surface anchor layer 2b are provided, it is possible to reduce the occurrence of distortion, warpage, and the like. Therefore, it is possible to reduce the occurrence of distortion and warpage of the entire decorative sheet. Further, since the coating liquid for forming the front surface anchor layer 2a and the coating liquid for forming the back surface anchor layer 2b can be shared, the manufacturing cost can be reduced and the work efficiency can be improved. be able to.

The content of the urethane resin containing salt and vinegar in the front surface anchor layers 2a and 3a or the acrylic resin containing salt and vinegar is the urethane resin or salt containing salt and vinegar in the back surface anchor layers 2b and 3b. It may be higher or lower than the content of the acrylic resin containing vinegar. The content of the urethane resin containing salt and vinegar in the front anchor layers 2a and 3a or the acrylic resin containing salt and vinegar is the urethane resin or salt and vinegar containing salt and vinegar in the back surface anchor layers 2b and 3b. When the content is higher or lower than the content of the acrylic resin containing the above, the physical properties of the front surface anchor layers 2a and 3a and the physical properties of the back surface anchor layers 2b and 3b are different, so that the front surface anchor layers 2a and 3a and the back surface anchor layer 2b Distortion, warpage, etc. can be imparted to each original fabric layer provided with 3b. In this way, by imparting distortion, warpage, etc. to each of the original fabric layers provided with the front surface anchor layers 2a, 3a and the back surface anchor layers 2b, 3b, the original fabric layer is provided with a gap in the base material or the like having a curved surface. Can be pasted together without. For example, the content of the urethane resin containing salt and vinegar in the front surface anchor layers 2a and 3a or the acrylic resin containing salt and vinegar is the urethane resin or salt containing salt and vinegar in the back surface anchor layers 2b and 3b. The content of the acrylic resin containing vinegar may be 1.1 times or more and 10 times or less, or 0.1 times or more and 0.9 times or less.

The thickness of the surface anchor layers 2a and 3a is, for example, in the range of 0.5 μm or more and 20 μm or less, and preferably in the range of 0.5 μm or more and 10 μm or less. Further, the thickness of the front surface anchor layers 2a and 3a may be the same as the thickness of the back surface anchor layers 2b and 3b. When the thickness of the front surface anchor layers 2a and 3a is the same as the thickness of the back surface anchor layers 2b and 3b, the physical properties of the front surface anchor layers 2a and 3a and the physical properties of the back surface anchor layers 2b and 3b are almost the same. In a state where the original fabric layer includes the front surface anchor layers 2a and 3a and the back surface anchor layers 2b and 3b, it is possible to reduce the occurrence of distortion and warpage.

Further, the thickness of the front surface anchor layers 2a and 3a may be thicker or thinner than the thickness of the back surface anchor layers 2b and 3b. By making the thicknesses of the front surface anchor layers 2a and 3a different from the thicknesses of the back surface anchor layers 2b and 3b, a difference in gloss is generated, so that the front surface side and the back surface side of each raw fabric layer can be easily visually recognized. .. By doing so, the pattern pattern layer 5 can be printed on the surface of the second raw fabric layer 3 without forming, for example, an identification mark indicating that it is a printing surface. As a result, product loss caused by forming the pattern layer 5 on the back surface (non-printing surface) side of the second raw fabric layer 3 can be reduced.

[Pattern pattern layer 5]
On the surface of the second original fabric layer 3 (surface anchor layer 3a), a pattern pattern layer 5 on which an arbitrary pattern is printed is provided. The type of the pattern formed by the pattern pattern layer 5 is not particularly limited, and is, for example, a wood grain pattern, a stone grain pattern, a cloth grain pattern, a sand grain pattern, an abstract pattern, a geometric figure, a character or a symbol, or a combination thereof. The type of printing ink used for forming the pattern layer 5 is not particularly limited, and a known printing ink used for forming a decorative sheet can be used. Specifically, for example, for binder resins such as polyvinyl chloride resin-based, vinyl chloride-vinyl acetate copolymer resin-based, butyral-based, acrylic-based, urethane-based, polyester-based, epoxy-based, alkyd-based, and polyamide-based binder resins. Organic or inorganic dyes or pigments, and if necessary, extender pigments, fillers, tackifiers, dispersants, defoaming agents, stabilizers and other additives are appropriately added, and a suitable diluting solvent is used to obtain the desired viscosity. It may be a adjusted printing ink.

[Adhesive layer]
An adhesive layer (not shown) may be formed on the pattern layer 5. The adhesive layer may be formed by applying a composition for forming an adhesive layer on the pattern layer 5. The adhesive contained in the adhesive layer can be arbitrarily selected from, for example, urethane-based, acrylic-based, polyester-based, etc., depending on the combination of the transparent thermoplastic resin contained in the transparent thermoplastic resin layer 6.

[Transparent thermoplastic resin layer 6]
The transparent thermoplastic resin layer 6 is, for example, a sheet-like layer made of a single layer. The transparent thermoplastic resin layer 6 is formed of, for example, a transparent thermoplastic resin so that the pattern of the pattern pattern layer 5 can be seen through. The thermoplastic resin contained in the transparent thermoplastic resin layer 6 may be transparent, and may be, for example, various resins other than vinyl chloride resin.
The transparent thermoplastic resin layer 6 may have an embossed pattern (not shown), which will be described later.
Further, the transparent thermoplastic resin layer 6 may not be a sheet-like layer composed of a single layer, but may be a sheet-like layer in which a plurality of layers are laminated. Various combinations of resins of each layer constituting the transparent thermoplastic resin layer 6 are possible depending on the desired characteristics.

The thickness of the transparent thermoplastic resin layer 6 is preferably in the range of 50 μm or more and 150 μm or less. When the thickness of the transparent thermoplastic resin layer 6 is within the above numerical range, high transparency is maintained, so that deterioration of visibility with respect to the pattern layer 5 can be prevented, and sufficient wear resistance can be obtained. Further, when the thickness of the transparent thermoplastic resin layer 6 is within the above numerical range, the flexibility and mechanical strength of the decorative sheet 10 are not impaired, and the processability to a decorative board such as in-line roll lamination is not impaired. Furthermore, it is easy to use because it does not interfere with the workability as a decorative board.

Further, an ultraviolet absorber may be added to the transparent thermoplastic resin layer 6. The ultraviolet absorber to be added to the transparent thermoplastic resin layer 6 is appropriately selected from benzotriazole-based, triazine-based, benzophenone-based and the like.
Examples of the benzotriazole-based ultraviolet absorber include 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, and 2- [2. -Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3- (3-) t-Butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3, Use 5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole and the like, and mixtures, modifications, polymers and derivatives thereof. Can be done.

Examples of the triazine-based ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-[(hexyl) oxy] -phenol and 2- [4- [(2-Hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[( 2-Hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4 dimethylphenyl) -1,3,5-triazine, 2,4-bis (2,4) -Dimethylphenyl) -6- (2-hydroxy-4-iso-octyloxyphenyl) -s-triazine and the like, mixtures, modified products, polymers and derivatives thereof can be used.

Further, as the benzophenone-based ultraviolet absorber, for example, octabenzone, a modified product, a polymer, a derivative or the like can be used. As the ultraviolet absorber, one having a hydroxyl group is particularly suitable because it can be expected to bond with the resin component by cross-linking by adding isocyanate. The number of copies to be added may be set according to the desired weather resistance, but is in the range of 0.1% or more and 50% or less, preferably 1% or more and 30% or less with respect to the resin solid content.
Examples of the light stabilizer to be added to the transparent thermoplastic resin layer 6 include bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethyl)]. Ethyl) -4-hydrixiphenyl] methyl] butylmalonate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4) -Poperidinyl) sebacate, bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, etc., and mixtures, modified products, polymers, derivatives, etc. of these may be used. it can.

The number of copies to be added may be adjusted according to the desired weather resistance, but is within the range of 0.1% by mass or more and 50% by mass or less, preferably 1% by mass or more and 30% by mass or less with respect to the resin solid content. And.
Other than the above, for example, a heat stabilizer, a flame retardant, an antiblocking agent and the like may be added. Examples of the heat stabilizer include pentaerythrityl-tetrax [3- (3,5-di-t-butyl-4-hydroxyphenyl)]-propionate, 2,4-bis- (n-octylthio) -6-. (4-Hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3 5-trimethyl-2,4,6-tris (3,5-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethyl) Hindered phenolic antioxidants such as benzyl) isocyanuric acid, 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), etc. Phenolic antioxidants, phosphorus antioxidants typified by tris (2,4-di-t-butylphenyl) phosphite, and mixtures thereof, that is, one or a combination of two or more. Can be used.

Further, as the flame retardant, for example, an inorganic compound such as aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, a phosphoric acid ester-based flame retardant, or the like can be used.
Further, as the blocking inhibitor, for example, an inorganic blocking inhibitor such as aluminum silicate, silicon oxide, hydrotalcite, calcium carbonate, an organic blocking inhibitor such as fatty acid amide, or the like can be used.

(Embossed pattern)
The embossed pattern is, for example, a pattern composed of concave portions and convex portions synchronized with the pattern of the pattern pattern layer 5. The embossed concave and convex parts make it possible to give a three-dimensional effect by visual or tactile sensation. The deviation between the embossed pattern and the pattern of the pattern pattern layer 5 is preferably within a range of 10 mm or less in the longitudinal direction and 3 mm or less in the lateral direction (width direction) with respect to the shape of the pattern. For example, when the pattern is wood grain, the direction in which the wood grain conduit extends is the "longitudinal direction with respect to the shape of the pattern", and the direction orthogonal to the longitudinal direction is the "short direction with respect to the shape of the pattern". Become. In particular, when the wood grain conduit extends along the longitudinal direction of the decorative sheet 10, the longitudinal direction of the decorative sheet 10 is the "longitudinal direction with respect to the shape of the pattern", and the lateral direction (width direction) of the decorative sheet 10 ) Is the "short direction with respect to the shape of the pattern". Since the transparent thermoplastic resin layer 6 and the surface protection layer 7 are transparent, the embossed pattern is strongly visible for the first time due to the reflection of oblique light. However, if the deviation between the embossed pattern and the pattern of the pattern layer 5 is within the above range. For example, since it is difficult to visually recognize the transmitted light of the pattern layer 5 at the same time as the reflected light, there is no sense of discomfort. By suppressing the deviation between the embossed pattern and the pattern of the pattern pattern layer 5 within a certain range, it is possible to obtain a decorative sheet 10 in which the shape and distribution of the pattern are the same and the pattern is accurately matched on the entire surface of the sheet. Further, the height difference between the concave portion and the convex portion of the embossed pattern is, for example, within the range of 3 μm or more and 200 μm or less. For the height difference, a numerical value suitable for the design of the target decorative sheet 10 can be selected. For example, it is possible to take a continuous multi-stage shape within the maximum height difference (200 μm). In particular, in order to obtain a shape as a macroscopic three-dimensional object, the height difference is more preferably in the range of 10 μm or more and 150 μm or less.

[Surface protection layer 7]
The surface protective layer 7 preferably contains an ionizing radiation curable resin such as an ultraviolet curable resin. Specifically, as the material of the surface protective layer 7, for example, a mixture (blended resin) of a thermosetting resin and an ultraviolet curable resin (UV curable resin) is preferable. As described above, since the surface protective layer 7 contains a thermosetting resin and an ultraviolet curable resin, that is, a resin having high hardness, the surface protective layer 7 exposed on the surface can improve the scratch resistance of the decorative sheet 10. Further, as the solvent, ethyl acetate or n-butyl acetate can be used.

As the thermosetting resin, for example, considering the deformation followability and scratch resistance of the decorative sheet 10, it is preferable to use a thermosetting resin having a urethane bond such as a two-component curable urethane resin.
As the two-component curable urethane resin, for example, a urethane resin containing a polyol as a main component and an isocyanate as a cross-linking agent (curing agent) can be used.
As the polyol, those having two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol can be used.

Further, as the isocyanate, a multivalent isocyanate having two or more isocyanate groups in the molecule can be used. Examples of the polyvalent isocyanate include aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, and 4,4'-diphenylmethane diisocyanate, or 1,6-hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated tolylene diisocyanate. , An aliphatic (or alicyclic) isocyanate such as hydrogenated diphenylmethane diisocyanate can be used. In addition, adducts or multimers of the above-mentioned various isocyanates can be used. For example, there are an adduct of tolylene diisocyanate, a trimer of tolylene diisocyanate, and the like. Among the above-mentioned isocyanates, the aliphatic (or alicyclic) isocyanate is preferable in that it can have good weather resistance and heat-resistant yellowing, and for example, 1,6-hexamethylene diisocyanate can be used.

As the ultraviolet curable resin, for example, (meth) acrylic resin, silicone resin, polyester resin, urethane resin, amide resin, and epoxy resin can be used.
Further, the surface protective layer 7 may contain inorganic fine particles such as silica. By adding inorganic fine particles such as silica to the surface protective layer 7, the decorative sheet 10 can be imparted with anti-slip properties. Further, the surface of the surface protective layer 7 can be given a matte feeling, and the design of the decorative sheet 10 can be improved.

[Back anchor layer]
The back surface anchor layers 2b and 3b are layers formed so as to cover the entire back surface of each raw fabric layer, and are layers for preventing powder falling off of the inorganic material 4a contained in each raw fabric layer. If the inorganic material 4a contained in each raw fabric layer during printing or resin coating falls off in the printing system, specifically, in the printing apparatus, the inside of the printing system may be contaminated.
Further, the back surface anchor layer 2b also has a function for improving the adhesion between the first raw fabric layer 2 and the primer layer (not shown) described later. If the back surface anchor layer 2b is not provided, the coating liquid forming the primer layer may peel off without adhering to the first raw fabric layer 2.
Further, the back surface anchor layer 3b also has a function for improving the adhesion between the second raw fabric layer 3 and the adhesive resin layer 8. If the back surface anchor layer 3b is not provided, the adhesive resin layer 8 may peel off without adhering to the second raw fabric layer 3.
The back surface anchor layers 2b and 3b preferably contain a urethane resin containing vinyl acetate or an acrylic resin containing vinyl acetate.

The content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layers 2b and 3b is, for example, 15% by mass or more and 100% by mass with respect to the mass of the back surface anchor layers 2b and 3b. It is preferably in the range of% or less, more preferably in the range of 80% by mass or more and 100% by mass or less, and further preferably in the range of 85% by mass or more and 95% by mass or less. When the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 2b is within the above numerical range, the interlayer strength between the back surface anchor layer 2b and the primer layer is sufficient. It is possible to form the back surface anchor layer 2b that is uniform and has no unevenness or chipping. If the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 3b is within the above numerical range, the back surface anchor layer 3b and the adhesive resin layer 8 are combined. It is possible to form the back surface anchor layer 3b which is uniform and has no unevenness or chipping while making the interlayer strength sufficient.

If the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 2b is less than 15% by mass with respect to the mass of the back surface anchor layer 2b, the back surface anchor layer The interlayer strength between 2b and the primer layer may be insufficient. Further, if the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 2b is less than 80% by mass with respect to the mass of the back surface anchor layer 2b, there is no problem in use. Although there is no problem, the ratio of the back surface anchor layer 2b to the first raw fabric layer 2 is lowered, and the interlayer strength between the back surface anchor layer 2b and the first raw fabric layer 2 is slightly lowered.

Further, when the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 3b is less than 15% by mass with respect to the mass of the back surface anchor layer 3b, the back surface anchor layer The interlayer strength between 3b and the adhesive resin layer 8 may be insufficient. Further, if the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 3b is less than 80% by mass with respect to the mass of the back surface anchor layer 3b, there is no problem in use. Although there is no problem, the ratio of the back surface anchor layer 3b to the second raw fabric layer 3 decreases, and the interlayer strength between the back surface anchor layer 3b and the second raw fabric layer 3 decreases slightly.

Further, if the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layers 2b and 3b is 100% by mass or less with respect to the mass of the back surface anchor layers 2b and 3b. There is no problem in use, but if it exceeds 95% by mass, or more accurately 98% by mass, the back surface anchor layers 2b and 3b may be chipped due to insufficient curing, or the back surface anchor layer 2b and the primer layer or the back surface anchor layer may be chipped. The interlayer strength between 3b and the adhesive resin layer 8 may decrease.
The thickness of the back surface anchor layers 2b and 3b is, for example, in the range of 0.5 μm or more and 20 μm or less, and preferably in the range of 0.5 μm or more and 10 μm or less.

[Primer layer]
The primer layer (not shown) is a layer for adhering the decorative sheet 10 to a base material such as a wood-based base material, an inorganic-based base material, a synthetic resin base material, and a metal-based base material. As the primer layer, for example, a polyester resin, a polyurethane resin, a mixture thereof, or the like can be used. Further, by adopting a two-component type using polyol and isocyanate, the adhesion between the first raw fabric layer 2 (back surface anchor layer 2b) and the primer layer and the cohesive force of the primer layer itself are improved. Examples of the polyol include an acrylic polyol and a polyester polyol. Examples of the isocyanate include aromatic systems such as tolylene diisocyanate and 4,4'diphenylmethane diisocyanate, and aliphatic systems such as hexamethylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate. Aromatic polyols are preferable in terms of quick reactivity and heat resistance.
The thickness of the primer layer is preferably 1 μm or more. If the thickness of the primer layer is less than 1 μm, it may be dissolved depending on the solvent type of the adhesive, and the primer layer disappears, so that the adhesiveness may not be improved.

(Manufacturing method of decorative sheet 10)
Hereinafter, an example of a method for manufacturing the decorative sheet 10 will be briefly described.
First, a raw fabric layer containing 20% by mass of polypropylene and 80% by mass of calcium carbonate is prepared. Then, this raw fabric layer is uniaxially stretched.
Next, anchor layers are formed on both sides of the uniaxially stretched raw fabric layer. After that, these raw fabric layers are laminated via the adhesive resin layer 8 so that the stretching directions intersect (orthogonally) with each other, and two layers of the first raw fabric layer 2 and the second raw fabric layer 3 are laminated. The base material layer 1 containing the above is prepared.
Next, the pattern layer 5 is formed by printing on the surface anchor layer 3a on the outermost surface layer of the base material layer 1.
Then, the transparent thermoplastic resin layer 6 is formed by laminating a layer formed by extruding the resin composition containing the molten transparent thermoplastic resin from the extruder on the pattern layer 5.
Next, the transparent thermoplastic resin layer 6 is embossed.
Finally, a resin composition obtained by adding a curing agent, an ultraviolet absorber, and a light stabilizer to, for example, a urethane resin is applied onto the embossed transparent thermoplastic resin layer 6, and then the resin composition is applied. Is dried to form the surface protective layer 7. In this way, the decorative sheet 10 according to the present embodiment is manufactured.
The method for producing the decorative sheet 10 according to the present embodiment may include a step of forming an adhesive layer (not shown) between the pattern layer 5 and the transparent thermoplastic resin layer 6.

(Effect of this embodiment)
In the decorative sheet 10 of the present embodiment, the pattern layer 5, the transparent thermoplastic resin layer 6, and the surface protective layer 7 are laminated in this order on the base material layer 1. The base material layer 1 includes at least a uniaxially stretched first raw fabric layer 2 and a uniaxially stretched second raw fabric layer 3 formed on the first raw fabric layer 2. .. Further, the first raw fabric layer 2 and the second raw fabric layer 3 contain a thermoplastic resin 4b and an inorganic material 4a, respectively. The content of the inorganic material 4a is in the range of 15% by mass or more and 90% by mass or less with respect to the mass of each raw fabric layer. Further, the stretching direction of the first raw fabric layer 2 and the stretching direction of the second raw fabric layer 3 intersect with each other.
With such a configuration, since the stretching direction of the first raw fabric layer 2 and the stretching direction of the second raw fabric layer 3 intersect with each other, the scratch resistance equivalent to that of the decorative sheet provided with the melamine plate is obtained. It is possible to provide a decorative sheet having properties and abrasion resistance, and having excellent processability and productivity.

More specifically, when a decorative sheet used for a flooring or the like is prepared by using a uniaxially stretched thick film raw fabric layer alone (one layer), there may be a difference in strength between the stretching direction and the direction orthogonal to it. .. In that case, the decorative sheet is likely to crack. Further, when the raw fabric layers of the uniaxially stretched thin film are laminated in the same stretching direction, the strength may be different between the stretching direction and the direction orthogonal to the stretching direction. Even in that case, the decorative sheet is likely to be cracked. Further, a decorative sheet used for a flooring material or the like, which is formed by laminating raw fabric layers in the same stretching direction, tends to warp due to environmental changes such as temperature and humidity.
On the other hand, the thickness and hardness can be imparted to the base material layer 1 by laminating the uniaxially stretched raw fabric layers so that the stretching directions are orthogonal to each other. Further, since the stretching directions are orthogonal to each other, the warp generated in each raw fabric layer cancels out inside the base material layer 1, and the warp of the entire decorative sheet used for the flooring material or the like is less likely to occur.

As described above, by stacking the raw fabric layers with the stretching directions of the raw fabric layers orthogonal to each other, the hardness and surface strength of the decorative sheet itself used for the flooring material can be increased, so that the scratch resistance can be improved. Impact resistant flooring can be made.
Further, by laminating a plurality of layers while making the stretching directions orthogonal to each other, it is possible to reduce the warp as a flooring material.
Further, by laminating a plurality of layers while making the stretching directions orthogonal to each other, it is possible to process and construct the floor material regardless of the cutting direction.
Further, the inorganic material 4a constituting each raw fabric layer provided in the decorative sheet 10 of the present embodiment has a powder shape, an average particle diameter in the range of 1 μm or more and 3 μm or less, and a maximum particle diameter of 50 μm or less. There may be.
With such a configuration, sufficient surface strength can be imparted to each raw fabric layer.

Further, the inorganic material 4a constituting each raw fabric layer provided in the decorative sheet 10 of the present embodiment includes antimony trioxide, antimony soda, zircon silicate, zircon oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, and borosand. , Zinc borate, calcium carbonate, molybdenum trioxide or antimony dimolybate and aluminum hydroxide complex, antimony trioxide and silica complex, antimony trioxide and zinc flower complex, silicic acid of zirconium, and zirconium It may be a complex of a compound and antimony trioxide, as well as at least one salt thereof.
With such a configuration, sufficient surface strength can be reliably imparted to each raw fabric layer.

Further, the thermoplastic resin 4b constituting each raw fabric layer provided in the decorative sheet 10 of the present embodiment may be at least one of vinyl chloride, polyethylene terephthalate, polypropylene, polyethylene and polyester.
With such a configuration, sufficient flexibility can be imparted to each raw fabric layer.
Further, the total content of the thermoplastic resin 4b and the inorganic material 4a constituting each raw fabric layer provided in the decorative sheet 10 of the present embodiment is 90% by mass or more and 100% by mass with respect to the mass of each raw fabric layer. It may be within the following range.
With such a configuration, sufficient surface strength and nonflammability can be imparted to each raw fabric layer.

Further, the thickness of each raw fabric layer provided on the decorative sheet 10 of the present embodiment may be in the range of 50 μm or more and 250 μm or less.
With such a configuration, sufficient surface strength can be imparted to each raw fabric layer.
Further, the front surface anchor layers 2a and 3a and the back surface anchor layers 2b and 3b provided on the decorative sheet 10 of the present embodiment each contain a urethane resin containing vinyl acetate or an acrylic resin containing vinyl acetate. You may.
With such a configuration, it is possible to prevent the inorganic material 4a from falling off.

Further, the stretching direction of the first raw fabric layer 2 provided in the decorative sheet 10 of the present embodiment and the stretching direction of the second raw fabric layer 3 may intersect with each other.
With such a configuration, sufficient surface strength can be imparted to each raw fabric layer.
Further, the decorative sheet 10 of this embodiment, the exothermic test by conforming to ISO5660-1 cone calorimeter testing machine (1) total amount of heat generated by the heating start after 20 minutes (MJ / ^{m 2)} is 8 MJ / ^{m 2} It is as follows: (2) The maximum heat generation rate for 20 minutes after the start of heating does not exceed ^{200 kW / m 2 continuously for 10 seconds or more.} ing.

(Example)
[Example 1]
First, a sheet containing polystyrene, which is a thermoplastic resin 4b, and silica (average particle diameter, 4 μm), which is an inorganic material 4a, was prepared. The silica content was 15% by mass with respect to the mass of each sheet.
Next, this sheet was uniaxially stretched to form a first raw fabric layer 2 and a second raw fabric layer 3. The thickness of each raw fabric layer was set to 45 μm.
After that, surface anchor layers 2a and 3a made of urethane resin containing salt and vinegar are formed on the surfaces of the first raw fabric layer 2 and the second raw fabric layer 3, respectively, and each raw fabric is formed. Backside anchor layers 2b and 3b made of urethane resin containing salt and vinegar were formed on the back surface of the layer, respectively.

Next, the first raw fabric layer 2 and the second raw fabric layer 3 provided with the front surface anchor layers 2a and 3a and the back surface anchor layers 2b and 3b are combined with the adhesive resin layer 8 made of a urethane resin adhesive. Laminated through. Then, this laminated body was compressed to prepare the base material layer 1. When the first raw fabric layer 2 and the second raw fabric layer 3 are laminated, the stretching direction of the first raw fabric layer 2 and the stretching direction of the second raw fabric layer 3 are 60 in a plan view. The first raw fabric layer 2 and the second raw fabric layer 3 were overlapped so as to intersect at an angle of °.
Next, a wood grain pattern was printed on the surface anchor layer 3a by a gravure printing method to form a pattern layer 5.

Subsequently, the transparent thermoplastic resin layer 6 was formed by extruding and laminating a layer containing the molten transparent thermoplastic resin on the pattern layer 5 with a T-die. The transparent thermoplastic resin layer 6 contains 0.2 parts by mass of a phenolic antioxidant (“IRGANOX1010” manufactured by Ciba Specialty Chemicals Co., Ltd.) and a hindered amine light stabilizer (Ciba Specialty Chemicals Co., Ltd.) in a transparent polypropylene resin. It was formed by adding 0.3 parts by mass of "TINUVIN622" manufactured by Ciba Specialty Chemicals Co., Ltd. and 0.5 parts by mass of a benzotriazole-based ultraviolet absorber ("TINUVIN326" manufactured by Ciba Specialty Chemicals Co., Ltd.).

At the same time, embossing and laminating were performed at the same time by niping the laminate of the base material layer 1, the pattern layer 5, and the transparent thermoplastic resin layer 6 by the conduit embossing plate and the rubber roll. Here, the thickness of the transparent thermoplastic resin layer 6 was set to 50 μm.
After surface treatment is applied to the embossed surface of this sheet, 10 mass of urethane resin ("URV238 varnish" manufactured by Toyo Ink Co., Ltd.) and a curing agent ("UR150B varnish" manufactured by Toyo Ink Co., Ltd.) are added as a top coat resin. 0.5 parts by mass of benzotriazole-based UV absorber (“TINUVIN326” manufactured by Ciba Specialty Chemicals Co., Ltd.) and 1 part by mass of hindered amine-based light stabilizer (“TINUVIN622” manufactured by Ciba Specialty Chemicals Co., Ltd.) The partially added material was coated with a varnish coat so that the coating amount after drying was 5 g / m ² to obtain a surface protective layer 7.

Subsequently, 10 parts by mass of silica was added to 100 parts by mass of a polyol (“Lamister EM” manufactured by Toyo Ink Co., Ltd.) on the back surface anchor layer 2b to contain isocyanate (“LPNYB” manufactured by Toyo Ink Co., Ltd.). "Curing agent") 3 parts by mass was added as a primer coating solution, and a primer layer was obtained by ^{coating with a gravure coat so that the coating amount after drying was 3 g / m 2.}
By such a procedure, the decorative sheet of Example 1 was formed.

[Example 2]
A decorative sheet was formed in the same manner as in Example 1 except that the silica content was 90% by mass with respect to the mass of each raw fabric layer.
[Example 3]
A decorative sheet was formed in the same manner as in Example 1 except that the average particle size of silica was 1 μm.
[Example 4]
A decorative sheet was formed in the same manner as in Example 1 except that the average particle size of silica was 3 μm.

[Example 5]
A decorative sheet was formed in the same manner as in Example 1 except that the inorganic material 4a contained in each raw fabric layer was antimony trioxide.
[Example 6]
A decorative sheet was formed in the same manner as in Example 1 except that the inorganic material 4a contained in each raw fabric layer was zircon oxide.
[Example 7]
A decorative sheet was formed in the same manner as in Example 1 except that the inorganic material 4a contained in each raw fabric layer was calcium carbonate.
[Example 8]
A decorative sheet was formed in the same manner as in Example 1 except that the inorganic material 4a contained in each raw fabric layer was a calcium carbonate salt.

[Example 9]
A decorative sheet was formed in the same manner as in Example 1 except that the thermoplastic resin 4b contained in each raw fabric layer was made of vinyl chloride.
[Example 10]
A decorative sheet was formed in the same manner as in Example 1 except that the thermoplastic resin 4b contained in each raw fabric layer was PET (polyethylene terephthalate).
[Example 11]
A decorative sheet was formed in the same manner as in Example 1 except that the thermoplastic resin 4b contained in each raw fabric layer was made of polypropylene.
[Example 12]
A decorative sheet was formed in the same manner as in Example 1 except that the thermoplastic resin 4b contained in each raw fabric layer was made of polyethylene.
[Example 13]
A decorative sheet was formed in the same manner as in Example 1 except that the thermoplastic resin 4b contained in each raw fabric layer was made of polyester.

[Example 14]
A decorative sheet was formed in the same manner as in Example 1 except that the thickness of each raw fabric layer was 50 μm.
[Example 15]
A decorative sheet was formed in the same manner as in Example 1 except that the thickness of each raw fabric layer was 250 μm.
[Example 16]
A decorative sheet was formed in the same manner as in Example 1 except that the stretching direction of the first raw fabric layer 2 and the stretching direction of the second raw fabric layer 3 were crossed at an angle of 70 ° in a plan view. ..
[Example 17]
A decorative sheet was formed in the same manner as in Example 1 except that the stretching direction of the first raw fabric layer 2 and the stretching direction of the second raw fabric layer 3 were crossed at an angle of 80 ° in a plan view. ..
[Example 18]
A decorative sheet was formed in the same manner as in Example 1 except that the stretching direction of the first raw fabric layer 2 and the stretching direction of the second raw fabric layer 3 were crossed at an angle of 90 ° in a plan view. ..

[Example 19]
Except that the inorganic material 4a contained in each raw fabric layer was calcium carbonate, the average particle size thereof was 1 μm, the thermoplastic resin 4b contained in each raw fabric layer was polypropylene, and the thickness of each raw fabric layer was 50 μm. , A decorative sheet was formed in the same manner as in Example 1.
[Example 20]
A decorative sheet was formed in the same manner as in Example 19 except that the number of laminated layers of each raw fabric was set to 4.

[Comparative Example 1]
A decorative sheet was formed in the same manner as in Example 1 except that the stretching direction of the first raw fabric layer 2 and the stretching direction of the second raw fabric layer 3 were overlapped in a plan view.
[Comparative Example 2]
A decorative sheet was formed in the same manner as in Example 1 except that the silica content was 13% by mass with respect to the mass of each raw fabric layer.
[Comparative Example 3]
A decorative sheet was formed in the same manner as in Example 1 except that the silica content was 92% by mass with respect to the mass of each raw fabric layer.

The evaluation items shown in Table 1 will be described below.
<Evaluation items>
An ethylene-vinyl acetate copolymer emulsion type adhesive was applied to a 6 mm MDF (medium density fiberboard), and a decorative sheet and a laminated decorative board were obtained. Then, the following tests were carried out using the decorative board and the decorative sheet alone of each Example and each Comparative Example.

[Abrasion resistance]
In the abrasion resistance test specified in the Japanese Agricultural Standards for JAS flooring, the number of rotations until the pattern disappeared was confirmed. The worn paper was replaced every 1000 rotations.
⊚: 3000 rotations or more ○: 2500 rotations or more and less than 3000 rotations Δ: 2000 rotations or more and less than 2500 rotations ×: 2000 rotations or less

[Scratch resistance]
The veneer was subjected to a pencil hardness test specified in JIS K 5600 to confirm how it was scratched.
⊚: No scratches at 7H or higher ○: No scratches at 4H to 6H △: No scratches at H to 3H ×: No scratches at a level softer than H

[Workability]
We confirmed the methods that can be selected when processing the decorative sheet into a decorative board.
◎: In-line roll laminating is possible.
◯: In-line roll laminating is possible. It requires some caution in processing.
Δ: In-line roll laminating is possible, but processing requires considerable caution.
×: Roll laminating is not possible. Only pasting with single leaves.

[Machinability]
The decorative board was cut with a circular saw and a cutting test was performed using a hand router to reach the MDF on the surface, and it was confirmed whether or not burrs were generated on the sheet.
⊚: No burr occurs.
◯: Some burrs are seen, but can be easily corrected.
Δ: Some burrs are seen and need to be corrected.
×: Burrs are generated on almost the entire surface, and it is difficult to correct them manually.

〔Productivity〕
The ease of production when the transparent thermoplastic resin layer 6 was extruded and laminated was confirmed.
◎: Stable production is possible.
○: It is necessary to pay more attention to production than ◎, but stable production is possible.
Δ: There is a possibility that the product may be rolled over time in long-run production, so caution is required in production.
×: Production is extremely difficult due to wrinkles and roll removal.

〔Incombustibility〕
It was evaluated whether or not the following requirements were satisfied in the heat generation test by the cone calorimeter tester conforming to ISO5660-1.
1. 1. Total calorific value is 8MJ / m ² or less 2. 2. The maximum heat generation rate does not exceed ^{200 kW / m 2 continuously for 10 seconds or more.} No cracks or holes penetrate to the back surface, which is harmful for flameproofing. A gypsum board was used as the nonflammable base material. The evaluation criteria are as follows.
◯: All of the above requirements are satisfied ×: At least one of the above requirements is not satisfied

[Occurrence of warpage]
A decorative plate cut into 10 cm squares was placed on a smooth table, and the warp (distance) from the surface of the table to the bottom of the decorative plate at the end of the decorative plate was measured using a metal scale. The evaluation criteria are as follows.
⊚: Almost no warpage is seen (0.5 mm or less).
〇: 5 mm or less Δ: 10 mm or less ×: 10 mm or more

As shown in Table 1, the decorative sheet according to the present embodiment is a decorative sheet having scratch resistance and abrasion resistance, and also excellent in processability and productivity. From the evaluation results of scratch resistance and abrasion resistance, it can be seen that the scratch resistance and abrasion resistance of the decorative sheet according to this embodiment are similar to those of the melamine plate.
Further, the decorative sheet according to this embodiment also has nonflammability. Further, the decorative sheet according to the present embodiment reduces the occurrence of warpage.

The decorative sheet of the present embodiment can be used for interior decoration of buildings such as floors, walls and ceilings, surface decorative materials for furniture and various cabinets, surface makeup of fittings, surface makeup used for vehicle interiors, etc. is there.

1: Base material layer 2: First raw fabric layer 2a: Surface anchor layer (first anchor layer)
2b: Back surface anchor layer (second anchor layer)
3: Second original fabric layer 3a: Surface anchor layer (first anchor layer)
3b: Back surface anchor layer (second anchor layer)
4a: Inorganic material 4b: Thermoplastic resin 4c: Void portion 5: Pattern layer 6: Transparent thermoplastic resin layer 7: Surface protective layer 8: Adhesive resin layer 10: Decorative sheet

Claims (9)

A pattern layer, a transparent thermoplastic resin layer, and a surface protective layer are laminated in this order on the base material layer.
The base material layer includes at least a uniaxially stretched first raw fabric layer and a uniaxially stretched second raw fabric layer formed on the first raw fabric layer.
The first raw fabric layer and the second raw fabric layer contain a thermoplastic resin and an inorganic material, respectively.
The content of the inorganic material is in the range of 15% by mass or more and 90% by mass or less with respect to the mass of each raw fabric layer.
A decorative sheet characterized in that the stretching direction of the first raw fabric layer and the stretching direction of the second raw fabric layer intersect with each other. The decorative sheet according to claim 1, wherein the inorganic material has a powder shape, an average particle diameter in the range of 1 μm or more and 3 μm or less, and a maximum particle diameter of 50 μm or less. The inorganic materials include antimony trioxide, antimony soda, zircon silicate, zircon oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borosand, zinc borate, calcium carbonate, molybdenum trioxide or antimony dimolybate and water. A complex with aluminum oxide, a complex with antimony trioxide and silica, a complex with antimony trioxide and zinc flower, a silicic acid of zirconium, and a complex with a zirconium compound and antimony trioxide, and at least one of their salts. The decorative sheet according to claim 1 or 2, wherein the decorative sheet is characterized by the above. The decorative sheet according to any one of claims 1 to 3, wherein the thermoplastic resin is at least one of vinyl chloride, polyethylene terephthalate, polypropylene, polyethylene and polyester. Claims 1 to 1, wherein the total content of the thermoplastic resin and the inorganic material is in the range of 90% by mass or more and 100% by mass or less with respect to the mass of each raw fabric layer. The decorative sheet according to any one of 4. The decorative sheet according to any one of claims 1 to 5, wherein the thickness of each raw fabric layer is within the range of 50 μm or more and 250 μm or less. A first anchor layer formed on the surface of each original fabric layer on the side of the pattern layer, and
Each raw fabric layer is further provided with a second anchor layer formed on a surface opposite to the surface on which the first anchor layer is formed.
Any of claims 1 to 6, wherein the first anchor layer and the second anchor layer each contain a urethane resin containing vinyl acetate or an acrylic resin containing vinyl acetate. Or the decorative sheet according to item 1. The method according to any one of claims 1 to 7, wherein the stretching direction of the first raw fabric layer and the stretching direction of the second raw fabric layer are orthogonal to each other. Cosmetic sheet. In a heat generation test using an ISO5660-1 compliant cone calorimeter tester, (1) the total calorific value (MJ / m ² ) for ^{20 minutes after the start of heating was 8 MJ / m 2} or less, and (2) 20 minutes after the start of heating. Claims 1 to 8 are characterized in that the maximum heat generation rate of the ^{above is not exceeding 200 kW / m 2} continuously for 10 seconds or more, and (3) has nonflammability satisfying the condition that there are no cracks or holes in the base material. The decorative sheet according to any one of the above.

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