JP7388041B2 - makeup sheet - Google Patents

Description

The present invention relates to a decorative sheet.

As a member having scratch resistance and wear resistance, for example, there is a member equipped with a melamine plate described in Patent Document 1. Since the size of this melamine board is limited to a certain extent, many parts of the melamine board are cut and discarded during product processing, which may impair productivity. Furthermore, when melamine boards are used, work efficiency is poor because the sheets are bonded together, and workability may be poor due to their weight.

Japanese Patent Application Publication No. 2014-188941

The present invention has been made to solve these problems, and its purpose is to provide the same scratch resistance and wear resistance as melamine sheets, even if the decorative sheet does not include melamine sheets. It is an object of the present invention to provide a decorative sheet that can be applied and has excellent processability and productivity.

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

With the decorative sheet according to one embodiment of the present invention, it is possible to provide a decorative sheet that has scratch resistance and wear resistance equivalent to that of a decorative sheet equipped with a melamine board, and has excellent processability and productivity. becomes.

FIG. 1 is a cross-sectional view showing the configuration of a decorative sheet according to an embodiment of the present invention.

Embodiments of the invention will be described below with reference to the drawings. However, it should be noted that the drawings are schematic and that the relationship between thickness and planar dimensions, the ratio of the thickness of each layer, etc. are different from reality. Therefore, specific thickness and dimensions should be determined with reference to the following explanation.
Furthermore, the embodiments shown below illustrate configurations for embodying the technical idea of the present invention. The arrangement, etc. is not specified as below. The technical idea of the present invention can be modified in various ways within the technical scope defined by the claims.

Embodiments of the present invention will be described below with reference to the drawings.
(Configuration of decorative sheet 10)
FIG. 1 shows an example of the structure of the decorative sheet 10 of this embodiment. The decorative sheet 10 is a decorative sheet that is attached to a base material such as a wood base material, an inorganic base material, a synthetic resin base material, a metal base material, etc., and is particularly suitable for areas where scratch resistance and abrasion resistance are required. This is a decorative sheet used. Hereinafter, the configuration of the decorative sheet 10 will be specifically explained.

The decorative sheet 10 includes a base layer 1, a pattern layer 5, a transparent thermoplastic resin layer 6, and a surface protection layer 7, which 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 each contain an inorganic material 4a and a thermoplastic resin 4b, and the content of the inorganic material 4a is different from that in each raw fabric layer (the second raw fabric layer 3). It is within the range of 15% by mass or more and 90% by mass or less based on the mass of the first raw fabric layer 2 and the second raw fabric layer 3). Furthermore, 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 in plan view.
Note that in FIG. 1, a void 4c is formed around the inorganic material 4a, but this is a void created when each original fabric layer is stretched.
The details of each of the above layers will be explained below.

[Base material layer 1]
The base material layer 1 is a layer that serves as the base material of the decorative sheet 10, and is a laminate 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 with an adhesive resin layer 8 in between. The first raw fabric layer 2 and the second raw fabric layer 3 are uniaxially stretched raw fabric layers, and their stretching directions intersect with each other in a plan view. Moreover, the first raw fabric layer 2 and the second raw fabric layer 3 are layers containing a thermoplastic resin 4b and an inorganic material 4a, respectively.
In addition, each raw fabric layer shown in FIG. 1 contains the following:

<Inorganic materials>
The content of the inorganic material 4a of this embodiment is within the range of 15% by mass or more and 90% by mass or less with respect to the mass of each of the first raw fabric layer 2 and the second raw fabric layer 3. It is sufficient if it is within the range of 20% by mass or more and 80% by mass or less, and even more preferably within 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 will be relatively large, so the surface of each raw fabric layer was tested using a Hoffman scratch tester. When the surface is scratched using a metal surface, visible scratches may occur, 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, when an anchor layer is coated or printed on the surface of each raw fabric layer, so-called "powdering" may occur on the surface of each raw fabric layer. Here, "powder blowing" means that the inorganic material 4a contained in each raw fabric layer stands out on the surface of each raw fabric layer. Furthermore, when forming the picture pattern layer 5, the inorganic material 4a that stands out from the second raw fabric layer 3 may make it difficult for the ink to be laminated, that is, the printability may deteriorate. In addition, the surface anchor layers (first anchor layers) 2a and 3a, the back surface anchor layers (second anchor layers) 2b and 3b, the pattern layer 5, the transparent thermoplastic resin layer 6, and the surface protective layer 7, which will be described later, are also included. When laminating at least one member in the form of a roll or sheet onto a wood base material or a stone base material, there is a tendency that lamination becomes difficult, that is, lamination suitability tends to decrease. Moreover, when the member forming at least one of the front anchor layers 2a, 3a, the back anchor layers 2b, 3b, the pattern layer 5, the transparent thermoplastic resin layer 6, and the surface protective layer 7 is bent and opened again, Cracks may occur from the bent portion, or the inorganic material 4a may fall. In addition, after pressing the cellophane tape onto the surface of the member on which the pattern layer 5 is formed, it is strongly peeled off to cause peeling within the pattern layer 5 or between the base layer 1 and the pattern layer 5, that is, ink adhesion. Sexuality may decrease.

In this way, 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, more preferably 60% by mass, based on the mass of each raw fabric layer. % or more and 80% by mass or less, it is possible to reduce the occurrence of powder blowing, improve printing suitability, improve lamination suitability, and reduce the occurrence of cracks at the folded portion of the sheet. 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 form (powder shape), and the average particle size is within the range of 1 μm or more and 3 μm or less, and the maximum particle size is 50 μm or less. preferable. If the average particle size and maximum particle size of the inorganic material 4a are within the above numerical range, the flatness of the surface of each raw fabric layer can be maintained while improving the dispersibility of the inorganic material 4a in the thermoplastic resin 4b. . When the average particle diameter of the inorganic material 4a is less than 1 μm, the cohesive force between the inorganic materials 4a increases, and the dispersibility in the thermoplastic resin 4b described later may decrease. In addition, when the average particle diameter of the inorganic material 4a exceeds 3 μm, the flatness of the surface of each raw fabric layer decreases, and the thickness of the front anchor layers 2a, 3a or the back anchor layers 2b, 3b becomes nonuniform or uneven. or chipping may occur. In addition, when the maximum particle size of the inorganic material 4a exceeds 50 μm, the flatness of the surface of each raw material layer decreases, and the thickness of the front anchor layers 2a, 3a or the back anchor layers 2b, 3b becomes uneven or uneven. or chipping may occur. In addition, in this embodiment, "average particle diameter" means a 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 and the like in a 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. If the powder contains 50% by mass or more of calcium carbonate, etc., it is possible to impart sufficient nonflammability or flame retardance to each raw fabric layer, as well as sufficient mechanical strength. can do.

In addition to the powder containing at least one of calcium carbonate and calcium carbonate salt, the inorganic material 4a may include, for example, silica (especially hollow silica), alumina, antimony trioxide, antimony soda, zircon silicate, zircon oxide, etc. Zirconium compounds, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borax, zinc borate, molybdenum trioxide or complexes of antimony trioxide and silica, such as complexes of antimony dimolybdate and aluminum hydroxide, trioxide Examples include at least one of a complex of antimony and zinc white, a silicic acid of zirconium, a complex of a zirconium compound and antimony trioxide, and salts thereof. In particular, calcium carbonate and calcium carbonate salts are easy to control particle size and compatibility with thermoplastic resin 4b through manufacturing methods, and are inexpensive in terms of material cost, so they are useful from the perspective of reducing the cost of decorative sheets. is also suitable.

Further, the inorganic material 4a may be a powder material with crystallinity, a so-called crystal powder, or a powder material without crystallinity, a so-called amorphous type powder material. If the inorganic material 4a is a powder material having crystallinity, the powder itself is homogeneous and has isotropy, so the mechanical strength of the powder itself is improved, and the scratch resistance and durability of the decorative sheet 10 tend to be improved. be. Furthermore, if the inorganic material 4a is an amorphous type powder material, it is possible to adjust the electrical conductivity, thermal conductivity, or light transmittance and light absorption rate of the powder itself, so that the texture, gloss, etc. It becomes possible to provide a design with a wide variety of variations.

An inorganic material 4a such as calcium carbonate whose surface is not coated generally has low powder fluidity and does not have high alkali resistance, so it tends to change the hue easily.
On the other hand, when an inorganic material 4a such as calcium carbonate that has been pretreated, that is, surface treated, is used, the fluidity of the powder is generally improved, and the alkali resistance and hue tend to be improved. Furthermore, weather resistance can also be improved by selecting an appropriate treatment agent for pretreatment.
Therefore, in the present embodiment, the inorganic material 4a such as calcium carbonate is subjected to various surface treatments as necessary for the purpose of improving powder fluidity, alkali resistance, hue, and other properties of the calcium carbonate filler. The surface may be treated (coated) with an agent. This point will be explained below.

The surface of the inorganic material 4a of this embodiment is treated with at least one of an organic phosphorus surface treatment agent, an inorganic phosphate surface treatment agent, a polycarboxylic acid surface treatment agent, and a coupling agent surface treatment agent. It may be something like that. Note that in this embodiment, "surface treatment" refers to the surface being covered with a surface treatment agent, that is, the surface is coated.

Examples of organic phosphorus surface treatment agents that can be used for 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 acids such as triphenyl phosphate, methyl phosphate, ethyl phosphate, and salts thereof.
Further, examples of inorganic phosphoric acid-based surface treatment agents that can be used for surface treatment of the inorganic material 4a include condensed phosphoric acids represented by pyrophosphoric acid, polyphosphoric acids, and hexametaphosphoric acid, and salts thereof.
Incidentally, these surface treating agents can be used alone or in combination of two or more as necessary.

In addition, examples of polycarboxylic acid surface treatment agents that can be used for surface treatment of the inorganic material 4a include monocarboxylic acids such as polyacrylic acid, methacrylic acid, and crotonic acid, and monocarboxylic acids such as itaconic acid, maleic acid, and fumaric acid. Examples include dicarboxylic acids. These may be used alone or in combination of two or more. Further, copolymers with compounds having functional groups such as polypropylene glycol (PPG) and polyethylene glycol (PEG) can also be used without problems.

In addition, examples of coupling agent-based surface treatment agents that can be used for surface treatment of the inorganic material 4a include silane-based coupling agents such as vinyltrimethoxysilane and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane. Examples include ring agents, titanate coupling agents represented by isopropyl triisostearoyl titanate, and silicone oils represented by methyl hydrogen. These may be used alone or in combination of two or more.

Among these surface treatment agents, trimethyl phosphate (TMP), triethyl phosphate (TEP), ), condensed phosphoric acids, and silicone-based treatments are preferred. In particular, in the case of a polyester resin having an ester bond, a surface treatment agent is suitable since the resin has low alkali resistance.

The amount of the surface treatment agent to be used varies depending on the specific surface area of the inorganic material 4a such as calcium carbonate, compounding conditions, etc., so it is difficult to specify it unconditionally, but from the purpose of this embodiment, it is usually It is preferably within the range of 0.01% by mass or more and 5% by mass or less based on 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 hue of the resin changes to yellow due to decomposition and volatilization of the surface treatment agent during resin kneading. Since such problems may occur, the content is more preferably in the range of 0.05% by mass or more and 3% by mass or less, and even more 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 to apply the surface treatment agent directly to the powder of the inorganic material 4a such as calcium carbonate. There is a dry treatment method in which a surface treatment agent is mixed and heated as necessary to treat the surface, or a surface treatment agent is dissolved in a water solvent etc. and heated as necessary in a suspension of inorganic material 4a such as calcium carbonate. After the treatment, the cake obtained by dehydrating the suspension of the inorganic material 4a such as calcium carbonate may be surface-treated by a wet treatment method of dehydration and drying, or a combination of both.
In addition, within the range that does not impede the effectiveness of each raw fabric layer, additives such as lubricants, antioxidants, optical brighteners, heat stabilizers, light stabilizers, ultraviolet absorbers, neutralizers, and antifogging agents may be added as necessary. , an anti-blocking agent, an antistatic agent, a slip agent, a coloring agent, etc. may be added.

<Thermoplastic resin>
The thermoplastic resin 4b of this 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.

Moreover, it is preferable that the total content of the thermoplastic resin 4b and the inorganic material 4a 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. If the total content of the thermoplastic resin 4b and the inorganic material 4a is within the above numerical range, sufficient surface strength can be obtained, printability and lamination suitability can be improved, and cracks occurring at the folded portion of the sheet can be reduced. can do. If the total content of the thermoplastic resin 4b and the inorganic material 4a is less than 90% by mass based on the mass of each raw fabric layer, sufficient surface strength may not be obtained. In addition, printability and lamination suitability may deteriorate, and cracks may occur at the folded portion of the sheet.

In addition, 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. % or less, and the content of the inorganic material 4a is preferably 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 within the range of 20% by mass or more and 80% by mass or less, and the content of the inorganic material 4a is within 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 be within the range of 20% by mass to 40% by mass, and the content of the inorganic material 4a be within the range of 60% by mass to 80% by mass. If the total content of the thermoplastic resin 4b and the inorganic material 4a is within the above numerical range, sufficient surface strength can be reliably obtained, printing suitability and lamination suitability can be reliably improved, and the occurrence of occurrence at the folded portion of the sheet can be ensured. It is possible to reliably reduce the occurrence of cracks.

Moreover, the thickness of each raw fabric layer is preferably within the range of 50 μm or more and 250 μm or less, and more preferably within the range of 70 μm or more and 200 μm or less. If 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 occurring at the folded portions of the sheet can be reduced. If the thickness of each raw fabric layer is less than 50 μm, lamination suitability tends to decrease. Moreover, if the thickness of each original fabric layer exceeds 250 μm, cracks may occur at the folded portion of the sheet.

In addition, on at least one of the front surface (the surface on the picture pattern layer 5 side) and the back surface (the surface on the opposite side to the picture pattern layer 5 side) of each raw fabric layer, for example, front surface anchor layers 2a, 3a and back surface anchor layer 2b are provided. , 3b, it is preferable to perform surface treatment such as corona treatment or plasma treatment. By performing surface treatment such as corona treatment or plasma treatment on at least one of the front and back surfaces of each raw fabric layer, the adhesiveness between the front anchor layers 2a, 3a and the back anchor layers 2b, 3b and each raw fabric layer is improved. (Adhesion) improves.
In addition, before forming the front anchor layers 2a, 3a and the back anchor layers 2b, 3b, for example, at least one of the front and back surfaces of each raw fabric layer is brushed and powdered with an inorganic material 4a, such as calcium carbonate. Powder containing at least one of the calcium carbonate salts may be dropped in advance.

[Modified example of base material layer 1]
Although FIG. 1 shows a structure 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, the present invention is not limited to this. do not have. The base material layer 1 may be, for example, a laminate in which three or more raw fabric layers are laminated. By laminating three or more raw fabric layers, 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 only need to intersect with each other, but the crossing angle is preferably 30°C or more. It is within the range of 90° or less, and more preferably within the range of 80°C or more and 90° or less.

[Surface anchor layer]
The surface anchor layers 2a and 3a are layers formed to cover the entire surface of each raw fabric layer, and are layers for preventing the inorganic material 4a contained in each raw fabric layer from falling off. If the inorganic material 4a contained in each original fabric layer falls off within the printing system, specifically within the printing device, during printing or resin coating, the inside of the printing system may be contaminated. Furthermore, if the inorganic material 4a contained in each web layer falls off, problems such as ink omission may occur. Here, "ink omission" refers to ink not being printed partially.

Furthermore, the surface anchor layer 2a also has a function of improving the adhesion between the first 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 not adhere to the first raw fabric layer 2 and may peel off.
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 picture pattern layer 5. If the surface anchor layer 3a is not provided, the ink forming the picture pattern layer 5 may not come into close contact with the second base layer 3 and may peel off.

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

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

The content of the urethane resin containing salt vinyl acetate or the acrylic resin containing salt vinyl acetate in the surface anchor layers 2a and 3a is 15% by mass or more and 100% by mass or less based on the mass of the surface anchor layers 2a and 3a. It is preferably in the range of 80% by mass or more and 100% by mass or less, and even more preferably in the range of 85% by mass or more and 95% by mass or less.
If the content of the urethane resin containing vinyl acetate salt or the acrylic resin containing vinyl acetate salt 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 will be improved. It is possible to form a uniform surface anchor layer 2a without unevenness or chipping while maintaining a sufficient surface anchoring layer. If the content of the urethane resin containing salt-vinyl acetate or the acrylic resin containing salt-vinyl acetate 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 The interlayer strength with the adhesive resin layer 8 may be insufficient.
Furthermore, if the content of the urethane resin containing vinyl acetate salt or the acrylic resin containing vinyl acetate salt in the surface anchor layer 2a is less than 80% by mass with respect to the mass of the surface anchor layer 2a, there will be no problem in use. Although there is no problem, the penetration ratio of the surface anchor layer 2a into the first fabric layer 2 may be reduced, and the interlayer strength between the surface anchor layer 2a and the first fabric layer 2 may be slightly reduced.

If the content of the urethane resin containing salt-vinyl acetate or the acrylic resin containing salt-vinyl acetate 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 can be reduced. It is possible to form a surface anchor layer 3a that is uniform and free from unevenness and chipping, while being sufficient. If the content of the urethane resin containing salt-vinyl acetate or the acrylic resin containing salt-vinyl acetate 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 The interlayer strength with the pattern layer 5 may be insufficient. Furthermore, if the content of the urethane resin containing vinyl acetate salt or the acrylic resin containing vinyl acetate salt in the surface anchor layer 3a is less than 80% by mass with respect to the mass of the surface anchor layer 3a, there will be no problem in use. Although there is no problem, the penetration ratio of the surface anchor layer 3a into the second raw fabric layer 3 may be reduced, and the interlayer strength between the surface anchor layer 3a and the second raw fabric layer 3 may be slightly reduced.

In addition, if the content of the urethane resin containing salt vinyl acetate or the acrylic resin containing salt vinyl acetate 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, more precisely 98% by mass, the surface anchor layers 2a and 3a may be chipped due to insufficient curing, and the surface anchor layer 2a and the adhesive resin layer 8, or The interlayer strength between the surface anchor layer 3a and the picture pattern layer 5 may decrease.

Further, the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front anchor layers 2a and 3a is the same as the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the back anchor layers 2b and 3b. The content may be the same as the content of acrylic resin containing vinyl acetate. That is, the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front anchor layers 2a and 3a is the same as that of the urethane resin containing vinyl acetate or salt in the back anchor layers 2b and 3b. The content may be 1.0 times (within a range of 0.95 times or more and 1.04 times or less) the content of the acrylic resin containing vinyl acetate. The content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front anchor layers 2a and 3a is higher than that of the urethane resin containing vinyl acetate or vinyl acetate in the back anchor layers 2b and 3b. If the content of the acrylic resin containing In a state where the front anchor layer 2a and the back anchor layer 2b are provided, the occurrence of distortion, warping, etc. can be reduced. Therefore, the occurrence of distortion, warping, etc. of the entire decorative sheet can be reduced. In addition, 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, manufacturing costs are reduced and work efficiency is improved. be able to.

Further, the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front anchor layers 2a and 3a is the same as the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the back anchor layers 2b and 3b. The content may be greater or less than the content of the acrylic resin containing vinyl acetate. The content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front anchor layers 2a and 3a is higher than that of the urethane resin containing vinyl acetate or vinyl acetate in the back anchor layers 2b and 3b. If the content of the acrylic resin is higher than or lower than the content of the acrylic resin containing , 3b can be given distortion, warp, etc. to each original fabric layer. In this way, by imparting distortion, warping, etc. to each raw fabric layer including the front anchor layers 2a, 3a and the back anchor layers 2b, 3b, the raw fabric layer can be used to create gaps in a base material etc. having a curved surface. It can be pasted without any problems. For example, the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front anchor layers 2a and 3a is the same as the content of the urethane resin containing vinyl acetate or salt in the back anchor layers 2b and 3b. It 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 content of the acrylic resin containing vinyl acetate.

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

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

[Picture pattern layer 5]
A picture pattern layer 5 on which an arbitrary picture is printed is provided on the surface of the second raw fabric layer 3 (surface anchor layer 3a). The type of pattern formed by the pattern layer 5 is not particularly limited, and may be, 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 to form the picture pattern layer 5 is not particularly limited, and any known printing ink used for forming decorative sheets can be used. Specifically, for example, binder resins such as polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, butyral, acrylic, urethane, polyester, epoxy, alkyd, polyamide, etc. Add organic or inorganic dyes or pigments, extender pigments, fillers, tackifiers, dispersants, antifoaming agents, stabilizers and other additives as necessary, and adjust to the desired viscosity with an appropriate diluting solvent. It may also be a modified printing ink.

[Adhesive layer]
An adhesive layer (not shown) may be formed on the picture pattern layer 5. The adhesive layer may be formed by applying a composition for forming the adhesive layer onto the picture 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 transparent thermoplastic resins contained in the transparent thermoplastic resin layer 6.

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

Further, the thickness of the transparent thermoplastic resin layer 6 is preferably within the range of 50 μm or more and 150 μm or less. If the thickness of the transparent thermoplastic resin layer 6 is within the above numerical range, high transparency is maintained, so that it is possible to prevent a decrease in the visibility of the picture pattern layer 5 and to obtain sufficient abrasion resistance. Further, if 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 will not be impaired, and the processability into decorative boards such as in-line roll lamination will be improved. Moreover, it does not affect the workability as a decorative board and is easy to use.

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

In addition, examples of triazine-based ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 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(2,4dimethylphenyl)-1,3,5-triazine, 2,4-bis(2,4 -dimethylphenyl)-6-(2-hydroxy-4-iso-octyloxyphenyl)-s-triazine, and mixtures, modified products, polymers, and derivatives thereof can be used.

Further, as the benzophenone ultraviolet absorber, for example, octabenzone, modified products, polymers, derivatives, etc. 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 through crosslinking by adding isocyanate. The number of parts to be added may be set depending on the desired weather resistance, but it is within the range of 0.1% to 50%, preferably 1% to 30%, based on the solid content of the resin.
Further, as the light stabilizer added to the transparent thermoplastic resin layer 6, for example, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethyl ethyl)-4-hydroxyphenyl]methyl]butyl malonate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl(1,2,2,6,6-pentamethyl-4 -poperidinyl) sebacate, decanedioic acid bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidinyl) ester, and mixtures, modified products, polymers, derivatives, etc. of these can be used. can.

The number of parts to be added may be added depending on the desired weather resistance, but it is within the range of 0.1% by mass to 50% by mass, preferably 1% by mass to 30% by mass, based on the resin solid content. shall be.
In addition to the above, for example, heat stabilizers, flame retardants, antiblocking agents, etc. may be added. Examples of the heat stabilizer include pentaerythrityl-tetrakis[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 represented by tris(2,4-di-t-butylphenyl) phosphite, etc., and mixtures thereof, i.e., one type or a combination of two or more types. can be used.

Further, as the flame retardant, for example, inorganic compounds such as aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, and phosphoric acid ester flame retardants can be used.
Further, as the antiblocking agent, for example, inorganic antiblocking agents such as aluminum silicate, silicon oxide, hydrotalcite, and calcium carbonate, organic antiblocking agents such as fatty acid amide, etc. can be used.

(embossed pattern)
The embossed pattern is, for example, a pattern consisting of concave portions and convex portions that are synchronized with the pattern of the pattern layer 5. The concave and convex portions of the embossed pattern can provide a three-dimensional effect visually or tactilely. It is preferable that the deviation between the embossed pattern and the pattern of the pattern layer 5 is within a range of, for example, 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, if the picture pattern is wood grain, the direction in which the wood grain conduit extends is the "longitudinal direction with respect to the shape of the picture pattern", and the direction perpendicular to the longitudinal direction is the "short direction with respect to the shape of the picture pattern". Become. In particular, when the wood grain conduits extend along the longitudinal direction of the decorative sheet 10, the longitudinal direction of the decorative sheet 10 becomes 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 picture pattern". Since the transparent thermoplastic resin layer 6 and the surface protection layer 7 are transparent, the embossed pattern is only strongly visible when reflected from oblique light. For example, since it is difficult to visually recognize the reflected light and the transmitted light of the picture pattern layer 5 at the same time, there is no sense of discomfort. By suppressing the deviation between the embossed pattern and the pattern of the patterned 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 even and accurately matched over the entire surface of the sheet. Further, the height difference between the concave portions and the convex portions of the embossed pattern is, for example, within a range of 3 μm or more and 200 μm or less. For the height difference, a value suitable for the intended design of the decorative sheet 10 can be selected. For example, it is also possible to take a continuous multi-step shape within the maximum height difference (200 μm). In particular, in order to obtain the shape of 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 protective layer 7]
It is preferable that the surface protective layer 7 contains an ionizing radiation curable resin such as an ultraviolet curable resin. Specifically, as the material for the surface protection layer 7, for example, a mixture (blend resin) of a thermosetting resin and an ultraviolet curable resin (UV curable resin) is preferable. In this way, since the surface protective layer 7 contains a thermosetting resin and an ultraviolet curable resin, that is, a resin with high hardness, the scratch resistance of the decorative sheet 10 can be improved by the surface protective layer 7 exposed on the surface. Moreover, ethyl acetate and n-butyl acetate can be used as the solvent.

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

Further, as the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule can be used. Examples of polyvalent isocyanates 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. , aliphatic (or cycloaliphatic) isocyanates such as hydrogenated diphenylmethane diisocyanate can be used. Further, adducts or multimers of the various isocyanates mentioned above can be used. Examples include tolylene diisocyanate adducts, tolylene diisocyanate trimers, and the like. In addition, among the above-mentioned isocyanates, aliphatic (or alicyclic) isocyanates are preferable in terms of good weather resistance and resistance to heat 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, anti-slip properties can be imparted to the decorative sheet 10. Moreover, a matte feel can be imparted to the surface of the surface protective layer 7, and the design of the decorative sheet 10 can be improved.

[Backside anchor layer]
The back anchor layers 2b and 3b are layers formed to cover the entire back surface of each raw fabric layer, and are layers for preventing the inorganic material 4a contained in each raw fabric layer from falling off. If the inorganic material 4a contained in each original fabric layer falls off within the printing system, specifically within the printing device, during printing or resin coating, the inside of the printing system may be contaminated.
The back anchor layer 2b also has a function of improving the adhesion between the first raw layer 2 and a primer layer (not shown) to be described later. If the back anchor layer 2b is not provided, the coating liquid forming the primer layer may not come into close contact with the first fabric layer 2 and may peel off.
Further, the back anchor layer 3b also has a function of improving the adhesion between the second raw fabric layer 3 and the adhesive resin layer 8. If the back anchor layer 3b is not provided, the adhesive resin layer 8 may not adhere to the second raw fabric layer 3 and may peel off.
The back 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 vinyl acetate salt or the acrylic resin containing vinyl acetate salt in the back anchor layers 2b and 3b is, for example, 15% by mass or more and 100% by mass based on the mass of the back anchor layers 2b and 3b. % or less, more preferably 80% by mass or more and 100% by mass or less, even more preferably 85% by mass or more and 95% by mass or less. If the content of the urethane resin containing salt-vinyl acetate or the acrylic resin containing salt-vinyl acetate in the back anchor layer 2b is within the above numerical range, the interlayer strength between the back anchor layer 2b and the primer layer can be maintained sufficiently. It is possible to form a uniform back anchor layer 2b without any unevenness or chipping while maintaining a high quality. Further, if the content of the urethane resin containing salt-vinyl acetate or the acrylic resin containing salt-vinyl acetate in the back anchor layer 3b is within the above numerical range, the back anchor layer 3b and the adhesive resin layer 8 can be bonded together. It is possible to form a uniform back anchor layer 3b without unevenness or chipping while maintaining sufficient interlayer strength.

In addition, if the content of the urethane resin containing vinyl acetate salt or the acrylic resin containing vinyl acetate salt in the back anchor layer 2b is less than 15% by mass with respect to the mass of the back anchor layer 2b, the back anchor layer The interlayer strength between 2b and the primer layer may be insufficient. Furthermore, if the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the back anchor layer 2b is less than 80% by mass with respect to the mass of the back anchor layer 2b, there will be no problems in use. Although there is no problem, the biting ratio of the back anchor layer 2b into the first fabric layer 2 may be reduced, and the interlayer strength between the back anchor layer 2b and the first fabric layer 2 may be slightly reduced.

In addition, if the content of the urethane resin containing salt-vinyl acetate or the acrylic resin containing salt-vinyl acetate in the back anchor layer 3b is less than 15% by mass with respect to the mass of the back anchor layer 3b, the back anchor layer The interlayer strength between the adhesive resin layer 3b and the adhesive resin layer 8 may be insufficient. Further, if the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the back anchor layer 3b is less than 80% by mass with respect to the weight of the back anchor layer 3b, there will be no problems in use. Although there is no problem, the penetration ratio of the back anchor layer 3b into the second raw fabric layer 3 may be reduced, and the interlayer strength between the back anchor layer 3b and the second raw fabric layer 3 may be slightly reduced.

Furthermore, if the content of the urethane resin containing salt-vinyl acetate or the acrylic resin containing salt-vinyl acetate in the back anchor layers 2b, 3b is 100% by mass or less with respect to the mass of the back anchor layers 2b, 3b. There is no problem in use, but if it exceeds 95% by mass, more precisely 98% by mass, the back anchor layers 2b and 3b may be chipped due to insufficient curing, or the back anchor layer 2b and primer layer or the back anchor layer may be damaged. The interlayer strength between the adhesive resin layer 3b and the adhesive resin layer 8 may decrease.
Further, the thickness of the back anchor layers 2b and 3b is, for example, in a range of 0.5 μm or more and 20 μm or less, preferably 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 base material, an inorganic base material, a synthetic resin base material, a metal base material, or the like. As this primer layer, for example, polyester resin, polyurethane resin, a mixture thereof, etc. can be used. Furthermore, by using a two-component type containing polyol and isocyanate, the adhesion between the first fabric layer 2 (back anchor layer 2b) and the primer layer and the cohesive force of the primer layer itself are improved. Examples of polyols include acrylic polyols and polyester polyols. Examples of isocyanates include aromatic ones such as tolylene diisocyanate and 4,4' diphenylmethane diisocyanate, and aliphatic ones such as hexamethylene diisocyanate, isophorone diisocyanate and xylene diisocyanate. Aromatic polyols are preferred 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 dissolve depending on the type of solvent used in the adhesive, and the primer layer may disappear, so that adhesion may not be improved.

(Method for manufacturing decorative sheet 10)
An example of a method for manufacturing the decorative sheet 10 will be briefly described below.
First, a raw fabric layer containing 20% by mass of polypropylene and 80% by mass of calcium carbonate is created. Thereafter, this original fabric layer is uniaxially stretched.
Next, anchor layers are formed on both sides of this uniaxially stretched original fabric layer. Thereafter, these raw fabric layers are laminated with the adhesive resin layer 8 in between so that the stretching directions cross (perpendicularly cross) each other to form two layers, the first raw fabric layer 2 and the second raw fabric layer 3. A base material layer 1 containing the following is created.
Next, a picture pattern layer 5 is formed on the surface anchor layer 3a, which is the outermost layer of the base material layer 1, by printing.
Thereafter, a layer formed by extruding a resin composition containing a molten transparent thermoplastic resin from an extruder is laminated on the pattern layer 5 to form a transparent thermoplastic resin layer 6.
Next, the transparent thermoplastic resin layer 6 is embossed.
Finally, on the embossed transparent thermoplastic resin layer 6, a resin composition prepared by adding a curing agent, an ultraviolet absorber, and a light stabilizer to a urethane resin, for example, is applied. is dried to form a surface protective layer 7. In this way, the decorative sheet 10 according to this embodiment is manufactured.
Note that the method for manufacturing the decorative sheet 10 according to the present embodiment may include a step of forming an adhesive layer (not shown) between the picture pattern layer 5 and the transparent thermoplastic resin layer 6.

(Effects of this embodiment)
In the decorative sheet 10 of this embodiment, a pattern layer 5, a transparent thermoplastic resin layer 6, and a surface protection layer 7 are laminated in this order on a base 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. . Moreover, the first raw fabric layer 2 and the second raw fabric layer 3 each contain a thermoplastic resin 4b and an inorganic material 4a. Moreover, the content of the inorganic material 4a 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. Furthermore, 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 is equivalent to that of a decorative sheet provided with a melamine board. This makes it possible to provide a decorative sheet that has excellent hardness and abrasion resistance, as well as excellent processability and productivity.

More specifically, when a decorative sheet used for flooring, etc. is made from a single thick uniaxially stretched original fabric layer, there may be a difference in strength between the stretching direction and the direction perpendicular to it. . In that case, cracks are likely to occur in the decorative sheet. Furthermore, when raw layers of uniaxially stretched thin films are laminated with their stretching directions aligned, there may be a difference in strength between the stretching direction and the direction orthogonal thereto. In that case as well, cracks are likely to occur in the decorative sheet. In addition, decorative sheets used for flooring and the like, which are made by stacking raw fabric layers with the stretching directions aligned, tend to warp due to environmental changes such as temperature and humidity.
On the other hand, thickness and hardness can be imparted to the base material layer 1 by laminating uniaxially stretched original fabric layers so that the stretching directions are perpendicular to each other. In addition, since the stretching directions are perpendicular to each other, the warpage that occurs in each original fabric layer is canceled out inside the base layer 1, making it difficult for the entire decorative sheet used for flooring, etc., to warp.

As described above, by stacking the raw fabric layers with their stretching directions orthogonal to each other, it is possible to increase the hardness and surface strength of the decorative sheet itself used for flooring, etc., thereby improving scratch resistance and Impact-resistant flooring can be made.
Furthermore, by laminating a plurality of layers with the stretching directions orthogonal to each other, warping as a flooring material can be reduced.
Furthermore, by laminating multiple layers with the stretching directions orthogonal to each other, it is possible to process and install the flooring material regardless of its cutting direction.
Further, the inorganic material 4a constituting each original fabric layer of the decorative sheet 10 of the present embodiment is in the form of a powder, and has an average particle size of 1 μm or more and 3 μm or less, and a maximum particle size 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 materials 4a constituting each original fabric layer of the decorative sheet 10 of this embodiment include antimony trioxide, antimony soda, zircon silicate, zircon oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, and borax. , zinc borate, calcium carbonate, complexes of molybdenum trioxide or antimony dimolybdate and aluminum hydroxide, complexes of antimony trioxide and silica, complexes of antimony trioxide and zinc white, silicic acid of zirconium, and zirconium It may be a complex of the compound and antimony trioxide, or at least one of their salts.
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 of the decorative sheet 10 of this 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 inorganic material 4a constituting each raw fabric layer of the decorative sheet 10 of this 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 included in the decorative sheet 10 of this embodiment may be within 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 anchor layers 2a, 3a and the back anchor layers 2b, 3b of the decorative sheet 10 of this embodiment each contain a urethane resin containing salt vinyl acetate or an acrylic resin containing salt vinyl acetate. You can.
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 and the stretching direction of the second raw fabric layer 3 included in the decorative sheet 10 of this embodiment may intersect with each other.
With such a configuration, sufficient surface strength can be imparted to each raw fabric layer.
In addition, in a heat generation test using a cone calorimeter tester in accordance with ISO5660-1, the decorative sheet 10 of the present embodiment has (1) a total calorific value (MJ/m ² ) of 8 MJ/m ² for 20 minutes after the start of heating. (2) The maximum heat generation rate for 20 minutes after the start of heating does not exceed 200kW/ ^m2 for 10 seconds or more (3) It is non-flammable and satisfies the condition that there are no cracks or holes in the base material. ing.

(Example)
[Example 1]
First, a sheet containing polystyrene as the thermoplastic resin 4b and silica (average particle size 4 μm) as the inorganic material 4a was created. Note that the content of silica 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. Note that the thickness of each original fabric layer was 45 μm.
Thereafter, surface anchor layers 2a and 3a made of urethane-based resin containing salt-vinyl acetate are formed on the surface of each of the first and second raw fabric layers 2 and 3, and each of the raw fabrics is Back anchor layers 2b and 3b made of urethane resin containing salt-vinyl acetate were formed on the back side of the layer, respectively.

Next, the first raw fabric layer 2 and the second raw fabric layer 3 having the front surface anchor layers 2a, 3a and the back surface anchor layers 2b, 3b are bonded together with an adhesive resin layer 8 made of a urethane resin adhesive. Laminated through. Thereafter, this laminate was compressed to create a base material layer 1. Note that when laminating the first raw fabric layer 2 and the second raw fabric layer 3, the stretching direction of the first raw fabric layer 2 and the stretching direction of the second raw fabric layer 3 are 60 mm in plan view. The first raw fabric layer 2 and the second raw fabric layer 3 were stacked so as to intersect at an angle of .
Next, a picture pattern layer 5 was formed by printing a wood grain pattern on the surface anchor layer 3a using a gravure printing method.

Subsequently, a transparent thermoplastic resin layer 6 was formed on the picture pattern layer 5 by extruding and laminating a layer containing a molten transparent thermoplastic resin using a T-die. The transparent thermoplastic resin layer 6 is made of transparent polypropylene resin, 0.2 parts by mass of a phenolic antioxidant ("IRGANOX1010" manufactured by Ciba Specialty Chemicals Co., Ltd.), and a hindered amine light stabilizer (manufactured by Ciba Specialty Chemicals Co., Ltd.). 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 ultraviolet absorber ("TINUVIN326" manufactured by Ciba Specialty Chemicals Co., Ltd.).

At the same time, the laminate of the base layer 1, pattern layer 5, and transparent thermoplastic resin layer 6 was nipped using a conduit embossing plate and a rubber roll to simultaneously perform embossing and lamination. 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 a hardening agent ("UR150B Varnish" manufactured by Toyo Ink Co., Ltd.) is added to a urethane resin ("URV238 Varnish" manufactured by Toyo Ink Co., Ltd.) as a top coat resin. 0.5 parts by mass of a benzotriazole ultraviolet absorber ("TINUVIN326" manufactured by Ciba Specialty Chemicals Co., Ltd.) and 1 mass part of a hindered amine light stabilizer ("TINUVIN622" manufactured by Ciba Specialty Chemicals Co., Ltd.) A surface protective layer 7 was obtained by gravure coating such that the coating amount after drying was 5 g/m ² .

Subsequently, 10 parts by mass of silica was added to 100 parts by mass of polyol ("Lamister EM" manufactured by Toyo Ink Co., Ltd.) on the back anchor layer 2b, and an isocyanate ("LPNYB" manufactured by Toyo Ink Co., Ltd.) was added. A primer coating solution was prepared by adding 3 parts by mass of "curing agent" and gravure coating was applied so that the coating amount after drying was 3 g/m ² to obtain a primer layer.
The decorative sheet of Example 1 was formed by such a procedure.

[Example 2]
A decorative sheet was formed in the same manner as in Example 1, except that the content of silica was 90% by mass based on 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 diameter of the silica was 1 μm.
[Example 4]
A decorative sheet was formed in the same manner as in Example 1 except that the average particle diameter of silica was 3 μm.

[Example 5]
A decorative sheet was formed in the same manner as in Example 1, except that antimony trioxide was used as the inorganic material 4a contained in each raw fabric layer.
[Example 6]
A decorative sheet was formed in the same manner as in Example 1, except that zircon oxide was used as the inorganic material 4a contained in each raw fabric layer.
[Example 7]
A decorative sheet was formed in the same manner as in Example 1, except that calcium carbonate was used as the inorganic material 4a contained in each raw fabric layer.
[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 vinyl chloride was used as the thermoplastic resin 4b contained in each raw fabric layer.
[Example 10]
A decorative sheet was formed in the same manner as in Example 1, except that PET (polyethylene terephthalate) was used as the thermoplastic resin 4b contained in each raw fabric layer.
[Example 11]
A decorative sheet was formed in the same manner as in Example 1, except that polypropylene was used as the thermoplastic resin 4b contained in each raw fabric layer.
[Example 12]
A decorative sheet was formed in the same manner as in Example 1, except that polyethylene was used as the thermoplastic resin 4b contained in each raw fabric layer.
[Example 13]
A decorative sheet was formed in the same manner as in Example 1, except that polyester was used as the thermoplastic resin 4b contained in each raw fabric layer.

[Example 14]
A decorative sheet was formed in the same manner as in Example 1 except that the thickness of each original 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 original 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 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 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 plan view. .

[Example 19]
Except that the inorganic material 4a contained in each raw fabric layer was calcium carbonate, its average particle diameter 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 layers of each raw fabric layer was 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 made to overlap in plan view.
[Comparative example 2]
A decorative sheet was formed in the same manner as in Example 1, except that the content of silica was 13% by mass based on 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 content of silica was 92% by mass based on the mass of each raw fabric layer.

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

[Abrasion resistance]
The decorative board was subjected to an abrasion resistance test stipulated by the Japanese Agricultural Standards for JAS Flooring, and the number of rotations until the pattern began to disappear was confirmed. The worn paper was replaced every 1000 revolutions.
◎: 3000 revolutions or more ○: 2500 revolutions or more and less than 3000 revolutions △: 2000 revolutions or more and less than 2500 revolutions ×: Less than 2000 revolutions

[Scratch resistance]
The decorative board was subjected to a pencil hardness test specified in JIS K 5600 to check for scratches.
◎: 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 decorative sheets into decorative boards.
◎: Inline roll lamination is possible.
○: In-line roll lamination is possible. Processing requires some care.
△: In-line roll lamination is possible, but requires great care in processing.
×: Roll lamination is not possible. Only sheet sheets can be pasted together.

[Cutability]
The decorative board was cut with a circular saw and a cutting test was conducted with a hand router in which the surface reached MDF, and the presence or absence of burrs on the sheet was confirmed.
◎: No burrs are generated.
○: Some burrs are visible, but they can be easily corrected.
△: Some burrs are seen and correction is required.
×: Burrs occur almost all over the surface, making manual correction difficult.

〔Productivity〕
The ease of production when extrusion laminating the transparent thermoplastic resin layer 6 was confirmed.
◎: Stable production possible.
○: It is necessary to pay more attention to production than ◎, but stable production is possible.
△: There is a possibility that the roll may come off over time due to long-run production, so careful production is required.
×: Production is extremely difficult due to occurrence of wrinkles and unrolling.

〔Incombustibility〕
It was evaluated whether the following requirements were met in a heat generation test using a cone calorimeter tester in accordance with ISO5660-1.
1. Total calorific value is 8MJ/ ^m2 or less 2. Maximum heat generation rate does not exceed 200kW/ ^m2 for 10 seconds or more 3. No cracks or holes penetrating the back surface, which would be detrimental to flame protection, were created. As the noncombustible base material, gypsum board was used. Moreover, the evaluation criteria are as follows.
○: All of the above requirements are met. ×: At least one of the above requirements is not met.

[Occurrence of warpage]
A decorative board cut into 10 cm squares was placed on a smooth table, and the warp (distance) at the end of the decorative board from the table surface to the bottom of the decorative board was measured using a metal ruler. Moreover, the evaluation criteria are as follows.
◎: Almost no warpage (0.5 mm or less).
〇: 5mm or less △: 10mm or less ×: More than 10mm

As shown in Table 1, the decorative sheet according to this example is a decorative sheet that has scratch resistance and wear resistance, and is also excellent in processability and productivity. In addition, from the evaluation results of the scratch resistance performance and the abrasion resistance performance, it can be seen that the scratch resistance performance and the abrasion resistance performance of the decorative sheet according to this example are comparable to those of the melamine board.
Furthermore, the decorative sheet according to this embodiment also has nonflammability. Furthermore, the decorative sheet according to this embodiment also reduces the occurrence of warpage.

The decorative sheet of this embodiment can be used as a surface decoration material for interior surfaces such as floors, walls, and ceilings of buildings, furniture, various cabinets, surface decorations for fittings, and surface decorations for vehicle interiors. be.

1: Base material layer 2: First raw fabric layer 2a: Surface anchor layer (first anchor layer)
2b: Back anchor layer (second anchor layer)
3: Second raw fabric layer 3a: Surface anchor layer (first anchor layer)
3b: Back anchor layer (second anchor layer)
4a: Inorganic material 4b: Thermoplastic resin 4c: Cavity 5: Picture pattern layer 6: Transparent thermoplastic resin layer 7: Surface protection layer 8: Adhesive resin layer 10: Decorative sheet

Claims (11)

A picture pattern layer, a transparent thermoplastic resin layer, and a surface protection layer are laminated in this order on the base 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 each contain a thermoplastic resin and an inorganic material,
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,
The stretching direction of the first raw fabric layer and the stretching direction of the second raw fabric layer intersect with each other , and the crossing angle is within a range of 30° or more and 80° or less. A decorative sheet. The decorative sheet according to claim 1, wherein the inorganic material is in the form of a powder, has an average particle size in a range of 1 μm or more and 3 μm or less, and has a maximum particle size of 50 μm or less. The inorganic materials include antimony trioxide, antimony soda, zircon silicate, zircon oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borax, zinc borate, calcium carbonate, molybdenum trioxide, or antimony dimolybdate and water. At least one of the following: a complex with aluminum oxide, a complex between antimony trioxide and silica, a complex between antimony trioxide and zinc white, a silicic acid of zirconium, a complex between a zirconium compound and antimony trioxide, and a salt thereof. The decorative sheet according to claim 1 or 2, characterized in that: The inorganic materials include antimony trioxide, antimony soda, zircon silicate, zircon oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borax, zinc borate , molybdenum trioxide, or antimony dimolybdate and aluminum hydroxide. A complex of antimony trioxide and silica, a complex of antimony trioxide and zinc white, a complex of zirconium silicic acid, a complex of a zirconium compound and antimony trioxide, and a salt thereof. The decorative sheet according to claim 1 or claim 2. The decorative sheet according to any one of claims 1 to 4 , wherein the thermoplastic resin is at least one of vinyl chloride, polyethylene terephthalate, polypropylene, polyethylene, and polyester. The total content of the thermoplastic resin and the inorganic material is within a range of 90% by mass or more and 100% by mass or less based on the mass of each raw fabric layer. 5. The decorative sheet according to any one of Item 5 . The decorative sheet according to any one of claims 1 to 6 , wherein the thickness of each original fabric layer is within a 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 picture pattern layer side;
further comprising a second anchor layer formed on a surface of each raw fabric layer opposite to the surface on which the first anchor layer is formed,
Any one of claims 1 to 7 , wherein the first anchor layer and the second anchor layer each contain a urethane resin containing salt vinyl acetate or an acrylic resin containing salt vinyl acetate. The decorative sheet according to item 1. In a heat generation test using a corn calorimeter tester in accordance with ISO5660-1, (1) the total calorific value (MJ/m ² ) for 20 minutes after the start of heating is 8 MJ/m ² or less, and (2) for 20 minutes after the start of heating Claims 1 to 8, characterized in that the maximum heat generation rate does not exceed 200 kW/ ^m2 for 10 seconds or more; (3) the base material has non-flammability that satisfies the condition that there are no cracks or holes; The decorative sheet according to any one of the above. The surface of the inorganic material is treated with at least one of an organic phosphorus surface treatment agent, an inorganic phosphoric acid surface treatment agent, a polycarboxylic acid surface treatment agent, and a coupling agent surface treatment agent. The decorative sheet according to any one of claims 1 to 9. A picture pattern layer, a transparent thermoplastic resin layer, and a surface protection layer are laminated in this order on the base 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 each contain a thermoplastic resin and an inorganic material,
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,
The stretching direction of the first raw fabric layer and the stretching direction of the second raw fabric layer intersect with each other ,
a first anchor layer formed on the surface of each original fabric layer on the picture pattern layer side;
further comprising a second anchor layer formed on a surface of each raw fabric layer opposite to the surface on which the first anchor layer is formed,
The decorative sheet is characterized in that the first anchor layer and the second anchor layer each contain a urethane resin containing vinyl acetate or an acrylic resin containing vinyl acetate.

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