JP7388038B2 - makeup sheet - Google Patents

Description

The present invention relates to a decorative sheet.

Conventionally, the mainstream of decorative sheets has been polyvinyl chloride resin films with patterns printed on them. In recent years, in consideration of environmental issues, decorative sheets have been developed that use non-chlorine resin films such as polyolefin resins, which are less likely to generate harmful substances such as hydrogen chloride or dioxins when burned. It is becoming widely used.

The above-mentioned decorative sheet may be required to have scratch resistance and abrasion resistance. Specifically, the decorative sheet is required to be free from scratches on its surface when it is hit by objects or rubbed during movement.
As a non-chlorine material having scratch resistance and wear resistance, there is, for example, a melamine board described in Patent Document 1, but the size of the melamine board has certain restrictions. For this reason, if there are many parts of the melamine board that are cut and removed during product processing of decorative sheets, the yield may be poor. 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, a decorative sheet according to one embodiment of the present invention has a pattern layer, an adhesive layer, a transparent thermoplastic resin layer, and a surface protection layer laminated in this order on a base layer, and The base material layer contains a thermoplastic resin and an inorganic material, and the content of the inorganic material is within a range of 15% by mass or more and 90% by mass or less based on the mass of the base material layer, and The thickness of the transparent thermoplastic resin layer is within the range of 50 μm or more and 150 μm or less, and the surface protective layer contains an ionizing radiation curable resin.

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 an olefin decorative sheet or a polyester decorative sheet that is laminated to a base material such as a wood base material, an inorganic base material, a synthetic resin base material, a metal base material, etc. This is a decorative sheet used in areas where abrasion resistance is required. Hereinafter, the configuration of the decorative sheet 10 will be specifically explained.

The decorative sheet 10 includes a primer layer 8, a back anchor layer 1b, a raw fabric layer (base layer) 1, a front anchor layer 1a, a pattern layer 2, an adhesive layer 5, a transparent thermoplastic resin layer 6, and a surface protective layer. 7 are stacked in this order. Further, the raw fabric layer 1 contains a thermoplastic resin and an inorganic material, and the content of the inorganic material is within a range of 15% by mass or more and 90% by mass or less based on the mass of the raw fabric layer 1. It is. Moreover, the thickness of the transparent thermoplastic resin layer 6 is within the range of 50 μm or more and 150 μm or less. Moreover, the surface protection layer 7 contains an ionizing radiation curable resin such as an ultraviolet ray curable resin.

Note that the transparent thermoplastic resin layer 6 is formed on the adhesive layer 5 side and includes a first resin layer 6a, and is formed on the first resin layer 6a, and the first resin is It may also include a second resin layer 6b containing a different second resin. Further, the first resin may be, for example, a transparent maleic acid-modified polypropylene resin, and the second resin may be, for example, a transparent polypropylene resin.
The details of each of the above layers will be explained below.

[Original fabric layer (base material layer) 1]
The raw fabric layer 1 is a layer (sheet) serving as a base material of the decorative sheet 10, and is a layer containing a thermoplastic resin and an inorganic material.
<Inorganic materials>
The content of the inorganic material of this embodiment may be within the range of 15% by mass or more and 90% by mass or less, and may be within the range of 20% by mass or more and 80% by mass or less, based on the mass of the raw fabric layer 1. It is more preferable if it is within the range of 60% by mass or more and 80% by mass or less. If the content of the inorganic material is less than 15% by mass with respect to the mass of the raw fabric layer 1, the proportion of thermoplastic resin will be relatively large, so the surface of the raw fabric layer 1 was tested using a Hoffman scratch tester. When scratched, visible scratches may occur, that is, sufficient surface hardness may not be obtained. On the other hand, when the content of the inorganic material exceeds 90% by mass with respect to the mass of the raw fabric layer 1, the proportion of the thermoplastic resin becomes relatively small. For this reason, when an anchor layer is coated or printed on the surface of the raw fabric layer 1, so-called "powder blowing" may occur on the surface of the raw fabric layer 1. Here, "powder blowing" means that the inorganic material contained in the raw fabric layer 1 comes out onto the surface of the raw fabric layer 1. Further, when forming the picture pattern layer 2, the inorganic material that stands out from the original fabric layer 1 may make it difficult for the ink to be laminated, that is, the printability may deteriorate. Also, when laminating a sheet on which at least one of the front anchor layer 1a, the back anchor layer 1b, the picture pattern layer 2, and the surface protective layer 7 is formed on a wood base material and a stone base material in a roll or sheet form, It becomes difficult to laminate, that is, the suitability for lamination tends to decrease. Furthermore, when the sheet on which at least one of the front anchor layer 1a, the back anchor layer 1b, the picture pattern layer 2, and the surface protective layer 7 is formed is folded and opened again, cracks may occur from the folded portion, and inorganic Materials may fall. In addition, after pressing the cellophane tape on the surface of the sheet on which the picture pattern layer 2 is formed, peel it off strongly and peel it off within the picture pattern layer 2 or between the raw fabric layer 1 (surface anchor layer 1a) and the picture pattern layer 2. may occur, that is, ink adhesion may deteriorate.

As described above, the content of the inorganic material of this 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, based on the mass of the raw fabric layer 1. If it is within the above range of 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, and moreover, It is possible to obtain a high surface hardness and improve ink adhesion.

Further, the inorganic material of this embodiment is preferably in powder form (powder shape), and preferably has an average particle size in the range of 1 μm or more and 3 μm or less, and a maximum particle size of 50 μm or less. . If the average particle size and maximum particle size of the inorganic material are within the above numerical ranges, the flatness of the surface of the original fabric layer 1 can be maintained while improving the dispersibility of the inorganic material in the thermoplastic resin. When the average particle diameter of the inorganic material is less than 1 μm, the cohesive force between the inorganic materials increases, and the dispersibility in the thermoplastic resin described below may decrease. In addition, when the average particle size of the inorganic material exceeds 3 μm, the flatness of the surface of the original fabric layer 1 decreases, and the thickness of the surface anchor layer 1a or back anchor layer 1b, which will be described later, may become uneven, uneven, or chipped. It may occur. Furthermore, when the maximum particle size of the inorganic material exceeds 50 μm, the flatness of the surface of the raw fabric layer 1 decreases, and the thickness of the surface anchor layer 1a or the back surface anchor layer 1b, which will be described later, may become uneven, uneven, or chipped. It may occur. In addition, in this embodiment, "average particle diameter" means a mode diameter.

The inorganic material 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 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 at least one of calcium carbonate and calcium carbonate salt containing 50% by mass or more of calcium carbonate, it is possible to impart sufficient nonflammability or sufficient flame retardancy to the raw fabric layer 1. At the same time, sufficient mechanical strength can be imparted.

In addition to powders containing at least one of the calcium carbonate and calcium carbonate salts, examples of inorganic materials include silica (especially hollow silica), alumina, antimony trioxide, antimony soda, zirconium silicate, and zirconium oxide. compounds, such as magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borax, zinc borate, molybdenum trioxide or complexes of antimony dimolybdate and aluminum hydroxide, complexes of antimony trioxide and silica, antimony trioxide Examples include at least one of complexes of zirconium and zinc white, silicic acid of zirconium, complexes of zirconium compounds 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 through manufacturing methods, and are also inexpensive in terms of material cost, so they are useful from the perspective of reducing the cost of decorative sheets. suitable.

Further, the inorganic material may be a powder material having crystallinity, a so-called crystalline powder, or a powder material having no crystallinity, a so-called amorphous type powder material. If the inorganic material 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 tend to be improved. In addition, if the inorganic material is an amorphous type powder material, it is possible to adjust the electrical conductivity and thermal conductivity of the powder itself, as well as the light transmittance and light absorption rate, resulting in variations in texture, gloss, etc. This makes it possible to provide a rich variety of designs.

Inorganic materials such as calcium carbonate whose surfaces are not coated generally have low powder fluidity and do not have high alkali resistance, so they tend to change color easily.
On the other hand, when an inorganic material 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 this embodiment, various surface treatment agents are applied to inorganic materials such as calcium carbonate, as necessary, for the purpose of improving powder fluidity, alkali resistance, hue improvement, and other properties of calcium carbonate fillers. Surface treatment (coating) may be performed. This point will be explained below.

The surface of the inorganic material of this embodiment 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. It may be something. 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 inorganic materials include 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilotrismethylenephosphonic acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, Examples include organic phosphoric acids such as triphenyl phosphate, methyl phosphate, and ethyl phosphate, and their salts.
Furthermore, examples of inorganic phosphoric acid surface treatment agents that can be used for surface treatment of inorganic materials include condensed phosphoric acids represented by pyrophosphoric acid, polyphosphoric acids, hexametaphosphoric acid, and salts thereof.
Incidentally, these surface treating agents can be used alone or in combination of two or more as necessary.

Polycarboxylic acid surface treatment agents that can be used for surface treatment of inorganic materials include, for example, monocarboxylic acids such as polyacrylic acid, methacrylic acid, and crotonic acid, and dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid. Examples include 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.

Coupling agent-based surface treatment agents that can be used for surface treatment of inorganic materials include, for example, silane-based coupling agents such as vinyltrimethoxysilane and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane. titanate coupling agents typified by isopropyl triisostearoyl titanate, silicone oils typified by methyl hydrogen, and the like. These may be used alone or in combination of two or more.

Among these surface treatment agents, trimethyl phosphate (TMP) and triethyl phosphate (TEP) are used from the viewpoint of compatibility with resins, heat resistance, inactivation of inorganic materials such as calcium carbonate, and dehydration/deaeration properties. , 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 surface treatment agent to be used varies depending on the specific surface area of the inorganic material such as calcium carbonate, the 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 material. 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 inorganic materials 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 mix the surface treatment agent directly into the powder of an inorganic material such as calcium carbonate. There is a dry treatment method in which the surface is treated by heating if necessary, or a surface treatment agent is dissolved in an aqueous solvent, etc., and the surface is treated in an inorganic material suspension such as calcium carbonate by heating if necessary. A cake obtained by dehydrating a suspension of an inorganic material such as calcium carbonate may be surface-treated by wet treatment methods such as dehydration, drying, or a combination of both.

In addition, as necessary, 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 may be added to the extent that the effectiveness of the raw fabric layer 1 is not impaired. , an anti-blocking agent, an antistatic agent, a slip agent, a coloring agent, etc. may be added.

<Thermoplastic resin>
The thermoplastic resin of this embodiment is preferably at least one of polypropylene, polyethylene, and polyester, and more preferably polypropylene. By using at least one of polypropylene, polyethylene, and polyester as the thermoplastic resin, the dispersibility of the inorganic material is improved. Further, by using polypropylene as the thermoplastic resin, the dispersibility of the inorganic material is further improved.

Further, the total content of the thermoplastic resin and the inorganic material is preferably in the range of 90% by mass or more and 100% by mass or less based on the mass of the raw fabric layer 1. If the total content of thermoplastic resin and inorganic material is within the above numerical range, sufficient surface strength can be obtained, printability and lamination suitability can be improved, and cracks that occur at the folded portion of the sheet can be reduced. I can do it. If the total content of the thermoplastic resin and the inorganic material is less than 90% by mass based on the mass of the raw layer 1, 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 and the inorganic material is 100% by mass with respect to the mass of the raw fabric layer 1, the content of the thermoplastic resin is 10% by mass or more and 85% by mass or less. The content of the inorganic material is preferably within 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 be within the range of 20% by mass to 80% by mass, and the content of the inorganic material be within the range of 20% by mass to 80% by mass. Further, it is more preferable that the content of the thermoplastic resin be within the range of 20% by mass to 40% by mass, and the content of the inorganic material be within the range of 60% by mass to 80% by mass. If the total content of thermoplastic resin and inorganic material is within the above numerical range, sufficient surface strength can be obtained, printability and lamination suitability can be improved, and cracks that occur at the folded portion of the sheet can be prevented. can be reliably reduced.

Further, the thickness of the raw fabric layer 1 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 the raw fabric layer 1 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 the raw fabric layer 1 is less than 50 μm, lamination suitability tends to decrease. Moreover, if the thickness of the original fabric layer 1 exceeds 250 μm, cracks may occur at the folded portion of the sheet.
Moreover, it is preferable that the raw fabric layer 1 is a non-stretched raw fabric layer. If the raw fabric layer 1 is a non-stretched raw fabric layer, the mechanical strength of the decorative sheet 10 as a whole can be increased.

Note that at least one of the front surface (the surface on the picture pattern layer 2 side) and the back surface (the surface on the primer layer 8 side) of the raw fabric layer 1 is coated with, for example, a surface anchor layer (first anchor layer) 1a and a back surface anchor, which will be described later. Before forming the layer (second anchor layer) 1b, it is preferable to perform a 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 the raw fabric layer 1, the adhesiveness (adhesion) between the front anchor layer 1a and the back anchor layer 1b and the raw fabric layer 1 is improved. will improve.
In addition, before forming the front anchor layer 1a and the back anchor layer 1b, for example, at least one of the front surface and the back surface of the original fabric layer 1 is brushed, and at least one of powdered inorganic materials such as calcium carbonate and calcium carbonate salt is applied. The powder containing one of the two may be dropped in advance.

[Surface anchor layer]
The surface anchor layer 1a is a layer formed to cover the entire surface of the raw fabric layer 1, and is a layer for preventing the inorganic material contained in the raw fabric layer 1 from falling off. If the inorganic material contained in the original fabric layer 1 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. Further, if the inorganic material contained in the original fabric layer 1 falls off, problems such as ink omission may occur. Here, "ink omission" refers to ink not being printed partially.

The surface anchor layer 1a also has a function of improving the adhesion between the original fabric layer 1 and the ink forming the picture pattern layer 2, which will be described later. If the surface anchor layer 1a is not provided, the ink forming the pattern layer 2 may not adhere to the original fabric layer 1 and may peel off.
The surface anchor layer 1a preferably contains 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 vinyl acetate salt or the acrylic resin containing vinyl acetate salt in the surface anchor layer 1a is within the range of 15% by mass or more and 100% by mass or less based on the mass of the surface anchor layer 1a. 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 salt-vinyl acetate or the acrylic resin containing salt-vinyl acetate in the surface anchor layer 1a is within the above numerical range, the interlayer strength between the surface anchor layer 1a and the pattern layer 2 can be increased. It is possible to form a uniform surface anchor layer 1a without any unevenness or chipping while making the surface anchor layer 1a sufficient. If the content of the urethane resin containing vinyl acetate salt or the acrylic resin containing vinyl acetate salt in the surface anchor layer 1a is less than 15% by mass with respect to the mass of the surface anchor layer 1a, the surface anchor layer 1a The interlayer strength with the picture pattern layer 2 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 1a is less than 80% by mass with respect to the mass of the surface anchor layer 1a, there will be no problem in use. Although there is no problem, the penetration ratio of the surface anchor layer 1a into the raw fabric layer 1 may be reduced, and the interlayer strength between the surface anchor layer 1a and the raw fabric layer 1 may be slightly reduced. Note that if the content of the urethane resin containing vinyl acetate salt or the acrylic resin containing vinyl acetate salt in the surface anchor layer 1a is 100% by mass or less based on the mass of the surface anchor layer 1a, there will be no problem in use. However, if it exceeds 95% by mass, more precisely 98% by mass, the surface anchor layer 1a may be chipped due to insufficient curing, or the surface anchor layer 1a and the original fabric layer 1, or the surface anchor layer 1a and the pattern may The interlayer strength with layer 2 may decrease.

The content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front anchor layer 1a is the same as the content of the urethane resin containing vinyl salt or vinyl acetate in the back anchor layer 1b, which will be described later. It may be the same as the content of the acrylic resin containing. That is, the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front anchor layer 1a is the same as the content of the urethane resin containing vinyl acetate or vinyl acetate in the back anchor layer 1b. 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. The content of the urethane resin containing vinyl acetate salt or the acrylic resin containing vinyl acetate salt in the front anchor layer 1a is the same as that of the urethane resin containing vinyl acetate salt or the acrylic resin containing vinyl acetate salt in the back anchor layer 1b. When the resin content is the same, the physical properties of the front anchor layer 1a and the back anchor layer 1b are almost the same, so the raw fabric layer 1 is provided with the front anchor layer 1a and the back anchor layer 1b. In this case, the occurrence of distortion, warpage, 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 1a and the coating liquid for forming the back surface anchor layer 1b can be shared, manufacturing costs are reduced and work efficiency is improved. be able to.

In addition, the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front anchor layer 1a is the same as the content of the urethane resin containing vinyl salt or vinyl acetate in the back anchor layer 1b. The content may be greater or less than the content of the acrylic resin. The content of the urethane resin containing vinyl acetate salt or the acrylic resin containing vinyl acetate salt in the front anchor layer 1a is the same as that of the urethane resin containing vinyl acetate salt or the acrylic resin containing vinyl acetate salt in the back anchor layer 1b. If the content is higher or lower than the resin content, the physical properties of the front anchor layer 1a and the back anchor layer 1b will be different, so the original fabric layer 1 including the front anchor layer 1a and the back anchor layer 1b will be strained. It is possible to add warpage, warpage, etc. In this way, by imparting distortion, warping, etc. to the raw fabric layer 1 including the front anchor layer 1a and the back anchor layer 1b, the raw fabric layer 1 can be bonded to a base material etc. with a curved surface without any gaps. be able to. For example, the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front anchor layer 1a is the same as the content of the urethane resin containing vinyl acetate or vinyl acetate in the back anchor layer 1b. The content of the acrylic resin 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 layer 1a is, for example, in the range of 0.5 μm or more and 20 μm or less, preferably in the range of 0.5 μm or more and 10 μm or less. Moreover, the thickness of the front surface anchor layer 1a may be the same as the thickness of the back surface anchor layer 1b. When the thickness of the front anchor layer 1a is the same as the thickness of the back anchor layer 1b, the physical properties of the front anchor layer 1a and the back anchor layer 1b are almost the same. And in the state provided with the back anchor layer 1b, the occurrence of distortion, warping, etc. can be reduced.
Moreover, the thickness of the front surface anchor layer 1a may be thicker or thinner than the thickness of the back surface anchor layer 1b. By making the thickness of the front anchor layer 1a different from the thickness of the back anchor layer 1b, a difference in gloss is generated, so that the front side and the back side of the original fabric layer 1 can be easily recognized visually. By doing so, the picture pattern layer 2 can be printed on the surface of the original fabric layer 1 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 pattern layer 2 on the back side (non-printing side) of the original fabric layer 1 can be reduced.

[Picture pattern layer 2]
A picture pattern layer 2 on which an arbitrary picture is printed is provided on the surface of the raw fabric layer 1 (surface anchor layer 1a). The type of pattern formed in the pattern layer 2 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 2 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 5]
An adhesive layer 5 is formed on the picture pattern layer 2. The adhesive layer 5 may be formed by applying a composition for forming the adhesive layer 5 onto the picture pattern layer 2. The adhesive contained in the adhesive layer 5 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 a layer in which an emboss is formed, and is, for example, a sheet-like layer consisting of a plurality of layers. Each layer constituting the transparent thermoplastic resin layer 6 is formed of, for example, a transparent thermoplastic resin so that the pattern of the pattern layer 2 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. Various combinations of resins in each layer constituting the transparent thermoplastic resin layer 6 are possible depending on the desired characteristics. In the transparent thermoplastic resin layer 6, the number of layers can be four or more, but the structure of the extruder becomes complicated and the work becomes complicated, so it is preferable to have up to three layers. Of course, there may be two layers or one layer.

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 2 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.
In FIG. 1, the transparent thermoplastic resin layer 6 includes, from the adhesive layer 5 side, a first resin layer 6a containing a predetermined resin (hereinafter also referred to as "first resin"); Two layers of the second resin layer 6b including a resin different from the first resin (hereinafter also referred to as "second resin") are laminated in this order.

In this embodiment, the thickness of the first resin layer 6a may be 10 μm or more, and may be 20% or less of the total thickness of the transparent thermoplastic resin layer 6. If the thickness of the first resin layer 6a is less than 10 μm, the uniformity of the thickness of the coating film or the planar smoothness will decrease, and therefore the adhesion stability of the first resin layer 6a will tend to decrease.
Furthermore, if the thickness of the first resin layer 6a exceeds 20% of the total thickness of the transparent thermoplastic resin layer 6, the thickness of the second resin layer 6b, which has excellent abrasion resistance, will be relatively thin. The surface strength of the decorative sheet 10 as a whole tends to decrease. In other words, if the thickness of the first resin layer 6a is 10 μm or more and 20% or less of the total thickness of the transparent thermoplastic resin layer 6, it is possible to maintain the adhesion stability of the first resin layer 6a while applying makeup. The surface strength of the entire sheet 10 can be maintained. Further, the thickness of the first resin layer 6a is 10 μm or more, and is 20 μm thicker than the entire thickness of the transparent thermoplastic resin layer 6, which is composed of only two layers, the first resin layer 6a and the second resin layer 6b. % or less, and even in that case, the surface strength of the entire decorative sheet 10 can be maintained while maintaining the adhesion stability of the first resin layer 6a.

Further, the content rate (mass %) of the transparent maleic acid-modified polypropylene resin in the first resin layer 6a may be greater than the content rate (mass %) of the transparent polypropylene resin in the second resin layer 6b. Even in this case, the surface strength of the entire decorative sheet 10 can be maintained while maintaining the adhesion stability of the first resin layer 6a. In addition, with the above configuration, the material design is such that the first resin layer 6a ensures adhesion with the adhesive layer 5, and the second resin layer 6b becomes the main part and is responsible for other physical properties. It becomes possible to widen the width. That is, by making the first resin layer 6a of transparent maleic acid-modified polypropylene, the adhesion between the layers can be improved. Further, by forming the second resin layer 6b as a layer containing transparent polypropylene, it is possible to exhibit an effect in preventing embrittlement inside the resin.

The first resin and the second resin are selected by considering, for example, the scratch resistance, weather resistance, stain resistance, light resistance, transparency, bendability, thermoformability, etc. of the surface of the decorative sheet 10, and also the materials. Considering cost and the like, the first resin is preferably a transparent maleic acid-modified polypropylene resin, and the second resin is preferably a transparent polypropylene resin. Note that the first resin layer 6a may be a layer containing either an ultraviolet absorber or a light stabilizer together with the first resin, which is a transparent maleic acid-modified polypropylene resin. Further, the second resin layer 6b may be a layer containing either an ultraviolet absorber or a light stabilizer together with a transparent polypropylene resin that is the second resin.

The transparent polypropylene resin of the present embodiment is, for example, a mixture of a polypropylene resin (a) to which free terminal long chain branching has been imparted and a polypropylene resin (b) to which free terminal long chain branching has not been imparted; The molecular weight distribution Mw/Mn defined as mass average molecular weight/number average molecular weight is within the range of 1 to 5, and the mixed resin of polypropylene resin (a) and polypropylene resin (b) is boiling heptane-compatible. It is also possible to use a material having an isotactic index defined as a residual fraction within a range of 1% or more and 90% or less. Thereby, whitening and cracking can be suppressed during bending after the decorative sheet 10 is bonded to, for example, a steel plate base material.

Here, when there are Ni molecules of molecular weight Mi, the number average molecular weight Mn=Σ(Mi×Ni)/ΣNi, and the mass average molecular weight Mw=Σ(Ni×Mi2)/Σ(Ni×Mi ), which is a value defined as Mw/Mn. The closer it is to 1, the narrower the molecular weight distribution and the higher the uniformity. When the molecular weight distribution is set to 5 or less, the molecular weight can be made uniform to a necessary and sufficient size, which contributes to suppressing whitening and cracking. Generally, molecular weight distribution can be measured by gel permeation chromatography (GPC).

Further, the isotactic index defined as the fraction of soluble residue in boiling heptane is useful as an index for examining the degree of crystallinity in polypropylene resin. Specifically, a sample is extracted with boiling n-heptane for a certain period of time, and the mass (%) of the unextracted portion is determined to calculate the isotactic index. Specifically, dry the thimble at 110 ± 5 ° C for 2 hours, leave it in a constant temperature and humidity room for at least 2 hours, then put 8 g or more of the sample (powder or flake) into the thimble, and weigh it. Weigh accurately using a cup and tweezers. Set this on top of an extractor containing about 80 cc of heptane, and assemble the extractor and cooler. This is heated in an oil bath or electric heater and extracted for 12 hours. The heating is adjusted so that the number of drops from the cooler is 130 drops or more per minute. Subsequently, the thimble containing the extraction residue is taken out, placed in a vacuum dryer, and dried for 5 hours at 80° C. and under a vacuum of 100 mmHg or less. After drying, the sample was left in a constant temperature and humidity environment for 2 hours, then accurately weighed, and the isotactic index was calculated by (P/Po) x 100. However, Po is the sample mass (g) before extraction, and P is the sample mass (g) after extraction.

By setting the isotactic index to 90% or less, sheet rigidity due to polypropylene crystals can be suppressed. Methods for lowering the isotactic index include, for example, partially using an amorphous polypropylene component (such as syndiotactic polypropylene or adactic polypropylene), or using one or more types of olefin monomers such as ethylene or α-olefin. Random copolymerization method, various rubber components (e.g. ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), butadiene rubber (BR) , isoprene rubber (IR), etc.) can be used.

In addition, the melt tension of a mixed resin of polypropylene resin (a) and polypropylene resin (b) (when extruded at 60 mm/min at 230°C and withdrawn at 2 mm/min using a 2.0 mm diameter nozzle capillary rheometer) (tension) is preferably within the range of 100 mN or more and 500 mN or less. If it exceeds 500 mN, the melt viscosity becomes too high and stable film formation becomes impossible. Moreover, if it is 100 mN or less, the long chain branching component becomes insufficient and it is difficult to obtain the desired performance.

In addition, by controlling the melt flow rate of the mixture of polypropylene resin (a) and polypropylene resin (b) at 230°C as specified in JIS-K6760 to be within the range of 5 g/10 min to 50 g/10 min, the molecular weight can be kept above a certain value and a stable film forming state can be maintained. A more preferable melt flow rate range is from 10 g/10 min to 30 g/10 min, and even more preferably from 10 g/10 min to 25 g/10 min. When the melt flow rate exceeds 50g/10min, the effect (neck-in) that the resin melted and extruded from the T-die tends to gather in the center becomes large during melt-extrusion using the T-die, and the resin is melt-extruded from the T-die. The end thickness of the resin increases. An increase in the thickness of the end portion reduces cooling efficiency and affects thickness stability in the width direction, making it difficult to form a stable film. In addition, if it is lower than 5g/10min, the draw resonance of the molten resin will be poor, and the molten resin will be in the gap between the velocity (initial velocity) of the molten resin immediately after coming out of the T-die and the velocity of the resin immediately after touching the cooling roll. This makes it difficult to form stable films.

Further, the ultraviolet absorber added to the transparent thermoplastic resin layer 6 is appropriately selected from benzotriazole-based, triazine-based, benzophenone-based, etc.
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. Moreover, the thickness of the transparent thermoplastic resin layer 6 is preferably within the range of 50 μm or more and 150 μm or less.

(embossed pattern)
The embossed pattern 9 is, for example, a pattern consisting of concave portions and convex portions that are synchronized with the pattern of the picture pattern layer 2. The concave portions and convex portions of the embossed pattern 9 can provide a three-dimensional effect visually or tactilely. It is preferable that the deviation between the embossed pattern 9 and the pattern of the pattern layer 2 be within the 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 9 is only strongly visible when reflected from oblique light, but the deviation between the embossed pattern 9 and the pattern of the picture pattern layer 2 is within the above range. If so, it would be difficult to visually recognize the transmitted light of the picture pattern layer 2 at the same time as the reflected light, so there would be no discomfort. By suppressing the deviation between the embossed pattern 9 and the pattern of the patterned pattern layer 2 within a certain range, it is possible to obtain a decorative sheet 10 in which the shape and distribution of the pattern are uniform and precisely matched over the entire surface of the sheet. Further, the height difference between the concave portion and the convex portion of the embossed pattern 9 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.

[Backside anchor layer]
The back anchor layer 1b is a layer formed to cover the entire back surface of the raw fabric layer 1, and is a layer for preventing the inorganic material contained in the raw fabric layer 1 from falling off. If the inorganic material contained in the original fabric layer 1 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.
Further, the back anchor layer 1b also has a function of improving the adhesion between the raw fabric layer 1 and a primer layer 8, which will be described later. If the back anchor layer 1b is not provided, the coating liquid forming the primer layer 8 may not adhere to the base layer 1 and may peel off.
The back anchor layer 1b preferably contains 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 layer 1b is, for example, in the range of 15% by mass or more and 100% by mass or less based on the mass of the back anchor layer 1b. 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 salt-vinyl acetate or the acrylic resin containing salt-vinyl acetate in the back anchor layer 1b is within the above numerical range, the interlayer strength between the back anchor layer 1b and the primer layer 8 can be maintained sufficiently. It is possible to form the back anchor layer 1b that is uniform and free from unevenness and chipping while maintaining the same properties. If the content of the urethane resin containing salt-vinyl acetate or the acrylic resin containing salt-vinyl acetate in the back anchor layer 1b is less than 15% by mass with respect to the mass of the back anchor layer 1b, the back anchor layer 1b The interlayer strength with the primer layer 8 may be insufficient. 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 1b is less than 80% by mass with respect to the mass of the back anchor layer 1b, there will be no problem in use. Although there is no problem, the penetration ratio of the back anchor layer 1b into the original fabric layer 1 may be reduced, and the interlayer strength between the back anchor layer 1b and the original fabric layer 1 may be slightly reduced. Note that if the content of the urethane resin containing vinyl acetate salt or the acrylic resin containing vinyl acetate salt in the back anchor layer 1b is 100% by mass or less based on the mass of the back anchor layer 1b, there will be no problem in use. However, if it exceeds 95% by mass, more precisely 98% by mass, the back anchor layer 1b may be chipped due to insufficient curing, or the back anchor layer 1b and the original fabric layer 1, or the back anchor layer 1b and the primer layer may be damaged. The interlayer strength with No. 8 may decrease.
Further, the thickness of the back anchor layer 1b is, for example, in the range of 0.5 μm or more and 20 μm or less, preferably in the range of 0.5 μm or more and 10 μm or less.

[Primer layer 8]
As the primer layer 8, 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 base layer 1 (back anchor layer 1b) and the primer layer 8 and the cohesive force of the primer layer 8 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 8 is preferably 1 μm or more. If the thickness of the primer layer 8 is less than 1 μm, it may dissolve depending on the type of solvent used in the adhesive, and the primer layer 8 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, anchor layers (the front anchor layer 1a and the back anchor layer 1b) are formed on both sides of the raw fabric layer 1. Next, a picture pattern layer 2 is formed on the surface anchor layer 1a by, for example, printing.
Thereafter, a plurality of layers formed by extruding a resin composition containing a molten transparent thermoplastic resin from a multilayer extruder are laminated on the picture pattern layer 2, thereby forming the transparent thermoplastic resin layer 6, that is, the first layer. A resin layer 6a and a second resin layer 6b are formed. Next, the transparent thermoplastic resin layer 6 is embossed. Finally, on the embossed transparent thermoplastic resin layer 6, a resin composition in which a curing agent, an ultraviolet absorber, and a light stabilizer are added, for example, to a urethane resin 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 5 between the picture pattern layer 2 and the transparent thermoplastic resin layer 6.

(Effects of this embodiment)
In the decorative sheet 10 of this embodiment, a picture pattern layer 2, an adhesive layer 5, a transparent thermoplastic resin layer 6, and a surface protection layer 7 are laminated in this order on a raw fabric layer 1. Further, the raw fabric layer 1 contains a thermoplastic resin and an inorganic material, and the content of the inorganic material is within a range of 15% by mass or more and 90% by mass or less based on the mass of the raw fabric layer 1. It is. Moreover, the thickness of the transparent thermoplastic resin layer 6 is within the range of 50 μm or more and 150 μm or less. Furthermore, the surface protective layer 7 contains an ultraviolet curable resin.
With such a configuration, it is possible to provide a decorative sheet that has scratch resistance and abrasion resistance equivalent to that of a decorative sheet provided with a melamine board, and has excellent processability and productivity.

Further, the transparent thermoplastic resin layer 6 provided in the decorative sheet 10 of the present embodiment is formed on the adhesive layer 5 side and includes a first resin layer 6a formed including a first resin, and a first resin layer 6a formed on the adhesive layer 5 side. A second resin layer 6b formed on the layer 6a and containing a second resin different from the first resin may be provided. Further, the first resin may be a transparent maleic acid-modified polypropylene resin, and the second resin may be a transparent polypropylene resin.
With such a configuration, the first resin layer 6a ensures adhesion with the raw fabric layer 1, and the second resin layer 6b becomes the main part of the layer and is responsible for other physical properties. It becomes possible to expand the range of designs. By making the first resin layer 6a a layer containing a transparent maleic acid-modified polypropylene resin, it is possible to improve the adhesion with the thermoplastic resin. Further, by forming the second resin layer 6b as a layer containing transparent polypropylene resin, it is possible to exhibit an effect on the embrittlement resistance inside the second resin layer 6b.

Further, the thickness of the first resin layer 6a provided in the decorative sheet 10 of this embodiment may be 10 μm or more and 20% or less of the total thickness of the transparent thermoplastic resin layer 6.
With such a configuration, the surface strength of the entire decorative sheet 10 can be maintained while improving the adhesion stability of the first resin layer 6a.
Further, the inorganic material constituting the original fabric layer 1 of the decorative sheet 10 of the present embodiment is in the form of a powder, and has an average particle size in the range of 1 μm or more and 3 μm or less, and a maximum particle size of 50 μm or less. You can.
With such a configuration, sufficient surface strength can be imparted to the raw fabric layer 1.

Inorganic materials constituting the raw fabric layer 1 of the decorative sheet 10 of this embodiment include antimony trioxide, antimony soda, zircon silicate, zircon oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, 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 compounds and antimony trioxide, or at least one of their salts.
With such a configuration, sufficient surface strength can be reliably imparted to the raw fabric layer 1.

Further, the thermoplastic resin constituting the raw fabric layer 1 of the decorative sheet 10 of this embodiment may be at least one of polypropylene, polyethylene, and polyester.
With such a configuration, sufficient flexibility can be imparted to the raw fabric layer 1.
Further, the total content of the thermoplastic resin and inorganic material constituting the raw fabric layer 1 of the decorative sheet 10 of the present embodiment is 90% by mass or more and 100% by mass or less with respect to the mass of the raw fabric layer 1. It may be within the range.
With such a configuration, sufficient surface strength and nonflammability can be imparted to the raw fabric layer 1.

Moreover, the thickness of the original fabric layer 1 provided 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 the raw fabric layer 1.
Further, the front anchor layer 1a and the back anchor layer 1b provided in the decorative sheet 10 of this embodiment may each contain a urethane resin containing salt vinyl acetate or an acrylic resin containing salt vinyl acetate.
With such a configuration, it is possible to prevent the inorganic material from falling off.

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]
As the raw fabric layer 1, a sheet containing polystyrene, which is a thermoplastic resin, and silica, which is an inorganic material, was used, and a surface anchor layer 1a was formed on the surface side. Note that the content of silica was 15% by mass based on the mass of the raw fabric layer 1. Further, the thickness of the original fabric layer 1 was 45 μm.
Next, a picture pattern layer 2 was formed by printing a wood grain pattern on the surface anchor layer 1a using a gravure printing method.
Subsequently, a urethane resin adhesive was applied onto the picture pattern layer 2 and dried with warm air to form an adhesive layer 5.

Subsequently, a transparent thermoplastic resin layer 6 was formed on the adhesive layer 5 by extruding and laminating multiple layers containing molten transparent thermoplastic resin using a T-die from a multi-axis extruder. The first resin contains 0.2 parts by mass of a phenolic antioxidant ("IRGANOX1010" manufactured by Ciba Specialty Chemicals Co., Ltd.) and a hindered amine light stabilizer ("TINUVIN622" manufactured by Ciba Specialty Chemicals Co., Ltd.) in a transparent polypropylene resin. ") and 0.5 parts by mass of a benzotriazole ultraviolet absorber ("TINUVIN326" manufactured by Ciba Specialty Chemicals Co., Ltd.) were used. The second resin was a resin modified with transparent maleic acid. Polypropylene resin (manufactured by Riken Vitamin Co., Ltd.) was used.

At the same time, the laminate of the raw fabric layer 1, pattern layer 2, adhesive layer 5, and transparent thermoplastic resin layer 6 was nipped using a conduit embossing plate and a rubber roll to perform embossing and lamination at the same time. Here, the thickness of the first resin layer 6a was 8 μm, and the thickness of the second resin layer 6b was 42 μm. That is, the thickness of the transparent thermoplastic resin layer 6 was set to 50 μm.
After surface treatment is applied to the embossed surface of the decorative sheet 10, a hardening agent ("UR150B Varnish" made by Toyo Ink Co., Ltd.) is applied to a urethane resin ("URV238 Varnish" made by Toyo Ink Co., Ltd.) as a top coat resin. To the 10 parts by mass added, 0.5 parts by mass of a benzotriazole ultraviolet absorber ("TINUVIN326" manufactured by Ciba Specialty Chemicals Co., Ltd.) and a hindered amine light stabilizer ("TINUVIN622" manufactured by Ciba Specialty Chemicals Co., Ltd.). A surface protective layer 7 was obtained by gravure coating with 1 part by mass added so that the coating amount after drying was 5 g/m ² .

Furthermore, after performing surface treatment on the back surface of the original fabric layer 1, a back anchor layer 1b was formed on this surface.
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 1b, 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 the primer layer 8 was obtained by gravure coating so that the coating amount after drying was 3 g/m ² .
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 thickness of the transparent thermoplastic resin layer 6 was 150 μm, and the thickness of the second resin layer 6b was 142 μm.
[Example 3]
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 the original fabric layer 1.
[Example 4]
A decorative sheet was formed in the same manner as in Example 3 except that the thickness of the transparent thermoplastic resin layer 6 was 150 μm.

[Example 5]
The first resin is a transparent maleic acid-modified polypropylene resin (manufactured by Riken Vitamin Co., Ltd.), and the second resin is a transparent polypropylene resin with a phenolic antioxidant (IRGANOX1010 manufactured by Ciba Specialty Chemicals Co., Ltd.). ''), 0.3 parts by mass of a hindered amine light stabilizer ("TINUVIN622" manufactured by Ciba Specialty Chemicals Co., Ltd.), and 0.3 parts by mass of a benzotriazole ultraviolet absorber ("TINUVIN326" manufactured by Ciba Specialty Chemicals Co., Ltd.). A decorative sheet was formed in the same manner as in Example 1, except that a resin to which 0.5 parts by mass of ) was added was used.

[Example 6]
A decorative sheet was formed in the same manner as in Example 1 except that the thickness of the first resin layer 6a was 10 μm.
[Example 7]
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 8]
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 9]
A decorative sheet was formed in the same manner as in Example 1, except that the inorganic material contained in the raw fabric layer 1 was antimony trioxide.
[Example 10]
A decorative sheet was formed in the same manner as in Example 1, except that the inorganic material contained in the raw fabric layer 1 was zircon oxide.
[Example 11]
A decorative sheet was formed in the same manner as in Example 1, except that the inorganic material contained in the raw fabric layer 1 was calcium carbonate.
[Example 12]
A decorative sheet was formed in the same manner as in Example 1, except that the inorganic material contained in the raw fabric layer 1 was calcium carbonate.

[Example 13]
A decorative sheet was formed in the same manner as in Example 1, except that the thermoplastic resin contained in the raw fabric layer 1 was polypropylene.
[Example 14]
A decorative sheet was formed in the same manner as in Example 1, except that polyethylene was used as the thermoplastic resin contained in the raw fabric layer 1.
[Example 15]
A decorative sheet was formed in the same manner as in Example 1, except that the thermoplastic resin contained in the raw fabric layer 1 was polyester.
[Example 16]
A decorative sheet was formed in the same manner as in Example 1, except that the thickness of the original fabric layer 1 was 50 μm.
[Example 17]
A decorative sheet was formed in the same manner as in Example 1 except that the thickness of the original fabric layer 1 was 250 μm.

[Example 18]
The inorganic material contained in the raw fabric layer 1 is calcium carbonate, the average particle diameter thereof is 1 μm, the thermoplastic resin contained in the raw fabric layer 1 is polypropylene, the thickness of the raw fabric layer 1 is 50 μm, and the first resin The thickness of the layer 6a is 10 μm, the first resin is a transparent maleic acid-modified polypropylene resin (manufactured by Riken Vitamin Co., Ltd.), and the second resin is a transparent polypropylene resin containing a phenolic antioxidant ( 0.2 parts by mass of a hindered amine light stabilizer ("TINUVIN622" manufactured by Ciba Specialty Chemicals Co., Ltd.), 0.3 parts by mass of a hindered amine light stabilizer ("TINUVIN622" manufactured by Ciba Specialty Chemicals Co., Ltd.), and a benzotriazole-based ultraviolet absorber (Ciba Specialty Chemicals Co., Ltd. "TINUVIN622"). A decorative sheet was formed in the same manner as in Example 1, except that a resin containing 0.5 parts by mass of "TINUVIN326" manufactured by Specialty Chemicals Co., Ltd. was used.

[Comparative example 1]
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 the original fabric layer 1.
[Comparative example 2]
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 the original fabric layer 1.
[Comparative example 3]
A decorative sheet was formed in the same manner as in Example 1, except that the thickness of the transparent thermoplastic resin layer 6 was 45 μm.
[Comparative example 4]
A decorative sheet was formed in the same manner as in Example 1, except that the thickness of the transparent thermoplastic resin layer 6 was 160 μm.

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 necessary.
×: 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 will come off over time during 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.

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. Furthermore, the decorative sheet according to this embodiment also has nonflammability.

The decorative sheet of this embodiment and the decorative sheet manufactured by the method of manufacturing a decorative sheet of this embodiment can be used for interior decoration such as floors, walls, and ceilings of buildings, surface decoration materials for furniture, various cabinets, etc., and surfaces of fittings. It can be used as surface decoration for cosmetics, vehicle interiors, etc.

1: Original fabric layer (base material layer)
1a: Surface anchor layer (first anchor layer)
1b: Back anchor layer (second anchor layer)
2: Picture pattern layer 5: Adhesive layer 6: Transparent thermoplastic resin layer 6a: Transparent thermoplastic resin layer (first resin layer)
6b: Transparent thermoplastic resin layer (second resin layer)
7: Surface protective layer 8: Primer layer 9: Embossed pattern 10: Decorative sheet

Claims (15)

A picture pattern layer, an adhesive layer, a transparent thermoplastic resin layer, and a surface protection layer are laminated in this order on the base layer,
The base layer contains 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 the base layer,
The thickness of the transparent thermoplastic resin layer is within the range of 50 μm or more and 150 μm or less,
The surface protective layer includes an ionizing radiation curable resin,
The transparent thermoplastic resin layer includes a first resin layer formed on the adhesive layer side and containing a first resin, and a first resin layer formed on the first resin layer and containing the first resin. a second resin layer formed including a second resin different from the
The first resin is a transparent polypropylene resin,
A decorative sheet , wherein the second resin is a transparent maleic acid-modified polypropylene resin . The decorative sheet according to claim 1 , wherein the thickness of the first resin layer is 10 μm or more and 20% or less of the total thickness of the transparent thermoplastic resin layer. The decorative sheet according to claim 1 or 2 , wherein the inorganic material is in a powder form, has an average particle size in the 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 any one of claims 1 to 3 , 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 any one of claims 1 to 3 . 6. The decorative sheet according to claim 1, wherein the thermoplastic resin contained in the base layer is at least one of polypropylene, polyethylene, and polyester. The decorative sheet according to any one of claims 1 to 5 , wherein the thermoplastic resin contained in the base layer is polyester . The total content of the thermoplastic resin and the inorganic material contained in the base layer is within a range of 90% by mass or more and 100% by mass or less based on the mass of the base layer. The decorative sheet according to any one of claims 1 to 7 . The decorative sheet according to any one of claims 1 to 8, wherein the thickness of the base layer is within a range of 50 μm or more and 250 μm or less. a first anchor layer formed on the surface of the base layer on the picture pattern layer side;
further comprising a second anchor layer formed on a surface of the base material layer opposite to the surface on which the first anchor layer is formed,
Any one of claims 1 to 9 , 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. The decorative sheet according to item 1. a first anchor layer formed on the surface of the base layer on the picture pattern layer side;
further comprising a second anchor layer formed on a surface of the base material layer opposite to the surface on which the first anchor layer is formed,
The decorative sheet according to any one of claims 1 to 9 , wherein the first anchor layer and the second anchor layer contain an acrylic resin containing salt-vinyl acetate. The thickness of the first anchor layer is within the range of 0.5 μm or more and 20 μm or less,
The decorative sheet according to claim 10 or 11, wherein the thickness of the second anchor layer is within a range of 0.5 μm or more and 20 μm or less. The decorative sheet according to any one of claims 10 to 12, wherein the thickness of the first anchor layer is the same as the thickness of the second anchor layer. The decorative sheet according to any one of claims 10 to 12, wherein the first anchor layer is thicker or thinner than the second anchor layer. 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 14 , characterized in that the maximum heat generation rate of the material does not exceed 200 kW/ ^m2 for 10 seconds or more; (3) it has nonflammability that satisfies the condition that there are no cracks or holes in the base material; The decorative sheet according to any one of the above.

Images