JP2021024238A - Decorative sheet - Google Patents

Abstract

To provide a decorative sheet excellent in processability and productivity, and capable of imparting scratch resistance and abrasion resistance equivalent to a melamine plate even with a decorative sheet not equipped with a melamine plate.SOLUTION: A decorative sheet 10 includes, on a raw fabric layer 1, a picture pattern layer 2, an adhesive layer 5, a transparent thermoplastic resin layer 6, and a surface protective layer 7 laminated in this order. The raw fabric layer 1 includes a thermoplastic resin and an inorganic material. A content of the inorganic material with regard to the mass of the raw fabric layer 1 is within a range of 15 to 90 mass%. Thickness of the transparent thermoplastic resin layer 6 is within a range of 50 to 150 μm. The surface protective layer 7 contains an ionization radiation curable resin composition.SELECTED DRAWING: Figure 1

Description

The present invention relates to a decorative sheet.

Conventionally, as a decorative sheet, a polyvinyl chloride resin film printed with a pattern has been the mainstream. In recent years, in consideration of dealing with environmental problems, decorative sheets using non-chlorine resin films such as polyolefin resins, which are less likely to generate harmful substances such as hydrogen chloride or dioxins during combustion, have been developed. It is becoming widely used.

The decorative sheet may be required to have scratch resistance and abrasion resistance. Specifically, the decorative sheet is required not to be scratched on the surface when it is hit by an object or rubbed during movement.
As a non-chlorine-based material having scratch resistance and abrasion resistance, for example, there is a melamine plate described in Patent Document 1, but the melamine plate has a certain size regulation. For this reason, if there are many parts where the melamine plate is cut and dropped during product processing of the decorative sheet, the yield may deteriorate. Further, when a melamine plate is used, the work efficiency is low because the laminating process is performed on a single leaf, and the workability may be poor due to its weight.

Japanese Unexamined Patent Publication No. 2014-188941

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

In order to solve the above problems, in the decorative sheet according to one aspect of the present invention, a pattern layer, an adhesive layer, a transparent thermoplastic resin layer, and a surface protective layer are laminated in this order on a base material layer. The base material layer contains a thermoplastic resin and an inorganic material, and the content of the inorganic material is in the range of 15% by mass or more and 90% by mass or less with respect to the mass of the base material layer. The thickness of the transparent thermoplastic resin layer is in the range of 50 μm or more and 150 μm or less, and the surface protective layer contains an ionizing radiation curable resin.

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

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

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

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
(Structure of decorative sheet 10)
An example of the structure of the decorative sheet 10 of the present embodiment is shown in FIG. The decorative sheet 10 is an olefin-based decorative sheet or a polyester-based decorative sheet that is attached to a base material such as a wood-based base material, an inorganic-based base material, a synthetic resin base material, or a metal-based base material, and is particularly scratch-resistant and scratch-resistant. A decorative sheet used for parts where wear resistance is required. Hereinafter, the configuration of the decorative sheet 10 will be specifically described.

The decorative sheet 10 includes a primer layer 8, a back surface anchor layer 1b, a raw fabric layer (base material layer) 1, a surface anchor layer 1a, a pattern layer 2, an adhesive layer 5, a transparent thermoplastic resin layer 6, and a surface protection layer. 7 are laminated 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 the range of 15% by mass or more and 90% by mass or less with respect to the mass of the raw fabric layer 1. Is. The thickness of the transparent thermoplastic resin layer 6 is in the range of 50 μm or more and 150 μm or less. Further, the surface protective layer 7 contains an ionizing radiation curable resin such as an ultraviolet curable resin.

The transparent thermoplastic resin layer 6 is formed on the adhesive layer 5 side and is formed on the first resin layer 6a containing the first resin and the first resin layer 6a, and the first resin is A second resin layer 6b containing a different second resin may be provided. 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 described below.

[Original layer (base material layer) 1]
The raw fabric layer 1 is a layer (sheet) that serves as a base material for the decorative sheet 10, and is a layer that contains a thermoplastic resin and an inorganic material.
<Inorganic material>
The content of the inorganic material of the present embodiment may be in the range of 15% by mass or more and 90% by mass or less with respect to the mass of the raw fabric layer 1, and may be in the range of 20% by mass or more and 80% by mass or less. It is more preferable, and more preferably in 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 the thermoplastic resin is relatively large. Therefore, the surface of the raw fabric layer 1 is subjected to a Hoffman scratch tester. When scratched, it may be scratched to the extent that it can be visually recognized, that is, sufficient surface hardness may not be obtained. On the other hand, when the content of the inorganic material 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, so-called "powder blowing" may occur on the surface of the raw fabric layer 1 when the anchor layer is applied or printed on the surface of the raw fabric layer 1. Here, "powder blowing" means that the inorganic material contained in the raw fabric layer 1 emerges on the surface of the raw fabric layer 1. Further, when the pattern layer 2 is formed, the inorganic material that emerges from the raw fabric layer 1 may make it difficult for the ink to be laminated, that is, the printability may be lowered. Further, when laminating a sheet forming at least one of the front surface anchor layer 1a, the back surface anchor layer 1b, the pattern layer 2, and the surface protection layer 7 on a wood-based base material and a stone-based base material in a roll shape or a single leaf. It becomes difficult to laminate, that is, the laminating suitability tends to decrease. Further, when the sheet forming at least one of the front surface anchor layer 1a, the back surface anchor layer 1b, the pattern pattern layer 2, and the surface protection layer 7 is bent and reopened, cracks are generated from the bent portion or the material is inorganic. The material may fall off. Further, after the cellophane tape is pressure-bonded to the surface of the sheet on which the pattern pattern layer 2 is formed, it is strongly peeled off and peeled off in the pattern pattern layer 2 or between the original fabric layer 1 (surface anchor layer 1a) and the pattern pattern layer 2. That is, the ink adhesion may decrease.

As described above, the content of the inorganic material of the present embodiment is 15% by mass or more and 90% by mass or less, preferably 20% by mass or more and 80% by mass or less, and more preferably 60% by mass with respect to the mass of the raw fabric layer 1. If it is within the range of 80% by mass or more, it is possible to reduce the occurrence of powder blowing, improve the printability, improve the laminating suitability, and reduce the occurrence of cracks in the bent portion of the sheet, which is more sufficient. Excellent surface hardness can be obtained, and ink adhesion can be improved.

Further, the inorganic material of the present embodiment is preferably in a powder shape (powder shape), and its average particle size is preferably in the range of 1 μm or more and 3 μm or less, and the maximum particle size is preferably 50 μm or less. .. When the average particle size and the maximum particle size of the inorganic material are within the above numerical ranges, the flatness of the surface of the raw fabric layer 1 can be maintained while improving the dispersibility of the inorganic material with respect to the thermoplastic resin. If the average particle size of the inorganic material is less than 1 μm, the cohesive force between the inorganic materials may increase, and the dispersibility in the thermoplastic resin described later may decrease. Further, when the average particle size of the inorganic material exceeds 3 μm, the flatness of the surface of the raw fabric layer 1 is lowered, and the thickness of the front surface anchor layer 1a or the back surface anchor layer 1b, which will be described later, becomes uneven, or unevenness or chipping occurs. It may occur. Further, when the maximum particle size of the inorganic material exceeds 50 μm, the flatness of the surface of the raw fabric layer 1 is lowered, and the thickness of the front surface anchor layer 1a or the back surface anchor layer 1b, which will be described later, becomes uneven, or unevenness or chipping occurs. It may occur. In this embodiment, the "average particle size" means the 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 is preferably contained in the range of 50% by mass or more and 100% by mass or less. That is, the purity of the powder containing at least one of calcium carbonate and calcium carbonate salt is preferably in the range of 50% by mass or more and 100% by mass or less of calcium carbonate or the like. If the powder contains at least one of calcium carbonate and calcium carbonate having a content of calcium carbonate or the like of 50% by mass or more, the raw fabric layer 1 can be provided with sufficient nonflammability or sufficient flame retardancy. At the same time, sufficient mechanical strength can be imparted.

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

Further, the inorganic material may be a powder material having crystallinity, so-called crystalline powder, or a powder material having no crystallinity, so-called amorphous type powder material. If the inorganic material is a crystalline powder material, the powder itself is homogeneous and hasotropic, so that the mechanical strength of the powder itself is improved, and the scratch resistance and durability of the decorative sheet tend to be improved. Further, if the inorganic material is an amorphous type powder material, the electric conductivity and thermal conductivity of the powder itself, or the light transmittance and light absorption rate can be appropriately adjusted, so that there are variations such as tactile sensation and luster. It is possible to give abundant design.

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

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

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

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

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

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

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

As a surface treatment method for an inorganic material such as calcium carbonate, for example, a mixer such as a super mixer, a Henschel mixer, a tumbler mixer, a kneader mixer, or a Banbury mixer is used, and a surface treatment agent is directly mixed with the inorganic material powder such as calcium carbonate. Then, a dry treatment method in which the surface is treated by heating as necessary, or a surface treatment agent is dissolved in an aqueous solvent or the like and then heated in a suspension of an inorganic material such as calcium carbonate as necessary to perform the surface treatment. , Dehydration, drying, or a combination of both may be used to surface-treat a cake obtained by dehydrating a suspension of an inorganic material such as calcium carbonate.

Further, as long as the efficacy of the raw fabric layer 1 is not impaired, for example, a lubricant, an antioxidant, a fluorescent whitening agent, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a neutralizing agent, and an antifogging agent. , Anti-blocking agent, antistatic agent, slip agent, colorant and the like may be blended.

<Thermoplastic resin>
The thermoplastic resin of the present 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 with respect to the mass of the raw fabric layer 1. When the total content of the thermoplastic resin and the inorganic material is within the above numerical range, it is necessary to improve printability and laminating suitability while obtaining sufficient surface strength, and reduce cracks generated in the bent portion of the sheet. Can be done. If the total content of the thermoplastic resin and the inorganic material is less than 90% by mass with respect to the mass of the raw fabric layer 1, sufficient surface strength may not be obtained. In addition, printability and laminating suitability may be reduced, and cracks may occur in the bent portion of the sheet.

When the total content of the thermoplastic resin 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. It is preferably within the range, and 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 is in the range of 20% by mass or more and 80% by mass or less, and the content of the inorganic material is in the range of 20% by mass or more and 80% by mass or less. Further, it is more preferable that the content of the thermoplastic resin is in the range of 20% by mass or more and 40% by mass or less, and the content of the inorganic material is in the range of 60% by mass or more and 80% by mass or less. When the total content of the thermoplastic resin and the inorganic material is within the above numerical range, sufficient surface strength is surely obtained, printability and laminating suitability are surely improved, and cracks generated in the bent portion of the sheet are surely obtained. Can be reliably reduced.

The thickness of the raw fabric layer 1 is preferably in the range of 50 μm or more and 250 μm or less, and more preferably in the range of 70 μm or more and 200 μm or less. When the thickness of the raw fabric layer 1 is within the above numerical range, the mechanical strength of the entire sheet can be improved and cracks generated in the bent portion of the sheet can be reduced. If the thickness of the raw fabric layer 1 is less than 50 μm, the laminating suitability tends to decrease. Further, if the thickness of the raw fabric layer 1 exceeds 250 μm, cracks may occur in the bent portion of the sheet.
Further, the raw fabric layer 1 is preferably a non-stretched raw fabric layer. If the raw fabric layer 1 is an unstretched raw fabric layer, the mechanical strength of the entire decorative sheet 10 can be increased.

In addition, on at least one of the front surface (the surface on the pattern layer 2 side) and the back surface (the surface on the primer layer 8 side) of the original fabric layer 1, for example, the surface anchor layer (first anchor layer) 1a and the back surface anchor described later. Before forming the layer (second anchor layer) 1b, it is preferable to perform surface treatment such as corona treatment and plasma treatment. By applying surface treatment such as corona treatment or plasma treatment to at least one of the front surface and the back surface of the raw fabric layer 1, the adhesiveness (adhesion) between the front surface anchor layer 1a and the back surface anchor layer 1b and the raw fabric layer 1 Is improved.
Further, before forming the front surface anchor layer 1a and the back surface anchor layer 1b, for example, at least one of the front surface and the back surface of the raw fabric layer 1 is brushed and powder-blown inorganic material, for example, at least calcium carbonate and calcium carbonate salt. The powder containing one of them may be dropped in advance.

[Surface anchor layer]
The surface anchor layer 1a is a layer formed so as to cover the entire surface of the raw fabric layer 1 and is a layer for preventing powder falling of the inorganic material contained in the raw fabric layer 1. If the inorganic material contained in the raw fabric layer 1 falls off in the printing system, specifically, in the printing apparatus during printing or resin coating, the inside of the printing system may be contaminated. Further, if the inorganic material contained in the raw fabric layer 1 is powdered off, problems such as ink loss may occur. Here, "ink missing" means that the ink is not partially printed.

Further, the surface anchor layer 1a also has a function for improving the adhesion between the raw fabric layer 1 and the ink forming the pattern pattern layer 2 described later. If the surface anchor layer 1a is not provided, the ink forming the pattern layer 2 may peel off without adhering to the original fabric layer 1.
The surface anchor layer 1a preferably contains a urethane-based resin containing vinyl acetate or an acrylic resin containing vinyl acetate. Here, "salt vinegar bi" means a copolymer of vinyl chloride and vinyl acetate. The "urethane resin containing salt vinegar" is a composition containing salt vinegar and urethane resin, and the ratio of the content of salt vinegar to the content of urethane resin (salt vinegar). The content (mass) of bi and the content (mass) of urethane resin may be in the range of 80/20 to 1/99, preferably in the range of 50/50 to 5/95, 20 It is more preferable if it is in the range of / 80 to 10/90.

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

The content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the surface anchor layer 1a is within the range of 15% by mass or more and 100% by mass or less with respect to the mass of the surface anchor layer 1a. It is more preferably in the range of 80% by mass or more and 100% by mass or less, and further preferably in the range of 85% by mass or more and 95% by mass or less. If the content of the urethane resin containing vinyl acetate or the acrylic resin containing 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 is increased. It is possible to form a uniform surface anchor layer 1a without unevenness or chipping while making the surface anchor layer sufficient. When the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the surface anchor layer 1a is less than 15% by mass with respect to the mass of the surface anchor layer 1a, the surface anchor layer 1a and The interlayer strength with the pattern layer 2 may be insufficient. Further, if the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the surface anchor layer 1a is less than 80% by mass with respect to the mass of the surface anchor layer 1a, there is no problem in use. Although there is no problem, the ratio of the surface anchor layer 1a to the raw fabric layer 1 is lowered, and the interlayer strength between the surface anchor layer 1a and the raw fabric layer 1 is slightly lowered. If the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the surface anchor layer 1a is 100% by mass or less with respect to the mass of the surface anchor layer 1a, there is no problem in use. However, if it exceeds 95% by mass, or more accurately 98% by mass, the surface anchor layer 1a may be chipped due to insufficient curing, or the surface anchor layer 1a and the raw fabric layer 1 or the surface anchor layer 1a and the pattern pattern. The interlayer strength with the layer 2 may decrease.

The content of the urethane resin containing salt vinegar in the front surface anchor layer 1a or the acrylic resin containing salt vinegar is the urethane resin containing salt vinegar or salt vinegar in the back surface anchor layer 1b described later. It may be the same as the content of the acrylic resin containing. That is, the content of the urethane resin containing salt and vinegar in the front surface anchor layer 1a or the acrylic resin containing salt and vinegar includes the urethane resin containing salt and vinegar or the salt and vinegar in the back surface anchor layer 1b. It may be 1.0 times (within the range of 0.95 times or more and 1.04 times or less) the content of the acrylic resin. The content of the urethane resin containing salt and vinegar in the front anchor layer 1a or the acrylic resin containing salt and vinegar is the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 1b. When the content is the same as the resin content, the physical properties of the front surface anchor layer 1a and the physical properties of the back surface anchor layer 1b are almost the same, so that the raw fabric layer 1 is provided with the front surface anchor layer 1a and the back surface anchor layer 1b. In, the occurrence of distortion, warpage, etc. can be reduced. Therefore, it is possible to reduce the occurrence of distortion and warpage of the entire decorative sheet. Further, since the coating liquid for forming the front surface anchor layer 1a and the coating liquid for forming the back surface anchor layer 1b can be shared, the manufacturing cost can be reduced and the work efficiency can be improved. be able to.

The content of the urethane resin containing salt vinegar or the acrylic resin containing salt vinegar in the front surface anchor layer 1a includes the urethane resin containing salt vinegar or salt vinegar in the back surface anchor layer 1b. It may be higher or lower than the content of the acrylic resin. The content of the urethane resin containing salt and vinegar in the front anchor layer 1a or the acrylic resin containing salt and vinegar is the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 1b. When the content is higher or lower than the resin content, the physical properties of the front surface anchor layer 1a and the physical properties of the back surface anchor layer 1b are different, so that the original fabric layer 1 provided with the front surface anchor layer 1a and the back surface anchor layer 1b is distorted. And warpage can be added. In this way, by imparting distortion, warpage, etc. to the raw fabric layer 1 provided with the front surface anchor layer 1a and the back surface anchor layer 1b, the raw fabric layer 1 is bonded to the base material or the like having a curved surface without gaps. be able to. For example, the content of the urethane resin containing salt and vinegar in the front surface anchor layer 1a or the acrylic resin containing salt and vinegar includes the urethane resin containing salt and vinegar or the salt and vinegar in the back surface 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. Further, 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 surface anchor layer 1a is the same as the thickness of the back surface anchor layer 1b, the physical properties of the front surface anchor layer 1a and the physical properties of the back surface anchor layer 1b are substantially the same, so that the original fabric layer 1 is the surface anchor layer 1a. In the state where the back surface anchor layer 1b is provided, it is possible to reduce the occurrence of distortion, warpage, and the like.
Further, 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 surface anchor layer 1a different from the thickness of the back surface anchor layer 1b, a difference in gloss is generated, so that the front surface side and the back surface side of the original fabric layer 1 can be easily visually recognized. By doing so, the pattern pattern layer 2 can be printed on the surface of the original fabric layer 1 without forming, for example, an identification mark indicating that it is a printing surface. As a result, product loss caused by forming the pattern layer 2 on the back surface (non-printing surface) side of the original fabric layer 1 can be reduced.

[Pattern pattern layer 2]
On the surface of the original fabric layer 1 (surface anchor layer 1a), a pattern pattern layer 2 on which an arbitrary pattern is printed is provided. The type of the pattern formed by the pattern pattern layer 2 is not particularly limited, and is, for example, a wood grain pattern, a stone grain pattern, a cloth grain pattern, a sand grain pattern, an abstract pattern, a geometric figure, a character or a symbol, or a combination thereof. The type of printing ink used for forming the pattern layer 2 is not particularly limited, and a known printing ink used for forming a decorative sheet can be used. Specifically, for example, for binder resins such as polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, butyral, acrylic, urethane, polyester, epoxy, alkyd, and polyamide. Organic or inorganic dyes or pigments, and if necessary, extender pigments, fillers, tackifiers, dispersants, antifoaming agents, stabilizers and other additives are appropriately added, and a suitable diluting solvent is used to obtain the desired viscosity. It may be a adjusted printing ink.

[Adhesive layer 5]
An adhesive layer 5 is formed on the pattern layer 2. The adhesive layer 5 may be formed by applying a composition for forming the adhesive layer 5 on the 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 the transparent thermoplastic resin contained in the transparent thermoplastic resin layer 6. ..

[Transparent thermoplastic resin layer 6]
The transparent thermoplastic resin layer 6 is a layer on which embossing is formed, and is, for example, a sheet-like layer composed 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 pattern layer 2 can be seen through. The thermoplastic resin contained in the transparent thermoplastic resin layer 6 may be transparent, and may be, for example, various resins other than vinyl chloride resin. Various combinations of resins of 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 up to three layers is preferable because the structure of the extruder becomes complicated and the work becomes complicated. Of course, it may be two layers or one layer.

The thickness of the transparent thermoplastic resin layer 6 is preferably in the range of 50 μm or more and 150 μm or less. When the thickness of the transparent thermoplastic resin layer 6 is within the above numerical range, high transparency is maintained, so that deterioration of visibility with respect to the pattern layer 2 can be prevented, and sufficient abrasion resistance can be obtained. Further, when the thickness of the transparent thermoplastic resin layer 6 is within the above numerical range, the flexibility and mechanical strength of the decorative sheet 10 are not impaired, and the processability to a decorative board such as in-line roll laminating is not impaired. Furthermore, it is easy to use because it does not interfere with the workability of the decorative board.
In FIG. 1, the transparent thermoplastic resin layer 6 is composed of a first resin layer 6a and a first resin layer 6a formed by containing a predetermined resin (hereinafter, also referred to as “first resin”) from the adhesive layer 5 side. Two layers of the second resin layer 6b, which is composed of a resin different from the resin of 1 (hereinafter, also referred to as “second resin”), are laminated in this order.

In the present embodiment, the thickness of the first resin layer 6a may be 10 μm or more, and may be 20% or less of the thickness of the entire 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 plane smoothness is lowered, so that the adhesion stability of the first resin layer 6a tends to be lowered.
Further, if the thickness of the first resin layer 6a exceeds 20% of the thickness of the entire transparent thermoplastic resin layer 6, the thickness of the second resin layer 6b having excellent wear resistance becomes relatively thin. The surface strength of the entire decorative sheet 10 tends to decrease. That is, if the thickness of the first resin layer 6a is 10 μm or more and 20% or less of the thickness of the entire transparent thermoplastic resin layer 6, the makeup is made while maintaining the adhesion stability of the first resin layer 6a. 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 the thickness of the entire transparent thermoplastic resin layer 6 composed of only two layers of the first resin layer 6a and the second resin layer 6b is 20. % 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 polypropylene resin with respect to the first resin layer 6a may be larger than the content rate (mass%) of the transparent polypropylene resin with respect to 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. Further, in the above configuration, the first resin layer 6a secures the adhesiveness with the adhesive layer 5, and the second resin layer 6b becomes the main part and bears other physical properties. It becomes possible to widen the width of. That is, by using transparent maleic acid-modified polypropylene for the first resin layer 6a, the adhesiveness between the layers can be improved. Further, by forming the second resin layer 6b as a layer containing transparent polypropylene, the effect of embrittlement resistance inside the resin can be exhibited.

As the first resin and the second resin, for example, in consideration of scratch resistance, weather resistance, stain resistance, light resistance, transparency, bendability, thermoforming property, etc. of the surface of the decorative sheet 10, further materials are used. 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. The first resin layer 6a may be a layer composed of either a ultraviolet absorber or a light stabilizer together with the transparent maleic acid-modified polypropylene resin which is the first resin. Further, the second resin layer 6b may be a layer composed of either a ultraviolet absorber or a light stabilizer together with the transparent polypropylene resin which is the second resin.

The transparent polypropylene resin of the present embodiment is, for example, a mixture of a polypropylene resin (a) having a free-ended long-chain branch and a polypropylene resin (b) not having a free-ended long-chain branch. The molecular weight distribution Mw / Mn defined as the mass average molecular weight / number average molecular weight of is in the range of 1 or more and 5 or less, and the mixed resin of the polypropylene resin (a) and the polypropylene resin (b) can be boiled heptane. An isotactic index defined as the undissolved residue ratio may be used in the range of 1% or more and 90% or less. As a result, whitening and cracking can be suppressed in the bending process after the decorative sheet 10 is attached to the steel plate base material, for example.

Here, the molecular weight distribution is such that when two molecules having a molecular weight Mi are present, the number average molecular weight Mn = Σ (Mi × Ni) / ΣNi and the mass average molecular weight Mw = Σ (Ni × Mi2) / Σ (Ni × Mi). ), A value defined as Mw / Mn. The closer it is to 1, the narrower the distribution of molecular weight and the higher the uniformity. If 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 the suppression of whitening and cracking. In general, the molecular weight distribution can be measured by gel permeation chromatography (GPC).

In addition, the isotactic index defined as the boiling heptane-soluble residue ratio is useful as an index for examining the crystallinity in the polypropylene resin. Specifically, the sample is extracted with boiling n-heptane for a certain period of time, and the mass (%) of the unextracted portion is calculated to calculate the isotactic index. Specifically, the cylindrical filter paper is dried at 110 ± 5 ° C. for 2 hours, left in a room at a constant temperature and humidity for 2 hours or more, and then 8 g or more and 10 g or less of a sample (powder or flakes) is placed in the cylindrical filter paper and weighed. Weigh accurately using a cup and tweezers. Set this on the top of the extractor containing about 80 cc of heptane, and assemble the extractor and cooler. This is heated in an oil bath or an 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 cylindrical filter paper containing the extraction residue is taken out, placed in a vacuum dryer, and dried at 80 ° C. and a vacuum degree of 100 mmHg or less for 5 hours. After drying, the mixture is allowed to stand in a constant temperature and humidity for 2 hours, then precisely weighed, and the isotactic index is calculated by (P / Po) × 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, the seat rigidity due to polypropylene crystals can be suppressed. As a method of lowering the isotactic index, for example, a method of partially using an amorphous polypropylene component (syndiotactic polypropylene, adaptive polypropylene, etc.) or one or more types of olefin monomers such as ethylene and α-olefin are used. Random copolymerization method, various rubber components (eg ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), butadiene rubber (BR)) , A component such as isoprene rubber (IR)) can be used.

Further, when the melt tension of a mixed resin of polypropylene resin (a) and polypropylene resin (b) is extruded at a temperature condition of 230 ° C. and 60 mm / min using a nozzle capillary reometer having a diameter of 2.0 mm and taken up at 2 mm / min. The tension) is preferably in 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 cannot be performed. Further, when it is 100 mN or less, the long chain branching component becomes insufficient, and it is difficult to obtain the desired performance.

Further, the molecular weight of the mixture of the polypropylene resin (a) and the polypropylene resin (b) is set within the range of 5 g / 10 min or more and 50 g / 10 min or less at 230 ° C. defined by JIS-K6760. It is possible to maintain a stable film-forming state above a certain value. A more preferable range of the melt flow rate is in the range of 10 g / 10 min or more and 30 g / 10 min or less, and more preferably in the range of 10 g / 10 min or more and 25 g / 10 min or less. When the melt flow rate exceeds 50 g / 10 min, the effect (neck-in) that the resin melt-extruded from the T-die tends to gather in the center during melt-extrusion by the T-die becomes large, and the resin is melt-extruded from the T-die. The thickness of the end of the resin increases. An increase in the thickness of the end affects the decrease in cooling efficiency and the thickness stability in the width direction, which makes it difficult to form a stable film. If it is lower than 5 g / 10 min, the draw resonance of the molten resin deteriorates, and the molten resin fills the gap between the velocity of the molten resin immediately after exiting the T-die (initial velocity) and the velocity of the resin immediately after touching the cooling roll. However, it becomes difficult to form a stable film.

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

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

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

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

Further, as the flame retardant, for example, an inorganic compound such as aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, a phosphoric acid ester flame retardant, or the like can be used. Further, as the blocking inhibitor, for example, an inorganic blocking inhibitor such as aluminum silicate, silicon oxide, hydrotalcite, calcium carbonate, or an organic blocking inhibitor such as fatty acid amide can be used. The thickness of the transparent thermoplastic resin layer 6 is preferably in the range of 50 μm or more and 150 μm or less.

(Embossed pattern)
The embossed pattern 9 is, for example, a pattern composed of concave portions and convex portions synchronized with the pattern of the pattern pattern layer 2. The concave and convex portions of the embossed pattern 9 make it possible to give a three-dimensional effect by visual or tactile sensation. The deviation between the embossed pattern 9 and the pattern of the pattern pattern layer 2 is preferably within a range of 10 mm or less in the longitudinal direction and 3 mm or less in the lateral direction (width direction) with respect to the shape of the pattern. .. For example, when the pattern is wood grain, the direction in which the wood grain conduit extends is the "longitudinal direction with respect to the shape of the pattern", and the direction orthogonal to the longitudinal direction is the "short direction with respect to the shape of the pattern". Become. In particular, when the wood grain conduit extends along the longitudinal direction of the decorative sheet 10, the longitudinal direction of the decorative sheet 10 is the "longitudinal direction with respect to the shape of the pattern", and the lateral direction (width direction) of the decorative sheet 10 ) Is the "short direction with respect to the shape of the pattern". Since the transparent thermoplastic resin layer 6 and the surface protection layer 7 are transparent, the embossed pattern 9 is strongly visible for the first time due to the reflection of oblique light, but the deviation between the embossed pattern 9 and the pattern layer 2 is within the above range. If this is the case, it is difficult to visually recognize the transmitted light of the pattern layer 2 at the same time as the reflected light, so that there is no sense of discomfort. By suppressing the deviation between the embossed pattern 9 and the pattern of the pattern pattern layer 2 within a certain range, it is possible to obtain a decorative sheet 10 in which the shape and distribution of the patterns are equal and accurately matched on the entire surface of the sheet. Further, the height difference between the concave portion and the convex portion of the embossed pattern 9 is, for example, within the range of 3 μm or more and 200 μm or less. For the height difference, a numerical value suitable for the design of the target decorative sheet 10 can be selected. For example, it is possible to take a continuous multi-stage shape within the maximum height difference (200 μm). In particular, in order to obtain a shape as a macroscopic three-dimensional object, the height difference is more preferably in the range of 10 μm or more and 150 μm or less.

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

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

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

[Back anchor layer]
The back surface anchor layer 1b is a layer formed so as to cover the entire back surface of the raw fabric layer 1 and is a layer for preventing powder falling of the inorganic material contained in the raw fabric layer 1. If the inorganic material contained in the raw fabric layer 1 falls off in the printing system, specifically, in the printing apparatus during printing or resin coating, the inside of the printing system may be contaminated.
Further, the back surface anchor layer 1b also has a function for improving the adhesion between the raw fabric layer 1 and the primer layer 8 described later. If the back surface anchor layer 1b is not provided, the coating liquid forming the primer layer 8 may peel off without adhering to the raw fabric layer 1.
The back surface 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 salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 1b is, for example, in the range of 15% by mass or more and 100% by mass or less with respect to the mass of the back surface anchor layer 1b. Is preferable, the range of 80% by mass or more and 100% by mass or less is more preferable, and the range of 85% by mass or more and 95% by mass or less is further preferable. If the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the back surface anchor layer 1b is within the above numerical range, the interlayer strength between the back surface anchor layer 1b and the primer layer 8 is sufficient. It is possible to form the back surface anchor layer 1b which is uniform and has no unevenness or chipping. When the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 1b is less than 15% by mass with respect to the mass of the back surface anchor layer 1b, the back surface anchor layer 1b and the back surface anchor layer 1b The interlayer strength with the primer layer 8 may be insufficient. Further, if the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 1b is less than 80% by mass with respect to the mass of the back surface anchor layer 1b, there is no problem in use. Although there is no problem, the ratio of the back surface anchor layer 1b to the original fabric layer 1 decreases, and the interlayer strength between the back surface anchor layer 1b and the original fabric layer 1 decreases slightly. If the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 1b is 100% by mass or less with respect to the mass of the back surface anchor layer 1b, there is no problem in use. However, if it exceeds 95% by mass, or more accurately 98% by mass, the back surface anchor layer 1b may be chipped due to insufficient curing, or the back surface anchor layer 1b and the original fabric layer 1 or the back surface anchor layer 1b and the primer layer may be chipped. The interlayer strength with 8 may decrease.
The thickness of the back surface anchor layer 1b is, for example, in the range of 0.5 μm or more and 20 μm or less, and preferably in the range of 0.5 μm or more and 10 μm or less.

[Primer layer 8]
As the primer layer 8, for example, a polyester resin, a polyurethane resin, a mixture thereof, or the like can be used. Further, by adopting a two-component type using polyol and isocyanate, the adhesion between the raw fabric layer 1 (back surface anchor layer 1b) and the primer layer 8 and the cohesive force of the primer layer 8 itself are improved. Examples of the polyol include an acrylic polyol and a polyester polyol. Examples of the isocyanate include aromatic systems such as tolylene diisocyanate and 4,4'diphenylmethane diisocyanate, and aliphatic systems such as hexamethylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate. Aromatic polyols are preferable in terms of quick reactivity and heat resistance.
The thickness of the primer layer 8 is preferably 1 μm or more. If the thickness of the primer layer 8 is less than 1 μm, it may be dissolved depending on the solvent type of the adhesive, and the primer layer 8 disappears, so that the adhesiveness may not be improved.

(Manufacturing method of decorative sheet 10)
Hereinafter, an example of a method for manufacturing the decorative sheet 10 will be briefly described.
First, anchor layers (front surface anchor layer 1a and back surface anchor layer 1b) are formed on both surfaces of the raw fabric layer 1. Next, the pattern layer 2 is formed on the surface anchor layer 1a by printing, for example.
Then, a plurality of layers formed by extruding a resin composition containing a molten transparent thermoplastic resin from a multilayer extruder are laminated on the pattern layer 2, whereby the transparent thermoplastic resin layer 6, that is, the first The resin layer 6a and the second resin layer 6b are formed. Next, the transparent thermoplastic resin layer 6 is embossed. Finally, a resin composition obtained by adding a curing agent, an ultraviolet absorber, and a light stabilizer to, for example, a urethane resin is applied onto the embossed transparent thermoplastic resin layer 6, and then the resin composition is applied. Is dried to form the surface protective layer 7. In this way, the decorative sheet 10 according to the present embodiment is manufactured.
The method for producing the decorative sheet 10 according to the present embodiment may include a step of forming an adhesive layer 5 between the pattern layer 2 and the transparent thermoplastic resin layer 6.

(Effect of this embodiment)
In the decorative sheet 10 of the present embodiment, a pattern layer 2, an adhesive layer 5, a transparent thermoplastic resin layer 6, and a surface protective layer 7 are laminated in this order on the 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 the range of 15% by mass or more and 90% by mass or less with respect to the mass of the raw fabric layer 1. Is. The thickness of the transparent thermoplastic resin layer 6 is in the range of 50 μm or more and 150 μm or less. Further, the surface protective layer 7 contains an ultraviolet curable resin.
With such a configuration, it is possible to provide a decorative sheet having scratch resistance and abrasion resistance equivalent to those of a decorative sheet provided with a melamine plate, and having excellent processability and productivity.

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 is formed by including the first resin, and the first resin layer 6a and the first resin. It may include a second resin layer 6b formed on the layer 6a and containing a second resin different from the first resin. 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 secures the adhesiveness with the raw fabric layer 1, and the second resin layer 6b becomes the main part of the layer and bears other physical properties. It is possible to expand the range of design. By forming the first resin layer 6a as a layer containing a transparent maleic acid-modified polypropylene resin, the adhesiveness with the thermoplastic resin can be improved. Further, by forming the second resin layer 6b as a layer containing a transparent polypropylene resin, the effect of embrittlement resistance inside the second resin layer 6b can be exhibited.

Further, the thickness of the first resin layer 6a provided on the decorative sheet 10 of the present embodiment may be 10 μm or more and 20% or less of the thickness of the entire 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 raw fabric layer 1 provided in the decorative sheet 10 of the present embodiment has a powder shape, 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 may.
With such a configuration, sufficient surface strength can be imparted to the raw fabric layer 1.

The inorganic materials constituting the raw fabric layer 1 provided in the decorative sheet 10 of the present embodiment include antimony trioxide, antimony soda, zircate silicate, zircon oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, and borosand. Zinc borate, calcium carbonate, molybdenum trioxide or antimony dimolybate and aluminum hydroxide complex, antimony trioxide and silica complex, antimony trioxide and zinc flower complex, silicic acid of zirconium, and zirconium compounds And antimony trioxide, as well as 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 provided in the decorative sheet 10 of the present 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 the inorganic material constituting the raw fabric layer 1 provided in 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.

Further, the thickness of the raw fabric layer 1 provided in the decorative sheet 10 of the present embodiment may be in the range of 50 μm or more and 250 μm or less.
With such a configuration, sufficient surface strength can be imparted to the raw fabric layer 1.
Further, the front surface anchor layer 1a and the back surface anchor layer 1b provided on the decorative sheet 10 of the present embodiment may each contain a urethane resin containing vinyl acetate or an acrylic resin containing vinyl acetate.
With such a configuration, it is possible to prevent the inorganic material from falling off.

Further, the decorative sheet 10 of this embodiment, the exothermic test by conforming to ISO5660-1 cone calorimeter testing machine (1) total amount of heat generated by the heating start after 20 minutes (MJ / ^{m 2)} is 8 MJ / ^{m 2} It has the following (2) maximum heat generation rate for 20 minutes after the start of heating, ^{does not exceed 200 kW / m 2} continuously for 10 seconds or more, and (3) has nonflammability that satisfies the condition that there are no cracks or holes in the substrate. 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. The silica content was 15% by mass with respect to the mass of the raw fabric layer 1. Further, the thickness of the raw fabric layer 1 was set to 45 μm.
Next, a wood grain pattern was printed on the surface anchor layer 1a by a gravure printing method to form a pattern layer 2.
Subsequently, a urethane resin-based adhesive was applied onto the pattern layer 2, and the adhesive layer 5 was formed by warm air drying.

Subsequently, a plurality of layers containing the melted transparent thermoplastic resin were extruded from the multi-axis extruder with a T-die and laminated on the adhesive layer 5 to form the transparent thermoplastic resin layer 6. The first resin is a transparent polypropylene resin containing 0.2 parts by mass of a phenolic antioxidant (“IRGANOX1010” manufactured by Ciba Specialty Chemicals Co., Ltd.) and a hindered amine light stabilizer (“TINUVIN 622” manufactured by Ciba Specialty Chemicals Co., Ltd.). A resin containing 0.3 parts by mass of) and 0.5 parts by mass of a benzotriazole-based ultraviolet absorber (“TINUVIN326” manufactured by Ciba Specialty Chemicals Co., Ltd.) was used, and the second resin was modified with transparent maleic acid. Polypropylene resin (manufactured by RIKEN Vitamin Co., Ltd.) was used.

At the same time, embossing and laminating were performed at the same time by niping the laminated body of the raw fabric layer 1, the pattern layer 2, the adhesive layer 5, and the transparent thermoplastic resin layer 6 by the conduit embossing plate and the rubber roll. Here, the thickness of the first resin layer 6a was set to 8 μm, and the thickness of the second resin layer 6b was set to 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 curing agent (“UR150B varnish” manufactured by Toyo Ink Co., Ltd.) is applied to a urethane resin (“URV238 varnish” manufactured by Toyo Ink Co., Ltd.) as a top coat resin. To add 10 parts by mass, 0.5 parts by mass of a benzotriazole-based ultraviolet absorber (“TINUVIN326” manufactured by Ciba Specialty Chemicals Co., Ltd.) and a hindered amine-based light stabilizer (“TINUVIN622” manufactured by Ciba Specialty Chemicals Co., Ltd.) 1 part by mass was added and coated with a varnish coat so that the coating amount after drying was 5 g / m ² to obtain a surface protective layer 7.

Further, after surface treatment was applied to the back surface of the raw fabric layer 1, a back surface 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 surface anchor layer 1b to contain isocyanate (“LPNYB” manufactured by Toyo Ink Co., Ltd.). A primer coating solution was prepared by adding 3 parts by mass of a curing agent, and coated with a gravure coat so that the coating amount after drying was 3 g / m ² to obtain a primer layer 8.
By such a procedure, the decorative sheet of Example 1 was formed.

[Example 2]
A decorative sheet was formed in the same manner as in Example 1 except that the 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 silica content was 90% by mass with respect to the mass of the raw 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 set to 150 μm.

[Example 5]
A transparent maleic acid-modified polypropylene resin (manufactured by RIKEN Vitamin Co., Ltd.) is used as the first resin, and a phenolic antioxidant (manufactured by Ciba Specialty Chemicals Co., Ltd.) is used as the second resin. 0.2 parts by mass, hindered amine-based light stabilizer (“TINUVIN622” manufactured by Ciba Specialty Chemicals Co., Ltd.), 0.3 parts by mass, benzotriazole-based ultraviolet absorber (“TINUVIN326” manufactured by Ciba Specialty Chemicals Co., Ltd.” ) Was added in an amount of 0.5 parts by mass, and a decorative sheet was formed in the same manner as in Example 1.

[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 size of silica was 1 μm.
[Example 8]
A decorative sheet was formed in the same manner as in Example 1 except that the average particle size of silica was 3 μm.

[Example 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 a calcium carbonate salt.

[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 the thermoplastic resin contained in the raw fabric layer 1 was polyethylene.
[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 raw 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 raw fabric layer 1 was 250 μm.

[Example 18]
The inorganic material contained in the raw fabric layer 1 is calcium carbonate, the average particle size 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, a transparent maleic acid-modified polypropylene resin (manufactured by RIKEN Vitamin Co., Ltd.) is used as the first resin, and a phenolic antioxidant (phenolic antioxidant) is used as the second resin. 0.2 parts by mass of "IRGANOX1010" manufactured by Ciba Specialty Chemicals Co., Ltd., 0.3 parts by mass of hindered amine light stabilizer ("TINUVIN622" manufactured by Ciba Specialty Chemicals Co., Ltd.), benzotriazole ultraviolet absorber (Ciba) 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 silica content was 13% by mass with respect to the mass of the raw fabric layer 1.
[Comparative Example 2]
A decorative sheet was formed in the same manner as in Example 1 except that the silica content was 92% by mass with respect to the mass of the raw 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 described below.
<Evaluation items>
An ethylene-vinyl acetate copolymer emulsion type adhesive was applied to a 6 mm MDF (medium density fiberboard), and a decorative sheet and a laminated decorative board were obtained. Then, the following tests were carried out using the decorative board and the decorative sheet alone of each Example and each Comparative Example.

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

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

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

[Machinability]
The decorative board was cut with a circular saw and a cutting test was performed using a hand router to reach the MDF surface, and the presence or absence of burr on the sheet was confirmed.
⊚: No burr occurs.
◯: Some burrs are seen, but can be easily corrected.
Δ: Some burrs are seen and need to be corrected.
×: Burrs are generated on almost the entire surface, and it is difficult to correct them manually.

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

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

As shown in Table 1, the decorative sheet according to the present embodiment is a decorative sheet having scratch resistance and abrasion resistance, and also excellent in processability and productivity. Further, the decorative sheet according to this embodiment also has nonflammability.

The decorative sheet of the present embodiment and the decorative sheet produced by the method for manufacturing the decorative sheet of the present embodiment include interiors such as floors, walls and ceilings of buildings, furniture, surface decorative materials such as various cabinets, and surfaces of fittings. It can be used for surface makeup used for makeup, vehicle interiors, etc.

1: Raw fabric layer (base material layer)
1a: Surface anchor layer (first anchor layer)
1b: Back surface anchor layer (second anchor layer)
2: Pattern 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 protection layer 8: Primer layer 9: Embossed pattern 10: Decorative sheet

Claims (10)

A pattern layer, an adhesive layer, a transparent thermoplastic resin layer, and a surface protective layer are laminated in this order on the base material layer.
The base material layer contains a thermoplastic resin and an inorganic material.
The content of the inorganic material is in the range of 15% by mass or more and 90% by mass or less with respect to the mass of the base material layer.
The thickness of the transparent thermoplastic resin layer is in the range of 50 μm or more and 150 μm or less.
The surface protective layer is a decorative sheet containing an ionizing radiation curable resin. The transparent thermoplastic resin layer is formed on the adhesive layer side, the first resin layer formed including the first resin, and the first resin layer. A second resin layer formed containing a second resin different from the above is provided.
The first resin is a transparent maleic acid-modified polypropylene resin.
The decorative sheet according to claim 1, wherein the second resin is a transparent polypropylene resin. The decorative sheet according to claim 2, wherein the thickness of the first resin layer is 10 μm or more and 20% or less of the thickness of the entire transparent thermoplastic resin layer. Any one of claims 1 to 3, wherein the inorganic material has a powder shape, 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. Cosmetic sheet described in. The inorganic materials include antimony trioxide, antimony soda, zircon silicate, zircon oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borosand, zinc borate, calcium carbonate, molybdenum trioxide or antimony dimolybate and water. A complex with aluminum oxide, a complex with antimony trioxide and silica, a complex with antimony trioxide and zinc flower, a silicic acid of zirconium, and a complex with a zirconium compound and antimony trioxide, and at least one of their salts. The decorative sheet according to any one of claims 1 to 4, wherein the decorative sheet is characterized by the above. The decorative sheet according to any one of claims 1 to 5, wherein the thermoplastic resin contained in the base material layer is at least one of polypropylene, polyethylene and polyester. The total content of the thermoplastic resin contained in the base material layer and the inorganic material is in the range of 90% by mass or more and 100% by mass or less with respect to the mass of the base material layer. The decorative sheet according to any one of claims 1 to 6. The decorative sheet according to any one of claims 1 to 7, wherein the thickness of the base material layer is within the range of 50 μm or more and 250 μm or less. A first anchor layer formed on the surface of the base material layer on the side of the pattern layer, and
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 of claims 1 to 8, wherein the first anchor layer and the second anchor layer each contain a urethane-based resin containing vinyl acetate or an acrylic resin containing vinyl acetate. Or the decorative sheet according to item 1. In the heat generation test by the cone calorimeter tester conforming to 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) 20 minutes after the start of heating. Claims 1 to 9 are characterized in that the maximum heat generation rate of the ^{above is not exceeding 200 kW / m 2} continuously for 10 seconds or more, and (3) has nonflammability satisfying the condition that there are no cracks or holes in the base material. The decorative sheet according to any one of the above.

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