JP7434823B2 - makeup sheet - Google Patents

Description

The present invention relates to a decorative sheet.

Conventionally, decorative sheets used in areas where scratch resistance and abrasion resistance are required have mainly 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.
In addition, decorative sheets are generally commercialized as decorative boards by pasting them onto a plate-shaped base material, and are often installed on-site, and in that case, machinability and other workability are also required. become.

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 with adhesives and has excellent workability such as cutting workability and yield.

In order to solve the above problems, a decorative sheet according to one aspect of the present invention includes a thermoplastic resin base sheet, a picture pattern layer, a first adhesive layer, a polyester resin layer, a second adhesive layer, a transparent A thermoplastic resin layer and a surface protective layer are laminated in this order, and at least the transparent thermoplastic resin layer is embossed, and the thickness of the transparent thermoplastic resin layer is within the range of 50 μm or more and 150 μm or less. Yes, the polyester resin layer is biaxially stretched, and the thickness of the polyester resin layer is in the range of 100 μm or more and 200 μm or less, and the thickness of the polyester resin layer and the transparent thermoplastic resin are The total thickness of the layers is in the range of 200 μm or more and 300 μm or less, and the surface protective layer contains an ionizing radiation-curable resin.

Further, a decorative sheet according to another aspect of the present invention includes a pattern layer, a first adhesive layer, a polyester resin layer, a second adhesive layer, a transparent thermoplastic resin layer, on a thermoplastic resin base sheet, and a surface protective layer are laminated in this order, at least the transparent thermoplastic resin layer is embossed, the thickness of the transparent thermoplastic resin layer is within the range of 50 μm or more and 150 μm or less, and the polyester-based The resin layer contains polyethylene terephthalate and is an unstretched layer, and the thickness of the polyester resin layer is within the range of 150 μm or more and 300 μm or less, and the thickness of the polyester resin layer and the transparent heat The total thickness of the plastic resin layer is in the range of 200 μm or more and 350 μm or less, and the surface protective layer contains an ionizing radiation curable resin.

Further, a decorative sheet according to another aspect of the present invention includes a pattern layer, a first adhesive layer, a polyester resin layer, a second adhesive layer, a transparent thermoplastic resin layer, on a thermoplastic resin base sheet, and a surface protective layer are laminated in this order, at least the transparent thermoplastic resin layer is embossed, the thickness of the transparent thermoplastic resin layer is within the range of 50 μm or more and 150 μm or less, and the polyester-based The resin layer is a layer containing polybutylene terephthalate, and the thickness of the polyester resin layer is within the range of 50 μm or more and 200 μm or less, and the thickness of the polyester resin layer and the transparent thermoplastic resin layer are in the range of 50 μm or more and 200 μm or less. The total thickness is within a range of 140 μm or more and 350 μm or less, and the surface protective layer contains an ionizing radiation-curable resin.

The decorative sheet according to one embodiment of the present invention has scratch resistance and abrasion resistance equivalent to that of a decorative sheet provided with a melamine board, and also has excellent processability such as cutting workability and yield. It becomes possible to provide

FIG. 1 is a cross-sectional view showing the configuration of a decorative sheet according to an embodiment of the present invention. It is a sectional view showing the composition of the decorative sheet concerning other embodiments 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)
An example of the structure of the decorative sheet 10 of this embodiment is shown in FIGS. 1 and 2. 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 has a pattern layer 2, a first adhesive layer 3, a polyester resin layer 4, a second adhesive layer 5, and a transparent thermoplastic resin layer 6 (6a, 6b) on a thermoplastic resin base sheet 1. ), and the surface protection layer 7 are laminated in this order. Further, at least the transparent thermoplastic resin layer 6 has an embossment 9 formed thereon. Moreover, the thickness of the transparent thermoplastic resin layer 6 is within the range of 50 μm or more and 150 μm or less.

The polyester resin layer 4 is biaxially stretched, and the thickness of the polyester resin layer 4 may be in the range of 100 μm or more and 200 μm or less. Moreover, the total value of the thickness of the polyester resin layer 4 and the thickness of the transparent thermoplastic resin layer 6 may be within the range of 200 μm or more and 300 μm or less.
Further, the polyester resin layer 4 may contain polyethylene terephthalate and may be a non-stretched layer. Further, the thickness of the polyester resin layer 4 may be within the range of 150 μm or more and 300 μm or less. Moreover, the total value of the thickness of the polyester resin layer 4 and the thickness of the transparent thermoplastic resin layer 6 may be within the range of 200 μm or more and 350 μm or less. That is, the polyester resin layer 4 may be an unstretched layer containing polyethylene terephthalate, but in that case, the thickness of the polyester resin layer 4 should be within the range of 150 μm or more and 300 μm or less, and the polyester resin layer 4 may be an unstretched layer containing polyethylene terephthalate. It is preferable that the total value of the thickness of the resin layer 4 and the thickness of the transparent thermoplastic resin layer 6 be within the range of 200 μm or more and 350 μm or less.

Moreover, the polyester resin layer 4 is a layer containing polybutylene terephthalate, and the thickness of the polyester resin layer 4 may be within the range of 50 μm or more and 200 μm or less. Moreover, the total value of the thickness of the polyester resin layer 4 and the thickness of the transparent thermoplastic resin layer 6 may be within the range of 140 μm or more and 350 μm or less.
Moreover, the surface protection layer 7 contains an ionizing radiation curable resin such as an ultraviolet ray curable resin.
The transparent thermoplastic resin layer 6 is formed on the polyester resin layer 4 side and includes a first resin layer 6a, and is formed on the first resin layer 6a and contains the first resin. may 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.
[Thermoplastic resin base sheet 1]
The thermoplastic resin base sheet 1 of this embodiment can be made of various materials other than vinyl chloride resin. A polyolefin material to which a color pigment is added can be suitably used.

Examples of the resin used for the thermoplastic resin base sheet 1 include polyolefin resins such as polyethylene resin, polypropylene resin, polyptene resin, and polymethylpentene resin, ethylene-vinyl acetate copolymer or its saponified product, and ethylene-( Polyolefin copolymer resins such as meth)acrylic acid (ester) copolymers, polyethylene terephthalate resins, polybutylene terephthalate resins, polyethylene naphthalate resins, polyarylate resins, polycarbonate resins, copolymerized polyester resins (typically Polyester resins such as 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin (commonly known as PET-G), acrylic resins such as polymethyl methacrylate, 6-nylon, 6,6 nylon, 6,10 nylon , polyamide resins such as 12 nylon, styrene resins such as polystyrene, AS resin, and ABS resin, cellulose resins such as cellulose acetate and nitrocellulose, and chlorine-containing resins such as polyvinyl chloride and polyvinylidene chloride. or fluororesins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, or copolymers or mixtures of two or more selected from these. can.
The thermoplastic resin base sheet 1 may be formed by adding a coloring pigment, a filler, a stabilizer, etc. to the above-mentioned resin component to homogenize the dispersion, and then molding the mixture into a sheet shape.

[Picture pattern layer 2]
A picture pattern layer 2 on which an arbitrary picture is printed is provided on the surface of the thermoplastic resin base sheet 1. 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.
As a printing method for the picture pattern layer 2, for example, printing methods such as gravure printing, inkjet printing, flexographic printing, and screen printing are used. As the printing ink, a printing ink suitable for each printing method can be used.

[First adhesive layer 3]
A first adhesive layer 3 is formed on the picture pattern layer 2. The first adhesive layer 3 may be formed by applying a composition for forming the first adhesive layer 3 onto the picture pattern layer 2. The adhesive contained in the first adhesive layer 3 is arbitrarily selected from, for example, urethane-based, acrylic-based, polyester-based, etc., depending on the combination with the transparent thermoplastic resin contained in the transparent thermoplastic resin layer 6. It is possible.

[Polyester resin layer 4]
For the polyester resin layer 4, for example, polyethylene terephthalate, polybutylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene naphthalate, polylactic acid, etc. are used. In particular, polyethylene terephthalate and polybutylene terephthalate are preferably used. Further, in order to improve the adhesion with the first adhesive layer 3 and the surface protection layer 7, an easily bonding layer may be provided, or corona treatment may be applied as appropriate, for example.
The polyester resin layer 4 is preferably a layer subjected to biaxial stretching treatment. Further, the thickness of the polyester resin layer 4 is preferably within the range of 100 μm or more and 200 μm or less. If the thickness of the polyester resin layer 4 is within the above-mentioned numerical range, the machinability can be improved when cutting using a circular saw or a hand router.

The polyester resin layer 4 may be a layer containing polyethylene terephthalate resin in the above-mentioned resin, or may be a layer composed only of polyethylene terephthalate resin. Hereinafter, a case where the polyester resin layer 4 is made of polyethylene terephthalate resin, that is, a case where the polyester resin layer 4 is made of a polyethylene terephthalate resin layer 4a will be described. In addition, when the polyester resin layer 4 is a layer containing polyethylene terephthalate resin (polyethylene terephthalate resin layer 4a), the content of the polyethylene terephthalate resin is 30 mass with respect to the mass of the entire polyester resin layer 4. % or more, preferably 50% by mass or more, and more preferably 80% by mass or more.

The polyethylene terephthalate resin layer 4a may be formed of a film that has not been subjected to stretching treatment. In this embodiment, the thickness of the polyethylene terephthalate resin layer 4a made of a polyethylene terephthalate film that has not been subjected to stretching treatment is preferably within the range of 150 μm or more and 300 μm or less, and preferably within the range of 200 μm or more and 250 μm or less. More preferred.
When a polyethylene terephthalate film that has not been stretched is used for the polyethylene terephthalate resin layer 4a, the mechanical strength of the decorative sheet 10 can be improved, and the wear resistance when made into a decorative board is excellent. For example, machinability can be improved when cutting with a circular saw or a hand router. Further, if the thickness of the polyethylene terephthalate resin layer 4a is within the above numerical range, the machinability can be further improved when cutting using a circular saw or a hand router.

Moreover, the polyester resin layer 4 may be a layer containing polybutylene terephthalate resin in the above-mentioned resin, or may be a layer composed only of polybutylene terephthalate resin. Hereinafter, a case where the polyester resin layer 4 is made of polybutylene terephthalate resin, that is, a case where the polyester resin layer 4 is made of the polybutylene terephthalate resin layer 4b will be described. In addition, when the polyester resin layer 4 is a layer containing polybutylene terephthalate resin (polybutylene terephthalate resin layer 4b), the content of the polybutylene terephthalate resin is based on the mass of the entire polyester resin layer 4. , 30% by mass or more, preferably 50% by mass or more, and more preferably 80% by mass or more.

The polybutylene terephthalate resin layer 4b may be formed of, for example, a film that has not been subjected to stretching treatment. In this embodiment, the thickness of the polybutylene terephthalate resin layer 4b made of a polybutylene terephthalate film is preferably within the range of 50 μm or more and 200 μm or less, and more preferably within the range of 100 μm or more and 150 μm or less. If the thickness of the polybutylene terephthalate resin layer 4b made of a polybutylene terephthalate film is less than 50 μm, the abrasion resistance may be insufficient. Further, if the thickness of the polybutylene terephthalate resin layer 4b made of a polybutylene terephthalate film exceeds 200 μm, problems may arise in processability when the decorative sheet 10 is bonded to a base material.

The decorative sheet 10 including the above-mentioned polyethylene terephthalate resin layer 4a as the polyester resin layer 4 has sufficient performance even for heavy walking use. However, although the decorative sheet 10 having the polyethylene terephthalate resin layer 4a as the polyester resin layer 4 complies with the Type 1 immersion peel test stipulated in the JAS standard, it may whiten and may not be exposed to underfloor heating or strong sunlight. It may not be suitable for the intended use.
Here, the decorative sheet and decorative material described in Patent Document 1 solve the problem of unevenness caused by the adherend and the problem of cohesive failure of the heat insulating layer caused by temperature differences in the decorative sheet for flooring. At the same time, we have proposed decorative sheets and decorative materials that have excellent heat insulation properties, scratch resistance, and caster resistance.

In order to solve these problems, the decorative sheet described in Patent Document 1 has a synthetic resin backer layer and a foamed resin backer layer laminated on the back side of the decorative layer. However, in recent years, with the spread of floor heating, it has been pointed out that not only surface flooring materials are not required to have thermal insulation properties, but may even impede the effectiveness of floor heating.
On the other hand, the decorative sheet 10 including the polybutylene terephthalate resin layer 4b as the polyester resin layer 4 has heat resistance that can be used for floor heating.

[Second adhesive layer 5]
A second adhesive layer 5 is formed on the polyester resin layer 4. The second adhesive layer 5 may be formed by applying a composition for forming the second adhesive layer 5 on the polyester resin layer 4 . The adhesive contained in the second 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. It is.

[Transparent thermoplastic resin layer 6]
The transparent thermoplastic resin layer 6 is a layer on which embossments 9 are formed, and is, for example, a sheet-like layer consisting of multiple 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.

Examples of the thermoplastic resin used for the transparent thermoplastic resin layer 6 include low density polyethylene resin (LDPE), high density polyethylene resin (HDPE), linear low density polyethylene resin (LLDPE), polypropylene resin (PP), and polyolefin. Polyolefin resins such as elastomers, polyester resins such as polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), polyethylene naphthalate resin (PEN), polymethyl methacrylate resin (PMMA), ethylene-vinyl acetate resin Copolymer resin (EVA), ionomer resin, polybutene resin, polyacrylonitrile resin, polyamide resin such as nylon-6 and nylon-66, polystyrene resin (PS), polyvinyl chloride resin (PVC), polyvinylidene chloride Examples include synthetic resins such as resin (PVDC), polycarbonate resin (PC), fluororesin, and urethane resin.

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, as shown in FIG. 2, the transparent thermoplastic resin layer 6 may be two layers, or as shown in FIG. 1, the transparent thermoplastic resin layer 6 may be one layer.
In addition, when the pattern layer 2 has a wood grain, the emboss 9 may express the conduit of natural wood with a recess, and even when the pattern layer 2 has a grain other than wood grain, the design can be enhanced by using sand grain or geometric pattern unevenness. is possible. By forming the embossing 9 in this way, it is possible to give a three-dimensional effect to the surface of the decorative sheet 10 and improve the design. Furthermore, the embossing 9 may extend not only to the transparent thermoplastic resin layer 6 but also to other layers. Methods for forming the emboss 9 include a post-emboss method in which each layer is pasted together, the whole is heated and an embossing roll is pressed against it, or a simultaneous extrusion embossing method in which the transparent thermoplastic resin layer 6 is extruded from a T-die and pressed against an embossing roll. The law, etc. can be used. In this way, the embossing 9 may be formed before the surface protection layer 7 is formed, or may be formed after the surface protection layer 7 is formed.

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, and more preferably within the range of 100 μm or more and 120 μm or less. If the thickness of the transparent thermoplastic resin layer 6 is within the above numerical range, there will be no problem in forming the unevenness by the embossing 9, and the abrasion resistance will be within the practical range enough against physical abrasion. be. Alternatively, in terms of design, the presence of the transparent thermoplastic resin layer 6, together with the picture pattern layer 2, has the effect of giving a sense of depth and depth. Specifically, if the thickness of the transparent thermoplastic resin layer 6 is less than 50 μm, wear resistance and scratch resistance may not be obtained. On the other hand, if the thickness of the transparent thermoplastic resin layer 6 exceeds 150 μm, the productivity during manufacturing may be poor and it may be disadvantageous in terms of cost.

Moreover, the total value of the thickness of the polyester resin layer 4 and the thickness of the transparent thermoplastic resin layer 6 is preferably within the range of 200 μm or more and 300 μm or less. If the total thickness of the polyester resin layer 4 and the transparent thermoplastic resin layer 6 is within the above numerical range, both the flexibility and mechanical strength of the decorative sheet 10 will not be impaired, and the in-line This improves usability without affecting the processability of roll lamination and other decorative laminates, as well as the processability of decorative laminates.
In addition, when using a polyethylene terephthalate resin layer 4a made of a polyethylene terephthalate film that has not been subjected to stretching treatment as the polyester resin layer 4, the thickness of the polyethylene terephthalate resin layer 4a and the thickness of the transparent thermoplastic resin layer 6 are The total value including the thickness is preferably within the range of 200 μm or more and 350 μm or less. If the total thickness of the polyethylene terephthalate resin layer 4a and the transparent thermoplastic resin layer 6 is within the above numerical range, both the flexibility and mechanical strength of the decorative sheet 10 will not be impaired, and the in-line This improves usability without affecting the processability of roll lamination and other decorative laminates, as well as the processability of decorative laminates.

In addition, when using a polybutylene terephthalate resin layer 4b made of a polybutylene terephthalate film as the polyester resin layer 4, the thickness of the polybutylene terephthalate resin layer 4b and the thickness of the transparent thermoplastic resin layer 6 may be different. The total value is preferably within the range of 140 μm or more and 350 μm or less. If the total thickness of the polybutylene terephthalate resin layer 4b and the transparent thermoplastic resin layer 6 is less than 140 μm, there will be concerns about wear resistance. Furthermore, if the total thickness of the polybutylene terephthalate resin layer 4b and the transparent thermoplastic resin layer 6 exceeds 350 μm, problems may arise in suitability for roll lamination when processing into a decorative board. Further, if the total thickness of the polybutylene terephthalate resin layer 4b and the transparent thermoplastic resin layer 6 is within the above numerical range, both the flexibility and mechanical strength of the decorative sheet 10 will not be impaired. In addition, there is no problem with processability into decorative laminates such as in-line roll lamination, and the processability as decorative laminates, improving usability.

In FIG. 2, the transparent thermoplastic resin layer 6 includes, from the polyester resin layer 4 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. Further, the transparent thermoplastic resin layer 6 may be composed of only two layers, the first resin layer 6a and the second resin layer 6b.

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. Further, the thickness of the first resin layer 6a is preferably 50 μm or more, and more preferably 10% 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 adhesion stability of the first resin layer 6a tends to decrease. Further, if the thickness of the first resin layer 6a exceeds 20% of the thickness of the entire transparent thermoplastic resin layer 6, the surface strength of the entire decorative sheet 10 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, the adhesion stability of the first resin layer 6a can be maintained. , the surface strength of the entire decorative 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, the first resin layer 6a and the second resin layer 6b. 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 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. Specifically, the content (mass%) of the transparent maleic acid-modified polypropylene resin in the first resin layer 6a is 80% by mass or more, and the content (mass%) of the transparent polypropylene resin in the second resin layer 6b is 80% by mass or more. ) may be larger.

When the first resin layer 6a and the second resin layer 6b are provided, the first resin layer 6a ensures adhesiveness with the thermoplastic resin base sheet 1, and the second resin layer 6b It becomes possible to expand the scope of material design by becoming the main part and taking charge of other physical properties. By including the transparent maleic acid-modified polypropylene resin in the first resin layer 6a, interlayer adhesion can be improved. Furthermore, by forming the second resin layer 6b as a layer containing transparent polypropylene resin, the resistance to embrittlement inside the resin can be reduced.
In addition, as a method of forming the transparent thermoplastic resin layer 6 consisting of two layers, the first resin layer 6a and the second resin layer 6b, the first resin layer 6a and the second resin layer 6a are formed using a twin-screw extruder. A preferred method is to extrude and bond the two layers together with the resin layer 6b.

As described above, the first resin and the second resin may have properties such as scratch resistance, weather resistance, stain resistance, light resistance, transparency, bendability, thermoformability, etc. of the surface of the decorative sheet 10. Considering this, and further considering material costs, 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 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) The tension (tension) is preferably in the range of 100 mN or more and 500 mN or less, more preferably 300 mN or more and 400 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 resin melted and extruded from the T-die tends to collect in the center (neck-in) during melt extrusion using the T-die, and the effect (neck-in) becomes large. 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. Can be done.

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.

[Surface protective layer 7]
The surface protective layer 7 is located on the outermost surface of the decorative sheet 10 and serves to protect the decorative sheet 10 from direct external forces such as being hit by objects or being rubbed during movement. . In other words, the surface protective layer 7 improves the surface properties of the decorative sheet 10, imparts scratch resistance, stain resistance, slipperiness, etc. to the surface of the decorative sheet 10, and does not affect gloss, texture, etc. be.
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.

[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 thermoplastic resin base sheet 1 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, and preferably 10 μm or less. 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)
The method for manufacturing the decorative sheet 10 will be briefly described below.
First, the pattern layer 2 is formed on the thermoplastic resin base sheet 1 by, for example, printing.
Thereafter, a polyester resin layer 4 is laminated onto the picture pattern layer 2 by dry lamination. Next, a plurality of layers formed by extruding a resin composition containing a molten transparent thermoplastic resin from a multilayer extruder are laminated on the polyester resin layer 4, 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 the first adhesive layer 3 between the picture pattern layer 2 and the polyester resin layer 4. The process may also include a step of forming a second adhesive layer 5 between the polyester resin layer 4 and the transparent thermoplastic resin layer 6.

(Effects of this embodiment)
The decorative sheet 10 of this embodiment includes a thermoplastic resin base sheet 1, a picture pattern layer 2, a first adhesive layer 3, a polyester resin layer 4, a second adhesive layer 5, and a transparent thermoplastic resin layer 6. , and the surface protection layer 7 are laminated in this order. Further, at least the transparent thermoplastic resin layer 6 is embossed. Moreover, the thickness of the transparent thermoplastic resin layer 6 is within the range of 50 μm or more and 150 μm or less. The polyester resin layer 4 is biaxially stretched, and the thickness of the polyester resin layer 4 is within the range of 100 μm or more and 200 μm or less. The total thickness of the polyester resin layer 4 and the transparent thermoplastic resin layer 6 is in the range of 200 μm or more and 300 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 also has excellent processability and yield.

The decorative sheet 10 of this embodiment includes a thermoplastic resin base sheet 1, a picture pattern layer 2, a first adhesive layer 3, a polyester resin layer 4, a second adhesive layer 5, and a transparent thermoplastic resin layer 6. , and the surface protection layer 7 are laminated in this order. Further, at least the transparent thermoplastic resin layer 6 is embossed. Moreover, the thickness of the transparent thermoplastic resin layer 6 is within the range of 50 μm or more and 150 μm or less. The polyester resin layer 4 is an unstretched layer containing polyethylene terephthalate (polyethylene terephthalate resin layer 4a), and the thickness of the polyester resin layer 4 is within the range of 150 μm or more and 300 μm or less. The total thickness of the polyester resin layer 4 (polyethylene terephthalate resin layer 4a) and the transparent thermoplastic resin layer 6 is within the range of 200 μm or more and 350 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 also has excellent processability and yield.

The decorative sheet 10 of this embodiment includes a thermoplastic resin base sheet 1, a picture pattern layer 2, a first adhesive layer 3, a polyester resin layer 4, a second adhesive layer 5, and a transparent thermoplastic resin layer 6. , and the surface protection layer 7 are laminated in this order. Further, at least the transparent thermoplastic resin layer 6 is embossed. Moreover, the thickness of the transparent thermoplastic resin layer 6 is within the range of 50 μm or more and 150 μm or less. The polyester resin layer 4 is a layer containing polybutylene terephthalate (polybutylene terephthalate resin layer 4b), and the thickness of the polyester resin layer 4 is within the range of 50 μm or more and 200 μm or less. The total thickness of the polyester resin layer 4 (polybutylene terephthalate resin layer 4b) and the transparent thermoplastic resin layer 6 is within the range of 140 μm or more and 350 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 also has excellent processability and yield. Furthermore, even in applications where underfloor heating or strong sunlight is expected, whitening of the surface of the decorative sheet is less likely to occur, so it can be used as a decorative sheet for floor heating.

Further, the transparent thermoplastic resin layer 6 provided in the decorative sheet 10 of this embodiment is formed on the polyester resin layer 4 side, and includes a first resin layer 6a formed including a first resin, and a first resin layer 6a formed on the polyester resin layer 4 side. A second resin layer 6b formed on the resin 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 adhesiveness with the thermoplastic resin base sheet 1, and the second resin layer 6b becomes the main part of the layer and is responsible for other physical properties. This makes it possible to expand the scope of material design. By making the first resin layer 6a a layer containing a transparent maleic acid-modified polypropylene resin, the adhesiveness with the thermoplastic resin base layer can be improved. Further, by forming the second resin layer 6b as a layer containing transparent polypropylene resin, the resistance to embrittlement inside the second resin layer 6b can be reduced.

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 method for manufacturing the decorative sheet 10 of the present embodiment is the method for manufacturing the decorative sheet 10 described above, in which the pattern layer 2 is formed by printing on the thermoplastic resin base sheet 1, and the pattern layer 2 is formed by printing on the thermoplastic resin base sheet 1. After laminating the polyester resin layer 4 on the top layer 2 by dry lamination, a plurality of layers formed by extruding a resin composition containing a molten transparent thermoplastic resin from a multilayer extruder are laminated to form a transparent thermoplastic resin. A layer 6 is formed and the transparent thermoplastic resin layer 6 is embossed.
With this kind of structure, you can obtain the characteristics such as flexibility, stain resistance, chemical resistance, weather resistance, scratch resistance, and design properties, mainly transparency, which are obtained with vinyl chloride resin, and improve reproducibility. Excellent embossing can be formed.

(First example)
[Example 1-1]
A polyolefin-based inorganic filled sheet ("OW" manufactured by RIKEN TECHNOS Co., Ltd.) with a thickness of 55 μm was used as the thermoplastic resin base sheet 1, and a pattern layer 2 was formed by printing a wood grain pattern on the surface side by a gravure printing method. .
Next, on this picture pattern layer 2, biaxially stretched polyethylene terephthalate ("Lumirror T60" manufactured by Toray Industries, Inc.) having a thickness of 125 μm that has been previously subjected to a corona treatment is dry laminated, and the first adhesive layer 3 and polyester-based A resin layer 4 was formed.
Subsequently, a urethane resin adhesive was applied onto this polyester resin layer 4 and dried with warm air to form a second adhesive layer 5.

Subsequently, a transparent thermoplastic resin layer 6 was formed on the second adhesive layer 5 by extruding two layers of molten transparent thermoplastic resin using a T-die using a multi-axis extruder. For the first resin, a transparent maleic acid-modified polypropylene resin (manufactured by Riken Vitamin Co., Ltd.) was used, and for the second resin, a phenolic antioxidant (manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to 100 parts by mass of the polypropylene resin. 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 benzotriazole ultraviolet absorber ("TINUVIN622" manufactured by Ciba Specialty Chemicals Co., Ltd.) A resin to which 0.5 parts by mass of TINUVIN326) was added was used.

At the same time as forming the transparent thermoplastic resin layer 6 consisting of two layers, all the layers are nipped with a conduit embossing plate and a rubber roll to form a thermoplastic resin base sheet 1, a pattern layer 2, and a pattern layer 2 as shown in FIG. A laminate consisting of a first adhesive layer 3, a polyester resin layer 4, a second adhesive layer 5, and a transparent thermoplastic resin layer 6 was obtained. Here, the thickness of the first resin layer 6a was 15 μm, and the thickness of the second resin layer 6b was 85 μm.
After surface treatment was applied to the embossed surface of this laminate, a curing agent (UR150B manufactured by Toyo Ink Co., Ltd.) was added to 100 parts by mass of a urethane resin (URV238 Varnish manufactured by Toyo Ink Co., Ltd.) as a top coat resin. varnish"), 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 resin composition containing 1 part by mass of was applied by gravure coating so that the coating amount after drying was 5 g/m ² , and immediately cured by irradiation with ultraviolet rays to form the surface protective layer 7.

After surface treatment was applied to the back side of the thermoplastic resin base sheet 1, this surface was treated with 100 parts by mass of polyol ("Lamister EM" manufactured by Toyo Ink Co., Ltd.), 10 parts by mass of silica, and A resin composition containing 3 parts by mass of "LPNYB Curing Agent" (manufactured by Co., Ltd.) was used as a primer coating liquid, and was applied with gravure coating so that the coating amount after drying was 3 g/ ^m2 , and dried to form a primer layer. 8 was formed.
Through such a procedure, the decorative sheet 10 of Example 1-1 was formed.

[Example 1-2]
A decorative sheet 10 was formed in the same manner as in Example 1-1 except that the thickness of the polyester resin layer 4 was 188 μm.
[Example 1-3]
A decorative sheet 10 was formed in the same manner as in Example 1-1 except that the thickness of the polyester resin layer 4 was 100 μm.
[Example 1-4]
A decorative sheet 10 was formed in the same manner as in Example 1-1, except that the thickness of the polyester resin layer 4 was 125 μm and the thickness of the transparent thermoplastic resin layer 6 was 150 μm.
[Example 1-5]
A decorative sheet 10 was formed in the same manner as in Example 1-1 except that the thickness of the polyester resin layer 4 was 188 μm and the thickness of the transparent thermoplastic resin layer 6 was 50 μm.

[Comparative example 1-1]
A decorative sheet 10 was formed in the same manner as in Example 1-1, except that the polyester resin layer 4 was made of polyethylene terephthalate (A-PET) that had not been subjected to the stretching process.
[Comparative example 1-2]
A decorative sheet 10 was formed in the same manner as in Example 1-1, except that the thickness of the polyester resin layer 4 was 75 μm and the thickness of the transparent thermoplastic resin layer 6 was 150 μm.
[Comparative example 1-3]
A decorative sheet 10 was formed in the same manner as in Example 1-1, except that the thickness of the polyester resin layer 4 was 100 μm and the thickness of the transparent thermoplastic resin layer 6 was 200 μm.
[Comparative example 1-4]
A decorative sheet 10 was formed in the same manner as in Example 1-1, except that the thickness of the polyester resin layer 4 was 100 μm and the thickness of the transparent thermoplastic resin layer 6 was 75 μm.

The nine types of decorative sheets obtained above were bonded to a 6 mm thick MDF (medium density wood fiberboard) using an ethylene-vinyl acetate copolymer resin emulsion type adhesive to form a decorative board.
The following evaluation tests were conducted using decorative sheets and decorative boards.

[Abrasion resistance]
The decorative board was subjected to an abrasion tester specified in the Japanese Agricultural Standards (JAS) for flooring, and the number of revolutions until the pattern began to disappear was determined. The abrasive paper was replaced with a new one 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 If the evaluation is "△" or more, it is at a practical level, so it was judged as "pass".

[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 In addition, if the rating is "△" or higher, it is at a practical level, so It was marked as "passed".

[Workability]
We confirmed the methods that can be selected when processing decorative sheets into decorative boards.
◎: In-line roll lamination is possible. ○: In-line roll lamination is possible, but requires some caution in processing. △: In-line roll lamination is possible, but considerable care is required in processing. ×: Roll lamination is not possible. Only sheet lamination is possible. If the evaluation is "△" or higher, it is at a practical level, so it was judged as "passed".

[Cutability]
The decorative sheet was cut using a circular saw and cut to reach the MDF using a hand router, and the occurrence of burrs on the decorative sheet was confirmed.
◎: No burrs occur. ○: Some burrs are seen, but they can be easily corrected. △: Some burrs are seen, and correction is necessary. If the evaluation is ``△'' or higher, it is at a practical level, so it is judged as ``pass''.

〔Productivity〕
The ease of production when extruding and laminating the transparent thermoplastic resin layer 6 was confirmed.
◎: Stable production is possible ○: Although it is necessary to be more careful than ◎, stable production is possible. △: During long-run production, there is a possibility that the roll may come off over time, so be careful in production. Required ×: Production is extremely difficult due to occurrence of wrinkles, unrolling, etc. Note that if the rating is ``△'' or higher, it is at a practical level, so it was rated as ``pass.''
The above evaluation results are summarized in Table 1.

In the column "Presence or absence of biaxial stretching" in Table 1, "○" is written when the biaxially stretched polyethylene terephthalate, that is, the polyester resin layer is biaxially stretched. In addition, polyethylene terephthalate that has not been subjected to stretching treatment, that is, when the polyester resin layer has not been biaxially stretched, is marked with "x".
As can be seen from these results, 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 yield.

(Second example)
[Example 2-1]
A polyolefin-based inorganic filled sheet ("OW" manufactured by RIKEN TECHNOS Co., Ltd.) with a thickness of 55 μm was used as the thermoplastic resin base sheet 1, and a pattern layer 2 was formed by printing a wood grain pattern on the surface side by a gravure printing method. .
Next, on this picture pattern layer 2, unstretched polyethylene terephthalate ("Lumirror T60" manufactured by Toray Industries, Inc.), which has been previously corona treated and has a thickness of 190 μm, is dry laminated, and the first adhesive layer 3 and polyester are A polyethylene terephthalate resin layer 4 (polyethylene terephthalate resin layer 4a) was formed.

Subsequently, a urethane resin adhesive was applied onto this polyester resin layer 4 and dried with warm air to form a second adhesive layer 5.
Subsequently, a transparent thermoplastic resin layer 6 was formed on the second adhesive layer 5 by extruding two layers of molten transparent thermoplastic resin through a T-die using a multi-axis extruder. For the first resin, a transparent maleic acid-modified polypropylene resin (manufactured by Riken Vitamin Co., Ltd.) was used, and for the second resin, a phenolic antioxidant (manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to 100 parts by mass of the polypropylene resin. 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 benzotriazole ultraviolet absorber ("TINUVIN622" manufactured by Ciba Specialty Chemicals Co., Ltd.) A resin to which 0.5 parts by mass of TINUVIN326) was added was used.

At the same time as forming the transparent thermoplastic resin layer 6 consisting of two layers, all the layers are nipped with a conduit embossing plate and a rubber roll to form a thermoplastic resin base sheet 1, a pattern layer 2, and a pattern layer 2 as shown in FIG. A laminate consisting of a first adhesive layer 3, a polyester resin layer 4, a second adhesive layer 5, and a transparent thermoplastic resin layer 6 was obtained. Here, the thickness of the transparent thermoplastic resin layer 6 was 90 μm.
After surface treatment was applied to the embossed surface of this laminate, a curing agent (UR150B manufactured by Toyo Ink Co., Ltd.) was added to 100 parts by mass of a urethane resin (URV238 Varnish manufactured by Toyo Ink Co., Ltd.) as a top coat resin. varnish"), 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 resin composition containing 1 part by mass of was applied by gravure coating so that the coating amount after drying was 5 g/m ² , and immediately cured by irradiation with ultraviolet rays to form the surface protective layer 7.

After surface treatment was applied to the back surface of the thermoplastic resin base sheet 1, this surface was treated with 10 parts by mass of silica and isocyanate (Toyo Ink Co., Ltd. "Lamister EM") per 100 parts by mass of polyol ("Lamister EM" manufactured by Toyo Ink Co., Ltd.). A resin composition to which 3 parts by mass of "LPNYB curing agent" manufactured by Co. ^, Ltd. Formed.
Through such a procedure, the decorative sheet 10 of Example 2-1 was formed. The total thickness of the polyester resin layer 4 (polyethylene terephthalate resin layer 4a) and the transparent thermoplastic resin layer 6 is 280 μm.

[Example 2-2]
The thickness of the polyester resin layer 4 is 250 μm, the thickness of the transparent thermoplastic resin layer 6 is 100 μm, and the thickness of the polyester resin layer 4 (polyethylene terephthalate resin layer 4a) and the thickness of the transparent thermoplastic resin layer 6 are A decorative sheet 10 was formed in the same manner as in Example 2-1 except that the total value was 350 μm.
[Example 2-3]
The thickness of the polyester resin layer 4 is 150 μm, the thickness of the transparent thermoplastic resin layer 6 is 100 μm, and the thickness of the polyester resin layer 4 (polyethylene terephthalate resin layer 4a) and the thickness of the transparent thermoplastic resin layer 6 are A decorative sheet 10 was formed in the same manner as in Example 2-1 except that the total value was 250 μm.

[Example 2-4]
The thickness of the polyester resin layer 4 is 190 μm, the thickness of the transparent thermoplastic resin layer 6 is 150 μm, and the thickness of the polyester resin layer 4 (polyethylene terephthalate resin layer 4a) and the thickness of the transparent thermoplastic resin layer 6 are A decorative sheet 10 was formed in the same manner as in Example 2-1 except that the total value was 340 μm.
[Example 2-5]
The thickness of the polyester resin layer 4 is 190 μm, the thickness of the transparent thermoplastic resin layer 6 is 50 μm, and the thickness of the polyester resin layer 4 (polyethylene terephthalate resin layer 4a) and the thickness of the transparent thermoplastic resin layer 6 are A decorative sheet 10 was formed in the same manner as in Example 2-1 except that the total value was 240 μm.

[Comparative example 2-1]
The polyester resin layer 4 is a layer formed of biaxially stretched polyethylene terephthalate and has a thickness of 95 μm, the transparent thermoplastic resin layer 6 has a thickness of 100 μm, and the polyester resin layer 4 (polyethylene terephthalate A decorative sheet 10 was formed in the same manner as in Example 2-1, except that the total thickness of the resin layer 4a) and the transparent thermoplastic resin layer 6 was 195 μm.

The six types of decorative sheets obtained above were bonded to a 6 mm thick MDF (medium density wood fiberboard) using an ethylene-vinyl acetate copolymer resin emulsion type adhesive to form a decorative board.
The following evaluation tests were conducted using decorative sheets and decorative boards.

[Abrasion resistance]
The decorative board was subjected to an abrasion tester specified in the Japanese Agricultural Standards (JAS) for flooring, and the number of revolutions until the pattern began to disappear was determined. The abrasive paper was replaced with a new one 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 If the evaluation is "△" or more, it is at a practical level, so it was judged as "pass".

[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 In addition, if the rating is "△" or higher, it is at a practical level, so It was marked as "passed".

[Workability]
We confirmed the methods that can be selected when processing decorative sheets into decorative boards.
◎: In-line roll lamination is possible. ○: In-line roll lamination is possible, but requires some caution in processing. △: In-line roll lamination is possible, but considerable care is required in processing. ×: Roll lamination is not possible. Only sheet lamination is possible. If the evaluation is "△" or higher, it is at a practical level, so it was judged as "passed".

[Machinability 1]
The decorative sheet was cut using a circular saw and cut to reach the MDF using a hand router, and the occurrence of burrs on the decorative sheet was confirmed.
◎: No burrs occur. ○: Some burrs are visible, but they can be easily corrected. △: Some burrs are visible, and correction is necessary. ×: Burrs occur on almost the entire surface, and it is difficult to correct them manually. If the evaluation is ``△'' or higher, it is at a practical level, so it is judged as ``pass''.

[Machinability 2]
The decorative board was cut with a circular saw and cut into MDF with a hand router, and the presence or absence of cohesive failure of the polyethylene terephthalate resin layer 4a of the decorative sheet was confirmed.
◎: Cohesive failure of the polyethylene terephthalate resin layer 4a does not occur. ○: Cohesive failure of the polyethylene terephthalate resin layer 4a is partially observed, but can be easily corrected. △: Cohesive failure of the polyethylene terephthalate resin layer 4a is partially observed, Correction required ×: Cohesive failure of the polyethylene terephthalate resin layer 4a occurred at almost all edges, and correction was difficult. Note that an evaluation of “△” or higher indicates a practical level, and therefore was judged as “pass”.

[Adhesion strength]
The adhesion strength between the polyester resin layer 4 (polyethylene terephthalate resin layer 4a) and the transparent thermoplastic resin layer 6 was confirmed. ◎: Adhesion strength is greater than 2.0 kgf/cm ² and is sufficient ×: Adhesion strength is sufficient If the strength is less than 2.0 kgf/ ^cm2 , the strength is not sufficient. If the evaluation is "◎", it is at a practical level, so it was judged as "passed".

〔Productivity〕
The ease of production when extruding and laminating the transparent thermoplastic resin layer 6 was confirmed.
◎: Stable production is possible ○: Although it is necessary to be more careful than ◎, stable production is possible. △: During long-run production, there is a possibility that the roll may come off over time, so be careful in production. Required ×: Production is extremely difficult due to occurrence of wrinkles, unrolling, etc. Note that if the rating is ``△'' or higher, it is at a practical level, so it was rated as ``pass.''
The above evaluation results are summarized in Table 2.

As can be seen from Table 2, Examples 2-1 to 2-5 are evaluated as "△" or higher in all evaluation items, but the thickness of the polyethylene terephthalate resin layer 4a is less than 150 μm. Comparative Example 1 was evaluated as "x" in machinability 2 and adhesion strength, resulting in poor practicality.
As can be seen from these results, the decorative sheet according to this example has excellent wear resistance when made into a decorative board, and has excellent machinability when cut using a circular saw or a hand router. be.

(Third example)
[Example 3-1]
A polyolefin-based inorganic filled sheet having a thickness of 55 μm was used as the thermoplastic resin base sheet 1, and a pattern layer 2 was formed by printing a wood grain pattern on the surface side by gravure printing.
Subsequently, a polybutylene terephthalate film with a thickness of 130 μm, which has been subjected to corona treatment in advance, is dry-laminated on this picture pattern layer 2 using an adhesive, and a first adhesive layer 3 and a polyester resin layer 4 (polybutylene A terephthalate resin layer 4b) was formed.

Subsequently, a urethane resin adhesive was applied onto this polyester resin layer 4 and dried with warm air to form a second adhesive layer 5.
Subsequently, a transparent thermoplastic resin layer 6 was formed on the second adhesive layer 5 by extruding two layers of molten transparent thermoplastic resin through a T-die using a multi-axis extruder. The first resin is a transparent maleic acid-modified polypropylene resin, and the second resin is 100 parts by mass of polypropylene resin, 0.2 parts by mass of a phenolic antioxidant, and 0.3 parts by mass of a hindered amine light stabilizer. A transparent resin to which 0.5 parts by mass of a benzotriazole ultraviolet absorber was added was used.

At the same time as forming the transparent thermoplastic resin layer 6 consisting of two layers, all the layers are nipped with a conduit embossing plate and a rubber roll to form a thermoplastic resin base sheet 1, a pattern layer 2, and a pattern layer 2 as shown in FIG. A laminate consisting of a first adhesive layer 3, a polyester resin layer 4, a second adhesive layer 5, and a transparent thermoplastic resin layer 6 was obtained. Here, the thickness of the first resin layer 6a was 15 μm, and the thickness of the second resin layer 6b was 75 μm.
After surface treatment is applied to the embossed surface of this laminate, 0.5 parts by mass of a benzotriazole ultraviolet absorber and 1 part by mass of a hindered amine light stabilizer are added to 100 parts by mass of urethane resin as a top coat resin. The resulting resin composition was coated and dried using a gravure coat so that the coating amount after drying was 7 g/m ² , and then an acrylic ultraviolet curable resin was coated using a gravure coat so that the coating amount was 7 g/m ² . The surface protective layer 7 was formed by irradiating and curing ultraviolet rays.

After surface treatment is applied to the back side of the thermoplastic resin base sheet 1, a resin composition in which 10 parts by mass of silica and 3 parts by mass of isocyanate are added to 100 parts by mass of polyol is used as a primer coating liquid, A primer layer 8 was formed by gravure coating so that the coating amount after drying was 3 g/m ² and dried.
Through such a procedure, the decorative sheet 10 of Example 3-1 was formed.

[Example 3-2]
A decorative sheet 10 was obtained in the same manner as in Example 3-1 except that the thickness of the polyester resin layer 4 was 200 μm.
[Example 3-3]
A decorative sheet 10 was obtained in the same manner as in Example 3-1 except that the thickness of the polyester resin layer 4 was 50 μm.

[Example 3-4]
A decorative sheet 10 was obtained in the same manner as in Example 3-1 except that the thickness of the polyester resin layer 4 was 130 μm and the thickness of the transparent thermoplastic resin layer 6 was 150 μm.
[Example 3-5]
A decorative sheet 10 was obtained in the same manner as in Example 3-1, except that the thickness of the polyester resin layer 4 was 130 μm and the thickness of the transparent thermoplastic resin layer 6 was 50 μm.

[Comparative example 3-1]
Example 3- except that a polyethylene terephthalate (A-PET) resin film with a thickness of 190 μm and not subjected to biaxial stretching treatment was used as the polyester resin layer 4, and the thickness of the transparent thermoplastic resin layer 6 was 100 μm. A decorative sheet 10 was obtained in the same manner as in Example 1.

The seven types of decorative sheets obtained above were bonded to a 6 mm thick MDF (medium density wood fiberboard) using an ethylene-vinyl acetate copolymer resin emulsion type adhesive to form a decorative board.
The following evaluation tests were conducted using decorative sheets and decorative boards.

[Abrasion resistance]
The decorative board was subjected to an abrasion tester specified in the Japanese Agricultural Standards (JAS) for flooring, and the number of revolutions until the pattern began to disappear was determined. The abrasive paper was replaced with a new one 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 If the evaluation is "△" or more, it is at a practical level, so it was judged as "pass".

[Scratch resistance]
The decorative board was subjected to a pencil hardness tester 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 In addition, if the rating is "△" or higher, it is at a practical level, so It was marked as "passed".

[Workability]
We confirmed the methods that can be selected when processing decorative sheets into decorative boards.
◎: In-line roll lamination is possible 〇: In-line roll lamination is possible, but requires some caution in processing △: In-line roll lamination is possible, but requires great care in processing ×: Roll lamination is not possible . Only sheet lamination is possible. If the evaluation is ``△'' or higher, it is at a practical level, so it is considered ``pass''.

[Machinability 1]
The decorative sheet was cut using a circular saw and cut to reach the MDF using a hand router, and the occurrence of burrs on the decorative sheet was confirmed.
◎: There are no burrs. ○: There are burrs in some areas, but they can be easily corrected. △: There are burrs in some areas, and correction is necessary. ×: There are burrs on almost the entire surface, and corrections can be made manually. Difficult If the evaluation is ``△'' or higher, it is at a practical level, so it is considered ``pass''.

[Machinability 2]
The decorative board was cut with a circular saw and cut into MDF with a hand router, and the state of occurrence of cohesive failure in the polyester resin layer 4 of the decorative sheet was confirmed.
◎: Cohesive failure of the polyester resin layer 4 does not occur. ○: Cohesive failure of the polyester resin layer 4 is partially observed, but can be easily corrected. △: Cohesive failure of the polyester resin layer 4 is partially observed, Correction required ×: Cohesive failure of the polyester resin layer 4 occurred at almost all edges, and correction was difficult. Note that an evaluation of "△" or higher indicates a practical level, so it was judged as "pass".

〔Productivity〕
The ease of production when extruding and laminating the transparent thermoplastic resin layer 6 was confirmed.
◎: Can be produced stably 〇: It is necessary to be more careful about production than ◎, but it can be produced stably △: During long-run production, there is a possibility that the roll may come off over time, so be careful in production. Required ×: Production is extremely difficult due to occurrence of wrinkles, unrolling, etc. Note that if the rating is ``△'' or higher, it is at a practical level, so it was rated as ``pass.''

[Adhesion strength]
The adhesion strength between the polyester resin layer 4 and the transparent thermoplastic resin layer 6 was confirmed. ◎: Adhesion strength is greater than 19.6 N/cm ² and is sufficient ×: Adhesion strength is 19.6 N/cm ² or less The strength is not sufficient. If the evaluation is "◎", it is at a practical level, so it was judged as "pass".

[Class 1 immersion peeling test]
Conduct the Class 1 immersion peeling test specified by JAS on the decorative board and check the surface condition. ◎: No whitening ×: Whitening If the evaluation is "◎", it is at a practical level, so it was judged as "passed". .
The above evaluation results are summarized in Table 3.

As can be seen from the results, the decorative sheet according to this example is well-balanced in sheet productivity, workability when processed into a decorative board, and various physical properties when made into a decorative board, and is resistant to heat and sunlight. It is useful as a decorative sheet for exposed floor heating flooring.

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

1: Thermoplastic resin base sheet 2: Picture pattern layer 3: First adhesive layer 4: Polyester resin layer 4a: Polyethylene terephthalate resin layer 4b: Polybutylene terephthalate resin layer 5: Second adhesive layer 6: Transparent heat Plastic 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: Emboss 10: Decorative sheet

Claims (4)

A picture pattern layer, a first adhesive layer, a polyester resin layer, a second adhesive layer, a transparent thermoplastic resin layer, and a surface protection layer are laminated in this order on a thermoplastic resin base sheet,
Embosses are formed on at least the transparent thermoplastic resin layer,
The thickness of the transparent thermoplastic resin layer is within the range of 100 μm or more and 150 μm or less,
The polyester resin layer contains polyethylene terephthalate and is a non-stretched layer,
The thickness of the polyester resin layer is within the range of 190 μm or more and 250 μm or less,
The total value of the thickness of the polyester resin layer and the transparent thermoplastic resin layer is within the range of 340 μm or more and 350 μm or less,
A decorative sheet, wherein the surface protective layer contains an ionizing radiation curable resin. A picture pattern layer, a first adhesive layer, a polyester resin layer, a second adhesive layer, a transparent thermoplastic resin layer, and a surface protection layer are laminated in this order on a thermoplastic resin base sheet,
Embosses are formed on at least the transparent thermoplastic resin layer,
The thickness of the transparent thermoplastic resin layer is within the range of 50 μm or more and 90 μm or less,
The polyester resin layer is a layer containing polybutylene terephthalate,
The thickness of the polyester resin layer is within the range of 50 μm or more and 130 μm or less,
The total value of the thickness of the polyester resin layer and the transparent thermoplastic resin layer is within the range of 140 μm or more and 180 μm or less,
A decorative sheet, wherein the surface protective layer contains an ionizing radiation curable resin. The transparent thermoplastic resin layer is formed on the polyester resin layer side and includes a first resin layer, and is formed on the first resin layer and includes a first resin layer. a second resin layer formed including a second resin different from the resin,
The first resin is a transparent maleic acid-modified polypropylene resin,
3. The decorative sheet according to claim 1, wherein the second resin is a transparent polypropylene resin. 4. The decorative sheet according to claim 3 , 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.

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