JP2024040028A - Decorative sheet and decorative panel - Google Patents

Abstract

To provide a decorative sheet and a decorative panel having excellent scratch resistance and antiviral properties.SOLUTION: In a decorative sheet 11, a picturesque pattern layer 2, a first adhesive layer 3, polyester-based resin 4, a second adhesive layer 5, a transparent thermoplastic resin layer 6, and a surface protection layer 7 are laminated in this order on a thermoplastic resin substrate sheet 1, at least the transparent thermoplastic resin layer 6 is embossed, the polyester-based resin 4 is biaxially stretched, the total value of the thickness of the polyester-based resin 4 and the thickness of the transparent thermoplastic resin layer 6 is within the range of 150 μm or more and 700 μm or less, and the surface protection layer 7 contains ionizing radiation-curable resin, an anti-viral agent within the range of 0.2 pts.mass or more and 25 pts.mass or less to the ionizing radiation-curable resin 100 pts.mass, and nucleating agent vesicles within the range of 0.05 pts.mass or more and 0.5 pts.mass or less in terms of nucleating agent in the nucleating agent vesicles.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to decorative sheets and decorative laminates.

In the past, many decorative sheets using olefin resin have been proposed as an alternative to decorative sheets made of polyvinyl chloride, but they have poor scratch resistance and are inferior to conventional polyvinyl chloride sheets. (For example, see Patent Document 1).

Japanese Patent Application Publication No. 2014-188941

In recent years, the demand for antiviral performance has increased, and the development of antiviral products has become an urgent need. However, when the decorative sheet is worn or damaged, the outermost surface is worn away, resulting in a decrease in antiviral properties. In particular, when using decorative floor sheets for shoes and heels, etc., the scratch resistance is poor and the surface of the decorative floor materials is easily scratched, and the top surface of the decorative floor sheets is coated with antiviral agents. There was a problem in that the wear and tear was noticeable.

The present disclosure has been made in view of the above circumstances, and an object of the present disclosure is to provide a decorative sheet and a decorative board that have excellent scratch resistance and antiviral properties.

In order to solve the above problems, a decorative sheet according to one aspect of the present disclosure 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 protection 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 500 μm or less. Yes, the polyester resin layer is biaxially stretched, and the thickness of the polyester resin layer is within 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 layer are The total thickness of the surface protective layer is in the range of 150 μm or more and 700 μm or less, and the surface protective layer is formed by applying nano-sized nucleation to a vesicle comprising an ionizing radiation-curable resin, an antiviral agent, and a monolayer outer membrane. The amount of the antiviral agent added in the surface protective layer is 0.2 parts by mass or more and 25 parts by mass or less based on 100 parts by mass of the ionizing radiation curable resin. The amount of the nucleating agent added in the surface protective layer is 0.05 parts by mass or more in terms of the nucleating agent in the nucleating agent vesicles, based on 100 parts by mass of the ionizing radiation curable resin. It is characterized by being within a range of 0.5 parts by mass or less.

In order to solve the above problems, a decorative board according to another aspect of the present disclosure includes a decorative board and a decorative board according to any one of claims 1 to 4, which is laminated to the decorative board. It is characterized by having a seat.

According to the aspect of the present disclosure, it is possible to provide a decorative sheet and a decorative board that have excellent scratch resistance and antiviral properties.

FIG. 1 is a cross-sectional view illustrating a configuration example of a decorative sheet according to a first embodiment of the present disclosure. It is a sectional view showing one example of composition of a decorative sheet concerning a modification of a first embodiment of this indication. It is a sectional view showing one example of composition of a decorative sheet concerning a second embodiment of the present disclosure. It is a sectional view showing one example of composition of a decorative sheet concerning a modification of a second embodiment of this indication. It is a sectional view showing one example of composition of a decorative board concerning a third embodiment of the present disclosure.

The embodiments of the present disclosure will be described below with reference to the drawings. However, it should be noted that the drawings are schematic, and the relationship between thickness and planar dimensions, the thickness ratio of each layer, etc., are different from the actual ones. Therefore, the specific thickness and dimensions should be determined by taking into consideration the following description.
Furthermore, the embodiments shown below are merely examples of configurations for embodying the technical ideas of the present invention, and the technical ideas of the present disclosure do not specify the materials of the components, or their shapes, structures, arrangements, etc. to those described below. The technical ideas of the present disclosure can be modified in various ways within the technical scope defined by the claims.
Hereinafter, embodiments of the present disclosure will be described with reference to the drawings.

<First embodiment>
(Configuration of decorative sheet 11)
FIG. 1 shows an example of the structure of the decorative sheet 11 of this embodiment. The decorative sheet 11 is an olefin-based decorative sheet or a polyester-based decorative sheet that is bonded 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 structure of the decorative sheet 11 will be specifically explained.
The decorative sheet 11 has a pattern layer 2, a first adhesive layer 3, a polyester resin layer 4, a second adhesive layer 5, a transparent thermoplastic resin layer 6, and a surface protection layer on a thermoplastic resin base sheet 1. The layers 70 are stacked 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 500 μm or less.

Moreover, 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. Moreover, the total value of the thickness of the polyester resin layer 4 and the thickness of the transparent thermoplastic resin layer 6 is within the range of 150 μm or more and 700 μm or less.
Furthermore, the surface protection layer 70 includes an ionizing radiation curable resin such as an ultraviolet curable resin.
By having the above-mentioned structure, the decorative sheet 11 can obtain excellent scratch resistance, and also has excellent stain resistance and abrasion resistance.

The decorative sheet 11 according to this embodiment can be used as a flooring material for use on floors where shoes are worn.
Conventionally, a known floor decorative material made of wood-based substrate is made by attaching a veneer to a plywood, processing grooves with a woodworking machine, coloring the grooves, and then applying and curing an ultraviolet-curing paint. However, since the veneer is made of natural wood, there is variation in color, making it difficult to harmonize the color with walls, ceilings, furniture, etc.

In addition, concave grooves are formed on the surface of the wood base material, a synthetic resin paint for conduit coloring is applied to the surface, and after removing the paint other than the conduit grooves, a conduit concave part with a wood grain pattern is formed, and the concave grooves are formed. A method of applying a transparent synthetic resin paint to the surface of a wood base material other than the above is also known.
Furthermore, decorative floor materials are also known, in which a decorative sheet made of thermoplastic resin (polyolefin resin) is laminated on a wooden base material, with a colored thermoplastic resin layer, a pattern layer, and a transparent thermoplastic resin layer provided in this order. It is being

These conventional floor decorative materials are mainly used for living rooms and are designed to be walked on bare feet or in socks, slippers, or the like. Therefore, when the above-mentioned decorative flooring material is used for shoes worn on the assumption that the flooring material is used for walking in shoes or heels, the scratch resistance necessary for a flooring material for shoes or shoes is insufficient, and the decorative flooring material is easily damaged. In particular, there have been problems such as the decorative sheet, which is the surface material of the decorative material, is easily scratched and the pattern is noticeably worn away.
The decorative sheet 11 according to the present embodiment has the above-mentioned configuration, so that scratch resistance can be improved, and furthermore, it has excellent abrasion resistance.

In the decorative sheet 11 according to the present embodiment, the surface protection layer 70 is formed by adding an antiviral agent and a nucleating agent to an ionizing radiation curable resin. That is, the surface protective layer 70 contains an ionizing radiation curable resin, an antiviral agent, and a nucleating agent. This imparts antiviral properties to the decorative sheet 11 and further improves scratch resistance.
Therefore, the decorative sheet 11 according to the present embodiment is a decorative sheet that has excellent scratch resistance and antiviral properties.

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-based material (polyolefin-based resin) to which a color pigment is added can be suitably used. That is, as the thermoplastic resin base sheet 1, it is preferable to use a colored thermoplastic resin base sheet whose main ingredient is a colored polyolefin resin.

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.
The thickness of the thermoplastic resin base sheet 1 is preferably within the range of 50 μm or more and 200 μm or less. If the thickness of the thermoplastic resin base sheet 1 is within the above-mentioned numerical range, the decorative sheet will have sufficient impact resistance, caster resistance, and processability required for floor material performance.

[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 70, for example, an easily bonding layer may be provided or a corona treatment may be performed as appropriate.
The polyester resin layer 4 is preferably biaxially stretched (a layer that has been subjected to a biaxial stretching process). 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. That is, the polyester resin layer 4 may contain polyethylene terephthalate and may be a non-stretched layer. 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 applications. 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 11 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 formed on the polyester resin layer 4 side, and is made of polypropylene resin.
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 a plurality of layers. Each layer constituting the transparent thermoplastic resin layer 6 is formed of, for example, a transparent thermoplastic resin so that the pattern of the pattern layer 2 can be seen through. The thermoplastic resin contained in the transparent thermoplastic resin layer 6 only needs to be transparent, and may be, for example, various resins other than vinyl chloride resin. Various combinations of resins in each layer constituting the transparent thermoplastic resin layer 6 are possible depending on the desired characteristics.

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 this embodiment, the thermoplastic resin layer used for the transparent thermoplastic resin layer 6 is preferably a transparent polypropylene resin. Details of the transparent polypropylene resin will be described later.

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 11 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 forming the surface protection layer 70, or may be formed after forming the surface protection layer 70.

Further, the thickness of the transparent thermoplastic resin layer 6 is preferably within the range of 50 μm or more and 500 μm or less, and more preferably within the range of 50 μm or more and 150 μm or less. If the thickness of the transparent thermoplastic resin layer 6 is within the above numerical range, 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 500 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 11 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 11 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.

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 11 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 type, triazine type, benzophenone type, etc.
Examples of benzotriazole-based ultraviolet absorbers include 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2 -Hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3- t-Butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3, Use of 5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, etc., or mixtures, modified products, polymers, and derivatives thereof. I can do it.

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

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

The number of parts to be added may be added depending on the desired weather resistance, but it is within the range of 0.1% by mass to 50% by mass, preferably 1% by mass to 30% by mass, based on the resin solid content. shall be.
In addition to the above, for example, heat stabilizers, flame retardants, antiblocking agents, etc. may be added. Examples of the heat stabilizer include pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)]-propionate, 2,4-bis-(n-octylthio)-6- (4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 1,3, 5-trimethyl-2,4,6-tris(3,5-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethyl) Hindered phenolic antioxidants such as benzyl) isocyanuric acid, 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), etc. phenolic antioxidants, phosphorus antioxidants represented by tris(2,4-di-t-butylphenyl) phosphite, etc., and mixtures thereof, i.e., one type or a combination of two or more types. can be used.

Further, as the flame retardant, for example, inorganic compounds such as aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, and phosphoric acid ester flame retardants can be used. Further, as the antiblocking agent, for example, inorganic antiblocking agents such as aluminum silicate, silicon oxide, hydrotalcite, and calcium carbonate, organic antiblocking agents such as fatty acid amide, etc. can be used. Moreover, the thickness of the transparent thermoplastic resin layer 6 is preferably in the range of 50 μm or more and 500 μm or less.

[Surface protective layer 70]
The surface protection layer 70 is located on the outermost surface of the decorative sheet 11 and serves to protect the decorative sheet 11 from direct external forces such as being hit by objects or being rubbed during movement. . In other words, the surface protective layer 70 improves the surface properties of the decorative sheet 11, imparts scratch resistance, stain resistance, slipperiness, weather resistance, durability, etc. to the surface of the decorative sheet 11, and improves design properties (gloss). This layer is provided to provide functions such as tactile sensation, tactile sensation, etc.
As the material for the surface protection layer 70, for example, an ionizing radiation-curable resin can be used in consideration of scratch resistance, weather resistance, and durability. In terms of scratch resistance, the surface protective layer 70 preferably has a hardness of H or higher in a pencil hardness test according to JIS K 5600.

Among the ionizing radiation curable resins, examples of the ultraviolet curable resins include (meth)acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, and epoxy resins. In addition, as an ionizing radiation-curable resin, for example, the main component is at least one of a prepolymer, an oligomer, and a monomer having a polymerizable unsaturated bond such as a (meth)acryloyl group that has the property of undergoing a crosslinking reaction when irradiated with ionizing radiation. A composition can be used. As the ionizing radiation, for example, an electron beam or ultraviolet light can be used. For example, additives such as a polymerization initiator and a sensitizer may be added to the ionizing radiation-curable resin, if necessary.

Examples of prepolymers and oligomers having polymerizable unsaturated bonds include melamine (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, and polyol (meth)acrylate. ) Acrylate etc. can be used. Examples of monomers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, hydroxyethyl (meth)acrylate, and glycidyl (meth)acrylate. monofunctional monomers such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, trimethylolpropane Polyfunctional monomers such as triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc. can be used.

Further, the surface protective layer 70 can be made of a mixture of an ionizing radiation-curable resin and an isocyanate-curable acrylic resin composition.
As the isocyanate-curable acrylic resin composition, for example, a reaction product containing an acrylic resin composition as a main ingredient and a polyisocyanate as a curing agent can be used. As the acrylic resin composition, for example, an acrylic polyol compound can be employed. Examples of acrylic polyol compounds include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, and methacrylate. Monomers containing hydroxyl groups such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl acrylate in addition to ordinary acrylic monomers such as 2-ethylhexyl. and, if necessary, copolymerizable monomers such as styrene, α-methylstyrene, vinyltoluene, divinylbenzene, vinyl acetate, vinyl butyrate, vinyl versatate, ethyl vinyl ether, acrylonitrile, methacrylonitrile, etc. are blended. An acrylic polymer compound having a hydroxyl group in a side chain and obtained by copolymerization can be used.

In addition, as the isocyanate prepolymer of polyisocyanate, for example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), hydrogen Added xylylene diisocyanate (hydrogenated XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), etc. can be used. In particular, a trimer of hexamethylene diisocyanate (HDI) can be used in consideration of weather resistance, yellowing, and productivity. That is, an isocyanurate type that uses HDI as a raw material, that is, HDI isocyanurate, which is a derivative of HDI, can be used. Further, as the side chain of the isocyanate prepolymer, for example, a urethane bond can be used in consideration of imparting flexibility to the surface protective layer 7.

Further, as the material for the surface protection layer 70, for example, a mixture (blend resin) of a thermosetting resin and an ultraviolet curable resin (UV curable resin) may be used.
Since the surface protective layer 70 contains an ionizing radiation curable resin (for example, an ultraviolet curable resin), that is, a resin with high hardness, the scratch resistance of the decorative sheet 11 can be improved by the surface protective layer 70 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 11, 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.

The surface protective layer 70 may contain various additives, such as ultraviolet absorbers, heat stabilizers, light stabilizers, antiblocking agents, catalyst scavengers, colorants, light scattering agents, and gloss control agents, as necessary. You may.
The method for forming the surface protective layer 70 is not particularly limited, and after coating the above-mentioned materials in a coating liquid using a conventional method such as gravure coating, microgravure coating, comma coating, knife coating, die coating, etc., thermal curing is performed. The surface protective layer 70 is formed by curing using a method suitable for the material, such as UV curing.

Moreover, a surfactant may be added to the surface protection layer 70. The surfactant includes at least one of a cationic surfactant, an amphoteric surfactant, or a nonionic surfactant. By adding a surfactant, the compatibility between the inorganic (for example, silver-based) antiviral agent described below and the binder of the surface protective layer is improved, and the concentration of the antiviral agent due to precipitation during coating is reduced. A decorative sheet with suppressed variations can be obtained.
Moreover, the layer thickness of the surface protective layer 70 is preferably within the range of 3 μm or more and 15 μm or less. If the thickness of the surface protective layer 70 is 3 μm or more, scratch resistance will be improved. If the thickness of the surface protection layer 70 is 15 μm or less, it is not necessary to use an unnecessarily large amount of resin material, and costs can be reduced.

(antiviral agent)
Furthermore, in the decorative sheet 11 according to the present embodiment, the surface protective layer 70 contains an antiviral agent. Therefore, the decorative sheet 11 is a decorative sheet having antiviral properties.
As the antiviral agent, for example, an inorganic antiviral agent may be contained. Examples of inorganic antiviral agents include antibacterial zeolite, antibacterial apatite, and antibacterial apatite formed by incorporating metal ions such as silver ions, copper ions, and zinc ions into inorganic compounds such as zeolite, apatite, and zirconia. Inorganic antibacterial agents such as zirconia can be used. In addition, zinc pyridione, 2-(4-thiazolyl)-benzimidazole, 10,10-oxybisphenoxanodine, organic nitrogen sulfur halogen, pyridine-2-thiol-oxide, etc. can be used as antiviral agents. Silver-based antiviral agents are superior in terms of their effectiveness against viruses. That is, the antiviral agent contained in the surface protective layer 70 in the decorative sheet 11 according to the present embodiment is preferably a silver-based material. Further, the surface protective layer 70 may contain only one kind of the above-mentioned inorganic antiviral agent, or may contain two or more kinds of inorganic antiviral agents.

Further, the antiviral agent may have a structure in which a silver-based material is supported on an inorganic material. Thereby, the decorative sheet 11 with excellent durability of antiviral effect can be obtained.
As the "inorganic material" that supports the silver-based material, for example, "glass" can be used, but the "inorganic material" is not limited to glass. By carrying silver in an inorganic material, it is possible to prevent the silver component from falling off over time and from transferring to the lower layer side (for example, the transparent thermoplastic resin layer 6 side). Since inorganic antiviral agents have excellent sustainability of antiviral effects, the sustainability of antiviral effects can be improved by adding inorganic antiviral agents.

The amount of the antiviral agent added in the surface protective layer 70 is preferably in the range of 0.2 parts by mass or more and 25 parts by mass or less, and 5 parts by mass or more and 15 parts by mass, based on 100 parts by mass of the ionizing radiation curable resin. It is more preferable that the amount is in the range of 100% or less.
When the amount of the antiviral agent added is 0.2 parts by mass or more per 100 parts by mass of the ionizing radiation curable resin, the antiviral agent acts effectively and the antiviral properties are improved. When the amount of the antiviral agent added is 25 parts by mass or less with respect to 100 parts by mass of the ionizing radiation curable resin, the scratch resistance is improved.

The average particle size of the antiviral agent is desirably 0.5 times or more and twice or less the thickness of the surface protective layer 70. That is, when the average particle diameter of the antiviral agent is Φ and the thickness of the surface protective layer is D, it is desirable that the relationship 0.5≦Φ≦2D holds true. When the average particle size of the antiviral agent is 0.5 times or more and less than 2 times that of the surface protective layer 70, the antiviral properties are improved by expanding the contact surface with the antiviral agent and expanding the surface area of the antiviral agent itself. Become.
Further, the average particle size of the antiviral agent is desirably 1 μm or more and 10 μm or less. When the average particle size of the antiviral agent is 1 μm or more, the contact area between the surface protective layer 70 and the antiviral agent is improved, and antiviral properties are improved. When the average particle size of the antiviral agent is 10 μm or less, scratch resistance is improved.

Further, it is preferable that the antiviral agent has a plurality of particle size peaks. Specifically, the particle size peak of the antiviral agent has two peaks, and the two peaks are a first peak in the range of 1 μm or more and 5 μm or less, and a second peak in the range of 5 μm or more and 10 μm or less. It is preferable that it contains. Here, the second peak of the particle size of the antiviral agent is set to a value larger than the first peak. Since the antiviral agent has a plurality of particle size peaks, the packing density of the antiviral agent can be further improved, and a larger amount of the antiviral agent can be added. Therefore, the contact area with the antiviral agent is expanded, and the surface area of the antiviral itself is also expanded, thereby improving antiviral properties.

Further, in the present disclosure, the antiviral agent contained in the surface protective layer 70 is not limited to an inorganic antiviral agent. The surface protective layer 70 may contain an organic antiviral agent. By using an organic antiviral agent whose active ingredient is an organic material, the decorative sheet 11 has excellent antiviral properties, and can exhibit a more immediate antiviral effect than inorganic antiviral agents. can.

In the decorative sheet 11 according to the present embodiment, examples of the organic antiviral agent added to the surface protective layer 70 include halocarban, chlorophenesine, lysozyme chloride, alkyldiaminoethylglycine hydrochloride, isopropylmethylphenol, thymol, and hexachlorophene. , berberine, thioxolone, salicylic acid and their derivatives, benzoic acid, sodium benzoate, paraoxybenzoic acid ester, parachlormetacresol, benzalkonium chloride, phenoxyethanol, isopropylmethylphenol, carbolic acid, sorbic acid, potassium sorbate, hexachlorophene , chlorhexidine chloride, trichlorocarbanilide, thianthol, hinokitiol, triclosan, trichlorohydroxydiphenyl ether, chlorhexidine gluconate, phenoxyethanol, resorcinol, azulene, salicylic acid, zinc pyrithione, mononitroguaiacol sodium, fennel extract, salamander extract, cetylpyridinium chloride, Examples include benzethonium chloride and undecylenic acid derivatives, alkylbenzenesulfonic acids or salts thereof, copolymers containing styrene sulfonates, anionic sodium salts, and the like.
Even when an organic antiviral agent is used, the content of the antiviral agent in the surface protective layer 70 is 0.2 parts by mass per 100 parts by mass of the ionizing radiation curable resin, as in the case where an inorganic antiviral agent is used. It is preferably within the range of 25 parts by mass or more.

In this embodiment, the surface protective layer 70 may contain only one type of the above-mentioned inorganic antiviral agent as an antiviral agent, or may contain two or more types of inorganic antiviral agents. good. Also. The surface protective layer 70 may be a mixture of the above-described inorganic antiviral agent and organic antiviral agent. In this case, only one type of organic antiviral agent described above may be included, or two or more types of organic antiviral agents may be included.
Furthermore, in order to further improve the scratch resistance of the decorative sheet 11, a nucleating agent that improves the crystallinity of the resin material is added to the surface protective layer 70.

That is, the surface protective layer 70 is formed by adding an antiviral agent and a nucleating agent to a resin material (for example, an ionizing radiation-curable resin). In this embodiment, the nucleating agent is added to the resin material in the form of nucleating agent vesicles which are enclosed in the outer membrane of the monolayer membrane and formed into vesicles. That is, in this embodiment, the surface protective layer 70 contains an ionizing radiation-curable resin and an antiviral agent, and further contains nano-sized structures in vesicles having a single-layer outer membrane for the ionizing radiation-curable resin. It is formed by adding nucleating agent vesicles containing a nucleating agent. Thereby, high scratch resistance can be imparted to the decorative sheet 11.
The nucleating agent contained in the surface protective layer 70 will be described in detail below.

[Nucleating agent]
As described above, in this embodiment, the surface protective layer 70 contains a nano-sized nucleating agent. The nano-sized nucleating agent is preferably used by being added to the polypropylene resin in the form of a nucleating agent vesicle, which is encapsulated in a vesicle having a monolayer outer membrane. Further, in this embodiment, the nucleating agent in the resin constituting the surface protective layer 70 may be encapsulated in a vesicle with a portion of the nucleating agent exposed. Since the surface protective layer 70 contains a nucleating agent, the degree of crystallinity can be improved, and the scratch resistance (scratch resistance) of the decorative sheet 11 can be improved.
The average particle size of the nano-sized nucleating agent is preferably 1/2 or less of the wavelength range of visible light. Specifically, since the wavelength range of visible light is 400 nm or more and 750 nm or less, the average particle size is preferably 375 nm or less.

Since nano-sized nucleating agents have extremely small particle sizes, the number of nucleating agents present per unit volume and the surface area increase in inverse proportion to the cube of the particle diameter. As a result, the distance between each nucleating agent particle becomes shorter, so that when crystal growth occurs from the surface of one nucleating agent particle added to the resin, the end where the crystal is growing will immediately The nucleating agent particle contacts the end of a crystal growing from the surface of another nucleating agent particle adjacent to the nucleating agent particle, and the ends of each crystal inhibit the growth of each crystal, thereby stopping the growth of each crystal. Therefore, the average particle size of spherulites in the crystal part of the crystalline resin can be reduced, for example, the spherulite size can be reduced to 1 μm or less. As a result, it is possible to create a highly hard resin film with a high degree of crystallinity, and the stress concentration between the spherulites that occurs during bending is efficiently dispersed, resulting in a resin that suppresses cracking and whitening during bending. film can be realized.

When a nucleating agent is simply added, the particle size increases due to secondary aggregation of the nucleating agent in the resin. On the other hand, when adding nucleating agent vesicles, the dispersibility in the resin improves, so the number of crystal nuclei relative to the amount of nucleating agent added increases significantly compared to the case where the nucleating agent is simply added. Therefore, the average particle size of spherulites in the crystalline portion of the resin becomes small, and the occurrence of cracks and whitening during bending can be suppressed. Therefore, by adding nucleating agent vesicles, the degree of crystallinity can be further increased, and it becomes possible to achieve both improved elastic modulus and processability.

The amount of nucleating agent vesicles added in the surface protective layer 70 is, for example, 0.05 parts by mass or more in terms of the nucleating agent in the nucleating agent vesicles, based on 100 parts by mass of the ionizing radiation-curable resin as the main component. The amount is preferably within the range of 0.5 parts by mass or less, and it is preferably formed from a resin material to which a nucleating agent is added within the range of 0.1 parts by mass or more and 0.3 parts by mass or less. When using a nucleating agent vesicle, the amount of the nucleating agent added to the resin material is the amount added in terms of the nucleating agent in the nucleating agent vesicle. When the amount of the nucleating agent added is less than 0.05 parts by mass, calculated as the nucleating agent in the nucleating agent vesicle, per 100 parts by mass of the ionizing radiation curable resin, the crystallinity of the resin material is insufficient. There is a possibility that the scratch resistance of the surface protective layer 70 will not be improved sufficiently. In addition, if the amount of the nucleating agent added exceeds 0.5 parts by mass, calculated as the nucleating agent in the nucleating agent vesicle, per 100 parts by mass of the ionizing radiation-curable resin, the ionizing radiation-curable resin may crystallize. There is a possibility that the scratch resistance of the surface protective layer 70 will not be improved reliably.

Here, the term "main component" refers to a resin material that accounts for 50% by mass or more of the resin material that constitutes the surface protection layer 70. Therefore, even when the resin material of the surface protective layer 70 is a mixture (blend resin) of an ionizing radiation-curable resin and another resin material (isocyanate-curable acrylic resin composition or thermosetting resin), the blend resin If 50 parts by mass or more of the ionizing radiation-curable resin, the nucleating agent vesicles may be added to the blend resin within the above range.

In addition, methods for nano-forming nucleating agents include, for example, the solid phase method, which mainly involves mechanically crushing the nucleating agent to obtain nano-sized particles, and the solid phase method, which involves dissolving the nucleating agent or the nucleating agent. methods such as the liquid phase method, which synthesizes and crystallizes nano-sized particles in a nucleating solution, and the gas-phase method, which synthesizes and crystallizes nano-sized particles from a nucleating agent or gas/steam containing the nucleating agent. It can be used as appropriate. Examples of solid phase methods include ball mills, bead mills, rod mills, colloid mills, conical mills, disk mills, hammer mills, jet mills, and the like. Further, examples of the liquid phase method include a crystallization method, a coprecipitation method, a sol-gel method, a liquid phase reduction method, and a hydrothermal synthesis method. Furthermore, examples of the gas phase method include an electric furnace method, a chemical flame method, a laser method, and a thermal plasma method.

As a method for nano-forming the nucleating agent, a supercritical reverse phase evaporation method is preferable. The supercritical reverse phase evaporation method is a method of producing capsules (nano-sized vesicles) containing a target substance using carbon dioxide under supercritical state, temperature conditions or pressure conditions above the critical point. Carbon dioxide in a supercritical state means carbon dioxide in a supercritical state at a critical temperature (30.98°C) and a critical pressure (7.3773 ± 0.0030 MPa) or above, and under a temperature condition above the critical point or Carbon dioxide under pressure means carbon dioxide under conditions where only the temperature or only the pressure exceeds the critical condition.

In addition, as a specific nano-forming process using supercritical reversed-phase evaporation method, first, an aqueous phase is injected into a mixed fluid of supercritical carbon dioxide, phospholipids as an outer membrane forming substance, and a nucleating agent as an encapsulating substance. Then, by stirring, an emulsion of supercritical carbon dioxide and an aqueous phase is generated. Next, by reducing the pressure, the carbon dioxide expands and evaporates, causing phase inversion, and the phospholipid generates nanocapsules (nanovesicles) in which the surface of the nucleating agent particles is covered with a monolayer film. By using this supercritical reversed-phase evaporation method, unlike the conventional encapsulation method in which the outer film forms a multilayer film on the surface of the nucleating agent particles, it is possible to easily produce capsules with a single layer film. Small diameter capsules can be prepared. That is, in this modification, the nucleating agent vesicle is preferably a vesicle formed by encapsulating the nucleating agent in a vesicle provided with a monolayer film by supercritical reverse phase evaporation.

The nucleating agent vesicles are prepared by, for example, the Bangham method, extrusion method, hydration method, surfactant dialysis method, reverse phase evaporation method, freeze-thaw method, supercritical reverse phase evaporation method, or the like. Nucleating agent vesicles are preferably prepared using supercritical reverse phase evaporation.
The outer membrane constituting the nucleating agent vesicle is composed of, for example, a single layer membrane. Further, the outer membrane is composed of a substance containing biological lipids such as phospholipids.

In this specification, a nucleating agent vesicle whose outer membrane is composed of a substance containing a biological lipid such as a phospholipid is referred to as a nucleating agent liposome.
Examples of the phospholipids constituting the outer membrane include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, hydrogenated soybean lecithin, etc. Examples include sphingophospholipids such as glycerophospholipid, sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.

Other substances forming the outer membrane of the vesicle include, for example, nonionic surfactants and dispersants such as mixtures of these and cholesterols or triacylglycerols. Among these, examples of nonionic surfactants include polyglycerin ether, dialkylglycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene polyoxypropylene copolymer. , polybutadiene-polyoxyethylene copolymer, polybutadiene-poly(2-vinylpyridine), polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. One type or two or more types can be used. As the cholesterol, for example, cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholate, or cholecalciferol can be used.

Furthermore, the outer membrane of the liposome may be formed from a mixture of a phospholipid and a dispersant. In the decorative sheet 11 of this modification, the nucleating agent vesicle is preferably a nucleating agent liposome (radical scavenger) having an outer membrane made of phospholipid. By forming the outer membrane from phospholipids, the compatibility between the resin material, which is the main component of the decorative sheet 10, and the vesicles can be improved.

The nucleating agent is not particularly limited as long as it is a substance that serves as a starting point for crystallization when the resin crystallizes. Examples of the nucleating agent include phosphate metal salts, benzoic acid metal salts, pimelic acid metal salts, rosin metal salts, benzylidene sorbitol, quinacridone, sodium oleate, cyanine blue, and talc. In particular, it is preferable to use sodium oleate. In addition, in order to obtain the maximum effect of nano treatment, it is also possible to use phosphate ester metal salts, benzoate metal salts, pimelic acid metal salts, and rosin metal salts, which are non-melting and can be expected to have good transparency. If the material itself can be made transparent by nano-processing, colored quinacridone, cyanine blue, talc, etc. can also be used. Furthermore, molten benzylidene sorbitol may be appropriately mixed with the non-melted nucleating agent.

In the decorative sheet 11 according to the present embodiment, the thermoplastic resin base sheet 1 contains a polyolefin resin, and has a thickness of 50 μm or more and 200 μm or less. Furthermore, in addition to the antiviral agent, the surface protective layer 70 of the decorative sheet 11 contains nucleating agent vesicles in which a nano-sized nucleating agent is encapsulated in a vesicle having a single-layer outer membrane. Thereby, it is possible to obtain a decorative sheet 11 that has antiviral properties and is provided with better scratch resistance and excellent flooring performance.
In the decorative sheet 11 according to the present embodiment, a silicone-based component (e.g., silicone resin) or a fluorine-based component (e.g., fluororesin) is set on the outermost surface (surface protective layer 70) of the decorative sheet 11, for example, as a measure to improve stain resistance. You may.

[Silicone resin]
When using silicone resin, it is preferable to use modified silicone from the viewpoint of adhesion and compatibility with the surroundings. When the curable resin constituting the surface protective layer 70 is formed from an ultraviolet curable resin or an electron beam curable resin, that is, an ionizing radiation curable resin, the modified silicone is a modified silicone resin that is reactive to ionizing radiation. It is preferable. Further, when the curable resin constituting the surface protective layer 70 is formed from a mixture of an ionizing radiation curable resin and a thermosetting resin, the modified silicone has at least one of ionizing radiation reactivity and thermal reactivity. It is preferable to use a modified silicone resin.

Modified silicones can be classified into reactive modified silicones and non-reactive silicones. Examples of heat-reactive modified silicones include monoamine-modified silicones, diamine-modified silicones, epoxy-modified silicones, carbinol-modified silicones, carboxy-modified silicones, mercapto-modified silicones, silanol-modified silicones, alcohol-modified silicones, and diol-modified silicones. Examples of modified silicones reactive with ionizing radiation include acrylic modified silicones and methacrylic modified silicones. Examples of non-reactive modified silicones include polyether-modified silicone, aralkyl-modified silicone, long-chain alkyl-modified silicone, and higher fatty acid ester-modified silicone. Manufacturers of these modified silicones include Shin-Etsu Chemical Co., Ltd., Dow Corning Toray Co., Ltd., Momentive Performance Materials Japan LLC, and Asahi Kasei Wacker Silicone Co., Ltd.

[Fluororesin]
Fluororesins are widely known to exhibit minimal levels of surface tension, making them suitable as stain-resistant materials. Examples of the fluororesin contained in the surface protective layer 70 include tetrafluoroethylene resin, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, and many other derivatives may also be used. can. Manufacturers of these fluororesins include Daikin Industries, Ltd. and Mitsui-DuPont Fluorochemicals, Inc. The amount of fluororesin contained in the surface protective layer 70 is preferably 10 parts by mass or more and 100 parts by mass or less. More preferably, it is 20 parts by mass or more. Here, the fluororesin itself may be a curable resin. That is, a part of the fluororesin may also serve as a part of the ionizing radiation-curable resin, which is the main component of the surface protection layer 70.

In this way, in the decorative sheet 11 according to the present embodiment, the surface protective layer 70, which is the outermost layer, may contain at least one of a silicone component and a fluorine component. Thereby, the stain resistance of the decorative sheet 11 can be improved. When the stain resistance is improved, it is possible to prevent viruses from remaining on the surface of the decorative sheet 11 for a long period of time, and as a result, the antiviral properties can be further improved.

[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 11)
The method for manufacturing the decorative sheet 11 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 transparent thermoplastic resin layer 6 is formed on the polyester resin layer 4 by extruding a resin composition containing a molten transparent thermoplastic resin from an extruder. Next, the transparent thermoplastic resin layer 6 is embossed. Finally, a resin composition in which an antiviral agent and nucleating agent vesicles are added to an ionizing radiation curable resin (for example, an ultraviolet curable resin) is gravure coated onto the embossed transparent thermoplastic resin layer 6. The surface protective layer 70 is formed by coating and curing using a method or the like. In this way, the decorative sheet 11 according to this embodiment is manufactured.

Note that the method for manufacturing the decorative sheet 11 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. Further, in the step of forming the transparent thermoplastic resin layer 6, an ultraviolet absorber and a light stabilizer may be added to the molten transparent thermoplastic resin.
Further, after performing surface treatment on the surface of the thermoplastic resin base sheet 1 opposite to the picture pattern layer 2, a primer coating liquid is applied by a gravure coating method or the like to form a primer layer 8. It may also include a step of.

(Modified example)
Next, a modification of the decorative sheet according to the first embodiment will be described using FIG. 2. FIG. 2 is a schematic cross-sectional view for explaining a configuration example of the decorative sheet 12 according to a modification of the first embodiment. The decorative sheet 12 according to the present modification differs from the first embodiment in that a nucleating agent that improves the crystallinity of the resin material is also added to the transparent thermoplastic resin layer in order to further improve the scratch resistance. It is different from the decorative sheet 11 according to.
The transparent thermoplastic resin layer 60 in the decorative sheet 12, which has a different configuration from the decorative sheet 11, will be described in detail below. Note that the configuration of the decorative sheet 12 other than the transparent thermoplastic resin layer 60 is the same as that of the decorative sheet 11. Therefore, the same reference numerals as those of the decorative sheet 11 are given, and detailed explanation will be omitted.

As shown in FIG. 2, the decorative sheet 12 includes a transparent thermoplastic resin layer 60. The transparent thermoplastic resin layer 60 is formed by adding a nucleating agent to a resin material (polypropylene resin). In this modification, the nucleating agent is added to the resin material in the form of nucleating agent vesicles, which are enclosed in the outer membrane of the single-layer membrane and formed into vesicles, as in the first embodiment.
That is, in this modification, the transparent thermoplastic resin layer 60 is formed using a polypropylene resin, and furthermore, a nano-sized nucleating agent is encapsulated in a vesicle having a single-layer outer membrane for the polypropylene resin. It is formed by adding nucleating agent vesicles. Thereby, even higher scratch resistance can be imparted to the decorative sheet 12.

In this way, the decorative sheet 12 according to the present modification differs from the first embodiment in that the transparent thermoplastic resin layer contains nucleating agent vesicles together with the surface protective layer.
Further, the nucleating agent contained in the transparent thermoplastic resin layer 60 is the same as the nucleating agent vesicle contained in the surface protective layer 70 in the first embodiment, and therefore detailed description thereof will be omitted. Further, since the transparent thermoplastic resin layer 60 has the same structure as the transparent thermoplastic resin layer 6 in the first embodiment except that it contains nucleating agent vesicles, detailed description thereof will be omitted.
In this modification, the nucleating agent in the polypropylene resin constituting the transparent thermoplastic resin layer 60 may be encapsulated in a vesicle with a portion of the nucleating agent exposed. Thereby, since the transparent thermoplastic resin layer 60 contains a nucleating agent, the degree of crystallinity can be improved, and the scratch resistance (scratch resistance) of the decorative sheet 12 can be further improved.

The addition amount of the nucleating agent vesicles in the transparent thermoplastic resin layer 60 is 0.05 parts by mass or more in terms of the nucleating agent in the nucleating agent vesicles per 100 parts by mass of the polypropylene resin as the main component. It is preferably within a range of 5 parts by mass or less, and more preferably within a range of 0.1 parts by mass or more and 0.3 parts by mass or less.
If the amount of the nucleating agent added is less than 0.05 parts by mass, the degree of crystallinity of the polypropylene may not be sufficiently improved, and the scratch resistance of the transparent thermoplastic resin layer 60 may not be sufficiently improved. In addition, when the amount of the nucleating agent added exceeds 0.5 parts by mass, the growth of spherulites of polypropylene is adversely inhibited due to excessive crystal nuclei, and as a result, the degree of crystallinity of polypropylene is not sufficiently improved. There is a possibility that the scratch resistance of the transparent thermoplastic resin layer 60 will not be sufficiently improved.
Here, the term "main component" refers to a resin material that accounts for 50% by mass or more of the resin material that constitutes the transparent thermoplastic resin layer 60.

Further, in this modification as well, as in the first embodiment, the thermoplastic resin base sheet 1 contains a polyolefin resin, and has a thickness of 50 μm or more and 200 μm or less. Thereby, the decorative sheet 12 can obtain excellent floor material performance (impact resistance, caster resistance, and workability) in addition to scratch resistance.
That is, in the decorative sheet 12 according to this modification, the thermoplastic resin base sheet 1 contains a polyolefin resin, has a thickness in the range of 50 μm or more and 200 μm or less, and the transparent thermoplastic resin layer 60 has a monolayer film. It is preferable that a nucleating agent vesicle containing a nano-sized nucleating agent is added to the vesicle having an outer membrane. Thereby, it is possible to obtain a decorative sheet that has antiviral properties and is provided with better scratch resistance and excellent flooring performance.

As described above, in the decorative sheet 12 which is a modified example of the decorative sheet according to the first embodiment, the thermoplastic resin base sheet contains a polyolefin resin, the thickness is within the range of 50 μm or more and 200 μm or less, and the surface protective layer 70 and the transparent thermoplastic resin layer 60 both contain nucleating agent vesicles in which a nano-sized nucleating agent is encapsulated in a vesicle having a single-layer outer membrane.
Thereby, it is possible to reliably impart excellent floor material performance and better scratch resistance, and it is possible to provide a decorative sheet that has even better scratch resistance and antiviral properties.

(Effects of the first embodiment)
As explained above, the decorative sheet 11 of the first embodiment has a picture pattern layer 2, a first adhesive layer 3, a polyester resin layer 4, a second adhesive layer 5 on a thermoplastic resin base sheet 1. , a transparent thermoplastic resin layer 6, and a surface protection layer 70 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 500 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 within the range of 150 μm or more and 700 μm or less. Furthermore, the surface protective layer 70 contains an ionizing radiation-curable resin, an antiviral agent, and nucleating agent vesicles.

With such a configuration, it is possible to provide a decorative sheet that has excellent scratch resistance and antiviral properties. In addition, with such a configuration, it is possible to provide a decorative sheet that has not only antiviral properties but also scratch resistance and abrasion resistance equivalent to decorative sheets equipped with melamine plates, and also has excellent processability and yield. becomes possible.
Further, in the decorative sheet according to the first embodiment, the thermoplastic resin base sheet 1 contains a polyolefin resin, has a thickness in the range of 50 μm or more and 200 μm or less, and the surface protective layer 70 and the transparent thermoplastic Nucleating agent vesicles in which a nano-sized nucleating agent is encapsulated in a vesicle having a single-layer outer membrane may be added to both of the resin layers 60.

That is, the decorative sheet according to the present embodiment may be a decorative sheet (decorative sheet 11) including the surface protective layer 70 to which nucleating agent vesicles are added, or a transparent thermoplastic sheet to which nucleating agent vesicles are added. A decorative sheet (decorative sheet 12) including a resin layer 60 and a surface protection layer 70 may be used.
With such a configuration, it is possible to provide a decorative sheet that has excellent floor material performance, better scratch resistance, and antiviral properties.

Further, in this embodiment, the surface protection layer 70 is formed by adding an antiviral agent to an ionizing radiation curable resin.
With such a configuration, it is possible to more reliably provide a decorative sheet that has excellent scratch resistance and antiviral properties.
The amount of the nucleating agent vesicles added in the surface protective layer 70 is 0.05 parts by mass or more and 0.5 parts by mass in terms of the nucleating agent in the nucleating agent vesicles per 100 parts by mass of the ionizing radiation curing resin. It is preferable that the amount is within the range of 100% or less.
With such a configuration, the degree of crystallinity of the resin material can be sufficiently improved, and the scratch resistance of the surface protection layer 70 can be reliably improved.

Further, in the decorative sheet 11 of this embodiment, the primer layer 8 may be provided on the surface of the thermoplastic resin base sheet 1 opposite to the picture pattern layer 2.
With such a configuration, it is possible to improve the adhesion with the adhesive used for bonding the decorative sheet 11 to the decorative material substrate provided on the side opposite to the picture pattern layer 2.
Further, in the decorative sheet 11 of this embodiment, the thickness of the transparent thermoplastic resin layer 6 may be within the range of 50 μm or more and 150 μm or less.
With such a configuration, the wear resistance and scratch resistance are sufficiently within the practical range, and the productivity during manufacturing is excellent, which is advantageous in terms of cost.

Further, the decorative sheet 11 may have the following configuration. That is, the decorative sheet 11 of the first embodiment of the present invention has a picture pattern layer 2, a first adhesive layer 3, a polyester resin layer 4, a second adhesive layer 5, on a thermoplastic resin base sheet 1. A transparent thermoplastic resin layer 6 and a surface protection layer 70 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 (polyethylene terephthalate resin layer 4a) containing polyethylene terephthalate, 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. Further, the surface protection layer 70 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 12 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.

<Second embodiment>
A decorative sheet according to a second embodiment of the present disclosure will be described using FIG. 3. FIG. 3 is a schematic cross-sectional view for explaining one configuration example of the decorative sheet 20 according to the second embodiment. The decorative sheet 20 according to the second embodiment differs from the decorative sheet 11 in that the transparent thermoplastic resin layer has a multilayer structure.
Hereinafter, the transparent thermoplastic resin layer 26 in the decorative sheet 20, which has a different configuration from the decorative sheet 10, will be described in detail. Note that the configuration of the decorative sheet 20 other than the transparent thermoplastic resin layer 26 is the same as that of the decorative sheet 10. Therefore, the same reference numerals as those of the decorative sheet 10 are given, and detailed explanation will be omitted.

As shown in FIG. 3, the decorative sheet 20 includes a transparent thermoplastic resin layer 26. The transparent thermoplastic resin layer 26 includes, from the polyester resin layer 4 side, a first resin layer 26a containing a predetermined resin (hereinafter also referred to as "first resin"), and a first resin layer 26a. The second resin layer 26b is formed by laminating two layers in this order, each of which includes a resin different from the first resin (hereinafter also referred to as "second resin"). Further, the transparent thermoplastic resin layer 26 may be composed of only two layers, the first resin layer 26a and the second resin layer 26b.
In the transparent thermoplastic resin layer according to the present disclosure, the number of layers can be four or more, but the number of layers is preferably up to three because the structure of the extruder becomes complicated and the work becomes more complicated. Of course, as shown in FIG. 2, in the present disclosure, the transparent thermoplastic resin layer (for example, the transparent thermoplastic resin layer 60) may be two layers, or as shown in FIG. 1, the transparent thermoplastic resin layer ( For example, the transparent thermoplastic resin layer 6) may be one layer.

In the second embodiment, the thickness of the first resin layer 26a may be 10 μm or more, and may be 20% or less of the total thickness of the transparent thermoplastic resin layer 26. Further, the thickness of the first resin layer 26a is preferably 50 μm or more, and more preferably 10% or less of the total thickness of the transparent thermoplastic resin layer 26. If the thickness of the first resin layer 26a is less than 10 μm, the adhesion stability of the first resin layer 26a tends to decrease. Further, if the thickness of the first resin layer 26a exceeds 20% of the thickness of the entire transparent thermoplastic resin layer 26, the surface strength of the entire decorative sheet 20 tends to decrease. In other words, if the thickness of the first resin layer 26a is 10 μm or more and 20% or less of the total thickness of the transparent thermoplastic resin layer 26, the adhesion stability of the first resin layer 26a can be maintained. , the surface strength of the entire decorative sheet 20 can be maintained. Further, the thickness of the first resin layer 26a is 10 μm or more, and the total thickness of the transparent thermoplastic resin layer 26 composed of only two layers, the first resin layer 26a and the second resin layer 26b. The surface strength of the decorative sheet 20 as a whole can be maintained while maintaining the adhesion stability of the first resin layer 26a.

Further, the content rate (mass %) of the transparent maleic acid-modified polypropylene resin in the first resin layer 26a may be greater than the content rate (mass %) of the transparent polypropylene resin in the second resin layer 26b. Even in this case, the surface strength of the entire decorative sheet 20 can be maintained while maintaining the adhesion stability of the first resin layer 26a. Specifically, the content (mass%) of the transparent maleic acid-modified polypropylene resin in the first resin layer 26a is 80% by mass or more, and the content (mass%) of the transparent polypropylene resin in the second resin layer 26b is 80% by mass or more. ) may be larger.

When the decorative sheet 20 includes the first resin layer 26a and the second resin layer 26b, the first resin layer 26a ensures adhesiveness with the thermoplastic resin base sheet 1, and the second The resin layer 26b becomes the main part and assumes other physical properties, making it possible to widen the scope of material design. By including transparent maleic acid-modified polypropylene resin in the first resin layer 26a, interlayer adhesion can be improved. Furthermore, by forming the second resin layer 26b as a layer containing transparent polypropylene resin, the resistance to embrittlement inside the resin can be reduced.
Note that, as a method for forming the transparent thermoplastic resin layer 26 consisting of two layers, the first resin layer 26a and the second resin layer 26b, a twin-screw extruder is used to form the first resin layer 26a and the second resin layer 26b. A preferred method is to simultaneously extrude and bond the two layers together with the resin layer 26b.

As described above, in the present disclosure, the transparent thermoplastic resin layer may be composed of a plurality of layers made of different types of polypropylene resins.
For example, the transparent thermoplastic resin layer 26 is formed using a polypropylene resin, and includes a first resin layer 26a formed including a first resin, and a first resin layer 26a formed on the first resin layer 26a, and a first resin layer 26a formed using a polypropylene resin. The second resin layer 26b may include a second resin different from the second resin layer 26b.
Examples of the first resin and second resin in the transparent thermoplastic resin layer include scratch resistance, weather resistance, stain resistance, light resistance, transparency, bendability, thermoformability, etc. of the surface of the decorative sheet 20. Taking this into consideration, 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 26b may be a layer containing either an ultraviolet absorber or a light stabilizer together with a transparent polypropylene resin that is the second resin.

(Method for manufacturing decorative sheet 20)
The method for manufacturing the decorative sheet 20 will be briefly described below.
The method for manufacturing the decorative sheet 20 is the same as the method for manufacturing the decorative sheet 11 according to the first embodiment in that the first resin layer 6a and the second resin layer 6b are formed in the step of forming the transparent thermoplastic resin layer 60. different from.
Specifically, in the method for manufacturing the decorative sheet 20 of the second embodiment, a picture pattern layer 2 is formed by printing on a thermoplastic resin base sheet 1, and a polyester resin layer 4 is formed on the picture pattern layer 2. are pasted together using dry lamination. After that, a transparent thermoplastic resin layer is formed by laminating a plurality of layers (first resin layer 26a, second resin layer 26b) formed by extruding a resin composition containing a molten transparent thermoplastic resin from a multilayer extruder. 26 is formed, and the transparent thermoplastic resin layer 26 is embossed.
With such a configuration, the decorative sheet 20 has the characteristics of flexibility, stain resistance, chemical resistance, weather resistance, scratch resistance, and designability mainly based on transparency, which are obtained with vinyl chloride resin. It is possible to form embossing with excellent reproducibility.

(Modified example)
A modification of the decorative sheet according to the second embodiment will be described using FIG. 4. FIG. 4 is a schematic cross-sectional view for explaining a configuration example of the decorative sheet 21 according to a modification of the second embodiment. The decorative sheet 21 according to this modification has the above-mentioned feature in that a nucleating agent that improves the crystallinity of the resin material is added to the transparent thermoplastic resin layer having a multilayer structure in order to further improve the scratch resistance. This is different from the decorative sheet 20 according to the second embodiment.
Hereinafter, the transparent thermoplastic resin layer 216 in the decorative sheet 21, which has a different configuration from the decorative sheet 20, will be described in detail. In addition, in the decorative sheet 21, the structure other than the transparent thermoplastic resin layer 216 is the same as that of the decorative sheet 20. Therefore, the same reference numerals as those of the decorative sheet 20 are given, and detailed explanation will be omitted.

As shown in FIG. 4, the decorative sheet 21 includes a transparent thermoplastic resin layer 216. The transparent thermoplastic resin layer 216 is formed by adding a nucleating agent to a resin material (polypropylene resin). In this modification, the nucleating agent is added to the resin material in the form of nucleating agent vesicles, which are enclosed in the outer membrane of the single-layer membrane and formed into vesicles, as in the first embodiment.
More specifically, the transparent thermoplastic resin layer 216 contains nucleating agent vesicles in the first resin forming the first resin layer 216a and the second resin forming the second resin layer 216b. There is.

That is, in this modification, the transparent thermoplastic resin layer 216 is formed using polypropylene resin, and includes a first resin layer 216a formed including a first resin (transparent maleic acid-modified polypropylene resin), and a first resin layer 216a formed using a polypropylene resin. A second resin layer is formed on the resin layer and includes a second resin (transparent polypropylene resin) different from the first resin. Further, in the transparent thermoplastic resin layer 216, nucleating agent vesicles are added to the polypropylene resins of both the first resin and the second resin. Thereby, even higher scratch resistance can be imparted to the decorative sheet 21.

As described above, the decorative sheet 21 according to the present modification differs from the decorative sheet 20 of the second embodiment in that the transparent thermoplastic resin layer of the multilayer structure includes nucleating agent vesicles.
Further, the nucleating agent contained in the transparent thermoplastic resin layer 216 is the same as the nucleating agent vesicle contained in the surface protection layer 70 of the first embodiment, so detailed description thereof will be omitted. Further, since the transparent thermoplastic resin layer 216 has the same structure as the transparent thermoplastic resin layer 26 shown in FIG. 3 except that it contains nucleating agent vesicles, detailed description thereof will be omitted.

In this modification, the nucleating agent in the polypropylene resin constituting the transparent thermoplastic resin layer 216 may be encapsulated in a vesicle with a portion of the nucleating agent exposed. As a result, since the first resin layer 216a and the second resin layer 216b of the transparent thermoplastic resin layer 216 contain a nucleating agent, the degree of crystallinity can be improved, and the scratch resistance (scratch resistance) of the decorative sheet 12 can be further improved. can be improved.
Further, the amount of the nucleating agent vesicle added in the transparent thermoplastic resin layer 216 is 0.05 parts by mass or more, calculated as the nucleating agent in the nucleating agent vesicle, per 100 parts by mass of the polypropylene resin as the main component. It is preferably within a range of 5 parts by mass or less, and more preferably within a range of 0.1 parts by mass or more and 0.3 parts by mass or less.

Here, the term "main component" refers to a resin material that accounts for 50% by mass or more of the resin materials that constitute the first resin layer 216a and the second resin layer 216b.
By adding the nucleating agent vesicles within the above range, the degree of crystallinity of polypropylene is sufficiently improved, and the crystallinity of the transparent thermoplastic resin layer 216 (first resin layer 216a, second resin layer 216b) is improved. Definitely improves scratch resistance.
Further, in this modification, as in the first embodiment, the thermoplastic resin base sheet 1 is configured to include a polyolefin resin, and preferably has a thickness in the range of 50 μm or more and 200 μm or less. Thereby, it is possible to obtain a decorative sheet that has antiviral properties and is provided with better scratch resistance and excellent flooring performance.

As described above, as the first modification of the decorative sheet according to the second embodiment, the polypropylene resin of both the first resin (transparent maleic acid-modified polypropylene resin) and the second resin (transparent polypropylene resin), that is, the first resin Although an example has been described in which the above-mentioned nucleating agent vesicles are added to both the layer 216a and the second resin layer 216b, the present disclosure is not limited thereto.

For example, a transparent thermoplastic resin layer having a multilayer structure including a first resin layer and a second resin layer, a first resin layer 216a containing nucleating agent vesicles, and a second resin layer 216a containing no nucleating agent vesicles. The resin layer 26b may be composed of a first resin layer 26a that does not contain nucleating agent vesicles and a second resin layer 216b containing nucleating agent vesicles.
That is, in the transparent thermoplastic resin layer having a multilayer structure, the nucleating agent vesicles may be contained only in the transparent maleic acid-modified polypropylene resin that is the first resin, that is, only the first resin layer, or the nucleating agent vesicles may be contained only in the transparent maleic acid-modified polypropylene resin that is the first resin. Nucleating agent vesicles may be contained only in the transparent polypropylene resin, that is, only in the second resin layer.

In other words, in the decorative sheet of the present disclosure, in the transparent thermoplastic resin layer having the first resin layer and the second resin layer, the polypropylene resin, which is at least one of the first resin and the second resin, is added to the nucleated resin. Agent vesicles may also be added. Thereby, it is possible to select a layer containing nucleating agent vesicles according to the purpose and cost, and to impart superior scratch resistance to the decorative sheet.
More specifically, in the decorative sheet of the present disclosure, the amount of nucleating agent vesicles added in the transparent thermoplastic resin layer 216 having the first resin layer and the second resin layer is higher than that of the first resin (transparent maleic acid). 0.05 parts by mass or more in terms of the nucleating agent in the nucleating agent vesicles, based on 100 parts by mass of at least one of the polypropylene resin (modified polypropylene resin) or the second resin (transparent polypropylene resin) It may be within the range of less than 100 yen.

In other words, when nucleating agent vesicles are added to the first resin, the amount of nucleating agent in the nucleating agent vesicles is calculated based on 100 parts by mass of polypropylene resin (transparent maleic acid-modified polypropylene resin) as the first resin. The nucleating agent vesicles may be added within a range of 0.05 parts by mass or more and 0.5 parts by mass or less. In addition, when nucleating agent vesicles are added to the second resin, 0% in terms of the nucleating agent in the nucleating agent vesicles per 100 parts by mass of polypropylene resin (transparent polypropylene resin) as the second resin. Nucleating agent vesicles may be added within a range of .05 parts by mass or more and 0.5 parts by mass or less. In addition, when nucleating agent vesicles are added to both the first resin and the second resin layer, the nucleating agent vesicles are added to 100 parts by mass of the polypropylene resin of each of the first resin and the second resin. Nucleating agent vesicles may be added within a range of 0.05 part by mass or more and 0.5 parts by mass or less in terms of the nucleating agent.
Thereby, it is possible to select a layer containing nucleating agent vesicles according to the application and cost, and to reliably impart superior scratch resistance to the decorative sheet.

Further, in the decorative sheet 21, the resin material (for example, ionizing radiation-curable resin) of the surface protection layer 70 includes the above-mentioned antiviral agent and a nano-sized nucleating agent encapsulated in vesicles having a monolayer outer membrane. Nucleating agent vesicles are added. Thereby, antiviral properties can be imparted to the decorative sheet 21, and higher scratch resistance can be imparted.
Note that the configuration of the decorative sheet 21 other than the surface protective layer 70 is the same as that of the decorative sheet 10. Therefore, the same reference numerals as those of the decorative sheet 10 are given, and detailed explanation will be omitted.

Moreover, the present disclosure is not limited to this. The decorative sheet according to this modification may have a structure in which the surface protective layer and at least one of the first resin layer and the second resin layer of the transparent thermoplastic resin layer contain nucleating agent vesicles. In this case, nucleating agent vesicles may be added to both the first resin layer and the second resin layer in the transparent thermoplastic resin layer, or one of the first resin layer or the second resin layer A nucleating agent vesicle may be added to the vesicle. This makes it possible to more flexibly select the layer containing nucleating agent vesicles in accordance with the application and cost, while reliably imparting superior scratch resistance to the decorative sheet.

(Effects of the second embodiment)
As explained above, in the decorative sheets (for example, decorative sheets 20, 21) of the second embodiment, the transparent thermoplastic resin layers 26, 216 are formed using polypropylene resin and are formed including the first resin. A second resin layer 26b, 216b formed on the first resin layer 26a, 216a and containing a second resin different from the first resin. The first resin is a transparent maleic acid-modified polypropylene resin among polypropylene resins, and the second resin is a transparent polypropylene resin among polypropylene resins. Furthermore, in the transparent thermoplastic resin layer 216, nucleating agent vesicles are added to at least one polypropylene resin of the first resin or the second resin.

According to this configuration, it is possible to select a layer containing nucleating agent vesicles according to the purpose and cost, and to impart superior scratch resistance to the decorative sheet.
Further, the amount of the nucleating agent vesicle added in the transparent thermoplastic resin layer 216 is determined based on 100 parts by mass of the polypropylene resin of at least one of the first resin and the second resin. It is within the range of 0.05 part by mass or more and 0.5 part by mass or less.
According to this configuration, it is possible to select a layer containing nucleating agent vesicles according to the purpose and cost, and to reliably impart superior scratch resistance to the decorative sheet.

<Third embodiment>
A decorative board according to a third embodiment of the present disclosure will be described using FIG. 5. FIG. 5 is a cross-sectional view for explaining one configuration example of the decorative board 100 according to the third embodiment of the present disclosure.

(Decorative board)
The decorative board 100 includes 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 on one side of a thermoplastic resin base sheet 1. , and a surface protection layer 70 are laminated in this order, and a primer layer 8 and a base material 19 are provided on the other side of the thermoplastic resin base sheet 1.
That is, the decorative board 100 differs from the decorative sheet 11 according to the first embodiment in that it includes the base material 19.
The base material 19 will be explained below. Note that each layer other than the base material 19 (picture pattern layer 2, first adhesive layer 3, polyester resin layer 4, second adhesive layer 5, transparent thermoplastic resin layer 6, surface protection layer 70, and primer layer 8) Since the structure is the same as that of each layer of the decorative sheet 11, the explanation thereof will be omitted.

(Base material)
The base material 19 is a base material for a decorative board. As the base material 19, a wooden base material or a metal base material can be used. As the wood base material, for example, wood veneer, wood plywood, laminated wood, particle board, medium density fiberboard, and hard fiberboard can be employed. By including the base material 19, which is a decorative material substrate, and the decorative sheet 11 laminated to the decorative material substrate, it is possible to provide a decorative board 100 that is excellent in scratch resistance and has antiviral properties. Furthermore, since the decorative board 100 has excellent scratch resistance, it is possible to suppress the occurrence of scratches caused by heels of shoes or pebbles during heavy walking.
Note that in this embodiment, the base material 19 is bonded to the decorative sheet 11 according to the first embodiment, but the present disclosure is not limited to this. Instead of the decorative sheet 11, a decorative sheet 12 according to a modification of the first embodiment (see FIG. 2), a decorative sheet 20 according to the second embodiment (see FIG. 3), a modification of the second embodiment A decorative material may be formed using any of such decorative sheets 21 (see FIG. 4).

<Effects of the third embodiment>
The decorative board 100 according to the third embodiment has the following effects in addition to the effects of the first and second embodiments.
The decorative board 100 of the third embodiment includes a base material 19 that is a decorative material substrate, and any one of decorative sheets 11, 12, 20, and 21 laminated to the decorative material substrate.
According to this configuration, it is possible to provide the decorative board 100 that has excellent scratch resistance and antiviral properties.

Hereinafter, the present disclosure will be explained in more detail with reference to Examples. Note that the present disclosure is not limited in any way by the examples.

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

Subsequently, two molten transparent thermoplastic resin layers were extruded using a T-die using a multi-axis extruder to form a two-layer transparent thermoplastic resin layer on the second adhesive layer. 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 a two-layer transparent thermoplastic resin layer, all the layers were nipped with a conduit embossing plate and a rubber roll to perform embossing and lamination simultaneously. As a result, the thermoplastic resin base sheet 1, the pattern layer 2, the first adhesive layer 3, the polyester resin layer 4, the second adhesive layer 5, and the transparent thermoplastic resin layer 26 as shown in FIG. A laminate having a structure consisting of (first resin layer 26a, second resin layer 26b) was obtained. Here, the thickness of the first resin layer was 15 μm, and the thickness of the second resin layer was 85 μm.

After surface treatment was applied to the embossed surface of this laminate, a hardening 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.). 1 part by mass, a silver-based inorganic antibacterial agent as described below as an antiviral agent, and an acrylic ultraviolet curable resin to which nucleating agent vesicles were added were gravure coated so that the coating amount after drying was 7 g/ ^m2 . The coating was immediately applied to the surface of the substrate and immediately cured by irradiation with ultraviolet rays to form a surface protective layer (corresponding to the surface protective layer 70 in FIG. 4). The thickness of the surface protective layer was 10 μm.

Here, the antiviral agent added to the surface protective layer will be described in detail.
As the antiviral agent, a silver-based inorganic antibacterial agent (Bioside TB-B100, manufactured by Taisho Technos Co., Ltd.) was used. In the antiviral agent, a silver-based material, which is an active ingredient, is supported by an inorganic material. The above antiviral agent was added in an amount of 0.2 parts by mass to 100 parts by mass of the acrylic ultraviolet curable resin forming the surface protective layer. The average particle size of the antiviral agent was 5 μm. The first peak of the particle size of the antiviral agent was 3 μm, and the second peak was 7 μm.
In addition, a nucleating agent vesicle in which a nano-sized nucleating agent is encapsulated in a vesicle having a single-layered outer membrane is added to 100 parts by mass of the acrylic ultraviolet curable resin forming the surface protective layer. 0.1 part by mass was added in terms of the nucleating agent in the vesicles.

The nucleating agent vesicles used were those made into vesicles by supercritical reverse phase evaporation. In the supercritical reverse phase evaporation method, first, 100 parts by weight of methanol, 70 parts by weight of sodium oleate as a dispersant, and 5 parts by weight of phosphatidylcholine as a substance constituting the outer membrane of vesicles are placed in a high-pressure stainless steel container kept at 60°C. The container was placed in a container and sealed, and carbon dioxide was injected into the container so that the pressure became 20 MPa to create a supercritical state. Thereafter, the inside of the container is vigorously stirred, and 100 parts by weight of ion-exchanged water is poured into the container. After stirring and mixing for an additional 15 minutes while maintaining the temperature and pressure in a supercritical state, carbon dioxide was discharged from the container and the pressure was returned to atmospheric pressure to obtain liposomes having an outer membrane made of phospholipid containing a dispersant. Note that when the outer membrane of the vesicle is made of a substance such as a dispersant, the above-mentioned dispersant may be used instead of phosphatidylcholine.

Furthermore, after performing surface treatment on the back side of the thermoplastic resin base sheet, 10 parts by weight of silica and 3 parts by weight of isocyanate were added to this surface to 100 parts by weight of polyol to form a primer. A coating solution was prepared, and a primer layer was obtained by gravure coating so that the coating amount after drying was 3 g/m ² .
Through these procedures, a decorative sheet of Example 1-1 was formed.

[Example 1-2]
The amount of antiviral agent added in the surface protective layer was changed to 15 parts by mass based on 100 parts by mass of the acrylic ultraviolet curable resin. A decorative sheet of Example 1-2 was produced in the same manner as in Example 1-1 except for the above.
[Example 1-3]
The amount of antiviral agent added in the surface protective layer was changed to 17 parts by mass based on 100 parts by mass of the acrylic ultraviolet curable resin. Further, the amount of the curing agent added was changed to 2.2 parts by mass with respect to 100 parts by mass of the urethane resin as the top coat resin. A decorative sheet of Example 1-3 was produced in the same manner as in Example 1-1 except for the above.
[Example 1-4]
The amount of antiviral agent added in the surface protective layer was changed to 25 parts by mass based on 100 parts by mass of the acrylic ultraviolet curable resin. The decorative sheet of Example 1-4 was produced in the same manner as in Example 1-1 except for the above.

[Example 1-5]
The average particle size of the antiviral agent was changed to 0.1 μm. The decorative sheet of Example 1-5 was produced in the same manner as in Example 1-2 except for the above.
[Example 1-6]
The average particle size of the antiviral agent was changed to 1 μm. A decorative sheet of Example 1-6 was produced in the same manner as in Example 1-2 except for the above.
[Example 1-7]
The average particle size of the antiviral agent was changed to 10 μm. A decorative sheet of Example 1-7 was produced in the same manner as in Example 1-2 except for the above.
[Example 1-8]
The average particle size of the antiviral agent was changed to 20 μm. A decorative sheet of Example 1-8 was produced in the same manner as in Example 1-2 except for the above.

[Example 1-9]
The first peak of the particle size of the antiviral agent was changed to 0.1 μm. A decorative sheet of Example 1-9 was produced in the same manner as in Example 1-2 except for the above.
[Example 1-10]
The first peak of the particle size of the antiviral agent was changed to 1 μm. A decorative sheet of Example 1-10 was produced in the same manner as in Example 1-2 except for the above.
[Example 1-11]
The first peak of the particle size of the antiviral agent was changed to 5 μm. A decorative sheet of Example 1-11 was produced in the same manner as in Example 1-2 except for the above.
[Example 1-12]
The first peak of the particle size of the antiviral agent was changed to 6 μm. A decorative sheet of Example 1-12 was produced in the same manner as in Example 1-2 except for the above.

[Example 1-13]
The second peak of the particle size of the antiviral agent was changed to 4 μm. A decorative sheet of Example 1-13 was produced in the same manner as in Example 1-2 except for the above.
[Example 1-14]
The second peak of the particle size of the antiviral agent was changed to 5 μm. A decorative sheet of Example 1-14 was produced in the same manner as in Example 1-2 except for the above.
[Example 1-15]
The second peak of the particle size of the antiviral agent was changed to 10 μm. A decorative sheet of Example 1-15 was produced in the same manner as in Example 1-2 except for the above.
[Example 1-16]
The second peak of the particle size of the antiviral agent was changed to 20 μm. A decorative sheet of Example 1-16 was produced in the same manner as in Example 1-2 except for the above.

[Example 1-17]
The first peak of the particle size of the antiviral agent was changed to 0.1 μm, and the second peak was changed to 4 μm. A decorative sheet of Example 1-17 was produced in the same manner as in Example 1-2 except for the above. [Example 1-18]
The first peak of the particle size of the antiviral agent was changed to 10 μm, and the second peak was changed to 20 μm. A decorative sheet of Example 1-18 was produced in the same manner as in Example 1-2 except for the above.
[Example 1-19]
The transparent thermoplastic resin layer was changed to a single layer structure. Specifically, one transparent thermoplastic resin layer is formed by providing only a second resin layer made of a second resin (polypropylene resin) without providing a first resin layer as a transparent thermoplastic resin layer. did. Otherwise, a decorative sheet of Example 1-19 was produced in the same manner as in Example 1-2.

[Comparative example 1-1]
No antiviral agent or nucleating agent vesicles were added to the surface protective layer. A decorative sheet of Comparative Example 1-1 was produced in the same manner as in Example 1-1 except for the above.
[Comparative example 1-2]
The amount of the antiviral agent added was changed to 0.1 parts by mass based on 100 parts by mass of the acrylic ultraviolet curable resin. A decorative sheet of Comparative Example 1-2 was produced in the same manner as in Example 1-1 except for the above.
[Comparative example 1-3]
The amount of the antiviral agent added was changed to 30 parts by mass based on 100 parts by mass of the acrylic ultraviolet curable resin. A decorative sheet of Comparative Example 1-3 was produced in the same manner as in Example 1-1 except for the above.
[Comparative example 1-4]
The amount of the antiviral agent added was changed to 15 parts by mass based on 100 parts by mass of the acrylic ultraviolet curable resin. Further, the amount of the nucleating agent added was 0.1 part by mass, calculated as the nucleating agent in the nucleating agent vesicle, per 100 parts by mass of the acrylic ultraviolet curable resin. A decorative sheet of Comparative Example 1-4 was produced in the same manner as in Example 1-1 except for the above.

<Evaluation Judgment>
The decorative sheets obtained in Examples 1-1 to 1-19 and Comparative Examples 1-1 to 1-4 described above were evaluated for antiviral performance, scratch resistance, and stain resistance using the following methods.

<Evaluation>
[Antiviral performance]
An antiviral test was conducted on the decorative sheets of Examples 1-1 to 1-19 and Comparative Examples 1-1 to 1-4 in accordance with ISO 21702. A 50 mm square test sample was placed in a sterile Petri dish, and 0.4 mL of virus solution was inoculated onto the sample. At this time, a virus solution containing an enveloped virus (influenza virus) was used. Thereafter, a 40 mm square polyethylene film was placed over the sample. After covering the petri dish, the sample and virus were inoculated under conditions of a temperature of 25° C. and a humidity of 90% or higher. After a predetermined time (24 hours later), 10 mL of SCDLP medium was poured into the petri dish to wash out the virus. The virus infectivity of the washout solution was measured by the plaque method.

<Measurement of virus infectivity titer (plaque method)>
Host cells were cultured in a monolayer on a 6-well plate, and 0.1 mL of the serially diluted washout solution was inoculated into each well. After culturing for 1 hour under conditions of 5% CO ₂ and 37°C to adsorb the virus to the cells, agar medium was poured into a 6-well plate and cultured for an additional 2 to 3 days. After culturing, the cells were fixed and stained, and the number of plaques formed was counted.

<Calculation of virus infection titer>
The virus infectivity titer per 1 cm ² of sample was calculated according to the following formula.
V=(10×C×D×N)/A
V: Viral infectivity per 1 cm ² of sample (PFU/cm ² )
C: Number of plaques measured D: Dilution ratio of wells where plaques were measured N: Amount of SCDLP A: Contact area of sample and virus (area of polyethylene film)

<Calculation of antiviral activity value>
The antiviral activity value was calculated according to the following formula. Here, when the antiviral activity value was 2log10 or more, it was determined that there was an antiviral effect.
Antiviral activity value = log (Vb) - log (Vc)
Log (Vb): Common logarithm value of the virus infectivity titer per 1 cm ² of the unprocessed sample after 24 hours Log (Vc): Common logarithm value of the virus infectivity titer per 1 cm ² of the antiviral treated sample after 24 hours Calculated anti-virus The virus activity value was evaluated in the following three grades: ◎, ○, and ×.

<Evaluation criteria>
◎: When the antiviral activity value is 3log10 or more ○: When the antiviral activity value is 2log10 or more ×: When the antiviral activity value is less than 2log10 In addition, if the evaluation is "○" or higher, it is at a practical level , it was marked as "passed".

[Scratch resistance]
The decorative board was subjected to a pencil hardness test specified in JIS K 5600 to check for scratches. The pencil hardness was measured using a decorative floor material made by bonding the prepared decorative sheet to 3 mm thick MDF (Medium Density Fiberboard) (hardwood type) via an adhesive layer. did.
◎: 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".

[Stain resistance]
The stain resistance of the decorative sheet was evaluated by a method based on the JAS stain A test. The case where there was no significant coloring on the decorative sheet was rated as "〇", and the case where there was residual coloring on the decorative sheet was rated as "x".
In addition, if the evaluation is "〇" or higher, it is at a practical level, so it is considered as "pass".
Table 1 shows the above evaluation results.

As shown in Table 1, the decorative sheet according to this example was found to have excellent scratch resistance and antiviral properties. Furthermore, the decorative sheet according to the present embodiment has well-balanced antiviral properties, scratch resistance, and stain resistance, and is useful as a decorative sheet for flooring.

(Second example)
[Example 2-1]
Nucleating agent vesicles were added to the surface protective layer, but no nucleating agent vesicles were added to the two-layered transparent thermoplastic resin layer. Otherwise, the decorative sheet of Example 2-1 was produced in the same manner as in Example 1-2.
Specifically, a nucleating agent vesicle in which a nano-sized nucleating agent is encapsulated in a vesicle having a single-layer outer membrane is added to 100 parts by mass of the acrylic ultraviolet curable resin forming the surface protective layer. Nucleating agent 0.05 part by mass was added in terms of the nucleating agent in the vesicle. The nucleating agent vesicles used were those made into vesicles by supercritical reverse phase evaporation. In the supercritical reverse phase evaporation method, first, 100 parts by weight of methanol, 70 parts by weight of sodium oleate as a dispersant, and 5 parts by weight of phosphatidylcholine as a substance constituting the outer membrane of vesicles are placed in a high-pressure stainless steel container kept at 60°C. The container was then sealed, and carbon dioxide was injected into the container so that the pressure was 20 MPa to create a supercritical state. Thereafter, the inside of the container is vigorously stirred, and 100 parts by weight of ion-exchanged water is poured into the container. After stirring and mixing for an additional 15 minutes while maintaining the temperature and pressure in a supercritical state, carbon dioxide was discharged from the container and the pressure was returned to atmospheric pressure to obtain liposomes having an outer membrane made of phospholipid containing a dispersant. Note that when the outer membrane of the vesicle is made of a substance such as a dispersant, the above-mentioned dispersant may be used instead of phosphatidylcholine.

[Example 2-2]
The amount of nucleating agent vesicles added in the surface protective layer was changed to 0.5 parts by mass, calculated as the nucleating agent in the nucleating agent vesicles, per 100 parts by mass of the acrylic ultraviolet curable resin. A decorative sheet of Example 2-2 was produced in the same manner as in Example 2-1 except for the above.
[Example 2-3]
Nucleating agent vesicles were not added to the surface protective layer, but nucleating agent vesicles were added to the first resin layer of the transparent thermoplastic resin layer. Specifically, for 100 parts by mass of the first resin (transparent maleic acid-modified polypropylene resin) forming the first resin layer of the transparent thermoplastic resin layer, the amount is calculated in terms of the nucleating agent in the nucleating agent vesicle. 0.05 part by mass was added. Note that nucleating agent vesicles were not added to the second resin (polypropylene resin) forming the second resin layer. A decorative sheet of Example 2-3 was produced in the same manner as in Example 2-1 except for the above.

[Example 2-4]
The amount added in terms of the nucleating agent in the nucleating agent vesicles in the first resin layer of the transparent thermoplastic resin layer was changed to 0.5 parts by mass. A decorative sheet of Example 2-4 was produced in the same manner as in Example 2-3 except for the above.
[Example 2-5]
Nucleating agent vesicles were not added to the surface protective layer, but nucleating agent vesicles were added to the second resin layer of the transparent thermoplastic resin layer. Specifically, with respect to 100 parts by mass of the second resin (transparent polypropylene resin) forming the second resin layer of the transparent thermoplastic resin layer, 0.00 parts by mass is added in terms of the nucleating agent in the nucleating agent vesicle. 05 parts by mass was added. A decorative sheet of Example 2-5 was produced in the same manner as in Example 2-1 except for the above.

[Example 2-6]
The amount of nucleating agent vesicles added in the second resin layer of the transparent thermoplastic resin layer was changed to 0.5 parts by mass in terms of the nucleating agent in the nucleating agent vesicles. A decorative sheet of Example 2-6 was produced in the same manner as in Example 2-5 except for the above.
[Example 2-7]
The nucleating agent in the nucleating agent vesicles was not added to the surface protective layer, and the nucleating agent in the nucleating agent vesicles was added to the first resin layer and the second resin layer of the transparent thermoplastic resin layer, based on 100 parts by mass of each. A calculated amount of 0.05 parts by mass of nucleating agent vesicles was added.
A decorative sheet of Example 2-7 was produced in the same manner as in Example 2-1 except for the above.

[Example 2-8]
The amount of nucleating agent vesicles added in the second resin layer of the transparent thermoplastic resin layer was changed to 0.5 parts by mass in terms of the nucleating agent in the nucleating agent vesicles. A decorative sheet of Example 2-8 was produced in the same manner as in Example 2-7 except for the above.
[Example 2-9]
The nucleating agent in the nucleating agent vesicles was not added to the surface protective layer, and the nucleating agent in the nucleating agent vesicles was added to the first resin layer and the second resin layer of the transparent thermoplastic resin layer, based on 100 parts by mass of each. A calculated amount of 0.5 parts by mass of nucleating agent vesicles was added.
A decorative sheet of Example 2-9 was produced in the same manner as in Example 2-1 except for the above.

[Example 2-10]
The amount of nucleating agent vesicles added in the second resin layer of the transparent thermoplastic resin layer was changed to 0.05 parts by mass in terms of the nucleating agent in the nucleating agent vesicles. A decorative sheet of Example 2-10 was produced in the same manner as in Example 2-9 except for the above.
[Example 2-11]
The amount of nucleating agent vesicles added in the surface protective layer was changed to 0.1 part by mass, calculated as the nucleating agent in the nucleating agent vesicles, per 100 parts by mass of the acrylic ultraviolet curable resin, and transparent heat Add 0.1 parts by mass of nucleating agent vesicles to the first resin layer and the second resin layer of the plastic resin layer, each in an amount of 0.1 parts by mass in terms of the nucleating agent in the nucleating agent vesicles, per 100 parts by mass. did.
A decorative sheet of Example 2-11 was produced in the same manner as in Example 2-1 except for the above.

[Example 2-12]
The first resin layer of the transparent thermoplastic resin layer was not formed, and only one transparent thermoplastic resin layer (only the second resin layer) was formed.
A decorative sheet of Example 2-12 was produced in the same manner as in Example 2-11 except for the above. [Example 2-13]
No nucleating agent vesicles were added to the transparent thermoplastic resin layer. A decorative sheet of Example 2-13 was produced in the same manner as in Example 2-12 except for the above.
[Example 2-14]
Nucleating agent vesicles were not added to the surface protective layer. A decorative sheet of Example 2-14 was produced in the same manner as in Example 2-12 except for the above.

<Evaluation Judgment>
The decorative sheets obtained in Examples 2-1 to 2-14 described above were evaluated for antiviral performance, scratch resistance, and stain resistance in the same manner as in the first example. The results of the evaluation are shown in Table 2.

As shown in Table 2, the decorative sheet according to this example does not contain nucleating agent vesicles because the nucleating agent vesicles are added to the surface protective layer or the transparent thermoplastic resin layer. It was found that the scratch resistance was higher than that of the decorative sheet of the first example. In other words, it was found that the decorative sheet according to this example had better scratch resistance and antiviral properties due to the addition of nucleating agent vesicles. Furthermore, the decorative sheet according to the present embodiment has antiviral properties and stain resistance, and has excellent symmetry, and is useful as a decorative sheet for use as a flooring material for shoes with shoes on.

Further, for example, the present invention can take the following configuration.
(1)
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 500 μm or less,
The polyester resin layer is biaxially stretched,
The thickness of the polyester resin layer is within the range of 100 μm or more and 200 μm or less,
The total value of the thickness of the polyester resin layer and the thickness of the transparent thermoplastic resin layer is within the range of 150 μm or more and 700 μm or less,
The surface protective layer includes an ionizing radiation-curable resin, an antiviral agent, and a nucleating agent vesicle in which a nano-sized nucleating agent is encapsulated in a vesicle comprising an outer membrane of a single layer,
The amount of the antiviral agent added in the surface protective layer is within the range of 0.2 parts by mass or more and 25 parts by mass or less based on 100 parts by mass of the ionizing radiation curable resin,
The amount of the nucleating agent added in the surface protective layer is 0.05 part by mass or more and 0.5 part by mass in terms of the nucleating agent in the nucleating agent vesicle, based on 100 parts by mass of the ionizing radiation curable resin. A decorative sheet characterized by falling within the following range.
(2)
The thermoplastic resin base sheet contains a polyolefin resin and has a thickness of 50 μm or more and 200 μm or less,
The decorative sheet according to (1) above, wherein the nucleating agent vesicles are added to the transparent thermoplastic resin layer.
(3)
The transparent thermoplastic resin layer is formed using a polypropylene resin, and includes a first resin layer formed including a first resin, and a first resin layer formed on the first resin layer. a second resin layer containing a different second resin;
The first resin is a transparent maleic acid-modified polypropylene resin among the polypropylene resins,
The second resin is a transparent polypropylene resin among the polypropylene resins,
The decorative sheet according to (2) above, wherein the nucleating agent vesicle is added to the polypropylene resin, which is at least one of the first resin and the second resin.
(4)
The amount of the nucleating agent vesicles added in the transparent thermoplastic resin layer is determined based on 100 parts by mass of the polypropylene resin of at least one of the first resin and the second resin. The decorative sheet according to (3) above, characterized in that the content is in the range of 0.05 parts by mass or more and 0.5 parts by mass or less in terms of the agent.
(5)
The decorative sheet according to (2) above, wherein the nucleating agent vesicle is a nucleating agent liposome having an outer membrane made of phospholipid.
(6)
The decorative sheet according to (2) above, wherein the nucleating agent vesicle is formed by encapsulating the nucleating agent in a vesicle provided with a monolayer film using a supercritical reverse phase evaporation method. .
(7)
The decorative sheet according to (1) above, wherein a primer layer is provided on a surface of the thermoplastic resin base sheet opposite to the picture pattern layer.
(8)
The decorative sheet according to (1) above, wherein the thickness of the transparent thermoplastic resin layer is within a range of 50 μm or more and 150 μm or less.
(9)
A substrate for decorative materials,
The decorative sheet according to any one of (1) to (8) above, which is laminated to the decorative material substrate;
A decorative board characterized by comprising:

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, 26, 216: Transparent thermoplastic resin layer 70: Surface protective layer 26a, 216a: Transparent thermoplastic resin layer (first resin layer)
26b, 216b: transparent thermoplastic resin layer (second resin layer)
8: Primer layer 9: Embossing 11, 12, 20, 21, 22: Decorative sheet 100: Decorative board

Claims (9)

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 500 μm or less,
The polyester resin layer is biaxially stretched,
The thickness of the polyester resin layer is within the range of 100 μm or more and 200 μm or less,
The total value of the thickness of the polyester resin layer and the thickness of the transparent thermoplastic resin layer is within the range of 150 μm or more and 700 μm or less,
The surface protective layer includes an ionizing radiation-curable resin, an antiviral agent, and a nucleating agent vesicle in which a nano-sized nucleating agent is encapsulated in a vesicle comprising an outer membrane of a single layer,
The amount of the antiviral agent added in the surface protective layer is within the range of 0.2 parts by mass or more and 25 parts by mass or less based on 100 parts by mass of the ionizing radiation curable resin,
The amount of the nucleating agent added in the surface protective layer is 0.05 part by mass or more and 0.5 part by mass in terms of the nucleating agent in the nucleating agent vesicle, based on 100 parts by mass of the ionizing radiation curable resin. A decorative sheet characterized by falling within the following range. The thermoplastic resin base sheet contains a polyolefin resin, and has a thickness of 50 μm or more and 200 μm or less,
The decorative sheet according to claim 1, wherein the nucleating agent vesicle is added to the transparent thermoplastic resin layer. The transparent thermoplastic resin layer is formed using a polypropylene resin, and includes a first resin layer formed including a first resin, and a first resin layer formed on the first resin layer. a second resin layer containing a different second resin;
The first resin is a transparent maleic acid-modified polypropylene resin among the polypropylene resins,
The second resin is a transparent polypropylene resin among the polypropylene resins,
The decorative sheet according to claim 2, wherein the nucleating agent vesicle is added to the polypropylene resin, which is at least one of the first resin and the second resin. The amount of the nucleating agent vesicles added in the transparent thermoplastic resin layer is the amount of nucleating agent vesicles added to 100 parts by mass of the polypropylene resin of at least one of the first resin and the second resin. The decorative sheet according to claim 3, characterized in that the content is in the range of 0.05 parts by mass or more and 0.5 parts by mass or less in terms of the agent. The decorative sheet according to claim 2, wherein the nucleating agent vesicle is a nucleating agent liposome having an outer membrane made of phospholipid. 3. The decorative sheet according to claim 2, wherein the nucleating agent vesicle is formed by encapsulating the nucleating agent in a vesicle provided with a monolayer film using a supercritical reverse phase evaporation method. The decorative sheet according to claim 1, wherein a primer layer is provided on a surface of the thermoplastic resin base sheet opposite to the picture pattern layer. The decorative sheet according to claim 1, wherein the thickness of the transparent thermoplastic resin layer is within a range of 50 μm or more and 150 μm or less. A substrate for decorative materials,
The decorative sheet according to any one of claims 1 to 8, which is laminated to the decorative material substrate;
A decorative board characterized by comprising:

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