Floor decorative sheet

Abstract

To provide a floor decorative sheet having sufficiently enough scratch resistance, abrasion resistance, caster resistance, shock resistance, and workability necessary as a shoes floor material.SOLUTION: In a floor decorative sheet 10, a picture pattern layer 12, a first adhesive layer 13, a first resin layer 14, a second adhesive layer 15, a second resin layer 16, and a protection layer 17 are laminated in this order on one surface of a base material sheet 11. The base material sheet 11 is 50 μm or more and 150 μm or less in thickness. The first adhesive layer 13 is a heat seal agent. The first resin layer 14 is 70 μm or more and 250 μm or less in thickness. The second resin layer 16 is a thermoplastic resin, has a thickness of 70 μm or more and 250 μm or less, and is formed with an emboss 10a. The protection layer 17 contains an ionization radiation hardening resin, and is formed with addition of a nucleating agent vesicle including a nano-sized nucleating agent to a vesicle comprising an outer membrane of a single layer.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a decorative sheet for floors. [Background technology]

[0002] A known flooring decorative material for planking made of a wood-based substrate is made by attaching a veneer to a plywood board, 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, the color varies, making it difficult to match the color tone with walls, ceilings, furniture, etc. Another known method is to provide a groove on the surface of the wood-based substrate, apply a synthetic resin paint for coloring ducts to the surface, remove the paint other than the grooves, form a duct recess with a wood grain pattern, and apply a transparent synthetic resin paint to the surface of the wood-based substrate other than the grooves.

[0003] Also known is a floor decorative material in which a thermoplastic resin decorative sheet is laminated on a wood-based substrate, the thermoplastic resin layer being provided with a colored thermoplastic resin layer, a design layer, and a transparent thermoplastic resin layer in that order. This floor decorative material is mainly used in living spaces, and is intended for walking on bare feet or in socks, slippers, etc. Therefore, when the floor decorative material is used for walking on shoes, such as in shoes or heels, the floor decorative material is easily damaged because it does not have sufficient performance (scratch resistance, abrasion resistance, caster resistance, impact resistance, etc.) required for a floor material for walking on shoes.

[0004] Therefore, if the thickness of the transparent thermoplastic resin layer and the colored thermoplastic resin layer are each increased to increase the hardness performance, it tends to be difficult to cut the sheet on the line when the decorative sheet and the wood-based substrate are continuously laminated and joined, which tends to cause a decrease in processability. Note that, for example, the technology described in Patent Document 1 is an example of a technology related to floor decorative materials. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2014-188941 A Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention has been made to solve these problems, and its object is to provide a decorative floor sheet that has sufficient scratch resistance, abrasion resistance, castor resistance, impact resistance, and processability required for a floor material for use when shoes are worn. [Means for solving the problem]

[0007] In order to solve the above-mentioned problems, the decorative floor sheet according to the present invention comprises a base sheet having a picture pattern layer, a first adhesive layer having optical transparency, a first resin layer having optical transparency, a second adhesive layer having optical transparency, a second resin layer having optical transparency, and a protective layer having optical transparency laminated in this order on one side of the base sheet, the base sheet having a thickness of 50 μm or more and 150 μm or less, and the first adhesive layer is Made of acrylic resin, polyester resin, and vinyl chloride acetate resin A heat sealing agent, the first resin layer being It is an acrylic resin, The thickness is 70 μm or more and 250 μm or less, the second resin layer is a thermoplastic resin, has a thickness of 70 μm or more and 250 μm or less, is embossed, and is formed from a transparent polypropylene resin in which nucleating agent vesicles containing a nano-sized nucleating agent are added to vesicles having a single-layer outer membrane, the protective layer has a base resin layer provided on the second adhesive layer side and containing a transparent maleic acid-modified polypropylene resin, and an enveloping resin layer provided on the base resin layer and containing a transparent polypropylene resin different from the base resin layer, the base resin layer has a thickness of 12.5 μm or more and 37.5 μm or less and its ratio to the total thickness of the second resin layer is 15% or more and 18% or less, and the protective layer contains an ionizing radiation-curable resin, and is formed by adding nucleating agent vesicles containing a nano-sized nucleating agent to vesicles having a single-layer outer membrane. Effect of the Invention

[0008] The decorative floor sheet according to the present invention can fully exhibit the scratch resistance, abrasion resistance, caster resistance, impact resistance and processability required for a floor material on which shoes are worn. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is a cross-sectional view showing a schematic configuration of a main embodiment of a decorative floor sheet according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the decorative floor sheet according to the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiment described with reference to the drawings.

[0011] [Main embodiment] A main embodiment of the decorative floor sheet according to the present invention will be described with reference to FIG.

[0012] <Floor Decorative Sheet 10> As shown in Figure 1, the floor decorative sheet 10 of this embodiment has a picture pattern layer 12, a first adhesive layer 13 having light transparency, a first resin layer 14 having light transparency, a second adhesive layer 15 having light transparency, a second resin layer 16 having light transparency, and a protective layer 17 having light transparency laminated in this order on one side (the upper side in Figure 1) of a base sheet 11, and a primer layer 18 is provided on the other side (the lower side in Figure 1) of the base sheet 11.

[0013] <Base sheet 11> The base sheet 11 is obtained by adding a color pigment, a filler, a stabilizer, etc. to a thermoplastic resin, dispersing and coloring the resin uniformly, and forming the resin into a sheet. As the resin material for the base sheet 11, various materials other than polyvinyl chloride resin can be used.

[0014] Specifically, for example, polyolefin resins such as polyethylene resin, polypropylene resin, polybutene resin, polymethylpentene resin, etc.; polyolefin copolymer resins such as ethylene-vinyl acetate copolymer or its saponification product, ethylene-(meth)acrylic acid (ester) copolymer, etc.; polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polyarylate resin, polycarbonate resin, copolymer polyester resin (typically 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin, commonly known as PET-G), etc. Examples of suitable resins include steric resins, acrylic resins such as polymethyl methacrylate, polyamide resins such as 6-nylon, 6,6-nylon, 6,10-nylon, and 12-nylon, styrene resins such as polystyrene, AS resin, and ABS resin, cellulose resins such as cellulose acetate and nitrocellulose, chlorine-containing resins such as polyvinyl chloride and polyvinylidene chloride, fluorine-containing resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, and ethylene-tetrafluoroethylene copolymers, and copolymers or mixtures of two or more of these. In particular, polyolefin materials to which a filler and a coloring pigment have been added are suitable, taking into consideration non-polluting properties, cost, performance, ease of coloring, and the like.

[0015] The thickness of the base sheet 11 is 50 μm or more and 150 μm or less. In particular, it is preferable that it is 50 μm or more and 100 μm or less, and more preferably, it is 55 μm or more and 70 μm or less. When the thickness of the base sheet 1 is within the above range, it can fully exhibit the scratch resistance, abrasion resistance, castor resistance, impact resistance, and processability required as a decorative sheet for floors where shoes are worn.

[0016] <Pattern layer 12> A picture pattern layer 12 having an arbitrary picture pattern printed thereon is provided on one surface (the upper surface in FIG. 1) of the base sheet 11. The type of the picture pattern of the picture pattern layer 12 is not particularly limited, and examples thereof include wood grain, stone grain, cloth grain, sand grain, abstract patterns, geometric figures, letters or symbols, or combinations thereof.

[0017] Examples of printing methods that can be used for the picture pattern layer 12 include gravure printing, inkjet printing, flexographic printing, screen printing, etc. The type of printing ink used to form the picture pattern layer 12 is not particularly limited, and any known printing ink that is generally used to form picture pattern layers in decorative floor sheets and is suitable for each printing method can be used.

[0018] Specifically, for example, organic or inorganic dyes or pigments, extender pigments, fillers, tackifiers, dispersants, defoamers, stabilizers, and other additives are added as necessary to binder resins such as polyvinyl chloride resins, vinyl chloride-vinyl acetate copolymer resins, butyral, acrylic, urethane, polyester, epoxy, alkyd, and polyamide binders, and the like, and the viscosity is adjusted with a diluting solvent or the like to an appropriate value for each printing method, etc., to obtain the desired composition.

[0019] <First adhesive layer 13> A colorless and transparent first adhesive layer 13 having optical transparency is provided on one surface (upper surface in FIG. 1) of the picture pattern layer 12. A heat seal agent is used as the first adhesive layer 13. Examples of the heat seal agent include thermosetting resins such as acrylic resin-polyester resin-vinyl chloride acetate resin and thermosetting urethane resin.

[0020] <First resin layer 14> A colorless and transparent first resin layer 14 having optical transparency is provided on one surface (upper surface in FIG. 1) of the first adhesive layer 13. Examples of materials for the first resin layer 14 include polyolefin resins such as polyethylene resin, polypropylene resin, polybutene resin, and polymethylpentene resin, and acrylic resins such as polymethylmethacrylate. In order to improve adhesion, it is also possible to perform, for example, corona treatment.

[0021] The first resin layer 14 has a thickness of 70 μm or more and 250 μm or less. In particular, it is preferable that the thickness is 80 μm or more and 230 μm or less, and more preferably, that the thickness is 100 μm or more and 200 μm or less. When the thickness of the first resin layer 14 is within the above range, the first resin layer 14 can fully exhibit the scratch resistance, abrasion resistance, castor resistance, impact resistance, and processability required for a decorative sheet for floors on which shoes are worn.

[0022] <Second adhesive layer 15> A colorless and transparent second adhesive layer 15 having optical transparency is provided on one surface (the upper surface in FIG. 1) of the first resin layer 14. The second adhesive layer 15 can be formed by applying a composition for forming the second adhesive layer 15 onto the first resin layer 14. The adhesive contained in the second adhesive layer 15 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 second resin layer 16.

[0023] <Second resin layer 16> A colorless and transparent second resin layer 16 having optical transparency is provided on one side (upper side in FIG. 1) of the second adhesive layer 15. The second resin layer 16 is formed with embossments 10a. When the picture pattern layer 12 has a wood grain, the embossments 10a formed on the second resin layer 16 are preferably formed to represent the vessels of natural wood with depressions, and even when the picture pattern layer 12 has a grain other than wood, it is also possible to enhance the design by forming unevenness of a sand grain or a geometric pattern. In this way, by forming the embossments 10a, a three-dimensional effect is given to the surface of the floor decorative sheet 10, and the design can be improved. Moreover, the embossments 10a can be formed not only on the second resin layer 16 but also on other layers.

[0024] The embossment 10a can be formed by a post-embossing method in which the layers are bonded together, the whole is heated, and an embossing roll is pressed against the layer, or a simultaneous extrusion and embossing method in which the second resin layer 16 is extruded from a T-die and pressed against an embossing roll. The embossment 10a can be formed before or after the protective layer 17 is provided.

[0025] The second resin layer 16 has a thickness of 70 μm or more and 250 μm or less. In particular, it is preferable that the thickness is 80 μm or more and 200 μm or less, and more preferably, it is 90 μm or more and 140 μm or less. When the thickness of the second resin layer 16 is within the above range, the unevenness of the embossment 10a can be formed without any problems, and in terms of design, in combination with the picture pattern layer 12, it is possible to make the depth and depth feel more. If the thickness of the second resin layer 16 is less than 70 μm, it becomes difficult to obtain sufficient scratch resistance, wear resistance, caster resistance, and impact resistance. On the other hand, if the thickness of the second resin layer 16 exceeds 250 μm, the processability during manufacturing decreases, resulting in high costs.

[0026] Furthermore, when the total thickness of the second resin layer 16 and the first resin layer 14 is within the range of 150 μm or more and 300 μm or less, this does not impair both the flexibility and mechanical strength of the floor decorative sheet 10, and does not impair the processability into a decorative board by in-line roll lamination, etc., or the processability as a decorative board, thereby improving usability, which is preferable.

[0027] The second resin layer 16 can also be in the form of a sheet having a plurality of layers stacked on top of each other. The second resin layer 16 can have four or more layers, but the structure of the extruder becomes complicated and the work becomes complicated, so up to three layers is preferable. Of course, it can also be two layers or one layer.

[0028] Each layer constituting the second resin layer 16 is formed of, for example, a colorless and transparent thermoplastic resin so that the pattern of the picture pattern layer 12 can be visually recognized. The thermoplastic resin contained in the second resin layer 16 can be, for example, various resins other than polyvinyl chloride resin. Various combinations of resin materials for the layers constituting the second resin layer 16 are possible depending on the desired characteristics.

[0029] Specific examples of the resin include polyolefin resins such as low-density polyethylene resin (LDPE), high-density polyethylene resin (HDPE), linear low-density polyethylene resin (LLDPE), polypropylene resin (PP), and polyolefin elastomers; polyester resins such as polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), and polyethylene naphthalate resin (PEN); polymethyl methacrylate resin (PMMA); ethylene-vinyl acetate copolymer resin (EVA); ionomer resins; polybutene resins; polyacrylonitrile resins; polyamide resins such as 6-nylon and 66-nylon; polystyrene resins (PS); polycarbonate resins (PC); fluorine resins; urethane resins; polyvinyl chloride resins (PVC); and polyvinylidene chloride resins (PVDC). In particular, transparent polypropylene resins are highly preferred.

[0030] <Polypropylene resin> Examples of polypropylene resins used in the second resin layer 16 include highly flexible random polypropylene resins containing ethylene content, and mixtures of random polypropylene resins or highly crystalline homopolypropylene resins with known amorphous polypropylene resins. In applications where processability such as bending is more important, for example, highly crystalline homopolypropylene resins can be mixed with random polypropylene resins or known amorphous polypropylene resins having an ethylene content within a predetermined range.

[0031] Moreover, examples of polypropylene resins used in the second resin layer 16 include those containing, for example, a highly crystalline homopolypropylene resin, which is a propylene homopolymer having an isotactic pentad fraction (mmmm fraction) of 95% or more, in a range of 30% by mass to 100% by mass with respect to the mass of the total polypropylene resin. Here, if the highly crystalline homopolypropylene resin is less than 30% by mass, the crystallinity is insufficient and sufficient strength may not be obtained, which is not preferable.

[0032] The isotactic pentad fraction (mmmm fraction) is the fraction of carbon (C) with mass number 13 (nuclide). 13 It is calculated from the electromagnetic wave absorption rate value obtained by resonating a resin material at a specified resonance frequency using C-NMR (nuclear magnetic resonance) measurement, and specifies the atomic arrangement, electronic structure, molecular microstructure, etc. of the resin material.

[0033] And the pentad fraction of crystalline polypropylene resin is, 13 The pentad fraction is the ratio of five propylene units arranged in a row determined by C-NMR and is used as a measure of crystallinity or stereoregularity. The pentad fraction is one of the important factors that mainly determine the scratch resistance of the surface, and basically the higher the pentad fraction, the higher the crystallinity.

[0034] Examples of polypropylene resins that can be used in the second resin layer 16 include mixtures of polypropylene resin (a) with free-end long-chain branching and polypropylene resin (b) without free-end long-chain branching, in which the molecular weight distribution Mw / Mn, defined as the mass average molecular weight / number average molecular weight of the mixture, is in the range of 1 to 5, and the isotactic index, defined as the boiling heptane soluble residue fraction, of the mixed resin of polypropylene resin (a) and polypropylene resin (b) is in the range of 1 to 90%. When such a polypropylene resin is used in the second resin layer 16, whitening and cracking can be suppressed when the decorative floor sheet 10 is folded.

[0035] Here, the molecular weight distribution is a value defined as the ratio Mw / Mn of number average molecular weight Mn = Σ(Mi x Ni) / ΣNi and mass average molecular weight Mw = Σ(Ni x Mi2) / Σ(Ni x Mi) when there are Ni molecules with molecular weight Mi. The closer to 1, the narrower the molecular weight distribution and the higher the uniformity.

[0036] By making this molecular weight distribution 5 or less, the molecular weight can be made equal to a necessary and sufficient size, which contributes to suppressing whitening and cracking. Generally, the molecular weight distribution can be measured by gel permeation chromatography (GPC).

[0037] The isotactic index, defined as the boiling heptane soluble residue, is useful as an index for examining the crystallinity of 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 calculated to calculate the isotactic index.

[0038] In detail, dry the cylindrical filter paper at 110±5℃ for 2 hours, leave it in a constant temperature and humidity room for at least 2 hours, then put 8g to 10g of sample (powder or flake form) into the cylindrical filter paper and weigh it precisely using a weighing cup and tweezers. Place this on top of an extractor containing about 80cc of heptane, and assemble a cooler to the extractor. Heat this with an oil bath or electric heater and extract for 12 hours. Adjust the heating so that the number of drops from the cooler is 130 or more per minute.

[0039] Next, take out the cylindrical filter paper containing the extraction residue and place it in a vacuum dryer and dry it for 5 hours at 80℃ and a vacuum of 100mmHg or less. After drying, leave it in a constant temperature and humidity room for 2 hours, then weigh it accurately and calculate the isotactic index by (P / Po) x 100, where Po is the sample mass (g) before extraction and P is the sample mass (g) after extraction.

[0040] By setting the isotactic index at 90% or less, the sheet stiffness caused by polypropylene crystals can be suppressed. Methods for lowering the isotactic index include, for example, using an amorphous polypropylene component (e.g., syndiotactic polypropylene, adactic polypropylene, etc.) in part, random copolymerization of one or more olefin monomers such as ethylene or α-olefin, and adding 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.).

[0041] The melt tension of the mixed resin of polypropylene resin (a) and polypropylene resin (b) is preferably in the range of 100 mN to 500 mN, more preferably in the range of 300 mN to 400 mN. If it exceeds 500 mN, the melt viscosity becomes too high, making it difficult to stably form a film. If it is less than 100 mN, the long chain branching component tends to be insufficient, making it difficult to obtain the desired performance. The above melt tension is the tension when extruding at 60 mm / min and taking up at 2 mm / min at a temperature of 230°C using a 2.0 mm diameter nozzle capillary rheometer.

[0042] In addition, it is preferable that the melt flow rate at 230°C of the mixture of polypropylene resin (a) and polypropylene resin (b) is in the range of 5 g / 10 min to 50 g / 10 min as specified in the Japanese Industrial Standard "JIS K6760", since the molecular weight can be kept at a certain value or more and a stable film formation state can be maintained. More preferably, it is in the range of 10 g / 10 min to 30 g / 10 min, and even more preferably, it is in the range of 10 g / 10 min to 25 g / 10 min.

[0043] If the melt flow rate exceeds 50g / 10min, the effect of the resin extruded from the T-die gathering in the center (neck-in) becomes large during melt extrusion through the T-die, and the thickness of the end of the resin extruded from the T-die increases. The increase in thickness at the end affects the decrease in cooling efficiency and the thickness stability in the width direction, making it difficult to produce a stable film. On the other hand, if the melt flow rate is less than 5g / 10min, the draw resonance of the molten resin becomes poor, and the molten resin cannot respond to the gap between the speed of the molten resin immediately after it leaves the T-die (initial speed) and the speed of the resin immediately after it touches the cooling roll, making it difficult to produce a stable film.

[0044] In this embodiment, the second resin layer 16 is provided on the second adhesive layer 15 side (the lower side in Figure 1) and has a base resin layer 16a containing a transparent maleic acid-modified polypropylene resin, and an surrounding resin layer 16b provided on the base resin layer 16a and containing a transparent polypropylene resin different from that of the base resin layer 16a.

[0045] The thickness of the base resin layer 16a is preferably, for example, 10 μm or more (more preferably 50 μm or more), and is preferably 20% or less of the total thickness of the second resin layer 16 (more preferably 10% or less). If the thickness of the base resin layer 16a is less than 10 μm, the adhesion stability decreases, which is not preferable. If the thickness of the base resin layer 16a exceeds 20% of the total thickness of the second resin layer 16, the overall surface strength of the floor decorative sheet 10 decreases, which is not preferable. In other words, if the thickness of the base resin layer 16a is 10 μm or more and at the same time 20% or less of the total thickness of the second resin layer 16, it is possible to increase the overall surface strength of the floor decorative sheet 10 and improve scratch resistance while exhibiting high adhesion stability.

[0046] The base resin layer 16a can have a transparent maleic acid-modified polypropylene resin content (mass%) greater than the transparent polypropylene resin content (mass%) of the surrounding resin layer 16b. Specifically, the base resin layer 16a can have a transparent maleic acid-modified polypropylene resin content (mass%) of 80% or more by mass. Even with such a base resin layer 16a, it is possible to increase the overall surface strength of the floor decorative sheet 10 and improve scratch resistance while exhibiting high adhesion stability.

[0047] In the second resin layer 16 having a base resin layer 16a and an surrounding resin layer 16b, the base resin layer 16a contains a transparent maleic acid-modified polypropylene resin, thereby improving the adhesion between the layers, and the surrounding resin layer 16b contains a transparent polypropylene resin, thereby reducing embrittlement.

[0048] The second resin layer 16, which has two layers, the base resin layer 16a and the surrounding resin layer 16b, is preferably formed by simultaneously extruding and bonding the two layers, the base resin layer 16a and the surrounding resin layer 16b, using a twin-screw extruder, as this is easy to produce.

[0049] In addition, the second resin layer 16 is preferably formed from a thermoplastic resin such as a polypropylene resin to which nucleating agent vesicles, which contain nano-sized nucleating agents in vesicles having a single layer outer membrane, have been added.

[0050] Nucleating agent vesicles The nucleating agent vesicle is a vesicle having a single-layer outer membrane in which a nano-sized nucleating agent is encapsulated, and is used by adding it to a polypropylene resin (thermoplastic resin). By containing a nucleating agent, the second resin layer 16 can improve the crystallinity, and can improve the scratch resistance, impact resistance, caster resistance, etc. of the floor decorative sheet 10. It is not a problem if the nucleating agent is encapsulated in the vesicle with a part of it exposed from the outer membrane of the vesicle.

[0051] The nano-sized nucleating agent preferably has an average particle size of 1 / 2 or less of the wavelength range of visible light. Specifically, since the wavelength range of visible light is within the range of 400 nm to 750 nm, the average particle size is preferably 375 nm or less.

[0052] Nano-sized nucleating agents have extremely small particle sizes, and therefore the number present per unit volume and the surface area increase inversely proportional to the cube of the particle diameter, making it possible to reduce the distance between particles and place the particles in close proximity.

[0053] Therefore, when crystal growth occurs from the surface of a particle of a nucleating agent added to a polypropylene resin, the end of the growing crystal immediately comes into contact with the end of a crystal growing from the surface of another particle of nucleating agent adjacent to the nucleating agent particle, inhibiting the growth of each crystal end and causing the growth of each crystal to immediately stop, thereby making it possible to reduce the average particle size of the spherulites in the crystalline portion of the crystalline polypropylene resin (for example, to 1 μm or less).

[0054] As a result, the polypropylene film can be highly crystallized to increase hardness, and the stress concentration between spherulites that occurs during bending can be efficiently dispersed, resulting in a polypropylene film that is suppressed from cracking or whitening during bending.

[0055] In addition, when the nucleating agent is simply added, the nucleating agent in the polypropylene resin undergoes secondary aggregation, the particle size of the nucleating agent becomes larger, and the number of crystal nuclei relative to the amount of nucleating agent added becomes significantly smaller than when the nucleating agent is added in the form of vesicles, and the average particle size of spherulites in the crystalline part of the polypropylene resin tends to become larger. As a result, it becomes difficult to sufficiently suppress cracking and whitening during bending processing, and it becomes difficult to achieve both improved elastic modulus and processability by increasing the crystallinity.

[0056] 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 metal salts of phosphate esters, metal salts of benzoic acid, metal salts of pimelic acid, metal salts of rosin, benzylidene sorbitol, quinacridone, cyanine blue, and talc.

[0057] In particular, in order to maximize the effect of the nano-processing, it is preferable to use non-melting types that are expected to have good transparency, such as metal salts of phosphates, metal salts of benzoates, metal salts of pimelic acids, and metal salts of rosin, but if the material itself can be made transparent by the nano-processing, it is also possible to apply colored quinacridone, cyanine blue, talc, etc. Also, non-melting nucleating agents can be applied by mixing them with melting benzylidene sorbitol, etc.

[0058] The nucleating agent vesicle is preferably added in an amount of 0.05 parts by mass or more and 0.5 parts by mass or less, and more preferably in an amount of 0.1 parts by mass or more and 0.3 parts by mass or less, per 100 parts by mass of a resin material such as a polypropylene resin. If the amount of the nucleating agent vesicle added is less than 0.05 parts by mass, it becomes difficult to obtain a sufficient degree of crystallinity, and it becomes difficult to obtain a sufficient modulus of elasticity (hardness). On the other hand, if the amount of the nucleating agent vesicle added exceeds 0.5 parts by mass, the crystal nuclei become excessive, and the growth of spherulites is inhibited, and as a result, it becomes difficult to obtain a sufficient degree of crystallinity, and it becomes difficult to obtain a sufficient modulus of elasticity (hardness).

[0059] In the case of the second resin layer 16 having two layers, the base resin layer 16a and the surrounding resin layer 16b, at least one of the base resin layer 16a and the surrounding resin layer 16b contains nucleating agent vesicles. In this case, the base resin layer 16a is preferably added with nucleating agent vesicles in an amount of 0.05 parts by mass to 0.5 parts by mass, and more preferably with 0.1 parts by mass to 0.3 parts by mass, per 100 parts by mass of a resin material such as transparent maleic acid modified polypropylene resin. On the other hand, the surrounding resin layer 16b is preferably added with nucleating agent vesicles in an amount of 0.05 parts by mass to 0.5 parts by mass, and more preferably with 0.1 parts by mass to 0.3 parts by mass, per 100 parts by mass of a resin material such as transparent polypropylene resin.

[0060] As a method for nano-sizing a nucleating agent, for example, a solid phase method in which the nucleating agent is primarily subjected to mechanical grinding to obtain nano-sized particles, a liquid phase method in which nano-sized particles are synthesized or crystallized in a solution in which the nucleating agent is dissolved, or a gas phase method in which nano-sized particles are synthesized or crystallized from a gas or vapor obtained by vaporizing the nucleating agent can be appropriately used.

[0061] Examples of the solid phase method include a ball mill, a bead mill, a rod mill, a colloid mill, a conical mill, a disk mill, a hammer mill, a jet mill, etc. Examples of the liquid phase method include a crystallization method, a coprecipitation method, a sol-gel method, a liquid phase reduction method, a hydrothermal synthesis method, etc. Examples of the gas phase method include an electric furnace method, a chemical flame method, a laser method, a thermal plasma method, etc.

[0062] The nucleating agent vesicle can be prepared by, for example, the Bangham method, the extrusion method, the hydration method, the surfactant dialysis method, the reverse phase evaporation method, the freeze-thaw method, the supercritical reverse phase evaporation method, etc. In particular, the supercritical reverse phase evaporation method is preferable as a method for nano-sizing the nucleating agent.

[0063] The supercritical reverse phase evaporation method is a method for producing capsules (nano-sized vesicles) encapsulating a target substance using carbon dioxide in a supercritical state or under temperature or pressure conditions above the critical point. Carbon dioxide in a supercritical state means carbon dioxide in a supercritical state above the critical temperature (30.98°C) and critical pressure (7.3773±0.0030MPa), and carbon dioxide under temperature or pressure conditions above the critical point means carbon dioxide under conditions where only the temperature or only the pressure exceeds the critical conditions.

[0064] Specifically, an emulsion of supercritical carbon dioxide and the aqueous phase is generated by injecting and stirring an aqueous phase into a fluid that is a mixture of supercritical carbon dioxide, a substance that forms an outer membrane, and a nucleating agent that is an encapsulating substance. When the pressure is reduced, the carbon dioxide expands and evaporates, causing a phase inversion, resulting in nanovesicles (nanocapsules) in which the surfaces of the nucleating agent particles are covered with a single layer of outer membrane.

[0065] By utilizing such a supercritical reverse phase evaporation method, it is easy to form capsules in which the nucleating agent particles are covered with a single layer of outer membrane, which makes it possible to produce capsules with a smaller diameter, unlike conventional encapsulation methods in which the surface of the nucleating agent particles is covered with multiple layers of outer membrane.

[0066] The outer membrane of the nucleating agent vesicle is composed of a single layer membrane. Examples of substances that form the outer membrane of the vesicle include dispersants such as nonionic surfactants and mixtures of nonionic surfactants with cholesterols or triacylglycerols, and phospholipids.

[0067] As the nonionic surfactant, for example, one or more of polyglycerin ether, dialkyl glycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, polybutadiene-polyoxyethylene copolymer, polybutadiene-poly 2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. can be used.

[0068] As the cholesterol, for example, cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadiene-3β-ol), sodium cholate, cholecalciferol, etc. can be applied.

[0069] The outer membrane constituting the nucleating agent vesicle is preferably a material containing a biological lipid such as a phospholipid. Examples of the phospholipid include glycerophospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, yolk egg lecithin, hydrogenated yolk egg lecithin, soybean lecithin, and hydrogenated soybean lecithin, and sphingophospholipids such as sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.

[0070] In this embodiment, the nucleating agent vesicle whose outer membrane is made of a substance containing a biological lipid such as a phospholipid is called a "nucleating agent liposome." The outer membrane of the nucleating agent liposome can also be formed from a mixture of a phospholipid and a dispersant. In the floor decorative sheet 10 according to this embodiment, it is preferable that the nucleating agent vesicle is a radical scavenger liposome having an outer membrane containing a phospholipid, and by forming the outer membrane from a phospholipid, compatibility with the resin component of the second resin layer 16 can be improved.

[0071] Other Additives Furthermore, in the second resin layer 16, the surrounding resin layer 16b preferably contains an ultraviolet absorbing agent, a light stabilizer, a heat stabilizer, a flame retardant, an antiblocking agent, and the like.

[0072] The amount of the ultraviolet absorber to be added is appropriately selected according to the desired weather resistance, and is preferably within the range of 0.1% by mass to 50% by mass, and more preferably within the range of 1% by mass to 30% by mass, based on the resin solid content. If the ultraviolet absorber has a hydroxyl group, it is particularly suitable because it is easy to bond with the resin component by crosslinking due to the addition of isocyanate. Benzotriazole-based, triazine-based, benzophenone-based, etc. can be used as the ultraviolet absorber.

[0073] 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-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, and 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, as well as mixtures, modified products, polymers, and derivatives thereof.

[0074] Examples of triazine-based ultraviolet absorbents 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(2,4-dimethylphenyl)-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.

[0075] As the benzophenone-based ultraviolet absorbing agent, for example, octabenzone, its modified product, polymer product, derivatives, etc. can be used.

[0076] Examples of light stabilizers that can be used include bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-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, and the like thereof.

[0077] Examples of heat stabilizers 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, Examples of the antioxidants that can be used include hindered phenol-based antioxidants such as 5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid, phenol-based antioxidants such as 2,2'-methylenebis(4-ethyl-6-t-butylphenol) and 2,2'-methylenebis(4-methyl-6-t-butylphenol), and phosphorus-based antioxidants represented by tris(2,4-di-t-butylphenyl)phosphite, as well as mixtures of these, i.e., combinations of two or more of these.

[0078] As the flame retardant, for example, inorganic compounds such as aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, etc., and phosphate-based flame retardants can be used.

[0079] As the blocking inhibitor, for example, inorganic blocking inhibitors such as aluminum silicate, silicon oxide, hydrotalcite, calcium carbonate, etc., and organic blocking inhibitors such as fatty acid amides, etc. can be used.

[0080] <Protective layer 17> A colorless and transparent protective layer 17 having optical transparency is provided on one surface (the upper surface in FIG. 1) of the second resin layer 16. The protective layer 17 is the outermost surface of the floor decorative sheet 10, and protects the floor decorative sheet 10 from direct external forces, such as collisions with objects or rubbing during movement. In other words, the protective layer 17 improves the surface properties of the floor decorative sheet 10, imparting scratch resistance, stain resistance, slipperiness, etc. to the surface, and also affects the gloss and feel of the surface.

[0081] The protective layer 17 contains an ionizing radiation curable resin such as an ultraviolet (UV) curable resin. Specifically, the protective layer 17 is preferably a mixture (blend resin) of a thermosetting resin and an ultraviolet curable resin. The protective layer 17 made by mixing such a thermosetting resin and an ultraviolet curable resin contains a resin with high hardness, and by covering the surface, scratch resistance can be improved. The solvent may be ethyl acetate, n-butyl acetate, or the like.

[0082] As the thermosetting resin, it is preferable to use a polyurethane resin having a urethane bond, for example, in consideration of scratch resistance, impact resistance, caster resistance, etc. Examples of the polyurethane resin include a two-component curing urethane resin that is mainly made of polyol and uses isocyanate as a crosslinking agent (curing agent).

[0083] The polyol has two or more hydroxyl groups in the molecule, and examples thereof include polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol, and the like.

[0084] As the isocyanate, polyvalent isocyanates having two or more isocyanate groups in the molecule can be used. Examples of polyvalent isocyanates include aromatic isocyanates such as 2,4-tolylene diisocyanate, xylylene diisocyanate, and 4,4'-diphenylmethane diisocyanate, aliphatic (or alicyclic) isocyanates such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate, and adducts or multimers thereof (e.g., adducts of tolylene diisocyanate, trimers of tolylene diisocyanate), etc. In particular, aliphatic (or alicyclic) isocyanates (e.g., 1,6-hexamethylene diisocyanate, etc.) are very preferred because they are excellent in terms of weather resistance, heat yellowing resistance, etc.

[0085] Examples of ultraviolet-curable resins include (meth)acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, and epoxy resins.

[0086] The protective layer 17 is formed by adding nucleating agent vesicles, which are vesicles having a single outer membrane and encapsulate a nano-sized nucleating agent, to a resin material. The nucleating agent vesicles are the same as those applied to the second resin layer 16, and are preferably added in an amount of 0.05 to 0.5 parts by mass, more preferably 0.1 to 0.3 parts by mass, calculated as the amount of nucleating agent added per 100 parts by mass of the resin material.

[0087] If the amount of nucleating agent vesicles added is less than 0.05 parts by mass, it may be difficult to obtain a sufficient degree of crystallinity, and it may be difficult to obtain a sufficient modulus of elasticity (hardness). On the other hand, if the amount of nucleating agent vesicles added is more than 0.5 parts by mass, the crystal nuclei become excessive, and the growth of spherulites is inhibited, and as a result, it becomes difficult to obtain a sufficient degree of crystallinity, and it may be difficult to obtain a sufficient modulus of elasticity (hardness).

[0088] <Primer layer 18> For example, polyester resin, polyurethane resin, a mixture of these, etc. can be used as the primer layer 18 provided on the other surface (lower surface in FIG. 1) of the base sheet 11. In particular, it is highly preferable to use a two-component curing type of polyol and isocyanate as the polyurethane resin, since this can improve the adhesion to the base sheet 11 and can also improve the cohesive force of the primer layer 18 itself.

[0089] Examples of the polyol include acrylic polyol, polyester polyol, etc., and aromatic polyols are particularly preferred from the viewpoints of rapid reactivity and heat resistance. Examples of the isocyanate include aromatic isocyanates such as tolylene diisocyanate, xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, etc., and aliphatic isocyanates such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, etc.

[0090] The thickness of the primer layer 18 is preferably 1 μm or more and 10 μm or less. If the thickness of the primer layer 18 is less than 1 μm, it may be dissolved and lost depending on the solvent type of the adhesive, and it may not be possible to improve the adhesion, which is not preferable. On the other hand, if the thickness exceeds 10 μm, it is not preferable because the cost becomes high.

[0091] <Method of manufacturing floor decorative sheet 10> A main embodiment of a method for producing the decorative floor sheet 10 as described above will now be described. First, a picture pattern is printed by a printing method on one side (the upper side in FIG. 1) of the base sheet 11 to form a picture pattern layer 12. Next, a heat seal agent is applied onto the picture pattern layer 12 to form a first adhesive layer 13, and then a film of an acrylic resin or an olefin resin that has been subjected to corona treatment in advance is provided on the first adhesive layer 13 and heat laminated to form a first resin layer 14.

[0092] Next, a urethane resin adhesive is applied onto the first resin layer 14 and dried with hot air to form a second adhesive layer 15. Then, a transparent maleic acid modified polypropylene resin to which nucleating agent vesicles have been added and a transparent polypropylene resin to which nucleating agent vesicles have been added are melt extruded from a multi-screw extruder through a T-die to laminate a base resin layer 16a and an envelope resin layer 16b on the second adhesive layer 15, thereby forming a second resin layer 16.

[0093] At the same time, the base sheet 11, the picture pattern layer 12, the first adhesive layer 13, the first resin layer 14, the second adhesive layer 15, and the second resin layer 16 are sandwiched between an embossing roll and a rubber roll and run to perform embossing while laminating. Then, the second resin layer 16 on which the embossments 10a are formed is surface-treated, and then a UV-curable resin containing nucleating agent vesicles is applied to the second resin layer 16 by a gravure coating method or the like and cured to form a protective layer 17.

[0094] Furthermore, after the other side of the base sheet 11 is subjected to a surface treatment, a primer coating liquid is applied onto the other side of the base sheet 11 by a gravure coating method or the like to form a primer layer 18. In this way, the floor decorative sheet 10 can be obtained.

[0095] 10 Benefits of Floor Decorative Sheets According to the floor decorative sheet 10 of this embodiment, the base sheet 11 has a thickness of 50 μm or more and 150 μm or less, the first resin layer 14 has a thickness of 70 μm or more and 250 μm or less, and the second resin layer 16 has a thickness of 70 μm or more and 250 μm or less, so that it is possible to fully exhibit the scratch resistance, abrasion resistance, caster resistance, impact resistance and processability required for a floor material for use when shoes are worn, and at the same time, the sheet can be easily cut on the line when it is continuously laminated and joined to the wood-based base material, improving processability, so that it can be easily processed by roll-to-roll, improving productivity.

[0096] Furthermore, not only is the protective layer 17 formed by containing an ultraviolet-curing resin and having nucleating agent vesicles added thereto, but the second resin layer 16 is formed from a transparent polypropylene resin to which nucleating agent vesicles have been added, thereby further improving the scratch resistance, abrasion resistance, castor resistance, impact resistance and processability required for a floor material for use when shoes are worn.

[0097] In addition, since the first adhesive layer 13 is a heat sealing agent, the first resin layer 14 can be bonded by heat lamination. This eliminates the need for a curing period, as is required for dry lamination, and thus simplifies the manufacturing process while improving the adhesion between layers.

[0098] In addition, since the second resin layer 16 has a base resin layer 16a containing a transparent maleic acid-modified polypropylene resin and an surrounding resin layer 16b containing a transparent polypropylene resin different from the transparent maleic acid-modified polypropylene resin, adhesion between the layers can be improved and embrittlement can be reduced. EXAMPLES

[0099] Examples of the decorative floor sheet according to the present invention will be specifically described below, but the present invention is not limited to only the following examples.

[0100] [Preparation of test specimens and comparison specimens] Example 1 A wood grain pattern was printed by gravure printing on one side of base sheet 11 consisting of a 55 μm thick polyolefin inorganic filling sheet to form picture pattern layer 12, and then a heat sealant consisting of acrylic resin-polyester resin-vinyl chloride acetate resin was applied onto picture pattern layer 12 to form first adhesive layer 13. A 100 μm thick acrylic resin film that had been corona treated in advance was placed on first adhesive layer 13 and heat laminated at a film surface temperature of 120°C to form first resin layer 14.

[0101] Next, a urethane resin adhesive was applied onto the first resin layer 14 and dried with hot air to form a second adhesive layer 15. Then, a material for the base resin layer 16a, in which 0.05 parts by mass of nucleating agent vesicles were added to 100 parts by mass of transparent maleic acid-modified polypropylene resin, and a material for the surrounding resin layer 16b, in which 0.2 parts by mass of a phenol-based antioxidant, 0.3 parts by mass of a hindered amine-based light stabilizer, 0.5 parts by mass of a benzotriazole-based ultraviolet absorber, and 0.05 parts by mass of a nucleating agent vesicle were melt-extruded from a multi-screw extruder by a T-die, respectively, to laminate the base resin layer 16a and the surrounding resin layer 16b on the second adhesive layer 15 to form the second resin layer 16.

[0102] At the same time, the base sheet 11, the picture pattern layer 12, the first adhesive layer 13, the first resin layer 14, the second adhesive layer 15, and the second resin layer 16 were sandwiched between an embossing plate roll with a duct pattern and a rubber roll and moved while being laminated and embossed. At this time, the thickness of the second resin layer 16 was adjusted to 100 μm (base resin layer 16a: 15 μm, surrounding resin layer 16b: 85 μm).

[0103] Next, the embossed surface of the second resin layer 16 is subjected to a surface treatment, and then a material obtained by adding 10 parts by mass of a hardener, 0.5 parts by mass of a benzotriazole-based ultraviolet absorber, 1 part by mass of a hindered amine-based light stabilizer, and 0.05 parts by mass of a nucleating agent vesicle to 100 parts by mass of a urethane-based resin is applied to the surface of the second resin layer 16 in an amount of 7 g / m after drying. 2 The resultant mixture was applied onto the second resin layer 16 by gravure printing so as to become as shown in FIG. 1, and then cured by irradiation with ultraviolet (UV) rays, thereby forming the protective layer 17.

[0104] Furthermore, after the other surface of the base sheet 11 is subjected to a surface treatment, a primer coating liquid containing 10 parts by mass of silica and 3 parts by mass of isocyanate added to 100 parts by mass of polyol is applied in an amount of 3 g / m2 after drying. 2 The primer layer 18 was formed by applying the primer onto the other surface of the base sheet 11 by gravure printing so as to form a primer layer 18. In this manner, a specimen 1A of the decorative floor sheet 10 of Example 1 was obtained.

[0105] Then, a two-liquid water-based emulsion adhesive (a mixture of "BA-10L (product number)" and "BA-11B (product number)" of "Rikabond (registered trademark)" manufactured by Japan Coating Resin Co., Ltd. in a ratio of 100:5) was applied to the primer layer 18 of the floor decorative sheet 10 at a rate of 2 g / m. 2 The coating was applied so that the thickness of the coating was 3 mm, and a medium density fiberboard (MDF) was attached using a laminator, and then the coating was cured for 12 hours. This resulted in a test specimen 1B of the floor decorative material of Example 1. For the impact resistance test described later, a test specimen 1C was used in which a 12 mm thick lauan board was further attached to the test specimen 1B.

[0106] Example 2 Specimen 2A of the floor decorative sheet 10 of Example 2 and specimens 2B and 2C of the floor decorative material were obtained by preparing them in the same manner as in Example 1, except that the thickness of the base sheet 11 was 150 μm, the thickness of the first resin layer 14 was 250 μm, and the thickness of the second resin layer 16 was 250 μm (base resin layer 16a: 37.5 μm, surrounding resin layer 16b: 212.5 μm).

[0107] Example 3 Specimen 3A of the floor decorative sheet 10 of Example 3 and specimens 3B and 3C of the floor decorative material were obtained by preparing them in the same manner as in Example 1, except that the thickness of the base sheet 11 was 50 μm, the thickness of the first resin layer 14 was 70 μm, and the thickness of the second resin layer 16 was 70 μm (base resin layer 16a: 12.5 μm, surrounding resin layer 16b: 57.5 μm).

[0108] Example 4 Specimen 4A of the floor decorative sheet 10 of Example 4 and specimens 4B and 4C of the floor decorative material were obtained by preparing the specimens in the same manner as in Example 1, except that the amount of nucleating agent vesicle added in the second resin layer 16 was 0.5 parts by mass and the amount of nucleating agent vesicle added in the protective layer 17 was 0.5 parts by mass.

[0109] Example 5 Specimen 5A of the floor decorative sheet 10 of Example 5 and specimens 5B and 5C of the floor decorative material were obtained by preparing them in the same manner as in Example 2, except that the amount of nucleating agent vesicle added in the second resin layer 16 was 0.5 parts by mass, and the amount of nucleating agent vesicle added in the protective layer 17 was 0.5 parts by mass.

[0110] Example 6 Specimen 6A of the floor decorative sheet 10 of Example 6 and specimens 6B and 6C of the floor decorative material were obtained by preparing them in the same manner as in Example 3, except that the amount of nucleating agent vesicle added in the second resin layer 16 was 0.5 parts by mass, and the amount of nucleating agent vesicle added in the protective layer 17 was 0.5 parts by mass.

[0111] Example 7 Specimen 7A of the floor decorative sheet 10 of Example 7 and specimens 7B and 7C of the floor decorative material were obtained by preparing the specimens in the same manner as in Example 1, except that no nucleating agent vesicles were added to the second resin layer 16.

[0112] Example 8 Specimen 8A of the floor decorative sheet 10 of Example 8 and specimens 8B and 8C of the floor decorative material were obtained by preparing the specimens in the same manner as in Example 2, except that no nucleating agent vesicles were added to the second resin layer 16.

[0113] Example 9 Specimen 9A of the floor decorative sheet 10 of Example 9 and specimens 9B and 9C of the floor decorative material were obtained by preparing them in the same manner as in Example 3, except that no nucleating agent vesicles were added to the second resin layer 16.

[0114] Example 10 Specimen 10A of the floor decorative sheet 10 of Example 10 and specimens 10B and 10C of the floor decorative material were obtained by preparing the specimens in the same manner as in Example 4, except that no nucleating agent vesicles were added to the second resin layer 16.

[0115] Example 11 Specimen 11A of the floor decorative sheet 10 of Example 11 and specimens 11B and 11C of the floor decorative material were obtained by preparing the specimens in the same manner as in Example 5, except that no nucleating agent vesicles were added to the second resin layer 16.

[0116] Example 12 Specimen 12A of the floor decorative sheet 10 of Example 12 and specimens 12B and 12C of the floor decorative material were obtained by preparing them in the same manner as in Example 6, except that no nucleating agent vesicles were added to the second resin layer 16.

[0117] Comparative Example 1 Comparative Example 1 was produced in the same manner as in Example 1, except that no nucleating agent vesicles were added to the second resin layer and the protective layer, to obtain Comparative Example 1A, which is a floor decorative sheet, and Comparative Example 1B and Comparative Example 1C, which are floor decorative materials.

[0118] Comparative Example 2 Comparative Example 2 was produced in the same manner as in Example 1, except that instead of thermal lamination using a heat sealing agent for the first adhesive layer 13, a thermosetting urethane-based adhesive was applied to the first adhesive layer and dry laminated, to obtain Comparative Example 2A, a floor decorative sheet, and Comparative Example 2B and Comparative Example 2C, a floor decorative material.

[0119] [Table 1]

[0120] [Test Method] <Scratch resistance> The test specimens 1B to 12B and the comparative specimens 1B and 2B were subjected to a pencil hardness test specified in the Japanese Industrial Standards (JIS) "K 5600" to check how they were scratched. The results are shown in Table 2.

[0121] However, in Table 2, "◎" indicates 5H or higher and no scratches, "○" indicates 2H to 4H and no scratches, "△" indicates HB to H and no scratches, and "×" indicates scratches at a level softer than B. Note that "△" or higher is a practical level, so it is considered to be "passed."

[0122] <Wear resistance> Abrasion tests were conducted on test specimens 1B to 12B and comparison specimens 1B and 2B using an abrasion tester specified in the Japanese Agricultural Standards (JAS) for flooring, and the number of revolutions until the pattern began to disappear was confirmed. The abrasive paper was replaced with a new one every 1000 revolutions. The results are shown in Table 2.

[0123] However, in Table 2, "◎" indicates 3000 rpm or more, "○" indicates 2500 rpm or more and less than 3000 rpm, "△" indicates 2000 rpm or more and less than 2500 rpm, and "×" indicates less than 2000 rpm. Note that if it is "△" or more, it is at a practical level and is therefore "passed."

[0124] <Caster resistance> A polycarbonate double caster (diameter 40 mm, width of one wheel 9 mm, width between two wheels 18 mm) was placed on the test specimens 1B to 12B and the comparative specimens 1B and 2B, and a weight (25 kg) was placed on the caster to apply a load (approximately 245 N), and the caster was moved back and forth (stroke length 20 cm or more, speed 20 cm / sec, 5,000 back and forth (10,000 times)), and the marks left afterwards were observed. The results are shown in Table 2.

[0125] In Table 2, "◎" indicates no significant change, "○" indicates slight change in gloss, "△" indicates slight change in gloss and scratches, and "×" indicates significant change in gloss and scratches. If it is "△" or better, it is at a practical level and is therefore rated as "pass."

[0126] Impact resistance Test specimens 1C-12C and comparative specimens 1C and 2C were subjected to a test conforming to the DuPont type drop ball test stipulated in the Japanese Industrial Standards (JIS) "K 5600". That is, a 500g weight was dropped from a height of 300mm onto test specimens 1C-12C and comparative specimens 1C and 2C, and the amount of dents generated in test specimens 1C-12C and comparative specimens 1C and 2C was measured, and the surfaces were observed. The results are shown in Table 2.

[0127] However, in Table 2, "◎" indicates a dent of 2.0 mm or less and no cracks on the surface, "○" indicates a dent of 2.0 mm or less and slight cracks on the surface, "△" indicates a dent of 2.0 mm or less and cracks on the surface, and "×" indicates a dent of 2.0 mm or more or significant cracks on the surface. If it is "△" or better, it is at a practical level and is therefore rated as "passed."

[0128] <Workability> The processing methods applicable to producing the test specimens 1B to 12B and the comparative specimens 1B and 2B from the test specimens 1A to 12A and the comparative specimens 1A and 2A were confirmed. The results are shown in Table 1.

[0129] However, in Table 2, "◎" indicates that in-line roll lamination is possible, "○" indicates that in-line roll lamination is possible but requires some careful processing, "△" indicates that in-line roll lamination is possible but requires considerable careful processing, and "×" indicates that roll lamination is not possible and only sheet lamination is possible. Note that anything above "△" is at a practical level and is therefore rated as "pass."

[0130] [Table 2]

[0131] [Test Results] As can be seen from Table 2, in Comparative Example 1 (no nucleating agent vesicle added), the scratch resistance did not reach a practical level. In Comparative Example 2 (dry laminate), the scratch resistance, abrasion resistance, caster resistance, impact resistance, and processability reached practical levels, but curing the first adhesive layer took time, and production was troublesome. In contrast, in Examples 1 to 12, the scratch resistance, abrasion resistance, caster resistance, impact resistance, and processability reached practical levels, and at the same time, there was no need to cure the first adhesive layer, and production could be carried out easily. [Industrial Applicability]

[0132] The decorative floor sheet of the present invention has sufficient scratch resistance, abrasion resistance, caster resistance, impact resistance and processability required for a floor material for use on shoes, and can therefore be used with great advantage in the construction industry and the like. [Explanation of symbols]

[0133] 10. Floor decorative sheets 10a Emboss 11 Base sheet 12 Pattern layer 13 First adhesive layer 14 First resin layer 15 Second adhesive layer 16 Second resin layer 16a Base resin layer 16b Surrounding resin layer 17 Protective layer 18 Primer layer

Claims

1. A picture pattern layer, a first adhesive layer having light transmittance, a first resin layer having light transmittance, a second adhesive layer having light transmittance, a second resin layer having light transmittance, and a protective layer having light transmittance are laminated in this order on one surface of a base sheet; The base sheet has a thickness of 50 μm or more and 150 μm or less, the first adhesive layer is a heat sealant made of an acrylic resin-polyester resin-vinyl chloride acetate resin; The first resin layer is an acrylic resin and has a thickness of 70 μm or more and 250 μm or less, the second resin layer is a thermoplastic resin, has a thickness of 70 μm or more and 250 μm or less, is embossed, and is formed from a transparent polypropylene resin in which a nucleating agent vesicle having a single-layer outer membrane and a nano-sized nucleating agent encapsulated therein is added; the second resin layer has a base resin layer provided on the second adhesive layer side and containing a transparent maleic acid-modified polypropylene resin; and an surrounding resin layer provided on the base resin layer and containing a transparent polypropylene resin different from that of the base resin layer; the base resin layer has a thickness of 12.5 μm or more and 37.5 μm or less, and the ratio of the thickness of the second resin layer to the total thickness is 15% or more and 18% or less; The protective layer contains an ionizing radiation curable resin and is formed by adding a nucleating agent vesicle containing a nano-sized nucleating agent to a vesicle having a single layer outer membrane. A decorative sheet for floors.

2. The amount of the nucleating agent vesicle added in the protective layer is within a range of 0.05 parts by mass or more and 0.5 parts by mass or less, calculated as the nucleating agent in the nucleating agent vesicle, per 100 parts by mass of the resin material.

2. The decorative floor sheet according to claim 1.

3. The amount of the nucleating agent vesicle added in the second resin layer is within a range of 0.05 parts by mass or more and 0.5 parts by mass or less in terms of the nucleating agent in the nucleating agent vesicle per 100 parts by mass of the resin material.

3. The decorative floor sheet according to claim 1 or 2.

4. The nucleating vesicle is a nucleating liposome with the outer membrane of phospholipids.

4. The decorative floor sheet according to claim 1.

5. The nucleating agent vesicle is one in which the nucleating agent is encapsulated in the vesicle by supercritical reverse phase evaporation.

5. The decorative floor sheet according to claim 1.

6. A primer layer is provided on the other surface of the base sheet.

6. The decorative floor sheet according to claim 1.

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