JP2021194903A - Decorative sheet - Google Patents

Abstract

To provide a decorative sheet which achieves scratch resistance, bending workability, and concealability.SOLUTION: A decorative sheet 1 includes a base material layer 2, and a surface protective layer 4 formed on the base material layer 2. The base material layer 2 has a core layer 2a obtained by mixing an inorganic pigment with a polypropylene resin, and skin layers 2b which are formed on both surfaces of the core layer 2a and are composed of a polypropylene resin. The skin layer 2b is formed by adding nucleating agent vesicle in which a nano-sized nucleating agent is included in the vesicle having an outer film of a single layer film, to a polypropylene resin. Martens hardness of the skin layer 2b is within a range of 50 N/mm2 or more and 120 N/mm2 or less. A thickness of the base material layer 2 is within a range of 40 μm or more and 200 μm or less. The surface protective layer 4 has a lower layer 4b formed on the base material layer 2 side and an upper layer 4a formed on the lower layer 4b. A spherical glossiness modifier 10a and a spherical antiwear agent 10b are added to the lower layer 4b.SELECTED DRAWING: Figure 1

Description

The present invention relates to a decorative sheet used for surface cosmetics such as interior / exterior of a building, fittings, furniture, building materials, flooring materials, etc., and particularly relates to a technique suitable for fittings / building action decorative sheets.

The decorative sheet is preferably scratch resistant and processable, especially when used as a fitting / building decorative sheet.
Here, as a decorative sheet in consideration of scratch resistance, for example, there is a decorative sheet described in Patent Document 1.
By the way, the decorative sheet is attached to the surface of a substrate such as a wood substrate, a metal substrate, or a non-combustible substrate to form a decorative board, and the decorative sheet imparts a design property to the decorative board according to the purpose. Therefore, the decorative sheet needs to be covered so that the surface of the substrate is completely invisible, if necessary. In this case, it is necessary to use a decorative sheet that is at least colored with a pigment and has concealing properties.

Japanese Unexamined Patent Publication No. 2013-83139

In recent years, in order to expand the use of decorative boards using decorative sheets and to increase consumers' awareness of quality, it is required to achieve both scratch resistance, bendability, and concealment.
In response to the above requirements, regarding scratch resistance, it is necessary to increase the thickness and hardness of the decorative sheet, but all of these deteriorate the bending workability and are in a trade-off relationship.
Further, in order to exhibit high hiding power, it is necessary to increase the concentration of the inorganic pigment, and in this case, powder floating on the surface of the base material layer and deterioration of interlayer adhesion may occur.

Here, the scratches include deep scratches that are scooped out and shallow scratches that cause a change in luster. The gloss change is visually noticeable when there is a change of 10% or more at the 60 ° gloss value. The scratches that cause this gloss change are often shallow scratches with a depth of 100 μm or less. Deep scratches such as gouging can be prevented by increasing the hardness of the resin. On the other hand, it is difficult to prevent shallow scratches that cause a change in luster simply by increasing the hardness of the resin, and another solution is required.

The present invention has been made by paying attention to the above points, and has both scratch resistance, bending workability, and concealing property. Especially for scratches, deep scratches such as scooping and gloss changes due to shallow scratches are exhibited. The purpose is to provide a suppressed cosmetic sheet.

The inventor has provided a nucleating agent for improving the crystallinity of polypropylene for the base material layer, which can be used as a decorative sheet and for the purpose of further improving scratch resistance, and a vesicle provided with an outer film of a single layer film. It is encapsulated in vesicles and added to polypropylene resin as a nucleating agent vesicles. Furthermore, various studies and experiments have been conducted on the manufacturing process to make the Martens hardness within the optimum range, and for the surface protective layer. The present invention was found by examining various gloss adjusting agents and abrasion resistant agents to be added.

In order to solve the problem, the decorative sheet according to one aspect of the present invention includes a base material layer and a surface protective layer formed on the base material layer, and the base material layer is made of polypropylene with an inorganic pigment. A core layer made of a mixture of resins and a skin layer made of polypropylene resin are provided on both sides of the core layer, and the skin layer is provided with a nano-sized nucleating agent on a vesicle provided with an outer film of a single-layer film. The encapsulated nucleating agent vesicle is added to the polypropylene resin to form the skin layer, and the martens hardness is in ^{the range of 50 N / mm 2} or more and 120 N / mm ² or less, and the thickness of the base material layer is Is in the range of 40 μm or more and 200 μm or less, and the surface protective layer has a lower layer formed on the base material layer side and an upper layer formed on the lower layer, and the lower layer has a spherical shape. The gist is that it contains a gloss adjuster and a spherical abrasion resistant agent.

According to one aspect of the present invention, for the substrate layer, a nucleating agent that improves the crystallinity of polypropylene is vesicled and added as a nucleating agent vesicle to optimize the maltens hardness, layer composition, and film thickness. For the surface protective layer, by adding a spherical gloss adjuster and an abrasion resistant agent, both scratch resistance, bending workability, and concealment are achieved. Especially for scratches, deep scratches and shallow scratches are gouged. It is possible to provide a decorative sheet that suppresses a change in luster due to scratches.

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

Hereinafter, the configuration of the decorative sheet according to the embodiment of the present invention will be described with reference to the drawings.
Here, the drawings are schematic, and the relationship between the thickness and the plane dimensions, the ratio of the thickness of each layer, and the like are different from the actual ones. Further, the embodiments shown below exemplify a configuration for embodying the technical idea of the present invention, and the technical idea of the present invention describes the material, shape, structure, etc. of the constituent parts as follows. It is not specific to things. The technical idea of the present invention may be modified in various ways within the technical scope specified by the claims described in the claims.

(composition)
As shown in FIG. 1, the decorative sheet 1 of the present embodiment is configured by laminating the pattern layer 3 and the surface protection layer 4 in this order on the surface side which is one surface of the base material layer 2. The decorative sheet 1 of the present embodiment is provided with a concealing layer 5 and a primer layer 6 on the back surface side, which is the other surface of the base material layer (raw fabric layer) 2. The concealing layer 5 and the primer layer 6 may be omitted.
It is preferable that the decorative sheet 1 of the present embodiment is designed so that the layer thickness thereof is within the range of 100 μm or more and 250 μm or less. If the layer thickness of the decorative sheet 1 is less than 100 μm, the strength of the decorative sheet 1 as a whole is insufficient, which may cause a problem in smoothness during the lapping process. If the layer thickness of the decorative sheet 1 exceeds 250 μm, the strength of the decorative sheet 1 as a whole may be too high, and problems may occur during bending.

Further, in the decorative sheet 1 of the present embodiment, an embossed uneven shape may be imparted to the surface of the base material layer 2 on the pattern layer 3 side in order to improve the design.
Then, as shown in FIG. 1, the decorative sheet 1 of the present embodiment constitutes the decorative material 11 by being bonded to the substrate B. The substrate B is not particularly limited, but is composed of, for example, wood boards, inorganic boards, metal plates, a composite plate made of a plurality of materials, and the like.

<Base layer 2>
The base material layer 2 is made of, for example, a three-layer colored polypropylene film having a core layer 2a as a center and skin layers 2b provided on both sides thereof. The core layer 2a is mainly made of polypropylene resin and is colored by mixing an inorganic pigment with the polypropylene resin. Further, the skin layer 2b is formed by containing a polypropylene resin and does not contain an inorganic pigment.
Further, a nano-sized nucleating agent is added to the skin layer 2b of the base material layer 2 in order to increase the crystallinity. In this embodiment, a nano-sized nucleating agent is added in the form of a nucleating agent vesicle.

(Polypropylene resin)
As the polypropylene resin used for the core layer 2a, considering the dispersibility of the inorganic pigment, a highly flexible random polypropylene resin having ethylene content, a known amorphous polypropylene resin as a random polypropylene resin, or a highly crystalline homopolypropylene is used. It is preferably mixed with a resin.
As the polypropylene resin used for the skin layer 2b, it is preferable to use highly crystalline homopolypropylene because it is not necessary to consider the dispersibility of the inorganic pigment, but the polypropylene resin is not limited to highly crystalline homopolypropylene. In applications where workability such as bending is more important, for example, a random polypropylene resin having ethylene content within a predetermined range or a known amorphous polypropylene resin can be mixed with the highly crystalline homopolypropylene. ..
The skin layer 2b of the base material layer 2 made of the colored polypropylene film adjusts the Martens hardness within the range ^{of 50 N / mm 2} or more and 120 N / mm ^{2 or less.}

When the Martens hardness of the skin layer 2b is ^{less than 50 N / mm 2} , it is highly likely that it will be difficult to secure practically necessary scratch resistance (particularly deep scratches). On the other hand, when the Martens hardness of the skin layer 2b ^{exceeds 120 N / mm 2} , the crystallinity is too high, and even when the nucleating agent vesicle is used, there is a possibility that problems such as whitening and cracking may occur in the bending process. ..
Suitable range of Martens hardness of the skin layer 2b of the base layer 2 is in the range of 70N / mm ² or more 100 N / mm ² or less. Within this range, both scratch resistance (particularly deep scratches) and bending workability can be achieved in excellent conditions.

Here, the Martens hardness is a kind of index indicating the hardness (hardness) of a substance, and a load is applied to an indenter to push it into the surface of a sample, and the depth (pushing) of a dent (indentation) formed at that time. Depth) is measured and defined as the quotient of the pushing force calculated from the load and the surface area of the depression calculated from the pushing depth. The measurement is performed by the method specified in ISO14577.
Further, it is important that the thickness of the base material layer 2 made of the colored polypropylene film is within the range of 40 μm or more and 200 μm or less.

When the thickness of the base material layer 2 is less than 40 μm, the film strength is insufficient even if the Martens hardness of the skin layer 2b is within the optimum range, and it is difficult to suppress the deterioration of scratch resistance. On the other hand, if the thickness of the base material layer 2 exceeds 200 μm, problems such as whitening and cracking may occur in the bending process.
A more preferable range of the thickness of the base material layer 2 is in the range of 60 μm or more and 150 μm or less. Within this range, both scratch resistance (particularly deep scratches) and bending workability can be achieved with sufficient margin.

Regarding the thickness of the skin layer 2b and the core layer 2a of the base material layer 2, it is preferable that the thickness of the core layer 2a is in the range of 3 times or more and 50 times or less of the thickness of one skin layer 2b. .. When the thickness of the core layer 2a is less than three times, it is difficult to satisfy the minimum concealing property required for a decorative sheet. When the thickness of the core layer 2a exceeds 50 times, the thickness of the skin layer 2b becomes relatively too small, resulting in insufficient film strength, and even if the Martens hardness is within the optimum range, scratch resistance (particularly). It is difficult to control the deterioration of (deep wounds).

A more preferable range of the thickness of the core layer 2a is a range in which the thickness of the core layer 2a is 10 times or more and 40 times or less the thickness of one skin layer 2b. Within this range, concealment, scratch resistance (particularly deep scratches), and bending workability can be achieved at the same time with sufficient margin.
In the present embodiment, it is preferable to use a polypropylene resin having high crystallinity as the polypropylene resin used for the skin layer 2b. In particular, the highly crystalline homopolypropylene resin, which is a propylene homopolymer having an isotactic pentad fraction (mmmm fraction) of 95% or more, is in the range of 30% by mass or more and 100% by mass or less with respect to the mass of all polypropylene resins. It is preferable to use it inside.

The crystallization temperature of the polypropylene resin is generally in the range of 100 ° C. to 130 ° C., and is in the range of 110 ° C. to 140 ° C. when a nucleating agent is added. In the skin layer 2b of the colored polypropylene film in the decorative sheet 1 of the present embodiment, the cooling time from the crystallization temperature to the curing completion temperature within this range is controlled by a known cooling process to obtain the Martens hardness. Is adjusted within the range of 50 N / mm ² or more and 120 N / mm ^{2 or less.} Further, when the amount of the highly crystalline homopolypropylene resin is less than 30% by mass, the crystallinity is insufficient, so that the Martens hardness may be lower than the preferable range even if the cooling process is controlled.

Here, the isotactic pentad fraction (mm mm fraction) refers to a resin material having a predetermined resonance frequency by a 13C-NMR measurement method (nuclear magnetic resonance measurement method) using carbon C (nuclear species) having a mass of 13. It is calculated from the numerical value (electromagnetic wave absorption rate) obtained by resonating with the above, and defines the atomic arrangement, electronic structure, and molecular fine structure in the resin material. The pentad fraction of the crystalline polypropylene resin is a ratio in which five propylene units determined by 13C-NMR are lined up, 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.

(Inorganic pigment)
As the inorganic pigment, a known inorganic pigment typified by titanium oxide for imparting concealment can be used. Examples of the inorganic pigment for coloring include composite oxides such as iron-zinc, chromium-antimony, iron-aluminum, iron oxide, etc., and these can be freely adjusted according to the desired color. be. Further, as the inorganic pigment, for example, a bright material such as an aluminum flake or a pearl pigment can be added. Further, for example, an organic pigment such as carbon black may be used in combination.
Further, an additive such as a fatty acid metal salt may be added in order to improve the dispersibility and the extrusion suitability.

(Nucleating agent vesicle)
Further, the skin layer 2b of the base material layer 2 contains a nano-sized nucleating agent. The nano-sized nucleating agent is used by being added to a polypropylene resin in the form of a nucleating agent vesicle contained in a vesicle having an outer membrane of a monolayer film. Since the skin layer 2b of the base material layer 2 contains a nucleating agent, the crystallinity can be improved and the scratch resistance of the base material layer 2 can be improved. In the present embodiment, the nucleating agent in the resin constituting the skin layer 2b of the base material layer 2 may be included in the vesicle with a part of the nucleating agent exposed.
The nano-sized nucleating agent preferably has an average particle size of 1/2 or less of the wavelength region of visible light, and specifically, since the wavelength region of visible light is 400 nm or more and 750 nm or less, the average particle size Is preferably 375 nm or less.

Since the particle size of nano-sized nucleating agents is extremely small, 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, since the distance between each nucleating agent particle becomes short, when crystal growth occurs from the surface of one nucleating agent particle added to the polypropylene resin, the end where the crystal is growing is immediately immediately. It comes into contact with the ends of crystals growing from the surface of another nucleating agent particle adjacent to one nucleating agent particle, and the ends of each crystal inhibit the growth and the growth of each crystal is stopped. Therefore, the average particle size of the spherulite in the crystal portion of the crystalline polypropylene resin can be made small, for example, the spherulite size can be made small to 1 μm or less. As a result, a high-hardness colored polypropylene film having a high degree of crystallinity can be obtained, and the stress concentration between spherulites generated during bending is efficiently dispersed, so that cracking and whitening during bending are suppressed. A colored polypropylene film can be realized.

Here, when the nucleating agent is simply added, the particle size increases due to the secondary aggregation of the nucleating agent in the polypropylene resin, and the number of crystal nuclei increases with respect to the amount of the added nucleating agent. It may be significantly less than when added as an agent vesicle. Therefore, the average particle size of the spherulites in the crystal portion of the polypropylene resin becomes large, and cracking and whitening during bending may not be suppressed. Therefore, it may not be possible to achieve both improvement in scratch resistance and workability by increasing the degree of crystallinity.

The skin layer 2b of the base material layer 2 made of a colored polypropylene film constituting the decorative sheet 1 of the present embodiment is 0.05 in terms of the amount of nucleating agent added to 100 parts by mass of the polypropylene resin as the main component. It may be added in the range of 0.1 parts by mass or more and 0.5 parts by mass or less, and it is preferable that the nucleating agent vesicle is added in the range of 0.1 parts by mass or more and 0.3 parts by mass or less. If the amount of the nucleating agent vesicle added is less than 0.05 parts by mass, the crystallinity may not be sufficiently improved and the required hardness may not be reached. Further, when the amount of the nucleating agent vesicle added exceeds 0.5 parts by mass, the spherulite growth is conversely inhibited due to the excess of crystal nuclei, and as a result, the crystallinity is not sufficiently improved. It may not reach the required hardness.

In addition, as a method for nanonizing the nucleating agent, for example, a solid phase method in which the nucleating agent is mainly mechanically pulverized to obtain nano-sized particles, or the nucleating agent or the nucleating agent is dissolved. Methods such as the liquid phase method for synthesizing and crystallizing nano-sized particles in a solution, and the vapor phase method for synthesizing and crystallizing nano-sized particles from gas / vapor consisting of a nucleating agent or a nucleating agent. It can be used as appropriate. Examples of the solid phase method include ball mills, bead mills, rod mills, colloid mills, conical mills, disc 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, a hydrothermal synthesis method and the like. Further, examples of the gas phase method include an electric furnace method, a chemical flame method, a laser method, a thermal plasma method, and the like.

The supercritical reverse phase evaporation method is preferable as a method for nanonizing the nucleating agent. The supercritical reverse phase evaporation method is a method for producing a capsule (nano-sized vesicle) containing a target substance by using carbon dioxide under supercritical state or temperature condition or pressure condition above the critical point. The supercritical carbon dioxide means carbon dioxide in a supercritical state having a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ± 0.0030 MPa) or higher, and is under temperature conditions above the critical point or. Carbon dioxide under pressure conditions means carbon dioxide under conditions where only temperature or pressure exceeds critical conditions.

In addition, as a specific nano-ization treatment by the supercritical reverse phase evaporation method, first, the aqueous phase is injected into a mixed fluid of supercritical carbon dioxide, phospholipid as an outer film forming substance, and a nucleating agent as an encapsulating substance. Then, by stirring, an emulsion of supercritical carbon dioxide and an aqueous phase is produced. Next, when the pressure is reduced, carbon dioxide expands and evaporates to cause phase inversion, and phospholipids form nanocapsules (nanovesicles) in which the surface of the nucleating agent particles is covered with a monolayer film. By using this supercritical reverse phase evaporation method, unlike the conventional encapsulation method in which the outer film is a multilayer film on the surface of the nucleating agent particles, a single-layer film capsule can be easily generated. Small diameter capsules can be prepared.

The nucleating agent vesicle can be prepared, for example, by a Bangham method, an extrusion method, a hydration method, a surfactant dialysis method, a reverse phase evaporation method, a freeze-thaw method, a supercritical reverse phase evaporation method, or the like. Among them, the supercritical reverse phase evaporation method is particularly preferable.
The outer membrane constituting the nucleating agent vesicle is composed of, for example, a monolayer membrane. The outer membrane is composed of a substance containing a biological lipid such as a phospholipid.
In the present specification, a nucleating agent vesicle whose outer membrane is composed of a substance containing a biolipid 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, yellow egg lecithin, hydrogenated yellow egg lecithin, soybean lecithin, hydrogenated soybean lecithin and the like. Examples thereof include glycerophospholipids, sphingomyelin, ceramide phosphorylethanolamine, ceramide phosphorylglycerol and other sphingolin lipids.

Other substances that form the outer membrane of the vesicle include, for example, nonionic surfactants and dispersants such as cholesterols or a mixture of triacylglycerols thereof. Among these, examples of the nonionic surfactant include polyglycerin ether, dialkyl glycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene polyoxypropylene copolymer. , Polybutadiene-polyoxyethylene copolymer, polybutadiene-poly2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactum copolymer, etc. Alternatively, 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 cholic acid, choleciferol and the like can be used.

Further, the outer membrane of the liposome may be formed from a mixture of a phospholipid and a dispersant. In the decorative sheet 1 of the present embodiment, the nucleating agent vesicle is preferably a radical scavenger liposome having an outer membrane made of phospholipid, and the outer membrane is composed of phospholipid to form a base material layer 2. It is possible to improve the compatibility between the resin material, which is the main component of the above, and the vesicle.

The nucleating agent is not particularly limited as long as it is a substance that becomes a starting point of crystallization when the resin crystallizes. Examples of the nucleating agent include phosphoric acid ester metal salt, benzoic acid metal salt, piperinate metal salt, rosin metal salt, benziliden sorbitol, quinacridone, cyanine blue and talc. In particular, in order to maximize the effect of the nanonization treatment, it is preferable to use a phosphoric acid ester metal salt, a benzoic acid metal salt, a pimelic acid metal salt, or a rosin metal salt, which is a non-melt type and can be expected to have good transparency. If the material itself can be made transparent by nano-treatment, colored quinacridone, cyanine blue, talc and the like can also be used. Further, the melt-type benzylidene sorbitol may be appropriately mixed and used with the non-melt-type nucleating agent.

As described above, one of the features of the decorative sheet 1 of the present embodiment is that "the skin layer 2b of the base material layer 2 contains a nucleating agent contained in the vesicle". Then, by adding the nucleating agent to the resin composition in a state of being encapsulated in the vesicle, the dispersibility of the nucleating agent in the resin material, that is, in the skin layer 2b of the base material layer 2 is dramatically improved. However, it can be said that it is impractical because it is assumed that it may be difficult depending on the situation to directly specify the characteristics by the structure and characteristics of the object in the state of the completed decorative sheet 1. The reason is as follows. The nucleating agent added in the vesicle state has a high dispersibility and is in a dispersed state, and even in the state of the prepared decorative sheet 1, the nucleating agent is the skin layer 2b of the base material layer 2. Highly dispersed in. However, in the process of producing the decorative sheet 1 after the nucleating agent is added in the form of a vesicle to the resin composition constituting the skin layer 2b of the base material layer 2 to prepare the base material layer 2, it is usually laminated. Various treatments such as compression treatment and hardening treatment are performed on the body, and by such treatment, the outer membrane of the vesicle containing the nucleating agent is crushed or chemically reacted, and the nucleating agent is formed on the outer membrane. There is a high possibility that it is not included (cover), and the state in which the outer membrane is crushed or chemically reacted varies depending on the treatment process of the decorative sheet 1. And, in the situation that this nucleating agent is not included in the outer membrane, it is difficult to specify the physical properties themselves in the numerical range, and is the constituent material of the crushed outer membrane the outer membrane of the vesicle? It may be difficult to determine whether the material was added separately from the nucleating agent. As described above, the present invention is different from the conventional one in that the nucleating agent is blended in a high dispersion with respect to the base material layer 2, but the present invention is added in the state of a vesicle containing the nucleating agent. In the state of the decorative sheet 1, it is assumed that it is impractical to specify the structure and characteristics of the decorative sheet 1 within the numerical range analyzed based on the measurement.

<Picture layer 3>
The pattern layer 3 is a layer for pattern printing applied to the base material layer 2 using ink.
As the binder of the ink, for example, nitrified cotton, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester or the like alone or each modified product can be appropriately selected and used. The binder may be an aqueous type, a solvent type, or an emulsion type, and may be a one-component type or a two-component type using a curing agent. Further, a method of using a curable ink and curing the ink by irradiation with ultraviolet rays, an electron beam, or the like may be used. Among them, the most common method is to use urethane-based ink and cure it with isocyanate. In addition to the binder, for example, pigments contained in ordinary inks, colorants such as dyes, extender pigments, solvents, various additives, and the like are added to the pattern layer 3. Examples of highly versatile pigments include pearl pigments such as condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and mica.

Further, it is also possible to apply a design to the pattern layer 3 by vapor deposition or sputtering of various metals separately from the application of ink. In particular, it is preferable that a light stabilizer is added to the ink, whereby deterioration of the decorative sheet 1 itself caused by photodegradation of the ink can be suppressed, and the life of the decorative sheet 1 can be extended.

<Surface protection layer 4>
The resin material as the main component of the surface protective layer 4 is appropriately selected from, for example, polyurethane-based, acrylic silicon-based, fluorine-based, epoxy-based, vinyl-based, polyester-based, melamine-based, aminoalkyd-based, and urea-based resin materials. Can be used. The form of the resin material is not particularly limited, such as water-based, emulsion, and solvent-based. As for the curing method, a one-component type, a two-component type, an ultraviolet curing method, or the like can be appropriately selected.
As the resin material of the surface protective layer 4, a thermosetting resin is suitable from the viewpoints of workability, price, adhesion to the pattern layer 3, and the like.

The thermosetting resin is formed, for example, by heat-curing a polymer (polyol) containing a hydroxyl group and an isocyanate compound described below.
The above-mentioned polyol compound is not particularly limited, but may be used, for example, to impart mechanical characteristic characteristics due to elongation of the molecular structure, and for example, various acrylic polyols, various polyester polyols, various polyether polyols, and the like. It is appropriately selected and used from various polycarbonate polyols, various caprolactone diols, and the like.

When an acrylic polyol is used as the polyol constituting the thermosetting resin, its mass average molecular weight is preferably in the range of 20,000 or more and 200,000 or less, and preferably in the range of 20,000 or more and 100,000 or less. It is more preferable to be inside. If the mass average molecular weight of the acrylic polyol is less than 20,000, coating may be difficult at the time of sheet preparation. On the other hand, if the mass average molecular weight exceeds 200,000, the solubility may be lowered and the design may be deteriorated.

The isocyanate compound is not particularly limited as described above, but is, for example, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H12MDI), hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI). ), Hydrogenated xylylene diisocyanate (H6XDI), isophorone diisocyanate (IPDI) and the like.

When the thermosetting resin constituting the surface protective layer 4 is composed of an acrylic polyol and an isocyanate curing agent, the glass transition point Tg of the thermosetting resin is preferably 60 ° C. or higher. If the glass transition point of the thermosetting resin is less than 60 ° C., the target Martens hardness as the surface protective layer 4 may not be secured, or coating may be difficult at the time of sheet preparation.

The surface protective layer 4 has a lower layer 4b on the pattern layer 3 side and an upper layer 4a formed on the lower layer 4b.
Surface protective layer 4 is preferably Martens hardness is a resin layer in the range of 140 N / mm ² or more 200 N / mm ² or less. If the resin constituting the surface protective layer 4 is a resin having a Martens hardness of ^{less than 140 N / mm 2} , deep scratches may enter the surface protective layer 4, which is not preferable. Further, when the resin constituting the surface protective layer 4 is a resin having a maltens hardness of more ^{than 200 N / mm 2} , the workability is lowered and whitening may occur at the time of bending, which is not preferable.

The upper layer 4a of the surface protective layer 4 preferably has a layer thickness in the range of 2 μm or more and 10 μm or less.
Further, the layer thickness of the upper layer 4a should be set within the range of 2 μm or more and 10 μm or less by applying the coating liquid for the upper layer 4a so that the coating amount after drying is within the range of 2 μm or more and 10 μm or less. Can be done. If the layer thickness of the upper layer 4a is less than 2 μm, the scratch resistance is lowered, which is not preferable. Further, when the layer thickness of the upper layer 4a is made thicker than 10 μm, the workability is lowered and whitening may occur at the time of bending, which is not preferable.

The lower layer 4b of the surface protective layer 4 preferably has a layer thickness in the range of 2 μm or more and 10 μm or less.
Further, the layer thickness of the lower layer 4b should be set within the range of 2 μm or more and 10 μm or less by applying the coating liquid for the lower layer 4b so that the coating amount after drying is within the range of 2 μm or more and 10 μm or less. Can be done. If the layer thickness of the lower layer 4b is less than 2 μm, the scratch resistance is lowered, which is not preferable. Further, when the layer thickness of the lower layer 4b is thicker than 10 μm, the workability is lowered and whitening may occur at the time of bending, which is not preferable.

The surface protective layer 4 of the decorative sheet 1 of the present embodiment contains a spherical gloss adjusting agent 10a with respect to at least the lower layer 4b.
The optimum shape of the gloss adjuster 10a is spherical. Here, the "spherical shape" includes a true spherical shape or an elliptical shape, and in the case of an elliptical shape, the ratio of the major axis to the minor axis is 2 or less. By making the shape of the gloss adjusting agent 10a spherical, the slipperiness is improved and the scratch resistance (particularly shallow scratches) is improved.

The optimum particle size (average particle size) of the gloss adjusting agent 10a is in the range of 2 μm or more and 15 μm or less. Here, the "particle size (average particle size)" may be a value (average value) obtained by measuring the particle size distribution of the particles to be used, or the particle size of a plurality of particles can be observed from the cross-sectional observation of the obtained decorative material. It may be a value obtained by actually measuring and averaging. Although the measurement methods of the two are different from each other, the obtained particle size values are substantially the same. When the particle size of the gloss adjusting agent 10a is less than 2 μm, the effect of adding the gloss adjusting agent 10a may not be obtained, which is not preferable. Further, when the particle size of the gloss adjusting agent 10a is made larger than 15 μm, the gloss adjusting agent 10a may fall off, which is not preferable.

The amount of the gloss adjusting agent 10a added is preferably in the range of 2 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin as the main component of the lower layer 4b. More preferably, it is within the range of 2 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin as the main component of the lower layer 4b. When the amount of the gloss adjusting agent 10a added is less than 2 parts by mass, the matting effect of the gloss adjusting agent 10a is small, which is not preferable. Further, when the amount of the gloss adjusting agent 10a added is 30 parts by mass or more, the gloss adjusting agent 10a may fall off, which is not preferable.

As the gloss adjusting agent 10a, commercially available known particles can be used. For example, any of organic materials such as PE wax, PP wax and resin beads, and inorganic materials such as silica, glass and alumina can be used as the gloss adjusting agent 10a. Porous silica is preferable in terms of matting performance. The oil absorption of silica is preferably 200 mL / 100 g or more. Silica, which absorbs a large amount of oil, has a large matting performance and has a large effect of reducing the required amount of matting material added.

The surface protective layer 4 of the decorative sheet 1 of the present embodiment contains a spherical abrasion resistant agent 10b with respect to at least the lower layer 4b.
The optimum shape of the wear resistant agent 10b is spherical. Here, the "spherical shape" includes a true spherical shape or an elliptical shape, and in the case of an elliptical shape, the ratio of the major axis to the minor axis is 2 or less. By making the shape of the wear resistant agent 10b spherical, the slipperiness is improved and the scratch resistance (particularly shallow scratches) is improved.

The optimum particle size (average particle size) of the wear resistant agent 10b is in the range of 2 μm or more and 15 μm or less. Here, the "particle size (average particle size)" may be a value (average value) obtained by measuring the particle size distribution of the particles to be used, or the particle size of a plurality of particles can be observed from the cross-sectional observation of the obtained decorative material. It may be a value obtained by actually measuring and averaging. Although the measurement methods of the two are different from each other, the obtained particle size values are substantially the same. When the particle size of the wear resistant agent 10b is less than 2 μm, the effect of adding the wear resistant agent 10b may not be obtained, which is not preferable. Further, when the particle size of the wear resistant agent 10b is made larger than 15 μm, the wear resistant agent 10b may fall off, which is not preferable.

The amount of the wear resistant agent 10b added is preferably in the range of 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the resin as the main component of the lower layer 4b. More preferably, it is within the range of 5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin as the main component of the lower layer 4b. If the amount of the wear resistant agent 10b added is less than 1 part by mass, the scratch resistance is lowered, which is not preferable. Further, when the amount of the abrasion resistant agent 10b added is 15 parts by mass or more, it is not preferable because the surfaces of the decorative sheets 1 may be rubbed and scratched when they are transported together.
As the wear resistant agent 10b, commercially available known particles can be used. From the viewpoint of wear resistance, it is preferable to contain at least one of silica and glass. Silica and glass have moderate hardness and therefore show good scratch resistance.

The surface protective layer 4 of the decorative sheet 1 of the present embodiment may contain a lubricant with respect to at least the upper layer 4a.
As the lubricant, a commercially available known lubricant can be used, and examples thereof include WAX and a surface conditioner.
The amount of the lubricant added is preferably in the range of 0.5 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the resin as the main component of the upper layer 5a. If the amount of the lubricant added is less than 0.5 parts by mass, the surfaces of the decorative sheets 1 may be rubbed and scratched when they are transported together. Further, if the amount of the lubricant added exceeds 5 parts by mass, the gloss change due to shallow scratches becomes large and the scratch resistance may decrease.

The surface protective layer 4 of the decorative sheet 1 of the present embodiment can optionally be added with functional additives such as an antibacterial agent and an antifungal agent in order to impart various functions. Further, an ultraviolet absorber and a light stabilizer can be added to the surface protective layer 4 as needed. As the ultraviolet absorber, for example, benzotriazole type, benzoate type, benzophenone type, triazine type and the like are generally added, and as the light stabilizer, for example, hindered amine type and the like are generally added in any combination.

<Concealment layer 5>
Further, when it is desired to impart concealing property to the substrate B to the decorative sheet 1, it can be dealt with by separately providing an opaque concealing layer 5.
The concealing layer 5 can be basically composed of the same material as the pattern layer 3, but since the purpose is concealment, for example, an opaque pigment, titanium oxide, iron oxide or the like is used as the pigment. Is preferable. It is also possible to add metals such as gold, silver, copper and aluminum in order to improve the concealing property. Generally, flake-shaped aluminum is often added.

<Primer layer 6>
As the primer layer 6, the same material as that of the pattern layer 3 can be used. Since the primer layer 6 is applied to the back surface of the decorative sheet 1, considering that the decorative sheet 1 is wound up in a web shape, the primer layer is used to avoid blocking and to improve the adhesion with the adhesive. An inorganic filler may be added to 6. Examples of the inorganic filler include silica, alumina, magnesia, titanium oxide, barium sulfate and the like.

(Production method)
An example of manufacturing the decorative sheet 1 will be described.
A vesicle is encapsulated with a nucleating agent to produce a vesicle of the nucleating agent, and the produced vesicle of the nucleating agent is added to a polypropylene resin to prepare a resin material for a skin layer. In addition, an inorganic pigment is added to the polypropylene resin to prepare a resin material for the core layer.
The nucleating agent vesicle is produced, for example, by encapsulating the nucleating agent in a vesicle having a single-layer film by a supercritical reverse-phase evaporation method to form a vesicle.
As the polypropylene resin used for the skin layer 2b, it is preferable to use a highly crystalline homopolypropylene resin having an isotactic pentad fraction (mmmm fraction) of 95% or more in an amount of 30% by mass or more and 100% by mass or less. ..

The resin material for the base material layer is individually heated and melted, and molded into a sheet having a thickness of 40 μm or more and 200 μm or less by extrusion molding or the like to obtain the base material layer 2.
The skin layer 2b and the core layer 2a can be molded separately and bonded together using, for example, a dry laminate to prepare the base material layer 2, but the molten resin is formed by using a T-die or a feed block in front of the T-die during extrusion molding. It is easy to prepare the base material layer 2 by co-extrusion molding, and the productivity is high.
At this time, by adjusting the cooling time from the crystallization temperature to the curing completion temperature by a known adjusting method, the maltens hardness of the skin layer 2b of the base material layer 2 is in ^{the range of 50 N / mm 2} or more and 120 N / mm ² or less. Control within.

When forming an uneven shape (embossed pattern) by embossing on the decorative sheet 1, the method of first laminating by the above laminating method and then embossing by heat pressure or providing an uneven pattern on the cooling roll and embossing at the same time as extruding laminating. A method of forming a pattern can be used.
Further, the pattern layer 3 is formed by printing on the upper surface of the base material layer 2, and the surface protective layer 4 is formed on the pattern layer 4 by printing.
At this time, it is preferable that the thickness of the surface protective layer 4 is within the range of 4 μm or more and 20 μm or less, and the total thickness of the decorative sheet 10 is within the range of 100 μm or more and 250 μm or less.

(Action and others)
The decorative sheet 1 of the present embodiment includes a base material layer 2 and a surface protective layer 4 formed on the base material layer 2, and the base material layer 2 is obtained by mixing an inorganic pigment with a polypropylene resin. The core layer 2a is formed on both sides of the core layer 2a and has a skin layer 2b made of polypropylene resin. The nucleating agent vesicle containing the agent is added to the polypropylene resin to form the skin layer 2b, and the martens hardness of the skin layer 2b is in ^{the range of 50 N / mm 2} or more and 120 N / mm ² or less, and the base material layer. The thickness of 2 is in the range of 40 μm or more and 200 μm or less, and the surface protective layer 4 comprises a lower layer 4b formed on the base material layer 2 side and an upper layer 4a formed on the lower layer 4b. By including the spherical gloss adjusting agent 10a and the spherical abrasion resistant agent 10b in the lower layer 4b, both scratch resistance, bending workability, and concealing property are achieved, and particularly scratches are scooped out. It is possible to provide a decorative sheet 1 in which the gloss change due to deep scratches and shallow scratches is suppressed.

(Modification example)
In the present embodiment, the embodiment including the spherical gloss adjusting agent 10a and the spherical abrasion resistant agent 10b with respect to at least the lower layer 4b of the surface protective layer 4 has been described, but the present invention is not limited thereto. .. For example, a spherical gloss adjusting agent 10a may be contained in the upper layer 4a of the surface protective layer 4. In that case, the amount of the gloss adjusting agent 10a added is preferably in the range of 2 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin as the main component of the upper layer 4a. More preferably, it is within the range of 2 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin as the main component of the upper layer 4a. When the amount of the gloss adjusting agent 10a added is less than 2 parts by mass, the matting effect of the gloss adjusting agent 10a is small, which is not preferable. Further, when the amount of the gloss adjusting agent 10a added is 30 parts by mass or more, the gloss adjusting agent 10a may fall off, which is not preferable.

When the gloss adjuster 10a is contained in both the upper layer 4a and the lower layer 4b, the content of the gloss adjuster 10a in the upper layer 4a is higher than the content of the gloss adjuster 10a and the wear resistant agent 10b in the lower layer 4b. You may have more. In that case, the amount of the gloss adjusting agent 10a added can be reduced to prevent the gloss adjusting agent 10a from falling off.
Further, when the gloss adjusting agent 10a is contained in both the upper layer 4a and the lower layer 4b, the content of the gloss adjusting agent 10a in the upper layer 4a may be smaller than the content of the gloss adjusting agent 10a in the lower layer 4b. .. In that case, the flexibility of the surface protective layer 4 of the decorative sheet as a whole can be increased.

Further, the thickness of the upper layer 4a may be made thinner than the thickness of the lower layer 4b. In that case, the flexibility of the surface protective layer 4 of the decorative sheet as a whole can be increased.
Further, the average particle size of the gloss adjusting agent 10a contained in the upper layer 4a may be larger than the average particle size of the gloss adjusting agent 10a contained in the lower layer 4b. In that case, the occurrence of deep scratches can be suppressed, and the occurrence of shallow scratches (change in gloss) can be effectively suppressed.
Further, the average particle size of the gloss adjusting agent 10a contained in the upper layer 5a may be smaller than the average particle size of the gloss adjusting agent 10a contained in the lower layer 4b. In that case, the occurrence of shallow scratches (change in gloss) can be suppressed, and the occurrence of deep scratches can be effectively suppressed.

Further, the martens hardness of the skin layer 2b located on the pattern layer 3 side and the martens hardness of the skin layer 2b located on the concealing layer 5 side may be the same value or may be different values. When the martence hardness of the skin layer 2b located on the pattern layer 3 side and the martence hardness of the skin layer 2b located on the concealment layer 5 side are different values, the martence of the skin layer 2b located on the pattern layer 3 side is different. The hardness may be set to a value higher or lower than the Martens hardness of the skin layer 2b located on the concealing layer 5 side. For example, the maltens hardness of the skin layer 2b located on the pattern layer 3 side may be within the range of 1, 1 or more and 3 times or less the maltens hardness of the skin layer 2b located on the concealing layer 5 side. It may be in the range of 0.5 times or more and 0.9 times or less. Within this range, both scratch resistance (particularly deep scratches) and bending workability can be achieved with sufficient margin.

Further, the Martens hardness of the skin layer 2b and the Martens hardness of the core layer 2a may have different values. The maltens hardness of the skin layer 2b may be higher or lower than the maltens hardness of the core layer 2a. For example, the maltens hardness of the skin layer 2b may be set within the range of 1, 1 times or more and 3 times or less of the maltens hardness of the core layer 2a, or 0.5 times or more and 0.9 times or less. You may. Within this range, both scratch resistance (particularly deep scratches) and bending workability can be achieved with sufficient margin.

[Example]
Hereinafter, specific examples of the decorative sheet 1 of the present embodiment will be described.
(Manufacturing method of nucleating agent vesicle)
First, a method for producing the nucleating agent liposome used in this example will be described.
The nucleating agent liposome uses 100 parts by mass of methanol and 70 parts by mass of a phosphate ester metal salt-based nucleating agent (Adecastab NA-21; manufactured by ADEKA) as a nucleating agent by using the above-mentioned supercritical reverse phase evaporation method. , 5 parts by mass of phosphatidylcholine as a phospholipid constituting the outer membrane of the vesicle is placed in a high-pressure stainless steel container kept at 60 ° C. and sealed, and carbon dioxide is injected into the container so that the pressure becomes 20 MPa. It was in a critical state. Then, the inside of the container was vigorously stirred, and 100 parts by mass of ion-exchanged water was injected. After stirring and mixing for another 15 minutes while keeping the temperature and pressure in a supercritical state, carbon dioxide is discharged from the container and returned to atmospheric pressure to apply a nucleating agent to the vesicle having a single-layer outer membrane made of phospholipids. The encapsulating nucleating agent vesicle was obtained.

<Example 1>
As a raw material for the core layer 2a of the colored polypropylene film, 60 parts by mass of a random polypropylene resin having a melt flow rate (MFR) of 12 g / 10 min (230 ° C.) containing 4% of an ethylene component and 40 mass of titanium oxide pigment as an inorganic pigment. As a raw material for the skin layer 2b, the melt flow rate (MFR) is 15 g / 10 min (230 ° C.), and the molecular weight distribution MWD (Mw / Mn) is 2.3. 50 parts by mass of a random polypropylene resin having a melt flow rate (MFR) of 12 g / 10 min (230 ° C.) containing 4% of an ethylene component with respect to 50 parts by mass of a highly crystalline homopolypropylene resin, and the above-mentioned nucleating agent vesicles are produced. A base layer 2 made of a colored polypropylene film having a core layer thickness of 120 μm and a skin layer thickness of 10 μm is produced by co-extruding using a melt extruder to add 0.1 parts by mass as a nucleating agent. Filmed.
Next, both sides of the base material layer 2 are subjected to corona treatment, and one of them is printed with a two-component curable urethane ink (V180; manufactured by Toyo Ink Mfg. Co., Ltd.) to form the pattern layer 3. did.

The following composition for forming a surface protective layer is used for the pattern layer 3, and the thermosetting composition (the amount applied after drying (the film thickness after drying; the same applies hereinafter) 5 μm) to be the lower layer 4b and the upper layer. The surface protective layer 4 was formed by sequentially laminating the thermosetting composition (applied amount 5 μm after drying) to be 4a, and a decorative sheet of Example 1 having a total thickness of 160 μm was obtained.

(Upper layer 4a)
The thermosetting composition to be the upper layer 4a was formed by blending the following polymer solution A with the following curing agent, ultraviolet absorber, and light stabilizer.

-Polymer solution A
80 g of methyl methacrylate and 20 g of 2-hydroxyethyl methacrylate were introduced into a four-necked flask equipped with a stirrer, a nitrogen introduction tube and a reflux condenser, and 100 g of ethyl acetate was added to dissolve the flask. The mixture was stirred. Polymerization was started by adding 0.2 g of α, α'-azobisisobutyronitrile to this, and heating and stirring were continued for 5 hours in an oil bath at 60 ° C. to obtain a colorless, sticky, polyol. The polymer solution A contained was obtained.
Formulation (amount of polymer solution A): 100 parts by mass

・ Hardener Product name: Duranate 24A-100 (manufactured by Asahi Kasei Corporation)
Formulation: 10 parts by mass, lubricant Product name: CERAFLOUR 991 (Big Chemie Japan Co., Ltd.)
Formulation: 0.5 parts by mass, UV absorber Product name: Tinuvin 400 (manufactured by BASF)
Formulation: 5.0 parts by mass, light stabilizer Product name: Tinuvin 123 (manufactured by BASF)
Formulation: 2.0 parts by mass / diluted solvent Product name: Ethyl acetate Formulation: 50 parts by mass

(Lower layer 4b)
The thermosetting composition to be the lower layer 4b was composed of the above polymer solution A mixed with the following curing agent, lubricant, gloss adjusting agent, abrasion resistant agent, ultraviolet absorber, and light stabilizer.

-Polymer solution A
Formulation (amount of polymer solution A): 100 parts by mass, curing agent Product name: Duranate 24A-100 (manufactured by Asahi Kasei Corporation)
Formulation: 5 parts by mass, gloss adjuster Product name: Sunsphere H-52 (manufactured by AGC Si-Tech Co., Ltd.)
Properties: Spherical, average particle diameter 5 μm, oil absorption 300 mL / 100 g
Formulation: 10 parts by mass, wear resistant agent Product name: Sunsphere NP-100 (manufactured by AGC Si-Tech Co., Ltd.)
Properties: Spherical, average particle diameter 10 μm
Formulation: 10 parts by mass, UV absorber Product name: Tinuvin 400 (manufactured by BASF)
Formulation: 5.0 parts by mass, light stabilizer Product name: Tinuvin 123 (manufactured by BASF)
Formulation: 2.0 parts by mass / diluted solvent Product name: Ethyl acetate Formulation: 50 parts by mass

<Example 2>
A decorative sheet of Example 2 was obtained in the same manner as in Example 1 except that the thickness of the core layer 2a of Example 1 was 30 μm and the thickness of the skin layer 2b was 5 μm.

<Example 3>
A decorative sheet of Example 3 was obtained in the same manner as in Example 1 except that the thickness of the core layer 2a of Example 1 was 170 μm and the thickness of the skin layer 2b was 10 μm.

<Example 4>
A decorative sheet of Example 4 was obtained in the same manner as in Example 1 except that the gloss adjusting agent of Example 1 was replaced with the following.
-Gloss adjuster Product name: Sunsphere H-32 (manufactured by AGC Si-Tech Co., Ltd.)
Properties: Spherical, average particle diameter 3 μm, oil absorption 300 mL / 100 g

<Example 5>
A decorative sheet of Example 5 was obtained in the same manner as in Example 1 except that the gloss adjusting agent of Example 1 was replaced with the following.
-Gloss adjuster Product name: Sunsphere H-122 (manufactured by AGC Si-Tech Co., Ltd.)
Properties: Spherical, average particle diameter 12 μm, oil absorption 300 mL / 100 g

<Example 6>
A decorative sheet of Example 6 was obtained in the same manner as in Example 1 except that the gloss adjusting agent of Example 1 was replaced with the following.
-Gloss adjuster Product name: Sunsphere H-201 (manufactured by AGC Si-Tech Co., Ltd.)
Properties: Spherical, average particle diameter 20 μm, oil absorption 150 mL / 100 g

<Example 7>
A decorative sheet of Example 7 was obtained in the same manner as in Example 1 except that the wear resistant agent of Example 1 was replaced with the following.
-Abrasion resistant agent Product name: Sunsphere NP-200 (manufactured by AGC Si-Tech Co., Ltd.)
Properties: Spherical, average particle diameter 20 μm

<Example 8>
A decorative sheet of Example 8 was obtained in the same manner as in Example 1 except that the polymer solution A of Example 1 was replaced with the following polymer solution B and the curing agent was replaced with the following.
-Polymer solution B
In a four-necked flask equipped with a stirrer, a nitrogen introduction tube and a reflux condenser, 50 g of methyl methacrylate, 10 g of 2-hydroxyethyl methacrylate and 40 g of butyl acrylate were introduced, and 100 g of ethyl acetate was added to dissolve the oil. The mixture was stirred on the bath under a nitrogen atmosphere. Polymerization was started by adding 0.2 g of α, α'-azobisisobutyronitrile to this, and heating and stirring were continued for 5 hours in an oil bath at 60 ° C. to obtain a colorless, sticky, polyol. The polymer solution B contained was obtained.
・ Hardener Product name: Takenate D-110 (manufactured by Mitsui Chemicals, Inc.)

<Example 9>
A decorative sheet of Example 9 was obtained in the same manner as in Example 1 except that the blending amount of the lubricant of Example 1 was replaced with 0.4 parts by mass.

<Example 10>
A decorative sheet of Example 10 was obtained in the same manner as in Example 1 except that the blending amount of the lubricant of Example 1 was replaced with 6 parts by mass.

<Example 11>
A decorative sheet of Example 11 was obtained in the same manner as in Example 1 except that the thickness of the core layer 2a of Example 1 was 75 μm and the thickness of the skin layer 2b was 30 μm.

<Example 12>
A decorative sheet of Example 12 was obtained in the same manner as in Example 1 except that the thickness of the core layer 2a of Example 1 was 165 μm and the thickness of the skin layer 2b was 3 μm.

<Example 13>
The thickness of the core layer 2a of Example 8 is 22 μm, the thickness of the skin layer 2b is 9 μm, the vesicle of the nucleating agent added to the skin layer 2b is 0.04 parts by mass as the nucleating agent, and the gloss adjusting agent and the resistance to resistance are set. The decorative sheet of Example 13 was obtained in the same manner as in Example 8 except that the abrasion agent was replaced with the following and the blending amount of the lubricant was replaced with 0.4 parts by mass.
-Gloss adjuster Product name: Sunsphere H-201 (manufactured by AGC Si-Tech Co., Ltd.)
Properties: Spherical, average particle diameter 20 μm, oil absorption 150 mL / 100 g
-Abrasion resistant agent Product name: Sunsphere NP-200 (manufactured by AGC Si-Tech Co., Ltd.)
Properties: Spherical, average particle diameter 20 μm

<Example 14>
The thickness of the core layer 2a of Example 13 is 180 μm, the thickness of the skin layer 2b is 3.5 μm, the nucleating agent vesicle added to the skin layer 2b is 0.6 parts by mass as the nucleating agent, and the lubricant is blended. A decorative sheet of Example 14 was obtained in the same manner as in Example 13 except that the amount was replaced with 6 parts by mass.

<Comparative Example 1>
A decorative sheet of Comparative Example 1 was obtained in the same manner as in Example 1 except that the gloss adjusting agent of Example 1 was replaced with the following.
・ Gloss adjuster Product name: Silysia 250N (manufactured by Fuji Silysia Chemical Ltd.)
Properties: Amorphous, average particle diameter 5 μm, oil absorption 330 mL / 100 g

<Comparative Example 2>
A decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 1 except that the wear resistant agent added in Example 1 was removed.

<Comparative Example 3>
A decorative sheet of Comparative Example 3 was obtained in the same manner as in Example 1 except that the nucleating agent vesicle added to the skin layer 2b of Example 1 was 0.04 parts by mass as the nucleating agent.

<Comparative Example 4>
A decorative sheet of Comparative Example 4 was obtained in the same manner as in Example 1 except that the nucleating agent vesicle added to the skin layer 2b of Example 1 was 0.6 parts by mass as the nucleating agent.

<Comparative Example 5>
A decorative sheet of Comparative Example 5 was obtained in the same manner as in Example 1 except that the thickness of the core layer 2a of Example 1 was 30 μm and the thickness of the skin layer 2b was 3 μm.

<Comparative Example 6>
A decorative sheet of Comparative Example 6 was obtained in the same manner as in Example 1 except that the thickness of the core layer 2a of Example 1 was 200 μm and the thickness of the skin layer 2b was 10 μm.

<Comparative Example 7>
A decorative sheet of Comparative Example 7 was obtained in the same manner as in Example 1 except that the untreated nucleating agent was used instead of the nucleating agent vesicle of Example 1.

(evaluation)
The decorative sheets of Examples 1 to 14 and Comparative Examples 1 to 7 obtained by the above method were measured for Martens hardness, and evaluated for scratch resistance, bending workability, and concealing property.
In this embodiment, if the evaluations are "◎", "○" and "Δ", there is no problem in using them, so they are passed.

<Martens hardness measurement method>
A method for measuring Martens hardness will be described. The Martens hardness of each decorative sheet was measured using a Martens hardness measuring device (Fisherscope HM2000; manufactured by Fisher Instruments Co., Ltd.) compliant with ISO14577. Since the measurement is performed from the cross section, the cross section of the decorative sheet 1 appears after the decorative sheet 1 is embedded in a resin such as a cold-curable epoxy resin or a UV curable resin and sufficiently cured. The measurement surface was obtained by cutting the sheet and applying mechanical polishing to the surface. As a specific measurement method, an indenter was pushed into the measurement surface of each sample, and the Martens hardness was calculated from the pushing depth and the load. The measurement was performed under the measurement conditions of a test force of 10 mN, a test force load required time of 10 seconds, and a test force holding time of 5 seconds. The calculated Martens hardness of each sample is as shown in Table 1.

<Scratch resistance>
After being attached to the wood substrate B using a urethane-based adhesive, a Hoffman scratch test was carried out using a Hoffman scratch hardness tester (manufactured by BYK-Gardner). The detailed evaluation method for each evaluation test will be described below.

-Evaluation of deep scratches For scratch resistance, especially deep scratches, a Hoffman scratch test was carried out in 100 g increments with a load of 300 g to 2000 g.
The evaluation criteria are as follows.
◎: No scratches at 1900 g to 2000 g 〇: No scratches at 1500 g to 1800 g △: No scratches at 1000 g to 1400 g ×: No scratches at 900 g or less

・ Evaluation of shallow scratches (gloss change) For scratch resistance, especially shallow scratches, a Hoffman scratch test was conducted 10 times in a row with a load of 500 g so that a thick line was formed, and then the glossiness before and after the Hoffman scratch test was measured. It was measured and the amount of change in gloss was calculated as follows.
Amount of change in gloss = (gloss after test-gloss before test) / gloss before test For gloss, 85 ° gloss was measured using Rhopoint IQ (manufactured by Konica Minolta).
The evaluation criteria are as follows.
⊚: Gloss change amount is less than 5% 〇: Gloss change amount is less than 10% △: Gloss change amount is 10% or more and less than 20% ×: Gloss change amount is 20% or more

<Bending workability>
After sticking to the wood substrate B using a urethane-based adhesive, a V-shaped groove is formed on the other surface of the decorative sheet 1 so that the decorative sheet 1 on the opposite side is not scratched. Insert it up to the boundary where the decorative sheet 1 is bonded. Next, the wooden substrate B is bent up to 90 degrees along the V-shaped groove so that the surface of the decorative sheet 1 is mountain-folded, and the bent portion of the surface of the decorative sheet 1 is not whitened or cracked. It was observed using an optical microscope and the state of bending workability was evaluated.
The evaluation criteria are as follows.
◎: No whitening or cracks are seen 〇: Slight whitening is visible in some parts △: Whitening is visible in some parts ×: Whitening is visible in the entire surface or cracks are visible in some parts

<Concealment>
In the evaluation of the concealment property, the spectrophotometer (530JP / LP) manufactured by x-rite was used, and the measurement was performed on the white background and the black background of the concealment test paper (byco-chart high brightness 2A) manufactured by BYK-Gardner. Judgment was made by color difference. It can be said that the smaller the color difference value is, the better the concealment property is.
The evaluation criteria are as follows.
⊚: Concealment is less than 0.3 〇: Concealment is 0.3 or more and less than 0.5 △: Concealment is 0.5 or more and less than 1.0 ×: Concealment is 1.0 or more

The evaluation results are shown in Table 1.

As shown in Table 1, the decorative sheets of Examples 1 to 14 have both scratch resistance, bending workability, and concealing property, and particularly for scratches, deep scratches such as scooping and gloss change due to shallow scratches. It is possible to provide a decorative sheet that suppresses.

1 Decorative sheet 2 Base material layer 2a Core layer 2b Skin layer 3 Picture layer 4 Surface protective layer 4a Upper layer 4b Lower layer 5 Concealing layer 6 Primer layer 10a Gloss adjuster 10b Abrasion resistant agent 11 Decorative material B Substrate

Claims (9)

A base material layer and a surface protective layer formed on the base material layer are provided.
The base material layer has a core layer containing an inorganic pigment and a polypropylene resin, and a skin layer formed on both sides of the core layer and containing a polypropylene resin.
The skin layer is formed by adding a nucleating agent vesicle containing a nano-sized nucleating agent in a vesicle having an outer film of a single-layer film to the polypropylene resin, and the skin layer has a maltens hardness. 50 N / mm ² or more is 120 N / mm ² within the following ranges,
The thickness of the base material layer is in the range of 40 μm or more and 200 μm or less.
The surface protective layer has a lower layer formed on the base material layer side and an upper layer formed on the lower layer.
A decorative sheet characterized by containing a spherical gloss adjuster and a spherical abrasion resistant agent in the lower layer. The gloss adjuster contained in the lower layer contains silica, and the average particle size thereof is in the range of 2 μm or more and 15 μm or less.
The decorative sheet according to claim 1, wherein the wear-resistant agent contained in the lower layer contains at least one of silica and glass, and the average particle size thereof is in the range of 2 μm or more and 15 μm or less. The main material of the resin component constituting the surface protective layer is a thermosetting resin.
The thermosetting resin is composed of an acrylic polyol and an isocyanate curing agent, to claim 1 or claim 2, wherein the Martens hardness is in the range of 140 N / mm ² or more 200 N / mm ² or less The described cosmetic sheet. Any of claims 1 to 3, wherein the upper layer contains a lubricant in a range of 0.5 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the resin as the main component of the upper layer. The decorative sheet according to item 1. The cosmetic according to any one of claims 1 to 4, wherein the layer thickness of the core layer is within the range of 3 times or more and 50 times or less with respect to the thickness of one of the skin layers. Sheet. The amount of the nucleating agent vesicle added is within the 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 with respect to 100 parts by mass of the polypropylene resin. The decorative sheet according to any one of claims 1 to 5, wherein the cosmetic sheet is characterized by the above-mentioned. The decorative sheet according to any one of claims 1 to 6, wherein the nucleating agent vesicle is a nucleating agent liposome having an outer membrane made of phospholipid. Any of claims 1 to 7, wherein the nucleating agent vesicle is formed by encapsulating the nucleating agent in a vesicle provided with a single-layer film by a supercritical reverse-phase evaporation method. The cosmetic sheet according to item 1. The decorative sheet according to any one of claims 1 to 8, wherein a pattern layer is laminated between the base material layer and the surface protective layer.

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