JP2020076015A - Decorative sheet and manufacturing method thereof - Google Patents

Abstract

Kind Code: A1 The present invention provides a decorative sheet that satisfies both problems during printing processing (printing processing suitability), scratch resistance, smoothness during wrapping processing (surface uniformity during wrapping processing), and bending workability, and a method for producing the same. intended to provide A decorative sheet 10 of this embodiment has a base layer 1 made of a colored polypropylene film obtained by mixing an inorganic pigment into a polypropylene resin. In addition, the substrate layer 1 contains a nano-sized nucleating agent, and the nucleating agent is added to the polypropylene resin in the form of nucleating agent vesicles that are encapsulated in the outer film of the monolayer film and formed into vesicles. . Further, the base material layer 1 has a Martens hardness of 50 N/mm 2 or more and 120 N/mm 2 or less. Moreover, the thickness of the base material layer 1 is 50 micrometers or more and 150 micrometers or less. [Selection drawing] Fig. 1

Description

  TECHNICAL FIELD The present invention relates to a decorative sheet used for interior and exterior of buildings, fittings, furniture, construction materials, surface makeup of flooring, and the like, and a method of manufacturing the same.

  In recent years, as shown in Patent Document 1, many decorative sheets (for example, polypropylene sheets) using an olefin resin have been proposed as a decorative sheet that replaces a decorative sheet made of polyvinyl chloride, which has a concern about environmental protection. ing. Since these decorative sheets do not use vinyl chloride resin, generation of toxic gas or the like during incineration is suppressed. However, polypropylene sheets generally have problems that they have poor scratch resistance due to their low elastic modulus, and that they tend to stretch when tension is applied to the sheet during the production of the sheet such as printing.

  By the way, a decorative sheet is attached to the surface of a substrate such as a wooden substrate, a metal substrate, or an incombustible substrate to form a decorative plate, and the decorative sheet gives the decorative plate a design property 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 a hiding property. The simplest makeup sheet can be said to have only a base material layer consisting of a single colored sheet (single layer). In the case of a decorative sheet consisting only of such a base material layer, the design that can be applied is usually limited to a monochromatic color without a pattern, but for example, by adding a glittering material such as aluminum flake or pearl pigment as a pigment Since it is possible to give a feeling, it is possible to express a necessary and sufficient design. Further, when it is desired to impart a higher design, it is effective to decorate the surface of the base material layer by printing or the like.

  On the other hand, as described above, since the colored polypropylene film has a low elastic modulus, when it is used as a single-layer decorative sheet, it is necessary to have scratch resistance and prevent stretching even when tension is applied during processing such as printing. The elongation at the time of applying tension can be improved by increasing the layer thickness of the conventional colored polypropylene film to about 60 μm or more. Regarding the scratch resistance, in the conventional colored polypropylene film, a transparent resin layer made of a polypropylene resin and a urethane thermosetting resin made of a polyol and an isocyanate were used as in Patent Documents 2 and 3. It is possible to improve by providing a top coat layer.

  Further, as in Patent Documents 2 and 3, by optimally selecting the polypropylene resin used for the colored polypropylene film, it is possible to improve scratch resistance and elongation during printing. However, while the elastic modulus is improved by increasing the crystallinity, the breaking stress does not rise in proportion to the elastic modulus, so that the film itself easily breaks and defects such as breakage easily occur during printing. Furthermore, during post-processing as a decorative sheet, especially during bending such as V-cutting, defects such as cracks and whitening at bent portions are likely to occur.

  Further, as described above, the decorative sheet is used as a decorative plate by pasting it on the surface of a substrate such as a wooden substrate. When attaching, the decorative sheet is attached not only to the surface of the wooden substrate or the like but also to the end portion thereof. Since the edges of the wooden substrate are rougher than the surface and there are steps in the bonded portion, the decorative sheet is required to have a uniform surface without following these irregularities.

Japanese Patent No. 3271022 Japanese Patent No. 3861472 Japanese Patent No. 3772634

  Conventionally, for a decorative sheet using a colored polypropylene film alone or a decorative sheet using a colored polypropylene film as a base layer, printability (difficulty in elongation, etc.), scratch resistance, bending workability, and wrapping It is required to achieve both surface uniformity during processing.

In response to the above requirements, it is necessary to thicken the decorative sheet and increase the elastic modulus for printing suitability, scratch resistance, and surface uniformity during lapping, but these all have bending workability. It makes it worse and there is a trade-off relationship.
The present invention has been made by paying attention to the above points, and is a decorative sheet using a single colored polypropylene film that is compatible with printing processability, scratch resistance, surface uniformity during lapping, and bending processability. Another object of the present invention is to provide a decorative sheet having a colored polypropylene film as a base layer, or a method for producing such a decorative sheet.

The present inventors have incorporated a nucleating agent for improving the crystallinity of polypropylene into a vesicle having an outer membrane of a monolayer film to form a vesicle, and add it to a polypropylene resin as a nucleating agent vesicle. Through various studies and experiments conducted on various processes, it was found that a decorative sheet and a method for producing the same can be provided by setting the Martens hardness within the optimum range.
In order to achieve the object, a decorative sheet according to one embodiment of the present invention has a base layer made of a colored polypropylene film obtained by mixing an inorganic pigment with a polypropylene resin, and the base layer contains the inorganic pigment. The polypropylene resin is formed by adding a nucleating agent vesicle containing a nano-sized nucleating agent to a vesicle having a single-layer outer film, and the base layer has a Martens hardness of 50 N / mm. ^{It is 2} or more and 120 N / mm ² or less, and the gist is that the thickness of the base material layer is 50 μm or more and 150 μm or less.

When at least one layer of the transparent resin layer and the top coat layer is laminated on one surface side of the base material layer, the total thickness of the decorative sheet is preferably 100 μm or more and 250 μm or less.
Here, the nucleating agent vesicle has a structure in which the nucleating agent is encapsulated in a capsule-shaped vesicle having an outer membrane of a monolayer film, and can be prepared by, for example, a supercritical reverse phase evaporation method. .. Further, the nucleating agent is a substance which becomes a starting point of crystallization in the crystalline polypropylene resin.

  According to one embodiment of the present invention, a nucleating agent that improves the crystallinity of polypropylene is vesicled and added as a nucleating agent vesicle, and the Martens hardness and the film thickness are optimized, thereby improving the printability (elongation). It is possible to provide a decorative sheet capable of achieving both scratch resistance, scratch resistance, surface uniformity during lapping and bending workability.

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

Embodiments of the present invention will be described below with reference to the drawings.
Here, the drawings are schematic, and the relationship between the thickness and the plane dimension, the thickness ratio of each layer, and the like are different from the actual ones. Further, the embodiments described below exemplify a configuration for embodying the technical idea of the present invention, and the technical idea of the present invention is that the material, shape, structure, etc. of the constituent parts are as follows. Not specific to a thing. The technical idea of the present invention can be variously modified within the technical scope defined by the claims described in the claims.

"Constitution"
The decorative sheet 10 of the embodiment shown in FIG. 1 is an example in the case of a single-layer structure having only the base material layer 1 (raw fabric layer).
The base material layer 1 of this embodiment is composed of a colored polypropylene film. The base material layer 1 formed of a colored polypropylene film contains a polypropylene resin mixed with an inorganic pigment for coloring and also contains a nano-sized nucleating agent. In the present embodiment, the nucleating agent is added to the polypropylene resin in the state of the vesicles, which are the vesicles that are included in the outer membrane and are vesicled.
The substrate layer 1 has a Martens hardness of 50 N / mm ² or more and 120 N / mm ² or less, and the thickness of the substrate layer 1 is 50 μm or more and 150 μm or less.
The polypropylene resin constituting the base material layer 1 is preferably a highly crystalline homopolypropylene resin having an isotactic pentad fraction (mmmm fraction) of 95% or more in an amount of 50% by mass or more and 100% by mass or less. ..

The addition amount of the nucleating agent vesicles is preferably 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 vesicles based on 100 parts by mass of the polypropylene resin. The nucleating agent vesicle is preferably a nucleating agent liposome having an outer membrane made of phospholipid.
If necessary, the design layer 2 may be formed (laminated) on one surface of the base material layer 1 to improve the design.
The decorative sheet 10 may have at least one layer of the transparent resin layer 3 and the top coat layer 4 laminated on one surface side of the base material layer 1. The decorative sheet 10 illustrated in FIG. This is an example in which the pattern layer 2, the transparent resin layer 3, and the top coat layer 4 are laminated in this order on one surface of the decorative sheet 10. One of the transparent resin layer 3 and the top coat layer 4 may be omitted. Further, the pattern layer 2 may be omitted.

  However, when the transparent resin layer 3 and the top coat layer 4 are provided, the decorative sheet 10 of the present embodiment is preferably designed so that the total thickness thereof is 100 μm or more and 250 μm or less. If the total thickness of the decorative sheet 10 is less than 100 μm, the strength of the decorative sheet 10 as a whole becomes insufficient, which may cause a problem in smoothness during lapping. When the total thickness of the decorative sheet 10 is more than 250 μm, the strength of the decorative sheet 10 as a whole is too high, and a defect may occur during bending.

When the transparent resin layer 3 and the top coat layer 4 are provided, for example, the base layer 1: 120 μm, the transparent resin layer 3: 115 μm, and the top coat layer 4:15 μm may be used. Here, of the base material layer 1, the pattern layer 2, the transparent resin layer 3, and the top coat layer 4, the pattern layer 2 has a small layer thickness, so that the thickness of the pattern layer 2 is ignored and the entire decorative sheet 10 is The total thickness may be designed to be 100 μm or more and 250 μm or less.
Here, at least one of the transparent resin layer 3 and the top coat layer 4 may be provided with an uneven shape by embossing depending on the design requirements. Further, from the requirement of scratch resistance and the like, a plurality of layers of at least one of the transparent resin layer 3 and the top coat layer 4 can be laminated, and other known layers may be arranged.

1 and 2, the symbol B represents a substrate. The substrate B is a substrate to which the decorative sheet 10 is attached. The substrate B is not particularly limited, and examples thereof include wood boards, inorganic boards, metal plates, and composite plates made of a plurality of materials. In addition, a primer layer, a masking layer, or the like may be appropriately provided between the decorative sheet 10 and the substrate B.
The range of the tensile elastic modulus of the decorative sheet 10 of the present embodiment, particularly the tensile elastic modulus of the base material layer 1 alone is preferably 700 MPa or more and 2000 MPa or less. If the tensile elastic modulus is less than 700 MPa, it may not be possible to suppress defects during printing, or it may be impossible to maintain the surface smoothness during lapping. When the tensile elastic modulus is more than 2000 MPa, the crystallinity is too high, and even when the nucleating agent vesicle is used, defects such as whitening and cracks may occur during bending. The preferred range of the tensile modulus is 1000 MPa or more and 1800 MPa or less. By setting it in this range, it is possible to achieve both excellent conditions such as defects during printing, scratch resistance, surface smoothness during lapping, and bending.

Next, each layer that constitutes the decorative sheet 10 will be described.
<Base material layer 1>
The base material layer 1 is made of a colored polypropylene film. The colored polypropylene film is mainly made of polypropylene resin and is colored by mixing an inorganic pigment with the polypropylene resin.
Furthermore, a nano-sized nucleating agent is added to the base material layer 1 in order to improve crystallinity. In this embodiment, the nano-sized nucleating agent is added in the form of nucleating agent vesicles.

(Polypropylene resin)
As the polypropylene resin, it is preferable to use a highly crystalline homopolypropylene described later, but the polypropylene resin is not limited to the highly crystalline homopolypropylene. In applications where workability such as bending is more important, for example, a random polypropylene resin having a ethylene content within a predetermined range or a known amorphous polypropylene resin can be mixed with the highly crystalline homopolypropylene. ..
The Martens hardness of the base material layer 1 made of a colored polypropylene film is adjusted to 50 N / mm ² or more and 120 N / mm ² or less.

If the Martens hardness is less than 50 N / mm ² , the surface may not be smooth during lapping, problems during printing may not be suppressed, and it may be difficult to secure the scratch resistance necessary for practical use. Is high. On the other hand, when the Martens hardness is more than 120 N / mm ² , the crystallinity is too high, and even when the nucleating agent vesicle is used, defects such as whitening and cracks may occur during bending.
The suitable range of the Martens hardness of the base material layer 1 is 80 N / mm ² or more and 100 N / mm ² or less. By setting it in this range, it is possible to achieve both excellent in the printing process, surface smoothness in the lapping process, scratch resistance and bending process in excellent condition.

Here, the Martens hardness is a kind of index indicating the hardness (hardness) of a substance, and it is pushed into the surface of the sample by applying a load to the indenter, and the depth of the depression (indentation) formed at that time (indentation) It is 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 defined in ISO14577.
It is important that the thickness of the base material layer 1 made of the colored polypropylene film is 50 μm or more and 150 μm or less.

If the thickness of the base material layer 1 is less than 50 μm, the film strength will be insufficient even if the Martens hardness is in the optimum range, so it is difficult to suppress defects during printing and deterioration of scratch resistance. It is also difficult to maintain the surface smoothness during lapping. On the other hand, if the thickness of the base material layer 1 exceeds 150 μm, there is a high possibility that defects such as whitening and cracking will occur during bending, and the following properties will be extremely high when following the end face of the wood substrate and the laminated portion during lapping. When the adhesive strength becomes poor and the adhesive strength becomes insufficient, a problem such as peeling over time may occur.
A more preferable range of the thickness of the base material layer 1 is 60 μm or more and 120 μm or less. Within this range, problems during printing, surface smoothness during lapping, scratch resistance, and bending can be compatible with sufficient margin.

In the present embodiment, it is preferable to use a polypropylene resin having high crystallinity as the polypropylene resin. Particularly, a highly crystalline homopolypropylene resin, which is a propylene homopolymer having an isotactic pentad fraction (mmmm fraction) of 95% or more, is in a range of 50% by mass or more and 100% by mass or less with respect to the mass of all polypropylene resins. It is preferable to use.
The crystallization temperature of the polypropylene resin is generally in the range of 100 to 130 ° C, and is in the range of 110 to 140 ° C when the nucleating agent is added. In the colored polypropylene film in the decorative sheet 10 of the present embodiment, the Martens hardness of 50 N / mm is obtained by controlling the cooling time from the crystallization temperature to the curing completion temperature within this range by a known cooling process. It is adjusted to ² or more 120 N / mm ² or less. Further, when a polypropylene resin having an isotactic pentad fraction (mmmm fraction) of less than 95% is used, the crystallinity is insufficient, so that even if the cooling process is controlled, the Martens hardness becomes lower than the preferable range. It may happen. Similarly, when the high crystalline homopolypropylene resin is less than 50% by mass, the crystallinity is also insufficient, and therefore the Martens hardness may be lower than the preferable range even if the cooling process is controlled.

  Here, the isotactic pentad fraction (mmmm fraction) means a resin material having a predetermined resonance frequency by a 13 C-NMR measurement method (nuclear magnetic resonance measurement method) using carbon C (nuclide) having a mass of 13. It is calculated from the numerical value (electromagnetic wave absorption rate) obtained by resonating at 1, and defines the atomic arrangement, electronic structure, and molecular fine structure in the resin material. The pentad fraction of the crystalline polypropylene resin is the ratio of five propylene units arranged by 13C-NMR, and is used as a measure of crystallinity or stereoregularity. The pentad fraction is one of the important factors that mainly determines 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 represented by titanium oxide for imparting hiding power can be used. Examples of inorganic pigments for coloring include complex oxides of iron-zinc, chromium-antimony, iron-aluminum and the like, iron oxides, etc., but these are those whose formulation is freely adjusted according to the desired color. is there. Further, as the inorganic pigment, a glittering material such as aluminum flake or pearl pigment may be added. Further, for example, an organic pigment such as carbon black may be used together.
Further, additives such as fatty acid metal salts may be added to improve dispersibility and extrusion suitability.

(Nucleating agent vesicle)
Moreover, the base material layer 1 contains a nano-sized nucleating agent. The nano-sized nucleating agent is used by being added to the polypropylene resin in the form of a nucleating agent vesicle, which is encapsulated in a vesicle having a single-layer outer membrane. Since the base material layer 1 contains the nucleating agent, the crystallinity can be improved, and the scratch resistance (scratch resistance) of the base material layer 1 can be improved. In the present embodiment, the nucleating agent in the resin forming the base material layer 1 may be encapsulated in the vesicle with a part of the nucleating agent exposed.
The average particle size of the nano-sized nucleating agent is preferably ½ or less of the visible light wavelength region. Specifically, since the visible light wavelength region is 400 nm or more and 750 nm or less, the average particle size is Is preferably 375 nm or less.

  Since the particle size of the nano-sized nucleating agent 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 the nucleating agent particles is close, when crystal growth occurs from the surface of the one nucleating agent particles added to the polypropylene resin, the end where the crystal is growing immediately, One of the nucleating agent particles is in contact with the end of the crystal growing from the surface of the other nucleating agent particles, because the end of each crystal inhibits the growth and the growth of each crystal stops, The average grain size of the spherulites in the crystal part of the crystalline polypropylene resin can be reduced, for example, the spherulite size can be reduced to 1 μm or less. As a result, it is possible to obtain a highly-hardened colored polypropylene film with high crystallinity, and since stress concentration between spherulites generated during bending is efficiently dispersed, 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 becomes large due to the secondary aggregation of the nucleating agent in the polypropylene resin, and the number of crystal nuclei is larger than the amount of the nucleating agent added. It may be significantly less than when added as an agent vesicle. Therefore, the average grain size of the spherulites in the crystal part of the polypropylene resin becomes large, and cracks and whitening during bending may not be suppressed. Therefore, the improvement of the elastic modulus by increasing the crystallinity and the workability may not be compatible.
The base material layer 1 made of a colored polypropylene film that constitutes the decorative sheet 10 of the present embodiment is 0.05 parts by mass or more in terms of the amount of the nucleating agent added with respect to 100 parts by mass of the polypropylene resin as the main component. It is preferable to add 0.5 part by mass or less, preferably 0.1 part by mass or more and 0.3 part by mass or less of the nucleating agent vesicle. When the addition amount of the nucleating agent vesicle is less than 0.05 parts by mass, the crystallinity may not be sufficiently improved and the required elastic modulus (hardness) may not be reached. On the other hand, when the amount added exceeds 0.5 parts by mass, spherulite growth is adversely affected due to excessive crystal nuclei, and as a result, the crystallinity is not sufficiently improved and the required elastic modulus (hardness) is obtained. It may not reach.

  Further, as a method for nanonizing the nucleating agent, for example, a solid phase method for obtaining nano-sized particles mainly by mechanically pulverizing the nucleating agent, dissolving the nucleating agent or the nucleating agent Methods such as liquid phase method for synthesizing and crystallization of nano-sized particles in a solution, gas phase method for synthesizing and crystallization of nano-sized particles from gas / vapor composed of nucleating agent and nucleating agent It can be used as appropriate. Examples of the solid phase method include a ball mill, a bead mill, a rod mill, a colloid mill, a conical mill, a disc mill, a hammer mill, and a jet mill. 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. Furthermore, examples of the vapor phase method include an electric furnace method, a chemical flame method, a laser method, and a thermal plasma method.

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

In addition, as a specific nano-izing treatment by the supercritical reverse phase evaporation method, first, an 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 inclusion substance. Then, by stirring, an emulsion of supercritical carbon dioxide and an aqueous phase is produced. Next, by reducing the pressure, carbon dioxide expands and evaporates to cause phase inversion, and the 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 multi-layered film on the surface of the nucleating agent particles, a single-layer film capsule can be easily produced. Capsules with a small diameter can be prepared.
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, 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 single layer membrane. The outer membrane is composed of a substance containing a biological lipid such as phospholipid.
In the present specification, a nucleating agent vesicle whose outer membrane is composed of a substance containing a biological lipid such as a phospholipid is referred to as a nucleating agent liposome.
Examples of the phospholipids constituting the outer membrane include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, yolk lecithin, hydrogenated yolk lecithin, soybean lecithin, and hydrogenated soybean lecithin. And sphingophospholipids such as glycerophospholipids, sphingomyelin, ceramide phosphoryl ethanolamine, and ceramide phosphoryl glycerol.

  Examples of the other substance that forms the outer membrane of the vesicle include a nonionic surfactant and a dispersant such as a mixture of the nonionic surfactant and cholesterol or triacylglycerol. Among these, nonionic surfactants include, for example, 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-poly2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. Alternatively, two or more kinds can be used. Examples of cholesterols that can be used include cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholate, cholecalciferol and the like.

The outer membrane of the liposome may also be formed from a mixture of phospholipid and dispersant. In the decorative sheet 10 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 made of phospholipid so that the base layer 1 The compatibility between the resin material, which is the main component of the vesicle, and the vesicle can be improved.
The nucleating agent is not particularly limited as long as it is a substance which becomes a starting point of crystallization when the resin is crystallized. Examples of the nucleating agent include phosphoric acid ester metal salts, benzoic acid metal salts, pimelic acid metal salts, rosin metal salts, benzylidene sorbitol, quinacridone, cyanine blue and talc. In particular, it is preferable to use a non-melting type phosphoric acid ester metal salt, which can be expected to have good transparency, a metal salt of benzoic acid, a metal salt of pimelic acid, and a metal salt of rosin, in order to maximize the effect of nano-treatment. When the material itself can be made transparent by the nano-treatment, colored quinacridone, cyanine blue, talc, etc. can also be used. Further, a melt type benzylidene sorbitol may be appropriately mixed and used with a non-melt type nucleating agent.

As described above, one of the features (invention specifying matter) of the decorative sheet 10 of the present embodiment is that "the base material layer 1 contains a nucleating agent encapsulated in vesicles". Then, by adding the nucleating agent to the resin composition in the state of being encapsulated in the vesicle, there is an effect that the dispersibility of the nucleating agent in the resin material, that is, the base material layer 1 is dramatically improved. However, it may be difficult to specify the characteristics directly by the structure or characteristics of the object in the state of the completed decorative sheet 10, and it can be said that it is impractical in some cases. The reason is as follows. The nucleating agent added in the state of vesicles is in a dispersed state with high dispersibility, and even in the state of the manufactured decorative sheet 10, the nucleating agent is highly dispersed in the base material layer 1. ing. However, in the manufacturing process of the decorative sheet 10 after the nucleating agent is added to the resin composition constituting the base material layer 1 in the form of vesicles to produce the base material layer 1, compression into a laminate is usually performed. Various treatments such as treatment and curing treatment are performed, but by such treatment, the outer membrane of the vesicles encapsulating the nucleating agent is crushed or chemically reacted, and the nucleating agent is included in the outer membrane (foreskin). This is because there is a high possibility that the outer membrane is not crushed or chemically reacted, depending on the treatment process of the decorative sheet 10. And, in the situation that this nucleating agent is not included in the outer membrane, it is difficult to specify the physical properties themselves within the numerical range, and whether the crushed outer membrane constituent material is the outer membrane of the vesicles. It may be difficult to determine whether the material is added separately from the nucleating agent. As described above, the present invention is different from the conventional one in that the nucleating agent is mixed in the base layer 1 in a highly dispersed state, but is added in the state of vesicles containing the nucleating agent. It may be impractical to specify the structure and characteristics of the decorative sheet 10 in the range of numerical values analyzed based on the measurement in the state of the decorative sheet 10.
Here, the nucleating agent vesicle having the above structure may be contained in the transparent resin layer 3 and the top coat layer 4.

(Pattern layer 2)
A pattern layer 2 for adding a pattern to the decorative sheet 10 can be provided on the surface of the colored polypropylene film (base material layer 1). As the pattern pattern, for example, a wood grain pattern, a stone grain pattern, a grain pattern, a tile pasting pattern, a brick pattern, a fabric pattern, a leather pattern, a geometrical pattern and the like can be used.
Further, a base solid ink layer (not shown) may be provided between the base material layer 1 and the pattern layer 2 depending on the intended degree of design. The base solid ink layer is provided so as to cover the entire surface of the base material layer 1. Further, the solid undercoat ink layer may have a multi-layer structure of two or more layers according to need such as hiding property. Furthermore, the pattern layer 2 may be formed by laminating as many color plates as necessary to express the desired design. As described above, the pattern layer 2 and the solid undercoat ink layer are various combinations depending on the desired design, that is, the design desired to be expressed, but are not particularly limited.

  The constituent materials of the underlying solid ink layer and the pattern layer 2 are not particularly limited. For example, a printing ink or coating agent obtained by dissolving and dispersing a matrix and a coloring agent such as a dye or a pigment in a solvent can be used. Examples of the matrix include oily nitrified cotton resin, two-component urethane resin, acrylic resin, styrene resin, polyester resin, urethane resin, polyvinyl resin, alkyd resin, epoxy resin, melamine resin, and fluorine. It is possible to use various synthetic resins such as resin, silicone resin, rubber resin, or a mixture or copolymer thereof. As the colorant, for example, inorganic pigments such as carbon black, titanium white, zinc white, petals, yellow lead, navy blue, cadmium red, azo pigments, lake pigments, anthraquinone pigments, phthalocyanine pigments, isoindolinone pigments, etc. , An organic pigment such as a dioxazine pigment, or a mixture thereof can be used. As the solvent, for example, toluene, xylene, ethyl acetate, butyl acetate, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, water, or the like, or a mixture thereof or the like can be used. .

In order to impart various functions to the solid undercoat ink layer and the pattern layer 2, for example, an extender pigment, a plasticizer, a dispersant, a surfactant, a tackifier, an adhesion aid, a drying agent, a curing agent, and a curing agent. You may add functional additives, such as an accelerator and a hardening retarder.
Here, the underlying solid ink layer and the pattern layer 2 can be formed by various printing methods such as a gravure printing method, an offset printing method, a screen printing method, an electrostatic printing method, and an inkjet printing method. Further, since the base solid ink layer covers the entire surface of the base material layer 1, it can be formed by various coating methods such as a roll coating method, a knife coating method, a microgravure coating method and a die coating method. These printing methods and coating methods may be selected separately depending on the layer to be formed, but it is efficient to select the same method and perform batch processing.

(Transparent resin layer 3)
The resin material used as the main component of the transparent resin layer 3 is preferably made of an olefin resin, and in addition to polypropylene, polyethylene, polybutene, etc., α-olefins (eg, propylene, 1-butene, 1-pentene, 1 -Hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1 -Nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4 -Dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, etc.) Polymerization or copolymerization of two or more kinds, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / butyl methacrylate copolymer Polymers, ethylene / methyl acrylate copolymers, ethylene / ethyl acrylate copolymers, ethylene / butyl acrylate copolymers, and the like, which are obtained by copolymerizing ethylene or α-olefin with other monomers can be mentioned. .. In addition, in order to improve the surface strength of the decorative sheet 10, it is preferable to use a highly crystalline polypropylene resin as in the base material layer 1.

Here, in this specification, the main component refers to 90% by mass or more of the target material, unless otherwise specified.
When the transparent resin layer 3 is provided, the layer thickness of the transparent resin layer 3 is preferably 50 μm or more and 100 μm or less. When it is less than 50 μm, the effect of improving the scratch resistance of the surface of the transparent resin layer 3 is low, and the significance of providing the transparent resin layer 3 may be reduced. If it exceeds 100 μm, defects such as whitening and cracking during bending may occur.
However, when the top coat layer 4 is provided on the transparent resin layer 3, the layer thickness of the transparent resin layer 3 may be less than 50 μm.
The resin composition forming the transparent resin layer 3 may have various functions such as a heat stabilizer, a light stabilizer, an antiblocking agent, a catalyst scavenger, a colorant, a light scattering agent and a luster modifier, if necessary. A sex additive may be included. These various functional additives can be appropriately selected and used from known ones.

(Top coat layer 4)
When it is necessary to further improve scratch resistance and adjust gloss, the top coat layer 4 can be provided on the surface of the transparent resin layer 3.
The resin material as the main component of the top coat layer 4 is appropriately selected from polyurethane-based, acrylic silicon-based, fluorine-based, epoxy-based, vinyl-based, polyester-based, melamine-based, aminoalkyd-based and urea-based resin materials, for example. Can be used. The form of the resin material is not particularly limited, such as aqueous, emulsion, solvent-based. As for the curing method, one-component type, two-component type, ultraviolet curing method or the like can be appropriately selected and performed.

  As the resin material used as the main component of the top coat layer 4, a urethane-based material using isocyanate is preferable from the viewpoints of workability, cost, cohesive force of the resin itself, and the like. Examples of the isocyanate include tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), bis (isocyanate methyl). It can be appropriately selected and used from hardening agents such as adducts, burettes, and isocyanurates, which are derivatives such as cyclohexane (HXDI) and trimethylhexamethylene diisocyanate (TMDI), but in consideration of weather resistance, it is linear. Curing agents based on hexamethylene diisocyanate (HMDI) or isophorone diisocyanate (IPDI) having the molecular structure of are suitable. In addition to this, in order to improve the surface hardness, it is preferable to use a resin that is cured by active energy rays such as ultraviolet rays and electron rays. Note that these resins can be used in combination with each other. For example, by using a hybrid type of thermosetting type and photocuring type, it is possible to improve surface hardness, suppress curing shrinkage, and improve adhesion. Can be planned.

  A gloss adjusting agent can be added to the top coat layer 4 for adjusting the gloss. As the gloss adjuster, a known commercially available product may be used. For example, fine particles made of an inorganic material such as silica, glass, alumina, calcium carbonate, barium sulfate may be used. Alternatively, fine particles made of an organic material such as acrylic can be used. However, when high transparency is required, it is desirable to use fine particles of highly transparent silica, glass, acrylic, or the like. In particular, among fine particles such as silica and glass, a luster modifier having a low bulk density formed by secondary agglomeration of fine primary particles, rather than solid true spherical particles, has a high matte effect with respect to the added amount. Therefore, by using such a gloss adjusting agent, the amount of the gloss adjusting agent added can be reduced.

Further, in order to impart various functions to the top coat layer 4, functional additives such as an antibacterial agent and an antifungal agent may be added. Moreover, you may add a ultraviolet absorber and a light stabilizer as needed. As the ultraviolet absorber, for example, a benzotriazole type, a benzoate type, a benzophenone type, a triazine type, or a cyanoacrylate type can be used. Further, as the light stabilizer, a hindered amine type can be used.
The layer thickness of the top coat layer 4 is preferably 3 μm or more and 15 μm or less. If the thickness is less than 3 μm, the effect of improving scratch resistance is low, and the significance of providing the topcoat layer 4 may be diminished. If it exceeds 15 μm, cracks or cracks may occur during bending, which may cause problems in design and weather resistance.

<Manufacturing method>
A manufacturing example of the decorative sheet 10 will be described.
Nucleating agent vesicles are prepared by encapsulating the nucleating agent in vesicles to form vesicles, and the prepared nucleating agent vesicles are added to a polypropylene resin together with an inorganic pigment to form a resin material for the base layer. To make.
The nucleating agent vesicle is produced by, for example, encapsulating the nucleating agent in a vesicle having a monolayer film by a supercritical reverse phase evaporation method to form a vesicle.
The polypropylene resin used is preferably a highly crystalline homopolypropylene resin having an isotactic pentad fraction (mmmm fraction) of 95% or more in 50% by mass or more and 100% by mass or less.

The resin material for the base material layer is heated and melted, and is extruded to form a base material layer 1 having a thickness of 50 μm or more and 150 μm or less.
At this time, the Martens hardness of the base material layer 1 is controlled to 50 N / mm ² or more and 120 N / mm ² or less by adjusting the cooling time from the crystallization temperature to the curing completion temperature by a known adjustment method.
Further, if necessary, the pattern layer 2 is formed on the upper surface of the base material layer 1 by printing, and at least one of the transparent resin layer 3 and the top coat layer 4 is formed on it by printing.
At this time, the thickness of the transparent resin layer 3 may be 50 μm or more and 100 μm or less, the thickness of the top coat layer 4 may be 3 μm or more and 15 μm or less, and the total thickness of the decorative sheet 10 may be 100 μm or more and 250 μm or less. preferable.

<Action and others>
(1) The decorative sheet 10 of the present embodiment has a base material layer 1 formed of a colored polypropylene film obtained by mixing an inorganic pigment with a polypropylene resin, and the base material layer 1 contains a nano-sized nucleating agent, The nucleating agent is added in the form of a vesicle-containing nucleating agent vesicle that is contained in an outer membrane, and the substrate layer 1 has a Martens hardness of 50 N / mm ² or more and 120 N / mm ² or less, The thickness of the layer 1 is 50 μm or more and 150 μm or less.
According to this configuration, a nucleating agent that improves the crystallinity of polypropylene is vesicled and added as a nucleating agent vesicle, and further, the Martens hardness and the film thickness are optimized to improve the printability (difficulty in elongation). Etc.), it is possible to provide a decorative sheet 10 that can achieve both surface smoothness during lapping, scratch resistance and bending workability.

(2) In the decorative sheet 10 of the present embodiment, 50% by mass or more and 100% by mass or less of the polypropylene resin constituting the base material layer 1 has a high isotactic pentad fraction (mmmm fraction) of 95% or more. It is preferably composed of a crystalline homopolypropylene resin.
According to this configuration, the Martens hardness can be more reliably adjusted to 50 N / mm ² or more and 120 N / mm ² or less.
(3) In the decorative sheet 10 of the present embodiment, the addition amount of the nucleating agent vesicles to the base material layer 1 is 0.10 in terms of the nucleating agent in the nucleating agent vesicles based on 100 parts by mass of the polypropylene resin. It is preferably from 05 parts by mass to 0.5 parts by mass.
According to this structure, the crystallinity of the colored polypropylene forming the base material layer 1 is sufficiently improved, and the required elastic modulus (hardness) can be reliably ensured.

(4) In the decorative sheet 10 of the present embodiment, the nucleating agent vesicle is preferably a nucleating agent liposome provided with an outer membrane made of phospholipid.
According to this configuration, the compatibility between the resin material, which is the main component of the base material layer 1, and the vesicle can be improved.
(5) In the decorative sheet 10 of the present embodiment, the pattern layer 2 is preferably laminated on one surface of the base material layer 1.
With this configuration, the design of the decorative sheet 10 can be improved.
(6) In the decorative sheet 10 of the present embodiment, at least one layer of the transparent resin layer 3 and the top coat layer 4 is laminated on one surface side of the base material layer 1, and the total thickness of the decorative sheet 10 is 100 μm or more. It is preferably 250 μm or less.
According to this configuration, during lapping, the ability to follow the end face and the laminated portion of the wooden substrate is significantly deteriorated, and the adhesive strength becomes insufficient, so that it is possible to suppress the occurrence of defects such as peeling over time. ..

[Example]
Hereinafter, specific examples of the decorative sheet 10 of this embodiment will be described.
(Method for producing nucleating agent vesicles)
First, a method for producing the nucleating agent liposome used in this example will be described.
The nucleating agent liposome is 100 parts by mass of methanol and 70 parts by mass of a phosphoric acid ester metal salt-based nucleating agent as a nucleating agent (ADEKA STAB NA-21; manufactured by ADEKA) using the above-mentioned supercritical reverse phase evaporation method. , 5 parts by mass of phosphatidylcholine as a phospholipid constituting the outer membrane of vesicles was placed in a high-pressure stainless steel container kept at 60 ° C. and sealed, and carbon dioxide was injected into the container so that the pressure became 20 MPa, and super Set to a critical state. Then, the inside of the container is vigorously stirred and 100 parts by mass of ion-exchanged water is injected. After stirring and mixing for 15 minutes while maintaining the temperature and pressure in the supercritical state, the nucleating agent was added to the vesicles having a monolayer outer membrane made of phospholipid by discharging carbon dioxide from the container and returning to atmospheric pressure. The nucleating agent vesicles to be encapsulated were obtained.

(Example 1)
A highly crystalline homopolypropylene resin having a pentad fraction of 97.8%, a melt flow rate (MFR) of 15 g / 10 min (230 ° C.), and a molecular weight distribution MWD (Mw / Mn) of 2.3 as a raw material for a colored polypropylene film. To 78 parts by mass, 6 parts by mass of titanium oxide pigment as an inorganic pigment, 16 parts by mass of chromium-antimony complex oxide pigment, and 0.05% by mass of the above-mentioned nucleating agent vesicle as a nucleating agent were added. Then, extrusion molding was performed using a melt extruder to form a base material layer 1 made of a colored polypropylene film having a thickness of 50 μm.
(Example 2)
Except that the above-mentioned nucleating agent vesicle was added as a nucleating agent so as to be 0.5 parts by mass, extrusion molding was performed using a melt extruder to form a base material layer 1 having a thickness of 50 μm. The film was formed.

(Example 3)
As a raw material for a colored polypropylene film, a highly crystalline homopolypropylene resin having a pentad fraction of 97.8%, a melt flow rate (MFR) of 15 g / 10 min (230 ° C.) and a molecular weight distribution MWD (Mw / Mn) of 2.3. 39 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, 39 parts by mass of a titanium oxide pigment as an inorganic pigment, and a chromium-antimony composite oxide. Pigment 16 parts by mass, the above-mentioned nucleating agent vesicles as a nucleating agent are added so as to be 0.05 parts by mass, and the mixture is extrusion-molded by using a melt extruder and is a substrate made of a colored polypropylene film having a thickness of 50 μm. Layer 1 was deposited.

(Example 4)
As in Example 3, except that the above-mentioned nucleating agent vesicle was added as a nucleating agent in an amount of 0.5 parts by mass, the base material layer 1 having a thickness of 50 μm was extrusion-molded using a melt extruder. The film was formed.
(Example 5)
Except that the above-mentioned nucleating agent vesicle was added as a nucleating agent so that the amount was 0.1 part by mass, extrusion molding was performed using a melt extruder to form a substrate layer 1 having a thickness of 100 μm. The film was formed.
(Example 6)
As in Example 1, extrusion molding was performed using a melt extruder to form a substrate layer 1 having a thickness of 150 μm.
(Example 7)
In the same manner as in Example 2, extrusion molding was performed using a melt extruder to form a base material layer 1 having a thickness of 150 μm.
(Example 8)
In the same manner as in Example 3, extrusion molding was performed using a melt extruder to form a base material layer 1 having a thickness of 150 μm.
(Example 9)
In the same manner as in Example 4, the base material layer 1 having a thickness of 150 μm was formed by extrusion molding using a melt extruder.

(Example 10)
Corona treatment was applied to both surfaces of the base material layer 1 having a thickness of 50 μm, which was prepared in the same manner as in Example 1, and one of the surfaces was treated with a two-component curable urethane ink (V180; manufactured by Toyo Ink Mfg. Co., Ltd.) Pattern printing was performed to form a pattern layer 2. Further, a two-component curing type urethane top coat (W184; manufactured by DIC Graphics, coating amount 10 g / m2) was applied to the surface of the pattern layer 2 to form the top coat layer 4 to obtain a decorative sheet 10. ..

(Example 11)
The topcoat layer 4 was formed in the same manner as in Example 10 on the base material layer 1 having a thickness of 50 μm, which was created in the same manner as in Example 2, to obtain a decorative sheet 10.
(Example 12)
The topcoat layer 4 was formed in the same manner as in Example 10 on the base material layer 1 having a thickness of 50 μm, which was created in the same manner as in Example 3, to obtain a decorative sheet 10.
(Example 13)
The top coat layer 4 was formed in the same manner as in Example 10 on the base material layer 1 having a thickness of 50 μm, which was created in the same manner as in Example 4, to obtain a decorative sheet 10.
(Example 14)
The top coat layer 4 was formed in the same manner as in Example 10 on the substrate layer 1 having a thickness of 100 μm, which was created in the same manner as in Example 5, to obtain a decorative sheet 10.

(Example 15)
The topcoat layer 4 was formed in the same manner as in Example 10 on the base material layer 1 having a thickness of 150 μm, which was created in the same manner as in Example 6, to obtain a decorative sheet 10.
(Example 16)
The top coat layer 4 was formed in the same manner as in Example 10 on the base material layer 1 having a thickness of 150 μm, which was created in the same manner as in Example 7, to obtain a decorative sheet 10.
(Example 17)
The topcoat layer 4 was formed in the same manner as in Example 10 on the base material layer 1 having a thickness of 150 μm, which was created in the same manner as in Example 8, to obtain a decorative sheet 10.
(Example 18)
The topcoat layer 4 was formed in the same manner as in Example 10 on the base material layer 1 having a thickness of 150 μm, which was created in the same manner as in Example 9, to obtain a decorative sheet 10.

(Example 19)
Corrosion treatment was applied to one surface of the base material layer 1 having a thickness of 50 μm, which was prepared in the same manner as in Example 1, so that the wetting tension of the surface was 40 dyn / cm or more. Subsequently, a highly crystalline homopolypropylene resin having a pentad fraction of 97.8%, a melt flow rate (MFR) of 15 g / 10 min (230 ° C.) and a molecular weight distribution MWD (Mw / Mn) of 2.3 was melt-extruded. A transparent resin layer 3 having a thickness of 90 μm was formed by extrusion molding using a machine, and corona treatment was applied to both surfaces of the transparent resin layer 3 to obtain a surface wetting tension of 40 dyn / cm or more.
Subsequently, a pattern was printed on the corona-treated surface of the substrate layer 1 with a two-component curing type urethane ink (V180; manufactured by Toyo Ink Mfg. Co., Ltd.) to form a pattern layer 2. Further, the transparent resin layer 3 was attached to the surface of the pattern layer 2 by a dry laminating method via an adhesive layer made of an adhesive for dry lamination (Takelac A540; manufactured by Mitsui Chemicals, Inc., coating amount 2 g / m ² ). I matched it. Next, after forming an embossed pattern on the surface of the transparent resin layer 3 using a die roll for embossing, a two-component curing type urethane top coat (W184; manufactured by DIC Graphics Corporation) so as to cover the embossed pattern. The coating amount of 10 g / m ² ) was applied to form the top coat layer 4 to obtain a decorative sheet 10.

(Example 20)
The transparent resin layer 3 and the top coat layer 4 were formed in the same manner as in Example 19 on the base material layer 1 having a thickness of 50 μm, which was created in the same manner as in Example 2, to obtain a decorative sheet 10.
(Example 21)
The transparent resin layer 3 and the top coat layer 4 were formed in the same manner as in Example 19 on the base material layer 1 having a thickness of 50 μm prepared in the same manner as in Example 3 to obtain a decorative sheet 10.
(Example 22)
The transparent resin layer 3 and the top coat layer 4 were formed in the same manner as in Example 19 on the base material layer 1 having a thickness of 50 μm prepared in the same manner as in Example 4 to obtain a decorative sheet 10.
(Example 23)
The transparent resin layer 3 and the top coat layer 4 were formed in the same manner as in Example 19 on the base material layer 1 having a thickness of 100 μm prepared in the same manner as in Example 5 to obtain a decorative sheet 10.

(Example 24)
The transparent resin layer 3 and the top coat layer 4 were formed in the same manner as in Example 19 on the base material layer 1 having a thickness of 150 μm prepared in the same manner as in Example 6 to obtain a decorative sheet 10.
(Example 25)
The transparent resin layer 3 and the top coat layer 4 were formed in the same manner as in Example 19 on the base material layer 1 having a thickness of 150 μm prepared in the same manner as in Example 7 to obtain a decorative sheet 10.
(Example 26)
The transparent resin layer 3 and the top coat layer 4 were formed in the same manner as in Example 19 on the base material layer 1 having a thickness of 150 μm, which was created in the same manner as in Example 8, to obtain a decorative sheet 10.
(Example 27)
The transparent resin layer 3 and the top coat layer 4 were formed in the same manner as in Example 19 on the base material layer 1 having a thickness of 150 μm, which was created in the same manner as in Example 9, to obtain a decorative sheet 10.

(Example 28)
As a raw material for a colored polypropylene film, a highly crystalline homopolypropylene resin having a pentad fraction of 97.8%, a melt flow rate (MFR) of 15 g / 10 min (230 ° C.) and a molecular weight distribution MWD (Mw / Mn) of 2.3. 46.8 parts of a random polypropylene resin having a melt flow rate (MFR) of 12 g / 10 min (230 ° C.) in which 4% of an ethylene component is blended with 31.2 parts by mass, 6 parts by mass of a titanium oxide pigment as an inorganic pigment, and chrome- 16 parts by mass of antimony complex oxide pigment and 1.0 part by mass of the above-mentioned nucleating agent vesicle as a nucleating agent are added and extrusion-molded using a melt extruder to obtain a colored polypropylene film having a thickness of 50 μm. The base material layer 1 consisting of was formed into a film.

(Example 29)
A highly crystalline homopolypropylene resin having a pentad fraction of 97.8%, a melt flow rate (MFR) of 15 g / 10 min (230 ° C.), and a molecular weight distribution MWD (Mw / Mn) of 2.3 as a raw material for a colored polypropylene film. To 78 parts by mass, 6 parts by mass of a titanium oxide pigment as an inorganic pigment, 16 parts by mass of a chromium-antimony complex oxide pigment, and 1.0 part by mass of the above nucleating agent vesicle as a nucleating agent were added. Then, extrusion molding was performed using a melt extruder to form a base material layer 1 made of a colored polypropylene film having a thickness of 50 μm.

(Comparative Example 1)
Except for using an untreated nucleating agent instead of the above-described nucleating agent vesicle, extrusion molding was performed using a melt extruder to form a base material layer 1 having a thickness of 50 μm. ..
(Comparative example 2)
Except for using an untreated nucleating agent instead of the above-described nucleating agent vesicle, extrusion molding was performed using a melt extruder to form a base material layer 1 having a thickness of 50 μm. ..
(Comparative example 3)
Except for using an untreated nucleating agent instead of the above-described nucleating agent vesicle, extrusion molding was performed using a melt extruder to form a base material layer 1 having a thickness of 50 μm in the same manner as in Example 3. ..
(Comparative example 4)
Except for using an untreated nucleating agent instead of the above-described nucleating agent vesicle, extrusion molding was performed using a melt extruder to form a base material layer 1 having a thickness of 50 μm in the same manner as in Example 4. ..

(Comparative example 5)
Except for using an untreated nucleating agent instead of the above-mentioned nucleating agent vesicle, extrusion molding was performed using a melt extruder to form a base material layer 1 having a thickness of 150 μm. ..
(Comparative example 6)
Except for using the untreated nucleating agent instead of the above-described nucleating agent vesicle, extrusion molding was performed using a melt extruder to form a substrate layer 1 having a thickness of 150 μm in the same manner as in Example 7. ..
(Comparative Example 7)
Except for using an untreated nucleating agent instead of the above-mentioned nucleating agent vesicle, extrusion molding was performed using a melt extruder to form a base material layer 1 having a thickness of 150 μm. ..
(Comparative Example 8)
Except for using an untreated nucleating agent instead of the above-described nucleating agent vesicle, extrusion molding was performed using a melt extruder to form a substrate layer 1 having a thickness of 150 μm in the same manner as in Example 9. ..

(Comparative Example 9)
In the same manner as in Comparative Example 2, extrusion molding was performed using a melt extruder to form a base material layer 1 having a thickness of 180 μm. Then, the transparent resin layer 3 and the top coat layer 4 were formed in the same manner as in Example 19 to obtain a decorative sheet 10.
(Comparative Example 10)
In the same manner as in Example 2, extrusion molding was performed using a melt extruder to form a substrate layer 1 having a thickness of 180 μm. Then, the transparent resin layer 3 and the top coat layer 4 were formed in the same manner as in Example 19 to obtain a decorative sheet 10.
(Comparative Example 11)
In the same manner as in Example 2, extrusion molding was performed using a melt extruder to form a base material layer 1 having a thickness of 40 μm.

(Comparative Example 12)
A highly crystalline homopolypropylene resin having a pentad fraction of 97.8%, a melt flow rate (MFR) of 15 g / 10 min (230 ° C.), and a molecular weight distribution MWD (Mw / Mn) of 2.3 as a raw material for a colored polypropylene film. 46.8 parts of a random polypropylene resin having a melt flow rate (MFR) of 12 g / 10 min (230 ° C.) in which 4% of an ethylene component is blended with 31.2 parts by mass, 6 parts by mass of a titanium oxide pigment as an inorganic pigment, and chrome- 16 parts by mass of antimony complex oxide pigment, 0.5 part by mass of the above-mentioned nucleating agent vesicle as a nucleating agent, and extrusion-molded using a melt extruder to obtain a colored polypropylene film having a thickness of 50 μm. The base material layer 1 consisting of was formed into a film.

(Comparative Example 13)
As a raw material for a colored polypropylene film, a highly crystalline homopolypropylene resin having a pentad fraction of 97.8%, a melt flow rate (MFR) of 15 g / 10 min (230 ° C.) and a molecular weight distribution MWD (Mw / Mn) of 2.3. 39 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, 39 parts by mass of a titanium oxide pigment as an inorganic pigment, and a chromium-antimony composite oxide. 16 parts by mass of pigment and 1.0 part by mass of the above-mentioned nucleating agent vesicle as a nucleating agent are added and extrusion-molded by using a melt extruder to form a substrate made of a colored polypropylene film having a thickness of 50 μm. Layer 1 was deposited.

(Evaluation)
Regarding Examples 1 to 29 and Comparative Examples 1 to 13 described above, the measurement of Martens hardness, the measurement of tensile modulus, the defect during printing (suitability for printing), scratch resistance, and the smoothness during lapping (lapping) The surface uniformity at the time) and the bending suitability were evaluated.
<Martens hardness>
The measurement was performed using a Martens hardness measuring device (Fisherscope HM2000; Fischer Instruments Co., Ltd.) according to ISO14577. The sample was taken from the cross section of the decorative sheet 10 in order to avoid the influence of the laminated resin layers other than the base material layer 1 during measurement. Specifically, the decorative sheet 10 is embedded in a resin such as a cold-curing type epoxy resin or a UV curable resin and sufficiently cured, and then cut so that the cross section of the decorative sheet 10 appears and mechanical polishing is performed. The measurement surface was obtained by applying. As a specific measuring method, the indenter is pushed into the base material layer 1 on the measurement surface of each sample, and the Martens hardness is calculated from the pushing depth and the load. The measurement conditions were 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.

<Tensile modulus>
For the measurement of the tensile elastic modulus, an autograph (AGS-500NX) manufactured by Shimadzu Corporation was used, and a tensile test was performed at a tensile speed of 50 mm / min to calculate the tensile elastic modulus.
<Problems during printing (printing suitability)>
The pattern layer 2 was formed by gravure printing using a gravure printing machine, and at this time, the base layer 1 was stretched by tension and misregistration when laminating each color was evaluated as a print defect.
When there is no need for register adjustment, it is "◎", when it can be easily adjusted by automatic register adjustment, it is "○", when attention is required for register adjustment, it is "△", register adjustment is impossible and printing cannot be continued. The case was designated as "x". Also, when the film being printed breaks frequently and there is a problem in mass productivity, it is also marked as “x”. If the evaluation is “Δ” or more, there is no problem in printing.

<Scratch resistance>
The scratch resistance was evaluated by conducting a pencil hardness test. In the pencil hardness test, a pencil of 3B was used, the angle of the pencil was fixed to 45 ± 1 ° with respect to the decorative sheet 10, and the surface of the decorative sheet 10 was slid while a load of 750 kg was applied to the pencil. The state was observed (based on the old JIS standard JISK5400). The test was conducted 5 times, and scratches and marks on the pencil were evaluated.
When there are no scratches or traces visible, it is "◎", when a slight pencil trace is visible, it is "○", when pencil traces are visible, it is "△", when the pencil scratches or the tear of the colored polypropylene film are visible. Was designated as "x".
There is no practical problem if the evaluation is “◯” or higher. Further, if the evaluation is “Δ” or more, no problem occurs, although it is limited to applications such as furniture and a vertical surface at a high position that is not touched by a person. It is preferable that the evaluation is “◯” or more.

<Aptitude for bending>
In the bending workability test, each decorative sheet 10 of Examples 1 to 29 and Comparative Examples 1 to 13 obtained by the above method was applied to one surface of a medium quality fiberboard (MDF) as the base material layer 1. Is attached using a urethane-based adhesive, and V-shaped grooves are formed on the other surface of the base material layer 1 so that the decorative sheet 10 on the opposite side is not scratched. Insert up to the boundary where and are pasted together. Next, the base material layer 1 is bent up to 90 degrees along the V-shaped groove so that the surface of the decorative sheet 10 becomes a mountain fold, and whitening or cracks are generated in the bent part of the surface of the decorative sheet 10. The presence or absence of the bending workability was evaluated by observing it with an optical microscope.
If there is no whitening or cracks at all, it is ◎, if there is slight whitening, it is ○, if there is whitening, it is △, and if there is whitening on all surfaces When a crack was visible, it was designated as "x". In addition, if the evaluation is “Δ” or more, there is no practical problem.

<Surface uniformity during lapping>
In the surface uniformity test at the time of lapping, a square material obtained by laminating 3 to 5 sheet materials or particle boards between two medium fiber boards (MDF) as the base material layer 1 was obtained by the above method. The decorative sheets 10 of Examples 1 to 29 and Comparative Examples 1 to 13 thus obtained were attached by lapping using a hot melt adhesive to obtain a decorative plate. Subsequently, the surface on which the decorative sheet 10 was attached was observed at the end of the plate material, and it was visually observed whether or not there were surface irregularities due to the unevenness of the plate material or the step difference of the bonded portion of the plate material. Furthermore, the obtained decorative plate was left in an environment of a temperature of 80 ° C. and a humidity of 85% for 1000 hours, and surface irregularities at the same place and peeling of the decorative sheet 10 were confirmed.
Initially and even after 1000 hours, no unevenness or steps were visible and smooth, “◎”; slightly rough surface, “○”; partial unevenness or steps were “△”; The case where the unevenness or the level difference was visible or the peeling of the decorative sheet 10 was observed after 1000 hours was defined as “x”. There is no practical problem if the evaluation is “Δ” or more, but the evaluation is preferably “◯” or more.
The results of these evaluations are shown in Table 1.

  As can be seen from Table 1, in the decorative sheets 10 of Examples 1 to 9, 28, and 29, the smoothness and the bending process during the lapping process are performed while ensuring the practically acceptable condition regarding the defect and the strength during the printing process. You can see that both are compatible. Further, in the decorative sheets 10 of Examples 10 to 18, it is understood that the scratch resistance is improved by stacking the pattern layer 2 and the top coat layer 4 on Examples 1 to 9. In addition, in the decorative sheets 10 of Examples 19 to 27, the pattern layer 2, the transparent resin layer 3 and the top coat layer 4 were laminated on Examples 1 to 9 to achieve both high design and high scratch resistance while lapping. It can be seen that both of the smoothness and the bending work are compatible.

  On the other hand, in the decorative sheets 10 of Comparative Examples 1 to 9, since the non-vesicle nucleating agent was used, the strength improvement due to the improvement of the crystallinity was not sufficient, and the film thickness was thin and the blend of the highly crystalline homopolypropylene resin was used. If the ratio is low, a problem occurs during printing. Further, even if there is no defect during the printing process, there may be a defect during the bending process or a defect in the smoothness during the lapping process. It is considered that these are due to a lower ability to improve the crystallinity and a larger spherulite size as compared with the vesicleized nucleating agent.

In addition, in the decorative sheets 10 of Comparative Examples 10 to 13, any one of the addition amount as a nucleating agent, the mixing ratio of the highly crystalline homopolypropylene resin, the film thickness of the base material layer 1 and the Martens hardness is the numerical value of the present application. Although it is beyond the range, it can be seen that one of the evaluation results has a problem.
Here, in Comparative Example 11, although the automatic register adjustment was possible, the film during printing broke frequently and the product could not be produced. It is considered that, although the Martens hardness and the tensile elastic modulus were sufficient, the thickness was too small, so that the film could not withstand the fluctuation in tension during printing, and the frequency of breakage increased. In Comparative Example 10, the peeling of the decorative sheet 10 was observed after 1000 hours in the evaluation of the lapping process. It is considered that this is because, as a result of the decorative sheet 10 being too thick in the state of high crystallinity, the followability to the wooden substrate was extremely poor, and the adhesion to the wooden substrate was insufficient.

From the above, the decorative sheets 10 of Examples 1 to 29 show all of the defects during printing (printing suitability), scratch resistance, smoothness during lapping (surface uniformity during lapping), and bending suitability. It became clear that the decorative sheet 10 was compatible.
The decorative sheet of the present invention is not limited to the above-described embodiments and examples, and various modifications can be made without departing from the features of the invention.

10 Decorative sheet 1 Base material layer 2 Picture layer 3 Transparent resin layer 4 Top coat layer B Substrate

Claims (10)

The base material layer comprises a colored polypropylene film obtained by mixing an inorganic pigment with a polypropylene resin, and the base material layer is a vesicle having a single-layer outer film for the polypropylene resin containing the inorganic pigment. A nucleating agent vesicle containing a nano-sized nucleating agent is added to form, and the substrate layer has a Martens hardness of 50 N / mm ^{2 to} 120 N / mm ² and the thickness of the substrate layer. Is 50 μm or more and 150 μm or less, a decorative sheet.   50 mass% or more and 100 mass% or less of the said polypropylene resin consists of highly crystalline homopolypropylene resin whose isotactic pentad fraction (mmmm fraction) is 95% or more, It was characterized by the above-mentioned. Makeup sheet.   The addition amount of the nucleating agent vesicle is 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, relative to 100 parts by mass of the polypropylene resin. The decorative sheet according to claim 1 or 2.   The decorative sheet according to any one of claims 1 to 3, wherein the nucleating agent vesicle is a nucleating agent liposome provided with an outer membrane made of a phospholipid.   The decorative sheet according to any one of claims 1 to 4, wherein a pattern layer is laminated on one surface of the base material layer. On one surface side of the base material layer, at least one layer of a transparent resin layer and a top coat layer is laminated,
The decorative sheet according to any one of claims 1 to 5, wherein the total thickness of the decorative sheet is 100 µm or more and 250 µm or less.   7. The nucleating agent vesicle is a vesicle obtained by encapsulating the nucleating agent in a vesicle having a monolayer film by a supercritical reverse phase evaporation method to form vesicles. The decorative sheet according to item 1. A method for manufacturing a decorative sheet according to any one of claims 1 to 7, comprising:
A nucleating agent vesicle is prepared by encapsulating the nucleating agent in a vesicle and converting the nucleating agent into vesicles.
From a resin material obtained by adding an inorganic pigment and the above-described prepared nucleating agent vesicles to a polypropylene resin, the substrate layer having a Martens hardness of 50 N / mm ² or more and 120 N / mm ² or less and a thickness of 50 μm or more and 150 μm or less is formed. A method for producing a decorative sheet, which comprises producing the decorative sheet. The method for producing a decorative sheet according to claim 8, wherein the Martens hardness of the base material layer is controlled to 50 N / mm ² or more and 120 N / mm ² or less when the base material layer is manufactured. On one surface side of the substrate layer, at least one layer of a transparent resin layer and a top coat layer is laminated,
When the transparent resin layer and the top coat layer are provided, the thickness of the transparent resin layer is 50 μm or more and 100 μm or less, the thickness of the top coat layer is 3 μm or more and 15 μm or less, and the total thickness of the decorative sheet is 100 μm or more and 250 μm. The method for producing a decorative sheet according to claim 8 or 9, wherein:

Images