JP2023136624A - Decorative sheet, decorative tack sheet, decorative plate, and manufacturing method of decorative sheet - Google Patents

Abstract

To provide a decorative sheet capable of reducing the number of manufacturing processes and capable of suppressing deformation due to moisture absorption and release of a base material.SOLUTION: A decorative sheet 10 includes a transparent original fabric 20 made of a transparent olefin sheet, a printed pattern layer 50 and a colored layer 40 formed in this order on one side of the transparent original fabric 20, and a surface protective layer 60 formed on the other surface of the transparent original fabric 20, wherein a dispersant as a nano-sized additive is added to the transparent original fabric 20, and any of both surfaces of the transparent original fabric 20 does not have a laminate layer formed of other film and has a hardness of 3B or more in a pencil hardness test according to JIS K 5600.SELECTED DRAWING: Figure 1

Description

The present invention relates to a decorative sheet, a decorative tack sheet, a decorative board, and a method for manufacturing a decorative sheet.

Conventionally, decorative sheets made from olefin materials have been mainly used in recent years due to the problem of gases during combustion (see Patent Documents 1 to 3).
In order to protect the design from surface abrasion, a multi-layer decorative sheet is widely used in which a transparent olefin sheet is laminated on top of a colored olefin sheet printed on it (paragraph [0034] of Patent Document 2). ] and FIG. 1; see paragraph [0059] and FIG. 1 of Patent Document 3).

Japanese Patent Application Publication No. 2006-110929 Japanese Patent Application Publication No. 2015-199313 JP2016-101663A

The production of the conventional decorative sheets described above has a problem in that a printing process and a laminating process are required. One way to solve this problem is to use the decorative sheet as a single-layer film printed on the back side of a transparent olefin sheet, which eliminates the lamination process and reduces the number of manufacturing steps from printing to applying a surface protective layer. is possible.
On the other hand, examples of the base material to which the decorative sheet is adhered include wood materials such as MDF (Medium Density Fiberboard), particle board, and plywood. Base materials made of these wood materials (hereinafter also referred to as wood base materials) expand and contract due to changes in moisture content due to moisture absorption and release. Furthermore, these wood base materials swell when the moisture content increases, and contract when the moisture content decreases. The dimensional change rate of wood base materials varies depending on the material, but particle board and MDF tend to have a larger rate of change than plywood. As a result, building materials may warp due to differences in temperature and humidity between indoors and outdoors. In order to reduce the influence of moisture on the wood base material, it is necessary to stop the movement of moisture inside and outside the wood base material. As a method, for example, there is a method of manufacturing a decorative sheet using a moisture-proof film such as a polysand sheet made by sandwiching PE (polyethylene) and paper, or an aluminum vapor-deposited sheet. However, when manufacturing a decorative sheet using a moisture-proof film, the manufacturing process may become complicated because a lamination process is required or a special equipment such as an aluminum vapor deposition machine is required. Another problem is that composite products of PE and paper are difficult to recycle.

The present invention has been made focusing on the above points, and provides a decorative sheet, a decorative tack sheet, and a decorative material that can reduce the number of manufacturing steps while suppressing deformation due to moisture absorption and desorption of the base material. The present invention aims to provide a method for manufacturing a decorative sheet.

The decorative sheet according to one aspect of the present invention includes a transparent original fabric made of a transparent olefin sheet, a printed pattern layer and a colored layer formed in this order on one side of the transparent original fabric, and the other side of the transparent original fabric. A dispersant as a nano-sized additive is added to the transparent original fabric, and a laminate layer consisting of other films is added to both sides of the transparent original fabric. The decorative sheet is characterized by having a hardness of 3B or more in a pencil hardness test according to JIS K 5600.
Further, a decorative tack sheet according to another aspect of the present invention is characterized in that an adhesive layer and a release paper are formed in this order on the side opposite to the surface protective layer of the decorative sheet of the above aspect. It is said that
Further, a decorative board according to another aspect of the present invention is characterized in that a substrate is adhered to the opposite side of the decorative sheet from the surface protective layer of the above aspect.
Furthermore, a method for manufacturing a decorative sheet according to another aspect of the present invention includes a first step in which a transparent original fabric is manufactured by adding a dispersant as a nano-sized additive to a transparent polyolefin thermoplastic resin and extruding the mixture. A second step of forming a printed pattern layer and a colored layer in this order on one side of the transparent original fabric produced in the first process, and a surface protection step on the other side of the transparent original fabric. and a third step of forming a layer, and is produced in-line, and is characterized in that it is formed so that the hardness of the decorative sheet in a pencil hardness test according to JIS K 5600 is 3B or more. .

According to one aspect of the present invention, it is possible to reduce the number of manufacturing steps while suppressing deformation of the base material due to moisture absorption and release.

1 is a cross-sectional view schematically showing an example of a decorative sheet according to Embodiment 1. FIG. FIG. 2 is a cross-sectional view schematically showing an example of a decorative sheet according to Embodiment 2. FIG. 7 is a cross-sectional view schematically showing an example of a decorative sheet according to Embodiment 3. FIG. 7 is a cross-sectional view schematically showing an example of a decorative sheet according to Embodiment 4.

(Embodiment 1)
Next, one embodiment of the present invention (hereinafter referred to as "Embodiment 1") will be described below with reference to the drawings.
Here, the drawings are schematic, and the relationship between the thickness and the planar dimension, the ratio of the thickness of each layer, etc. are different from the actual one. In addition, the embodiments shown below illustrate configurations for embodying the technical idea of the present invention, and the technical idea of the present invention is that the materials, shapes, structures, etc. of the component parts are It is not something specific. The technical idea of the present invention can be modified in various ways within the technical scope defined by the claims.

FIG. 1 is a cross-sectional view schematically showing a decorative sheet according to a first embodiment. In FIG. 1, 10 is a decorative sheet, which is not shown, but is used indoors, for example, for fittings (interior doors, entrance storage), construction materials (partitions, edges, baseboards, window frames, door frames), etc. It is pasted on surfaces and used to match the patterns of fittings and fixtures for each house or room.
The decorative sheet 10 includes the following layers, and each layer is provided in order from (1).
Note that the following (1) to (5) will be described later.
(1) Primer layer 30
(2) Colored layer 40
(3) Printed pattern layer 50
(4) Transparent original fabric 20
(5) Surface protective layer 60
The decorative sheet 10 having such a configuration has a hardness of 3B or more in a pencil hardness test according to JIS K 5600, and thus has a moisture permeability of 5 g/m ² ·24 hours or less.

Note that each layer of the decorative sheet 10 is not limited to the above (1) to (5), and for example, as shown in FIG. ) A release paper 80 may be added to form the decorative tack sheet 11. Further, the decorative sheet 10 may have an embossed portion 90 formed on the surface side of the surface protection layer 60 in synchronization with the pattern of the printed pattern layer 50, and although not shown, the colored layer 40 of the primer layer 30 may be A substrate may be glued to the opposite surface to form a decorative board.
Moreover, the above-mentioned "(1) primer layer 30" may be omitted. That is, if the above "(2) colored layer 40" has a function as a primer layer, the primer layer 30 can be omitted.
In addition, as shown in FIG. 2, a sealer layer 100 is provided between the printed pattern layer 50 and the transparent original fabric 20 in order to improve the printing suitability of the transparent fabric 20 and the adhesion with the printed pattern layer 50. It may be provided.
Further, a moisture-proof layer may be provided on the side of the primer layer 30. In this case, a moisture-proof layer may be provided on the opposite side of the primer layer 30 from the colored layer 40, and when the primer layer 30 is not provided, A moisture-proof layer may be provided on the opposite side of the colored layer 40 from the printed pattern layer 50.

(Main features of decorative sheet 10)
The main features of the decorative sheet 10 according to the first embodiment are as follows.
(1) The decorative sheet 10 includes a printed pattern layer 50, a colored layer 40, and a primer layer 30, which are formed by printing a pattern on the back side of a transparent raw fabric 20, which is a single-layer film made of a transparent olefin sheet. A surface protective layer 60 is formed on the front side of the transparent original fabric 20, and a laminate layer made of another film is formed on both the front side and the back side of the transparent original fabric 20. It is a decorative sheet that does not have The transparent raw fabric 20 is made of a transparent polypropylene thermoplastic resin so that it is a single layer or has a structure of two types and three layers in the order of a transparent skin layer 21, a transparent core layer 22, and a transparent skin layer 21. In the case of a single-layer structure, a dispersant as a nano-sized additive is added to the transparent original fabric, and in the case of a two-layer, three-layer structure, to the transparent skin layer 21. has been added.

Since the decorative sheet 10 according to Embodiment 1 does not require a lamination process with other sheets during manufacturing, the number of manufacturing processes can be reduced, and the manufacturing process from printing to applying the surface protective layer 60 can be reduced to one. Can be done inline in the process.
Further, the decorative sheet 10 according to the first embodiment can be made to match the pattern by applying a gloss/matte coating to the surface protective layer 60, if necessary.
Furthermore, since conventional decorative sheets are multi-layered, there are limits to film formation in thinning the sheet, and there was also the problem that the hardness of the sheet could not be obtained. Since the decorative sheet 10 is a single layer, it can be easily made into a thin film, and by using nano-sized additives, the sheet can be made hard even with a thin film. Thereby, it can have excellent moisture resistance.

(2) The decorative sheet 10 according to Embodiment 1 contains an inorganic filler in addition to a dispersant as a nano-sized additive.
Therefore, the film can be made even thinner and scratch resistance can be improved.
(3) The decorative sheet 10 according to the first embodiment is formed so that the hardness in the pencil hardness test according to JIS K 5600 is 3B or more, that is, 3B or harder than 3B.
Here, the applicant believes that the higher the hardness of the decorative sheet 10 in the pencil hardness test according to JIS K 5600, the lower the moisture permeability. It was found that the humidity was less than about 5 g/m ² for 24 hours.
Therefore, by forming the decorative sheet 10 so that the hardness in the pencil hardness test according to JIS K 5600 is 3B or more, the decorative sheet 10 with low moisture permeability can be obtained without using a polysand sheet or a moisture-proof film. This makes it possible to suppress the occurrence of warping, dimensional changes, etc. when attached to a wood base material. Furthermore, a decorative sheet with low moisture permeability can be easily obtained without increasing the number of manufacturing steps. In addition, since it is possible to obtain a decorative sheet that has low moisture permeability and consists of a single layer, it can be realized without using a special machine to suppress moisture permeability, and it is also easy to recycle by making it a monomaterial. can be done.
(4) By setting the moisture permeability of the decorative sheet 10 according to Example 1 to about 5 g/m ² · 24 hours or less, it is possible to suppress warping of the decorative sheet 10 due to moisture absorption and desorption, and preferably the transparent By manufacturing the decorative sheet 10 so that the humidity is approximately 3 g/m ² ·24 hours or less, warping of the decorative sheet 10 due to moisture absorption and release can be more reliably suppressed.
(5) The decorative sheet 10 according to the first embodiment has an embossed portion 90 that is synchronized with the pattern of the printed pattern layer 50.
Here, when the decorative sheet is multi-layered, it is difficult to provide the printed pattern layer 50 and express the same synchronization with the surface protective layer 60 on the surface of the laminate film. On the other hand, in the decorative sheet 10 according to the first embodiment, the pattern printing and the embossed portions 90 are applied in-line to the front and back sides of the transparent raw fabric 20, which is a transparent olefin sheet, so that synchronization can be easily achieved. can.

(6) According to the decorative sheet 10 according to Embodiment 1, firstly, if the frame material is made of a single color, it is possible to adapt in advance to any pattern of the door part. It is now possible to decide on the pattern of the door later, and even when the door becomes obsolete and the pattern needs to be changed, it is possible to change only the door without having to destroy and replace the frame material. I also do it. Of course, the door itself can also be made in a single color. Furthermore, according to the decorative sheet 10 according to the first embodiment, by unifying all the rooms in an apartment or the like with a single color, it becomes easier to increase the number of lots and increase productivity and lower the unit price. There are benefits to using it.
Furthermore, even if the decorative sheet 10 according to Embodiment 1 is finished in white and then desired to have a wood grain texture, the decorative sheet 10 is hard even if it is thin, so it is possible to change the decorative sheet 10 to a wood grain texture later. It is.
For example, if you later want to make the surface of a decorative board finished in white woodgrain, you can change it to woodgrain by laminating the decorative tack sheet 11 according to Embodiment 1 on top. It is.

(7) Since the decorative tack sheet 11 according to the first embodiment has the adhesive layer 70 and the release paper 80 on the side of the primer layer 30, it can be easily and quickly adhered.

(8) Since the decorative board according to Embodiment 1 has the substrate adhered to the primer layer 30 side, it can be easily and quickly used as a decorative board.
(9) By using the method for manufacturing the decorative sheet 10 according to Embodiment 1, the highly functional decorative sheet 10 can be manufactured simply and quickly.

(Composition of each layer)
(Transparent original fabric 20)
The transparent original fabric 20 serves as a support for the decorative sheet 10 and is made of a transparent olefin sheet.
As shown in FIG. 1, the transparent original fabric 20 is manufactured with three layers of two types in this order: a transparent skin layer 21, a transparent core layer 22 made of transparent polypropylene, and a transparent skin layer 21.
The transparent skin layer 21 is formed by adding a dispersant as a nano-sized additive to a transparent polypropylene thermoplastic resin. Furthermore, in addition to a dispersant as a nano-sized additive, an inorganic filler is added to the transparent skin layer 21.

(Primer layer 30)
As shown in FIG. 1, the primer layer 30 is located on the opposite side of the colored layer 40 from the printed pattern layer 50, and is provided mainly for the purpose of improving adhesion.
In addition to improving adhesion, the functions of the primer layer 30 include surface stabilization after surface treatment, corrosion prevention of metal surfaces, imparting tackiness, and prevention of adhesive deterioration.
The primer layer 30 is formed by applying a urethane resin to a solid content of 1 g/m ² using, for example, a gravure printing method.
The primer layer 30 may be made of, for example, urethane, acrylic, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyester, or the like. In particular, a two-component curable urethane primer made of a polyester polyol and a polyisocyanate is preferred. Furthermore, forming the primer layer 30 by adding inorganic powder such as silica, barium sulfate, or calcium carbonate to these materials is effective in improving adhesive strength due to the anchoring effect.

(Colored layer 40)
As shown in FIG. 1, the colored layer 40 is located on the opposite side of the printed pattern layer 50 from the transparent original fabric 20, is formed using a printing method, and is mainly provided for the purpose of providing concealment. It is a layer. The colored layer 40 is printed by, for example, a gravure printing method using a two-component urethane resin in which a white pigment of titanium oxide is mixed with a urethane resin. Note that the colored layer 40 may be a solid layer.

(Print pattern layer 50)
As shown in FIG. 1, the printed pattern layer 50 is located on the opposite side of the transparent raw fabric 20 from the surface protective layer 60, is formed using a printing method, and has the purpose of imparting design to the decorative sheet 10. It is set up in
The printed pattern layer 50 has a pattern printed with urethane resin by, for example, a gravure printing method.
Examples of printing methods include, for example, gravure printing, but are not limited thereto, and include various printing methods such as offset printing, letterpress printing, flexo printing, screen printing, inkjet printing, and electrostatic printing. method can be applied.

The type of pattern of the printed pattern layer 50 is arbitrary depending on the purpose of use and the user's preference, and for example, a wood grain pattern, a stone grain pattern, an abstract pattern, etc. are common. The type of pattern is not limited to the types exemplified above, and may be, for example, full-surface solid printing.
The printing ink is exemplified by urethane resin, but is not limited to this, and may also be a coloring agent such as an organic or inorganic dye or pigment, or a filler, a tackifier, a plasticizer, It is dispersed in a binder made of synthetic resin, etc., along with appropriate additives such as stabilizers, dispersants, antifoaming agents, leveling agents, surfactants, and drying agents, as well as solvents or diluents. be.

(Surface protective layer 60)
The surface protective layer 60 is also called a top coat, and as shown in FIG. 1, it is located on the opposite side of the transparent original fabric 20 from the printed pattern layer 50, is formed using a printing method, and has abrasion resistance and water resistance. It is provided for the purpose of imparting surface properties such as.
As shown in FIG. 1, the surface protective layer 60 is composed of an undercoat layer 61 applied to the surface of the transparent original fabric 20, and an overcoat layer 62 applied to the surface of the undercoat layer 61, and the overcoat layer 62 is an undercoat layer. The luster is lower than 61.

The undercoat layer 61 is a two-component curable acrylic resin (acrylic urethane resin manufactured by DIC Graphics Co., Ltd.) applied to a thickness of 6 μm.
The overcoat layer 62 is coated with the same resin with a lower gloss, and is printed with a pattern that is synchronized with the printed pattern layer 50.
That is, by applying a gloss/matte coating to the surface protective layer 60, it is possible to synchronize with the pattern.

Further, an embossed portion 90 may be formed on the surface of the overcoat layer 62 in synchronization with the pattern of the printed pattern layer 50.
Here, the embossed part 90 gives an image of a certain height difference, but the difference in height between the undercoat 61 and the topcoat layer 62 that is in sync with the pattern is actually only on the order of several μm, and the surface protective layer It has the same meaning as the expression that by applying a gloss/matte coat to 60, it will match the pattern.

Furthermore, the surface protective layer 60 is subjected to anti-virus treatment.
As the antiviral treatment, an antiviral agent is added to the surface protective layer 60. As the antiviral agent, for example, a silver-based inorganic additive (Biocide TB-B100) manufactured by Taisho Technos Co., Ltd. that carries silver ions is used.
Here, since the surface protective layer 60 is composed of an undercoat layer 61 and an overcoat layer 62, the antiviral agent can be added to both the undercoat layer 61 and the overcoat layer 62. Alternatively, it may be attached only to the top coat layer 62 located on the surface side of the surface protection layer 60.
Although the antiviral agent is added to the surface protective layer 60, the present invention is not limited thereto, and the antiviral agent may be applied to the surface side of the surface protective layer 60, at least to the surface of the top coat layer 62.

(Transparent core layer 22)
In the drawing, the transparent raw fabric 20 is depicted as having a transparent core layer 22 and a transparent skin layer 21 as separate layers, but in reality, the transparent core layer 22 and the transparent skin layer 21 are continuous, and the interface is This is a non-existent configuration.
The transparent core layer 22 is made of, for example, a transparent polypropylene resin blended with a weathering agent.
Although the transparent original fabric 20 is composed of the transparent skin layer 21/transparent core layer 22/transparent skin layer 21 composed of a transparent olefin sheet, the present invention is not limited thereto, and as shown in FIG. It may be constructed from a single layer film (transparent layer). At this time, the single layer film (transparent layer) corresponds to the transparent original fabric 20.
The "transparent layer" of the single layer film (transparent layer) has a dispersant added thereto as a nano-sized additive, similar to the transparent skin layer 21 described later. In addition, a weathering agent is also blended into the "transparent layer" similarly to the transparent core layer 22 described later.

(Transparent skin layer 21)
In addition to a dispersant as a nano-sized additive, an inorganic filler is added to the transparent skin layer 21, and a transparent polypropylene resin is used.
Transparent skin layer 21:transparent core layer 22:transparent skin layer 21 are coextruded so that the thickness ratio is 0.5:9:0.5 to produce a transparent original fabric 20 with a total thickness of 50 μm.

(Resin material of transparent core layer 22)
Examples of the resin material constituting the transparent core layer 22 include thermoplastic resin. The thermoplastic resin is not particularly limited, and the same material as the thermoplastic resin used for the base layer and the like in the conventional decorative sheet 10 can be used.

Examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, polyethylene terephthalate, Polybutylene terephthalate, polytetramethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, 1,4-cyclohexanedimethanol copolymerization Polyester resins such as polyethylene terephthalate, polyarylate, polycarbonate, ethylene-vinyl acetate copolymer olefin copolymer resins such as ethylene-vinyl alcohol copolymers, ethylene-(meth)acrylic acid (ester) copolymers, ethylene-unsaturated carboxylic acid copolymers, metal neutralized products (ionomers), etc. Polyolefin resins, poly(meth)acrylonitrile, polymethyl(meth)acrylate, polyethyl(meth)acrylate, polybutyl(meth)acrylate, acrylic resins such as polyacrylamide, 6-nylon, 6,6-nylon, 6,10- Polyamide resins such as nylon, styrene resins such as polystyrene, AS resins, ABS resins, vinyl resins such as polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral, polyvinyl fluoride, polyvinylidene fluoride, Fluororesins such as polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, ethylene-perfluoroalkyl vinyl ether copolymer, etc., or mixtures, copolymers, composites, laminates, etc. of two or more thereof. Can be used.

In particular, in view of the growing social concern about environmental issues in recent years, it is not desirable to use thermoplastic resins that contain chlorine (halogen), such as polyvinyl chloride resin, and it is preferable to use non-halogen-based thermoplastic resins. Preference is given to using thermoplastic resins.
In particular, polyester resins (amorphous or biaxially oriented) or polyolefin resins, especially polyolefin resins, are used as non-halogen thermoplastic resins from the viewpoint of various physical properties, processability, versatility, economic efficiency, etc. Most preferably. For example, as the polyolefin resin, it is preferable to use a polypropylene resin containing 30% by mass or more and 100% by mass or less of a highly crystalline homopolypropylene resin having an isotactic pentad fraction (mmmm fraction) of 95% or more.
The transparent core layer 22 may contain fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, and antifungal agents, as necessary. One or more types selected from various additives such as an abrasive agent, a light scattering agent, and a gloss control agent may be added.

(Resin material of transparent skin layer 21)
Examples of the resin material constituting the transparent skin layer 21 include thermoplastic resin. The thermoplastic resin is not particularly limited, and the same resin material as the transparent core layer 22 can be used.

(Nano-sized additives, etc. (nucleating agents))
The transparent skin layer 21 contains an inorganic filler in addition to a dispersant as a nano-sized additive, and is also referred to as a "nano-sized nucleating agent" hereinafter.
The nano-sized nucleating agent is preferably used by being added to the polypropylene resin in the form of a nucleating agent vesicle, which is encapsulated in a vesicle having a monolayer outer membrane.
Further, in the decorative sheet 10 according to the first embodiment, the nucleating agent in the resin constituting the transparent skin layer 21 may be encapsulated in a vesicle with a part of the nucleating agent exposed. Since the transparent skin layer 21 contains a nucleating agent, the degree of crystallinity can be improved, and the scratch resistance (scratch resistance) of the decorative sheet 10 can be improved.

(Particle size of nano-sized nucleating agent)
The average particle size of the nano-sized nucleating agent is preferably 1/2 or less of the wavelength range of visible light. Specifically, since the wavelength range of visible light is 400 nm or more and 750 nm or less, the average particle size is preferably 375 nm or less.
Since nano-sized nucleating agents have extremely small particle sizes, the number of nucleating agents present per unit volume and the surface area increase in inverse proportion to the cube of the particle diameter. As a result, the distance between each nucleating agent particle becomes shorter, so that when crystal growth occurs from the surface of one nucleating agent particle added to the resin, the end where the crystal is growing will immediately The nucleating agent particle contacts the end of a crystal growing from the surface of another nucleating agent particle adjacent to the nucleating agent particle, and the ends of each crystal inhibit the growth of each crystal, thereby stopping the growth of each crystal. Therefore, the average particle size of spherulites in the crystal part of the crystalline resin can be reduced, for example, the spherulite size can be reduced to 1 μm or less.

As a result, it is possible to create a highly hard resin film with a high degree of crystallinity, and the stress concentration between the spherulites that occurs during bending is efficiently dispersed, resulting in a resin that suppresses cracking and whitening during bending. film can be realized.
When a nucleating agent is simply added, the particle size increases due to secondary aggregation of the nucleating agent in the resin.
On the other hand, when adding nucleating agent vesicles, the dispersibility in the resin improves, so the number of crystal nuclei for the amount of nucleating agent added increases significantly compared to when the nucleating agent is simply added. do.
Therefore, the average particle size of spherulites in the crystalline portion of the resin becomes small, and the occurrence of cracks and whitening during bending can be suppressed. Therefore, by adding nucleating agent vesicles, the degree of crystallinity can be further increased, and it becomes possible to achieve both improved elastic modulus and processability.

The transparent skin layer 21 preferably contains, for example, 0.05 parts by mass or more and 0.5 parts by mass or less, more preferably 0.1 parts by mass or more and 0.3 parts by mass, based on 100 parts by mass of polypropylene resin as the main component. It is formed from a resin material to which a nucleating agent is added within the following range.
When using a nucleating agent vesicle, the amount of the nucleating agent added to the resin material is the amount added in terms of the nucleating agent in the nucleating agent vesicle.
If the amount of the nucleating agent added is less than 0.05 part by mass, the degree of crystallinity of the polypropylene may not be sufficiently improved, and the scratch resistance of the transparent skin layer 21 may not be sufficiently improved.
Furthermore, when the amount of the nucleating agent added exceeds 0.5 parts by mass, the growth of polypropylene spherulites is inhibited due to excessive crystal nuclei, and as a result, the crystallinity of polypropylene is not sufficiently improved. There is a possibility that the scratch resistance of the transparent skin layer 21 will not be sufficiently improved.
Here, the term "main component" refers to a resin material that accounts for 50% by mass or more of the resin material that constitutes the transparent skin layer 21.

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

(Supercritical reverse phase evaporation method)
As a method for nano-forming the nucleating agent, a supercritical reverse phase evaporation method is preferable. The supercritical reverse phase evaporation method is a method of producing capsules (nano-sized vesicles) containing a target substance using carbon dioxide under supercritical state, temperature conditions or pressure conditions above the critical point.
Carbon dioxide in a supercritical state means carbon dioxide in a supercritical state at a critical temperature (30.98°C) and a critical pressure (7.3773 ± 0.0030 MPa) or above, and under a temperature condition above the critical point or Carbon dioxide under pressure means carbon dioxide under conditions where only the temperature or only the pressure exceeds the critical condition.
In addition, as a specific nano-forming process using supercritical reversed-phase evaporation method, first, an aqueous phase is injected into a mixed fluid of supercritical carbon dioxide, phospholipids as an outer membrane forming substance, and a nucleating agent as an encapsulating substance. Then, by stirring, an emulsion of supercritical carbon dioxide and an aqueous phase is generated.

Next, by reducing the pressure, the carbon dioxide expands and evaporates, causing phase inversion, and the phospholipid generates nanocapsules (nanovesicles) in which the surface of the nucleating agent particles is covered with a monolayer film.
By using this supercritical reversed-phase evaporation method, unlike the conventional encapsulation method in which the outer film forms a multilayer film on the surface of the nucleating agent particles, it is possible to easily produce capsules with a single layer film. Small diameter capsules can be prepared.
The nucleating agent vesicles are prepared by, for example, the Bangham method, extrusion method, hydration method, surfactant dialysis method, reverse phase evaporation method, freeze-thaw method, supercritical reverse phase evaporation method, or the like. Nucleating agent vesicles are preferably prepared using supercritical reverse phase evaporation.

(Outer membrane that constitutes the nucleating agent vesicle)
The outer membrane constituting the nucleating agent vesicle is composed of, for example, a single layer membrane. Further, the outer membrane is composed of a substance containing biological lipids such as phospholipids.
In this specification, a nucleating agent vesicle whose outer membrane is composed of a substance containing a biological lipid such as a phospholipid is referred to as a nucleating agent liposome.
Examples of the phospholipids constituting the outer membrane include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, hydrogenated soybean lecithin, etc. Examples include sphingophospholipids such as glycerophospholipids, sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.

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

In the decorative sheet 10 according to the first embodiment, the nucleating agent vesicle is preferably a radical scavenger liposome having an outer membrane made of phospholipid. It is possible to improve the compatibility between the resin material which is the main component of the vesicles and the vesicles.
The nucleating agent is not particularly limited as long as it is a substance that serves as a starting point for crystallization when the resin crystallizes. Examples of the nucleating agent include phosphate metal salts, benzoic acid metal salts, pimelic acid metal salts, rosin metal salts, benzylidene sorbitol, quinacridone, cyanine blue, and talc. In particular, in order to maximize the effect of the nano treatment, it is preferable to use phosphate ester metal salts, benzoate metal salts, pimelic acid metal salts, and rosin metal salts, which are non-melting and can be expected to have good transparency. If the material itself can be made transparent by nano-processing, colored quinacridone, cyanine blue, talc, etc. can also be used. Furthermore, molten benzylidene sorbitol may be appropriately mixed with the non-molten nucleating agent.

(Characteristics of transparent skin layer 21)
As described above, the decorative sheet 10 according to the first embodiment is characterized in that the transparent skin layer 21 contains a resin material and a nucleating agent.
Furthermore, the decorative sheet 10 according to the first embodiment is characterized in that when forming the transparent skin layer 21, a nucleating agent encapsulated in vesicles is added to the resin material to crystallize the resin material. have. By adding the nucleating agent to the resin composition while being encapsulated in vesicles, the effect of dramatically improving the dispersibility of the nucleating agent into the resin material, that is, into the transparent skin layer 21 is achieved. On the other hand, it may be difficult to directly identify the nucleating agent encapsulated in the vesicles based on the structure and characteristics of the finished decorative sheet 10, and this may be impractical. . The reason is as follows.

The nucleating agent added in the form of vesicles has high dispersibility and is in a dispersed state, and even in the state of the laminate, which is the precursor of the produced decorative sheet 10, it forms in the transparent skin layer 21. Highly distributed.
However, in the manufacturing process of the decorative sheet 10, the laminate is usually subjected to various treatments such as compression treatment and hardening treatment, and these treatments may cause the outer membrane of the vesicles containing the nucleating agent to be crushed or cause chemical damage. A reaction may occur.
For this reason, during the processing process of the decorative sheet 10, the outer membrane of the nucleating agent in the finished decorative sheet 10 may be crushed, the state of chemical reaction may vary, and the nucleating agent may be enclosed (enveloped) in the outer membrane. There is a high possibility that there will be no.

If the nucleating agent is not included in the outer membrane, it is difficult to specify the physical properties of the nucleating agent itself in a numerical range, and whether the constituent material of the fractured outer membrane is 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, although the present disclosure differs from the conventional decorative sheet 10 in that the nucleating agent is blended in a highly dispersed manner, the nucleating agent is added in the form of vesicles containing the nucleating agent. There may be cases in which it is impractical to determine whether or not this is due to the structure and characteristics of the decorative sheet 10 based on a numerical range analyzed based on measurements.
(Sealer layer 100)
The sealer layer 100 is provided to improve the adhesion between the transparent original fabric 20 and the printed pattern layer 50. The material of the sealer layer 100 is, for example, urethane resin, acrylic resin, salt-vinyl acetate resin, or the like. The material for the sealer layer 100 may be transparent ink obtained by removing colorants such as dyes or pigments from the ink used in the printed pattern layer 50. In addition, the sealer layer 100 may contain appropriate additives such as fillers, tackifiers, plasticizers, stabilizers, dispersants, antifoaming agents, leveling agents, surfactants, desiccants, and solvents or diluting solvents. Additionally, it may be dispersed in a binder made of synthetic resin. Since the decorative sheet 10 has the sealer layer 100, the printability of the transparent raw fabric 20 and the adhesion with the printed pattern layer 50 can be improved.
Note that the sealer layer 100 does not necessarily need to be provided.
(Hardness of decorative sheet 10)
The decorative sheet 10 is formed so that the hardness in a pencil hardness test according to JIS K 5600 is 3B or more, that is, 3B or harder than 3B. That is, each layer constituting the decorative sheet 10 is formed so that the hardness of the decorative sheet 10 is 3B or more in the pencil hardness test. Possible methods for adjusting the hardness of the decorative sheet 10 include, for example, adjusting the thickness of the transparent raw fabric 20, and adding or not adding a dispersant as a nano-sized additive to the transparent raw fabric 20. It will be done.
(Moisture permeability of decorative sheet 10)
The decorative sheet 10 preferably has a moisture permeability of 5 g/m ² ·24 hours or less, and from the viewpoint of suppressing warping of the decorative board, it is preferable that the moisture permeability is 3 g/m ² ·24 hours or less. .

(Method for manufacturing decorative sheet 10)
The decorative sheet 10 has the above-described configuration, and its manufacturing method includes the following first to third steps, and is manufactured in-line.
Here, "in-line" means that since there is no lamination process in which films are laminated together, printing, which normally requires multiple steps, can be performed in one line, that is, one line. That is, the manufacturing process from printing to applying the surface protective layer 60 can be performed in-line in one step.

(1) First step The first step involves forming a transparent core layer 22 made of a transparent polypropylene thermoplastic resin, and forming nano-sized particles on the thermoplastic resin. This is a step of manufacturing a transparent raw fabric 20 by extrusion molding a transparent skin layer 21 to which a dispersant as an additive is added.

(2) Second step The second step is to form a printed pattern layer 50, a colored layer 40, and a primer layer 30 on one side (back side) of the transparent original fabric 20 produced in the first step. This is a step of sequentially forming.
Note that the layers formed in the second step are not limited to the three layers of the printed pattern layer 50, the colored layer 40, and the primer layer 30, but may be, for example, only one layer including at least the printed pattern layer 50; In addition to the layer 50, one layer of the colored layer 40 or the primer layer 30 may be added, a total of two layers, or there may be four or more layers.

(3) Third step In the third step, after or prior to the second step, on the other side (front surface) side of the transparent original fabric 20 manufactured in the first step, This is a step of forming a surface protective layer 60.
There are two orders of the steps: the order of the first step, the second step, and the third step, and the order of the first step, the third step, and the second step.

(Cosmetic tack sheet 11)
As shown in FIG. 1, the decorative tack sheet 11 is a decorative sheet 10 having the above-described configuration, with an adhesive layer 70 and a release paper 80 attached to the primer layer 30 side.

(Decorative board)
Although not shown, the decorative board is made by adhering a substrate to the primer layer 30 side of the decorative sheet 10 having the above-described structure using an adhesive or the like. The decorative board can also be constructed by peeling off the release paper 80 of the decorative tack sheet 11 in FIG. 1 and directly bonding the substrate to the adhesive layer 70.
Here, the substrate may be of any type such as wood, steel, resin, etc., but may be made of, for example, a steel plate with non-combustible specifications or a non-combustible material specified in Ministry of Construction Notification No. 1400.

(Other embodiments of the layer structure on the back side of the transparent original fabric 20)
Although the layer structure on the back side of the transparent original fabric 20 is not shown, the following embodiment may be used.
(a) Only the printed pattern layer 50 and the colored layer 40 may be formed in this order on the back side of the transparent original fabric 20.
(b) Only the printed pattern layer 50, colored layer 40, and primer layer 30 may be formed in this order on the back side of the transparent original fabric 20.

(Embodiment 2)
Next, a decorative sheet 10 according to a second embodiment of the present invention will be described using FIG. 2.
The second embodiment is characterized firstly in that the embossed portion 90 extends deeply from the surface protection layer 60 to the transparent original fabric 20.
That is, the embossed portion 90 of the first embodiment extends from the surface of the surface protection layer 60 toward the transparent original fabric 20 and reaches the top coat layer 62. On the other hand, as shown in FIG. 2, the embossed portion 90 of the second embodiment extends from the surface of the surface protection layer 60 toward the transparent original fabric 20, and partially penetrates into the transparent original fabric 20.
The embossed portion 90 is formed before the resin of the transparent original fabric 20 is cured. This is because the hardness of the resin increases after it hardens.
Compared to the embossed part 90 of Embodiment 1, the embossed part 90 extends to the transparent original fabric 20, so that the outline of the recessed part becomes clear and sharp, and the three-dimensional design feeling can be further improved.
Note that other points in the second embodiment are denoted by the same reference numerals as those in the first embodiment in FIG. 1, and explanations thereof will be omitted.

(Embodiment 3)
Next, a decorative sheet according to Embodiment 3 of the present invention will be described using FIG. 3.
The feature of Embodiment 3 is that the transparent original fabric 20 is formed of a single layer.
That is, in the decorative sheet 10 according to the first embodiment shown in FIG. 1, the transparent original fabric 20 is composed of two types and three layers. On the other hand, the transparent original fabric 20 of Embodiment 3 is composed of a single layer, as shown in FIG. 3.
The transparent original fabric 20 is characterized in that a dispersant as a nano-sized additive is added thereto.
The transparent original fabric 20 is a single layer compared to the multi-layered transparent original fabric 20 of Embodiment 1, so it is easier to form a thin film, and by using nano-sized additives, even a thin film can be made into a thin film. Can be made hard.
Note that other points in the third embodiment are denoted by the same reference numerals as those in the first embodiment in FIG. 1, and description thereof will be omitted.

(Method for manufacturing decorative sheet 10 of Embodiment 3)
A method for manufacturing the decorative sheet 10 of Embodiment 3 will be described below.
The manufacturing method of the third embodiment includes the first to third steps, and is manufactured in-line, as in the first embodiment described above.
The first step is to manufacture a transparent original fabric by adding a dispersant as a nano-sized additive to a transparent polyolefin thermoplastic resin and extrusion molding the same. The second step is a step of forming a printed pattern layer on the back side of the transparent original fabric produced in the first step. The third step is a step of forming a surface protective layer on the surface side of the transparent original fabric after or prior to the second step.

(Embodiment 4)
Next, a decorative sheet according to Embodiment 4 of the present invention will be described using FIG. 4.
The fourth embodiment has one feature point of the second embodiment and one feature point of the third embodiment.
Note that other points of the fourth embodiment are denoted by the same reference numerals as those of the first embodiment shown in FIG. 1, the second embodiment shown in FIG. 2, and the third embodiment shown in FIG. 3, and the description thereof will be omitted.

Examples 1 to 5 and Comparative Examples 1 to 3 of decorative sheets according to the present invention will be described below.
Note that the present invention is not limited to Example 1 below.

(Example 1)
In Example 1, a decorative sheet, which is a single layer sheet, was produced using the following materials and procedures.
First, a transparent original fabric having a thickness of 100 μm was produced by extrusion molding using a transparent polypropylene resin to which a weathering agent, a dispersant as a nano-sized additive, etc. were added.
Second, a pattern was printed on the back side of the transparent original fabric using a urethane resin using a gravure printing method, and a colored layer was formed thereon using a two-component urethane resin.
Thirdly, a urethane resin was applied onto the colored layer using a gravure printing method so that the solid content was 1 g/m ² to form a primer layer.
Fourth, a low-gloss acrylic two-component curing resin (acrylic urethane resin manufactured by DIC Graphics Corporation) is applied to the surface side of the transparent original fabric to a thickness of 6 μm as a surface protective layer, and an undercoat layer is formed. On top of that, an overcoat layer was formed by printing the same resin with a high gloss pattern in a pattern that was synchronized with the printed pattern layer.
(Example 2)
Example 2 is the same as the decorative sheet of Example 1 except that the thickness of the transparent original fabric was reduced from 100 μm to 70 μm.
(Example 3)
Example 3 is the same as the decorative sheet of Example 1 except that the surface protective layer was formed of an ultraviolet curable resin.
(Example 4)
Example 4 is the same as Example 3 except that the thickness of the transparent original fabric was 90 μm.
(Example 5)
Example 5 is the same as the decorative sheet of Example 1 except that the thickness of the transparent original fabric was changed to 60 μm.
(Comparative example 1)
Comparative Example 1 is different from Examples 1 and 2 in that a dispersant or the like as a nano-sized additive is not added to the transparent original fabric.
(Comparative example 2)
In Comparative Example 2, a single-layer decorative sheet was produced using the following materials and the following procedure.
First, using a pigment-containing colored polyester sheet having a thickness of 60 μm, a pattern printing layer was formed using a urethane resin by gravure printing.
Second, a urethane resin was applied to the surface of the pattern printing layer using a gravure printing method so that the solid content was 1 g/m ² to form a primer layer.
Third, an undercoat layer was formed by applying a low-gloss two-component acrylic curing resin to a thickness of 9 μm as a surface protective layer on the opposite side of the pigment-containing colored polyester sheet from the pattern printing layer. A decorative sheet of Comparative Example 2 was prepared by forming the same resin with a higher gloss as an overcoat layer thereon.
(Comparative example 3)
Comparative Example 3 is the same as Comparative Example 1 except that the thickness of the transparent original fabric was 70 μm.
(Evaluation method and evaluation criteria)
Performance evaluation was performed on each of the decorative sheets of Examples 1 to 5 and Comparative Examples 1 to 3 produced as described above. The evaluation method is as follows.
(1) Scratch test (2) Scratch hardness test (pencil hardness)
(3) Moisture permeability test

In the (1) scratch test and (2) scratch hardness test (pencil hardness), each decorative sheet of the example and comparative example was placed on a 3 mm thick MDF (medium density fiberboard) using a water-based urethane adhesive. was applied, laminated, and compressed using a press at a temperature of 30°C or higher and 50°C or lower to form a decorative board for evaluation. In addition, (3) the moisture permeability test is conducted in the state of a decorative sheet.
(Scratch test)
In the scratch test, a coin scratch test was performed on each decorative sheet attached to MDF, and the load was measured when no continuous scratches were produced on the surface of the decorative sheet.
In the scratch test, a 10 yen coin was applied to the surface of the decorative sheet, the test was started with a load of 1 kg, and the load was gradually increased in 1 kg increments until the test reached 4 kg.

(Scratch hardness test)
The scratch hardness test was conducted on each decorative sheet attached to MDF using the scratch hardness (pencil method) specified in JIS K5600-5-4:1999, and it was determined that no scratches were produced on the surface of the decorative sheet. The hardness of the hardest pencil (pencil hardness) was measured.
(Moisture permeability measurement (cup method))
JIS A 1324 Method for Measuring Moisture Permeability of Building Materials The method specified in the cup method is used. Specifically, a moisture absorbent is placed in the bottom of a cup that is impermeable to water vapor, and decorative sheets to be used as samples are attached to the four cups and sealed with aluminum tape. The sample is placed in a constant temperature and humidity chamber set at a temperature of 23° C. and a relative humidity of 50%, and the sample is taken out after 120 hours. The increase in mass of the cup was measured to determine the amount of sample permeation.

(Evaluation criteria)
In the scratch test, a load of 1 kg or more was considered to be a pass, and anything else was judged to be a fail.
In the scratch hardness test, pencil hardness (pencil hardness) of "3B" or higher was considered to be a pass, "2B" or higher was evaluated as "○", and "3B" was evaluated as "△". Moreover, when it was softer than "3B", it was marked as "×".
In the moisture permeability test, when the obtained moisture permeability is 5 g/m ² · 24 hours or less, it is judged as a pass, and when the moisture permeability is greater than 5 g / m ² · 24 hours, it is judged as a failure, and further, When the moisture permeability was 3 g/m ² 24 hours or less, it was rated "◎", and when the moisture permeability was greater than 3 g/m ² 24 hours and smaller than 5 g/m ² 24 hours, it was rated "○".

(Evaluation results)
The evaluation results for each decorative sheet are shown in Table 1 below.

(Examples 1 to 5 and Comparative Examples 1 to 3)
The decorative sheets of Examples 1 to 5 had a scratch hardness of 3B or more, and passed both the scratch test and moisture permeability. That is, it was confirmed that if the scratch hardness was 3B or more, a moisture permeability lower than 5 g/m ² ·24 hours could be obtained.
On the other hand, as shown in Comparative Examples 1 and 3, in the case of decorative sheets with a scratch hardness of less than 3B, it was confirmed that the moisture permeability was greater than 5 g/m ² ·24 hours. Further, as shown in Comparative Example 2, when a colored polyester sheet is used as the original fabric instead of a transparent original fabric made of a transparent olefin sheet, the scratch hardness is 3B or more, but the moisture permeability is 5g/m ²・It was confirmed that the time is longer than 24 hours.

10 Decorative sheet 11 Decorative tack sheet 20 Transparent raw fabric 21 Transparent skin layer 22 Transparent core layer 30 Primer layer 40 Colored layer 50 Printed pattern layer 60 Surface protection layer 61 Undercoat layer 62 Topcoat layer 70 Adhesive layer 80 Release paper 90 Embossed part 100 sealer layer

Claims (13)

A transparent original fabric made of a transparent olefin sheet,
A printed pattern layer and a colored layer formed in this order on one side of the transparent original fabric;
a surface protective layer formed on the other surface of the transparent original fabric,
A decorative sheet in which a dispersant as a nano-sized additive is added to the transparent original fabric, and does not have a laminate layer made of another film on either side of the transparent original fabric,
A decorative sheet having a hardness of 3B or more in a pencil hardness test according to JIS K 5600. The decorative sheet according to claim 1, having a moisture permeability of 5 g/m ² ·24 hours or less. 3. The decorative sheet according to claim 1, wherein the transparent original fabric has two types and three layers, each of which is laminated in this order: a transparent skin layer, a transparent core layer, and a transparent skin layer. 4. The decorative sheet according to claim 3, wherein an inorganic filler is added to the transparent skin layer. The decorative sheet according to any one of claims 1 to 4, wherein an embossed portion that matches a pattern of the printed pattern layer is formed on the surface of the surface protection layer. 6. The method according to claim 1, further comprising a sealer layer between the transparent original fabric and the printed pattern layer to improve adhesion to the printed pattern layer. Cosmetic sheet. 7. The decorative sheet according to claim 1, further comprising a primer layer formed on a side opposite to the surface protection layer. 7. The decorative sheet according to claim 1, further comprising a moisture-proof layer formed on a side opposite to the surface protective layer. 7. The decorative sheet according to claim 1, wherein a moisture-proof layer and a primer layer are formed in this order on the side opposite to the surface protective layer. The decorative sheet according to any one of claims 1 to 9, wherein an adhesive layer and a release paper are formed in this order on the side opposite to the surface protective layer. Makeup tack sheet. A decorative board using the decorative sheet according to any one of claims 1 to 9, wherein a substrate is adhered to a side opposite to the surface protection layer. 12. The decorative board according to claim 11, wherein a moisture-proof film is adhered to a side of the substrate opposite to the decorative sheet. A method for manufacturing a decorative sheet,
A first step of producing a transparent original fabric by adding a dispersant as a nano-sized additive to a transparent polyolefin-based thermoplastic resin and extruding it;
a second step of forming a printed pattern layer and a colored layer in this order on one side of the transparent original fabric produced in the first step;
a third step of forming a surface protective layer on the other side of the transparent original fabric,
A method for producing a decorative sheet, which is produced in-line, and is formed so that the hardness of the decorative sheet in a pencil hardness test according to JIS K 5600 is 3B or more.

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