JP2022011844A - Decorative sheet and method for manufacturing the same - Google Patents

Abstract

To provide a decorative sheet which is used in a room and is stuck to a surface of a fitting and a fixture material, and is used so as to match patters of fittings and fixture materials for a house and each room, and a method for manufacturing the same, and a decorative sheet which can achieve scratch resistant performance.SOLUTION: In a decorative sheet, a coloring layer 40, a printing pattern layer 30, a transparent raw fabric layer 20 and a surface protective layer 60 are positioned in this order, the transparent raw fabric layer 20 is composed of a transparent core layer 21, a surface side transparent skin layer 22 which is on the side of the surface protective layer 60 and is positioned on a surface of the transparent core layer 21, and a rear face side transparent skin layer 23 which is on a side opposite to the surface side transparent skin layer 22 across the transparent core layer 21 and is positioned on a rear face of the transparent core layer 21. The surface side transparent skin layer 22 and the rear face side transparent skin layer 23 use the same kind of thermoplastic resin, and a dispersant is added thereto as a nano-sized additive. An inorganic filler may be added to the surface side transparent skin layer 22 and the rear side transparent skin layer 23.SELECTED DRAWING: Figure 1

Description

The present invention is used indoors and is attached to the surface of fittings (interior doors, entrance storage), building materials (parting, surrounding edges, skirting boards, window frames, door frames), etc. The present invention relates to a decorative sheet used by matching the patterns of materials and a method for manufacturing the same.

Conventionally, in recent years, olefin-based materials have been mainly used in decorative sheets due to the problem of gas during combustion (see Patent Documents 1 to 3).
Further, conventionally, in order to protect a pattern from wear on the surface, a decorative sheet having a plurality of layers and a transparent olefin sheet bonded on a printed sheet on a colored olefin sheet is widely used (Patent Document 2). See paragraph [0034] and FIG. 1, paragraph [0059] and FIG. 1 of Patent Document 3).

Japanese Unexamined Patent Publication No. 2006-110929 JP-A-2015-199313 Japanese Unexamined Patent Publication No. 2016-101663

The production of the above-mentioned conventional decorative sheet has a problem that a plurality of steps of a printing step and a laminating step are required.
Further, since the conventional decorative sheet has a plurality of layers, there is a problem that the limit in film formation and the hardness of the sheet cannot be obtained even when the sheet is thinned.
The present invention focuses on the above points, and an object of the present invention is to provide a decorative sheet capable of achieving scratch resistance, which was difficult with conventional olefin-based decorative sheets, and a method for producing the same. ..

The decorative sheet according to one aspect of the present invention is located in the order of a colored layer, a printed pattern layer, a transparent raw fabric layer, and a surface protective layer, and the transparent raw fabric layer is on the side of the transparent core layer and the surface protective layer. The surface-side transparent skin layer located on the surface of the transparent core layer and the transparent core layer on the opposite side of the transparent core layer and located on the back surface of the transparent core layer. It is composed of a back surface side transparent skin layer, and the front surface side transparent skin layer and the back surface side transparent skin layer are made of the same type of thermoplastic resin, and a dispersant as a nano-sized additive is added. It is a feature.

Further, the decorative sheet according to one aspect of the present invention is characterized in that an inorganic filler is added to the front surface side transparent skin layer and the back surface side transparent skin layer.
The decorative sheet according to one aspect of the present invention is characterized in that a print coat layer on which a synchronized pattern synchronized with the print pattern of the print pattern layer is printed is formed on the surface of the surface protective layer.
The decorative sheet according to one aspect of the present invention is characterized in that an uneven pattern portion is formed on the surface side of the surface side transparent skin layer.

The method for producing a decorative sheet according to one aspect of the present invention is located in the order of a colored layer, a printed pattern layer, a transparent raw fabric layer, and a surface protective layer, and the transparent raw fabric layer is a transparent core layer and the surface protective layer. On the side of the transparent core layer, the surface side transparent skin layer located on the surface of the transparent core layer and the back surface of the transparent core layer on the opposite side of the transparent core layer and opposite to the front surface side transparent skin layer. A method for producing a decorative sheet composed of a back surface side transparent skin layer located in the above, wherein the front surface side transparent skin layer and the back surface side transparent skin layer use the same kind of thermoplastic resin and are added in nano size. A dispersant as an agent is added, and the transparent raw fabric layer is characterized by being simultaneously extruded.
The method for producing a decorative sheet according to one aspect of the present invention is characterized in that an inorganic filler is added to the front surface side transparent skin layer and the back surface side transparent skin layer.

According to one aspect of the present invention, it is possible to provide a decorative sheet capable of achieving scratch resistance and a method for producing the same.

It is sectional drawing of the decorative sheet which concerns on Embodiment 1. FIG. It is sectional drawing which extracted the transparent original fabric layer of FIG. It is sectional drawing of the decorative sheet which concerns on Embodiment 2. FIG. It is sectional drawing of the decorative sheet which concerns on Comparative Example 1. FIG.

(Cosmetic sheet 10 according to the first embodiment)
In FIG. 1, 10 is a decorative sheet according to the first embodiment, which is not shown, but is used indoors, and is used for fittings (for example, interior doors, entrance storage), building materials (for example, parting line, peripheral edge, skirting board, window frame). , Door frame), etc., and is used by matching the patterns of fittings and construction materials for each house or room.
The decorative sheet 10 includes the following layers.
The following (1) to (5) will be described later.
(1) Transparent original fabric layer 20
(2) Printed pattern layer 30
(3) Colored layer 40
(4) Primer layer 50
(5) Surface protective layer 60

The decorative sheet 10 is located in the order of the primer layer 50, the colored layer 40, the printed pattern layer 30, the transparent raw fabric layer 20, and the surface protective layer 60, and may be provided in that order, for example.
The decorative sheet 10 is not limited to (1) to (5) described above, and for example, "(4) primer layer 50" may be omitted, or, although not shown, the color and design of the base material may be utilized at the same time. In consideration of the case, "(3) Colored layer 40" may be omitted, and further, as shown in FIG. 3 described later, a print coat layer 70 may be formed on the surface of the surface protective layer 60. "

(Transparent original layer 20)
As shown in FIG. 2, the transparent raw fabric layer 20 is formed of the following three layers.
Note that (1) to (3) will be described later.
(1) Transparent core layer 21
(2) Surface side transparent skin layer 22
(3) Back side transparent skin layer 23
In the transparent original fabric layer 20, the back surface side transparent skin layer 23, the transparent core layer 21, and the front surface side transparent skin layer 22 are sequentially laminated.

(Transparent core layer 21)
As the transparent core layer 21, a polypropylene resin blended with a weather resistant agent is used.
The transparent core layer 21 is, for example, a transparent polypropylene resin film.
The thickness of the transparent core layer 21 is preferably, for example, 40 μm or more and 200 μm or less, and more preferably 120 μm or more and 160 μm or less.
When the thickness of the transparent core layer 21 is 40 μm or more, it has sufficient strength as a base material and can suppress deterioration of scratch resistance. On the other hand, when the thickness of the transparent core layer 21 is 200 μm or less, sufficient transparency can be maintained so that the pattern of the printed pattern layer can be seen from the sheet surface, and problems such as whitening and cracking occur during bending. It can be suppressed.

(Resin material)
Examples of the resin material constituting the transparent core layer 21 include a thermoplastic resin. The thermoplastic resin is not particularly limited, and the same material as the thermoplastic resin used as the base material layer or the like in the conventional decorative sheet 10 can be used.
Examples of the thermoplastic resin include polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, ethylene-α-olefin copolymer, propylene-α-olefin copolymer and other polyolefin resins, polyethylene terephthalate, and the like. Polybutylene terephthalate, polytetramethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, 1,4-cyclohexanedimethanol copolymer polyethylene terephthalate, polyallylate, polyester resin such as polycarbonate, ethylene-vinyl acetate copolymer Combined, ethylene-vinyl alcohol copolymer, ethylene- (meth) acrylic acid (ester) copolymer, ethylene-unsaturated carboxylic acid copolymer metal neutralizer (ionomer) and other olefin copolymer resins, etc. Acrylic resins such as polyolefin resins, poly (meth) acrylonitrile, polymethyl (meth) acrylates, polyethyl (meth) acrylates, polybutyl (meth) acrylates, and polyacrylamides, 6-nylon, 6,6-nylon, 6,10- Polyamide resin such as nylon, styrene resin such as polystyrene, AS resin, ABS resin, vinyl resin such as polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral, polyvinyl fluoride, vinylidene fluoride, Fluororesin such as polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, ethylene-perfluoroalkyl vinyl ether copolymer, or a mixture of two or more of them, a copolymer, a composite, a laminate, etc. Can be used.

In particular, in view of the growing social concern about environmental problems in recent years, it is not preferable to use a thermoplastic resin containing chlorine (halogen) such as polyvinyl chloride resin as the thermoplastic resin, and it is a non-halogen type. It is preferable to use a thermoplastic resin.
In particular, polyester-based resin (amorphous or biaxially stretched) or polyolefin-based resin, especially polyolefin-based resin, is used as the non-halogen-based thermoplastic resin from the viewpoints of various physical properties, processability, versatility, economy, etc. It is most preferable to do. 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 21 may include, for example, a filler, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a lubricant, a flame retardant, an antibacterial agent, an antifungal agent, and a reduction agent, if necessary. One or more selected from various additives such as a lubricant, a light scattering agent, and a gloss adjusting agent may be added.

(Front side transparent skin layer 22 and back side transparent skin layer 23)
The front surface side transparent skin layer 22 and the back surface side transparent skin layer 23 (hereinafter, also referred to as “transparent skin layers 22, 23”) use the same type of thermoplastic resin, for example, a transparent polypropylene resin, as a nano-sized additive. (Hereinafter, also referred to as "dispersant nano-specification").
Therefore, the transparent raw fabric layer 20 is formed of two types and three layers.
Further, the transparent skin layers 22 and 23 also used are blended with a weather resistant agent in the same manner as the transparent core layer 21.
Further, the transparent skin layers 22 and 23 may be formed by adding an inorganic filler in addition to the dispersant (hereinafter, also referred to as “inorganic nanoparticles specification”). That is, the transparent skin layers 22 and 23 may have only the dispersant nano-specification, or may have an inorganic nanoparticle specification in addition to the dispersant nano-specification.

(Surface transparent skin layer 22)
The surface-side transparent skin layer 22 is on the side of the surface protection layer 60 and is located on the surface of the transparent core layer 21.
Surface side As shown in FIG. 2, an uneven pattern portion 24 is formed on the surface side of the transparent skin layer 22. The uneven pattern portion 24 is formed in an embossed plate into a shape that matches the desired design and performance when the original fabric is formed.

(Transparent skin layer 23 on the back side)
The back surface side transparent skin layer 23 is located on the opposite side of the front surface side transparent skin layer 22 with the transparent core layer 21 sandwiched between them, that is, on the back surface side of the transparent core layer 21 which is the side of the printed pattern layer 30.

(Transparent skin layers 22, 23)
The transparent skin layers 22 and 23 are layers containing a resin material and a nucleating agent that improves the crystallinity of the resin material, and have an uneven shape on the surface. In the present embodiment, the nucleating agent is added to the resin material in the form of a vesicle of the nucleating agent contained in the outer membrane.
The thickness of the transparent skin layers 22 and 23 is preferably, for example, 1 μm or more and 50 μm or less, and more preferably 2 μm or more and 10 μm or less. When the thickness of the transparent skin layers 22 and 23 is 1 μm or more, the scratch resistance of the decorative sheet 1 is sufficiently high. Further, when the thicknesses of the transparent skin layers 22 and 23 are 50 μm or less, the bendability of the decorative sheet 1 does not become too high, and the decorative sheet is not flat even when the surface to which the decorative sheet 1 is attached is not flat. It can be installed in a state where the 10 is in close contact with the sticking surface.
Further, in the transparent raw fabric layer 20, for example, the thickness ratio of "front surface side transparent skin layer 22: transparent core layer 21: back surface side transparent skin layer 23" is "0.5: 9: 0.5". It is formed by simultaneous extrusion.

(Resin material)
Examples of the resin material constituting the transparent skin layers 22 and 23 include thermoplastic resins. The thermoplastic resin is not particularly limited, and the same resin material as the transparent core layer 21 can be used.

(Nucleating agent)
The transparent skin layers 22 and 23 contain a nano-sized nucleating agent. The nano-sized nucleating agent is preferably used by being added to the polypropylene resin in the form of a nucleating agent vesicle contained in a vesicle having an outer film of a single-layer film. Further, in the present embodiment, the nucleating agent in the resin constituting the transparent skin layers 22 and 23 may be included in the vesicle with a part of the nucleating agent exposed. Since the transparent skin layers 22 and 23 contain a nucleating agent, the crystallinity can be improved, and the scratch resistance (scratch resistance) of the decorative sheet 10 can be improved.
The nano-sized nucleating agent preferably has an average particle size of 1/2 or less of the wavelength region of visible light, and specifically, since the wavelength region of visible light is 400 nm or more and 750 nm or less, the average particle size Is preferably 375 nm or less.

Since the particle size of nano-sized nucleating agents is extremely small, the number of nucleating agents present per unit volume and the surface area increase in inverse proportion to the cube of the particle diameter. As a result, the distance between the nucleating agent particles 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 is immediately one. It comes into contact with the ends of crystals growing from the surface of other nucleating agent particles adjacent to the nucleating agent particles, and the ends of each crystal inhibit the growth and the growth of each crystal is stopped. Therefore, the average particle size of the spherulite in the crystal portion of the crystalline resin can be made small, for example, the spherulite size can be made small to 1 μm or less.
As a result, a resin film having a high degree of crystallinity and a high hardness can be obtained, and the stress concentration between the spherulites generated during the bending process is efficiently dispersed, so that the resin suppresses cracking and whitening during the bending process. A film can be realized.

When the nucleating agent is simply added, the nucleating agent in the resin secondarily aggregates to increase the particle size.
On the other hand, when the nucleating agent vesicle is added, the dispersibility in the resin is improved, so that the number of crystal nuclei relative to the amount of the added nucleating agent is significantly increased as compared with the case where the nucleating agent is simply added. do.
Therefore, the average particle size of the spherulites in the crystal portion of the resin becomes small, and it is possible to suppress the occurrence of cracking and whitening during bending. Therefore, the crystallinity can be further increased by adding the nucleating agent vesicle, and the elastic modulus can be improved and the processability can be further achieved.

The transparent skin layers 22 and 23 are, for example, preferably 0.05 parts by mass or more and 0.5 parts by mass or less, and more preferably 0.1 parts by mass or more and 0.3 parts by mass with respect to 100 parts by mass of the polypropylene resin as a main component. It is formed of a resin material to which a nucleating agent is added within the range of less than a part.
When the nucleating agent vesicle is used, the amount of the nucleating agent added to the resin material is the amount converted into the nucleating agent in the nucleating agent vesicle. If the amount of the nucleating agent added is less than 0.05 parts by mass, the crystallinity of polypropylene may not be sufficiently improved, and the scratch resistance of the transparent skin layers 22 and 23 may not be sufficiently improved. Further, when the amount of the nucleating agent added exceeds 0.5 parts by mass, the spherulite growth of polypropylene is conversely inhibited due to the excess of crystal nuclei, and as a result, the crystallinity of polypropylene is not sufficiently improved. The scratch resistance of the transparent skin layers 22 and 23 may not be sufficiently improved.
Here, the "main component" refers to a resin material that occupies 50% by mass or more of the resin materials constituting the transparent skin layers 22 and 23.

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

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

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

The outer membrane constituting the nucleating agent vesicle is composed of, for example, a monolayer membrane. The outer membrane is composed of a substance containing a biological lipid such as a phospholipid.
In the present specification, a nucleating agent vesicle whose outer membrane is composed of a substance containing a biolipid such as a phospholipid is referred to as a nucleating agent liposome.
Examples of the phospholipids constituting the outer membrane include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, yellow egg lecithin, hydrogenated yellow egg lecithin, soybean lecithin, hydrogenated soybean lecithin and the like. Examples thereof include glycerophospholipids, sphingomyelin, ceramide phosphorylethanolamine, ceramide phosphorylglycerol and other sphingolin lipids.

Other substances that form the outer membrane of the vesicle include, for example, nonionic surfactants and dispersants such as cholesterols or a mixture of triacylglycerols thereof.
Among these, examples of the nonionic surfactant include polyglycerin ether, dialkyl glycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene polyoxypropylene. Copolymer, polybutadiene-polyoxyethylene copolymer, polybutadiene-poly (2-vinylpyridine), polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactum copolymer, etc. One or more of the above can be used. As cholesterols, for example, cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholic acid, choleciferol and the like can be used.

Further, the outer membrane of the liposome may be formed from a mixture of a phospholipid and a dispersant.
In the decorative sheet 10 of the present embodiment, the nucleating agent vesicle is preferably a radical scavenger liposome having an outer membrane made of phospholipids, and by forming the outer membrane made of phospholipids, the decorative sheet 10 The compatibility between the resin material as the main component and the vesicle can be improved.
The nucleating agent is not particularly limited as long as it is a substance that becomes a starting point of crystallization when the resin crystallizes. Examples of the nucleating agent include phosphoric acid ester metal salt, benzoic acid metal salt, pimelic acid metal salt, rosin metal salt, benziliden sorbitol, quinacridone, cyanine blue and talc. In particular, in order to maximize the effect of the nanonization treatment, it is preferable to use a phosphoric acid ester metal salt, a benzoic acid metal salt, a pimelic acid metal salt, or a rosin metal salt, which is a non-melt type and can be expected to have good transparency. If the material itself can be made transparent by nano-treatment, colored quinacridone, cyanine blue, talc and the like can also be used. Further, the melt-type benzylidene sorbitol may be appropriately mixed and used with the non-melt-type nucleating agent.

As described above, the decorative sheet 10 of the present embodiment is characterized in that the transparent skin layers 22 and 23 contain a resin material and a nucleating agent.
Further, the decorative sheet 10 of the present embodiment is characterized in that when the transparent skin layers 22 and 23 are formed, a nucleating agent contained in a vesicle is added to the resin material to crystallize the resin material. Have. By adding the nucleating agent to the resin composition in a state of being encapsulated in the vesicle, the effect of dramatically improving the dispersibility of the nucleating agent in the resin material, that is, in the transparent skin layers 22 and 23 is achieved. .. On the other hand, it can be said that it is impractical because it is assumed that it may be difficult to directly identify the nucleating agent contained in the vesicle by the structure and characteristics of the finished product in the state of the decorative sheet 10. .. The reason is as follows.

The nucleating agent added in the vesicle state has a high dispersibility and is in a dispersed state, and even in the state of the laminated body which is the precursor of the produced decorative sheet 10, the transparent skin layer 22, It is highly dispersed in 23.
However, in the process of producing the decorative sheet 10, the laminate is usually subjected to various treatments such as compression treatment and hardening treatment, and such treatment causes the outer film of the vesicle containing the nucleating agent to be crushed or chemically treated. May react.

Therefore, depending on the treatment step of the decorative sheet 10, the outer film of the nucleating agent in the completed decorative sheet 10 is crushed or the state of chemical reaction varies, and the nucleating agent is included (foreskin) in the outer film. There is a high possibility that it has not been done.
If the enucleating agent is not included in the outer membrane, it is difficult to specify the physical properties of the enucleating agent in the numerical range, and is the constituent material of the crushed outer membrane the outer membrane of the vesicle? It may be difficult to determine whether the material was added separately from the nucleating agent.
As described above, the present disclosure is added in the state of a vesicle containing the nucleating agent, although there is a difference in that the nucleating agent is blended in a high dispersion with respect to the decorative sheet 10 as compared with the conventional case. In the state of the decorative sheet 10, it is assumed that it is impractical to specify the structure and characteristics of the decorative sheet 10 within the numerical range analyzed based on the measurement.

At least one surface of the transparent skin layers 22 and 23 has an uneven shape. The uneven shape is provided on one or both of the transparent skin layer 22 on the front surface side (the side of the surface protective layer 60) and the transparent skin layer 23 on the back surface side (the side of the printed pattern layer 30), and the uneven shape is provided on the front surface side (surface protection). It is preferably provided on the transparent skin layer 22 (on the side of the layer 60).

(Printed pattern layer 30)
As shown in FIG. 1, the printed pattern layer 30 is obtained by printing a printed pattern on the back surface side (lower side in the same figure) of the transparent raw fabric layer 20 by a gravure printing method, for example, with a urethane resin.

(Colored layer 40)
As shown in FIG. 1, the colored layer 40 is further mixed with a white pigment of titanium oxide with a urethane resin, for example, by a gravure printing method on the back surface side (lower side in the same figure) of the printed pattern layer 30. It is printed with a two-component urethane resin.

(Primer layer 50)
As shown in FIG. 1, the primer layer 50 is coated with a urethane resin on the back surface side (lower side in the same figure) of the colored layer 40 so that the solid content is 1 g / m ² by, for example, a gravure printing method. It was formed by

(Surface protection layer 60)
The surface protective layer 60 is also referred to as a top coat layer, and as shown in FIG. 1, the surface side (upper side in the same figure) of the transparent raw fabric layer 20 is subjected to corona treatment, and then an acrylic two-component curable resin (DIC) is applied. Acrylic urethane resin manufactured by Graphic Corporation) is applied to a thickness of 6 μm.

(Manufacturing method of decorative sheet 10)
As a method for manufacturing the decorative sheet 10, the transparent raw fabric layer 20 is simultaneously extruded to form the decorative sheet 10.
At this time, that is, at the time of forming the original fabric, the uneven pattern portion 24 is formed on the surface side of the surface side transparent skin layer 22.
The printed pattern layer 30, the colored layer 40, and the primer layer 50 are formed in this order on the back surface side of the produced transparent raw fabric layer 20.
Further, a surface protective layer 60 is formed on the surface side of the transparent raw fabric layer 20 to manufacture a decorative sheet 10.

(Effect of Embodiment 1)
According to the first embodiment, it is difficult to prepare a transparent raw fabric layer 20 having two or three layers by utilizing a technique of adding a dispersant as a nano-sized additive, which is difficult with conventional olefin-based decorative sheets. It has become possible to achieve scratch-resistant performance.

(Explanation of Embodiment 2 shown in FIG. 3)
The second embodiment will be described with reference to FIG.
As shown in FIG. 3, the second embodiment is characterized in that a print coat layer 70 is formed on the surface of the surface protective layer 60 by printing a synchronized pattern synchronized with the print pattern of the print pattern layer 30.
That is, the print coat layer 70 uses a low-gloss resin for the surface protection layer 60, uses the same resin as the surface protection layer 60 and has a high gloss, and is synchronized with the print pattern of the print pattern layer 30. The pattern is printed on the surface side of the surface protective layer 60.

(Effect of Embodiment 2)
According to the second embodiment, it was difficult to add the printed pattern layer to the multi-layer sheet and to express the synchronization with the surface protective layer on the surface of the decorative sheet. By giving it, it can be easily synchronized.

Hereinafter, Examples 1 and 2 of the sheet according to the present invention and Comparative Example 1 will be described. The present invention is not limited to the following Examples 1 and 2.

(Example 1)
In Example 1, an evaluation sheet was prepared by the following materials and procedures.
A blend of polypropylene resin and a weather resistant agent is used for the transparent core layer 21 (core layer) of the transparent raw fabric layer 20, and nano is used for the front surface side transparent skin layer 22 and the back surface side transparent skin layer 23 (skin layer). Using a transparent polypropylene resin formulated to add a dispersant as a size additive, "front side transparent skin layer 22: transparent core layer 21: back side transparent skin layer 23" is "0.5: 9: 0. Simultaneously extruded to a thickness ratio of "5" to prepare a transparent raw fabric layer 20 with a total thickness of 130 μm.

A pattern is printed on the back surface side of the transparent original fabric layer 20 with a urethane resin by a gravure printing method, and after the printed pattern layer 30 is applied, white titanium oxide is used with a urethane resin by a gravure printing method to conceal the printed pattern layer 30. The colored layer 40 was applied with a two-component urethane resin mixed with a pigment.
Further, a urethane resin was applied so that the solid content was 1 g / m ² by a gravure printing method to form a primer layer 50.
Then, after corona treatment is applied to the surface side of the transparent raw fabric layer 20, an acrylic two-component curable resin (acrylic urethane resin manufactured by DIC Graphic Corporation) having a thickness of 6 μm is used as the surface protective layer 60 (top coat layer). An evaluation sheet was prepared by applying the coating so as to be stubborn.

(Example 2)
Example 2 is the same as that of Example 1, but a transparent raw fabric layer 20 having a layer thickness of 50 μm is prepared, a low-gloss resin is used for the surface protection layer 60 (top coat layer), and a surface protection layer is used on the surface protection layer 60 (top coat layer). A synchronized pattern synchronized with the printed pattern of the printed pattern layer 30 was printed with the same resin as 60 to increase the gloss, and as shown in FIG. 3, a print coat layer 70 was formed to prepare an evaluation sheet.

(Comparative Example 1)
In Comparative Example 1, as shown in FIG. 4, a pigment-blended colored polyethylene sheet (manufactured by RIKEN TECHNOS) having a thickness of 55 μm is used as the colored raw fabric layer 110.
A pattern printing layer 120 was formed on the surface side of the colored raw fabric layer 110 by gravure printing using urethane ink (Lamister manufactured by Toyo Ink Mfg. Co., Ltd.).
70 μm of homopolypropylene resin (manufactured by Prime Polymer Co., Ltd.) is extruded and laminated on the surface side of the pattern printing layer 120 as a transparent PP layer 130, and further, the same acrylic two-component solution as in Example 1 is used as a surface protection layer 140 (top coat layer). Apply curable resin (acrylic urethane resin manufactured by DIC Graphic) to a thickness of 6 μm.
Further, the same primer layer 150 as in Example 1 was applied to the back surface side of the colored raw fabric layer 110 to prepare an evaluation sheet (decorative sheet 100 of Comparative Example 1).

(Evaluation method and evaluation criteria)
The evaluation method of the evaluation sheet prepared above is as follows.
(1) Scratch test (2) Scratch hardness test (pencil hardness)
(Scratch test)
In the scratch test, a coin scratch test was performed on each of the evaluation sheets, and the load when no continuous scar was generated on the surface of the evaluation sheet was measured.
In the scratch test, a 10-yen coin was applied to the surface of the evaluation sheet, the test was started from a load of 1 kg, the load was gradually increased by 1 kg, and the test was performed up to 4 kg.

(Scratch hardness test)
The scratch hardness test was performed on each evaluation sheet by the scratch hardness (pencil method) test specified in JIS K5600-5-4: 1999, and the hardness of the hardest pencil (pencil) that did not cause scars on the surface of the evaluation sheet. Hardness) was measured.

(Evaluation criteria)
In the scratch test, a load of "1 kg" or more was passed, and other than that, it was rejected.
In the scratch hardness test, the pencil hardness (pencil hardness) of "2B" or higher was accepted, and the others were rejected.

(Evaluation results)
The evaluation results of the evaluation sheet are shown in Table 1 below.

(Examples 1 and 2 and Comparative Example 1)
Of the three evaluation sheets of Examples 1 and 2 and Comparative Example 1, only the two evaluation sheets of Examples 1 and 2 are "passed".
The remaining one evaluation sheet of Comparative Example 1 was "Fail".
It can be inferred that Comparative Example 1 is caused by the fact that the colored raw fabric layer 110 is not nano-processed.
Further, it can be inferred that the difference between the scratch test and the scratch hardness test in Example 1 and Example 2 is due to the thickness of the evaluation sheet. That is, it can be inferred that the thicker evaluation sheet of Example 1 is more advantageous in the scratch test and the scratch hardness test than in Example 2.

10 Decorative sheet 20 Transparent raw fabric layer 21 Transparent core layer 22 Front side transparent skin layer 23 Back side transparent skin layer 24 Concavo-convex pattern part 30 Printed pattern layer 40 Colored layer 50 Primer layer 60 Surface protective layer 70 Printed coat layer 100 Comparative example 1 Decorative sheet 110 Colored original fabric layer 120 Picture printing layer 130 Transparent PP layer 140 Surface protection layer 150 Primer layer

Claims (6)

It is located in the order of colored layer, printed pattern layer, transparent raw fabric layer, and surface protection layer.
The transparent raw fabric layer is
With a transparent core layer,
A surface-side transparent skin layer located on the surface of the transparent core layer, which is on the side of the surface protective layer,
A back surface side transparent skin layer located on the back surface of the transparent core layer on the opposite side of the front surface side transparent skin layer across the transparent core layer.
Consists of
The front surface side transparent skin layer and the back surface side transparent skin layer are
Using the same type of thermoplastic resin,
A decorative sheet characterized by the addition of a dispersant as a nano-sized additive. The front surface side transparent skin layer and the back surface side transparent skin layer are
The decorative sheet according to claim 1, wherein an inorganic filler is added. On the surface of the surface protective layer,
The decorative sheet according to claim 1 or 2, wherein a print coat layer is formed by printing a synchronized pattern synchronized with the printed pattern of the printed pattern layer. On the surface side of the surface side transparent skin layer,
The decorative sheet according to any one of claims 1 to 3, wherein an uneven pattern portion is formed. It is located in the order of colored layer, printed pattern layer, transparent raw fabric layer, and surface protection layer.
The transparent raw fabric layer is
With a transparent core layer,
A surface-side transparent skin layer located on the surface of the transparent core layer, which is on the side of the surface protective layer,
A back surface side transparent skin layer located on the back surface of the transparent core layer on the opposite side of the front surface side transparent skin layer across the transparent core layer.
It is a manufacturing method of a decorative sheet composed of
The front surface side transparent skin layer and the back surface side transparent skin layer are
Using the same type of thermoplastic resin,
Add a dispersant as a nano-sized additive,
The transparent raw fabric layer is
A method for manufacturing a decorative sheet, which comprises simultaneous extrusion molding. The front surface side transparent skin layer and the back surface side transparent skin layer are
The method for producing a decorative sheet according to claim 5, wherein an inorganic filler is added.

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