JP2017170732A - Cosmetic sheet and cosmetic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet and a decorative material having excellent weather resistance and flame-shielding performance. SOLUTION: A decorative sheet 10 is printed on a vinyl chloride resin raw fabric layer 1 formed by using a vinyl chloride resin and on the vinyl chloride resin raw fabric layer 1 without using carbon black as a black pigment. A layer 3 and a transparent acrylic resin layer 5 formed on the printing layer 3 using an acrylic resin are provided. Perylene black is used as the black pigment in the printing layer 3. The transparent acrylic resin layer 5 may be formed of the acrylic resin alone, or may be formed of a mixture of the acrylic resin and polyvinylidene fluoride or a two-layer structure. Here, the content of the acrylic resin in the entire resin contained in the transparent acrylic resin layer is preferably 90% or more and 100% or less, and the content of polyvinylidene fluoride is preferably 0% or more and 10% or less. [Selection diagram] Fig. 1

Description

  The present invention relates to a decorative sheet used indoors and outdoors as a building material and a decorative material using the same.

  Conventionally, a decorative sheet using an olefin-based resin having excellent weather resistance as a base material layer has been used for exterior members such as entrance doors, frame materials, and window frames (see Patent Document 1).

JP 2013-78847 A

  However, a decorative sheet mainly composed of an olefin resin is excellent in weather resistance, but has a problem that it does not have flameproof performance.

  This invention is made | formed in view of such a situation, Comprising: It aims at providing the decorative sheet and cosmetics which are excellent in a weather resistance and have flame-shielding performance.

  In order to solve the above problems, a decorative sheet according to an aspect of the present invention is formed on a vinyl chloride resin original fabric layer formed using a vinyl chloride resin, and on the vinyl chloride resin original fabric layer, and It is characterized by comprising a printing layer not using carbon black as a black pigment, and a transparent acrylic resin layer formed using an acrylic resin on the printing layer.

  The decorative material according to one aspect of the present invention is the above-described decorative sheet, and a metal plate on which the back side of the surface on which the printed layer of the vinyl chloride resin original layer is formed is bonded to the decorative sheet, It is characterized by providing.

  According to one embodiment of the present invention, it is possible to provide a decorative sheet and a decorative material having excellent weather resistance and flameproof performance.

It is sectional drawing which shows typically the structural example of the decorative sheet 10 and the decorative material 20 which concern on one Embodiment of this invention.

<Embodiment>
Hereinafter, a decorative sheet and a decorative material according to an embodiment of the present invention will be described with reference to the drawings. Here, the drawings are schematic, and the relationship between the thickness and the planar dimensions, the ratio of the thickness of each layer, and the like are different from the actual ones. Further, the embodiment described below exemplifies a configuration for embodying the technical idea of the present invention, and the technical idea of the present invention is that the material, shape, structure, etc. of the component parts are as follows. It is not something specific. The technical idea of the present invention can be variously modified within the technical scope defined by the claims described in the claims.

  As shown in FIG. 1, the decorative material 20 according to this embodiment includes a base material 11, an adhesive layer 12, and a decorative sheet 10. Here, the base material 11, the adhesive layer 12, and the decorative sheet 10 are laminated in this order. The decorative material 20 is used as a fireproof decorative material for exteriors such as an entrance door.

(Base material)
The base material 11 is used by sticking (laminating) the decorative sheet 10 to the surface. Examples of the base material 11 include various materials such as a metal base material and a wood base material. Examples of the metal-based substrate include a metal plate (single unit) and an alpolic material. As the metal plate, aluminum, galvalume steel plate, stainless steel, titanium or the like is used. The Alpolic material is an aluminum resin composite plate in which a resin material is sandwiched between metal plates that have been subjected to surface processing such as painting or mirror finishing. As this resin material, for example, polyethylene alone or a material obtained by adding an inorganic material to polyethylene is used. Moreover, as a wood-type base material, MDF (medium density fiberboard), a plywood, a particle board etc. are used, for example.
In this embodiment, from the viewpoint of imparting fireproof performance (fireproof performance) to the decorative material 20, a metal plate is particularly preferable as the base material 11. The thickness of the base material 11 is preferably about 0.3 mm or more and 1.0 mm or less.

(Adhesive layer)
The adhesive layer 12 is a layer formed using an adhesive to bond the base material 11 and the decorative sheet 10 together. Any adhesive may be used as long as it is a known adhesive used for bonding a decorative sheet and a substrate. In the present embodiment, for example, the adhesive layer 12 can be formed using a reactive hot-melt adhesive. In particular, the adhesive layer 12 may be formed using a two-component polyurethane adhesive among reactive hot-melt adhesives. Among such adhesive layers 12, in this embodiment, it is particularly desirable to use a member that has been certified non-combustible according to the regulations of the Japan Wallcovering Association. The adhesive layer 12 may contain an ultraviolet absorber or a light stabilizer. The thickness of the adhesive layer 12 is preferably about 5 μm or more and 50 μm or less.

  In addition, depending on the kind of adhesive which affixes the decorative sheet 10 to the base material 11, the adhesiveness with resin which comprises the lower layer (adhesion side) of the decorative sheet 10 may be considered. In consideration of such a case, a primer layer (not shown) made of a primer agent (undercoating agent) may be provided between the adhesive layer 12 and the decorative sheet 10. Alternatively, the adhesive layer 12 itself may be a primer layer made of a primer agent. The primer agent is not particularly limited, and a known primer agent can be used. For example, various primer agents such as urethane, acrylic, ethylene-vinyl acetate copolymer system, vinyl chloride-vinyl acetate copolymer system and the like can be used. Moreover, you may add powder, such as a silica, an alumina, a calcium carbonate, barium sulfate, to the primer agent which comprises a primer layer. Thereby, the surface of a primer layer can be roughened, the blocking at the time of winding-up preservation | save of the decorative sheet 10 can be prevented, and adhesiveness with the adhesive agent for lamination can be improved by the anchoring effect.

(Decorative sheet)
The decorative sheet 10 is a thermoplastic decorative sheet, and includes a vinyl chloride resin original fabric layer 1, a printed layer 3 formed on the vinyl chloride resin original fabric layer 1, and a transparent acrylic resin layer formed on the printed layer 3. 5 is provided.
Moreover, the back side (namely, back side) of the surface in which the printing layer 3 of the vinyl chloride resin raw fabric layer 1 was formed in the decorative sheet 10 is attached to the base material 11 via the adhesive layer 12. .

(Vinyl chloride resin raw layer)
The vinyl chloride resin original fabric layer 1 is a sheet base material layer (original fabric) formed using a vinyl chloride resin. In this embodiment, the vinyl chloride resin is not a semi-rigid vinyl chloride resin but an ordinary vinyl chloride resin (including a soft vinyl chloride resin). The resin constituting the vinyl chloride resin original fabric layer 1 is preferably only a normal vinyl chloride resin. That is, the vinyl chloride resin original fabric layer 1 is preferably a resin sheet made of a normal vinyl chloride resin alone. The vinyl chloride resin original fabric layer 1 can be obtained by molding a vinyl chloride resin into a sheet shape by an extrusion molding method, an inflation molding method, a calendar molding method or the like. The thickness of the vinyl chloride resin original fabric layer 1 is preferably about 70 μm or more and 150 μm or less.

  Moreover, you may add an ultraviolet absorber (a benzotriazole type ultraviolet absorber, a triazine type ultraviolet absorber, a benzophenone type ultraviolet absorber etc.) to the vinyl chloride resin original fabric layer 1 as a weather resistance prescription. The addition amount of the ultraviolet absorber may be added according to the desired weather resistance, but is 0.1% or more and 10% or less, preferably 1% or more and 5% or less with respect to the resin solid content.

  Among the UV absorbers, examples of the benzotriazole UV absorber include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole and 2- (5-methyl-2-hydroxyphenyl) benzo. Triazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole , 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-o (Cutylphenyl) benzotriazole and the like, mixtures thereof, modified products, polymers and derivatives.

Examples of the triazine ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4- [(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[( 2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4dimethylphenyl) -1,3,5-triazine, 2,4-bis (2,4 -Dimethylphenyl) -6- (2-hydroxy-4-iso-octyloxyphenyl) -s-triazine and the like, and mixtures, modified products, polymerized products and derivatives thereof can be used.
Furthermore, as the benzophenone-based ultraviolet absorber, for example, octabenzone, modified products thereof, polymers, and derivatives can be used.

In addition, a hindered amine light stabilizer may be added to the original vinyl chloride resin layer 1 in order to prevent the resin itself from being deteriorated by light, heat, water or the like. The hindered amine light stabilizer may be added in accordance with the desired weather resistance, but is 0.1% or more and 10% or less, preferably 1% or more and 5% or less with respect to the resin solid content.
Examples of hindered amine light stabilizers include bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl]. Methyl] butyl malonate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-popperidinyl) sebacate, bis-decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, etc., and mixtures, modified products, polymers, derivatives, etc. thereof can be used.

Furthermore, for the vinyl chloride resin constituting the original vinyl chloride resin layer 1, an antioxidant, a heat stabilizer, a plasticizer, a lubricant, an antistatic agent, a flame retardant, a filler, etc., depending on the use of the decorative sheet 10 These additives may be added.
Examples of the antioxidant include phenol-based, sulfur-based, and phosphorus-based agents. Examples of the heat stabilizer include hindered phenols, sulfurs, and hydrazines. Moreover, as a plasticizer, although it depends on the kind of resin, for example, phthalic acid ester type, phosphoric acid ester type, fatty acid ester type, aliphatic dibasic acid ester type, oxybenzoic acid ester type, epoxy type, polyester type Etc. Furthermore, examples of the lubricant include fatty acid ester, fatty acid, metal soap, fatty acid amide, higher alcohol, and paraffin. Examples of the antistatic agent include cationic, anionic, nonionic, amphoteric and the like. Furthermore, examples of the flame retardant include bromine, phosphorus, chlorine, nitrogen, aluminum, antimony, magnesium, boron, and zirconium. Examples of the filler include calcium carbonate, barium sulfate, talc, wax, and kaolin.

(Print layer)
The printed layer 3 is provided for the purpose of imparting a desired decorative design to the target decorative sheet. In the present invention, a printed layer 3 having an appropriate pattern is provided on the surface of the original vinyl chloride resin layer 1 by means of a printing method or the like. The printing layer 3 is provided using a pigment suitable for the vinyl chloride resin original fabric layer 1.

  As the pigment, a perylene-based black pigment is used as the black pigment. A typical perylene black pigment is perylene black. Existing decorative sheets often use carbon black as a black pigment and have low reflectance in the near-infrared light region (0.781 μm to 2.5 μm). In the decorative sheet 10 according to the present embodiment, carbon black is not used as a black pigment (carbon black is not used), and a perylene-based black pigment is used. Therefore, heat storage action occurs due to heat absorption by infrared light. The problem can be improved. Thereby, the thermal insulation performance is provided to the decorative sheet 10, and the problem of warping when used as a surface member such as an entrance door can be solved.

Alternatively, black may be expressed by mixing an isoindolinone pigment (yellow), a diketopyrrolopyrrole pigment (red), and a phthalocyanine pigment (blue) without using a black pigment.
Further, as the pigment other than the black pigment, at least one pigment of isoindolinone, disazo, polyazo, diketopyrrolopyrrole, quinacridone, phthalocyanine, and titanium oxide is used for the printing layer 3.
The same applies to the pigment used for coloring the vinyl chloride resin raw fabric layer 1 that is the base of the printing layer 3.

The inventors of the present invention printed a pattern using the above pigments, and measured the total infrared light transmittance of the printed layer 3. According to this measurement, the transmittance of light having a wavelength of 0.781 μm or more and 2.5 μm or less was 40% or more.
In addition, for the printing layer 3, for example, extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesion aids, drying agents, heat stabilizers, weathering stabilizers, curing agents, curing accelerators, as necessary. Various additives such as an agent or a curing retarder can also be added as appropriate.

  The method for forming the printing layer 3 is not particularly limited, and various conventional printing methods such as a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an ink jet printing method are used. can do. In addition, for example, in the case of a solid surface, in addition to the above-described various printing methods, for example, roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method Various coating methods such as a dip coating method can also be used. In addition, for example, a hand-drawn method, ink-sink method, photographic method, laser beam or electron beam drawing method, partial vapor deposition method or etching method of metal or the like, or a combination of these methods can of course be performed.

Further, prior to the formation of the printing layer 3, the surface of the vinyl chloride resin raw fabric layer 1 is subjected to, for example, corona treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, anchor or primer treatment as necessary. By performing the surface treatment, adhesion between the vinyl chloride resin original fabric layer 1 and the printing layer 3 can be improved.
There are no particular restrictions on the type of the pattern that the printed layer 3 constitutes, and a wood grain pattern, a stone pattern, a cloth pattern, an abstract pattern, a geometric pattern, or the like that has been widely used in the field of decorative sheets, or a simple coloring. In the case of aiming at color adjustment, it may be a solid color. In short, any desired picture can be adopted depending on the intended use of the decorative sheet.

(Transparent acrylic resin layer)
The transparent acrylic resin layer 5 is a transparent film-like layer made of an acrylic resin. Here, “transparent” means that light in almost the entire wavelength range of visible light, or light in a part of the wavelength range of visible light passes through the transparent acrylic resin layer 5, and A state in which the other side can be seen from one side.
The transparent acrylic resin layer 5 needs to have transparency that allows the pattern print layer 2 to be seen through, and is most preferably colorless and transparent, but may be colored and translucent. As long as that is the case, the transparent acrylic resin layer 5 may contain a colorant and a filler.

As the acrylic resin, for example, those obtained by singly or copolymerizing an acrylic acid derivative such as acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, acrylic ester, or methacrylic ester as a main component may be used. it can. In particular, a resin mainly composed of a methacrylic acid ester such as methyl methacrylate, for example, from a long-chain alkyl ester of methacrylic acid such as butyl methacrylate, an acrylic acid ester such as methyl acrylate, methacrylic acid or acrylic acid, etc. Flexibility and thermoforming by adding selected monomers as copolymerization components or graft copolymerization, block copolymerization or blending of rubber components such as styrene-butadiene rubber or methyl methacrylate-butadiene rubber Resin etc. which improve property can be used conveniently.
In this embodiment, polymethyl methacrylate (PMMA) resin is used as an example of the acrylic resin.

Moreover, in this embodiment, the transparent acrylic resin layer 5 is a single layer (one layer) structure by the acrylic resin single-piece | unit or the mixture of an acrylic resin and polyvinylidene fluoride (PVDF), or an acrylic resin and polyvinylidene fluoride (PVDF). The two-layer structure is used.
Further, acrylic resin rubber may be mixed with the acrylic resin. That is, the layer containing an acrylic resin may be formed of a mixture of an acrylic resin and an acrylic resin rubber.
In addition, it is preferable to add an ultraviolet absorber and a hindered amine light stabilizer to the transparent acrylic resin layer 5.

Further, the thickness of the transparent acrylic resin layer 5 is preferably thicker than 40 μm and about 70 μm or less. For example, when the thickness of the transparent acrylic resin layer 5 is 50 μm, the thickness of the acrylic resin is 50 μm when the transparent acrylic resin layer 5 is formed of a single acrylic resin. In addition, when formed with a two-layer structure of an acrylic resin and polyvinylidene fluoride (PVDF), the acrylic resin is the lower layer, the polyvinylidene fluoride (PVDF) is the upper layer, the thickness of the acrylic resin is 45 μm, and the polyvinylidene fluoride. The thickness of (PVDF) is 5 μm. That is, PVDF / acrylic resin = 1/9.
In other words, the acrylic resin content in the entire resin contained in the transparent acrylic resin layer 5 is 90% to 100%, and the polyvinylidene fluoride (PVDF) content is 0% to 10% (however, the acrylic resin). And the total content of polyvinylidene fluoride (PVDF) are preferably 100%).
Thus, the content rate of polyvinylidene fluoride (PVDF) is 0% or more and 10% or less, which is preferable from the viewpoint of weather resistance related to moisture. In addition, when the content rate of a polyvinylidene fluoride (PVDF) is 0%, the transparent acrylic resin layer 5 becomes a single | mono layer (one layer) structure by an acrylic resin single-piece | unit. In addition, since the cost increases when the content of polyvinylidene fluoride (PVDF) exceeds 10%, the content of polyvinylidene fluoride (PVDF) is to suppress the increase in cost while ensuring the necessary weather resistance. About 10% or less is sufficient.

(Uneven pattern)
A desired appropriate uneven pattern (emboss) may be provided on the surface of the transparent acrylic resin layer 5 as necessary. As the uneven pattern, for example, various patterns such as wood grain (particularly conduit pattern), cork, stone pattern, abstract pattern, simple matte shape, grain shape, hairline shape, suede tone, etc. You can choose a concavo-convex pattern suitable for your needs. Further, the concavo-convex pattern can be further improved in design by synchronizing with the pattern of the pattern printing layer 2, but if not necessary, the pattern may be out of sync with the pattern of the pattern printing layer 2. It is good also as an uneven | corrugated pattern including both the uneven | corrugated pattern synchronized with the pattern of the printing layer 2, and the uneven | corrugated pattern which does not synchronize with a pattern.

The method for forming the uneven pattern is not particularly limited, and a known forming method can be used. For example, a mechanical embossing method using a metal embossing plate may be used. Moreover, the formation time of the concavo-convex pattern is not particularly limited, and any time of before or after the lamination of the transparent acrylic resin layer 5 or after the lamination can be used. In addition, you may complete a concavo-convex pattern in multiple times by forming the same or different concavo-convex pattern in several periods.
Furthermore, it does not specifically limit as a formation method of the transparent acrylic resin layer 5, A known formation method can be used. For example, an extrusion molding method, an inflation molding method, a calendar molding method, or a cast molding method may be used.

(Effect of this embodiment)
As described above, the decorative sheet 10 according to the present embodiment is formed on the vinyl chloride resin original fabric layer 1 formed using the vinyl chloride resin, the vinyl chloride resin original fabric layer 1, and as a black pigment. A carbon black-free printing layer 3 and a transparent acrylic resin layer 5 formed on the printing layer 3 using an acrylic resin are provided.
Thereby, since the decorative sheet 10 has excellent weather resistance and flame retardancy, for example, a decorative material in which the decorative sheet 10 is attached to a metal plate (base material 11) selected from aluminum, stainless steel, copper, and a steel plate. 20 can pass the flame-proof performance test mentioned later. Therefore, it is possible to provide the decorative sheet 10 and the decorative material 20 having excellent weather resistance and flameproof performance.

Examples of the present embodiment and comparative examples are shown below. In addition, this embodiment is not limited to the following Example.
[Example 1]
A vinyl chloride resin raw material in which 3 parts by weight of a hindered phenolic antioxidant, 1 part by weight of an ultraviolet absorber, 1 part by weight of a hindered amine light stabilizer, and 23 parts by weight of titanium oxide are added to 100 parts by weight of a vinyl chloride resin. Layer 1 was formed. The thickness of the vinyl chloride resin original fabric layer 1 is 70 μm.
2 parts of hexamethylene diisocyanate and isophorone diisocyanate are added to 100 parts by mass of a binder resin in which urethane resin and vinyl chloride = vinyl acetate copolymer resin are mixed at a ratio of 7: 3 on the surface of the original vinyl chloride resin layer 1. : Using a printing ink in which 3 parts by weight of a curing agent mixed at a ratio of 8 is added, black pigment is perylene black, and pigments other than black pigment are 3 parts by weight of a pigment composed of isoindolinone, polyazo, and phthalocyanine Then, an aluminum-like hairline pattern was formed by gravure printing to obtain a printing layer 3. The thickness of the printing layer 3 is 2 μm.
Next, a mixture of 40:60 polymethyl methacrylate (PMMA) resin and PMMA resin rubber by mass ratio on the printing layer 3 (however, 0.5 mass percent of benzotriazole ultraviolet absorber: Tinuvin 326) (Wt%) addition) was used to form the transparent acrylic resin layer 5. The thickness of the transparent acrylic resin layer 5 is 50 μm.
Here, the decorative acrylic sheet 10 of Example 1 was obtained by laminating the transparent acrylic resin layer 5 on the printing layer 3 by a thermal laminating method. Then, this decorative sheet 10 was bonded to a 0.5 mm-thick galvanized steel sheet (metal plate) serving as the base material 11 via the adhesive layer 12 to obtain a decorative material 20 of Example 1. That is, the decorative material 20 is a decorative steel plate material.

(Mixture for forming transparent acrylic resin layer)
The composition of the mixture for forming the transparent acrylic resin layer is as follows.
Acrylic resin (constituent unit: methyl methacrylate): 40 parts by mass Acrylic resin rubber ("SA-FW001 (trade name)", manufactured by Kuraray Co., Ltd., methacrylic resin, constituent unit: methyl methacrylate, particulate, average Particle size: 100 nm): 60 parts by mass

[Example 2]
The composition of the mixture for forming the transparent acrylic resin layer was changed as follows.
Acrylic resin (constituent unit: methyl methacrylate): 36 parts by mass Acrylic resin rubber ("SA-FW001 (trade name)", manufactured by Kuraray Co., Ltd., methacrylic resin, constituent unit: methyl methacrylate, particulate, average (Particle diameter: 100 nm): 54 parts by mass / polyvinylidene fluoride (PVDF): 10 parts by mass Note that a two-layer structure of acrylic resin (+ acrylic resin rubber) and polyvinylidene fluoride (PVDF) may be used. In this case, the thickness of the acrylic resin (+ acrylic resin rubber) is 45 μm, the thickness of polyvinylidene fluoride (PVDF) is 5 μm, and the total thickness of the transparent acrylic resin layer 5 is 50 μm.
Otherwise, the decorative sheet 10 and the decorative material 20 of Example 2 were obtained in the same manner as in Example 1.

[Comparative Example 1]
Instead of the original vinyl chloride resin layer 1, 3 parts by mass of a hindered phenol antioxidant, 1 part by mass of an ultraviolet absorber, 100 parts by mass of a hindered amine light stabilizer, based on 100 parts by mass of an olefin resin polypropylene resin (PP) An olefin resin original fabric layer to which 1 part by mass and 23 parts by mass of titanium oxide were added was formed into a film. The thickness of this olefin resin raw fabric layer is 70 μm.
Hexamethylene diisocyanate and isophorone diisocyanate are mixed with 100 parts by mass of binder resin in which urethane resin and vinyl chloride = vinyl acetate copolymer resin are mixed at a ratio of 7: 3 on this olefinic resin raw material layer. 3 parts by weight of a curing agent mixed at a ratio of 8 is used, and a printing ink in which 3 parts by weight of a pigment composed of carbon black as a black pigment and isoindolinone, polyazo, and phthalocyanine as a pigment other than a black pigment is added, An aluminum-like hairline pattern was formed by gravure printing to obtain a printed layer.
Next, a solution obtained by adding 0.5 parts by mass of a benzotriazole-based ultraviolet absorber and 0.3 parts by mass of a hindered amine-based light stabilizer to 100 parts by mass of a random polypropylene-based resin on this printing layer by melt extrusion. An overlay film layer formed into a film was formed. The thickness of the overlay film layer after drying is 70 μm.
Thereby, the decorative sheet of Comparative Example 1 was obtained. Then, this decorative sheet was bonded to a metal plate to obtain a decorative material of Comparative Example 1.

(Test method)
(1) Flame-proof performance test As a flame-proof performance test, a test specimen (decorative material) is installed on the front surface of the wall furnace, and from the rear surface of the test specimen, the heating temperature is set to the standard heating temperature curve specified in ISO834 for 20 minutes. Heating. As a judgment method, it is confirmed whether or not the fire spreads to the non-heated side of the specimen during the heating time. Specifically, a case where the following (i) to (iii) are satisfied is regarded as acceptable.
(I) There shall be no flame eruption continuing over 10 seconds to the non-heating side.
(Ii) There should be no flame that continues for more than 10 seconds on the non-heated surface.
(Iii) No damage such as cracks through which the flame passes and no gaps.

(2) Thermal barrier performance test The solar reflectance of the coating film was measured according to JISK5602. The measurement was performed using a spectrophotometer UV3600 manufactured by Shimadzu Corporation. Here, a case where the solar reflectance of the coating film is 40% or more is regarded as acceptable “◯”, and a case where the solar reflectance of the coating film is 40% or less is regarded as unacceptable “x”.

(3) Thermal storage performance test The decorative sheet 10 was bonded only on one side to an uncoated steel sheet having a length of 21 cm, a width of 29.7 cm, and a thickness of 0.5 mm using an adhesive. A halogen bulb is installed at a position 15 cm above the decorative sheet 10, and the decorative sheet 10 is continuously irradiated with light from the halogen bulb for 120 minutes, and the temperatures of the front and back surfaces of the steel sheet are recorded every minute. The maximum value was measured.

(4) Weather resistance test As a weather resistance test, the test body (decorative material) is subjected to a test with a sunshine weather meter for 4000 hours. The test conditions are as follows. Then, the visual fading and peeling of the appearance of the specimen are confirmed by visual confirmation. A case where there is no significant discoloration and peeling is a pass “◯”, and a case where there is a significant discoloration and separation is a “fail”.
・ Irradiance 255 ± 25 W / m ²
・ Black panel temperature 63 ℃
・ There is rainfall for 12 minutes out of 60 minutes

(5) Bending performance test As a bending performance test, the specimen (decorative material) is press-bent at a right angle in a 23 ° C atmosphere. The case where there is no crack at the bent part is determined as “good”, and the case where a crack is generated at the bent part is determined as “failed”.

(Test results)
The results of the above test are shown in Table 1 below. In Table 1, a circle (◯) indicates pass, a double circle (◎) indicates pass and particularly good, and a cross (×) indicates fail.

As shown in Table 1, Example 1 and Example 2 all passed the results of the flame shielding performance test, the heat shielding performance test, the weather resistance test, and the bending work performance test. Particularly, in Example 2, the results of the weather resistance test were very good. Moreover, about the temperature of the surface and back surface of the steel plate in a thermal storage performance test, Example 1 was 62 degreeC and Example 2 was 60 degreeC.
On the other hand, in Comparative Example 1, the results of the flame barrier performance test, the thermal barrier performance test, and the bending performance test were unacceptable. Moreover, the comparative example 1 was 70 degreeC about the temperature of the surface and the back surface of the steel plate in a thermal storage performance test.

From the above results, it was confirmed that the specimens (decorative materials) of Example 1 and Example 2 had flame shielding performance, heat shielding performance, and weather resistance, and were excellent in bending performance.
In particular, it can be confirmed that the test specimen of Example 2 has improved weather resistance even when compared with the test specimen of Example 1. Thereby, it turned out that weather resistance improves further by combining an acrylic resin and a polyvinylidene fluoride (PVDF) appropriately rather than when an acrylic resin is used alone.

  Since the decorative sheet and the decorative material of the present invention described above are less likely to warp even when exposed to sunlight, they are surface members such as building materials used in places where they may be exposed to sunlight, both indoors and outdoors. It is suitable for use as.

  While the present invention has been described with reference to specific embodiments, it is not intended that the invention be limited by these descriptions. From the description of the invention, other embodiments of the invention will be apparent to persons skilled in the art, along with various variations of the disclosed embodiments. Therefore, it is to be understood that the claims encompass these modifications and embodiments that fall within the scope and spirit of the present invention.

DESCRIPTION OF SYMBOLS 1 Vinyl chloride resin raw fabric layer 3 Printing layer 5 Transparent acrylic resin layer 10 Cosmetic sheet 11 Base material 12 Adhesive layer 20 Cosmetics

Claims (6)

A vinyl chloride resin raw fabric layer formed using a vinyl chloride resin;
A printing layer formed on the vinyl chloride resin raw fabric layer and not using carbon black as a black pigment;
A transparent acrylic resin layer formed using an acrylic resin on the printed layer;
A decorative sheet comprising:   The decorative sheet according to claim 1, wherein perylene black is used as the black pigment in the printed layer.   The decorative acrylic sheet according to claim 1 or 2, wherein the transparent acrylic resin layer is formed of a single acrylic resin.   The decorative sheet according to claim 1 or 2, wherein the transparent acrylic resin layer is formed of a mixture or a two-layer structure of an acrylic resin and polyvinylidene fluoride.   5. The acrylic resin content in the entire resin contained in the transparent acrylic resin layer is 90% to 100%, and the polyvinylidene fluoride content is 0% to 10%. The decorative sheet described in 1. A decorative sheet according to any one of claims 1 to 5,
A cosmetic material, comprising: a metal plate to which a back side of the surface of the vinyl chloride resin original fabric layer on which the printed layer is formed is attached.

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