JP2017177375A - Decorative sheet and decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet and a decorative material having heat shielding performance and fireproof performance.SOLUTION: A printed layer 13 on which a picture is printed and a plurality of transparent thermoplastic resin layers are sequentially laminated on one surface side of a colored thermoplastic resin substrate layer 11. A thermoplastic resin layer, which is an inner layer other than an outermost layer, of the plurality of transparent thermoplastic resin layers is composed of an acrylic resin, a transparent thermoplastic resin layer, which is the outermost layer, is composed of a fluorine resin and the moisture permeability of the fluorine resin is lower than the moisture permeability of the acrylic resin. The colored thermoplastic resin substrate layer 11 contains 10% or more and 45% or less of an inorganic material to have fireproof performance. Particularly, the thermoplastic resin substrate layer 11 contains at least one of calcium carbonate, titanium oxide and iron oxide as the inorganic material. In addition, thermoplastic resin substrate layer 11 may contain 3% or more and 5% or less of a bromine compound in order to improve fireproof performance and further may contain 1% or more and 2% or less of an antimony compound in order to improve fireproof performance.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative sheet used as a building material and a decorative material using the decorative sheet. The decorative sheet and the decorative material of the present invention are particularly suitable for use as an exterior.

A decorative sheet is used for various uses such as indoor and outdoor buildings and furniture and furniture as a building material that is inexpensive and excellent in processability. Among such decorative sheets, an exterior decorative sheet used outdoors is used by being attached to the surface of an exterior decorative steel sheet such as an entrance. The exterior decorative sheet is required to have weather resistance higher than that of the interior decorative sheet.
As decorative sheets having high weather resistance, decorative sheets using olefin-based materials are currently in practical use. The weather resistance is evaluated by actual outdoor exposure and accelerated weather resistance test. The weather resistance of a decorative sheet using an olefin-based material satisfies a practical condition. Such a decorative sheet is described in Patent Document 1, for example.

JP 2012-131112 A

However, the existing exterior decorative sheet was evaluated for weather resistance against ultraviolet light of sunlight, and although it was formulated, weather resistance against infrared light was not considered. In the exterior decorative sheet, heat is stored by absorbing infrared light, and expansion is caused by the stored heat being transmitted to the base material of the decorative sheet. When the base material of the decorative sheet expands, the decorative material to which the decorative sheet is bonded is warped, and the beauty of the building material and the function of protecting the building are deteriorated.
Furthermore, since the decorative sheet for exterior is often used as a building material as its application, fire prevention performance is also required.
The present invention has been made in view of the above points, and has an object to provide a decorative sheet and a decorative material having heat insulation performance, preventing warpage due to infrared light, and further having fire prevention performance. And

  In order to solve the above-described problem, the decorative sheet of one embodiment of the present invention includes a printed layer having a pattern printed on one surface side of the colored thermoplastic resin base material layer, and a plurality of transparent thermoplastic resin layers sequentially. Are stacked. Among the plurality of transparent thermoplastic resin layers, the thermoplastic resin layer that is the inner layer other than the outermost layer is made of an acrylic resin, the transparent thermoplastic resin layer that is the outermost layer is made of a fluororesin, and the moisture permeability of the fluororesin is Lower than moisture permeability of acrylic resin. The colored thermoplastic resin base material layer has fireproof performance by containing 10% or more and 45% or less of an inorganic material.

  Specifically, the colored thermoplastic resin substrate layer contains at least one of calcium carbonate, titanium oxide, and iron oxide as an inorganic material. The colored thermoplastic resin substrate layer may further contain 3% or more and 5% or less of a bromine compound in order to improve fire prevention performance. Moreover, the colored thermoplastic resin base material layer may further contain an antimony compound in an amount of 1% to 2% in order to improve fireproof performance.

  ADVANTAGE OF THE INVENTION According to this invention, while having heat insulation performance, while preventing the curvature by infrared light, the decorative sheet and decorative material which have fireproof performance further can be provided.

1 is a cross-sectional view of a decorative sheet according to an embodiment of the present invention and a decorative material using the decorative sheet.

  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.

(Cosmetic materials)
FIG. 1 is a cross-sectional view for explaining a decorative material 1 of the present embodiment. The decorative material 1 of the present embodiment includes a decorative sheet 3, a base material 20, and an adhesive layer 21 that bonds the decorative sheet 3 and the base material 20.
The decorative material 1 of the present embodiment increases the transmittance of the printing layer 13 for infrared light having a wavelength of 0.7 μm or more and 1000 μm or less, and reflects the transmitted infrared light by the colored thermoplastic resin base material layer 11. The heat storage of the base material 20 is prevented.

(Base material)
The base material 20 is used by attaching (laminating) the decorative sheet 3 to the surface. For example, a metal-based substrate can be used as the substrate 20. Examples of the metal base material include a metal plate and an Alpolic material. 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 the metal plate, for example, aluminum, galvalume steel plate, stainless steel, titanium or the like is used. As the resin material, for example, polyethylene alone or polyethylene added with an inorganic material is used.

(Adhesive layer)
Any adhesive layer 21 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 attaching the decorative sheet 3 to the base material 20, the adhesive layer 21 can be formed using an appropriate adhesive such as urethane or vinyl acetate. Alternatively, for example, the adhesive layer 21 can be formed using a reactive hot-melt adhesive. In particular, the adhesive layer 21 may be formed using a two-component polyurethane adhesive among reactive hot-melt adhesives. Furthermore, the adhesive layer 21 may contain an ultraviolet absorber, a light stabilizer, or the like.

  In addition, depending on the kind of adhesive which affixes the decorative sheet 3 to the base material 20, the case where the adhesiveness with resin which comprises the lower layer (adhesion side) of the decorative sheet 3 is inadequate is also 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 21 and the decorative sheet 3. Alternatively, the adhesive layer 21 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 3 of the present embodiment is obtained by sequentially laminating a printed layer 13 on which a pattern is printed and a plurality of transparent thermoplastic resin layers 5 on one side of a colored thermoplastic resin base material layer 11. That is, the decorative sheet 3 has a colored thermoplastic resin base material layer 11, a printing layer 13, a heat seal layer 15, and a transparent thermoplastic resin layer 5. The plurality of transparent thermoplastic resin layers 5 are composed of two or more transparent thermoplastic resin layers including an outermost layer 53 that is an outermost layer of the decorative sheet 3 and an inner layer 51 that is positioned below the outermost layer 53. . The outermost layer 53 and the inner layer 51 are both transparent thermoplastic resin layers, but the resins are different from each other.

Hereinafter, each layer of the decorative sheet 3 will be described.
(Colored thermoplastic resin base material layer)
The colored thermoplastic resin substrate layer 11 is a thermoplastic resin substrate layer such as a colored base film layer. Examples of the thermoplastic resin used for the colored thermoplastic resin base material layer 11 include polyolefin resins such as polyethylene, polypropylene, polybutene, and polymethylpentene, ethylene-vinyl acetate copolymer or a saponified product thereof, and ethylene- (meth). Polyolefin copolymers such as acrylic acid (ester) copolymers, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, copolymer polyester (typically 1,4-cyclohexanedimethanol copolymer polyethylene) Polyester resins such as terephthalate resin, commonly known as PET-G), acrylic resins such as polymethyl methacrylate, polyamide resins such as 6-nylon, 6,6-nylon, 6,10-nylon, 12-nylon, Styrene resins such as styrene, AS resin, ABS resin, cellulose derivatives, cellulose derivatives such as nitrocellulose, chlorine resins such as polyvinyl chloride and polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, Fluorine resins such as ethylene-tetrafluoroethylene copolymer, or two or more kinds of copolymers or mixtures selected from these, mixtures, composites, laminates, and the like can be used.
In this embodiment, a polyethylene raw fabric is used as an example of the colored thermoplastic resin base material layer 11.

As described above, the colored thermoplastic resin base material layer 11 contains a colorant to conceal the surface of the base material 20 or the like to which the decorative sheet 3 is bonded, but is not particularly limited thereto. The surface or the back surface may be provided with a concealing layer (not shown) or the pigment may be solid-printed.
In addition to the colorant, the colored thermoplastic resin base material layer 11 includes a filler (silica, talc, titanium oxide, barium sulfate, etc.), an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, One or more selected from various additives such as lubricants (stearic acid, metal soap, etc.), flame retardants, antibacterial agents, antifungal agents, antifriction agents, light scattering agents, gloss adjusting agents, etc. may be added. .

Moreover, in this embodiment, in order to raise the reflectance of the infrared light in the colored thermoplastic resin base material layer 11, you may add a titanium oxide to the said material, and you may make it contain in the colored thermoplastic resin base material layer 11. FIG. At this time, in this embodiment, when the colored thermoplastic resin base material layer 11 contains 23 parts by mass or more of titanium oxide, the heat shielding property is improved. When titanium oxide is used as the concealing layer, the total content of titanium oxide as the concealing layer and added titanium oxide may be 23 parts by mass or more. Moreover, when the coloring thermoplastic resin base material layer 11 contains 23 mass parts or more of titanium oxide as a concealing layer, it is not necessary to add titanium oxide any more.
However, when the amount of titanium oxide added to the colored thermoplastic resin substrate layer 11 increases, the titanium oxide affects the film quality of the colored thermoplastic resin substrate layer 11. For this reason, suitable content of the titanium oxide of the colored thermoplastic resin base material layer 11 is 23 to 40 mass parts.

  In the present embodiment, as shown in FIG. 1, a titanium oxide layer 111 may be provided by applying titanium oxide to the surface of the colored thermoplastic resin base material layer 11 on the printed layer 13 side. Even when the titanium oxide layer 111 is provided, if the colored thermoplastic resin base material layer 11 contains 23 parts by mass or more of titanium oxide by the titanium oxide layer 111, the base material 20 by the colored thermoplastic resin base material layer 11 is used. Improves heat insulation. Under such conditions, the thickness of the titanium oxide layer 111 is preferably 5 μm or more and 10 μm or less.

Specifically, the thickness of the colored thermoplastic resin base material layer 11 is about 20 μm or more and 300 μm or less, more preferably about 50 μm or more and 200 μm or less, although it depends on the use of the decorative sheet and the type of resin. good.
As a molding method of the colored thermoplastic resin base material layer 11, for example, an extrusion molding method, an inflation molding method, a calendar molding method, a cast molding method, or the like can be used.

[Fireproof performance]
Here, the colored thermoplastic resin base material layer 11 of this embodiment has fireproof performance (fireproof performance) by containing an inorganic material. As the inorganic material, for example, at least one of calcium carbonate, titanium oxide, iron oxide and the like can be used, and calcium carbonate is particularly preferable. In practice, titanium oxide and iron oxide may be added as inorganic pigments. The content of the inorganic material is preferably about 10% to 45%. When the content of the inorganic material is less than 10%, it becomes difficult to exhibit sufficient fire prevention performance. However, even if the total content of the inorganic material is 45% or less, if the content of calcium carbonate exceeds 20%, the roll of the machine may be scraped during the production of the base material, so the calcium carbonate itself The content of is preferably about 10% to 20%.

  Moreover, it is preferable that the colored thermoplastic resin base material layer 11 of the present embodiment also contains a bromine compound (bromine flame retardant) which is an organic flame retardant for improving fire prevention performance. As the bromine compound, for example, brominated flame retardants other than RoHS regulated substances such as polybrominated biphenyl (PBB) and polybrominated diphenyl ether (PBDE) can be used. The bromine compound content is preferably about 3% to 5%.

  Furthermore, the colored thermoplastic resin base material layer 11 of the present embodiment may also contain an antimony compound that is an inorganic flame retardant in order to improve fire prevention performance. The antimony compound is sometimes used as an auxiliary agent that increases the flame retardancy of the bromine compound. As the antimony compound, for example, antimony trioxide, antimony pentoxide and the like can be used, and antimony trioxide is particularly preferable. The content of the antimony compound is preferably about 1% to 2%.

  Thereby, in addition to heat insulation performance, high fireproof performance can be suitably imparted to the decorative sheet 3 according to the present embodiment. As a test method of fireproof performance, the decorative sheet 3 is stuck on one side of the base material 20, and the door which made the decorative sheet 3 the surface is created. The base material 20 with the decorative sheet 3 attached must be used for the non-heated side of the door, but whether or not the base material 20 with the decorative sheet 3 attached is used for the heated side of the door. is there. For example, if it is a door for fire prevention equipment for the purpose of preventing the spread of fire, the base material 20 with the decorative sheet 3 attached may not be used on the heating side of the door. On the other hand, if it is a door for the specific fire prevention equipment used for a fire prevention division, you must use the base material 20 which affixed the decorative sheet 3 also about the heating side of a door. Then, the heating side of this door is exposed to fire and heated, and if it is a door for fire prevention equipment, it will be confirmed that it will not spread to the non-heating side of this door for 20 minutes, if it is a door for specific fire prevention equipment To do. Specifically, there should be no flame eruption that continues for more than 10 seconds to the non-heated side, no flame that continues for more than 10 seconds on the non-heated surface, damage such as cracks through which the flame passes, and gaps. Check that it does not occur.

(Print layer)
The printing layer 13 of the present embodiment is provided by gravure printing or the like using an ink using a pigment. The printing layer 13 of this embodiment includes a solid printing layer 131 and a pattern layer 132. The solid print layer 131 is a print layer without a pattern, and the picture layer 132 is a layer for applying an arbitrary pattern to the decorative sheet 3. Examples of the pattern include a wood grain pattern, a stone pattern, a cloth pattern, an abstract pattern, and a geometric pattern. Furthermore, when the design is simply colored or color-adjusted, it may be a solid color. As the pattern of the pattern layer 132, an arbitrary pattern can be adopted according to the use of the decorative sheet 3.

Further, the solid print layer 131 and the pattern layer 132 may be either a single layer or a laminate of a plurality of layers.
The ink used for the solid print layer 131 and the pattern layer 132 may be any ink that can be printed on the colored thermoplastic resin base material layer 11. Specifically, the colored thermoplastic resin base material layer 11 is a random polypropylene type. If it is resin, the mixture of urethane resin and vinyl chloride = vinyl acetate copolymer resin is used suitably.

  In the present embodiment, a perylene pigment is used as the black pigment as the pigment used in the solid print layer 131. A typical perylene pigment is, for example, perylene black. Existing decorative sheets often use carbon black as a black pigment and have a low reflectance in the near-infrared light region (0.781 μm to 2.5 μm), but by using perylene black, infrared light Absorption of heat caused by heat can improve the problem of heat storage.

  Alternatively, an azomethine azo pigment may be used as the black pigment. By using an azomethine azo pigment, it is possible to reduce the absorption of infrared rays into the printing layer 13, suppress the heat storage function, and increase the infrared reflectance as a decorative sheet. The azomethine azo pigments have a diazonium group that is a reaction compound of tetrachlorophthalimide and aminoaniline, and those having a particle diameter of 0.1 μm to 0.3 μm are particularly suitable. By using these, characteristics such as absorption in the visible part and reflection in the infrared part are remarkably exhibited.

  Further, as the pigment other than the black pigment, for example, at least one selected from isoindolinone, disazo, polyazo, diketopyrrolopyrrole, quinacridone, phthalocyanine, and titanium oxide is used. Thus, the printing ink has an infrared light transmittance of 80% or more. Therefore, the printing layer 13 transmits infrared light, and the colored thermoplastic resin base material layer 11 reflects the transmitted infrared light, so that the heat storage effect due to the heat of infrared light is reduced.

  Also, when a solid print layer 131 is provided and, for example, a conduit of wood is expressed by the pattern layer 132, a black pigment is not used, but an isoindolinone pigment (yellow), a diketopyrrolopyrrole pigment (red). And black is expressed by mixing the phthalocyanine pigment (blue).

  With this configuration, the present embodiment obtains a deep design by combining the pattern layer 132 with the solid print layer 131, suppresses color change over time, and makes the reflectance in the infrared region more than a certain level. It is possible to raise.

  The inventors of the present invention printed a wood grain pattern on the solid print layer 131 using a perylene pigment, and measured the total infrared light transmittance of the print layer 13. 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.

  The inventors of the present invention printed a wood grain pattern on the solid print layer 131 using an azomethine azo pigment, and measured the total infrared light transmittance of the print layer 13. According to this measurement, the transmittance of light having a wavelength of 0.781 μm or more and 2.5 μm or less was 80% or more.

  In addition, for the printing layer 13, for example, extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesion assistants, drying agents, heat stabilizers, weathering stabilizers, curing agents, curing accelerators. Various additives such as an agent or a curing retarder can also be added as appropriate.

  The method for forming the printing layer 13 is not particularly limited, and various known 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. be able to. 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 13, if necessary, the surface of the colored thermoplastic resin base material layer 11 is treated with, for example, corona treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, anchor or primer treatment, etc. By performing this surface treatment, the adhesion between the colored thermoplastic resin base material layer 11 and the printing layer 13 can be improved.

(Heat seal layer)
The heat seal layer 15 is appropriately used when the colored thermoplastic resin base material layer 11 and the transparent thermoplastic resin layer 5 are firmly bonded. Although it is not necessary when the colored thermoplastic resin base layer 11 and the transparent thermoplastic resin layer 5 have adhesiveness, it is preferably used for increasing the interlayer strength. As the heat sealant used for the heat seal layer 15, an acrylic-polyester-vinyl acetate resin is suitable. However, the heat seal layer 15 of the present embodiment is not particularly limited to the acrylic-polyester-vinyl acetate resin.

(Transparent thermoplastic resin layer)
As described above, the transparent thermoplastic resin layer 5 of the present embodiment has a two-layer structure of the outermost layer 53 and the inner layer 51. As the inner layer 51, an acrylic resin is used. Specifically, for the inner layer 51, a methyl methacrylate resin, a polymethyl methacrylate resin (Tg is about −20 ° C.), or the like can be used. The thickness of the inner layer 51 is preferably in the range of 85% or more and 90% or less in the ratio of the total thickness of the transparent thermoplastic resin layer 5 in terms of weather resistance. Further, a known ultraviolet absorber may be added to the inner layer 51.

For the outermost layer 53 of this embodiment, a resin having a moisture permeability lower than the moisture permeability of the acrylic resin used for the inner layer 51 is used. In consideration of various resistances on the surface of the outermost layer 53, a fluororesin is preferably used for the outermost layer 53.
Specifically, as the material of the outermost layer 53, polyvinylidene fluoride (PVDF), tetrafluoroethylene resin (PTFE), tetrafluoroethylene perfluoroalkoxy vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoride Propylene copolymer (FEP), polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), polyvinyl fluoride (PVF), etc. Polyvinylidene fluoride (PVDF Tg is −39 ° C.) is particularly preferable in terms of bending whitening and adhesion to the acrylic resin layer.
In addition, it is preferable in terms of weather resistance that the outermost layer 53 contains moisture in a range of 5% to 15% of the total thickness of the transparent thermoplastic resin layer 5.
The total thickness of the outermost layer 53 and the inner layer 51 of the transparent thermoplastic resin layer 5 is preferably 20 μm or more and 80 μm or less, and particularly preferably 30 μm or more and 60 μm or less in terms of weather resistance.

  As described above, according to this embodiment, fire resistance can be imparted by adding an inorganic material to the colored thermoplastic resin substrate layer 11. Furthermore, fireproof performance can be improved by adding a brominated flame retardant or antimony trioxide as necessary.

  Further, according to the present embodiment, a perylene pigment or an azomethine azo pigment is used as a black pigment, or an isoindolinone pigment (yellow), a diketopyrrolopyrrole pigment (red), and a phthalocyanine pigment (blue) are mixed. Since black is expressed, the light transmittance in the printing layer 13 is higher than that of the existing decorative sheet. Since the infrared light transmitted through the printing layer 13 is reflected by the colored thermoplastic resin base material layer 11, heat is not transmitted to the base material 20, and heat storage of the base material 20 can be prevented. And by preventing the heat storage of the base material 20, it is possible to obtain a cosmetic material 1 that is less likely to be warped by sunlight even when used outdoors.

  In the present embodiment, the moisture permeability of the transparent thermoplastic resin layer of the outermost layer 53 is lower than the moisture permeability of the acrylic resin of the inner layer 51, so that makeup can be applied in addition to the weather resistance of the acrylic resin. The moisture content on the surface of the sheet 3 is suppressed. Accordingly, in the present embodiment, the decorative sheet can be made to be free from chalking whitening or crack whitening even in a long-term weather resistance test.

The embodiment described above exemplifies a configuration for embodying the technical idea of the present invention, and the technical idea of the present invention is based on the material, shape, structure, arrangement, etc. of the component parts. It is not specific to the above. The technical idea of the present invention can be variously modified within the technical scope defined by the claims described in the claims.
In addition, it should be noted that the drawings in the embodiments 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. Therefore, specific thicknesses and dimensions should be determined in consideration of the above description.

Examples of the present embodiment and comparative examples are shown below. In addition, this embodiment is not limited to the following Example.
[Example 1]
In Example 1, 3 parts by mass of a hindered phenol antioxidant, 1 part by mass of an ultraviolet absorber, 1 part by mass of a hindered amine light stabilizer, 23 parts by mass of titanium oxide are added to 100 parts by mass of a polypropylene resin, and the thickness is 70 μm. A colored thermoplastic resin substrate layer was formed.

  Next, in Example 1, a solid printing layer was formed on the surface of the colored thermoplastic resin base material layer. The solid printing layer ink is a mixture of urethane resin and vinyl chloride = vinyl acetate copolymer resin in a ratio of 7: 3, and hexamethylene diisocyanate and isophorone diisocyanate as a curing agent in a ratio of 2: 8. 3 parts by mass of the product was added, and 5.3 parts by mass of isoindolinone, 2.4 parts by mass of polyazo, and 1.7 parts by mass of phthalocyanine were added as pigments. The solid print layer is formed by printing such an ink on the entire surface of the colored thermoplastic resin base material layer.

  Next, in Example 1, the first layer of the pattern layer was printed on the surface of the solid print layer. The ink of the first layer of the pattern layer is a mixture of urethane resin and vinyl chloride = vinyl acetate copolymer resin at a ratio of 7: 3, and hexamethylene diisocyanate and isophorone diisocyanate as a curing agent in a ratio of 2: 8. It was manufactured by adding 3 parts by mass of a mixture mixed at a ratio, and adding 6.0 parts by mass of polyazo and 3.1 parts by mass of phthalocyanine as pigments. The first layer of the pattern layer is for printing the bark portion of the wood grain pattern.

  Next, in Example 1, the second layer of the pattern layer was printed. The ink of the second layer of the pattern layer is a mixture of urethane resin and vinyl chloride = vinyl acetate copolymer resin in a ratio of 7: 3, and hexamethylene diisocyanate and isophorone diisocyanate as a curing agent in a ratio of 2: 8. It was manufactured by adding 3 parts by mass of the mixture in a proportion and adding 2.4 parts by mass of isoindolinone, 5.2 parts by mass of polyazo, and 2.7 parts by mass of phthalocyanine as pigments. The second layer of the pattern layer is for printing the bark portion of the wood grain pattern.

  Next, in Example 1, the third layer of the pattern layer was printed. The ink of the third layer of the pattern layer is a mixture of urethane resin and vinyl chloride = vinyl acetate copolymer resin in a ratio of 7: 3, and hexamethylene diisocyanate and isophorone diisocyanate as a curing agent in a ratio of 2: 8. It was manufactured by adding 3 parts by weight of the mixture in a proportion and adding 3.2 parts by weight of isoindolinone, 4.9 parts by weight of polyazo, and 3.0 parts by weight of phthalocyanine as pigments. The third layer of the pattern layer is to print a wood-patterned conduit portion.

Further, in Example 1, a heat seal layer was formed on the print layer. The heat seal layer is formed by applying an acrylic-polyester-vinyl chloride thermal adhesive resin (acrylic / polyester / vinyl chloride = 30/30/30) to a coating amount of 1.5 g / m ² after drying. It was done by coating by gravure coating method.

Next, in Example 1, a transparent thermoplastic resin layer serving as an outermost layer and a transparent thermoplastic resin layer serving as an inner layer were extruded onto a heat sheet layer and laminated to obtain a decorative sheet. For the outermost layer, a polyvinylidene fluoride resin having a thickness of 5 μm and a moisture permeability of 5.0 g / m ² · 24 h (according to JIS-K-7129-1992) is used, and as the transparent thermoplastic resin layer of the inner layer, the thickness is A methyl methacrylate resin of 45 μm and moisture permeability of 200 g / m ² · 24 h (according to JIS-K-7129-1992) was used. The outermost layer and the inner layer were laminated with the heat sheet layer at the same time as forming as a two-layer sheet by melt extrusion.

[Example 2]
In Example 2, a decorative sheet was prepared by changing only the material of the colored thermoplastic resin substrate layer among the preparation conditions of the decorative sheet of Example 1. In Example 2, a colored thermoplastic resin base material layer was produced using 100 parts by mass of polyethylene resin instead of 100 parts by mass of polypropylene resin.
[Example 3]
In Example 3, a decorative sheet was prepared by changing only the pigment of the colored thermoplastic resin substrate layer among the preparation conditions of the decorative sheet of Example 1. In Example 3, 2 parts by mass of diketopyrrolopyrrole, 2 parts by mass of quinacridone, 1 part by mass of phthalocyanine and 23 parts by mass of titanium oxide were added to 100 parts by mass of polypropylene resin to prepare a colored thermoplastic resin base material layer.

[Comparative example]
In the comparative example, only the condition of the black pigment used for the printed layer of Example 1 was changed to prepare a decorative sheet. The decorative sheet of the comparative example was produced using an ink using carbon black as a black pigment.
[Evaluation]
The inventors of the present invention evaluated the heat shielding performance, the heat storage performance, and the weather resistance of Example 1, Example 2, Example 3, and Comparative Example, respectively.

(Weatherability)
The inventors of the present invention evaluated the accelerated weather resistance of a decorative sheet using a metal halide lamp type super accelerated weather resistance tester (manufactured by Daipura Wintes Co., Ltd.). The test was performed under the conditions of a metal halide lamp irradiance of 650 W / m ² and a black panel temperature (test piece temperature) of 53 ° C. And after irradiation, the case where there was no remarkable change in the test piece was evaluated as “◯”, and the case where the surface resin layer was cracked or peeled was evaluated as “x”.
Such an accelerated weather resistance test method is defined in JIS standard K5602.

(Heat insulation performance)
The inventors of the present invention measured the heat shielding performance using a method for measuring the solar reflectance of a coating film defined in JIS standard, K5602. The measurement was performed with a spectrophotometer UV3600 (product name) manufactured by Shimadzu Corporation. And according to the regulation of JIS standard K5602, if the solar reflectance of the coating film was 40% or more, it was evaluated as “◯”, and if it was 40% or less, it was evaluated as “x”.

(Heat storage performance)
In the evaluation of the heat storage performance, the inventors of the present invention bonded a decorative sheet to the surface of one side of 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. Produced. Then, a halogen sphere is installed at a position 15 cm away from the surface directly above the surface of the test piece, and the temperature of the front and back surfaces of the test piece is measured every minute while irradiating with halogen light for 120 minutes. The maximum temperature was recorded.

  Table 1 summarizes the evaluation of the heat shielding performance, the heat storage performance, and the weather resistance. According to Table 1, the decorative sheets of Example 1, Example 2 and Example 3 in which isoindolinone pigment (yellow), diketopyrrolopyrrole pigment (red) and phthalocyanine pigment (blue) are mixed to represent black. All obtained a rating of “◯” for weather resistance and heat shielding performance. On the other hand, although the decorative sheet of the comparative example obtained an evaluation of “◯” for the weather resistance performance, it was evaluated as “×” for the heat shielding performance.

  Moreover, about the thermal storage performance, the test piece of Example 1, Example 2 and Example 3 became 61 degreeC or 62 degreeC all, whereas the temperature of the test piece of the comparative example rose to 71 degreeC. . This difference is different from Example 1 to Example 3 in which isoindolinone pigment (yellow), diketopyrrolopyrrole pigment (red) and phthalocyanine pigment (blue) are mixed to represent black. The example is thought to have arisen due to the use of carbon black as the black pigment.

  The decorative base material and decorative sheet of the present invention described above are suitable for outdoor use because they do not easily warp even when exposed to sunlight.

  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 Cosmetic material 3 Cosmetic sheet 5 Transparent thermoplastic resin layer 11 Colored thermoplastic resin base material layer 13 Print layer 15 Heat seal layer 20 Base material 21 Adhesive layer 51 Inner layer 53 Outermost layer 111 Titanium oxide layer 131 Solid printing layer 132 Picture layer

Claims (8)

On one surface side of the colored thermoplastic resin base material layer, a printed layer on which a pattern is printed and a plurality of transparent thermoplastic resin layers are sequentially laminated,
Among the plurality of transparent thermoplastic resin layers, the thermoplastic resin layer that is an inner layer other than the outermost layer is made of an acrylic resin, the transparent thermoplastic resin layer that is the outermost layer is made of a fluororesin, and the fluororesin transparent Humidity is lower than the moisture permeability of the acrylic resin,
The said colored thermoplastic resin base material layer has fireproof performance by containing 10% or more and 45% or less of inorganic materials, The decorative sheet characterized by the above-mentioned.   The decorative sheet according to claim 1, wherein the colored thermoplastic resin base material layer contains at least one of calcium carbonate, titanium oxide, and iron oxide as the inorganic material.   The decorative sheet according to claim 1 or 2, wherein the colored thermoplastic resin base material layer further contains 3% or more and 5% or less of a bromine compound in order to improve the fireproof performance.   The decorative sheet according to claim 3, wherein the colored thermoplastic resin base material layer further contains an antimony compound in an amount of 1% to 2% in order to improve the fireproof performance.   The colored thermoplastic resin base material layer has a film made of a paint containing titanium oxide as a pigment on the surface on the printed layer side, or contains titanium oxide as a pigment. The decorative sheet according to any one of the above.   The printed layer contains at least a perylene pigment or an azomethine azo pigment as a black pigment, and when further containing other pigments, isoindolinone, disazo, polyazo, diketopyrrolopyrrole, quinacridone, phthalocyanine, and titanium oxide. The decorative sheet according to any one of claims 1 to 5, comprising at least one pigment among them. The printing layer, a solid printing layer and a pattern layer are sequentially laminated from the colored thermoplastic resin base material layer side,
In the solid printing layer, at least one pigment is selected from isoindolinone, disazo, polyazo, diketopyrrolopyrrole, quinacridone, phthalocyanine, and titanium oxide,
The decorative sheet according to any one of claims 1 to 5, wherein the pattern layer is expressed by mixing black with an inindolinone pigment, a diketopyrrolopyrrole pigment, and a phthalocyanine pigment.   A decorative material comprising the decorative sheet according to any one of claims 1 to 7 bonded to a base material.

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