JP2017177376A - 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: There is provided a decorative sheet 3 in which a thermoplastic resin substrate layer 11, a printed layer 13 and a top coat layer 19 are sequentially laminated. The thermoplastic resin substrate layer 11 is composed of a polyolefin-based resin. The top coat layer 19 is composed of an acrylic urethane-based resin containing a benzotriazole-based ultraviolet absorber. The top coat layer 19 has a thickness of 5 g/mor more and 10 g/mor less in terms of solid content coating amount. The 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, the thermoplastic resin substrate layer 11 may contain 3% or more and 5% or less of a bromine compound and further may contain 1% or more and 2% or less of an antimony compound.SELECTED DRAWING: Figure 1

Description

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

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 problems, a decorative sheet and a decorative material according to one embodiment of the present invention have a thermoplastic resin base material layer, a printing layer, and a coating layer that are sequentially laminated. A thermoplastic resin base material layer consists of polyolefin resin. The coating layer is made of an acrylic urethane resin containing a benzotriazole ultraviolet absorber. The thickness of the coating layer is 5 g / m ² or more and 10 g / m ² or less in terms of solid content. A thermoplastic resin base material layer has fireproof performance by containing 10% or more and 45% or less of an inorganic material.

  Specifically, the thermoplastic resin substrate layer contains at least one of calcium carbonate, titanium oxide, and iron oxide as an inorganic material. The 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 thermoplastic resin base material layer may further contain an antimony compound in an amount of 1% to 2% in order to improve fire prevention 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 according to the present embodiment. The decorative material 1 according to the present embodiment includes a base material 20, a decorative sheet 3 bonded to the base material 20, and a first adhesive layer 21 that bonds the base material 20 and the decorative sheet 3. .

(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.

(First adhesive layer)
As the 1st contact bonding layer 21, if it is a well-known adhesive used for bonding of a decorative sheet and a base material, what kind of thing may be used. In the present embodiment, for attaching the decorative sheet 3 to the base material 20, the first adhesive layer 21 can be formed using an appropriate adhesive such as urethane or vinyl acetate. Alternatively, for example, the first adhesive layer 21 can be formed using a reactive hot-melt adhesive. In particular, the first adhesive layer 21 may be formed using a two-component polyurethane adhesive among reactive hot-melt adhesives. Furthermore, the 1st contact bonding layer 21 may contain a ultraviolet absorber, a light stabilizer, etc.

  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 (undercoat agent) may be provided between the first adhesive layer 21 and the decorative sheet 3. Alternatively, the first 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 according to the present embodiment is obtained by providing a top coat layer 19 as a coating layer on one surface side of the thermoplastic resin base material layer 11. That is, the decorative sheet 3 includes a thermoplastic resin base material layer 11, a printing layer 13, a second adhesive layer 15, an overlay film layer 17, and a topcoat layer 19 that are provided in this order from the first adhesive layer 21 side. Yes.
The decorative material 1 according to 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 thermoplastic resin base layer 11. The heat storage of the base material 20 is prevented.

Hereinafter, each layer of the decorative sheet 3 will be described.
(Thermoplastic resin base material layer)
As the thermoplastic resin base material layer 11, a layer made of a polyolefin resin is used. As the thermoplastic resin base material layer 11, a translucent material, a colored material, or the like can be selected depending on the application. In this embodiment, the thermoplastic resin base material layer 11 is a colored base material.
By using a polyolefin-based resin for the thermoplastic resin substrate layer 11, the decorative material 1 does not have a problem even if it is incinerated, unlike a fluorine-based resin. As the polyolefin resin, for example, polyethylene, polypropylene, or a modified resin thereof is generally used. In this embodiment, a polyethylene raw fabric is used as an example of the thermoplastic resin base material layer 11.

Moreover, you may add a ultraviolet absorber (a benzotriazole type, a triazine type, a benzophenone type etc.) to the thermoplastic resin base material layer 11 as a weather resistance prescription. The addition amount 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 ultraviolet absorbers, examples of the benzotriazole series include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 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-octylphenyl) Benzotriazole, and mixtures thereof, modified products, polymers, derivatives.

Examples of the triazine series 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, polymers, and derivatives thereof can be used.
Further, as the benzophenone series, for example, octabenzone, modified products thereof, polymers, and derivatives can be used.

Further, a hindered amine light stabilizer may be added in order to prevent the resin itself from being deteriorated by light, heat, water or the like. The added part 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.
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.

The thermoplastic resin base layer 11 can be obtained by appropriately blending the above materials and molding it into a film by an extrusion molding method, an inflation molding method, a calendar molding method, or the like. The thickness of the thermoplastic resin base material layer 11 is suitably about 30 μm or more and 120 μm or less considering the ease of adhesive bonding, weather resistance, transparency, and the like.
Moreover, in this embodiment, in order to improve the reflectance of the infrared light in the thermoplastic resin base material layer 11, you may add a titanium oxide to the said material and make it contain in the thermoplastic resin base material layer 11. FIG. At this time, when the thermoplastic resin base material layer 11 contains 23 parts by mass or more of titanium oxide, the heat shielding performance is improved.

Moreover, when using a titanium oxide as a hiding layer for the thermoplastic resin base material layer 11, the sum total of content of the titanium oxide as a hiding layer and the added titanium oxide should just be 23 mass parts or more. Moreover, when the 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 thermoplastic resin substrate layer 11 increases, the titanium oxide affects the film quality of the thermoplastic resin substrate layer 11. For this reason, suitable content of the titanium oxide of the thermoplastic resin base material layer 11 is 23 mass parts or more and 40 mass parts or less.

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 thermoplastic resin base material layer 11 on the printed layer 13 side. Even when the titanium oxide layer 111 is provided, if the thermoplastic resin base material layer 11 contains 23 parts by mass or more of titanium oxide by the titanium oxide layer 111, the thermoplastic resin base material layer 11 can be applied to the base material 20. Heat insulation performance is improved. Under such conditions, the thickness of the titanium oxide layer 111 is preferably 5 μm or more and 10 μm or less.
Further, instead of the titanium oxide layer 111, a layer made of a pigment (isoindolinone, disazo, polyazo, diketopyrrolopyrrole, quinacridone, phthalocyanine) may be provided.

[Fireproof performance]
Here, the 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 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 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 thermoplastic resin base material layer 11. Specifically, the thermoplastic resin base material layer 11 is a random polypropylene resin. If present, a mixture of urethane resin and vinyl chloride = vinyl acetate copolymer resin is preferably used.

  As the pigment, a perylene pigment is used as the black pigment. 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, since the printing layer 13 transmits infrared light and the transmitted infrared light is reflected by the thermoplastic resin base material layer 11, 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 full 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, the surface of the thermoplastic resin substrate layer 11 may be 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, the adhesion between the thermoplastic resin base material layer 11 and the printing layer 13 can be improved.

(Second adhesive layer)
The second adhesive layer 15 is provided for the purpose of allowing adhesion between the printed layer 13 and the overlay film layer 17 by a dry laminating method and developing adhesive strength between the two layers. Adhesive made of urethane resin with main chain resin as main chain. As an adhesive made of a urethane resin, a two-component urethane resin adhesive of hexamethylene diisocyanate, tolylene diisocyanate, and a mixture thereof as a polyester polyol type and a curing agent was applied with a thickness of 2 μm to 10 μm after drying. Things can be used.
For the second adhesive layer 15, depending on the intended use of the decorative sheet, for example, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, a lubricant, an antistatic agent, a flame retardant, One or more conventionally known various additives such as fillers may be added.

  A primer layer (not shown) made of a primer agent (undercoating agent) may be provided between the second adhesive layer 15 and the overlay film layer 17. Alternatively, the second adhesive layer 15 itself may be a primer layer made of a primer agent. The primer agent is as described above.

(Overlay film layer)
For the overlay film layer 17, a material resin is selected in consideration of interlayer adhesion with the thermoplastic resin base material layer 11 and the print layer 13. Specifically, if the thermoplastic resin base material layer 11 is any one of a homopolypropylene resin, a random polypropylene resin, and a polyethylene resin, any of the same homopolypropylene resin, random polypropylene resin, and polyethylene resin is used. Is selected. In addition, it is preferable to add an ultraviolet absorber and a hindered amine light stabilizer to the overlay film layer 17.

  In addition, when the overlay film layer 17 becomes a surface layer without providing the top coat layer 19 as an upper layer, it is preferable to use a polymethylmethacrylic resin as the overlay film layer 17. At this time, it is preferable to add an ultraviolet absorber and a hindered phenol antioxidant to the overlay film layer 17. Further, in consideration of interlayer adhesion with the printing layer 13, the printing layer 13 is attached to the printing layer 13 with an adhesive made of at least one of acrylic resin, polyester resin, vinyl chloride = vinyl acetate copolymer resin. Combined.

The overlay film layer 17 needs to have transparency that allows at least seeing the printing layer 13 thereunder, and is most preferably colorless and transparent, but may be colored and translucent. . As long as that is the case, the overlay film layer 17 may contain a pigment or a filler.
The surface of the overlay film layer 17 can be appropriately provided with an emboss having a desired pattern as necessary. The type of embossed pattern is not particularly limited, and may be various patterns such as, for example, wood grain (especially a conduit pattern), stone texture, fabric texture, Japanese paper texture, geometric pattern, or the like. It may be a simple matte shape, a grain shape, a hairline shape, a suede tone or the like. Further, the design can be further improved by synchronizing these embossed patterns with the pattern of the printed layer 13, but if not necessary, the pattern of the printed layer 13 may be out of sync. Embossing of a pattern including both a pattern synchronized with and a pattern not synchronized can be provided.

  The embossing method is not particularly limited, but a mechanical embossing method using a metal embossing plate is the most common. Moreover, there is no restriction | limiting in particular also in the formation time of the embossing with respect to the overlay film layer 17, Arbitrary time can be selected from before lamination | stacking to the thermoplastic resin base material layer 11, simultaneous lamination | stacking, or after lamination | stacking, Embossing of the same or different pattern can be applied a plurality of times at a plurality of times selected from these times.

  The thickness of the overlay film layer 17 is preferably about 50 μm or more and 150 μm or less, more preferably about 70 μm or more and 100 μm or less. As a method for forming the overlay film layer 17, for example, an extrusion method, an inflation method, a calendar method, a cast method, or the like can be used.

(Topcoat layer)
The top coat layer 19 is a transparent sheet-like layer formed by coating a hard resin to protect the surface of the decorative sheet 3. As the hard resin, for example, an acrylic urethane resin obtained by adding isocyanate to an acrylic polyol and curing it can be used as the main resin.
The topcoat layer 19 of this embodiment is produced by adding an ultraviolet absorber and a hindered amine light stabilizer to an acrylic polyol as a main resin and hexamethylene diisocyanate as a curing agent. A benzotriazole ultraviolet absorber is used as the ultraviolet absorber.

  In the present embodiment, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2-benzotriazole-based ultraviolet absorber, [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-octylphenyl) benzene Nzotriazole and the like, mixtures thereof, modified products, polymers, and derivatives can be used.

The thickness of the top coat layer 19 is 5 g / m ² or more and 10 g / m ² or less in terms of solid content. Still more preferably 6 g / ^{m 2} or more 9 g / ^{m 2} or less. Thereby, versatility, such as the coating property of the topcoat layer 19 of this embodiment and storage, becomes high.

  In the present embodiment, the coating layer is the topcoat layer 19 that is the uppermost layer of the decorative sheet 3, but the present embodiment is not limited to the topcoat layer 19 being the coating layer. For example, the coating layer below the top coat layer 19 may contain a benzotriazole-based ultraviolet absorber, or another coating layer may be appropriately provided on the coating layer containing the benzotriazole-based ultraviolet absorber. good.

  As described above, 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). As a result, the light transmittance in the printed 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 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, an acrylic urethane-based resin is used as the top coat layer 19, a benzotriazole-based UV absorber having a good compatibility with this is used, and the solid content coating amount is set to 5 g / m ² or more. It is possible to form a coating film that has an excellent ultraviolet shielding ability and does not deteriorate with the passage of time. Moreover, the coating film without the crack of the topcoat layer 19 can be formed also at the time of the lamination to an uneven | corrugated | grooved part by making solid content application amount into 10 g / m < ² > or less.

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, as a thermoplastic resin substrate layer, 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, 100 parts by mass of polypropylene resin. A film having a thickness of 70 μm was formed.

  Next, in Example 1, a solid printing layer was formed on the surface of the 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 thermoplastic resin base material layer.

  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.

  In Example 1, an overlay film layer was formed on the printed layer. The overlay film layer is formed by melting and extruding a material obtained by adding 0.5 parts by mass of a benzotriazole ultraviolet absorber and 0.3 parts by mass of a hindered amine light stabilizer to 100 parts by mass of a random polypropylene resin. It is produced by. The thickness of the overlay film layer after drying is 70 μm.

Furthermore, in Example 1, the topcoat layer was formed on the surface of the overlay film layer. The top coat layer is composed of 10 parts by mass of hexamethylene diisocyanate, 100 parts by mass of acrylic polyol, methyl 3- (3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate, 3 parts by mass of 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole UV absorber for 1 part by mass of the benzotriazole UV absorber mainly comprising the reaction product of polyethylene glycol 300, and a hindered amine light stabilizer It was formed by coating what added 5 mass parts of agent. The thickness of the top coat layer was 9 g / m ² in terms of solid content, and in Example 1, it was 9 μm.

(Example 2)
In Example 2, 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 produce a thermoplastic resin base material layer. Otherwise, a decorative sheet was produced under the same conditions as in Example 1.

(Example 3)
In Example 3, the thickness of the topcoat layer was 12 μm. Otherwise, a decorative sheet was produced under the same conditions as in Example 1.
Example 4
In Example 4, the thickness of the topcoat layer was 15 μm. Otherwise, a decorative sheet was produced under the same conditions as in Example 1.

(Comparative Example 1)
In Comparative Example 1, a decorative sheet was produced by changing only the conditions of the black pigment used in the printed layer of Example 1. The decorative sheet of Comparative Example 1 was produced using an ink using carbon black as a black pigment.
(Evaluation)
The inventors of the present invention evaluated the weather resistance, the heat shielding performance, and the heat storage performance of Example 1, Example 2, Example 3, Example 4, and Comparative Example 1, 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. There were four types of evaluation time of 96 hours, 216 hours, 312 hours, and 408 hours, and each time a metal halide lamp was irradiated to the test piece. 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 below collectively shows the evaluation results of the weather resistance, heat shielding performance, and heat storage performance.

  According to Table 1, the decorative sheets of Example 1, Example 2, Example 3 and Example 4 all obtained an evaluation of “◯” for weather resistance and heat shielding performance. On the other hand, although the decorative sheet of Comparative Example 1 obtained an evaluation of “◯” for the weather resistance performance, it was evaluated as “x” for the heat shielding performance.

  Moreover, about the heat storage performance, the test piece of Example 1 and Example 3 became 61 degreeC, the test piece of Example 2 and Example 4 became 60 degreeC, whereas the test piece of Comparative Example 1 became 70 degreeC. The temperature rose to.

  The difference is that Example 1, Example 2, Example 3 and Example 4 are mixed with isoindolinone pigment (yellow), diketopyrrolopyrrole pigment (red) and phthalocyanine pigment (blue) to produce black. In contrast to this, it is considered that Comparative Example 1 occurred because carbon black was used as the black pigment.

The inventors of the present invention applied the topcoat layer so that the solid content was 5 g / m ^2, and other conditions were as in Example 1, Example 2, Example 3 and Example 4. The same decorative sheet was produced. In addition, the inventors of the present invention applied the top coat layer so that the solid content was 10 g / m ^2, and the other conditions were as in Example 1, Example 2, Example 3 and Example 4. The same decorative sheet was produced. And about such a decorative sheet, the weather resistance and heat-insulating performance were evaluated. In this evaluation, the inventors of the present invention obtained good weather resistance and heat shielding performance in the same manner as in Example 1, Example 2, Example 3, and Example 4.

Furthermore, the inventors of the present invention measured the transmittance of each ink used in the printed layer. The printing ink has an infrared light transmittance of 40% or more. Therefore, since the printing layer 13 transmits infrared light and the transmitted infrared light is reflected by the thermoplastic resin base material layer 11, the heat storage effect due to the heat of infrared light is reduced.
Here, as a method for measuring the transmittance of the ink (printing ink), for example, a pigment is used so that the basis weight is 1 g / m ² with respect to a biaxially stretched PET film having a thickness of 25 μm (Lumirror S50 manufactured by Toray Industries, Inc.). Printed with the dispersed ink, and measured the transmittance of 860 measuring points every 2 nm in the region of wavelength 782 nm or more and 2500 nm or less with a spectrophotometer UV3600 manufactured by Shimadzu Corporation, and the total transmittance (% T) of each wavelength There is a method in which the division result obtained by dividing the value by the number of measurement points is used as the infrared light transmittance. That is, it is calculated by the formula “transmittance of infrared light = total measured transmittance (% T) of infrared wavelengths (782 nm to 2500 nm)” ÷ number of measurement points (860) ”.
From the above results, it can be seen that the inks used in Example 1, Example 2, Example 3 and Example 4 have high transmittance for infrared light.

  The decorative sheet and the decorative material 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 11 Thermoplastic resin base material layer 111 Titanium oxide layer 13 Print layer 131 Solid print layer 132 Picture layer 15 2nd adhesive layer 17 Overlay film layer 19 Topcoat layer 20 Base material 21 1st adhesive layer

Claims (8)

A thermoplastic resin base material layer, a printing layer, and a coating layer are sequentially laminated,
The thermoplastic resin substrate layer is made of a polyolefin resin,
The coating layer is composed of an acrylic urethane resin containing a benzotriazole ultraviolet absorber,
The thickness of the coating layer is 5 g / m ² or more and 10 g / m ² or less in solid content coating amount,
The said 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 thermoplastic resin base material layer contains at least one of calcium carbonate, titanium oxide, and iron oxide as an inorganic material.   The decorative sheet according to claim 1 or 2, wherein the thermoplastic resin base material layer further contains a bromine compound in an amount of 3% to 5% in order to improve the fireproof performance.   The decorative sheet according to claim 3, wherein the 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 thermoplastic resin base material layer has a film made of a paint containing titanium oxide as a pigment on the surface on the side of the printing layer, or contains titanium oxide as a pigment. The decorative sheet according to claim 1.   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 is formed by sequentially laminating a solid printing layer and a pattern layer from the 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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