JP6620406B2 - Decorative sheet and decorative plate - Google Patents

Description

  The present invention relates to a decorative sheet and a decorative board.

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

JP 2013-78847 A

However, although the olefin resin is excellent in weather resistance, it has a heat storage function of storing heat of infrared light contained in sunlight. Therefore, a decorative sheet using an olefin-based resin as a base material layer has a temperature difference between the front and back surfaces exposed to sunlight, and the thermal expansion amount on the front surface is larger than the thermal expansion amount on the back surface due to this temperature difference. And warping may occur.
This invention pays attention to the above points, and it aims at providing the decorative sheet which can be excellent in a weather resistance, and can suppress generation | occurrence | production of the curvature by sunlight, and a decorative board.

  In order to solve the above-described problems, a decorative sheet according to one embodiment of the present invention includes a pattern printed layer, a transparent adhesive layer, an anchor layer, and a transparent layer formed by printing on one surface side of a colored thermoplastic resin layer. The acrylic resin layer is laminated in this order, the transparent adhesive layer is made of a urethane-based adhesive having a polyester-based resin as a main chain, and the anchor layer is made of a urethane-based anchor agent having an acrylic-based resin as a main chain. The transparent acrylic resin layer contains a triazine ultraviolet absorber as an ultraviolet absorber, the colored thermoplastic resin layer uses titanium oxide as a pigment, and the pattern printing layer has an infrared light transmittance of 40% or more. A certain ink is used as a printing ink.

  According to one aspect of the present invention, since the anchor layer is made of a urethane-based adhesive having an acrylic resin as a main chain, it can be excellent in weather resistance. In addition, since the pattern printing layer transmits infrared light, and the colored thermoplastic resin layer reflects the transmitted infrared light, the heat storage effect of infrared heat can be reduced, and the infrared light (sunlight) is applied. The temperature difference between the front surface and the back surface can be reduced, and the occurrence of warpage due to sunlight can be suppressed. Thereby, according to 1 aspect of this invention, while being excellent in weather resistance, the decorative sheet which can suppress generation | occurrence | production of the curvature by sunlight can be provided.

It is sectional drawing which shows the decorative board which concerns on embodiment based on this invention.

Next, embodiments 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.

(Decorative board 10)
As shown in FIG. 1, the decorative board 10 of the present embodiment has a pattern printing layer 2, a transparent adhesive layer 3, an anchor layer 4, and a transparent acrylic resin layer on one surface side of the colored thermoplastic resin layer 1. 5 are laminated in this order to form a decorative sheet 20, and a base material 7 is bonded to the other surface side of the colored thermoplastic resin layer 1 via a primer layer 6. The decorative board 10 of the present embodiment is particularly suitable for exterior applications such as entrance doors, roofs, outer walls, and louvers.

(Colored thermoplastic resin layer 1)
The colored thermoplastic resin layer 1 is a sheet-like layer made of a thermoplastic resin. It does not specifically limit as a thermoplastic resin, A well-known thermoplastic resin can be used. For example, polypropylene resins such as homopolypropylene resins and random polypropylene resins, or polyethylene resins are preferable. Moreover, you may add a hindered phenolic antioxidant, a ultraviolet absorber, a hindered amine light stabilizer, etc. to the thermoplastic resin of the colored thermoplastic resin layer 1. FIG.

Further, the resin constituting the colored thermoplastic resin layer 1 contains titanium oxide as a pigment. Thereby, if the infrared light permeate | transmits the pattern printing layer 2, the colored thermoplastic resin layer 1 will reflect the transmitted infrared light. Moreover, titanium oxide is contained in the range of 23 to 50 mass parts with respect to 100 mass parts of thermoplastic resins. Thereby, the infrared light which the pattern printing layer 2 permeate | transmitted can be reflected more appropriately, and the colored thermoplastic resin layer 1 can be formed more appropriately (film formation).
In this embodiment, an example in which titanium oxide, which is a pigment, is included in the resin of the colored thermoplastic resin layer 1 has been described, but other configurations may be employed. For example, it is good also as a structure which coats the coating material which uses a titanium oxide as a pigment on the surface at the side of the pattern printing layer 2 of the colored thermoplastic resin layer 1.

(Picture printing layer 2)
The pattern printing layer 2 is a layer formed by printing a pattern for imparting design properties. As the pattern, for example, a pattern suitable for a place where the decorative sheet 20 is used, such as a grain, a stone pattern, an abstract pattern, or the like, can be selected. The printing ink contains, for example, any one of isoindolinone, disazo, polyazo, diketopyrrolopyrrole, quinacridone, phthalocyanine, and titanium oxide, or a mixture thereof as a pigment. Accordingly, the printing ink has an infrared light transmittance of 40% or more. Therefore, since the pattern printing layer 2 transmits infrared light, and the colored thermoplastic resin layer 1 reflects the transmitted infrared light, the heat storage action due to the heat of infrared light is reduced.

Here, as a method for measuring the transmittance of the printing ink, for example, printing is performed with an ink in which a pigment is dispersed so as to have a weight of 1 g / m ^{2 on a} 25 μm-thick biaxially stretched PET film (Lumirror S50 manufactured by Toray Industries, Inc.) Then, using a spectrophotometer UV3600 manufactured by Shimadzu Corporation, the transmittance of 860 measuring points is measured every 2 nm in the region of wavelength 782 nm to 2500 nm, and the total value of the transmittance (% T) of each wavelength is measured by the number of measuring points. There is a method in which the division result is used as 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) ”.
The thickness of the pattern printing layer 2 is preferably 5 μm or more and 10 μm or less. Furthermore, the ratio of titanium oxide in the resin constituting the pattern print layer 2 is preferably 50% or less.

(Transparent adhesive layer 3)
The transparent adhesive layer 3 is a transparent sheet-like layer made of a urethane adhesive having a polyester resin as a main chain. As the urethane-based adhesive having a polyester resin as a main chain, for example, a two-component urethane resin-based adhesive composed of a polyester polyol and the like and hexamethylene diisocyanate, tolylene diisocyanate, or a mixture thereof can be used. . Thereby, the laminated body of the colored thermoplastic resin layer 1 and the pattern printing layer 2 and the laminated body of the anchor layer 4 and the transparent acrylic resin layer 5 can be firmly bonded by the dry lamination method.
The urethane adhesive constituting the transparent adhesive layer 3 includes an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, a lubricant, and an antistatic agent depending on the use of the decorative sheet 20. Additives such as flame retardants and fillers may be added.

(Anchor layer 4)
The anchor layer 4 is a transparent sheet-like layer made of a urethane anchor agent having an acrylic resin as a main chain. As the urethane anchor agent having an acrylic resin as a main chain, for example, a two-component curable urethane resin composed of acrylic polyol and hexamethylene diisocyanate can be used. Thus, by cross-linking and curing the two-component curable urethane resin after lamination, the adhesive strength is not lost even under high temperature use conditions, and sufficient peel resistance can be maintained. Therefore, the adhesive strength between the transparent adhesive layer 3 and the transparent acrylic resin layer 5 can be improved.

As the two-component curable urethane resin, for example, one obtained by adding 3 parts by mass or more and 10 parts by mass or less of an isocyanate compound of hexamethylene diisocyanate to 10 parts by mass of the main component mainly composed of an acrylic polyol resin is preferable. Thus, by using the main agent which has acrylic resin as a main component (main chain), both adhesiveness and weather resistance with the transparent acrylic resin layer 5 can be made favorable. Moreover, both the adhesiveness to the transparent adhesive layer 3 and the heat resistance can be improved by crosslinking and curing the two-component curable urethane resin.
The acrylic polyol resin preferably has a glass transition temperature of 95 ° C. or more and 105 ° C. or less in consideration of adhesion and heat resistance. When the glass transition temperature is lower than 95 ° C., the heat resistance is lowered, and the anchor layer 4 is softened by being immersed in a heated rainwater or the like, thereby generating voids, and the colored thermoplastic resin layer 1 And the adhesion between the transparent acrylic resin layer 5 are reduced.
In addition, the resin constituting the anchor layer 4 includes an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, a lubricant, an antistatic agent, a flame retardant, and a filling depending on the use of the decorative sheet 20. You may add additives, such as an agent.

(Transparent acrylic resin layer 5)
The transparent acrylic resin layer 5 is a transparent sheet-like layer made of a transparent acrylic resin. As the transparent acrylic resin, for example, a resin 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 is used. be able to. 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.
An ultraviolet absorber is added to the resin constituting the transparent acrylic resin layer 5. As a UV absorber, only a triazine UV absorber is used. Furthermore, the resin constituting the transparent acrylic resin layer 5 includes an antioxidant, a light stabilizer, a heat stabilizer, a plasticizer, a lubricant, an antistatic agent, a flame retardant, and a filler depending on the use of the decorative sheet 20. Additives such as may be added.

  Examples of the antioxidant include phenol-based, sulfur-based, and phosphorus-based agents. Examples of light stabilizers include hindered amines and nickel complexes. Furthermore, 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. Further, 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.

The transparent acrylic resin layer 5 needs to have transparency that allows the pattern printing 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.
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 in synchronism 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, the uneven | corrugated pattern may be completed in multiple times by forming the same or different uneven | corrugated pattern in several time.
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.

(Primer layer 6)
The primer layer 6 is a sheet-like 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 the primer layer 6. FIG. Thereby, the surface of the primer layer 6 can be roughened, blocking at the time of winding and storing the decorative sheet 20 can be prevented, and the adhesion with the laminating adhesive can be improved by the anchoring effect.

(Substrate 7)
The base material 7 is a plate-like member made of a metal system or a wood system. As the metal system, for example, aluminum, steel, stainless steel, or a composite panel can be used. As a composite panel, for example, there is a panel provided with a resin layer serving as a core and metal plates (aluminum, galvalume, stainless steel, etc.) attached to both surfaces of the resin layer. Moreover, as a wood system, MDF (medium density fiberboard), a plywood, and a particle board can be used.

(Effect of this embodiment)
The invention according to this embodiment has the following effects.
(1) The decorative sheet 20 according to the present embodiment has a pattern printing layer 2 formed by printing, a transparent adhesive layer 3, an anchor layer 4, and a transparent acrylic type on one surface side of the colored thermoplastic resin layer 1. The resin layer 5 is configured by being laminated in this order. The transparent adhesive layer 3 is made of a urethane adhesive having a polyester resin as a main chain, and the anchor layer 4 is made of a urethane anchor agent having an acrylic resin as a main chain, and the transparent acrylic resin layer 5 is made. Contains a triazine-based ultraviolet absorber as an ultraviolet absorber, the colored thermoplastic resin layer 1 is made of titanium oxide as a pigment, and the pattern printing layer 2 is a printing ink that has an infrared light transmittance of 40% or more. And
According to such a structure, since the anchor layer 4 consists of a urethane type adhesive which has acrylic resin as a principal chain, it can be made excellent in weather resistance. Moreover, since the pattern printing layer 2 transmits infrared light, and the colored thermoplastic resin layer 1 reflects the transmitted infrared light, the heat storage effect of the heat of infrared light can be reduced, and infrared light (sunlight) The temperature difference between the front surface and the back surface can be reduced, and the occurrence of warpage due to sunlight can be suppressed. Thereby, while being excellent in weather resistance, the decorative sheet 20 which can suppress generation | occurrence | production of the curvature by sunlight can be provided.

(2) In the decorative sheet 20 according to the present embodiment, the printing ink for the pattern printing layer 2 is any one of isoindolinone, disazo, polyazo, diketopyrrolopyrrole, quinacridone, phthalocyanine, and titanium oxide, or a mixture thereof. As a pigment.
According to such a configuration, the colored thermoplastic resin layer 1 and the pattern print layer 2 can be appropriately formed.
(3) In the decorative sheet 20 according to the present embodiment, the colored thermoplastic resin layer 1 contains titanium oxide within a range of 23 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.
According to such a configuration, infrared light transmitted through the pattern printing layer 2 can be reflected more appropriately, and the colored thermoplastic resin layer 1 can be appropriately formed (film formation).
(4) The decorative board 10 according to the present embodiment is formed by bonding the decorative sheet 20 to the base material 7.
According to such a structure, generation | occurrence | production of the curvature by the infrared light of the decorative sheet 20 can be suppressed.

Next, examples according to the present invention will be described.
(Example 1)
In Example 1, 3 parts by mass of a hindered phenolic antioxidant, 1 part by mass of an ultraviolet absorber, 1 part by mass of a hindered amine light stabilizer, and 23 parts by mass of titanium oxide with respect to 100 parts by mass of a polypropylene resin. The colored thermoplastic resin layer 1 was provided using the added mixture. The thickness of the colored thermoplastic resin layer 1 was 70 μm. Subsequently, hexamethylene diisocyanate and isophorone diisocyanate are mixed in a ratio of 2: 8 with respect to 100 parts by mass of a mixture of urethane resin and vinyl chloride = vinyl acetate copolymer resin in a ratio of 7: 3 on the surface of the colored thermoplastic resin layer 1. Print the pattern (wood grain pattern) by gravure printing using ink containing 3 parts by weight of the curing agent mixed in step 3 and 3 parts by weight of a pigment composed of isoindolinone, polyazo, and phthalocyanine to provide the pattern printing layer 2 It was. The transmittance of the infrared light of the printing ink of the pattern printing layer 2 was 40%.

Then, the transparent acrylic resin layer 5 was provided using the transparent acrylic resin film (Mitsubishi Rayon Co., Ltd. product "HBX-777") containing a triazine type ultraviolet absorber. An anchor agent (“UC Clear” manufactured by DIC Corporation) having an acrylic resin having a glass transition temperature of 100 ° C. as a main chain is applied to the surface of the transparent acrylic resin layer 5 by a gravure coating method to form the anchor layer 4. Formed. The coating amount of the anchor layer 4 (coating amount after drying) was 1 g / m ² . Thereby, the laminated body which consists of the transparent acrylic resin layer 5 and the anchor layer 4 was provided.
Subsequently, a transparent adhesive layer 3 was formed by applying a urethane adhesive (“TM-593” manufactured by Toyo Morton Co., Ltd.) having a polyester resin as a main chain on the pattern printing layer 2. The coating amount (coating amount after drying) of the transparent adhesive layer 3 was 6 g / m ² . And the laminated body formed above was adhered on the transparent adhesive layer 3 by a dry laminating method, and the decorative sheet 20 was provided.

(Example 2)
In Example 2, the colored thermoplastic resin layer 1 was provided using a polyethylene resin instead of the polypropylene resin. Otherwise, the decorative sheet 20 of Example 2 was produced by the same procedure as in Example 1.
(Comparative example)
In the comparative example, the pigment used for the pattern printing layer 2 was carbon black. Otherwise, the decorative sheet 20 of the comparative example was produced by the same procedure as in Example 1.

(Evaluation judgment)
The following evaluation was implemented about the decorative sheet 20 of each above Example and each comparative example.
(Weatherability)
Using a metal halide lamp type super-accelerated weathering tester (Daipura Wintes Co., Ltd.), the test was conducted at an illuminance of 650 W / m ² and a black panel temperature of 53 ° C. It was confirmed. At that time, the case where there was no crack or peeling in the appearance was judged as “good”, and the case where there was a crack or peeling in the appearance was judged as “failed”.

(Heat insulation)
Based on JISK5602, the solar reflectance of the coating film was measured. The measurement was performed using a spectrophotometer UV3600 manufactured by Shimadzu Corporation. In that case, the case where the solar reflectance of a coating film was 40% or more was set as the pass "(circle)", and the case where it was 40% or less was set as the rejection "x".
(Heat storage)
The decorative sheet 20 was bonded to only 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. Then, a halogen bulb is installed at a position 15 cm above the decorative sheet 20, and light is continuously irradiated from the halogen bulb to the decorative sheet 20 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.

  The evaluation results are shown in Table 1.

From Table 1, the anchor layer 4 is composed of a urethane anchor agent having an acrylic resin as a main chain, the colored thermoplastic resin layer 1 is made of titanium oxide as a pigment, and the pattern printing layer 2 has an infrared light transmittance of 40. In Example 1 and Example 2 satisfying the scope of the present invention using an ink having a% or more as a printing ink, it was found that the weather resistance, heat shielding properties, and heat storage properties were all good. That is, it turned out that it is excellent in a weather resistance and can suppress generation | occurrence | production of the curvature by sunlight.
In contrast, in the comparative example, the weather resistance is acceptable “◯”, but the heat shielding property is “failed” “x”, and the temperature of the steel sheet represented by the heat storage property is about 10 ° C. than in Example 1 and Example 2. It has become expensive.
In Example 1, the anchor layer 4 is made of a urethane anchor agent having an acrylic resin as a main chain, the colored thermoplastic resin layer 1 is made of titanium oxide as a pigment, and the pattern printing layer 2 is transparent to infrared light. When an ink having a rate of 40% or more was used as a printing ink and adjusted within the scope of the present invention, the same effects as in Examples 1 and 2 were obtained.

DESCRIPTION OF SYMBOLS 1 Colored thermoplastic resin layer 2 Picture printing layer 3 Transparent adhesive layer 4 Anchor layer 5 Transparent acrylic resin layer 6 Primer layer 7 Base material 10 Decorative board 20 Decorative sheet

Claims (8)

On one surface side of the colored thermoplastic resin layer, a pattern printing layer formed by printing, a transparent adhesive layer, an anchor layer, and a transparent acrylic resin layer are laminated in this order,
The transparent adhesive layer is made of a urethane adhesive having a polyester resin as a main chain,
The anchor layer is made of a urethane anchor agent having an acrylic resin as a main chain,
The transparent acrylic resin layer contains a triazine ultraviolet absorber as an ultraviolet absorber,
The colored thermoplastic resin layer uses titanium oxide as a pigment,
The pattern printing layer uses printing ink as an ink having an infrared light transmittance of 40% or more,
The printing ink contains any one of isoindolinone, disazo, polyazo, diketopyrrolopyrrole, quinacridone, phthalocyanine, and titanium oxide as a pigment,
The infrared light transmittance is defined by the following formula (1) in a state where a weight of 1 g / m ² is printed on a biaxially stretched PET film having a thickness of 25 μm with the ink. Makeup sheet.
Infrared light transmittance = measured transmittance (% T) of infrared wavelengths (782 nm to 2500 nm) total value ÷ number of measurement points (1)   2. The decorative sheet according to claim 1, wherein the colored thermoplastic resin layer contains titanium oxide in a range of 23 parts by mass to 50 parts by mass with respect to 100 parts by mass of the thermoplastic resin. The decorative sheet according to claim 1 or 2, further comprising a coating film containing titanium oxide between the colored thermoplastic resin layer and the pattern printing layer.   The decorative sheet according to any one of claims 1 to 3, wherein the pattern printing layer has a thickness in a range of 5 µm to 10 µm. The decorative sheet according to any one of claims 1 to 4, wherein the printing ink contains any one of disazo, polyazo, diketopyrrolopyrrole, and titanium oxide as a pigment. On one surface side of the colored thermoplastic resin layer, a pattern printing layer formed by printing, a transparent adhesive layer, an anchor layer, and a transparent acrylic resin layer are laminated in this order,
The transparent adhesive layer is made of a urethane adhesive having a polyester resin as a main chain,
The anchor layer is made of a urethane anchor agent having an acrylic resin as a main chain,
The transparent acrylic resin layer contains a triazine ultraviolet absorber as an ultraviolet absorber,
The colored thermoplastic resin layer uses titanium oxide as a pigment,
The pattern printing layer uses printing ink as an ink having an infrared light transmittance of 40% or more,
The printing ink may include a titanium oxide, isoindolinone, disazo, polyazo, diketopyrrolopyrrole, Kiinakuridon, and any phthalocyanine down, or a mixture thereof, as a pigment,
The infrared light transmittance is defined by the following formula ( 2 ) in a state where a weight of 1 g / m ² is printed on the biaxially stretched PET film having a thickness of 25 μm with the ink. Makeup sheet.
Infrared light transmittance = total measured transmittance (% T) of infrared wavelengths (782 nm or more and 2500 nm or less) ÷ number of measurement points ( 2 ) The decorative sheet according to claim 6, wherein the content of the titanium oxide in the pattern print layer is 50% by mass or less. A decorative board comprising the decorative sheet according to any one of claims 1 to 7 bonded to a base material.

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