JP2024033460A - Decorative sheets and metal decorative parts using them - Google Patents

Abstract

The present invention provides a decorative sheet that exhibits excellent heat and humidity resistance and weather resistance while having sufficient adhesive properties, and a decorative metallic member using the same. [Solution] A base material layer 11, a weather resistant layer 14 provided on the base material layer 11, a stain resistant layer 15 provided on the weather resistant layer 14, and a base material layer 11 and the weather resistant layer 14. In the decorative sheet 10 including an adhesive layer 13 provided in between, the adhesive layer 13 contains a polyester resin and a bisphenol A type epoxy resin, and the polyester resin has phthalic acid, a linear dicarboxylic acid, and an alkylene diol as constituent elements. It is characterized in that the mass ratio of polyester resin and bisphenol A epoxy resin (polyester resin:bisphenol A epoxy resin) is within the range of 50:50 to 90:10. [Selection diagram] Figure 1

Description

The present invention relates to a decorative sheet applied to the exterior of a building, and a metal decorative member using the same.

Decorative sheets applied to the interior of buildings usually have a structure in which resin layers endowed with various functions are bonded to a base material via an adhesive layer and laminated. This adhesive layer is generally made of polyester resin, which has excellent adhesive properties.

JP2017-042975A JP2020-192797A

When conventional decorative sheets such as those mentioned above are applied to the exterior of buildings, they are exposed to outdoor environments for long periods of time, which causes the polyester resin in the adhesive layer to undergo hydrolysis, causing the bond between the base material and the resin layer to deteriorate. There was a risk of causing peeling.

In view of the above, an object of the present invention is to provide a decorative sheet that can exhibit excellent heat and humidity resistance and weather resistance while having sufficient adhesive properties, and a decorative metal member using the same.

In order to solve the above-mentioned problems, the decorative sheet according to the present invention includes a base material layer, a weather-resistant layer provided on the base material layer, a stain-resistant layer provided on the weather-resistant layer, and a base layer provided on the base material layer. In a decorative sheet comprising an adhesive layer provided between a base layer and the weather-resistant layer, the adhesive layer contains a polyester resin and a bisphenol A epoxy resin, and the polyester resin contains phthalic acid, linear It has a dicarboxylic acid and an alkylene diol as constituent elements, and the mass ratio of the polyester resin and the bisphenol A epoxy resin (polyester resin: bisphenol A epoxy resin) is within the range of 50:50 to 90:10. characterized by something.

Further, in the decorative sheet according to the present invention, in the decorative sheet described above, the molar ratio of the phthalic acid and the linear dicarboxylic acid (phthalic acid: linear carboxylic acid) is in the range of 45:55 to 85:15. It is preferable if it is within.

Further, in the decorative sheet according to the present invention, in the decorative sheet described above, it is preferable that the alkylene diol contains neopentyl glycol.

Moreover, in the decorative sheet according to the present invention, it is preferable that a pattern layer is provided between the base material layer and the adhesive layer in the decorative sheet described above.

Further, in the decorative sheet according to the present invention, in the decorative sheet described above, it is preferable that the pattern layer contains a urethane resin having polycaprolactone polyol, polyalkylene glycol, and polyisocyanate as constituent elements as a binder resin.

Moreover, in the decorative sheet according to the present invention, it is preferable that the urethane resin further contains neopentyl glycol as a component in the decorative sheet described above.

Moreover, in the decorative sheet according to the present invention, the polyalkylene glycol in the decorative sheet described above is preferably polytetramethylene glycol.

Moreover, in the decorative sheet according to the present invention, the polyisocyanate in the decorative sheet described above is preferably isophorone diisocyanate.

On the other hand, a metal decorative member according to the present invention for solving the above-mentioned problems includes a decorative sheet according to the present invention, a metal substrate attached to the base material layer of the decorative sheet, and a metal decorative member attached to the base material layer of the decorative sheet. The present invention is characterized by comprising an adhesive that adheres to the base material layer of the decorative sheet.

Further, in the metal decorative member according to the present invention, a base layer is provided on the base layer so as to be located between the base layer of the decorative sheet and the adhesive. That's preferable.

According to the decorative sheet and metal decorative member using the same according to the present invention, the adhesive layer contains a polyester resin and a bisphenol A epoxy resin, and the polyester resin comprises phthalic acid, a linear dicarboxylic acid, and an alkylene diol. Since the mass ratio of polyester resin and bisphenol A epoxy resin (polyester resin: bisphenol A epoxy resin) is within the range of 50:50 to 90:10, sufficient adhesion is achieved. However, since it can exhibit excellent heat and humidity resistance and weather resistance, it can also be applied to the exterior of buildings that are exposed to outdoor environments for a long period of time.

1 is a sectional view showing a schematic configuration of a main embodiment of a decorative sheet according to the present invention. 1 is a sectional view showing a schematic configuration of a main embodiment of a decorative metal member according to the present invention.

Embodiments of a decorative sheet and a metal decorative member using the same according to the present invention will be described below based on the drawings. Note that the present invention is not limited to the following embodiments described based on the drawings, and the technical matters described in each embodiment can be combined as appropriate.

[Main embodiment]
Main embodiments of a decorative sheet and a metal decorative member using the same according to the present invention will be described based on FIGS. 1 and 2.

<Cosmetic sheet>
As shown in FIG. 1, a pattern layer 12 on which a pattern is printed is provided on a base material layer 11. A weather-resistant layer 14 having weather resistance is provided on the pattern layer 12. A stain-resistant layer 15 having stain resistance is provided on the weather-resistant layer 14 . An adhesive layer 13 is provided between the pattern layer 12 and the weather-resistant layer 14 for bonding them together.

That is, the decorative sheet 10 according to the present embodiment includes the base layer 11, the weather-resistant layer 14 provided on the base layer 11, the stain-resistant layer 15 provided on the weather-resistant layer 14, and the base layer 11. 11 and an adhesive layer 13 provided between the base material layer 11 and the weather-resistant layer 14, and a pattern layer 12 is provided between the base material layer 11 and the adhesive layer 13.

The thickness of such a decorative sheet 10 in the lamination direction is preferably 100 μm or more and 150 μm or less, more preferably 110 μm or more and 130 μm or less. If it is less than 100 μm, it tends to cause a decrease in weather resistance, which is not very preferable. If it exceeds 150 μm, it tends to cause a decrease in workability, which is not very preferable.

<Base material layer 11>
The base material layer 11 is a sheet-shaped layer made of thermoplastic resin. Examples of the thermoplastic resin constituting the base layer 11 include polyolefin resins such as polyethylene, polypropylene, polybutene, and polymethylpentene, ethylene-vinyl acetate copolymers or saponified products thereof, and ethylene-(meth)acrylic acid ( ester) copolymers such as polyolefin copolymers, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylates, polycarbonates, copolymerized polyesters (typically 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin) Polyester resins such as PET-G), acrylic resins such as polymethyl methacrylate, polyamide resins such as 6-nylon, 6,6-nylon, 6,10-nylon, and 12-nylon, polystyrene, and AS. Resins, styrene resins such as ABS resins, cellulose derivatives such as cellulose acetate and nitrocellulose, chlorine resins such as polyvinyl chloride and polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetra Examples include fluororesins such as fluoroethylene copolymers, copolymers, mixtures, and composites of two or more selected from these.

In particular, in consideration of productivity in a melt extrusion device, environmental compatibility, mechanical strength as a floor material, durability, price, etc., it is more preferable that the base material layer 11 is made of a polyolefin resin. Here, the base material layer 11 can also have a laminated structure in which a plurality of layers made of the above thermoplastic resin are stacked.

The base material layer 11 is preferably colored. For example, the colored base layer 11 can be obtained by mixing and kneading a coloring agent into the thermoplastic resin material that constitutes the base layer 11. Examples of the coloring agent include organic dyes and inorganic pigments (including titanium oxide). Further, before providing the pattern layer 12 on the base layer 11, it is also possible to separately provide a colored layer to serve as a solid ink layer on the base layer 11 by a coating method or a printing method. The hue of the base material layer 11 is appropriately selected as the base color of the pattern layer 12. The colored base material layer 11 can hide a substrate (details will be described later) that is bonded to the decorative sheet 10.

The base material layer 11 may be previously subjected to surface treatment such as corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet treatment, dichromic acid treatment, etc., in order to further improve adhesion with adjacent layers. It is. Further, the base material layer 11 can be imparted with flame retardancy and anti-fading property by adding a flame retardant, an ultraviolet absorber, or the like.

Flame retardants include inorganic (aluminum hydroxide, magnesium hydroxide, antimony trioxide, etc.), phosphorus (organic: phosphate ester, ammonium phosphate, etc., inorganic: red phosphorus), and reactive (vinyl-added) Examples include vinyl compounds to be polymerized, compounds having functional groups such as carboxylic acid groups, hydroxyl groups, and epoxy groups, and used as some raw materials for polymers (copolymerization monomers). Particularly preferred are aluminum hydroxide and magnesium hydroxide, which are excellent in terms of compatibility with resins, flame retardant effects, environmental safety, and the like.

Examples of ultraviolet absorbers include triazine-based, benzophenone-based, benzotriazole-based, salicylate-based, cyanoacrylate-based, formamidine-based, oxanilide-based, etc.; examples of light stabilizers include hindered amine-based, etc. . In particular, triazine-based, benzotriazole-based, oxanilide-based, hindered amine-based, or mixtures thereof are preferred because they have excellent ultraviolet absorption and photostability as well as excellent compatibility with olefin resins and the like.

In addition, the thickness of the base material layer 11 in the lamination direction is preferably 50 μm or more and 100 μm or less, and more preferably 60 μm or more and 80 μm or less. If it is less than 50 μm, it tends to cause a decrease in weather resistance, which is not very preferable. If it exceeds 100 μm, it tends to cause a decrease in workability, which is not very preferable.

<Picture layer 12>
The pattern layer 12 provides a design with a printed pattern. As the design, a desired pattern can be appropriately selected depending on the purpose, such as a wood grain pattern, a cork pattern, a stone grain pattern, a tile pattern, a pottery pattern, an abstract pattern, and the like. Moreover, known printing methods such as gravure printing, offset printing, silk screen printing, flexographic printing, and inkjet printing can be applied to the pattern layer 2. Furthermore, when the pattern layer 12 is entirely colored, it is possible to apply a coating method or apparatus in addition to a printing method.

The ink used to form the pattern layer 12 contains a binder resin. The binder resin can be used alone or appropriately selected from among nitrified cotton, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, etc., or each modified resin. , solvent-based, and emulsion types are applicable, and both one-component type and two-component type using a hardening agent are applicable.

The binder resin contained in the pattern layer 12 may be a urethane resin having a general-purpose polyester polyol as a component, but from the viewpoint of adhesion to the base layer 11 and moist heat resistance, polycaprolactone polyol, polyalkylene glycol, etc. It is preferable that the resin is a urethane resin having polyisocyanate as a constituent element.

Polycaprolactone polyol, which is a component of the urethane resin according to this embodiment, is a material obtained by ring-opening polymerization of ε-caprolactone, and has an ester bond inside, so it has good adhesion to the base layer 11. (Base material adhesion) can be improved. The above-mentioned polycaprolactone polyol has excellent hydrolysis resistance, for example, as compared to a general-purpose polyester polyol obtained by polycondensation of a dicarboxylic acid such as adipic acid and a diol.

The polyalkylene glycol, which is a component of the urethane resin according to this embodiment, has a polyether structure and has better hydrolysis resistance than the above-mentioned polycaprolactone polyol, but has poor heat resistance and adhesion to the substrate. They tend to be inferior in gender. Therefore, in this embodiment, by using polyalkylene glycol and polycaprolactone polyol in combination, both substrate adhesion and heat-and-moisture resistance are improved.

Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. In particular, when polytetramethylene glycol is applied, hydrophobicity can be increased and moist heat resistance can be improved. Therefore, it is preferable.

The polycaprolactone polyol and the polyalkylene glycol can be appropriately selected from various commercially available materials in terms of molecular weight, number of functional groups (number of hydroxyl groups per molecule), and the like.

Examples of the polyisocyanate that is a component of the urethane resin according to the present embodiment include diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, and hydrogenated products thereof, and in particular, isophorone diisocyanate. It is preferable if it exists because it can improve the heat and humidity resistance.

It is preferable that the urethane resin according to the present embodiment further contains neopentyl glycol as a component, since this can further improve the heat and humidity resistance.

The composition of the urethane resin according to the present embodiment is not particularly limited, but since the pattern layer 12 is usually formed by a printing method, each part of the urethane resin (caprolactone unit (CL)) shown in the structural formula below , alkylene glycol unit (AG), diisocyanate unit (I), neopentyl glycol (NPG)) as X, Y, Z, and N, respectively, the following formulas (1) to (3) It is preferable that the relationship is satisfied because printing suitability can be easily improved.

3<(X+Y+N)/Z<50...(1)
0.1<X/Y<10 (2)
N/(X+Y+Z+N)<0.2...(3)

The molecular weight of the urethane resin according to the present embodiment is not particularly limited, but since the pattern layer 12 is usually formed by a printing method, the weight average molecular weight (MW) is set within the range of 5000 to 100000. This is preferable because printing suitability can be easily improved.

The curing agent used for curing the urethane resin according to the present embodiment is not particularly limited, but examples include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), xylylene diisocyanate (HDI), and Examples include those containing isocyanate (XDI) and its hydrogenated product, or diphenylmethane diisocyanate (MDI) and its hydrogenated product, and commercially available curing agents containing these can be appropriately selected and used. It is possible.

The pattern layer 12 is formed by printing a pattern ink containing the above-mentioned urethane resin as a binder resin onto the base layer 11, but it is also possible to contain other resin components as necessary. be. Components other than the binder resin of such a pattern ink include, for example, various additives such as colorants such as pigments and dyes, extender pigments, solvents, and light stabilizers.

Examples of pigments include pearl pigments such as condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and mica.

<Adhesive layer 13>
The adhesive layer 13 contains a polyester resin and a bisphenol A epoxy resin. The bisphenol A type epoxy resin can be appropriately selected and used from various commonly available grades having different molecular weights and epoxy equivalents. From the viewpoint of achieving both heat and humidity resistance and adhesiveness, the bisphenol A type epoxy resin preferably has a molecular weight (mass average molecular weight MW) in the range of 1000 to 4000, and preferably in the range of 1000 to 2000. is particularly preferred.

The above polyester resin has phthalic acid, linear dicarboxylic acid, and alkylene diol as constituent elements. Such a polyester resin can be produced by a known technique (for example, a polycondensation reaction between a dicarboxylic acid and a diol). By mixing the polyester resin and the bisphenol A type epoxy resin, the adhesive layer 13 can exhibit moisture and heat resistance sufficient for practical use as a decorative sheet.

Phthalic acid (in this specification, it is a general term including orthophthalic acid and terephthalic acid), which is a constituent element of the polyester resin, is used to enhance the heat-and-moisture resistance. The linear dicarboxylic acid that is a component of the polyester resin is not particularly limited, but examples include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. can.

The alkylene diol that is a component of the polyester resin is not particularly limited, but examples include (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, (poly)hexamethylene glycol, etc. can be mentioned. Here, it is preferable to further contain neopentyl glycol as the alkylene diol, since the moisture and heat resistance can be further improved.

The mass ratio of the polyester resin and the bisphenol A epoxy resin (polyester resin:bisphenol A epoxy resin) needs to be within the range of 50:50 to 90:10. If the bisphenol A type epoxy resin is less than the above-mentioned proportion, the desired moisture and heat resistance cannot be obtained, and if it is greater than the above-mentioned proportion, the required adhesiveness cannot be obtained.

Further, the molar ratio of phthalic acid and linear dicarboxylic acid (phthalic acid: linear dicarboxylic acid) is preferably within the range of 45:55 to 85:15. If the phthalic acid content is greater than the above-mentioned ratio, it is undesirable because it tends to cause embrittlement and may lead to a decrease in adhesive properties. On the other hand, if the phthalic acid content is smaller than the above ratio, it tends to cause a decrease in cohesive force, which may lead to a decrease in adhesiveness, which is not preferable.

Furthermore, the molar ratio of alkylene diol to phthalic acid and linear dicarboxylic acid (alkylene diol: (phthalic acid + linear dicarboxylic acid)) is preferably within the range of 40:60 to 60:40. If it is outside the above range, the molecular weight of the polyester resin may become small, leading to a decrease in adhesiveness and heat resistance, which is not preferable.

The adhesive layer 13 can be formed, for example, by applying a general coating method or adhesion method such as gravure coating, microgravure coating, comma coating, knife coating, or die coating.

The thickness of the adhesive layer 13 in the lamination direction is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less. If it is less than 0.5 μm, it becomes difficult to develop sufficient adhesion, which is not very preferable. If it exceeds 10 μm, it will be too much than necessary and is not very preferable.

<Weather-resistant layer 14>
The weather-resistant layer 14 is preferably made of a mixture of acrylic resin (polymethyl methacrylate resin) and acrylic rubber (polymethyl methacrylate rubber). The mass ratio of acrylic resin and acrylic rubber (acrylic resin: acrylic rubber) is preferably within the range of 40:60 to 70:30. In other words, in forming the weather-resistant layer 14, it is preferable that the mixing ratio of the acrylic resin is 40% by mass or more and 70% by mass or less, and the mixing ratio of the acrylic rubber is 30% by mass or more and 60% by mass or less. .

The weather-resistant layer 14 preferably contains an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazole type and triazine type, and these can be used alone or in combination. By adding and mixing an ultraviolet absorber to the material (mixture of acrylic resin and acrylic rubber) constituting the weather-resistant layer 14, light resistance and weather resistance can be further improved.

The weather-resistant layer 14 preferably contains an ultraviolet absorber in an amount of 0.2% by mass or more and 0.8% by mass or less based on the total mass of the acrylic resin and acrylic rubber. If the content of the ultraviolet absorber is less than 0.2% by mass, it may become difficult to fully express the performance of the ultraviolet absorber. If the content of the ultraviolet absorber exceeds 0.8%, it may become difficult for the ultraviolet absorber to be uniformly dispersed in the weather-resistant layer 14. For example, if the ultraviolet absorber is mixed in such an amount that the weather-resistant layer 14 is colored, it will be undesirable.

The thickness of the weather-resistant layer 14 in the lamination direction is preferably 20 μm or more and 70 μm or less, more preferably 40 μm or more and 60 μm or less. If it is less than 20 μm, it becomes difficult to obtain sufficient weather resistance, which is not very preferable. If it exceeds 70 μm, it tends to cause a decrease in workability, which is not very preferable. Note that the weather-resistant layer 14 may be patterned with an uneven pattern, such as embossing, in order to improve the design.

<Stain-resistant layer 15>
The stain-resistant layer 15 is preferably a resin layer containing fluororesin or ethylene vinyl alcohol resin (ethylene vinyl alcohol copolymer resin) (EVOH), which has excellent solvent resistance, oil resistance, stain resistance, and transparency. In particular, it is more preferable to use a fluororesin. Moreover, the stain-resistant layer 15 can also further contain an acrylic resin.

Examples of fluororesins include polyvinyl fluoride resin (PVF), ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and tetrafluoroethylene copolymer (FEP). Examples include perfluoroalkyl vinyl ether copolymer (PFA). In particular, ethylene-tetrafluoroethylene copolymer (ETFE) and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) are more preferable because they have excellent not only stain resistance but also melt moldability.

There are two types of EVOH: a type with an ethylene content of 82 mol% or more and 90 mol% or less, and a type with an ethylene content of 25 mol% or more and 50 mol% or less. It is preferable because it has better solvent resistance, oil resistance, stain resistance, and transparency.

Like the weather-resistant layer 14, the stain-resistant layer 15 preferably contains an ultraviolet absorber because light resistance and weather resistance can be further improved. By adding and mixing an ultraviolet absorber to the material (mixture of acrylic resin and acrylic rubber) constituting the stain-resistant layer 15, light resistance and weather resistance can be further improved. It should be noted that it is not preferable to mix the ultraviolet absorber in such an amount that the weather-resistant layer 14 is colored.

The stain-resistant layer 15 can be provided by coating its surface with a fluororesin or EVOH, or by laminating a fluororesin film or an EVOH film to the weather-resistant layer 14.

In the case where the stain-resistant layer 15 is formed using a fluororesin film, when an uneven pattern such as embossing is to be applied to the surface, the fluororesin film is bonded to the weather-resistant layer 14 and then the uneven pattern is applied. It is preferable to process it.

In addition, when forming the stain-resistant layer 15 using EVOH, when processing an uneven pattern such as embossing on the surface, the EVOH film is laminated to the weather-resistant layer 14 and then the uneven pattern is processed. Alternatively, it is preferable to apply a pattern with an uneven shape when heat-melting Ruder coating the EVOH. For example, when the material of the weather-resistant layer 14 and EVOH are co-extruded and laminated with an extruder, it is preferable to simultaneously process the material with an uneven pattern.

The combined thickness of the weather-resistant layer 14 and stain-resistant layer 15 in the lamination direction is preferably 20 μm or more and 80 μm or less, and more preferably 40 μm or more and 60 μm or less. If it is less than 20 μm, it becomes difficult to sufficiently develop weather resistance, which is not very preferable. If it exceeds 80 μm, it will cause a decrease in nonflammability, which is not very preferable.

<Method for manufacturing decorative sheet 10>
In the decorative sheet 10 according to the present embodiment having such a structure, after printing the pattern layer 12 on the base layer 11, the adhesive layer 13 is applied and adhered, and the weather-resistant layer 14 and the stain-resistant layer 15 are formed. It can be manufactured by laminating and thermally laminating (for example, at 150° C. for 1 minute).

<Effects of decorative sheet 10>
In the decorative sheet 10 according to the present embodiment obtained in this manner, the adhesive layer 13 contains a polyester resin and a bisphenol A type epoxy resin, and the polyester resin constitutes phthalic acid, linear dicarboxylic acid, and alkylene diol. Since the mass ratio of polyester resin and bisphenol A epoxy resin (polyester resin: bisphenol A epoxy resin) is within the range of 50:50 to 90:10, it has sufficient adhesive properties. However, it can exhibit excellent heat and humidity resistance and weather resistance, and can be applied to the exterior of buildings that are exposed to outdoor environments for a long period of time.

Moreover, when the molar ratio of phthalic acid and linear dicarboxylic acid (phthalic acid: linear carboxylic acid) is within the range of 45:55 to 85:15, adhesiveness can be further improved.

Furthermore, when the molar ratio of alkylene diol to phthalic acid and linear dicarboxylic acid (alkylene diol: (phthalic acid + linear dicarboxylic acid)) is within the range of 40:60 to 60:40, adhesive properties are improved. It is possible to prevent a decrease in heat resistance and heat resistance.

In addition, when neopentyl glycol is further contained as the alkylene diol, the heat and humidity resistance can be further improved.

<Metal decorative parts>
As shown in FIG. 2, an adhesive 102 is applied onto a substrate 101 made of metal such as aluminum, stainless steel, copper, or steel plate. A base layer 16 is provided between the adhesive 102 and the base layer 11 of the decorative sheet 10 to improve adhesiveness.

That is, the metal decorative member 100 according to the present embodiment includes a metal substrate 101 that is attached to the base layer 11 of the decorative sheet 10, and an adhesive 102 that adheres the substrate 101 to the base layer 11 of the decorative sheet 10. In addition, a base layer 16 is provided on the base layer 11 so as to be located between the base layer 11 of the decorative sheet 10 and the adhesive 102.

Although the adhesive 102 is not particularly limited, for example, a two-component curing type urethane adhesive can be used. Further, the base layer 16 is not particularly limited, but may be made of, for example, the same material as the pattern layer 12 described above (urethane resin).

According to the metal decorative member 100 according to the present embodiment, the cone calorimeter complies with the fire resistance test method and performance evaluation standard based on Article 2, Item 9 of the Building Standards Act and Article 108-2 of the Building Standards Act Enforcement Order. In the exothermic test using a testing machine, (1) the total calorific value for 20 minutes after the start of heating was 8 MJ/m2 or ^less , and (2) the maximum exothermic rate was 200 KW/m for 20 minutes after the start of heating for 10 seconds or more. m ² and (3) have noncombustibility to the extent that there are no cracks or holes harmful to fire protection for 20 minutes after the start of heating.

[Other embodiments]
In addition, in the embodiment mentioned above, the case of the decorative sheet 10 having the one-component adhesive layer 13 was described, but the present invention is not limited to this. As another embodiment, it is also possible to use a two-component adhesive layer that uses a curing agent, for example.

Further, in the embodiment described above, a case has been described in which the decorative sheet 10 has the adhesive layer 13 and the weather-resistant layer 14 directly adhered to each other, but the present invention is not limited to this. As another embodiment, it is also possible to provide a decorative sheet in which, for example, an anchor layer is interposed between the adhesive layer 13 and the weather-resistant layer 14 to further improve adhesiveness.

Further, in the embodiment described above, the case of the decorative sheet 10 having the pattern layer 12 was described, but the present invention is not limited to this. As another embodiment, for example, it is also possible to provide a decorative sheet in which the pattern layer 12 is omitted.

Further, in the above-described embodiment, the metal decorative member 100 was described in which the decorative sheet 10 provided with the base layer 16 and the substrate 101 were bonded via the adhesive 102, but the present invention is not limited to this. As another embodiment, for example, the base layer 16 may be omitted, and a metal decorative member may be obtained by bonding the base material 11 of the decorative sheet 10 and the substrate 101 via the adhesive 102.

Examples of the decorative sheet and the metal decorative member using the same according to the present invention will be specifically described below. It should be noted that the present invention is not limited to the specific examples described below, and the technical matters of each example can be appropriately combined as necessary.

[Preparation of test specimen and comparison specimen]
<Test specimen 1>
《Base material layer》
A colored polyethylene sheet (70 μm thick) with concealing properties was prepared and used as a base layer.

《Picture layer》
Using polycaprolactone diol, polytetramethylene glycol, and neopentyl glycol as polyols and isophorone diisocyanate as polyisocyanate, a hydroxyl-terminated urethane resin with a number average molecular weight of 2 x 10 ⁴ was synthesized by a known addition polymerization method. did. A pigment was added to the urethane resin and mixed and dispersed so that the mass ratio of the urethane resin and the copper phthalocyanine pigment (urethane resin:pigment) was 80:20 to prepare an ink for a pattern layer. This ink for the pattern layer was gravure printed on the base material layer to form a wood grain pattern pattern layer (thickness: 1 μm) on the base material layer.

《Base layer》
A diluent solvent (ethyl acetate and methyl isobutyl ketone in a 1:1 mass ratio) is added to 100 parts by mass of a two-component curable polyester urethane (a mixture of polyester polyol and polyisocyanate in a 100:5 mass ratio). Mixed product) 20 parts by mass were added and mixed and stirred. This was applied to the base material layer by a gravure coating method and dried to form a base layer (thickness: 1 μm).

《Adhesive layer》
Polyester diol (polyester resin) ( P) was synthesized (IP:AD=90:10 (mole ratio), number average molecular weight: 1×10 ⁴ , solid content hydroxyl value: 10 mgKOH/g).

The solid content mass ratio (P: EP A raw material solution for the adhesive layer is prepared by adding bisphenol A type epoxy resin (EP) to polyester diol (polyester resin) (P) and mixing with a diluting solvent so that the ratio of 70:30 is obtained. Then, the raw material liquid was applied by gravure coating onto the pattern layer of the base material layer so that the thickness after heating and solidification was 1 μm.

《Weather-resistant layer and stain-resistant layer》
40 parts by mass of acrylic resin (PPMA resin, structural unit: methyl methacrylate), acrylic rubber (PMMA rubber "Parapet (registered trademark) SA-FW001 (product number)" manufactured by Kuraray Co., Ltd., structural unit: methyl methacrylate, average particle) Diameter: 100 nm) and 0.5 parts by mass of an ultraviolet absorber (benzotriazole ultraviolet absorber "Tinuvin (registered trademark) 326 (product number)" manufactured by BASF Japan Co., Ltd.) were mixed to form a weather-resistant layer. The raw materials were adjusted.

By melting and extruding the above mixture of raw materials for the weather-resistant layer and polyvinylidene fluoride resin (fluororesin) using a T-die, a weather-resistant layer (thickness 15 μm) and a stain-resistant layer (thickness A laminate (thickness: 20 μm) was obtained. The above laminate was laminated on the pattern layer of the base material layer via an adhesive layer, and then thermally laminated (150° C. for 1 minute) to obtain a decorative sheet (thickness: 120 μm).

《Metal decorative parts》
After applying a two-component curable urethane adhesive to an aluminum substrate (thickness 1 mm) at a dry coating weight of 25 g/ ^m2 , the metallic decorative adhesive is bonded to the base layer of the decorative sheet. A specimen 1 of the member was obtained.

<Test specimen 2>
Same as test specimen 1 except that the solid mass ratio (P:EP) of polyester diol (polyester resin) (P) and bisphenol A type epoxy resin (EP) in the adhesive layer is 80:20. As a result, a test piece 2 of a metal decorative member was obtained.

<Test specimen 3>
Same as test specimen 1 except that the solid mass ratio (P:EP) of polyester diol (polyester resin) (P) and bisphenol A type epoxy resin (EP) in the adhesive layer is 60:40. As a result, a test piece 3 of a metal decorative member was obtained.

<Test specimen 4>
Same as test specimen 1 except that the solid mass ratio (P:EP) of polyester diol (polyester resin) (P) and bisphenol A type epoxy resin (EP) in the adhesive layer is 50:50. As a result, a test piece 4 of a metal decorative member was obtained.

<Test specimen 5>
Same as test specimen 1 except that the solid mass ratio (P:EP) of polyester diol (polyester resin) (P) and bisphenol A type epoxy resin (EP) in the adhesive layer is 90:10. As a result, a test piece 4 of a metal decorative member was obtained.

<Test specimen 6>
Same as test specimen 1 except that the molar ratio (IP:AD) of isophthalic acid (IP) as phthalic acid and adipic acid (AD) as linear dicarboxylic acid in the adhesive layer is 65:35. As a result, a test piece 6 of a metal decorative member was obtained.

<Test specimen 7>
Same as test specimen 1 except that the molar ratio (IP:AD) of isophthalic acid (IP) as phthalic acid and adipic acid (AD) as linear dicarboxylic acid in the adhesive layer is 85:15. As a result, a test piece 7 of a metal decorative member was obtained.

<Test specimen 8>
Same as test specimen 1 except that the molar ratio (IP:AD) of isophthalic acid (IP) as phthalic acid and adipic acid (AD) as linear dicarboxylic acid in the adhesive layer is 45:55. As a result, a test piece 8 of a metal decorative member was obtained.

<Test specimen 9>
Same as test specimen 1 except that the molar ratio (IP:AD) of isophthalic acid (IP) as phthalic acid and adipic acid (AD) as linear dicarboxylic acid in the adhesive layer is 40:60. As a result, a test piece 9 of a metal decorative member was obtained.

<Test specimen 10>
A metallic decorative member test specimen 10 was obtained in the same manner as the test specimen 6 except that neopentyl glycol (NPG) was used as the diol in the adhesive layer in combination with ethylene glycol and hexanediol.

<Comparative body 1>
The solid content mass ratio (P:EP) of polyester diol (polyester resin) (P) and bisphenol A type epoxy resin (EP) in the adhesive layer is 100:0, that is, bisphenol A type epoxy resin (EP) is omitted. Comparative body 1 of a metal decorative member was obtained by using the same method as test body 10 except that only polyester diol (polyester resin) (P) was used.

<Comparative body 2>
Same as test specimen 10 except that the solid mass ratio (P:EP) of polyester diol (polyester resin) (P) and bisphenol A type epoxy resin (EP) in the adhesive layer was 40:60. Comparative body 2 of the metal decorative member was thus obtained.

[contents of the test]
<Adhesion test>
Samples (width 25 mm) were cut from test specimens 1 to 10 and comparative specimens 1 and 2, and stored at room temperature for 24 hours. The T-peel strength between the pattern layer (base material layer) and the weather-resistant layer ( The tensile speed: 50 mm/min) was measured. The results are shown in Table 1 below. In Table 1, "◎" indicates that the base material is broken without peeling at the interface, "○" indicates that peeling occurs at the interface while the base material layer is deformed, and "△" indicates that the base material layer is damaged. An "X" indicates that peeling occurs at the interface without deformation, and that measurement is not possible due to peeling during handling of the sample. An evaluation result of "◎" or "○" was considered to be a pass.

<Moisture heat resistance test>
Samples (width 25 mm) were cut from each of test specimens 1 to 10 and comparison specimens 1 and 2 and stored at room temperature for 24 hours, and then subjected to a pressure cooker test (PCT) using a highly accelerated life test device (HAST chamber). The test was conducted under the following conditions.
・Temperature: 105℃
・Humidity: 100%RH
・Time: 96 hours

Subsequently, the T-peel strength (tensile speed: 50 mm/min) between the pattern layer (base material layer) and the weather-resistant layer was measured. The results are shown in Table 1 below. In Table 1, "◎" indicates that the base material is broken without peeling at the interface, "○" indicates that peeling occurs at the interface while the base material layer is deformed, and "△" indicates that the base material layer is damaged. An "X" indicates that peeling occurs at the interface without deformation, and that measurement is not possible due to peeling during handling of the sample. An evaluation result of "◎" or "○" was considered to be a pass.

<Weather resistance test>
Test specimens 1 to 10 and comparative specimens 1 and 2 were tested in ultraviolet irradiation mode (20 hours) and dew condensation mode (4 hours) under the following conditions using a super accelerated weathering tester (metal halide lamp weather meter). 25 cycles (600 hours) were performed, with this as one cycle (24 hours).

《Ultraviolet irradiation mode》
・Illuminance: 65mW/ ^cm2
・Black panel temperature: 63℃
・Relative humidity: 50%

《Condensation mode》
・Environmental temperature: 30℃
・Relative humidity 98%
*Shower spray for 10 seconds when switching modes

After the test was completed, test specimens 1 to 10 and comparative specimens 1 and 2 were taken out of the testing machine and their appearance was visually checked. The results are shown in Table 1 below. In Table 1, "○" indicates that neither significant discoloration or fading nor peeling occurred, "△" indicates that either significant discoloration or fading or peeling has occurred, and "x" indicates that significant discoloration and fading or peeling has occurred. This means that both of these are occurring. An evaluation result of "○" was considered a pass.

[Test results]
The test results of each test are shown in Table 1.

As can be seen from Table 1, the solid mass ratio (P:EP) of polyester diol (polyester resin) (P) and bisphenol A type epoxy resin (EP) in the adhesive layer is 100:0, that is, bisphenol A type Comparative Example 1, in which the epoxy resin (EP) was omitted and only the polyester diol (polyester resin) (P) was used, had excellent adhesiveness, but poor moist heat resistance and poor weather resistance.

In addition, in Comparative Body 2 in which the solid content mass ratio (P:EP) of polyester diol (polyester resin) (P) and bisphenol A type epoxy resin (EP) in the adhesive layer was 40:60, the adhesiveness was Not only was it bad, but its moist heat resistance and weather resistance were also bad.

On the other hand, the solid mass ratio (P:EP) of polyester diol (polyester resin) (P) and bisphenol A type epoxy resin (EP) in the adhesive layer is within the range of 50:50 to 90:10. It was confirmed that test specimens 1 to 10 shown in 1. gave good results in terms of adhesion, heat and humidity resistance, and weather resistance.

Among them, test specimens 6 to 8 in which the molar ratio of isophthalic acid (IP) to adipic acid (AD) in the adhesive layer (IP:AD) was within the range of 45:55 to 85:15. It was confirmed that excellent adhesiveness could be obtained.

In particular, it was confirmed that in test specimen 10 in which neopentyl glycol (NPG) was used in combination with ethylene glycol and hexanediol as the diol in the adhesive layer, even better adhesiveness and heat-and-moisture resistance could be obtained.

The decorative sheet according to the present invention and the decorative metal member using the same can be applied to the exterior of buildings that are exposed to outdoor environments for a long period of time, and therefore are extremely useful in various industries including the construction industry. can be used.

10 Decorative sheet 11 Base material layer 12 Pattern layer 13 Adhesive layer 14 Weather-resistant layer 15 Stain-resistant layer 16 Base layer 100 Metallic decorative member 101 Substrate 102 Adhesive

Claims (10)

a base material layer;
a weather-resistant layer provided on the base layer;
a stain-resistant layer provided on the weather-resistant layer;
A decorative sheet comprising: an adhesive layer provided between the base layer and the weather-resistant layer,
The adhesive layer is
Contains polyester resin and bisphenol A type epoxy resin,
The polyester resin has phthalic acid, a linear dicarboxylic acid, and an alkylene diol as constituent elements,
A decorative sheet characterized in that a mass ratio of the polyester resin and the bisphenol A epoxy resin (polyester resin:bisphenol A epoxy resin) is within a range of 50:50 to 90:10. The decorative sheet according to claim 1, wherein the molar ratio of the phthalic acid and the linear dicarboxylic acid (phthalic acid: linear carboxylic acid) is within the range of 45:55 to 85:1. . The decorative sheet according to claim 1, wherein the alkylene diol contains neopentyl glycol. The decorative sheet according to claim 1, wherein a pattern layer is provided between the base material layer and the adhesive layer. The decorative sheet according to claim 4, wherein the pattern layer contains, as a binder resin, a urethane resin having polycaprolactone polyol, polyalkylene glycol, and polyisocyanate as constituent elements. The decorative sheet according to claim 5, wherein the urethane resin further contains neopentyl glycol as a constituent element. The decorative sheet according to claim 5, wherein the polyalkylene glycol is polytetramethylene glycol. The decorative sheet according to claim 5, wherein the polyisocyanate is isophorone diisocyanate. The decorative sheet according to any one of claims 1 to 8,
a metal substrate attached to the base layer of the decorative sheet;
and an adhesive for bonding the substrate to the base layer of the decorative sheet. The metal decorative member according to claim 9, wherein a base layer is provided on the base layer so as to be located between the base layer of the decorative sheet and the adhesive.

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