JP6476952B2 - Decorative sheet and metal decorative board - Google Patents

Description

  The present invention relates to a decorative sheet used for architectural interiors, partitions, surface decorative materials such as storage furniture, etc., architectural quasi-exterior (entrance doors, the same frame materials, window frames), a bay window counter, and the like.

  Conventionally, as a decorative sheet, for example, there is a technology described in Patent Document 1 (paragraph 0003). In the technique described in Patent Document 1, an acrylic resin excellent in weather resistance is used as the outermost layer.

Unexamined-Japanese-Patent No. 2000-326451

However, although acrylic resin is excellent in weather resistance, it has a problem that stains are likely to be attached due to low stain resistance, oil resistance and solvent resistance, and that the adhered stains can not be wiped off with a solvent. is there. There is also the problem of low processability and low non-combustibility.
The present invention focuses on the above points, and has a weather resistance, a stain resistance, and a solvent resistance, as well as a decorative board capable of improving nonflammability, processability, and weather resistance together. The purpose is to provide.

In order to solve the said subject, the decorative sheet which is 1 aspect of this invention laminates | stacks a weather resistant resin layer and a fluorine resin layer in this order on a base material layer, and a weather resistant resin layer is an acrylic resin and an acrylic resin. The mixture ratio is 40 mass% or more and 70 mass% or less of the acrylic resin, and 30 mass% or more and 60 mass% or less of the acrylic resin type rubber, and the thickness and the weather resistance of the fluorine resin layer It is characterized in that the ratio to the thickness of the conductive resin layer is in the range of 10:90 to 40:60, and it has noncombustibility.
Here, the non-combustibility is a corn calorimeter tester according to the fireproof test method and performance evaluation standard based on Building Standard Act Article 2 No. 9 and Building Standard Act Construction Order Article 108-2 in accordance with ISO 5660-1. in exothermic test (1) the total amount of heat generated by the heating start after 20 minutes is at 8 MJ / ^{m 2} or less (2) heating starts after 20 minutes, a 200 KW / ^{m 2} continues up-heating rate above 10 seconds exceeded by (3) It is preferable to have a non-combustibility sufficient to satisfy no fire damage harmful cracks and holes for 20 minutes after the start of heating.

  According to one aspect of the present invention, since the weather resistant resin layer and the fluorine resin layer are laminated on the base material layer, it has weather resistance, stain resistance, and solvent resistance. In addition, the acrylic resin of the weather resistant resin layer is 40% by mass to 70% by mass, and the acrylic resin rubber is 30% by mass to 60% by mass, and the ratio of the thickness of the fluorine resin layer to the thickness of the weather resistant resin layer is Since the range is 10:90 to 40:60, it is possible to improve the nonflammability, the processability and the weather resistance. Thus, according to one aspect of the present invention, there is provided a decorative sheet having weatherability, stain resistance, and solvent resistance, as well as being capable of improving nonflammability, processability, and weatherability together. be able to.

It is a sectional view showing a metal decorative board concerning an embodiment based on the present 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 dimension, the ratio of the thickness of each layer, and the like are different from actual ones. Moreover, the embodiment shown below exemplifies the structure for embodying the technical idea of this invention, Comprising: The technical idea of this invention is the material of a component, a shape, a structure, etc. Not specific to The technical idea of the present invention can be variously modified within the technical scope defined by the claims described in the claims.

(Metal decorative plate 20)
In the metal decorative board 20 of the present embodiment, as shown in FIG. 1, the weather resistant resin layer 4 and the fluorine resin layer 5 are laminated in this order on one surface side of the base material layer 1 to form a decorative sheet 10. The metal plate 7 is bonded to the other surface of the base layer 1 via the adhesive layer 6. Thereby, the decorative sheet 10 and the metal decorative plate 20 have weather resistance, stain resistance and solvent resistance.
In FIG. 1, the decorative sheet 10 has the patterned layer 2 between the base material layer 1 and the weather resistant resin layer 4, and the patterned layer 2 and the weather resistant resin layer 4 are adhered by the transparent adhesive layer 3. The case is illustrated. The pattern layer 2 and the transparent adhesive layer 3 may be omitted.

(Base material layer 1)
The base material layer 1 is a sheet-like layer made of a thermoplastic resin. The thermoplastic resin is not particularly limited, and known thermoplastic resins can be used. For example, polyolefin resins such as polyethylene, polypropylene, polybutene and polymethylpentene, ethylene-vinyl acetate copolymer or saponified product thereof, and polyolefin copolymers such as ethylene- (meth) acrylic acid (ester) copolymer Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, copolymerized polyester (typically called 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin, commonly known as PET-G), poly Acrylic resins such as methyl methacrylate, polyamide resins such as 6-nylon, 6,6-nylon, 6,10-nylon and 12-nylon, polystyrene, AS resins, styrene resins such as ABS resin, cells Cellulose derivatives such as cellulose acetate and nitrocellulose, chlorinated resins such as polyvinyl chloride and polyvinylidene chloride, fluorinated resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene and ethylene-tetrafluoroethylene copolymer Or 2 or 3 or more copolymers, mixtures, composites, laminates and the like selected from these. In particular, polyolefin resins are more preferable in consideration of productivity in a melt extrusion apparatus, environmental compatibility, mechanical strength, durability, price and the like. In addition, the thermoplastic resin is colored by mixing a pigment, and a base color matched to the design of the decorative sheet 10 is set.

(Pattern pattern layer 2)
The picture pattern layer 2 is a layer on which a picture for giving design is printed. As the pattern, for example, a pattern suitable for a place using the decorative sheet 10, such as wood grain, cork, stone, tile, grill, abstract pattern, etc. can be selected. The printing ink is not particularly limited as far as printing suitability and weatherability are taken into consideration, and known printing inks can be used. For example, printing inks having pigments of isoindolinone, disazo, polyazo, diketopyrrolopyrrole, quinacridone, phthalocyanine, titanium oxide, carbon black can be used. Moreover, the expression of a pattern can be enriched by combining and mix | blending a pigment. Moreover, weather resistance can also be made favorable by adding an ultraviolet absorber, a light stabilizer, etc.
Moreover, as a printing method of a pattern, for example, known printing methods such as gravure printing, offset printing, silk screen printing, inkjet printing, etc. can be used, and in the case of coloring the same color on the entire surface, A coating method or apparatus may be used.

(Transparent adhesive layer 3)
The transparent adhesive layer 3 is a sheet-like layer made of a transparent adhesive. The transparent adhesive is not particularly limited, and known adhesives can be used. For example, thermoplastic resins such as polyamide resin, acrylic resin and vinyl acetate resin, and curable resins such as thermosetting urethane resin can be used. Further, for example, a two-component curable urethane resin or a polyester resin may be used, in which an isocyanate is used as a curing agent. In this embodiment, an acrylic resin-polyester resin-vinyl chloride-based resin which is a heat sealing agent is used as a transparent adhesive.

(Weatherproof resin layer 4)
The weather resistant resin layer 4 is a sheet-like layer made of a mixture of an acrylic resin and an acrylic resin rubber. The acrylic resin is not particularly limited, and known acrylic resins can be used. For example, methyl methacrylate resin and polymethyl methacrylate resin (Tg is about -20 ° C) can be used. Moreover, you may add a well-known ultraviolet absorber and light stabilizer to acrylic resin. The mixing ratio of these is set to 40% by mass to 70% by mass of the acrylic resin, and 30% by mass to 60% by mass of the acrylic resin rubber. Thereby, processability can be improved. “The mixing ratio is 40 mass% or more and 70 mass% or less of the acrylic resin, and 30 mass% or more and 60 mass% or less of the acrylic resin type rubber”, the mixing ratio of the acrylic resin and the acrylic resin type rubber is mass The ratio refers to 4: 6 to 7: 3.

(Fluororesin layer 5)
The fluorine resin layer 5 is a sheet-like layer made of a fluorine resin. The fluorine resin is not particularly limited, and known fluorine resins can be used. For example, polyvinylidene fluoride (PVDF), tetrafluoroethylene resin (PTFE), tetrafluoroethylene perfluoroalkoxyvinylether copolymer (PFA), tetrafluoroethylene · hexafluoropropylene copolymer (FEP), polychloro Trifluoroethylene (PCTFE), tetrafluoroethylene-ethylene copolymer (ETFE), chlorotrifluoroethylene-ethylene copolymer (ECTFE), polyvinyl fluoride (PVF) can be used. In particular, polyvinylidene fluoride (the PVDF has a Tg of −39 ° C.) is more preferable in consideration of the whitening resistance against bending and the adhesion to the weather resistant resin layer 4. Moreover, it is more preferable to set the ratio of the thickness of the fluororesin layer 5 to 20% or more and 40% or less with respect to the thickness of the weather resistant resin layer 4 in terms of whitening resistance. When the decorative sheet 10 of the present embodiment is folded after being bonded to the metal plate 7, the outermost layer (fluororesin layer 5) has a larger extension than the inner layer (weather resistant resin layer 4), but the outermost layer ( Since the Tg of the fluororesin layer 5) is low, it becomes difficult to generate fine cracks that cause whitening.
Moreover, it is preferable to set the ratio of the thickness of the fluororesin layer 5 to the thickness of the fluororesin layer 5 in the range of 10:90 to 40:60. Thereby, nonflammability can be improved. Furthermore, in consideration of the bending whitening property and the weather resistance, the total thickness of the thickness of the weather resistant resin layer 4 and the thickness of the fluorine resin layer 5 is preferably set in the range of 20 μm to 80 μm. In particular, 30 μm or more and 60 μm or less is more preferable in terms of whitening resistance to folding and weatherability.

(Adhesive layer 6)
The adhesive layer 6 is a sheet-like layer made of an adhesive. The adhesive is not particularly limited, and known adhesives can be used. For example, thermoplastic resins such as polyamide resin, acrylic resin and vinyl acetate resin, and curable resins such as thermosetting urethane resin can be used. Further, for example, a two-component curable urethane resin or a polyester resin may be used, in which an isocyanate is used as a curing agent.
(Metal plate 7)
The metal plate 7 is a plate-like member made of metal. The metal is not particularly limited, and known metals can be used. For example, aluminum, steel, stainless steel can be used.
(Other configuration)
An uneven pattern may be added to the surface of the decorative sheet 10. Examples of the method of forming the concavo-convex pattern include heat embossing. Thereby, the designability of the metal decorative board 20 can be improved.

(Effect of this embodiment)
The invention which concerns on this embodiment has the following effects.
(1) In the decorative sheet 10 according to the present embodiment, the weather resistant resin layer 4 and the fluorine resin layer 5 are laminated in this order on the base material layer 1, and the weather resistant resin layer 4 comprises acrylic resin and acrylic resin rubber. And a mixture ratio of the acrylic resin is 40% by mass to 70% by mass, and the acrylic resin rubber is 30% by mass to 60% by mass, and the fluorocarbon resin layer 5 and the weather resistant resin layer The ratio of 4 is in the range of 10:90 to 40:60 and is nonflammable.
According to such a configuration, since the weather resistant resin layer 4 and the fluorocarbon resin layer 5 are laminated on the base material layer 1, it has weather resistance, stain resistance, and solvent resistance. In addition, the thickness of the fluororesin layer 5 and the thickness of the weather resistant resin layer 4 are set so that the acrylic resin of the weather resistant resin layer 4 is 40 mass% or more and 70 mass% or less and the acrylic resin rubber is 30 mass% or more Since the ratio of (10) is in the range of 10:90 to 40:60, both nonflammability, processability and weatherability can be improved. Thereby, it is possible to provide the decorative sheet 10 having weather resistance, stain resistance, and solvent resistance, as well as being capable of improving the nonflammability, the processability, and the weather resistance.

(2) The metal decorative plate 20 according to the present embodiment is formed by bonding the decorative sheet 10 according to the present embodiment to the metal plate 7.
According to such a configuration, it is possible to provide a metal decorative board 20 having weatherability, stain resistance, and solvent resistance, and capable of improving nonflammability, processability, and weatherability.
(3) The metal decorative board 20 which concerns on this embodiment has an uneven | corrugated pattern on the decorative sheet surface.
According to such a configuration, the design of the metal decorative plate 20 can be improved.

Next, an embodiment based on the present invention will be described.
Example 1
In Example 1, the base material layer 1 was provided using colored polypropylene resin. The thickness of the base material layer 1 was 70 μm. After corona discharge treatment was applied to each of the surface and the back surface of the base layer 1, a wood pattern was printed on the surface of the base layer 1 by gravure printing with urethane printing ink to provide a patterned layer 2. Then, the back surface primer layer was provided in the back surface of the base material layer 1 by gravure printing with the coating liquid for back surface primer layers. The composition of the coating liquid for the back surface primer layer is a two-component curable polyester urethane (a mixture of polyester polyol and polyisocyanate in a ratio of 100: 5 (mass ratio)): 100 parts by mass, a dilution solvent (ethyl acetate and methyl isobutyl ketone) Mixed solvent mixed at a ratio of 1: 1 (mass ratio): 20 parts by mass. The thickness of the back surface primer layer was 1 μm.

  Subsequently, the polyvinylidene fluoride resin and the mixture for forming a weather resistant resin layer were melted and extruded using a T-die, and a laminate composed of the fluorine resin layer 5 and the weather resistant resin layer 4 was provided. Composition of the mixture for forming a weather resistant resin layer is 20 parts by mass of acrylic resin (structural unit: methyl methacrylate, PMMA resin), acrylic rubber ("SA-FW001 (trade name)", Kuraray Co., Ltd., methacrylic resin) Structural unit: Methyl methacrylate, particulate, average particle diameter: 100 nm, PMMA resin rubber): 80 parts by mass. The weather resistant resin layer 4 had a mass ratio of acrylic resin (PMMA resin) to acrylic resin rubber (PMMA resin rubber) as 40:60. In the laminate, the thickness of the fluorine resin layer 5 is 5 μm, the thickness of the weather resistant resin layer 4 is 45 μm, the total thickness is 50 μm, and the thickness of the fluorine resin layer 5: the thickness of the weather resistant resin layer 4 = 10: 90.

Subsequently, a coating liquid composed of a two-component curable urethane adhesive having a polyester resin as a main chain is coated on the pattern pattern layer 2 to form a transparent adhesive layer 3 (thickness in a dry state: 6 μm) The laminated body thus formed was laminated by a dry lamination method to provide a decorative sheet 10. Thereafter, the adhesive layer 6 is formed on the decorative sheet 10 with a two-component curable urethane adhesive (coating amount 25 g / m ² in the dry state), and then the metal plate 7 is bonded via the adhesive layer 6 The metal decorative plate 20 was obtained. An aluminum plate was used as the metal plate 7. The thickness of the metal plate 7 was 1 mm.

(Example 2)
The thickness of the fluorine resin layer 5 was adjusted to 20 μm, and the thickness of the weather resistant resin layer 4 was adjusted to 30 μm, that is, the thickness of the fluorine resin layer 5: the thickness of the weather resistant resin layer 4 = 40:60. A decorative sheet 10 of Example 2 was produced in the same manner as in Example 1 except for the above.
(Example 3)
The mass ratio of the acrylic resin to the acrylic resin rubber of the weather resistant resin layer 4 was adjusted to 70:30. A decorative sheet 10 of Example 3 was produced in the same manner as in Example 1 except for the above.
(Example 4)
The thickness of the fluorine resin layer 5 was adjusted to 20 μm, and the thickness of the weather resistant resin layer 4 was adjusted to 30 μm, that is, the thickness of the fluorine resin layer 5: the thickness of the weather resistant resin layer 4 = 40:60. A decorative sheet 10 of Example 4 was produced in the same manner as in Example 3 except for the above.

(Comparative example 1)
The thickness of the fluorine resin layer 5 was adjusted to 10 μm, and the thickness of the weather resistant resin layer 4 was adjusted to 40 μm, that is, the thickness of the fluorine resin layer 5: the thickness of the weather resistant resin layer 4 = 20:80. Further, the mass ratio of the acrylic resin to the acrylic resin rubber of the weather resistant resin layer 4 was adjusted to 20:80. A decorative sheet 10 of Comparative Example 1 was produced in the same manner as in Example 1 except for the above.
(Comparative example 2)
The mass ratio of the acrylic resin to the acrylic resin rubber of the weather resistant resin layer 4 was adjusted to 80:20. A decorative sheet 10 of Comparative Example 2 was produced in the same manner as Comparative Example 1 except for the above.

(Comparative example 3)
The thickness of the fluorine resin layer 5 was adjusted to 2 μm, and the thickness of the weather resistant resin layer 4 was adjusted to 48 μm, that is, the thickness of the fluorine resin layer 5: the thickness of the weather resistant resin layer 4 = 4:96. Further, the mass ratio of the acrylic resin to the acrylic resin rubber of the weather resistant resin layer 4 was adjusted to 50:50. A decorative sheet 10 of Comparative Example 3 was produced in the same manner as in Example 1 except for the above.
(Comparative example 4)
The thickness of the fluorine resin layer 5 was adjusted to 25 μm, and the thickness of the weather resistant resin layer 4 was adjusted to 25 μm, that is, the thickness of the fluorine resin layer 5: the thickness of the weather resistant resin layer 4 = 50:50. Except for that, the decorative sheet 10 of Comparative Example 4 was produced by the same procedure as Comparative Example 3.

(Evaluation judgment)
The following evaluation was implemented about the decorative sheet 10 of each above Example and each comparative example.
(Non Flammable)
The nonflammability was evaluated as follows.
Based on ISO5660-1, fire resistance test was carried out with a corn calorimeter tester according to the fire resistance test method and performance evaluation standard based on Building Standard Act Article 2 No. 9 and Building Standard Act Construction Order Article 108-2. . The gross calorific value of the heating starting after 20 min (MJ / ^{m 2)} is at 8 MJ / ^{m 2} or less, the maximum heat release rate of the start of heating after 20 minutes, not exceed 200 kW / ^{m 2} to continue for 10 seconds or more For example, it was accepted as "○". However, the cracks of the substrate were also evaluated, and the condition that the substrate had no cracks or holes was also considered.
(Lapping appropriate (processability))
Lapping appropriateness, that is, processability was evaluated as follows.
Lapping process (profile process) was performed. Then, immediately after the lapping process, one having no sheet peeling due to the stress of the decorative sheet 10 was regarded as a pass "○".

(Weatherability)
The weatherability was evaluated as follows.
Weather resistance was evaluated as follows using a metal weather.
After carrying out the irradiation mode of the following conditions for 20 hours, it carried out for 1 hour (one 24 hours) as a cycle (24 hours) of carrying out the condensation state for 4 hours in the condensation mode of the following conditions.
Irradiation mode: illuminance 65 mW / cm 2 (measured with Unimeter UIT-101 manufactured by Ushio), BP temperature 53 ° C., humidity 50%, irradiation for 20 hours Dew condensation mode: 30 ° C. 98%, 4 hours (before and after condensation mode) 30 seconds shower spray)
After conducting the test for 312 hours under the above conditions, the degree of discoloration and peeling of the appearance were confirmed by visual inspection. And when there was no remarkable discoloring or peeling, it was set as the pass "(circle)."

  The evaluation results are shown in Tables 1 and 2.

  From Table 1 and Table 2, as represented by Examples 1 to 4, the acrylic resin is 40% by mass to 70% by mass, and the acrylic resin rubber is 30% by mass to 60% by mass The ratio of the thickness of the fluorine resin layer 5 to the thickness of the weather resistant resin layer 4 is in the range of 10:90 to 40:60, and when the range of the present invention is satisfied, nonflammability, processability, and weather resistance It turned out that both sexes are good. Here, in Example 1, the acrylic resin is 40% by mass to 70% by mass, the acrylic resin rubber is 30% by mass to 60% by mass, the thickness of the fluorine resin layer 5 and the thickness of the weather resistant resin layer 4 When adjusted and implemented in the range of the present invention as the ratio of 10:90 to 40:60, the same effect as in Examples 1 to 4 was obtained.

  In addition, as typified by Comparative Example 1, when the acrylic resin is smaller than 40% by mass (lower limit) and the acrylic resin rubber is larger than 60% by mass (upper limit), the weather resistance is rejected “× It became ". Also, as represented by Comparative Example 2, when the acrylic resin is larger than 70% by mass (upper limit) and the acrylic resin rubber is larger than 30% by mass (lower limit), the processability is rejected “× It became ". On the other hand, typified by Examples 1 to 4, when the content of the acrylic resin of the weather resistant resin layer 4 is 40% by mass to 70% by mass and the content of the acrylic resin rubber is 30% by mass to 60% by mass. Both weatherability and processability could be improved.

  Further, as represented by Comparative Example 3, when the ratio of the fluororesin layer 5 to the weather resistant resin layer 4 is out of the range of 10:90 to 40:60 (4:96), the non-combustibility Was rejected “x”. Further, as represented by Comparative Example 4, when the ratio of the fluororesin layer 5 to the weather resistant resin layer 4 is out of the range of 10:90 to 40:60 (50:50), the processability is It became rejection "x". On the other hand, when the ratio of the fluorine resin layer 5 and the weather resistant resin layer 4 is in the range of 10:90 to 40:60 as represented by Examples 1 to 4, the nonflammability and processability are improved. Both were able to be good.

Reference Signs List 1 base material layer 2 design pattern layer 3 transparent adhesive layer 4 weather resistant resin layer 5 fluorocarbon resin layer 6 adhesive layer 7 metal plate 10 decorative sheet 20 metal decorative plate

Claims (5)

A transparent adhesive layer, a weather resistant resin layer and a fluorine resin layer are laminated in this order on the base material layer,
The weather resistant resin layer is made of a mixture of an acrylic resin and an acrylic resin-based rubber, and the mixing ratio thereof is 40% by mass to 70% by mass of the acrylic resin, and 30% by mass to 60% by mass of the acrylic resin-based rubber % Or less,
The ratio of the thickness of the fluorine resin layer to the thickness of the weather resistant resin layer is in the range of 10:90 to 40:60, and the nonflammability certification acquisition requirement is satisfied in the heat generation test according to ISO 5660-1;
The said transparent adhesive layer contains a thermosetting urethane resin as an adhesive agent, The decorative sheet characterized by the above-mentioned. The decorative sheet according to claim 1, wherein the transparent adhesive layer contains a two-component curable urethane adhesive having a polyester resin as a main chain. An adhesive layer is provided on the surface of the base layer opposite to the transparent adhesive layer side,
The decorative sheet according to claim 1 or 2, wherein the adhesive layer contains a polyamide resin or a thermosetting urethane resin as the adhesive. The decorative sheet according to any one of claims 1 to 3 is adhered to a metal plate. The metal decorative board according to claim 4 , wherein the decorative sheet surface has a concavo-convex pattern.

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