JP2016147388A - Decorative sheet and metal decorative member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet which has weather resistance, contamination resistance and solvent resistance, and has excellent bending and whitening resistance; and a metal decorative member.SOLUTION: A decorative sheet 10 is constituted by forming a weather-resistant resin layer 4, and a contamination-resistant resin layer 5 formed of a fluorine resin or an ethylene vinyl alcohol copolymer resin on a sheet base material 1 in this order. The weather-resistant resin layer 4 is formed of a mixture of an acrylic resin and an acrylic resin-based rubber, has a mass ratio of the acrylic resin and the acrylic resin-based rubber in a range of 40:60 to 70:30, and contains at least one or more ultraviolet absorbing agents selected from a benzotriazole-based ultraviolet absorbing agent and a triazine-based ultraviolet absorbing agent. The total thickness of the decorative sheet 10 is regulated to 200 μm or less, and the total thickness of the weather-resistant resin layer 4 and the contamination-resistant resin layer 5 is regulated to 20 μm or more and 80 μm or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative sheet and a metal decorative member having weather resistance, stain resistance and solvent resistance. For example, surface decorative materials such as architectural interiors, partitions, and storage furniture, and semi-exterior exteriors, that is, entrance doors and frame materials. The present invention relates to a decorative sheet and a metal decorative member used for window frames and bay window counters.

Conventionally, decorative sheets used for building interiors, partitioning, storage furniture, etc., and semi-exterior of buildings, that is, entrance doors, frame materials, window frames, bay window counters, etc., acrylic resin with good weather resistance to vinyl chloride resin Most of them were laminated.
However, a laminate of acrylic resin on vinyl chloride resin has low stain resistance, oil resistance and solvent resistance, so that dirt is likely to adhere and the attached dirt cannot be wiped off with a solvent. Since the vinyl chloride resin is laminated, there is a risk that dioxins are generated during combustion after disposal, and thus there is a problem that combustion processing is difficult.
There exists a thing of patent document 1 as a decorative sheet corresponding to this. The decorative sheet described in Patent Document 1 has weather resistance, stain resistance, and solvent resistance.

JP-A-11-3009095

Even a decorative sheet using a non-vinyl chloride material and a decorative member to which the decorative sheet is applied are desired to have nonflammability.
The present invention has been made paying attention to the above points, and provides a decorative sheet and a metallic decorative member having weather resistance, contamination resistance and solvent resistance, and also excellent in nonflammability. It is aimed.

  In order to solve the problems, a decorative sheet which is one embodiment of the present invention is formed by forming a weather resistant resin layer, a stain resistant resin layer made of a fluororesin or an ethylene vinyl alcohol copolymer resin in this order on a sheet base material. The weather resistant resin layer is made of a mixture of an acrylic resin and an acrylic resin rubber, and the mass ratio of the acrylic resin and the acrylic resin rubber is set in a range of 40:60 to 70:30, Containing at least one ultraviolet absorber selected from benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers, regulating the total thickness of the decorative sheet to 200 μm or less, and the weather-resistant resin layer and the stain-resistant resin layer The total thickness is regulated to 20 μm or more and 80 μm or less.

In addition, the metal decorative member which is one embodiment of the present invention is formed by bonding the decorative sheet which is one embodiment of the present invention to a metal substrate.
Examples of the metal constituting the substrate include aluminum, stainless steel, copper, and a steel plate.

According to this invention, it has a weather resistance, contamination resistance, and solvent resistance by making a decorative sheet into the said structure. Furthermore, by mixing acrylic resin rubber with the weather resistant resin layer, the bending processability is improved and the bending whitening resistance is also excellent.
In addition, according to the present invention, the decorative sheet has a total thickness of 200 μm or less, and the total thickness of the weather-resistant resin layer and the contamination-resistant resin layer is regulated to 20 μm or more and 80 μm or less, thereby providing nonflammability. It becomes possible.

As non-flammability, heat generated by a cone calorimeter tester conforming to ISO 5660-1 and conforming to the Fire Protection Test Method and Performance Evaluation Standards based on Article 9 of the Building Standards Act and Article 108-2 of the Building Standards Act (1) The total calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less. (2) The maximum heat generation rate continues for 10 seconds or more for 20 minutes after the start of heating and does not exceed 200 kW / m ² ( 3) Nonflammability that satisfies the condition that there are no cracks and holes harmful to fire prevention is preferred for 20 minutes after the start of heating.

It is typical sectional drawing for demonstrating the decorative sheet 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.
As shown in FIG. 1, the decorative sheet 10 of the present embodiment includes a pattern layer 2, an adhesive layer 3, a weather resistant resin layer 4, and a fluororesin layer or an ethylene vinyl alcohol copolymer resin on a sheet base material 1. The contamination-resistant resin layer 5 is laminated in this order.
The total thickness of the decorative sheet 10 is preferably set to 200 μm or less.

<Sheet substrate 1>
The sheet substrate 1 is a sheet-like layer made of a thermoplastic resin. The thermoplastic resin is preferably colored.
Examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene, polybutene, and polymethylpentene, ethylene-vinyl acetate copolymer or a saponified product thereof, and ethylene- (meth) acrylic acid (ester) copolymer. Polyolefin copolymer, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, copolymerized polyester (typically known as PET-G which is a 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin), etc. Polyester resins, acrylic resins such as polymethyl methacrylate, polyamide resins such as 6-nylon, 6, 6-nylon, 6, 10-nylon, 12-nylon, polystyrene, AS resin, ABS resin, etc. Styrene resins, cellulose derivatives such as cellulose acetate, nitrocellulose, chlorine resins such as polyvinyl chloride and polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, etc. And two or more types of copolymers, mixtures and composites selected from these. The sheet substrate 1 may be composed of a laminate made of such a thermoplastic resin. A flame retardant, an ultraviolet absorber, or the like can be mixed into the sheet base material 1 to retain the flame retardancy or anti-fading property.

In particular, polyolefin resin is more preferable in consideration of productivity in a melt extrusion apparatus, environmental compatibility, mechanical strength as a flooring material, durability, price, and the like.
By coloring the sheet base material 1, the substrate on which the decorative sheet 10 is bonded can be concealed, and the hue can be appropriately selected as the background color of the pattern layer 2. For example, coloring can be performed by mixing and kneading a coloring agent such as a pigment. Alternatively, a colored layer can be provided under the picture layer 2 by using a coating or printing technique as a solid ink layer before the picture layer 2 is provided.

  Organic and inorganic pigments (including titanium oxide) can be used as the colorant. In addition, benzophenone series, benzotriazole series, salicylate series, cyanoacrylate series, formamidine series oxanilide series and hindered amine series can be used as UV absorbers, but benzotriazole series, oxanilide series, hindered amine series and mixtures thereof are UV absorbing. It can be preferably used because of its excellent properties and compatibility with olefin resins. Flame retardants include inorganic (aluminum hydroxide, magnesium hydroxide, antimony trioxide, etc.), phosphorus (organic: phosphate ester, ammonium phosphate, etc., inorganic: red phosphorus), reaction type (vinyl addition) It has functional groups such as vinyl compounds to be polymerized, carboxylic acid groups, hydroxyl groups, and epoxy groups, and can be used as a part of polymer materials (copolymerized monomers :), but is compatible with resins, Aluminum hydroxide and magnesium hydroxide, which are excellent in terms of flame retardancy and environmental safety, can be preferably used.

(Picture layer 2)
The pattern layer 2 imparts design properties as a cosmetic material. As a design as a design, a desired printed pattern suitable for a place to be used such as a cork, a stone, a tile, a ceramic, an abstract pattern, etc. can be selected in addition to the grain.
The printing ink used for printing is not particularly limited in consideration of printability and weather resistance. As the pigment used in the pattern, for example, at least one of isoindolinone, disazo, polyazo, diketopyrrolopyrrole, quinacridone, phthalocyanine, titanium oxide, and carbon black is used. In addition, by combining these pigments, it is possible to make the expression of the pattern rich. Moreover, you may improve a weather resistance by adding a ultraviolet absorber, a light stabilizer, etc. FIG.

As for the printing method, known printing methods such as gravure printing, offset printing, silk screen printing, and ink jet printing can be used. When coloring the entire surface, in addition to the printing method, a coating method or apparatus is used. Also good.
The colored layer and the image layer 2 are mainly composed of a colorant and a resin. As the colorant, organic pigments and inorganic pigments having good light resistance and weather resistance can be used. Since the light resistance and weather resistance often differ depending on the combination, it can be supplemented by using an ultraviolet absorber or the like as appropriate. Perinone orange, flavathlon yellow, Hansa yellow and the like can be preferably used as pigments having good light resistance and weather resistance with little interaction with the resin. In addition, as the resin, avoid the use of vinyl chloride resin, vinylidene chloride or chlorinated polypropylene resin, which easily deteriorates due to the effects of light and inorganic pigments, and generates harmful hydrogen chloride gas during combustion. Vinyl copolymer, ethylene vinyl alcohol copolymer, ethylene vinyl butyral copolymer, cellulose resin, polyester resin, acrylic resin, alkyd resin having hydroxyl group (—OH), acrylic resin, cellulose derivative resin, polyvinyl Polyisocyanate resin having polyol resin such as alcohol resin, amino resin having amino group (—NH ₂ ), active hydrogen such as carboxylic acid having carboxyl group (—COOH), and isocyanate group (—NCO) Can be used as a two-component resin Lower layer adhesion and layer of an ethylene vinyl acetate copolymer and said two-liquid mixed resin excellent in terms of flexibility of the (urethane ink) can be preferably used.

(Adhesive layer 3)
The adhesive layer 3 of the present embodiment is preferably a transparent adhesive. For example, it is composed of a thermoplastic resin such as a polyamide resin, an acrylic resin or a vinyl acetate resin, or a curable resin such as a thermosetting urethane resin. Further, a two-component curable urethane resin or polyester resin using isocyanate as a curing agent may be used.

<Weather-resistant resin layer 4>
The weather resistant resin layer 4 is made of a mixture of an acrylic resin (polymethyl methacrylate resin) and an acrylic resin rubber (polymethyl methacrylate resin rubber). The mass ratio of the acrylic resin to the acrylic resin rubber is in the range of 40:60 to 70:30. That is, the mass ratio is set so that the acrylic resin is 40 to 70% by mass and the acrylic resin rubber is 30 to 60% by mass.

Furthermore, the weather resistant resin layer 4 contains at least one ultraviolet absorber selected from benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers.
The addition of the ultraviolet absorber is set to 0.2% or more and 0.8% or less, for example. If it is less than 0.2%, the effect of adding the ultraviolet absorber may be lowered. If it exceeds 0.8%, it may be difficult to add uniformly.

The ultraviolet absorber to be added may be a benzotriazole ultraviolet absorber or a triazine ultraviolet absorber alone, or a mixture of both.
By adding an ultraviolet absorber, light resistance and weather resistance can be improved (however, such an addition that colors the resin is not desirable).
The thickness of the weather resistant resin layer 4 can be used in the range of 10 to 200 μm.
Furthermore, a design feeling can be improved by providing unevenness such as embossing on the resin layer.

<Contamination resistant resin layer 5>
The contamination resistant resin layer 5 is a resin layer composed of either a fluororesin or an ethylene vinyl alcohol resin. As the contamination-resistant resin layer 5, a fluororesin is more preferable.
The contamination-resistant resin layer 5 made of fluororesin may be provided by coating, but polyvinyl fluoride resin (PVF), ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexa You may bond together using fluororesin films, such as a fluoropropylene copolymer (FEP) and a tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA). In particular, an ethylene-tetrafluoroethylene copolymer (ETFE) and a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) that are excellent in terms of melt moldability and stain resistance can be preferably used.

Furthermore, it is possible to improve the light resistance and weather resistance by using an ultraviolet absorber together (however, it is not desirable to add such a color that the resin is colored). In the case of using a fluororesin film, the unevenness of the uneven pattern such as embossing It is desirable to perform the processing after being bonded onto the weather resistant resin layer 4.
Further, as the resin layer made of the ethylene vinyl alcohol copolymer resin (EVOH), two types of EVOH having an ethylene content of 82 to 90 mol% and 25 to 50 mol% are known. An EVOH having an ethylene content of 25 to 50 mol%, which is excellent in terms of contamination resistance and transparency, can be preferably used. Furthermore, it is possible to improve the light resistance and weather resistance by using an ultraviolet absorber together (however, it is not desirable to add such a color that the resin is colored). Further, the uneven processing such as embossing may be performed after being bonded onto the weather resistant resin layer 4, or the EVOH may be embossed during hot melt ruder coating (the weather resistant resin layer 4 and the EVOH resin are both co-processed). Including embossing during extrusion extruder lamination).

  And the decorative sheet 10 of this embodiment is used for surface decoration materials, such as a building interior, a partition, and storage furniture, and a building semi-exterior, ie, an entrance door, the frame material, a window frame, a bay window counter, etc., for example. This decorative sheet 10 is provided with a weather resistant resin layer 4 on the sheet substrate 1 and further laminating a stain resistant resin layer 5, thereby forming a decorative sheet 10 having weather resistance, stain resistance and solvent resistance, Conventionally, since the stain resistance, oil resistance and solvent resistance are low, such as those obtained by laminating an acrylic resin on a vinyl chloride resin, dirt is likely to adhere, and the attached dirt cannot be wiped off with a solvent, Since the vinyl chloride resin is laminated, the decorative sheet 10 has the risk of generating a dioxin at the time of combustion at the time of disposal, so that the problem that the combustion process is difficult can be solved.

That is, the decorative sheet 10 of the present embodiment has weather resistance, stain resistance, and solvent resistance, and has improved resistance to bending whitening.
The sheet substrate 1 is colored, and a pattern layer 2 is formed between the sheet substrate 1 and the weather resistant resin layer 4. Moreover, the uneven | corrugated pattern is provided from the upper side of the weather resistant resin layer 4 by the heat shaping process.

Thereby, it can be set as the outstanding decorative sheet 10 which had design nature and a real feeling.
Furthermore, it is preferable that the total thickness of the decorative sheet is 200 μm or less, and the total thickness of the weather resistant resin layer 4 and the stain resistant resin layer 5 is in the range of 20 μm to 80 μm.
According to this, in the state which bonded this decorative sheet 10 to the metal plate chosen from aluminum, stainless steel, copper, and a steel plate, Building Standard Act Article 2 No. 9 and Building Standard Act Construction Order Article 108-2 (1) The total calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less (2) for 20 minutes after the start of heating. The maximum heat generation rate continues for 10 seconds or more and does not exceed 200 KW / m ² (3) 20 minutes after the start of heating, provided with non-flammability that does not have harmful cracks and holes for fire prevention.

<Metallic decorative parts>
The metal decorative member is configured by attaching the decorative sheet 10 of the above embodiment to a metal plate.
Examples of the metal constituting the metal plate include aluminum, stainless steel, copper, and steel plate.

Next, examples according to the present invention will be described.
<Example 1>
(Decorative sheet 10)
As the sheet substrate 1, a resin sheet made of a colored polypropylene resin and having a thickness of 70 μm was prepared. After the corona discharge treatment was applied to the front and back surfaces of the sheet substrate 1, a wood grain pattern was formed on the surface by gravure printing using urethane printing ink to obtain a pattern layer 2 (thickness: 2 μm).

On the other hand, the back surface primer layer (thickness: 1 μm) was formed on the back surface of the sheet substrate 1 by gravure printing using a back surface primer layer coating solution having the following composition.
Subsequently, the polyvinylidene fluoride resin (fluororesin) and the weathering resin layer forming mixture are melted and extruded by a T-die, and the PMMA resin and the PMMA resin rubber are 40:60 by mass ratio. Laminated body (thickness of fluororesin layer 5: 5 μm, thickness of weathering resin layer 4: 15 μm) composed of weathering resin layer 4 (however, benzotriazole ultraviolet absorber: tinuvin 326 added at 0.5 wt%) (Total thickness: 20 μm).
On the pattern layer 2, a coating solution made of a two-component curable urethane adhesive having a polyester resin as a main chain was applied to form an adhesive layer (thickness in a dry state: 6 μm). On top of this, the above laminate was laminated by a dry laminating method to obtain the present decorative sheet 10.

(Backside primer layer coating solution)
The composition of the above-mentioned back surface primer layer coating solution is as follows.
Two-component curable polyester urethane (mixed polyester polyol and polyisocyanate in a ratio of 100: 5 (mass ratio)): 100 parts by weight Diluting solvent (mixed in a ratio of 1: 1 (mass ratio) of ethyl acetate and methyl isobutyl ketone) Mixed solvent): 20 parts by mass

(Mixture for forming weather resistant resin layer)
The composition of the above weather-resistant resin layer forming mixture is as follows.
Acrylic resin (constitutional unit: methyl methacrylate): 20 parts by mass Acrylic rubber ("SA-FW001 (trade name)", manufactured by Kuraray Co., Ltd., methacrylic resin, constitutional unit: methyl methacrylate, particulate, average particle diameter: 100 nm ): 80 parts by mass

(Metal decorative member)
A decorative member was prepared by bonding the decorative sheet 10 to a 1 mm thick aluminum plate via a two-component curable urethane adhesive (amount applied in a dry state: 25 g / m ² ).
<Example 2>
A decorative member was obtained in the same manner as in Example 1 except that the fluororesin layer 5 was changed to an ethylene vinyl alcohol resin layer.

<Example 3>
A decorative member was obtained in the same manner as in Example 1 except that the mass ratio of the PMMA resin and the PMMA resin rubber in the weather resistant resin layer 4 was set to 70:30.
<Example 4>
A decorative member was obtained in the same manner as in Example 3 except that the fluororesin layer 5 was changed to an ethylene vinyl alcohol resin layer.

<Example 5>
A decorative member in the same manner as in Example 1 except that the thickness of the laminate of the fluororesin and the acrylic resin is 80 μm (the thickness of the fluororesin layer 5: 5 μm, the thickness of the weather resistant resin layer 4: 75 μm). Got.
<Comparative example 1>
A decorative member was obtained in the same manner as in Example 1 except that the mass ratio of the PMMA resin and the PMMA resin rubber in the weather resistant resin layer 4 was 20:80.

<Comparative example 2>
A decorative member was obtained in the same manner as in Example 1 except that the mass ratio of the PMMA resin and the PMMA resin rubber in the weather resistant resin layer 4 was 80:20.

<Comparative Example 3>
A decorative member in the same manner as in Example 1 except that the thickness of the laminate of the fluororesin and the acrylic resin is 15 μm (the thickness of the fluororesin layer 5: 5 μm, the thickness of the weather resistant resin layer 4: 10 μm). Got.
<Comparative example 4>
A decorative member in the same manner as in Example 1 except that the thickness of the laminate of the fluororesin and the acrylic resin is 90 μm (the thickness of the fluororesin layer 5: 5 μm, the thickness of the weather resistant resin layer 4: 85 μm). Got.
<Comparative Example 5>
A decorative member was obtained in the same manner as in Example 1 except that no ultraviolet absorbent was added to the weather resistant resin layer 4.

<Evaluation judgment method>
(Nonflammability evaluation)
In accordance with ISO 5660-1, a fire resistance test was conducted using a cone calorimeter tester in accordance with the fire prevention test method and performance evaluation standards based on Article 9-2 of the Building Standards Act and Article 108-2 of the Building Standards Act Construction Order. .

The gross calorific value of the heating starting after 20 min (MJ / ^{m 2)} is, and the 8 MJ / ^{m 2} or less, the maximum heat release rate of the start of heating after 20 minutes, exceed 200 kW / ^{m 2} to continue for 10 seconds or more Otherwise, it was determined to be a pass “◯”. However, it was also a condition that the substrate had no cracks or holes.

<Weatherability>
The weather resistance was evaluated as follows.
Using a metal weather, a weather resistance test was performed as follows.
After irradiating the irradiation mode under the following conditions for 20 hours, performing the condensation state for 4 hours in the condensation mode under the following conditions was performed for 312 hours as one cycle (24 hours).
・ Irradiation mode: Illuminance 65 mW / cm ² (measured with Ushio Unimeter UIT-101), BP temperature 53 ° C., humidity 50%, 20 hours irradiation • Condensation mode: 30 ° C., 98%, 4 hours (in condensation mode) 30 seconds shower spray before and after)
After conducting the test for 312 hours under the above conditions, the appearance fading and peeling were confirmed by visual confirmation.
And when there was no remarkable discoloration and peeling, it was set as a pass “◯”.

<Contamination resistance>
Write on the surface of the decorative board with black magic with a width of 1 cm, dip ethanol into absorbent cotton, and wipe off the black magic. If there is no significant change in the appearance of the surface after wiping, a pass “◯” is given.
<Lapping aptitude evaluation>
A wrapping process was performed, and immediately after the wrapping process, a sheet that did not peel off due to the stress of the decorative sheet 10 was regarded as acceptable.
The evaluation results are shown in Tables 1 and 2.

As can be seen from Tables 1 and 2, the decorative member to which the decorative sheet within the scope of the present invention is applied has good incombustibility, weather resistance, stain resistance, and lapping suitability.
On the other hand, when the mass ratio of the PMMA resin and the PMMA resin rubber in the weather resistant resin layer 4 is out of the present invention as in Comparative Examples 1 and 2, the weather resistance and the lapping suitability are reduced as compared with the decorative sheets of the examples.

It can be seen that, as in Comparative Example 3, if the total thickness of the weather resistant resin layer 4 and the stain resistant resin layer 5 is thinner than the range of the present invention, it is disadvantageous in terms of weather resistance. On the other hand, when the total thickness of the weather resistant resin layer 4 and the stain resistant resin layer 5 is thicker than the range of the present invention as in Comparative Example 4, the desired nonflammability cannot be ensured.
Moreover, it turns out that a weather resistance improves by containing a ultraviolet absorber so that the comparative example 5 may show.

DESCRIPTION OF SYMBOLS 1 Sheet base material 2 Picture layer 3 Adhesive layer 4 Weather resistant resin layer 5 Contamination resistant resin layer 10 Cosmetic sheet

Claims (4)

On the sheet base material, a weather resistant resin layer, a contamination resistant resin layer made of a fluororesin or an ethylene vinyl alcohol copolymer resin is formed in this order,
The weather resistant resin layer is made of a mixture of an acrylic resin and an acrylic resin rubber, and the mass ratio of the acrylic resin to the acrylic resin rubber is set in a range of 40:60 to 70:30, and Containing at least one UV absorber selected from triazole UV absorbers and triazine UV absorbers;
A decorative sheet, wherein the total thickness of the decorative sheet is regulated to 200 μm or less, and the total thickness of the weather resistant resin layer and the contamination resistant resin layer is regulated to 20 μm or more and 80 μm or less.   The decorative sheet according to claim 1, wherein the sheet base material is colored, and a pattern layer is formed between the sheet base material and the weather resistant resin layer.   The decorative sheet according to claim 1, wherein an uneven pattern is formed on the weather resistant resin layer.   A metal decorative member obtained by bonding the decorative sheet according to any one of claims 1 to 3 to a metal substrate.

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