JP6497124B2 - Non-combustible decorative sheet and non-combustible decorative member - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a non-combustible decorative sheet and a non-combustible decorative member, and in particular, a non-combustible decorative sheet and a non-combustible cosmetic suitable for surface decoration of a building member that requires weather resistance and heat resistance such as, for example, an entrance sliding door. It relates to members.

The decorative sheet is used, for example, for interior and exterior materials of buildings such as houses, building materials such as construction materials and fittings, furniture fixtures, vehicle interiors, housing equipment, furniture for furniture, and the like.
Conventionally, a decorative sheet made of a polyvinyl chloride resin, which is inexpensive and excellent in processability, has been most commonly used as a decorative sheet for use in various applications as described above. This decorative sheet includes a single-layer decorative sheet and a multi-layer decorative sheet. The decorative sheet having a single layer structure is obtained by appropriately printing a desired pattern on the front surface or the back surface of a thermoplastic resin substrate made of a polyvinyl chloride resin. The decorative sheet having a multilayer structure is formed by printing a pattern on the surface of a thermoplastic resin base material made of polyvinyl chloride resin and laminating a surface resin layer made of transparent polyvinyl chloride resin on the printed surface.

Among them, the latter multi-layered decorative sheet is protected by a polyvinyl chloride resin layer from both the front and back, and is advantageous in terms of processing and durability. It has been used more widely than single-layer decorative sheets because it can easily be highly concealed by coloring.
In addition to the above, there was also a decorative sheet made of a combination of a polyvinyl chloride resin and another thermoplastic resin. For example, some semi-exterior applications that require weather resistance include those that use an acrylic resin with excellent weather resistance for the surface resin layer, and for applications that require high definition such as for steel sheets. Some polyester resins having excellent transparency and surface smoothness were used for the surface resin layer. And the decorative sheet composed of polyvinyl chloride resins or a combination of polyvinyl chloride resin and other thermoplastic resin is made by the thermal laminating method using the excellent thermal adhesiveness of polyvinyl chloride resin. It was most common to produce.

  However, in recent years, it has been pointed out that polyvinyl chloride resin generates a large amount of chlorine gas, hydrogen chloride gas, etc. during combustion, which is a direct or indirect factor in the generation of toxic substances dioxin, From the viewpoint, development of a decorative sheet using a material replacing polyvinyl chloride resin has been demanded. In response to such demands, for example, decorative sheets using thermoplastic resins containing no chlorine other than polyvinyl chloride, such as polyolefin resins, acrylic resins, and polyester resins, have already been developed and put to practical use. Substitution of decorative sheets made of polyvinyl chloride resin is gradually progressing.

  However, all of these alternative resins are inferior in thermal adhesiveness compared to polyvinyl chloride resin, and as in the case of decorative sheets using conventional polyvinyl chloride resin, makeup is performed by thermal lamination. When trying to manufacture a sheet, there is a problem that it is difficult to obtain a necessary adhesive strength. In particular, when polyolefin resin is used, the range of temperature conditions where heat bonding is possible is very narrow and the bonding temperature is high, resulting in poor lamination such as sheet breakage, elongation, deformation and deterioration. There was a risk of doing so. In addition, when thermal lamination is performed in a low temperature range where these disadvantages do not occur, the laminate strength is extremely low, and it is impossible to obtain a sheet that can be used practically as a decorative sheet.

  In order to cope with such problems, a thermoadhesive resin comprising a vinyl chloride-vinyl acetate copolymer resin (hereinafter referred to as vinyl acetate) -acrylic resin between the thermoplastic resin substrate and the surface resin layer. A method of providing a layer has been proposed (Patent Document 1). According to this method, by performing thermal lamination by interposing a heat-adhesive resin layer that is sufficiently thermally activated and expresses adhesiveness in a low-temperature region where no breakage, elongation, deformation, deterioration, etc. of the sheet occur, There is an advantage that sufficient laminate strength can be achieved without causing poor lamination. In particular, the vinyl chloride-based resin improves the adhesion between the thermoplastic resin substrate and the surface resin layer.

  However, the heat-adhesive resin layer (a layer made of a heat sealing agent) may be made of a resin having poor heat resistance, and the resulting decorative sheet may be inferior in heat resistance. For example, when water is immersed on the surface of a decorative surface in a semi-exterior application, and the temperature is increased by direct sunlight, the heat-adhesive resin layer is softened by the increased temperature, and fine voids are generated in the heat-adhesive resin layer. There is a problem that the surface state appears to be whitened due to irregular reflection of light. This problem may theoretically be improved by using a heat-adhesive resin with a high heat softening temperature, but as a result, it is necessary to raise the laminating temperature inevitably. Lamination failure such as rupture, elongation, deformation, and deterioration of the sheet is caused, and the intended purpose cannot be achieved.

  Therefore, a cross-linking agent such as an isocyanate compound is blended in the thermoadhesive resin, and the adhesiveness is expressed by the heat at the time of laminating to bond the thermoplastic resin substrate and the surface resin layer, and at the same time, thermal adhesiveness. It is also conceivable to improve the heat resistance after laminating by causing a cross-linking reaction inside the resin. However, in such a method, if a time is taken until the heat laminating process after applying the thermoadhesive resin to the thermoplastic resin base material, the cross-linking reaction proceeds during that time. Since there is a possibility that it will not be expressed, it is necessary to immediately perform a heat laminating process. Therefore, the progress management of the decorative sheet manufacturing process is cumbersome, and it is not possible to make a large amount of printed thermoplastic resin base material coated with a heat-adhesive resin. There is a problem that it is very difficult to deal with.

There is also a proposal of a melt extrusion laminating method as a laminating method replacing the thermal laminating method. However, this requires large-scale and expensive manufacturing equipment, and it is difficult to meet the demands for high-mix low-volume production and short delivery times. Could not be substituted.
There is also a proposal to use an acrylic resin with excellent weather resistance for the surface transparent resin layer by the dry laminating method, but when the thermoplastic resin substrate is an olefin substrate, there is no good adhesive layer and it is suitable for exterior use Usable adhesiveness was not obtained.

  In recent years, as consumers' awareness of the safety of living spaces has increased, non-flammability is required for decorative sheets for decorating window frames and entrances, which are exterior materials for houses, etc. There are many things that need to be received.

JP 2000-326451 A Japanese Patent No. 5630161

  The present invention has been made paying attention to such problems, and an object thereof is to provide a decorative sheet having good heat resistance and nonflammability, and a nonflammable decorative member using the same.

  In order to solve the problems, an incombustible decorative sheet which is one embodiment of the present invention includes an adhesive layer, an acrylic resin layer, and a fluororesin layer formed in this order on a base material, and the acrylic resin layer includes an acrylic rubber. And an acrylic resin, and a mass ratio of the acrylic rubber and the acrylic resin is set to 30:70 to 60:40. The adhesive layer contains an isocyanate compound as a curing agent and mainly includes a polyester resin. The adhesive layer has two layers of an adhesive layer composed of a urethane adhesive as a chain and an anchor layer composed of a urethane anchor agent containing an isocyanate compound as a curing agent and having an acrylic resin as a main chain. Is arranged on the substrate side.

Here, the nonflammability of the nonflammable decorative sheet of the present invention is determined by the corn calorie combustion test based on ISO5660-1 and the nonflammable decorative sheet and a substrate made of a metal selected from aluminum, iron, stainless steel, and copper. When the total calorific value with respect to time and the heat generation rate with respect to time of the incombustible decorative board formed by sticking were determined, (i) the total calorific value for 20 minutes after the start of heating was 8 MJ / m ² or less, and (ii) heating 20 minutes after the start, the maximum heat generation rate continues for 10 seconds or more and does not exceed 200 kW / m ² , and (iii) 20 minutes after the start of heating, the non-combustion satisfying that there are no cracks and holes penetrating to the rear side which is harmful for fire prevention It is preferable to have properties.

According to this invention, it has nonflammability by comprising an acrylic resin layer from the mixture by which mass ratio of acrylic rubber and this acrylic resin was set to 30: 70-60: 40.
Further, by disposing a fluororesin layer on the surface side, surface properties such as acid resistance, alkali resistance, solvent resistance, and contamination resistance are imparted.
Furthermore, the adhesive layer and the anchor layer are provided with an adhesive layer made of a urethane-based adhesive having a polyester resin as a main chain and an anchor layer made of a urethane-based anchor having an acrylic resin as a main chain. The curing agent composed of the isocyanate compound contained causes a cross-linking reaction inside the adhesive layer and the anchor layer, thereby being excellent in heat resistance adhesion between the base material layer and the acrylic resin layer.

As a result, according to the present invention, it is possible to provide a decorative sheet having good heat resistance and having nonflammability, and a nonflammable decorative member using the same.
Here, when an ultraviolet absorber is added to an anchor layer made of a urethane-based anchor agent having an acrylic resin as a main chain, the ultraviolet shielding ability is improved, and a decorative sheet having excellent weather-resistant adhesion in addition to heat-resistant adhesion is obtained. There is an effect that it can be obtained.

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.

<Incombustible decorative sheet 10>
As shown in FIG. 1, the nonflammable decorative sheet 10 of this embodiment has a pattern layer 2, an adhesive layer 5, an acrylic resin layer 6, and a fluororesin layer 7 formed in this order on a substrate 1.
The pattern layer 2 may be omitted. When the pattern layer 2 is provided, the acrylic resin layer 6 and the fluororesin layer 7 are preferably transparent so that the pattern pattern of the pattern layer 2 can be visually recognized.

(Substrate 1)
The base material 1 is a sheet-like member 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 base material 1 may be comprised with the laminated body which consists of such a thermoplastic resin.

Here, when the substrate 1 is composed of a polypropylene resin, it is preferred that the organic solid weight is 44 g / ^{m 2} or more 67 g / ^{m 2} or less. By setting it as this range, even if a polypropylene resin is used as the base material 1, nonflammability can be reliably ensured.
In view of productivity in a melt extrusion apparatus, environmental compatibility, mechanical strength as a flooring material, durability, price, and the like, a polyolefin resin is more preferable.

  By coloring the base material 1, the substrate made of a metal to which the decorative sheet 10 is bonded can be concealed, and the hue can be appropriately selected as the background color of the design 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 pattern layer 2 by using a coating or printing technique as a solid ink layer before the pattern layer 2 is provided.

(Picture pattern 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. Also, 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.

(Adhesive layer 5)
The adhesive layer 5 of this embodiment is composed of an adhesive layer 3 and an anchor layer 4. In addition, when providing the pattern pattern layer 2, it is preferable that the contact bonding layer 5 has transparency which can visually recognize a pattern pattern.
The adhesive layer 3 is made of a urethane adhesive having a polyester resin as a main chain.
The anchor layer 4 is made of a urethane anchor agent having an acrylic resin as a main chain.
Here, the urethane-based adhesive having a polyester-based resin as a main chain is a polyester polyol and an isocyanate, and the urethane-based anchor agent having an acrylic resin as a main chain is a urethane bond by reacting an acrylic polyol with an isocyanate. It is what you have.
Moreover, it is preferable that the ultraviolet absorber is added to the urethane type anchor agent.
Examples of the ultraviolet absorber include benzophenone series, benzotriazole series, salicylate series, cyanoacrylate series, formamidine series, and oxanilide series.

(Acrylic resin layer 6)
It is preferable that the acrylic resin layer 6 has transparency so that the pattern or pattern of the lower pattern pattern layer 2 is visible.
The acrylic resin layer 6 of the present embodiment is composed of a mixture of acrylic rubber and acrylic resin, and the mass ratio of the acrylic rubber to the acrylic resin is set to 30:70 to 60:40. The acrylic resin layer 6 may be appropriately added with an additive such as a known ultraviolet absorber.

By making the mass ratio of the acrylic rubber and the acrylic resin 30:70 to 60:40, the decorative sheet 10 and a substrate made of metal are bonded by a corn calorie combustion test based on ISO5660-1. When the total calorific value with respect to time of the decorative board and the heat generation rate with respect to time were determined, (i) the total calorific value for 20 minutes after the start of heating was 8 MJ / m ² or less, and (ii) the maximum for 20 minutes after the start of heating. It is possible to ensure non-flammability satisfying the fact that the heat generation rate does not exceed 200 kW / m ² continuously for 10 seconds or more and (iii) there are no cracks and holes penetrating to the back side which is harmful for fire prevention for 20 minutes after the start of heating. .

  Here, if the mass ratio is smaller than 30:70, that is, the amount of the acrylic rubber is too small, excellent nonflammability cannot be obtained, and bending workability is deteriorated. On the other hand, when the mass ratio is larger than 60:40, that is, when the amount of the acrylic rubber is too large, it becomes difficult to form the acrylic resin layer 6 and the weather resistance is lowered. From such a viewpoint, the mass ratio between the acrylic rubber and the acrylic resin is preferably 30:70 to 60:40.

Moreover, 30-80 micrometers is preferable and, as for the thickness of the acrylic resin layer 6, 30-70 micrometers is more preferable. When the thickness is 30 μm or more, excellent weather resistance is obtained, and when it is 80 μm or less, excellent bending workability is obtained and nonflammability is also obtained.
The acrylic rubber constituting the acrylic resin layer 6 is not particularly limited, but is preferably a synthetic rubber made of a polymer having at least a (meth) acrylic acid ester monomer as a structural unit. The acrylic rubber preferably contains 60% by mass or more of the structural unit, more preferably 70% by mass or more, and still more preferably 80% by mass or more. Examples of the (meth) acrylic acid ester monomer include (meth) acrylic acid alkyl ester, (meth) acrylic acid alkoxyalkyl ester, and the like.

  The (meth) acrylic acid alkyl ester is preferably an ester of an alkanol having 1 to 8 carbon atoms and (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n- (meth) acrylic acid. Propyl, n-butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. Is mentioned. Of these, ethyl (meth) acrylate and n-butyl (meth) acrylate are preferred.

The (meth) acrylic acid alkoxyalkyl ester is preferably an ester of an alkoxyalkanol having 2 to 8 carbon atoms and (meth) acrylic acid, (meth) acrylic acid methoxymethyl, (meth) acrylic acid ethoxymethyl, (meth) 2-ethoxyethyl acrylate, 2-butoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, (meth) Examples include 4-methoxybutyl acrylate. Among these, 2-ethoxyethyl (meth) acrylate and 2-methoxyethyl (meth) acrylate are preferable.
Moreover, a polyfunctional (meth) acrylic acid ester monomer is also preferably exemplified as the (meth) acrylic acid ester monomer.

  Examples of the polyfunctional (meth) acrylic acid ester monomers include esters of unsaturated monocarboxylic acids such as (meth) acrylic acid and unsaturated alcohols such as allyl alcohol, unsaturated monocarboxylic acids and ethylene glycol, Preferable examples include diesters with glycols such as butanediol and hexanediol, and esters of dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and maleic acid with the unsaturated alcohol. More specifically, allyl (meth) acrylate, methallyl (meth) acrylate, allyl cinnamate, methallyl cinnamate, diallyl maleate, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, divinylbenzene, ethylene glycol di (Meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate and the like.

  The acrylic rubber is preferably a copolymer containing a structural unit having a crosslinking point. Since a rubber composition using such a copolymer as an acrylic rubber can be effectively crosslinked during molding, an elastic crosslinked product can be obtained. Examples of the structural unit having a crosslinking point include those having a carboxyl group, a halogen atom, an epoxy group, or a hydroxyl group.

  The shape of the acrylic rubber is not particularly limited, but is preferably in the form of particles in consideration of workability. When the acrylic rubber is in the form of particles, the average particle size is preferably 30 to 150 nm, more preferably 40 to 120 nm, considering transparency and moldability of the acrylic resin layer 6. The acrylic resin used in the acrylic resin layer 6 is not particularly limited, but is preferably a polymer having at least a (meth) acrylic acid ester monomer as a structural unit. More specifically, a homopolymer of (meth) acrylate monomer, a copolymer of two or more different (meth) acrylate monomers, or a copolymer of (meth) acrylate monomers and other monomers. Polymers are preferred.

  Here, examples of the (meth) acrylate monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclohexyl (meth) acrylate, and normal butyl (meth) acrylate. , Isobutyl (meth) acrylate, secondary butyl (meth) acrylate, tertiary butyl (meth) acrylate, isobonyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2- Adamantyl (meth) acrylate and the like are preferable, and methyl (meth) acrylate is more preferable in consideration of bending workability and weather resistance.

Examples of the copolymer of two or more different (meth) acrylic acid ester monomers include a copolymer of two or more (meth) acrylic acid esters selected from those exemplified above, and these copolymers May be a random copolymer or a block copolymer.
The other monomer that forms a copolymer with the (meth) acrylic acid ester monomer is not particularly limited as long as it is copolymerizable with the (meth) acrylic acid ester, but in the present invention, (meth) acrylic acid, Styrene, maleic anhydride, fumaric acid, divinylbenzene, vinylbiphenyl, vinylnaphthalene, diphenylethylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinyl alcohol, acrylonitrile, acrylamide, butadiene, isoprene, isobutene, 1-butene, Alicyclic olefin monomers such as 2-butene, N-vinyl-2-pyrrolidone, dicyclopentadiene, ethylidene norbornene, norbornene, vinylcaprolactam, citraconic anhydride, maleimides such as N-phenylmaleimide, vinyl ethers, etc. It is preferably exemplified, in particular styrene and (anhydrous) maleic acid is preferable as a copolymerization component. That is, a binary copolymer of (meth) acrylic acid ester and styrene or (anhydrous) maleic acid, or a terpolymer of (meth) acrylic acid ester, styrene and (anhydrous) maleic acid is preferable. In addition, the copolymer of (meth) acrylic acid ester and another monomer may be a random copolymer or a block copolymer.

(Fluorine resin layer 7)
It is preferable that the fluororesin layer 7 has transparency so that the pattern or pattern of the lower pattern pattern layer 2 is visible. The fluororesin layer 7 imparts surface properties such as acid resistance, alkali resistance, solvent resistance, and contamination resistance to the decorative sheet 10.
As the fluororesin, known ones can be used. For example, polyvinylidene fluoride, tetrafluoroethylene resin, tetrafluoroethylene perfluoroalkoxy vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer , Polychlorotrifluoroethylene, tetrafluoroethylene / ethylene copolymer, chlorotrifluoroethylene / ethylene copolymer, polyvinyl fluoride (PVF), etc. can be used. Polyvinylidene fluoride is preferred in terms of adhesion to the layer 6. The glass transition point (Tg) of polyvinylidene fluoride is -39 ° C.

  The thickness of the fluororesin layer 7 is preferably about 1 to 15 μm, and more preferably 1 to 10 μm. The fluororesin layer 7 has a ratio (thickness of the fluororesin layer 7 / thickness of the acrylic resin layer 6) to the thickness of the transparent thermoplastic resin layer from the viewpoint of nonflammability and bending workability. 05-1.0 are preferable and 0.05-0.8 are more preferable.

(Other configurations)
An uneven pattern may be added to the surface of the decorative sheet 10. The concavo-convex pattern may be added by employing a known means such as hot embossing.
<Non-combustible decorative material>
The nonflammable decorative member of this embodiment is configured by sticking the nonflammable decorative sheet 10 to a substrate made of a metal selected from aluminum, iron, stainless steel, and copper.
Here, the shape of the substrate is not limited to a flat plate shape, and the cross-sectional profile of the surface shape may be a desired three-dimensional shape such as a rectangle, a circle, or a triangle.

<Effect of this embodiment>
(1) By making the fluororesin layer 7 on the surface layer side, it is possible to impart surface characteristics such as acid resistance, alkali resistance, solvent resistance, and contamination resistance to the decorative sheet 10.
(2) The acrylic resin layer 6 is composed of a mixture in which the mass ratio between the acrylic rubber and the acrylic resin is set to 30:70 to 60:40.

Thus, when the total calorific value with respect to time and the heat generation rate with respect to time of the decorative board formed by adhering the decorative sheet 10 and the substrate made of metal were determined by a corn calorie combustion test in accordance with ISO 5660-1, i) The total calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less, (ii) 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 , and (iii) ) 20 minutes after the start of heating, it becomes possible to ensure nonflammability that satisfies the absence of cracks and holes penetrating to the back side, which is harmful to fire prevention.

(3) The adhesive layer 5 includes two layers of an adhesive layer 3 made of a urethane-based adhesive having a polyester resin as a main chain and an anchor layer 4 made of a urethane-based anchor agent having an acrylic resin as a main chain. Have.
The hardener made of an isocyanate compound contained in the adhesive layer 3 and the anchor layer 4 causes a cross-linking reaction inside the adhesive layer 3 and the anchor layer 4 so that the heat-resistant adhesion between the base material 1 layer and the acrylic resin layer 6 is achieved. Excellent in properties.
The anchor layer 4 also has a function of protecting the adhesive layer 3.
From the above effects, the decorative sheet 10 and the decorative member of the present embodiment can have weather resistance even during long-term outdoor exposure, can have good heat resistance, and can have nonflammability.

(4) When an ultraviolet absorber is added to the anchor layer 4 made of a urethane anchor having an acrylic resin as the main chain, the ultraviolet shielding ability is improved, and the decorative sheet has excellent weather resistance adhesion in addition to heat resistance adhesion. There is an effect that 10 can be obtained.
(5) The organic solid content of the polypropylene resin constituting the substrate ^1, by a ^{44g / m 2, 67g / m} 2, thereby improving the nonflammable decorative sheet 10.
(6) The decorative sheet 10 has an uneven pattern on the surface.
This improves the design of the aluminum decorative member.

Next, examples according to the present invention will be described.
<Example 1>
As the substrate 1, a resin sheet (thickness: 70 μm) made of a colored polypropylene resin and having a total organic solid content mass of 60.4 g / m ² was prepared.
After the corona discharge treatment was applied to the front and back surfaces of the substrate 1, a wood grain pattern was formed on the surface by gravure printing using urethane printing ink to obtain a pattern layer (thickness: 2 μm).

On the other hand, the back surface primer layer (thickness: 1 μm) was formed on the back surface of the substrate 1 by gravure printing using a back surface primer layer coating solution having the following composition.
Next, a polyvinylidene fluoride resin (fluororesin) and a mixture for forming an acrylic resin layer were melted and extruded by a T-die, and a laminate composed of the fluororesin layer 7 and the acrylic resin layer 6 (thickness of the fluororesin layer 7: 5 μm). The thickness of the acrylic resin layer 6 was 45 μm).

Furthermore, a urethane anchor layer 4 (thickness: 1.5 μm) having an acrylic resin containing a triazine ultraviolet absorber (5 parts by mass) as a main chain was formed on the acrylic resin side of the laminate by gravure printing. (Hereinafter referred to as “Laminate A”.)
On top of the above pattern layer, a coating solution made of a two-component curable urethane adhesive having a polyester resin as a main chain is applied to form an adhesive layer 5 (thickness in a dry state: 6 μm). The laminate A was laminated by a dry laminating method to obtain the decorative sheet 10.

(Backside primer layer coating solution)
The coating solution for the back primer layer 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

(Acrylic resin layer forming mixture)
The composition of the acrylic resin layer forming mixture is as follows.
Acrylic resin (constituent unit: methyl methacrylate): 45 parts by mass Acrylic rubber (“SA-FW001 (trade name)”, manufactured by Kuraray Co., Ltd., methacrylic resin, constituent unit: methyl methacrylate, particulate, average particle diameter: 100 nm ): 55 parts by mass

<Comparative example 1>
A decorative sheet 10 was obtained in the same manner as in Example 1 except that the total organic solid content of the resin sheet made of the colored polypropylene resin was 77.6 g / m ² (thickness: 90 μm).
<Comparative example 2>
A decorative sheet 10 was obtained in the same manner as in Example 1 except that the total mass of the organic solid content of the resin sheet made of the colored polypropylene resin was 40.0 g / m ² (thickness: 50 μm).

<Comparative Example 3>
A decorative sheet 10 was obtained in the same manner as in Example 1 except that the ultraviolet absorber was not added to the urethane anchor layer 4 and the urethane anchor layer 4 was formed.
<Comparative example 4>
A decorative sheet 10 was obtained in the same manner as in Example 1 except that the urethane anchor layer 4 was not formed.
<Comparative Example 5>
A decorative sheet 10 was obtained in the same manner as in Example 1 except that no urethane-based adhesive was formed.

<Comparative Example 6>
As the substrate 1, a resin sheet made of a colored polypropylene resin (thickness: 70 μm) was prepared.
After the corona discharge treatment was applied to the front and back surfaces of the substrate 1, a wood grain pattern was formed by gravure printing on the surface using urethane printing ink to obtain a picture pattern layer (thickness: 2 μm).

On the other hand, the back surface primer layer (thickness: 1 μm) was formed on the back surface of the substrate 1 by gravure printing using a back surface primer layer coating solution having the following composition.
Next, a polyvinylidene fluoride resin (fluororesin) and an acrylic resin layer forming mixture are melted with a T-die and extruded, and a laminate composed of the fluororesin layer 7 and the acrylic resin layer 6 (thickness of the fluororesin layer 7: 5 μm, acrylic resin layer 6 thickness: 45 μm) was formed. (Hereinafter referred to as “Laminate B”.)
On the pattern pattern layer, an adhesive layer 5 (thickness in a dry state: 1.5 μm) is formed by applying a one-component coating solution composed of an acrylic-salt vinegar-polyester resin, and then laminating the laminate. The body B was laminated by a heat laminating method to obtain a decorative sheet 10.

(Backside primer layer coating solution)
The following were used as the coating solution for the back primer layer.
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

(Acrylic resin layer forming mixture)
The following was used as the mixture for forming an acrylic resin layer.
Acrylic resin (constituent unit: methyl methacrylate): 45 parts by mass Acrylic rubber (“SA-FW001 (trade name)”, manufactured by Kuraray Co., Ltd., methacrylic resin, constituent unit: methyl methacrylate, particulate, average particle diameter: 100 nm ): 55 parts by mass

<Evaluation judgment method>
The following evaluation judgment was implemented with respect to the Example and the comparative example.
(Nonflammability evaluation)
Conforms to ISO5660-1 The total heating value (MJ / m ² ) for 20 minutes after starting heating is 8 MJ / m ² or less, and the maximum heating rate for 20 minutes after starting heating is 200 kW / m ² continuously for 10 seconds or more. If it does not exceed, it was determined as a pass “○”. However, the evaluation of cracks in the substrate 1 was made on condition that there were no cracks or holes.
(Water and heat resistant adhesion)
After dipping for 48 hours in 80 ° C. warm water and drying, a crosscut was made on the surface, and Cellotape (registered trademark) was pressure-bonded. And it peeled off vigorously and the presence or absence of peeling was confirmed.

(Weather resistant adhesion)
Weather resistance adhesion was evaluated as follows using a metal weather.
After irradiating for 20 hours in the irradiation mode under the following conditions, and performing the condensation state for 4 hours in the condensation mode under the following conditions as one cycle, after 1512 hours, a crosscut is put on the surface, and cello tape (registered trademark) is crimped. did. Then, it peeled off vigorously and the presence or absence of peeling was confirmed.
・ 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 Before and after condensation mode 30 seconds shower spray

<Weather resistance>
Using the above metal weather, after 1512 hours under the same conditions as described above, the appearance fading and peeling were confirmed by visual confirmation.
And when there is no remarkable discoloration and peeling, it is set as a pass.
The evaluation results are shown in Table 1.

As can be seen from Table 1, when the mass ratio of the acrylic rubber to the acrylic resin in the acrylic resin layer 6 is set to 30:70 to 60:40, the nonflammability becomes good. Furthermore, the use of polypropylene resin to the substrate 1, by the organic solid mass and 44 g / m ² or more 67 g / m ² or less, it can be seen that incombustible is ensured good.
Here, the organic solid mass of the polypropylene resin constituting the substrate 1, and also confirmed that it is now the same evaluation as in Example 1 in a case of a 44 g / m ^2, and 67 g / m ^2.

Also, the adhesive layer 5 is made into an adhesive layer 3 and an anchor layer 4 according to the present invention, an ultraviolet absorber is added to the anchor layer 4, the base material 1 is made of polypropylene resin, and the organic solid content mass is 44 g / It can be seen that the water resistant and heat resistant adhesiveness, weather resistant adhesiveness, and weather fading resistance are all good when the value is m ² or more and 67 g / m ² or less.
On the other hand, in the case of Comparative Example 3 in which no ultraviolet absorber is added to the urethane anchor layer 4, the weather fading resistance is rejected.
Moreover, in the case of the comparative example 4 which does not form the urethane type anchor layer 4 in the contact bonding layer 5, a weather-resistant adhesiveness and a weather-fading property are disqualified.

DESCRIPTION OF SYMBOLS 1 Base material 2 Picture pattern layer 3 Adhesive layer 4 Anchor layer 5 Adhesive layer 6 Acrylic resin layer 7 Fluororesin layer 10 Nonflammable decorative sheet

Claims (5)

On the substrate, an adhesive layer, an acrylic resin layer, and a fluororesin layer are formed in this order,
The acrylic resin layer includes an acrylic rubber and an acrylic resin, and is composed of a mixture in which the mass ratio of the acrylic rubber and the acrylic resin is set to 30:70 to 60:40,
The adhesive layer includes an adhesive layer made of a urethane-based adhesive containing an isocyanate compound as a curing agent and having a polyester resin as a main chain, and a urethane-based adhesive containing an isocyanate compound as a curing agent and having an acrylic resin as a main chain. It has two layers with an anchor layer made of an anchor agent, and the adhesive layer is disposed on the substrate side,
A triazine-based, benzophenone-based, benzotriazole-based, salicylate-based, cyanoacrylate-based, formamidine-based, or oxanilide-based UV absorber is added to the urethane-based anchor agent ,
A nonflammable decorative sheet characterized by satisfying the requirements for obtaining nonflammable certification in an exothermic test according to ISO5660-1 . A primer layer is formed on the surface of the substrate opposite to the adhesive layer,
The nonflammable decorative sheet according to claim 1, wherein the primer layer contains a two-component curable polyester urethane. The base material, non-combustible decorative sheet according to claim 1 or claim 2, characterized in that it consists of polypropylene resin. The nonflammable decorative sheet according to any one of claims 1 to 3 , wherein the fluororesin constituting the fluororesin layer is a polyvinylidene fluoride resin. A nonflammable decorative sheet obtained by sticking the nonflammable decorative sheet according to any one of claims 1 to 4 to a substrate made of a metal selected from aluminum, iron, stainless steel, and copper. Cosmetic material.

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