JP2018058284A - Decorative sheet and decorative member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet and a decorative member which have sufficient weather resistance even when exposed to the outdoor over a long period of time, are excellent in solvent resistance, and have improved bending whitening phenomenon and incombustibility.SOLUTION: A decorative sheet 1 has an adhesion layer 4, an acrylic resin layer 5 and a fluororesin layer 6 in this order on a base material 2, where a weight of an organic solid content of the base material 2 formed of a polypropylene resin is 44 g/mor more and 67 g/mor less, the adhesion layer 4 is formed by layering an adhesive layer 4A formed of an urethane adhesive agent having a polyester-based resin as the main chain and an anchor layer 4B formed of an urethane anchor agent having an acrylic resin as the main chain, and the acrylic resin layer 5 has a rate of elongation when a No. 1 dumbbell-shaped test piece prepared in accordance with JIS K 6251 is elongated by 20 mm at a tensile speed of 10 mm/min of 145% to 155% and has a haze of 89% or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative sheet and a decorative member, and more particularly, to a non-flammable decorative sheet and an exterior non-flammable decorative member suitable for surface decoration of a building member that requires weather resistance and heat resistance such as an entrance sliding door.

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.

  However, in recent years, it has been pointed out that polyvinyl chloride resin becomes a direct or indirect factor in the generation of toxic substance dioxin during combustion, and a material that replaces polyvinyl chloride resin was used from the viewpoint of environmental protection. The development of decorative sheets has come to be requested. In response to such demands, for example, decorative sheets using thermoplastic resins 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 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 a decorative sheet using conventional polyvinyl chloride resin, cosmetics are applied by thermal lamination. When trying to manufacture a sheet, there is a problem that it is difficult to obtain a necessary adhesive strength.

Therefore, a method of providing a thermoadhesive resin layer made of vinyl chloride-vinyl acetate copolymer resin (hereinafter sometimes referred to as vinyl acetate) -acrylic resin between the thermoplastic resin substrate and the surface resin layer, etc. Has also been proposed (see Patent Document 1).
According to this method, it is sufficient to perform thermal lamination by interposing a heat-adhesive resin layer that is sufficiently thermally activated and exhibits adhesiveness in a low-temperature region where no breakage, elongation, deformation, deterioration, or the like of the sheet occurs. There is an advantage that a good laminate strength can be achieved. However, the heat-adhesive resin layer may be made of a resin having inferior heat resistance, and the resulting decorative sheet may have inferior heat resistance.

There are proposals for melt extrusion laminating as an alternative to thermal laminating, but these require large-scale and expensive manufacturing equipment, and are difficult to use for high-mix low-volume production and short delivery times. Due to the problem that the type of resin is limited, the heat laminating method cannot be completely replaced.
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 can be used for exterior applications 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. It has become increasingly necessary to receive (see Patent Document 2).

JP 2000-326451 A Japanese Patent No. 5630161

However, a decorative sheet formed by laminating an acrylic resin layer and an olefin resin layer via a heat seal agent is laminated on a steel sheet with an adhesive, and then the bending portion is white by performing a bending process called roll forming. A phenomenon sometimes occurred.
This is because when bending is performed, a gap is created between the crosslinked rubber and the acrylic resin contained in the acrylic resin layer, and it appears white. Usually, crosslinked rubber is used to give acrylic resin flexibility, and a graft polymer is applied around the crosslinked rubber. If this graft polymer is brittle and easily cracked, whitening occurs at the bent part. End up. In addition, the acrylic resin has a problem that its solvent resistance is low, and it is an urgent need to achieve both improvement of bending whitening.
There is also a proposal for laminating an acrylic resin layer and a base material via an adhesive by a dry laminating method, but when the base material is an olefin base material, both have no good adhesive layer and are used for exterior applications No possible adhesion was obtained.

  The present invention has been made in view of such circumstances, and has a sufficient weather resistance even in outdoor exposure over a long period of time, has excellent solvent resistance, and has improved bending whitening phenomenon and nonflammability, and An object is to provide a decorative member.

In one embodiment of the present invention for solving the above problems, an adhesive layer, an acrylic resin layer, and a fluororesin layer are formed in this order on a substrate.
Said substrate, with consists of a polypropylene resin, an organic solids weight, 44 g / ^{m 2} or more 67 g / ^{m 2} or less,
The adhesive layer is formed by laminating 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 agent having an acrylic resin as a main chain,
The laminate of the acrylic resin layer and the fluororesin layer has an elongation rate of 145% to 155% when a No. 1 dumbbell-shaped test piece prepared in accordance with JIS K6251 is stretched by 20 mm at a tensile speed of 10 mm / min. And a decorative sheet having a haze of 89% or more.

Another embodiment of the present invention for solving the above problems is a decorative member formed by attaching a decorative sheet and a substrate made of a metal selected from aluminum, iron, stainless steel, and copper, and the decorative sheet. On the base material, an adhesive layer, an acrylic resin layer, and a fluororesin layer are formed in this order,
Said substrate, with consists of a polypropylene resin, an organic solids weight, 44 g / ^{m 2} or more 67 g / ^{m 2} or less,
The adhesive layer is formed by laminating 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 agent having an acrylic resin as a main chain,
The laminate of the acrylic resin layer and the fluororesin layer has an elongation rate of 145% to 155% when a No. 1 dumbbell-shaped test piece prepared in accordance with JIS K6251 is stretched by 20 mm at a tensile speed of 10 mm / min. And a decorative sheet having a haze of 89% or more.

Here, the nonflammability of the decorative member of the present invention is obtained by pasting the nonflammable decorative sheet and a substrate made of a metal selected from aluminum, iron, stainless steel, and copper by a corn calorie combustion test based on ISO5660-1. When the total calorific value with respect to time and the heat generation rate with respect to time of the incombustible decorative member obtained are determined, (i) the total calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less, and (ii) after the start of heating 20 minutes, 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, non-flammability satisfying that there are no cracks and holes penetrating to the rear side which is harmful for fire prevention It is preferable to have.

  According to one embodiment of the present invention, it is possible to provide a decorative sheet and a decorative member that have sufficient weather resistance even during outdoor exposure over a long period of time, have excellent solvent resistance, and have improved bending whitening and nonflammability. it can.

It is typical sectional drawing for demonstrating the decorative sheet which concerns on embodiment based on this invention. It is a graph which shows the transmittance | permeability in each wavelength after the uniaxial stretching of the laminated body which consists of a fluororesin layer used in Example 1, and an acrylic resin layer, "Blank data", "Vertical tensile data" at the time of extending | stretching to a vertical direction And “horizontal tension data” when stretched in the transverse direction. It is a graph which shows the transmittance | permeability in each wavelength after the uniaxial stretching of the laminated body which consists of a fluororesin layer and an acrylic resin layer used for the comparative example 1, "Blank data", "Vertical tensile data" at the time of extending | stretching to a vertical direction And “horizontal tension data” when stretched in the transverse direction.

Next, an embodiment 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.

<Non-combustible decorative sheet>
As shown in FIG. 1, the decorative sheet 1 of the present embodiment has a pattern pattern layer 3, an adhesive layer 4, an acrylic resin layer 5, and a fluororesin layer 6 formed in this order on a substrate 2.
The pattern pattern layer 3 may be omitted. When the pattern layer 3 is provided, it is preferable that the acrylic resin layer 5 and the fluororesin layer 6 have transparency that allows the pattern pattern of the pattern layer 3 to be visually recognized.

<Base material>
The base material 2 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. Or two or more kinds of copolymers, mixtures, and composites selected from these. The base material 2 may be comprised with the laminated body which consists of such a thermoplastic resin.

Here, when the substrate 2 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 it uses a polypropylene resin as the base material 2, nonflammability can be ensured reliably. That is, by setting the above range, 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 1 and the substrate made of metal by a corn calorie combustion test according to ISO 5660-1. When determined, (i) the total calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less, and (ii) the maximum heat generation rate continues for 10 seconds or more for 20 minutes after the start of heating, and 200 kW / m ² is obtained. (Iii) 20 minutes after the start of heating, it is possible to ensure nonflammability that satisfies the absence of cracks and holes penetrating to the back side, which is harmful to fire prevention.
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 2, the substrate made of a metal to which the decorative sheet 1 is bonded can be concealed, and the hue can be appropriately selected as the background color of the design pattern layer 3. 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 3 by using a coating or printing technique as a solid ink layer before the pattern layer 3 is provided.

<Pattern pattern layer>
The pattern layer 3 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.
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. May be.

<Adhesive layer>
The adhesive layer 4 is composed of an adhesive layer 4A and an anchor layer 4B. In addition, when providing the pattern pattern layer 3, it is preferable that the contact bonding layer 4 has transparency which can visually recognize a pattern pattern.
The adhesive layer 4A is made of a urethane adhesive having a polyester resin as a main chain.
The anchor layer 4B 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, benzotriazole, salicylate, cyanoacrylate, formamidine, oxanilide and the like.

<Acrylic resin layer>
It is preferable that the acrylic resin layer 5 has transparency so that the pattern or pattern of the lower pattern pattern layer 3 is visible. The acrylic resin layer 5 is preferably made of a mixture of acrylic rubber and acrylic resin. Additives such as known ultraviolet absorbers may be appropriately added to the acrylic resin layer 5.

  Moreover, 30-80 micrometers is preferable and, as for the thickness of the acrylic resin layer 5, 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 5 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 5. The acrylic resin used in the acrylic resin layer 5 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>
It is preferable that the fluororesin layer 6 has transparency so that the pattern or pattern of the lower pattern pattern layer 3 can be visually recognized. The fluororesin layer 6 imparts surface characteristics such as acid resistance, alkali resistance, solvent resistance, and contamination resistance to the decorative sheet 1.

  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 5. The glass transition point (Tg) of polyvinylidene fluoride is -39 ° C.

  The thickness of the fluororesin layer 6 is preferably about 1 to 15 μm, and more preferably 1 to 10 μm. The fluororesin layer 6 has a ratio to the thickness of the transparent thermoplastic resin layer (thickness of the fluororesin layer 6 / thickness of the acrylic resin layer 5) 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 1. 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 adhering the decorative sheet 1 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) The adhesive layer 4 includes two layers of an adhesive layer 4A made of a urethane-based adhesive having a polyester-based resin as a main chain and an anchor layer 4B made of a urethane-based anchoring agent having an acrylic-based resin as a main chain. Have.
The heat-resistant adhesiveness between the base material 2 and the acrylic resin layer 5 is caused by a curing agent made of an isocyanate compound contained in the adhesive layer 4A and the anchor layer 4B causing a crosslinking reaction inside the adhesive layer 4A and the anchor layer 4B. Excellent.
The anchor layer 4B also has a function of protecting the adhesive layer 4A.
Therefore, it is possible to provide a decorative sheet 1 that can have weather resistance even in outdoor exposure over a long period of time, has good heat resistance, and has nonflammability.
Further, the organic solid mass of the polypropylene resin constituting the base material 2, 44 g / m ² or more 67 g / m ² by mass or less, thereby improving the nonflammable decorative sheet 1.
Furthermore, the laminated body of the acrylic resin layer 5 and the fluororesin layer 6 has an elongation rate of 145% when a No. 1 dumbbell-shaped test piece produced according to JIS K6251 is stretched by 20 mm at a tensile speed of 10 mm / min. 155% and haze is 89% or more. As a result, it is possible to provide the decorative sheet 1 that is adhered to a metal plate and improved in whitening by bending.

(2) The UV absorber of the anchor layer 4B with a urethane-based anchor agent having an acrylic resin as the main chain improves the UV shielding ability, and it is possible to obtain a decorative sheet with excellent weather resistance in addition to heat resistance It has the effect of becoming.
(3) Since the fluororesin constituting the fluororesin layer 6 disposed on the outermost surface is a polyvinylidene fluoride resin, it is possible to obtain a nonflammable decorative sheet having solvent resistance.

(4) It is possible to obtain a non-combustible decorative member having improved durability with ultraviolet rays, excellent weather resistance, and being bonded to a metal plate with little bending whitening and having solvent resistance.
(5) When the total calorific value with respect to time and the heat generation rate with respect to time of the decorative member 10 formed by adhering the decorative sheet 1 and the substrate made of metal are obtained by a corn calorie combustion test based on 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.

Next, examples according to the present invention will be described.
Example 1
As the substrate 2, a resin sheet (thickness: 60 μm) made of a colored polypropylene resin and having a total organic solid content weight of 49.6 g / m ² was prepared.
After the corona discharge treatment was performed on the front surface and the back surface of the substrate 2, a wood grain pattern was formed by gravure printing on the surface using urethane printing ink, and the pattern layer 3 was formed with a thickness of 2 μm.

On the other hand, the back surface primer layer 8 was formed on the back surface of the substrate 2 by gravure printing with a thickness of 1 μm using a back surface primer layer coating solution having the following composition.
<Backside primer layer coating solution>
・ Two-component curable polyester urethane (Polyester polyol and polyisocyanate are mixed in a ratio of 100: 3 (mass ratio)) ... 100 parts by weightDilute solvent (1: 1 (mass of ethyl acetate and methyl isobutyl ketone) Mixed solvent mixed at a ratio of 20) part by mass

  On the other hand, a polyvinylidene fluoride resin (fluororesin) and an acrylic resin layer-forming mixture were melted with a T-die and extruded to form a laminate composed of the fluororesin layer 6 and the acrylic resin layer 5. The thickness of the fluororesin layer 6 in this laminate was 5 μm, and the thickness of the acrylic resin layer 5 was 45 μm.

Thereafter, on the acrylic resin layer 5 side in the laminate, a urethane anchor layer 4B (thickness: 1.5 μm) having an acrylic resin as a main chain containing a triazine ultraviolet absorber (5 parts by mass) is obtained by gravure printing. Formed. Hereinafter, a laminate in which the fluororesin layer 6 and the acrylic resin layer 5 are laminated is referred to as “laminate A”, and a laminate in which the urethane anchor layer 4B is laminated on the acrylic resin layer 5 side of the “laminate A” is referred to as “laminate”. Sometimes referred to as “body B”. That is, the thickness of the laminated body A of Example 1 was 50 μm.
Next, a coating solution made of a two-component curable urethane-based adhesive having a polyester resin as a main chain was applied onto the pattern layer 3 to form an adhesive layer 4A (thickness in a dry state: 6 μm). . Thereafter, the laminate B was laminated on the adhesive layer 4A by a dry laminating method to obtain a decorative sheet 1 of Example 1.
Furthermore, the decorative sheet 1 of Example 1 was obtained by sufficiently adhering an aluminum alloy rod having a thickness of 2 mm to the decorative sheet 1 via a urethane-based adhesive (2 liquids).

Here, the laminate A of Example 1 was produced by punching a No. 1 dumbbell-shaped test piece in accordance with JIS K6251 and extending the test piece by 20 mm at a tensile speed of 10 mm / min. Were 145% to 155% in length and width, respectively. In the vertical and horizontal directions, the flow direction during film formation of the laminate A is defined as the vertical direction, and the direction perpendicular to the flow direction on the laminate A is defined as the horizontal direction.
And the transmittance | permeability (haze,% T) in the wavelength 450-750 nm of the test piece after extending | stretching of each direction was measured with the spectrophotometer (room temperature 25 degreeC humidity 60% environment). As a result, the transmittance of the laminate A of Example 1 was 89% or more in both the longitudinal and lateral stretching, as shown in FIG.
In addition, the blank data of the present Example 1 is a result measured without punching after being punched into a No. 1 dumbbell shape (at room temperature of 25 ° C. and humidity of 60%).

(Comparative Example 1)
A decorative sheet and a decorative member of Comparative Example 1 were obtained in the same manner as in Example 1 except that the laminate A in Example 1 was “Acryprene FBS006” manufactured by Mitsubishi Rayon Co., Ltd.
Here, the laminate A of Comparative Example 1 was prepared by punching a No. 1 dumbbell-shaped test piece in accordance with JIS K6251, stretched in the same manner as in Example 1, and each direction of the test piece after stretching. The transmittance (haze) was measured. As a result, as shown in FIG. 3, the transmittance (haze) was 89% or more in the stretching in the longitudinal direction, but the transmittance (haze) was less than 89% in the stretching in the transverse direction. In addition, the blank data of the comparative example 1 is a result measured after being punched into a No. 1 dumbbell shape and not stretched (at room temperature of 25 ° C. and humidity of 60%).

(Comparative Example 2)
Comparative Example 2 was performed in the same manner as in Example 1 except that the base material in Example 1 was a resin sheet (thickness: 90 μm) having a total organic solid content weight of 77.6 g / m ² made of a colored polypropylene resin. A decorative sheet and a decorative member were obtained.

(Evaluation)
<Bending whitening test>
The decorative sheets produced in Example 1 and Comparative Examples 1 and 2 were sufficiently adhered to a steel plate having a thickness of 2 mm using a urethane-based adhesive (2 liquids), and at normal temperature (25 ° C.) and low temperature (5 ° C.). The whitening state of the bent part was observed when it was bent 90 ° in the vertical and horizontal directions under the environment.
The evaluation criteria were “accepted: ◯” if the bent portion was not white in the vertical direction and the horizontal direction, and “failed: x” if it was white. The results are shown in Table 1.

<Nonflammable>
About the decorative member produced in Example 1 and Comparative Examples 1 and 2, in the corn calorie combustion test based on ISO5660-1, if the following (i) to (iii) are satisfied, “pass: ○” is satisfied, and either If not, it was determined as “Fail: x”. The results are shown in Table 1.
(I) The total calorific value (MJ / m ² ) for 20 minutes after the start of heating is 8 MJ / m ² or less (ii) As the maximum heat generation rate for 20 minutes after the start of heating, 200 kW / m ² is continuously maintained for 10 seconds or more. (Iii) Evaluation of base material cracks No cracks or holes

As shown in Table 1, the decorative sheet of Example 1 having a haze of 89% or more even when a No. 1 dumbbell-shaped test piece produced from the laminate A according to JIS K6251 is stretched in the vertical and horizontal directions, Good results were obtained in the bending whitening test.
The base material is, it becomes a polypropylene resin, an organic solids weight, 44 g / m ² or more 67 g / m ² or less is decorative member of Example 1 was one that exhibits good incombustibility.

On the other hand, even when a No. 1 dumbbell-shaped test piece prepared in accordance with JIS K6251 is stretched in the vertical and horizontal directions from the laminate 6 composed of an acrylic resin layer and a fluororesin layer, either haze is less than 89%. A decorative sheet of Comparative Example 1 did not give good results in a bending whitening test.
The base material is, it becomes a polypropylene resin, an organic solids weight, 44 g / m ² or more 67 g / m ² or less in Comparative Example 2 not within the scope of the decorative member did not exhibit satisfactory non-flammable.

  That is, according to Example 1, it is possible to provide a decorative sheet and a decorative member that have sufficient weather resistance even in outdoor exposure over a long period of time and that have improved the bending whitening phenomenon and nonflammability. Further, by providing the decorative sheet 1 with surface properties such as acid resistance, alkali resistance, solvent resistance, and contamination resistance by providing the fluororesin layer 6, a decorative sheet and a decorative member having excellent solvent resistance can be obtained. Can be provided.

DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Base material 3 Picture pattern layer 4 Adhesive layer 4A Adhesive layer 4B Anchor layer 5 Acrylic resin layer 6 Fluorine resin layer 7 Metal substrate 8 Primer layer 10 Cosmetic member

Claims (5)

On the substrate, an adhesive layer, an acrylic resin layer, and a fluororesin layer are formed in this order,
Said substrate, with consists of a polypropylene resin, an organic solids weight, 44 g / ^{m 2} or more 67 g / ^{m 2} or less,
The adhesive layer is formed by laminating 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 agent having an acrylic resin as a main chain,
The laminate of the acrylic resin layer and the fluororesin layer has an elongation rate of 145% to 155% when a No. 1 dumbbell-shaped test piece prepared in accordance with JIS K6251 is stretched by 20 mm at a tensile speed of 10 mm / min. And a decorative sheet characterized by having a haze of 89% or more.   The decorative sheet according to claim 1, wherein the urethane-based anchor agent contains an ultraviolet absorber.   The decorative sheet according to claim 1, wherein the fluororesin constituting the fluororesin layer is a polyvinylidene fluoride resin.   A decorative member comprising the decorative sheet according to any one of claims 1 to 3 and a substrate made of a metal selected from aluminum, iron, stainless steel, and copper. The decorative member according to claim 4, wherein, in a corn calorie combustion test based on ISO 5660-1, the following (i) to (iii) are satisfied for 20 minutes after the start of heating.
(I) The total heat generation amount is 8 MJ / m ² or less (ii) The maximum heat generation rate continues for 10 seconds or more and 200 kW / m ² or less (iii) No cracks or holes penetrating to the rear side which is harmful to fire prevention.

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