JP2020062775A - Embossed decorative sheet - Google Patents

Abstract

To provide an olefin resin decorative sheet having excellent designability and scratch resistance/weather resistance in an embossed decorative sheet, and having practical incombustibility in accordance with Building Standard Act.SOLUTION: An embossed decorative sheet is such that: a picture pattern layer, an adhesive layer, a transparent thermoplastic resin layer, and a surface protective layer are laminated on a thermoplastic resin base material sheet in this order; and an embossment is formed at least in the transparent thermoplastic resin layer. In the embossed decorative sheet, the thermoplastic resin base material sheet comprises polyester resin with 35-85 μm thickness, and the transparent thermoplastic resin layer comprises a polypropylene layer with 30-60 μm thickness.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an embossed decorative sheet.

BACKGROUND ART Conventionally, there is an embossed decorative sheet in which a decorative board is formed by adhering the surface of wooden boards, inorganic boards, steel plate or the like with an adhesive. As such an embossed decorative sheet, a sheet using a vinyl chloride resin has been generally used, but in recent years, there has been a demand for a sheet not using a vinyl chloride resin because of a problem such as chlorine generation during incineration.
An olefinic thermoplastic resin sheet is generally used as an alternative to such vinyl chloride resin. (Patent Document 1)

By the way, the building materials used for "special buildings" specified in the Building Standard Act construction examples and for "fireproof areas" specified by the City Planning Act are required to be non-combustible materials.
Specifically, the exothermic test prescribed by the Building Standards Act / Construction Order of the same (non-combustible material: heated with a cone calorimeter tester for 20 minutes, total calorific value less than 8 MJ / m ² , maximum calorific value) It is necessary to apply for and pass the 200 kW / m ² excess time of less than 10 seconds) and pass the certification of the Ministry of Land, Infrastructure, Transport and Tourism.

  However, the olefin resin that is usually used has higher combustion energy than vinyl chloride resin, and does not have self-extinguishing property like vinyl chloride resin. Therefore, it is very difficult to meet the standard of the above exothermicity test.

Some single-layer sheets made of polyester resin have passed the non-combustible application prescribed by the Building Standards Act in the past, but the single-layer sheet has a monotonous design surface, scratch resistance, and weather resistance. There were problems such as inferiority.
(Patent Document 2)

JP, 6-328635, A JP, 2003-311901, A

  The present invention focuses on the above points, and has a decorative sheet of an olefinic resin having excellent designability, scratch resistance and weather resistance, and having sufficient nonflammability in accordance with the Building Standards Law. It is intended to be provided.

In order to solve the above problems, the embossed decorative sheet of the present invention,
On the thermoplastic resin substrate sheet, a pattern layer, an adhesive layer, a transparent thermoplastic resin layer, and a surface protective layer are laminated in this order, and at least an emboss is formed on the transparent thermoplastic resin layer. It is an embossed decorative sheet,
The embossed decorative sheet is characterized in that the thermoplastic resin substrate sheet is made of a polyester resin having a thickness of 35 to 85 μm, and the transparent thermoplastic resin layer is made of a polypropylene layer having a thickness of 30 to 60 μm.

Further, the embossed decorative sheet of the present invention,
The transparent thermoplastic resin layer comprises, from the thermoplastic resin substrate sheet side, a first resin layer containing a first resin and a second resin different from the first resin. The embossed decorative sheet is characterized in that two resin layers are laminated in this order.

Furthermore, the embossed decorative sheet of the present invention,
The first resin layer is a layer containing transparent maleic acid-modified polypropylene, and the second resin layer is a layer made of transparent polypropylene containing an ultraviolet absorber and a light stabilizer. It is a sheet.

The embossed decorative sheet of the present invention,
The total weight of the thermoplastic resin substrate sheet is 40 g / m ² or more, and the organic mass is 70 g / m ² or less, and the organic mass of the transparent thermoplastic resin layer is 25 to 55 g / m ² , The embossed decorative sheet has an organic mass of 130 g / m ² or less as a whole.

  According to the embossed decorative sheet of the present invention, even if a thermoplastic polyolefin resin is used, the sheet has nonflammability, and further can have excellent designability, abrasion resistance, and underlayer concealability by embossing.

  In addition, according to the embossed decorative sheet of the present invention, the first resin layer ensures the adhesiveness to the base sheet, while the second resin layer serves as a main part of the layer and bears other physical properties. It is possible to widen the range of design.

  Further, according to the embossed decorative sheet of the present invention, by using the transparent maleic acid-modified polypropylene as the first resin layer, it is possible to improve the adhesiveness with the thermoplastic resin substrate sheet and to make the second layer transparent. By forming a layer containing any one of polypropylene, an ultraviolet absorber and a light stabilizer, or a composite thereof, it is possible to exhibit an effect of embrittlement resistance inside the resin and obtain practical weather resistance.

Further, according to the embossed decorative sheet of the present invention, the organic mass of the entire embossed decorative sheet is 130 g / m ² or less, so that excellent nonflammability can be obtained.

It is a schematic sectional drawing which shows the layer constitution of the embossing decorative sheet of this invention.

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 plane dimension, the ratio of the thickness of each layer, and the like are different from the actual ones. Further, the embodiments described below exemplify 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 constituent parts are as follows. It is not specific to one. Various changes can be added to the technical idea of the present invention within the technical scope defined by the claims described in the claims.

(Embossed cosmetic sheet 1)
As shown in FIG. 1, the embossed decorative sheet 1 according to the present embodiment has a pattern printing layer 3, an adhesive layer 4, and a transparent thermoplastic resin layer 5 laminated in this order on a thermoplastic resin base sheet 2. Is formed.
The transparent thermoplastic resin layer 5 has at least two layers, and is formed by laminating a first resin layer and a second resin layer in this order from the side of the thermoplastic resin base sheet 2 via the adhesive layer 4. All of these layers are made of transparent thermoplastic resin.

Further, at least on the side of the transparent thermoplastic resin layer 5 close to the surface of the second resin layer, an emboss is formed in order to adjust the gloss of the surface and give a three-dimensional effect. Further, the surface protection layer 6 is laminated on the emboss. A surface activation treatment is applied to the back surface side of the thermoplastic resin substrate sheet 2, and a primer layer 7 is provided on the surface activation-treated surface.
In FIG. 1, the layers are shown separated from each other for the sake of simplicity, but in reality, the layers are in close contact with each other.
Hereinafter, each of these layers will be described in detail.

(Thermoplastic resin base sheet 2)
The thermoplastic resin base sheet 2 is a base sheet containing a thermoplastic resin.
As the thermoplastic resin, a polyester resin can be used. Specifically, polyethylene terephthalate, polybutylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene naphthalate, polylactic acid, etc. are used. Particularly, polybutylene terephthalate is preferably used. Further, in order to improve the adhesion with the adhesive layer 3, an easily adhesive layer may be provided, or a corona treatment may be appropriately performed.

  As a coloring method, a dry color method in which a fine powdery coloring agent obtained by treating a pigment with a dispersion aid or a surfactant is used, a master batch pellet in which a resin and a high-concentration pigment are melt-kneaded and pre-dispersed is prepared. However, a master batch method or the like in which an ordinary resin that is not colored in the extrusion hopper is dry-blended can be used, and the method is not particularly limited.

  The type of pigment is not particularly limited, but in consideration of weather resistance, heat resistance and the like, inorganic pigments such as titanium oxide, ultramarine blue, cadmium pigment and iron oxide are preferable. Further, as an organic pigment, a phthalocyanine pigment, a quinacridone pigment or the like can be used. The color and blending ratio of the pigment are arbitrarily determined in view of the degree of hiding, designability, etc., and are not particularly limited.

  According to the technical study by the present inventor, it was found that the thickness of the thermoplastic resin base sheet 2 should be 35 to 85 μm. When the thickness is less than 35 μm, unevenness derived from the base of the object to which the decorative sheet is attached may be projected on the surface through the decorative sheet. When the thickness exceeds 85 μm, the organic mass of the entire sheet increases and impairs the nonflammability.

(Pattern layer 3)
The picture pattern layer 3 is a layer which is formed by printing on the thermoplastic resin substrate sheet 2 and which is provided with a picture for imparting a design property. As the picture pattern, for example, a wood pattern, a cork pattern, a stone pattern, a tile pattern, an abstract pattern, or the like can be used.

  As the pigment of the printing ink, for example, any one of isoindolinone yellow, polyazo red, phthalocyanine blue, carbon black, iron oxide, titanium oxide, or a mixture thereof can be used. Further, as the binder, for example, ethyl acetate, n-butyl acetate, isobutanol and methyl isobutyl ketone can be used. Particularly, considering the adhesiveness with the thermoplastic resin substrate sheet 2, etc., a binder containing an isocyanate curing agent and active hydrogen is preferable.

  Further, a plasticizer, a stabilizer, a wax, a grease, a desiccant, a curing agent, a thickener, a dispersant, a filler and the like may be added to the printing ink. Further, as the printing method, for example, gravure printing, screen printing, offset printing, gravure offset printing, intaglio printing, silk printing, electrostatic printing, inkjet printing, flexographic printing can be used.

(Adhesive layer 4)
The adhesive layer 4 is a layer containing an adhesive that bonds the pattern layer 3 and the transparent thermoplastic resin layer 5. The adhesive is appropriately selected from urethane-based, acrylic-based, polyester-based, etc. depending on the combination of the printing ink forming the pattern layer 3 and the resin forming the transparent thermoplastic resin layer 5.

(Transparent thermoplastic resin layer 5)
The transparent thermoplastic resin layer 5 is a sheet-like layer composed of a plurality of layers. Each layer is formed of a transparent thermoplastic resin through which the pattern of the pattern pattern layer 3 can be seen. As the thermoplastic resin, for example, various resins other than vinyl chloride resin can be used. Various combinations of resins for each layer are possible depending on desired characteristics. As for the number of layers, four or more layers are possible, but the structure of the extruder is complicated and the complexity of the work is increased, so that three layers or less are preferable.

In the example of FIG. 1, the transparent thermoplastic resin layer 5 is a first intermediate layer that includes a predetermined resin (hereinafter, also referred to as “first resin”) from the thermoplastic resin substrate sheet 2 side. Two layers of a second resin layer 52 are formed in this order as a surface layer containing a resin layer 51 and a resin different from the first resin (hereinafter, also referred to as “second resin”). There is.
As the first resin and the second resin, for example, in consideration of scratch resistance, weather resistance, stain resistance, light resistance, transparency, bendability, thermoformability, etc. of the surface of the embossed decorative sheet 1, a further material Considering costs and the like, the first resin is a layer containing transparent maleic acid-modified polypropylene, and the second resin is transparent polypropylene, an ultraviolet absorber, or a light stabilizer, or a composite composition thereof. It is preferably a layer containing.

  According to the technical study of the present inventor, it was found that the thickness of the transparent thermoplastic resin layer 5 should be 30 to 60 μm. If the thickness is less than 30 μm, the abrasion resistance is insufficient, and scratches reaching the pattern print layer may remain and impair the design. When the thickness exceeds 60 μm, the organic mass of the entire sheet increases and impairs the nonflammability.

(Polypropylene resin)
Examples of the polypropylene resin used for the transparent thermoplastic resin layer 5 of the present embodiment include a polypropylene resin (a) having a free-end long chain branch and a polypropylene resin (b) having no free-end long chain branch. Of the mixed resin of (a) and (b), wherein the mixture has a molecular weight distribution Mw / Mn defined as mass average molecular weight / number average molecular weight of the mixture of 1 to 5 and An isotactic index defined as a heptane-soluble residue rate may be in the range of 1% or more and 90% or less.
Thereby, whitening and cracks can be suppressed in the bending process after the embossed decorative sheet 1 is attached to the steel plate base material.

Here, the molecular weight distribution is number average molecular weight Mn = Σ (Mi × Ni) / ΣNi, mass average molecular weight Mw = Σ (Ni × Mi ² ) / Σ (Ni × The ratio of Mi) is a value defined as Mw / Mn.
The closer the molecular weight distribution is to 1, the narrower the molecular weight distribution and the higher the uniformity. If the molecular weight distribution is 5 or less, the molecular weights can be adjusted to a necessary and sufficient size, which contributes to suppression of whitening and cracking. Generally, the molecular weight distribution can be measured by gel permeation chromatograph (GPC).

The isotactic index defined as the boiling heptane-soluble residue rate is useful as an index for examining the crystallinity in the polypropylene resin.
Specifically, the sample is extracted with boiling n-heptane for a certain period of time, the mass (%) of the unextracted portion is determined, and the isotactic index is calculated. Specifically, the cylindrical filter paper is dried at 110 ± 5 ° C. for 2 hours, left in a constant temperature and humidity room for 2 hours or more, and then 8 g or more and 10 g or less of the sample (powder or flake) is put into the cylindrical filter paper and weighed. Weigh accurately using a cup and tweezers. This is set on the upper part of the extractor containing about 80 cc of heptane, and the extractor and the cooler are assembled. This is heated with an oil bath or an electric heater and extracted for 12 hours. The heating is adjusted so that the number of drops from the cooler is 130 drops or more per minute. Then, the cylindrical filter paper containing the extraction residue is taken out, put in a vacuum dryer and dried at 80 ° C. under a vacuum degree of 100 mmHg or less for 5 hours. After drying, the sample is allowed to stand in a constant temperature and constant humidity for 2 hours, then precisely weighed, and the isotactic index is calculated by (P / Po) × 100. However, Po is the sample mass (g) before extraction, and P is the sample mass (g) after extraction.

  By setting the isotactic index to 90% or less, the sheet rigidity due to polypropylene crystals can be suppressed. As a method of lowering the isotactic index, for example, a method in which an amorphous polypropylene component (such as syndiotactic polypropylene or atactic polypropylene) is partially used, or one or more kinds of olefin monomers such as ethylene and α-olefin are used. Random copolymerization method, various rubber components (eg ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), butadiene rubber (BR) , A component such as isoprene rubber (IR)) can be used.

  Further, the melt tension of the mixed resin of polypropylene resin (a) and (b) (using a nozzle capillary rheometer with a diameter of 2.0 mm, the tension when extruding at a temperature condition of 230 ° C. and 60 mm / min and pulling out at 2 mm / min) ) Is preferably in the range of 100 mN or more and 500 mN or less. If it exceeds 500 mN, the melt viscosity becomes too high and stable film formation cannot be achieved. If it is 100 mN or less, the long-chain branched component becomes insufficient, and it is difficult to obtain desired performance.

  In addition, the molecular weight of the mixture of the polypropylene resins (a) and (b) is controlled by setting the melt flow rate at 230 ° C. defined by JIS-K6760 within the range of 5 g / 10 min or more and 50 g / 10 min or less. It is possible to maintain a stable film-forming state with a certain value or more. A more preferable melt flow rate range is 10 g / 10 min or more and 30 g / 10 min or less, and further preferably 10 g / 10 min or more and 25 g / 10 min or less.

If the melt flow rate exceeds 50 g / 10 min, the resin melt-extruded from the T-die will have a greater effect (neck-in) of gathering in the center during melt-extrusion with the T-die, and the resin will be melt-extruded from the T-die. The end thickness of the resin increases. The increase in the thickness of the end portion affects the cooling efficiency and the thickness stability in the width direction, which makes it difficult to form a stable film.
Also, if it is lower than 5 g / 10 min, the draw resonance of the molten resin becomes poor, and the molten resin has a gap between the velocity (initial velocity) of the molten resin immediately after exiting from the T die and the velocity of the resin immediately after touching the cooling roll. However, it becomes difficult to form a stable film.

The ultraviolet absorber added to the transparent thermoplastic resin layer 5 is appropriately selected from benzotriazole type, triazine type, benzophenone type and the like.
Examples of the benzotriazole-based ultraviolet absorber include 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy. -3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t- Butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5- Di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazo Etc., and mixtures thereof, modified products, polymers can be used derivatives.

  Further, as the triazine-based ultraviolet absorber, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4-[( 2-Hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2- Hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4dimethylphenyl) -1,3,5-triazine, 2,4-bis (2,4-dimethyl) It is possible to use phenyl) -6- (2-hydroxy-4-iso-octyloxyphenyl) -s-triazine and the like, and mixtures, modified products, polymers and derivatives thereof.

  Further, as the benzophenone-based ultraviolet absorber, octabenzone, modified products, polymers, derivatives and the like can be used. As the ultraviolet absorber, one having a hydroxyl group is particularly suitable because it can be expected to be bonded to the resin component by crosslinking by adding an isocyanate. The number of parts added may be set according to the desired weather resistance, but is 0.1% or more and 50% or less, preferably 1% or more and 30% or less with respect to the resin solid content.

The light stabilizer added to the transparent thermoplastic resin layer 5 includes bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-Hydroxyphenyl] methyl] butyl malonate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-poperidinyl) ) Sebacate, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester and the like, and mixtures, modified products, polymers and derivatives thereof can be used.
The number of parts to be added may be added according to the desired weather resistance, but is 0.1% by mass or more and 50% by mass or less, preferably 1% by mass or more and 30% by mass or less, based on the resin solid content.

  Other than the above, for example, a heat stabilizer, a flame retardant, an antiblocking agent, etc. may be added. As a heat stabilizer, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl)]-propionate, 2,4-bis- (n-octylthio) -6- (4 -Hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5- Trimethyl-2,4,6-tris (3,5-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) Hindered phenolic antioxidants such as isocyanuric acid, 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butyl) A phenolic antioxidant such as phenol), a phosphorus antioxidant represented by tris (2,4-di-t-butylphenyl) phosphite, or a mixture thereof, that is, one kind or two or more kinds. A combination can be used.

  As the flame retardant, it is possible to use an inorganic compound such as aluminum hydroxide, magnesium hydroxide, calcium carbonate or magnesium carbonate, or a phosphate ester flame retardant. Further, as the antiblocking agent, an inorganic antiblocking agent such as aluminum silicate, silicon oxide, hydrotalcite, calcium carbonate, and the like, an organic antiblocking agent such as fatty acid amide, and the like can be used. The thickness of the transparent thermoplastic resin layer 5 is preferably 10 μm or more and 100 μm or less.

(Primer layer 7)
As the primer layer 7, for example, a polyester resin, a polyurethane resin, a mixture thereof, or the like can be used. Further, by adopting a two-component type of polyol and isocyanate, the adhesion between the sheet and the primer and the cohesive force of the primer itself are improved. Examples of the polyol include acrylic polyol and polyester polyol.
Examples of the isocyanate include aromatic type such as tolylene diisocyanate and 4,4 ′ diphenylmethane diisocyanate, and aliphatic type such as hexamethylene diisocyanate, isophorone diisocyanate and xylene diisocyanate. Aromatic compounds are preferred from the viewpoint of high reactivity and heat resistance.

  The thickness of the primer layer is preferably 1 μm or more. If it is less than 1 μm, it is dissolved depending on the solvent species of the adhesive and the primer layer disappears, so that the adhesiveness is not improved.

If the silica contained in the primer has a particle size of 1 to 4 μm and a pore volume of 0.4 to 2.0 mL / g, the adhesive absorbs well and does not affect the cohesive force of the primer.
The content of silica is 5 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the primer resin in consideration of the absorption / penetration of the adhesive and the blocking resistance. If it is less than 5 parts by weight, the adhesive strength and blocking resistance are poor, and if it exceeds 30 parts by weight, the delamination phenomenon of the primer is observed.

Next, examples and comparative examples of the present invention will be described.
(Example 1)
A polybutylene-based inorganic filled sheet (manufactured by Okura Industry Co., Ltd.) having a thickness of 60 μm and a weight of 75 g / m ² was used as the thermoplastic resin base sheet 2, and a wood grain was formed on the thermoplastic resin base sheet 2 by a gravure printing method. The pattern was printed to form the pattern layer 3.
Subsequently, a urethane resin adhesive was applied onto this pattern layer 3 and dried with warm air to form an adhesive layer 4. Then, a transparent thermoplastic resin layer 5 was formed on the adhesive layer 4 by extruding a plurality of layers containing a molten transparent thermoplastic resin with a T-die through a multi-axis extruder and laminating the layers.

  A transparent maleic acid-modified polypropylene (manufactured by Riken Vitamin Co., Ltd.) is used for the first resin layer 51 of the transparent thermoplastic resin layer 5, and a polypropylene resin and a phenolic antioxidant (Ciba) are used for the second resin layer 52. 0.2 parts by weight of "IRGANOX 1010" manufactured by Specialty Chemicals Co., Ltd., 0.3 part by weight of a hindered amine light stabilizer ("TINUVIN 622" manufactured by Ciba Specialty Chemicals Co., Ltd.), and a benzotriazole ultraviolet absorber (Ciba Specialty Co., Ltd.) A resin containing 0.5 parts by weight of "TINUVIN 326" manufactured by Chemicals Co., Ltd. was used.

At the same time, a conduit embossing plate (plate depth of 30 μm) and a rubber roll are used to nip a laminate of the thermoplastic resin substrate sheet 2, the pattern layer 3, the adhesive layer 4 and the transparent thermoplastic resin layer 5 for embossing. Lamination was performed simultaneously. Here, the thickness of (first resin + second resin) was 40 μm, and the weight at that time was 36 g / m ² .

After applying a surface treatment to the embossed surface of this decorative sheet, a urethane-based resin (“URV238 varnish” manufactured by Toyo Ink Co., Ltd.) as a top coat resin and a curing agent (“UR150B varnish” manufactured by Toyo Ink Co., Ltd.) 10 0.5 parts by weight of a benzotriazole-based UV absorber (“TINUVIN 326” manufactured by Ciba Specialty Chemicals Co., Ltd.) and 1 part of a hindered amine-based light stabilizer (“TINUVIN 622” manufactured by Ciba Specialty Chemicals Co., Ltd.) were added to 1 part by weight. The parts added in parts by weight were coated by gravure coating so that the coating amount after drying was 6 g / m ² to obtain a surface protective layer 6.

Further, after the back surface of the thermoplastic resin substrate sheet 2 is subjected to a surface treatment, 10 parts by weight of silica is added to 100 parts by weight of polyol (“Lamistar EM” manufactured by Toyo Ink Co., Ltd.) on this surface. A primer coating solution containing 3 parts by weight of isocyanate (“LPNYB curing agent” manufactured by Toyo Ink Co., Ltd.) was used as a primer coating solution and was coated by gravure coating so that the coating amount after drying was 3 g / m ^2. Primer layer 7 was obtained.

By such a procedure, the embossed decorative sheet 1 of Example 1 was formed.
At this time, the total weight of the sheet was 121 g, and the organic mass was 109 g.

(Example 2) (upper base thickness upper limit)
An embossed decorative sheet 1 was formed in the same manner as in Example 1 except that the thickness of (first resin + second resin) was 60 μm and the weight was 54 g / m ² .

(Example 3) (Upper base thickness lower limit)
The embossed decorative sheet 1 was formed in the same manner as in Example 1 except that the thickness of the (first resin + second resin) was 30 μm and the weight was 27 g / m ² .

(Example 4) (upper base thickness upper limit)
An embossed decorative sheet 1 was formed in the same manner as in Example 1 except that the thickness of the polybutylene-based inorganic filled sheet was 85 μm and the weight was 107 g / m ² .

(Example 5) (lower limit of lower thickness)
An embossed decorative sheet 1 was formed in the same manner as in Example 1 except that the thickness of the polybutylene-based inorganic filled sheet was 35 μm and the weight was 44 g / m ² .

(Comparative Example 1) (Todai resin thickness is too thick)
An embossed decorative sheet 1 was formed in the same manner as in Example 1 except that the thickness of (first resin + second resin) was 65 μm and the weight was 59 g / m ² .

(Comparative Example 2) (Upper base resin thickness is too thin)
An embossed decorative sheet 1 was formed in the same manner as in Example 1 except that the thickness of the (first resin + second resin) was 25 μm and the weight was 23 g / m ² .

(Comparative example 3) (The thickness of the lower table is too thick)
An embossed decorative sheet 1 was formed in the same manner as in Example 1 except that the thickness of the polybutylene-based inorganic filling sheet was 90 μm and the weight was 112 g / m ² .

(Comparative Example 4) (The thickness of the lower table is too thin)
An embossed decorative sheet 1 was formed in the same manner as in Example 1 except that the thickness of the polybutylene-based inorganic filled sheet was 30 μm and the weight was 40 g / m ² .

(Comparative Example 5) (single layer of upper resin)
The transparent thermoplastic resin layer 5 does not use the transparent maleic acid-modified polypropylene which is the first resin, but the polypropylene resin which is the second resin contains a phenolic antioxidant (“IRGANOX 1010” manufactured by Ciba Specialty Chemicals Co., Ltd.) 0 0.2 parts by weight, 0.3 parts by weight of a hindered amine light stabilizer (“TINUVIN 622” manufactured by Ciba Specialty Chemicals Co., Ltd.), and benzotriazole ultraviolet absorber (“TINUVIN 326” manufactured by Ciba Specialty Chemicals Co., Ltd.) of 0.3 parts by weight. An embossed decorative sheet 1 was formed in the same manner as in Example 1 except that only the resin added in an amount of 5 parts by weight was used.

(Comparative Example 6) (No weathering agent used in the thermoplastic resin layer)
An embossed decorative sheet 1 was formed in the same manner as in Example 1 except that the light stabilizer / ultraviolet absorber was not used in the second resin.

(Evaluation methods)
Confirmation of total weight and calculation of organic mass: A 100 mm square test piece was cut out and the mass before and after complete combustion was measured to confirm the total weight and calculate the organic mass.

  Exothermic test: A 99 mm square test piece was cut out and subjected to a combustion test (heating for 20 minutes) using a cone calorimeter.

<Standards for non-combustible materials>
-The total calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less.
-For 20 minutes after the start of heating, there should be no cracks or holes that penetrate to the back surface, which is harmful for fire protection.
-The maximum heat generation rate should not exceed 200 kW / m ² for 10 minutes or more for 20 minutes after the start of heating.
○: Meets the standards for non-combustible materials ×: Does not meet the standards for non-combustible materials

Abrasion resistance: A 12 mm MDF substrate was coated with an ethylene-vinyl acetate copolymer emulsion type adhesive to obtain a laminated decorative plate with the primer layer 7 side of the embossed decorative sheet 1.
A 120 mm square sample was cut out from the above decorative plate and subjected to a wear C test described in Japanese Agricultural Standards of plywood to confirm the surface condition.
◯: No scratches reaching the pattern print layer were generated.
Δ: There is a scratch reaching the pattern print layer, but the degree of pattern disappearance is very slight.
X: There is a scratch reaching the pattern print layer, which greatly impairs the design.

Weather resistance evaluation: A 144 h accelerated weather resistance test was performed under the following test conditions using a metal weather tester (Daipla Metal Weather KU-R5DC1-A manufactured by DAIPLA WANTES CO., LTD.).
Test conditions: Illuminance of 65 mW / cm ² , Light (53 ° C., 50% RH) for 20 h, and Dew (30 ° C., 95% RH) for 4 h complete one cycle. Watering is 30 seconds before and after Dew.
The evaluation items are as follows.
◯: No cracks or cracks on the surface and no discoloration or discoloration of the pattern print layer. Δ: Minor cracks or discoloration were confirmed.
×: Confirmed obvious cracks and discoloration.

Interlayer adhesion evaluation: A state in which the embossed decorative sheet is cut into a width of 1 inch and a part of the thermoplastic resin layer of the embossed decorative sheet is peeled off from the pattern printing layer by using a solvent (in the figure, the first resin layer 51 and After peeling at the interface of the adhesive layer 4 or at the interface of the adhesive layer 4 and the pattern printing layer 3, a 180 ° peel test was performed at 20 mm / min using Tensilon to measure the interlayer adhesion strength. The evaluation items are as follows.
◯: 20 N / inch or more (has sufficient interlayer adhesion strength for practical use)
×: less than 20 N / inch or zipper peeling

Substrate hiding property: An ethylene-vinyl acetate copolymer emulsion type adhesive was applied to a 12 mm MDF base material to obtain a laminated decorative plate on the primer layer 7 side of the embossed decorative sheet 1.
The surface condition of the decorative board was confirmed.
⊚: Good surface condition without removing foreign matter from the base.
◯: Good surface condition without picking up irregularities derived from the base.
Δ: Concavities and convexities derived from the base are confirmed through the embossed decorative sheet, but the effect on the design is slight.
X: Unevenness derived from the base is confirmed through the embossed decorative sheet, and significantly impairs the design.

(Evaluation results)
The evaluation results are shown in the table below.

  From the above evaluation results, by creating an embossed decorative sheet within the range of the examples, while having heat generation performance as a non-combustible material, it has abrasion resistance and weather resistance that can withstand practical use, and correlation adhesion It is possible to provide an embossed decorative sheet having a base concealing property.

1: Embossed decorative sheet 2: Thermoplastic resin base sheet 3: Pattern print layer 4: Adhesive layer 5: Transparent thermoplastic resin layer 51: First resin layer 52: Second resin layer 6: Surface protective layer 7 : Primer layer

Claims (4)

On the thermoplastic resin substrate sheet, a pattern layer, an adhesive layer, a transparent thermoplastic resin layer, and a surface protective layer are laminated in this order, and at least an emboss is formed on the transparent thermoplastic resin layer. It is an embossed decorative sheet,
An embossed decorative sheet, wherein the thermoplastic resin substrate sheet is made of a polyester resin having a thickness of 35 to 85 μm, and the transparent thermoplastic resin layer is made of a polypropylene layer having a thickness of 30 to 60 μm.   The transparent thermoplastic resin layer comprises, from the thermoplastic resin substrate sheet side, a first resin layer containing a first resin and a second resin different from the first resin. The embossed decorative sheet according to claim 1, wherein the two resin layers are laminated in this order.   The first resin layer is a layer containing transparent maleic acid-modified polypropylene, and the second resin layer is a layer made of transparent polypropylene containing an ultraviolet absorber and a light stabilizer. The embossed decorative sheet according to Item 1 or 2. The total weight of the thermoplastic resin substrate sheet is 40 g / m ² or more, and the organic mass is 70 g / m ² or less, and the organic mass of the transparent thermoplastic resin layer is 25 to 55 g / m ² , The embossed decorative sheet according to any one of claims 1 to 3, wherein the total organic mass of the embossed decorative sheet is 130 g / m ² or less.

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