JP6743605B2 - Embossed decorative sheet and manufacturing method thereof - Google Patents

Description

The present invention relates to an embossed decorative sheet and a method for manufacturing the same.

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, a sheet which does not use a vinyl chloride resin has been demanded due to problems such as chlorine generation during incineration. For example, see Patent Document 1).

JP, 2010-058350, A

However, in the technique described in Patent Document 1, unlike the embossed decorative sheet using a vinyl chloride resin, the embossed decorative sheet has flexibility, embossability, abrasion resistance, surface hardness, chemical resistance, and stain resistance. It was difficult to have various characteristics such as.
The present invention focuses on the above points, and an object thereof is to provide an embossed decorative sheet that can have various characteristics and a method for manufacturing the same.

In order to solve the above problems, the embossed decorative sheet of one embodiment of the present invention has a pattern layer, an adhesive layer, a transparent thermoplastic resin layer, and a surface protective layer laminated in this order on a thermoplastic resin substrate sheet. The transparent thermoplastic resin layer has a first layer containing a transparent maleic acid-modified polypropylene resin, and is disposed on the surface protective layer side of the first layer. And a second layer containing a transparent polypropylene resin to which at least one of an ultraviolet absorber and a light stabilizer is added, and the adhesive layer is a plurality of layers containing a two-component curable polyester anchor coating agent. It is characterized by consisting of.

According to one aspect of the present invention, it is possible to provide an embossed decorative sheet that can have various properties by selecting the number of transparent thermoplastic resin layers, the material of each layer, the thickness, and the like.

It is sectional drawing showing the structure of the embossing decorative sheet which concerns on embodiment. It is sectional drawing showing the structure of the embossing decorative sheet which concerns on a modification. It is explanatory drawing showing the manufacturing method of the embossing decorative sheet which concerns on embodiment. It is explanatory drawing showing the manufacturing method of the embossing decorative sheet which concerns on a modification.

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 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 components are as follows. It is not specific to one. The technical idea of the present invention can be variously modified 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 layer 3, an adhesive layer 4, a transparent thermoplastic resin layer 5 and a surface protective layer 6 on a thermoplastic resin base sheet 2. It is formed by laminating in this order. An emboss 7 is formed on at least the outermost layer, that is, the surface protective layer 6, in order to adjust the gloss of the surface and give a three-dimensional effect. The thickness of the embossed decorative sheet 1 is preferably 50 μm or more and 200 μm or less in consideration of weather resistance, suppression of whitening due to bending, and the like.

(Thermoplastic resin base sheet 2)
The thermoplastic resin base sheet 2 is a base sheet formed by including a thermoplastic resin. As the thermoplastic resin, various resins other than vinyl chloride resin can be used. For example, polyolefin resin, acrylic resin, polyester resin, ethylene vinyl acetate resin, polyimide resin and the like can be used. Polyolefin resins are particularly preferable in view of pollution-free property, low price, high performance, and easy coloring. More specifically, crystalline polyolefin and thermoplastic polyolefin-based elastomer are preferable.

In addition, according to the thermoplastic polyolefin-based elastomer, since the rubber such as hydrogenated butadiene is contained as the soft segment in the olefin-based resin called the hard segment, the flexibility which the conventional polyolefin-based resin does not have. Can be obtained. Further, it is possible to obtain a product which is excellent in pollution-free property, price, and easiness of coloring by adding a pigment.
As the thermoplastic elastomer, there are styrene resin, urethane resin, polyester resin, etc. in addition to olefin resin. Styrene resin is difficult to color due to its structure, and urethane resin is poor in weather resistance. The polyester-based resin is not suitable as the polyolefin-based resin for the thermoplastic resin substrate sheet 2 because of poor workability due to the hardness of the film.

Other than the above, for example, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, polystyrene, ABS, polymethyl methacrylate, polymethyl acrylate, polybutyl acrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl Acetal, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyurethane, polyamide, nylon 6, nylon 66, polylactic acid, paper and the like may be used, or these may be used in combination.

As a coloring method, a dry color method using a fine powdery colorant obtained by treating a pigment with a dispersion aid or a surfactant, a master batch pellet in which a resin and a high-concentration pigment are melt-mixed and preliminarily dispersed. A master batch method or the like in which an ordinary resin which is produced and is not colored in an extrusion hopper is dry-blended can be used, and the method is not particularly limited. The type of pigment is not particularly limited, but inorganic pigments such as titanium oxide, ultramarine blue, cadmium pigment and iron oxide are preferable in view of weather resistance and heat resistance. 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.

Further, the thermoplastic resin substrate sheet 2 may be provided with an antioxidant or a weather resistant prescription. Further, in consideration of improving the adhesiveness with wooden boards, inorganic boards, metal plates, etc., a primer layer may be provided on the back surface of the embossed decorative sheet 1. As the primer layer, for example, a polyester resin, a polyurethane resin, a mixture thereof, or the like can be used. Further, the thickness of the thermoplastic resin substrate sheet 2 is preferably 10 μm or more and 100 μm or less in consideration of being generally used.

(Pattern layer 3)
The picture pattern layer 3 is a layer which is formed by printing on the thermoplastic resin base sheet 2 and which is provided with a picture for imparting a design property. As the picture pattern, for example, a wood grain 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 the desired characteristics. The number of layers can be four or more, but the structure of the extruder becomes complicated and the complexity of the work becomes large.

In the example of FIG. 1, the transparent thermoplastic resin layer 5 includes a first layer 51 including a predetermined resin (hereinafter also referred to as “first resin”) from the side of the thermoplastic resin base sheet 2 and adhesive. An adhesive layer 52 containing an agent and a second layer 53 containing a resin different from the first resin (hereinafter also referred to as “second resin”) are laminated in this order. Depending on the combination of the first resin and the second resin, the adhesive layer 52 may be omitted as shown in FIG.

As the first resin and the second resin, for example, in consideration of high adhesive strength due to the action of an acid group based on maleic acid, a transparent maleic acid-modified polypropylene resin is used as the first resin, A transparent polypropylene resin is preferably used as the second resin. At least one of an ultraviolet absorber and a light stabilizer is added to the transparent polypropylene resin. As the transparent maleic acid-modified polypropylene resin, for example, a transparent resin obtained by reacting polypropylene with maleic anhydride and introducing a maleic acid residue into a linear polyolefin is used.

Further, for example, considering the scratch resistance, weather resistance, stain resistance, light resistance, transparency, bendability, thermoformability, etc. of the surface of the embossed decorative sheet 1, the first resin may be a thermoplastic acrylic resin. Use a mixture of polyvinylidene fluoride resin added to or a thermoplastic acrylic resin, and use a mixture of polyvinylidene fluoride resin added to a thermoplastic acrylic resin or polyvinylidene fluoride resin as the second resin. Is preferred. In this case, if a mixture of polyvinylidene fluoride resin, a root and a plastic acrylic resin is used as the adhesive layer 52, the adhesive force between the first layer 51 and the second layer 53 can be secured.

Further, for example, considering the unique texture, suppleness (flexibility), material cost, etc. on the surface side of the embossed decorative sheet 1, a polyolefin-based elastomer resin is used as the first resin, and the second resin is used. For this, it is preferable to use a polyurethane elastomer resin.
In addition, for example, considering the scratch resistance, stain resistance, weather resistance, flexibility, transparency (depth) of the surface of the embossed decorative sheet 1 and cost reduction due to the omission of the adhesive layer 52, the first resin is selected. Is preferably a soft acrylic resin, and the second resin is preferably a hard acrylic resin.

Further, for example, in consideration of scratch resistance, chemical resistance, stain resistance of the surface of the embossed decorative sheet 1, cost reduction by omitting the adhesive layer 4, etc., a polypropylene resin is used as the first resin, and It is preferable to use polyethylene terephthalate resin as the resin. In this case, as the adhesive layer 52, a special adhesive that bonds both the first and second resins is used.
Further, for example, considering cost reduction by omitting the adhesive layer 52 and the adhesive layer 4, a polypropylene resin is used for the first resin, and an olefin-based elastomer resin is used for the second resin. It is preferable.

(Polypropylene resin)
The polypropylene resin of the present embodiment is, for example, a mixture of a polypropylene resin (a) having free-end long chain branching and a polypropylene resin (b) having no free-end long chain branching, and the mass of the mixture. The molecular weight distribution Mw/Mn defined as the average molecular weight/number average molecular weight is in the range of 1 or more and 5 or less, and is defined as the boiling heptane-soluble residue ratio of the mixed resin (a) and (b). The isotactic index 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×Mi2)/Σ(Ni×Mi) when Ni molecules of molecular weight Mi are present. ), the value defined as Mw/Mn. The closer it 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).

Further, 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 and 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 in an oil bath or 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. and 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 (syndiotactic polypropylene, atactic polypropylene, etc.) 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 (for example, 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.

In addition, 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.

Further, the melt flow rate of the mixture of the polypropylene resins (a) and (b) at 230° C. defined by JIS-K6760 is within the range of 5 g/10 min or more and 50 g/10 min or less so that the molecular weight is It is possible to maintain a stable film-forming state with a certain value or more. A more preferable range of the melt flow rate 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. When the melt flow rate exceeds 50 g/10 min, the resin melt-extruded from the T-die has a large effect (neck-in) of gathering in the center during melt-extrusion with the T-die, and the resin is melt-extruded from the T-die. The edge thickness of the resin increases. The increase in the thickness of the end portions affects the cooling efficiency and the thickness stability in the width direction, which makes it difficult to form a stable film. If it is lower than 5 g/10 min, the draw resonance of the molten resin becomes poor, and the molten resin is formed in the gap between the velocity of the molten resin immediately after exiting the T-die (initial velocity) and the velocity of the resin immediately after touching the cooling roll. However, it becomes difficult to achieve stable film formation.

In order to formulate the transparent thermoplastic resin layer 5 in a weather resistant manner, an ultraviolet absorber (benzotriazole type, triazine type, benzophenone type, etc.), a hindered amine type light stabilizer, etc. may be added. 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. 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)benzotriazole and the like, and mixtures, modified products, polymers and derivatives thereof can be used. ..

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) Phenyl)-6-(2-hydroxy-4-iso-octyloxyphenyl)-s-triazine and the like, and mixtures, modified products, polymers and derivatives thereof can be used.

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 addition of an isocyanate.
Further, in order to prevent deterioration of the resin itself due to light, heat, water, etc., a hindered amine light stabilizer may be appropriately added. Although the number of parts to be added may be added according to the desired weather resistance, it 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. Specifically, 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, bis(2,2,2)decanedioate 6,6-Tetramethyl-1(octyloxy)-4-piperidinyl) ester and the like and mixtures, modified products, polymers and derivatives thereof can be used.

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, phenols such as 2,2'-methylenebis(4-ethyl-6-t-butylphenol) and 2,2'-methylenebis(4-methyl-6-t-butylphenol) -Based antioxidants, phosphorus-based antioxidants represented by tris(2,4-di-t-butylphenyl)phosphite, and mixtures thereof, that is, one kind or a combination of two or more kinds is used. be able to.

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 phosphoric acid ester type flame retardant. Further, as the antiblocking agent, an inorganic antiblocking agent such as aluminum silicate, silicon oxide, hydrotalcite, calcium carbonate, or the like, an organic antiblocking agent such as fatty acid amide, or 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.

(Surface protection layer 6)
The surface protective layer 6 is a layer formed on the transparent thermoplastic resin layer 5 and covering the transparent thermoplastic resin layer 5. As the material of the surface protective layer 6, for example, a thermosetting resin, an ionizing radiation curable resin, or a material containing a mixture of these resins can be used. As the thermosetting resin, for example, a thermosetting resin having a urethane bond such as a two-component curing urethane resin can be used. As the ionizing radiation curable resin, for example, an ultraviolet curable resin can be used. As the ultraviolet curable resin, for example, (meth)acrylic resin, silicone resin, polyester resin, urethane resin, amide resin, epoxy resin can be used. Thereby, the hardness of the surface protective layer 6, that is, the outermost surface layer of the embossed decorative sheet 1 can be improved, and surface physical properties such as abrasion resistance, scratch resistance, and solvent resistance can be improved.

In addition, in order to impart various functions to the surface protective layer 6, functional additives such as antibacterial agents and fungicides may be added. Moreover, you may add a ultraviolet absorber and a light stabilizer as needed. As the ultraviolet absorber, a benzotriazole type, a benzoate type, a benzophenone type, or a triazine type can be used. Further, as the light stabilizer, a hindered amine type can be used. Furthermore, a release agent having a silicone skeleton can be added when antifouling performance and Cellotape (registered trademark) releasability are required. In this case, the type of the release agent is not particularly limited, but by using a silicone release agent having a terminal functional group reactive with the resin composition, antifouling performance and cellotape (registered trademark) release properties can be obtained. The durability of can be improved.

(Method for manufacturing embossed decorative sheet 1)
Next, a method for manufacturing the embossed decorative sheet 1 of this embodiment will be described.
First, the pattern layer 3 is formed on the thermoplastic resin base sheet 2 by printing. Then, an adhesive is applied on the pattern layer 3 to form the adhesive layer 4. Then, as shown in FIG. 3, a transparent thermoplastic resin layer 5 is formed on the adhesive layer 4 by extruding a plurality of layers containing a molten transparent thermoplastic resin from the multilayer extruder 11 and stacking the layers. Form. At the same time, the embossing roll 8 and the pressure roll 9 nip the laminate of the thermoplastic resin substrate sheet 2, the pattern layer 3, the adhesive layer 4 and the transparent thermoplastic resin layer 5 to perform embossing and lamination. Do at the same time. The sheet integrated by embossing and laminating moves along the outer periphery of the embossing roll 8 and is peeled off by the peeling roll 10 to form irregularities by the embossing on the transparent thermoplastic resin layer 5. After that, by coating a thermosetting resin, an ultraviolet curable resin or a mixture of these resins on the transparent thermoplastic resin layer 5 to form the surface protective layer 6, the surface protective layer 6, that is, the outermost layer is formed. The embossed decorative sheet 1 on which the embossments 7 are formed is obtained.

Each of the embossing roll 8, the pressure roll 9, and the peeling roll 10 has a cooling mechanism inside, and lowers the temperature of the molten transparent thermoplastic resin to solidify it. In this embodiment, the embossing roll 8 is a metal roll, and the pressure roll 9 and the peeling roll 10 are rubber rolls. Therefore, most of the cooling effect is carried by the embossing roll 8, and the production speed is determined by the diameter of the embossing roll 8. Here, the larger the diameter of the embossing roll 8, the higher the production speed, but the manufacturing cost of the embossing roll 8 also increases. Therefore, in order to minimize the manufacturing cost, the diameter of the embossing roll 8, the production efficiency, and the extruder Competence must be considered comprehensively.

In the example of FIG. 3, a laminated body including the thermoplastic resin base sheet 2, the pattern layer 3, and the adhesive layer 4, the transparent thermoplastic resin layer 5, the embossing roll 8 and the pressure roll 9 are provided. However, the stack may be inserted between the embossing roll 8 and the peeling roll 10 as shown in FIG. Thereby, it is necessary to secure the adhesiveness with an adhesive or the like, but it is effective when the thickness of the thermoplastic resin substrate sheet 2 is thin and the heat resistance is poor.

(Effect of this embodiment)
The invention according to this embodiment has the following effects.
(1) As described above, in the embossed decorative sheet 1 according to the present embodiment, since the transparent thermoplastic resin layer 5 is composed of a plurality of layers, the number of layers of the transparent thermoplastic resin layer 5, the material of each layer, and the thickness of each layer. It is possible to provide the embossed decorative sheet 1 that can have various properties by selecting the above. As a result, it is possible to obtain properties such as designability mainly obtained from flexibility, stain resistance, chemical resistance, weather resistance, scratch resistance and transparency, which are obtained by using a vinyl chloride resin. ..

(2) In addition, the transparent thermoplastic resin layer 5 includes, from the thermoplastic resin base sheet 2 side, a first layer 51 containing the first resin and a second resin different from the first resin. The second layer 53 containing the layers was laminated in this order. Therefore, the second layer 53 can realize the performance on the surface side of the embossed decorative sheet 1, and the first layer 51 can realize the other physical properties of the embossed decorative sheet 1, and the embossed decorative sheet 1 has various characteristics. Can have
(3) Further, the first resin may be a transparent maleic acid-modified polypropylene resin, and the second resin may be a transparent polypropylene resin to which at least one of an ultraviolet absorber and a light stabilizer is added. Thereby, the adhesive strength can be improved by the action of the acid group by maleic acid.

(4) The first resin is a mixture of a thermoplastic acrylic resin and a polyvinylidene fluoride resin, or a thermoplastic acrylic resin, and the second resin is a polyvinylidene fluoride resin and a thermoplastic acrylic resin. It may be a mixture added or a polyvinylidene fluoride resin. As a result, the polyvinylidene fluoride resin on the surface side can provide the surface with scratch resistance, weather resistance, stain resistance, and the like, and the intermediate acrylic resin can have the light resistance, transparency, and the like. In addition, the bendability and thermoformability of the embossed decorative sheet 1 can be improved.
In particular, the first resin is a mixture obtained by adding a polyvinylidene fluoride resin to a thermoplastic acrylic resin, and the second resin is a mixture obtained by adding a thermoplastic acrylic resin to a polyvinylidene fluoride resin. , The adhesive strength of the second resin can be secured, and the adhesive layer 52 can be omitted.

(5) Further, the first resin may be a polyolefin-based elastomer resin and the second resin may be a polyurethane-based elastomer resin. This makes it possible to give the surface side a unique texture and pliability, and since the polyolefin-based elastomer resin is used on the intermediate side, the characteristics of the surface side can be utilized and the material cost can be reduced.
(6) Further, the first resin may be a soft acrylic resin and the second resin may be a hard acrylic resin. As a result, it is possible to make the surface layer excellent in scratch resistance, stain resistance, weather resistance, and flexibility, and at the same time, make the surface layer very transparent. Further, as shown in FIG. 2, since the adhesive layer 52 can be omitted, the material cost can be reduced.

(7) Further, the first resin may be a polypropylene resin and the second resin may be a polyethylene terephthalate resin. As a result, the adhesive layer 4 can be omitted while the surface has excellent scratch resistance, chemical resistance, and stain resistance, and thus material costs can be reduced.
(8) Further, the first resin may be a polypropylene resin and the second resin may be an olefin elastomer resin. As a result, the adhesive layer 52 and the adhesive layer 4 can be dispensed with, and the material cost can be reduced. Although the transparency and weather resistance of the surface layer are slightly inferior, they can be sufficiently used for indoor interior materials.

(9) Further, the surface protective layer 6 may include a thermosetting resin, an ionizing radiation curable resin, or a composite of these resins, to which at least one of an ultraviolet absorber and a light stabilizer is added. Thereby, the hardness of the surface protective layer 6, that is, the outermost surface layer of the embossed decorative sheet 1 can be improved, and surface physical properties such as abrasion resistance, scratch resistance, and solvent resistance can be improved.
(10) In the method for producing the embossed decorative sheet 1 according to the present embodiment, after the pattern layer 3 is formed by printing on the thermoplastic resin substrate sheet 2, the transparent transparent heat melted on the pattern layer 3 is formed. A transparent thermoplastic resin layer 5 is formed by extruding a plurality of layers containing a plastic resin from a multi-layer extruder 11 and laminating the transparent thermoplastic resin layer 5. At the same time, the transparent thermoplastic resin layer 5 is embossed, and then the transparent thermoplastic resin 5 is formed. The surface protective layer 6 was formed on the layer 5. As a result, the embossing 7 having excellent reproducibility is formed while obtaining characteristics such as flexibility, stain resistance, chemical resistance, weather resistance, scratch resistance, and transparency, which are the same as those of vinyl chloride resin. can do.

In addition, since the transparent thermoplastic resin is extruded and immediately embossed, the reproducibility of the embossed shape can be improved. Further, since the extruded resin is inevitably cooled rapidly, it is possible to maintain the transparency of the resin such as polyvinylidene fluoride which tends to become cloudy due to crystallization.
Further, since the molten transparent thermoplastic resin is extruded to form a sheet, for example, there is less energy loss as compared with the case where a plurality of sheet-shaped resins once formed into a film are reheated to be bonded and embossed. The cost can be improved.

Next, examples and comparative examples of the present invention will be described.
(Example 1)
In Example 1, a polypropylene film (“FZ” manufactured by RIKEN TECHNOS CORPORATION) was used as the thermoplastic resin substrate sheet 2. The thickness of the thermoplastic resin base sheet 2 was 55 μm. Then, a grain pattern was printed on the thermoplastic resin substrate sheet 2 by a gravure printing machine to form a pattern layer 3. As the printing ink, gravure ink (“Lamistar” manufactured by Toyo Ink Co., Ltd.) was used. Subsequently, a silica powder-containing primer layer (manufactured by Toyo Ink Co., Ltd.) was applied to the surface (back surface) of the thermoplastic resin substrate sheet 2 opposite to the pattern layer 3. The coating thickness of the silica powder-containing primer layer was 1 μm. Subsequently, a two-component curable polyester anchor coating agent (manufactured by Mitsui Chemicals, Inc.) was applied onto the pattern layer 3 to form an adhesive layer 4. The coating thickness of the adhesive layer 4 was 1 μm.

Subsequently, on the adhesive layer 4, a first layer 51 containing a transparent maleic acid-modified polypropylene (“AT2102” manufactured by Mitsui Chemicals, Inc.) as a molten transparent thermoplastic resin, and a transparent polypropylene (prime A transparent thermoplastic resin layer 5 was formed by extruding a second layer 53 containing polymer “E2000” manufactured by Co., Ltd.) from the multilayer extruder 11 and laminating the second layer 53. The film thickness ratio between the first layer 51 and the second layer 53 was set to 1:9. The thickness of the transparent thermoplastic resin layer 5 is 70 to 80 μm. At the same time, the embossing roll 8 and the pressure roll 9 nip the laminate of the thermoplastic resin substrate sheet 2, the pattern layer 3, the adhesive layer 4 and the transparent thermoplastic resin layer 5 to perform embossing and lamination. I went at the same time. The sheet integrated with the embossing process and the laminating process moved along the outer circumference of the embossing roll 8 and was peeled off by the peeling roll 10 to form irregularities by the embossing process on the transparent thermoplastic resin layer 5.

Then, on the transparent thermoplastic resin layer 5, a thermosetting resin (urethane acrylate resin manufactured by DIC Graphics Co., Ltd.) was applied as a surface protective layer 6 mainly made of a curable resin. The coating amount of the ultraviolet curable resin was 6 to 7 g/m ² after drying. Subsequently, the embossed decorative sheet 1 of Example 1 was obtained in which the surface protective layer 6 was formed by curing by ultraviolet irradiation, and the embossed layer 7 was formed on the surface protective layer 6, that is, the outermost layer.
The embossed decorative sheet 1 thus obtained had a high adhesive strength between the transparent thermoplastic resin layer 5 and the adhesive layer 4 (the pattern layer 3) due to the action of the acid group by maleic acid.

(Example 2)
In Example 2, a polyolefin-based inorganic filling sheet (“OW” manufactured by RIKEN TECHNOS CORPORATION) was used as the thermoplastic resin substrate sheet 2. A urethane resin adhesive was used as the adhesive layer 4. Further, in the transparent thermoplastic resin layer 5, a thermoplastic acrylic resin (“Acrypet IRS404” manufactured by Mitsubishi Rayon Co., Ltd.) was used as the first layer 51 (first resin), and the adhesive layer 52 (adhesive) was used. As the agent, a mixture of 50 mass% of polyvinylidene fluoride resin (“Neotron PVDF” manufactured by Daikin Co., Ltd.) and 50 mass% of thermoplastic acrylic resin (“Acrypet IRS404” manufactured by Mitsubishi Rayon Co., Ltd.) is used. For the second layer 53 (second resin), polyvinylidene fluoride resin (“Neotron PVDF” manufactured by Daikin Co., Ltd.) was used. The thickness of the second layer 53 was 10 μm, the thickness of the adhesive layer 52 was 10 μm, and the thickness of the first layer 51 was 40 μm. The other configurations were the same as those in Example 1. The embossed decorative sheet 1 thus obtained has appropriate flexibility, is excellent in scratch resistance and weather resistance of the surface, is excellent in stain resistance, and has extremely good reproducibility of the emboss 7. And had high commercial value. Further, there was no particular problem in terms of adhesive strength between the layers.

(Example 3)
In Example 3, in the transparent thermoplastic resin layer 5, the first layer 51 (first resin) contained 80% by mass of a thermoplastic acrylic resin (“Acrypet IRS404” manufactured by Mitsubishi Rayon Co., Ltd.) and polyfluoride. A mixture of 20% by weight of vinylidene fluoride resin (“Neotron PVDF” manufactured by Daikin Co., Ltd.) is used, and the second layer 53 (second resin) is a polyvinylidene fluoride resin (“Neoflon manufactured by Daikin Co., Ltd.” PVDF") 80% by mass and a thermoplastic acrylic resin ("Acrypet IRS404" manufactured by Mitsubishi Rayon Co., Ltd.) 20% by mass were used. As shown in FIG. 2, the adhesive layer 52 is omitted. The thickness of the second layer 53 was 10 μm, and the thickness of the first layer 51 was 40 μm. The other configurations were the same as those of the second embodiment. The embossed decorative sheet 1 thus obtained had a slightly lower surface resistance than the embossed decorative sheet 1 of Example 2, but was inferior to the decorative sheet using a vinyl chloride resin. Was not seen.

(Example 4)
In Example 3, in the transparent thermoplastic resin layer 5, a polyolefin-based elastomer resin (“MILASTOMER” manufactured by Mitsui Petrochemical Industry Co., Ltd.) was used as the first layer 51 (first resin), and the adhesive layer A graft polymerization type special adhesive resin was used for 52 (adhesive), and a polyurethane elastomer resin (“Miractron” manufactured by Nippon Miractron Co., Ltd.) was used for the second layer 53 (second resin). .. The other configurations were the same as those of the second embodiment. The embossed decorative sheet 1 thus obtained had a unique texture and flexibility (flexibility) on the surface side. Moreover, it was cheaper in cost than the embossed decorative sheets 1 of Examples 1 to 3.

(Example 5)
In Example 5, in the transparent thermoplastic resin layer 5, a soft acrylic resin (“Acrypet SV” manufactured by Mitsubishi Rayon Co., Ltd.) was used as the first layer 51 (first resin), and the second layer was used. As 53 (second resin), a hard acrylic resin (“Acrypet IRG304” manufactured by Mitsubishi Rayon Co., Ltd.) was used. As shown in FIG. 2, the adhesive layer 52 is omitted. The thickness of the second layer 53 was 10 μm, and the thickness of the first layer 51 was 40 μm. The other configurations were the same as those of the second embodiment. The embossed decorative sheet 1 thus obtained had a good transparency of the surface layer and was excellent in design which gives a feeling of depth. In addition, the surface has good balance between scratch resistance and flexibility, and the cost was lower than that of the embossed decorative sheets 1 of Examples 1 to 4. However, the solvent resistance was slightly inferior to the embossed decorative sheets 1 of Examples 1 to 4.

(Example 6)
In Example 6, in the transparent thermoplastic resin layer 5, polypropylene resin (“E2000” manufactured by Prime Polymer Co., Ltd., “Daicel PP” manufactured by Daicel Polymer Co., Ltd.) was used as the first layer 51 (first resin). Etc.), a graft polymerization type special adhesive resin is used for the adhesive layer 52 (adhesive), and a polyethylene terephthalate resin (manufactured by Toyobo Co., Ltd.) is used for the second layer 53 (second resin). E5100", "T60" manufactured by Toray Industries, Inc., etc.) were used. The other configurations were the same as those of the second embodiment. The embossed decorative sheet 1 thus obtained has excellent surface scratch resistance, chemical resistance, and stain resistance, while omitting the adhesive layer 4, and can reduce material costs at low cost.

(Example 7)
In Example 7, in the transparent thermoplastic resin layer 5, the first layer 51 (first resin) was a polypropylene resin (“E2000” manufactured by Prime Polymer Co., Ltd., “Daicel PP” manufactured by Daicel Polymer Co., Ltd.). And the like), and an olefin elastomer resin (“MILASTOMER” manufactured by Mitsui Petrochemical Co., Ltd.) was used for the second layer 53 (second resin). The thickness of the second layer 53 was 10 μm, and the thickness of the first layer 51 was 40 μm. The other configurations were the same as those of the second embodiment. The embossed decorative sheet 1 thus obtained was sufficiently inferior in transparency and weather resistance of the surface layer, but could be sufficiently used as an indoor interior material. Further, since neither the adhesive layer 52 nor the adhesive (adhesive layer 4) applied to the base material is required, it was possible to produce at the lowest cost.

DESCRIPTION OF SYMBOLS 1... Embossing decorative sheet, 2... Thermoplastic resin base sheet, 3... Picture pattern layer, 4... Adhesive layer, 5... Transparent thermoplastic resin layer, 6... Surface protective layer, 7... Embossing, 8... Embossing roll, 9... Pressure roll, 10... Peeling roll, 11... Multilayer extruder, 51... First layer, 52... Adhesive layer, 53... Second 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 the outermost layer is embossed,
The transparent thermoplastic resin layer is disposed on the first layer containing a transparent maleic acid-modified polypropylene resin and the surface protective layer side of the first layer, and at least one of an ultraviolet absorber and a light stabilizer is added. A second layer containing transparent polypropylene resin,
The embossed decorative sheet , wherein the adhesive layer contains a two-component curing type polyester anchor coating agent . The embossed decorative sheet according to claim 1, wherein the thickness of the first layer is 7 μm to 8 μm. The surface protective layer comprises a thermosetting resin, an ionizing radiation curable resin, or a mixture of these resins, to which at least one of an ultraviolet absorber and a light stabilizer is added. The embossed decorative sheet according to 1 or 2 . It is a manufacturing method of the embossing decorative sheet according to any one of claims 1 to 3 ,
On the thermoplastic resin substrate sheet, after forming a picture pattern layer by printing, on the picture pattern layer, by laminating a plurality of layers containing a molten transparent thermoplastic resin by extrusion from a multilayer extruder, A method for producing an embossed decorative sheet, comprising forming a transparent thermoplastic resin layer and simultaneously embossing the transparent thermoplastic resin layer, and then forming a surface protective layer on the transparent thermoplastic resin layer.

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