JPH0948072A - Laminated sheet and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated sheet which is almost entirely free from the generation of an unevenly streamy pattern on the surface, even if the sheet is stretched when molded. SOLUTION: This laminated sheet is composed of a skin layer 8 having a surface layer composed mainly of a thermoplastic resin elastomer and a base layer composed mainly of a thermoplastic resin, and a foam layer 5 composed mainly of the thermoplastic resin. In addition, the laminated sheet has an uneven pattern X formed, being extended from the surface layer side to the foam layer 5.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated sheet having a textured pattern or an embossed pattern as a concavo-convex pattern on its surface, and more particularly to a laminated sheet suitable for coating the surface of a plastic molding. INDUSTRIAL APPLICABILITY The laminated sheet of the present invention is, for example, a molded article used for interior materials for automobiles, housings such as OA equipment and home appliances, stationery, sanitary products, daily necessities or interior materials for building materials. Used for coating.

[0002]

2. Description of the Related Art Conventionally, as the above-mentioned covering sheet, for example, a sheet comprising a polyvinyl chloride layer having an embossed surface, and a foam layer laminated on the back surface thereof as required has been used. There is.

However, the above-mentioned coating sheet using polyvinyl chloride is not sufficiently flexible and requires many steps in manufacturing. Therefore, for example, as described in JP-B-1-14023, a coating laminate in which a foam layer made of polyethylene or polypropylene is laminated on the back side of a polyolefin-based thermoplastic elastomer layer having an embossed surface. Sheets are proposed.

[0004]

However, in the covering laminated sheet described in JP-B-1-14023, the rubber elasticity of the laminated sheet itself is low, and therefore the surface of the molded article is stretched by, for example, stamping molding. When applied to, there was a problem that the unevenness of the grain pattern on the surface was extended by stretching and the grain pattern flowed.

An object of the present invention is to overcome the above-mentioned disadvantages,
Another object of the present invention is to provide a laminated sheet in which an uneven pattern on the surface hardly flows even when it is stretched when applied to a molded product.

[0006]

The present invention has been made to achieve the above object, and the invention according to claim 1 is a surface layer containing a thermoplastic resin elastomer as a main component, A base material layer containing a thermoplastic resin as a main component and a foam layer containing a thermoplastic resin as a main component, which is a laminated sheet laminated in this order, and an uneven pattern is provided from the surface layer side, The uneven pattern is formed so as to reach the foam layer.

Further, the invention according to claim 2 is a covering laminated sheet for forming a covering on the surface of a molded article, wherein the aforementioned laminated sheet. In the invention according to claim 3, the thermoplastic resin elastomer is a thermoplastic urethane elastomer, and the thermoplastic resin forming the base material is formed of a thermoplastic elastomer.

Further, the invention according to claim 4 is the method for producing a laminated sheet according to the present invention, wherein a surface layer containing a thermoplastic resin elastomer as a main component and a base material layer containing a thermoplastic resin as a main component. And a step of forming a skin layer by co-extrusion, a first roller, and a second outer surface having irregularities.
Between the roll and the outer skin layer, a foam layer containing a thermoplastic resin as a main component is supplied, the foam layer is laminated on the outer skin layer, and the surface layer side of the second roll is used. A step of bringing the outer peripheral surface into contact with at least one-fourth or more of the peripheral direction so as to apply a concavo-convex pattern to the foam layer from the surface layer side.

The laminated sheet of the present invention and the method for producing the same will be described below in detail. Thermoplastic Resin Elastomer for Surface Layer In the present invention, the thermoplastic resin elastomer used to form the surface layer has rubber elasticity at room temperature and is plasticized at a high temperature to be molded into various shapes. It shall include a wide range of molecular materials. As such a thermoplastic resin elastomer, polystyrene type, polyurethane type, polyolefin type, polyester type, polyvinyl chloride type, polyamide type, ionomer type, natural rubber type, fluorine type, 1,2-polybutadiene type, trans-1 , 4
-A polyisoprene type etc. are mentioned.

In general, the thermoplastic resin elastomer often shares a rubber component (soft segment) having entropy elasticity in the molecule and a molecular restraint component (hard segment) for preventing plastic deformation. In the moldable range, it may partially have a crosslinked structure, but does not have a wide range of three-dimensional network structure.

The hardness of the above-mentioned thermoplastic resin elastomer varies depending on the contact feeling to be obtained and the hardness of the elastic fine particles and the lubricant to be used, but it is generally JSI K-63.
The A hardness of 01 is preferably in the range of 50 to 98, more preferably in the range of 75 to 98. If the hardness of the thermoplastic resin elastomer is low, the wear resistance is generally lowered, and if the hardness is high, the contact feeling is deteriorated.

As the above thermoplastic resin elastomer,
More specifically, for example, in the case of a polyurethane-based thermoplastic resin elastomer, a block copolymer having polyurethane as the hard segment and polyether, polyester, polycarbonate or the like as the soft segment can be mentioned.

As the polystyrene-based thermoplastic resin elastomer, polystyrene is used as the hard segment, polybutadiene, polyisoprene or polyethylene-polybutylene is used as the soft segment, or a block copolymer having hydrogen is added to the block copolymer. Examples thereof include functional groups.

The polyolefin-based thermoplastic resin elastomer has polypropylene as the hard segment and ethylene, ethylene and a small amount of diene component as the soft segment, those obtained by blending a plurality of these, and Further, those partially cross-linked by adding an organic peroxide, those graft-modified with a derivative of an unsaturated hydroxy monomer or an unsaturated carboxylic acid, or those having butyl rubber grafted polyethylene, etc. may be mentioned. it can. Examples of those having a small amount of diene component together with ethylene include those having an ethylene-propylene-methylene bond (EPM) and an ethylene-propylene-diene-methylene bond (EPDM).

Examples of the polyester-based thermoplastic resin elastomer include polyester as a hard segment,
Examples of the soft segment include a copolymer having a polyether.

As the above polyvinyl chloride-based thermoplastic resin elastomer, a method of extremely increasing the polymerization degree of polyvinyl chloride, a method of introducing a three-dimensional crosslinked structure into a part of polyvinyl chloride, or an ionic crosslinked structure is introduced. Examples thereof include those obtained by the method.

Examples of the thermoplastic polyamide-based elastomer include those using polyamide as the hard segment and polyether as the soft segment.

The type of the thermoplastic resin elastomer is
It is selected according to the desired balance of various performances. For example, when scratch resistance and abrasion resistance are strongly required in a coating sheet having an excellent soft touch feeling,
A thermoplastic urethane elastomer is preferably used.
Further, when durability such as weather resistance and heat resistance is strongly required, it is preferable to use a non-yellowing type thermoplastic urethane elastomer using an aliphatic isocyanate.

In the invention described in claim 2, the thermoplastic urethane elastomer is used as the thermoplastic resin elastomer. This thermoplastic urethane elastomer generally has polyether, polyester, polycarbonate as a soft segment having entropy elasticity in the molecule, and has a segment composed of a urethane bond as a hard segment for preventing plastic modification. . The thermoplastic urethane elastomer is
Provides excellent scratch resistance to the surface layer. In order to sufficiently express this scratch resistance, it is preferable that the glass transition point (Tg) of the urethane elastomer falls within the range of -50 to 20 ° C, and the molecular weight is preferably high from the viewpoint of rigidity, Weight average molecular weight of 20,000 to 3,000,
000 is preferable. Also, the hardness of the thermoplastic urethane elastomer is preferably in the range of 50 to 98 in JIS A hardness as described above.

As the thermoplastic urethane elastomer, for example, Asahi Glass Co., Ltd., trade name: PN03, PN3
429, L425, and Dainippon Ink and Chemicals, Inc., trade name: T7890.

In the present invention, elastic fine particles may be contained in the surface layer in order to enhance the matte feeling (suede feeling) of the surface of the surface layer. The elastic fine particles broadly include fine particles having a property of elastically recovering when pressure is released after pressurizing until the shape is deformed. Examples of such elastic fine particles include those made of polyurethane, acrylic resin, acrylic-urethane resin, polystyrene, styrene-isoprene copolymer, and the like.
A material that does not melt during the melt-kneading and molding of the thermoplastic resin elastomer is used.

The shape of the elastic fine particles is not limited to a spherical shape, and a non-spherical shape obtained by means such as freeze pulverization may be used, and a hollow shape may be used. When the average particle size of the elastic fine particles is small, it may be difficult to obtain a surface layer having a sufficient soft touch feeling. On the other hand, when the average particle size of the elastic fine particles is large, the surface layer is extruded into a sheet shape and cracks are likely to occur on the surface when the elastic layer is spread. Therefore, the average particle size of the elastic fine particles is 1
The thickness is preferably in the range of ˜50 μm, and more preferably in the range of 5 to 40 μm.

When the content of the elastic fine particles is low, it becomes difficult to impart a good matte feeling to the surface of the surface layer. On the contrary, when the content is high, the surface layer is extruded and spread on the surface. The cracks are likely to occur. Therefore, the elastic fine particles are preferably contained in the range of 20 to 200 parts by weight, more preferably 50 to 150 parts by weight, based on 100 parts by weight of the thermoplastic resin elastomer.

As the elastic fine particles, only one kind of elastic fine particles may be used, or two or more kinds of elastic fine particles may be used in combination. Further, when a thermoplastic urethane elastomer having excellent flexibility is used as the thermoplastic resin elastomer, or when a surface layer having a slightly hard feel is desired, the elastic fine particles may include, for example, crosslinked poly (methyl methacrylate) or Hard particles made of an inorganic material may be mixed and used.

Base Material Layer In the present invention, the base material layer contains a thermoplastic resin as a main component. Examples of such a thermoplastic resin include a thermoplastic resin elastomer, polystyrene resin, acrylic resin, polycarbonate, polyvinyl chloride resin, polyethylene resin, polypropylene resin, acrylonitrile-butadiene-styrene copolymer, and modified resin. Examples thereof include polyphenylene oxide, polyphenylene sulfide, polyetherimide, polyetheretherketone, and ionomer resin (ethylene-methacrylic acid copolymer metal salt). However, it is preferable to use a thermoplastic resin elastomer because it can impart a soft touch feeling.

As the thermoplastic resin elastomer forming the base layer, the thermoplastic resin elastomer used for forming the surface layer can be used. However, as the thermoplastic resin elastomer constituting the base material layer, a thermoplastic polyolefin-based elastomer (EPR) which is excellent in moldability and cost is preferable. The thermoplastic polyolefin-based elastomer has polypropylene as a hard segment and polyethylene as a soft segment (EPM), has a copolymer of ethylene and a small amount of diene (EPDM), or is obtained by blending these. Those obtained, or those partially cross-linked with an organic peroxide can be used.

Specific examples of the above-mentioned thermoplastic olefin-based elastomer include Mitsui Petrochemical Co., Ltd., trade names: Mirastoma 5030N, 6030N and 7030.
N, 8030N, 9020N, and Sumitomo Chemical Co., Ltd. product names: WT340, WT341, 4552, 3655 and the like.

The hardness of the thermoplastic polyolefin-based elastomer is generally 50 to JIS A hardness in consideration of the performance of imparting sufficient flexibility to the covering sheet to enhance the contact feeling and the moldability of the covering sheet. It is preferably in the range of 98.

Further, in order to improve the extrusion moldability of the thermoplastic polyolefin elastomer, a polyolefin resin such as polypropylene or linear low-density polyethylene may be blended.

Further, in the presence of a special polypropylene resin, that is, a titanium compound and an aluminum compound, first, a titanium-containing polypropylene resin obtained by prepolymerizing a propylene resin, and the presence of the above titanium compound and aluminum compound. In the following, it is also preferable to use a polypropylene resin composed of a propylene-ethylene copolymer or a propylene-α-olefin copolymer obtained by copolymerizing propylene and ethylene or propylene and an α-olefin.

The above-mentioned special polypropylene resin has a weight average molecular weight of 80,000 to 600,000, and an elution amount of less than 10 ° C. by the cross fractionation method is 20 to 80% by weight of the total polypropylene resin, and The elution amount at 10 to 65 ° C is 10 to 50% by weight of the total polypropylene resin, 65
The elution amount at ~ 90 ° C is 1 to 1 of the total polypropylene resin amount.
It is preferable to use 5% by weight and an elution amount at 90 to 125 ° C. of 10 to 35% by weight based on the total amount of polypropylene resin.

Foam Layer In the present invention, the foam layer contains a thermoplastic resin as a main component as described above. Examples of the resin constituting the foam layer include polyolefin resins such as polypropylene and polyethylene, polystyrene, polystyrene resins such as styrene-maleic anhydride copolymer, polyurethane resins, polyvinyl chloride resins, and various heat-resistant resins. A wide variety of thermoplastic resin materials capable of foaming a plastic elastomer or the like can be used. The foaming ratio of the foam is preferably about 5 to 50 times, particularly preferably about 10 to 40 times, in order to exhibit good cushioning properties and soft touch feeling.

Adhesive Layer In the coating sheet of the present invention, an adhesive layer for adhering the surface layer and the base material layer may be provided between the surface layer and the base material layer, if necessary.

As the resin forming the adhesive layer, a polymer or oligomer having compatibility with the resin forming the surface layer and the base material layer is used. More specifically, a polymer or oligomer containing a compound having a functional group such as a hydroxyl group, an amide group, an epoxy group, a carboxylic acid group, or a carboxylic acid ester group in its main chain or side chain is used.

Further, as the resin constituting the adhesive layer,
Among the above functional groups, those having a carboxylic acid group are particularly preferable, and the amount of the carboxylic acid is preferably such that the acid value of the polymer or oligomer is 1 to 30 mgKOH / g. When the resin constituting the adhesive layer is a polymer, its molecular weight is not particularly limited, but generally,
It is about 0.2 to 500,000. The softening point of the resin forming the adhesive layer is preferably about 100 to 220 ° C. If the softening point is lower than this range, the heat resistance of the obtained sheet may deteriorate, and if it is too high, the adhesiveness tends to decrease.

When a thermoplastic polyolefin elastomer is used as the base material layer, the resin constituting the adhesive layer is chlorinated polyolefin, ionomer resin, acid-modified polyolefin resin, acid-modified styrene. -Butadiene-styrene copolymer, acid-modified styrene-ethylene / butylene-styrene copolymer, etc. are used, and in particular, those exhibiting properties as an elastomer themselves (for example, JIS A hardness of about 50 to 98). Is preferred.

The adhesive layer is not essential in the laminated sheet of the present invention. For example, when the surface layer and the base material layer are laminated by coextrusion, the surface layer and the base material layer are sufficiently fused to each other. No adhesive layer is required if so obtained. Further, instead of using the adhesive layer, an adhesiveness-imparting agent may be added to the base material layer. Examples of such an adhesiveness-imparting agent include an olefin polymer having at least one functional group selected from the group consisting of a hydroxyl group, an amide group, an epoxy group, a carboxylic acid group and a carboxylic acid ester group in its main chain or side chain. Or, an oligomer may be mentioned, and one having a carboxylic acid group is particularly preferable. If the amount of this carboxylic acid group is too large, the fluidity will deteriorate, and if it is too small, the adhesiveness will decrease. Therefore, the acid value of the polymer having a carboxylic acid group is preferably in the range of 10 to 60 mg KOH / g.

If the softening point of the adhesion-imparting agent is too low, the heat resistance of the laminated sheet is deteriorated, and if it is too high, the adhesion-imparting effect is lowered, so that the softening point of the adhesion-imparting agent is 100. It is preferably in the range of 220 ° C.

If the amount of the above-mentioned adhesion-imparting agent added is too small, sufficient adhesiveness cannot be obtained, and if it is too large, the tensile stress of the base material layer decreases, so the thermoplastic resin 1 constituting the base material layer 1
The amount is preferably 1 to 30 parts by weight, more preferably 3 to 15 parts by weight with respect to 00 parts by weight. Further, when the thermoplastic resin forming the base material layer contains a thermoplastic polyolefin-based elastomer and a crosslinked olefin-based resin, the adhesiveness-imparting agent is blended in the above-mentioned ratio with respect to 100 parts by weight of these in total. Is desirable.

Other Addable Components The coating sheet of the present invention comprises the above-mentioned surface layer, base material layer and foam layer, and an adhesive layer which is optionally added. If necessary, various additives such as a colorant, an antioxidant, an ultraviolet absorber, an antistatic agent, a conductive material, an anti-condensation agent, a photochromic compound, an anticorrosive agent, a deodorant, and an antifungal agent of the present invention are added. You may contain in the range which does not inhibit the objective.

Concavo- convex pattern In the laminated sheet of the present invention, a concavo-convex pattern is provided from the surface layer side, and the concavo-convex pattern is formed so as to reach the foam layer as described above. Examples of the uneven pattern include a textured pattern and an embossed pattern that give a good appearance and a feeling of contact to the surface when used as a covering laminated sheet, and examples thereof include a textured grain and a geometric pattern grain.

The depth of the uneven pattern is not particularly limited, but R measured in accordance with JIS B0601.
The value of _max is preferably in the range of 100 to 600 μm, and by setting it in this range, for example, when a surface coating layer such as an interior material of an automobile or a housing material of OA equipment is formed, a good contact feeling and appearance can be obtained. Can be given.

The method of forming the uneven pattern on the surface layer is not particularly limited, but a transfer method of transferring the member having the uneven pattern by pressing it to the surface layer for transfer is generally used. To be As this transfer method, for example, a method generally adopted as an extrusion laminating method is preferably used. When the extrusion laminating method is used, for example, when the skin layer consisting of the surface layer and the base material layer is extrusion laminated on the foam layer, the roll pressed against the surface layer side is provided with an uneven pattern on the outer peripheral surface. It is conceivable that a concavo-convex pattern is imparted by contacting at least one-fourth or more of the peripheral surface of the outer surface of the embossed roll with the surface layer side contacting the embossed roll.

In the present invention, the uneven pattern is formed so as to reach the foam layer. In order to form the uneven pattern, the foam is preheated prior to extrusion lamination. Is effective, and thereby the uneven pattern can be surely formed so as to reach the foam layer. The preheating temperature of the foam in this case is not particularly limited, but it is preferably room temperature or higher and a temperature not higher than the softening point of the thermoplastic resin forming the foam layer.

The laminated sheet of the present invention is formed by laminating the surface layer, the base material layer and the foam layer as described above, and is provided with an uneven pattern extending from the surface layer side to the foam layer. However, the thickness of each layer is not particularly limited and may be appropriately determined depending on the application. Generally, the surface layer is 5 to 100 μm, and the base layer is 2
00-1000 μm, the adhesive layer formed as required is 5-100 μm, and the foam layer is 1000-5000.
The thickness is about μm.

Method for Producing Laminated Sheet of the Present Invention The invention described in claim 4 is a method for producing the laminated sheet of the present invention. In this manufacturing method, first, a surface layer containing a thermoplastic resin elastomer as a main component and a base material layer containing a thermoplastic resin as a main component are coextruded to form a skin layer.

The coextrusion method uses two or more extruders,
It means a method of joining the resins extruded from each extruder into one to obtain a sheet having a multilayer structure. The resin joining method in this coextrusion molding includes a feed block method, a multi-manifold method, a multi-throttle die method and the like. The feed block method is a method in which the resin is joined by a special block attached immediately before entering the die, and is also called a black box method. The multi-manifold method is a method in which as many manifolds as the number of layers are provided in the die. The multi-throttle die method is a method in which separate resin flows are set in the die, and the layers made of the respective resins are adhered immediately after leaving the die.

As the coextrusion method, any of the above methods may be used, but the multi-manifold method is preferable in order to improve the thickness accuracy of each layer and the adhesiveness between the layers. Also,
In the present invention, the lamination of the skin layer and the foam layer formed by the co-extrusion is such that the skin layer and the heat layer are formed between the first roller and the second roll having the uneven pattern on the outer peripheral surface. This is performed by supplying the foam layer containing a plastic resin as a main component and pressing between the first and second rolls. Further, in the manufacturing method of the present invention, at the same time as this lamination, the surface layer side is at least 1 / th of the circumferential direction of the outer peripheral surface of the second roll.
Four or more portions are brought into contact with each other, whereby the uneven pattern of the outer peripheral surface of the second roll is applied from the surface layer side, and the uneven pattern is also applied to the foam layer.

In this case, the temperature of the second roll on which the uneven pattern is formed is lower than the softening point of the thermoplastic resin elastomer which is the main component of the surface layer, preferably room temperature to 1
The temperature is maintained at about 00 ° C., whereby the concavo-convex pattern can be more surely imparted from the surface layer to the foam layer.

Preferably, as described above, the foam layer may be preheated prior to the application of the uneven pattern. By preheating the foam layer, it is possible to surely give the uneven pattern so as to reach the foam layer.
In this case, the preheating temperature is preferably a temperature not higher than the softening point of the thermoplastic resin forming the foam layer. This is because when the foam layer is heated to a temperature exceeding the softening point, the shape of the foam layer becomes unstable.

Utilization of Coating Sheet of the Present Invention The laminated sheet obtained in the present invention covers a resin molded article,
It is preferably used to give a good contact feeling and appearance to the surface of a molded product. When applied to a molded product, sheet stamping molding, vacuum molding or the like is used. In stamping molding, the resin that makes up the molded product is injected into the mold,
By arranging the covering laminated sheet of the present invention and pressing in that state, molding of a molded article and sticking of the covering laminated sheet on the surface of the molded article are simultaneously performed. Further, the vacuum forming is a method in which a heated coating laminated sheet is arranged on the surface of a molded article formed in advance and the coating laminated sheet is brought into close contact with the surface of the molded article by vacuum suction.

By any of the above-mentioned molding methods, the coating laminated sheet of the present invention can be surely stuck to the surface of the molded article, and a good contact feeling can be imparted to the surface of the molded article by the coating laminated sheet. .

[0053] In the laminated sheet of the invention described in the action claim 1, the surface layer as described above, the laminated sheet base layer and foam layer are laminated, uneven pattern from the surface layer side to the foam layer Since it is formed in such a manner that even when it is stretched when applied to the surface of the molded product by the stamping molding or vacuum molding, the uneven pattern is difficult to extend. That is, since the uneven pattern is deeply formed so as to reach the foam layer, the extension of the uneven pattern is suppressed by the strength of the foam layer, and thus the coating layer provided with the desired embossed pattern or embossed pattern. It is possible to stably obtain an attached molded product.

In the invention according to claim 4, after the step of forming the skin layer by coextruding the surface layer and the base material layer,
By extrusion laminating the foam layer and bringing the surface layer side into contact with the outer peripheral surface of the second roll, an uneven pattern extending from the surface layer side to the foam layer can be reliably provided. Therefore, it is possible to provide the laminated sheet in which the uneven pattern such as the embossed pattern or the embossed pattern is difficult to extend by a relatively simple process.

[0055]

The present invention will be clarified below by describing non-limiting examples of the present invention. In addition, below, the compounding part number shall show the number part by weight in solid content. Raw material resins used in the following examples and comparative examples, and extrusion conditions are as follows.

Raw material resin surface layer: thermoplastic urethane elastomer (manufactured by Asahi Glass Co., Ltd.,
Product name: PN3429, JIS A hardness = 85) 100
And 50 parts of polyurethane-based elastic beads (average particle size 8 μm) as elastic fine particles are mixed.

Adhesive layer: Acid-modified polyethylene. Base material layer: 50 parts of thermoplastic polyolefin-based elastomer (Mitsui Petrochemical Co., Ltd., trade name: Mirastoma 9020N), 30 parts of thermoplastic polyolefin-based elastomer (Mitsui Petrochemical Co., Ltd., trade name: Elastomer 6030N), and straight chain Low density polyethylene (Mitsui Petrochemical Co., Ltd., trade name:
Pellet blend with 20 parts of UZ2081C). Foam layer: Polypropylene foam (thickness 3 mm, foaming ratio 15 times).

Extrusion Conditions A laminated sheet was manufactured using the multi-layer feed block type co-extrusion device and rolls shown in FIG. In FIG.
Reference numeral 1 denotes a co-extrusion apparatus, and reference numerals 1a to 1c denote an adhesive layer-forming resin extruder, a base layer-forming resin extruder, and a surface layer-forming resin extruder, respectively. In addition, below the co-extrusion device 1 in FIG. 1, a pinch roll 2 as a first roll and an embossing roll 3 as a second roll are arranged at a predetermined interval. The embossed roll 3 has a diameter of 400 mm and has an embossed pattern having an R _max value of 500 μm formed on the outer peripheral surface. Further, the clearance between the pinch roll 2 and the chevrolet roll 3 was set to 1.5 mm.

In the production of a laminated sheet, a laminate of a coextruded base material layer, an adhesive layer and a surface layer, that is, a skin layer 4 and a separately prepared foam layer 5 are used as the pinch roll 2 and the chevrolet 3 described above. By supplying and laminating between the above and the third roll 6 and changing the position of the third roll 6, the outer peripheral surface region of the grain roll 3 with which the surface layer side of the laminated sheet abuts was adjusted.

The extrusion conditions for the extruder and the coextrusion are as follows. Extruder 1a ... GT-4 manufactured by Plastic Engineering Laboratory Co., Ltd.
0, 40 mm extruder, L / D = 26, compression ratio = 3. Extruder 1b ... GT-5 manufactured by Plastic Engineering Laboratory Co., Ltd.
0, 50 mm extruder, L / D = 26, compression ratio = 3. Extruder 1c ... UT-4 manufactured by Plastic Engineering Laboratory Co., Ltd.
0, 40 mm extruder, L / D = 26, compression ratio = 3. Dice (50 with 5 channel feed block manufactured by Krollen)
0 mm width, trade name: Epoch 3201).

The extrusion temperature is 190 ° C. for the surface layer,
190 ° C for the adhesive layer and 230 for the base material layer
C. and the mold temperature was 200.degree. The take-up speed of the laminated sheet was 5 m / min.

Example 1 The surface layer, the adhesive layer and the substrate layer were coextruded under the above-mentioned extrusion conditions by the multi-layer feedblock type coextrusion device 1 shown in FIG. 1 to obtain a skin layer 4 and the extruded skin. The foam layer 5 was laminated on the layer 4 to obtain a laminated sheet 7. In this case, the third
The roll 6 was placed so that the upper end of the roll 6 was higher than the upper end of the embossed roll 3, and the laminated sheet was taken out. Therefore,
The laminated sheet was abutted on the outer peripheral surface of the Chevrolet roll 3 in the circumferential direction in a region of 1/2 or more as shown in FIG.

As described above, the average thickness of the surface layer is 1
0 μm, the average thickness of the adhesive layer is 10 μm, the average thickness of the base material layer is 500 μm, and the average thickness of the foam layer is 3 mm.
To obtain a laminated sheet.

Example 2 A laminated sheet was obtained in the same manner as in Example 1 except that the embossed roll having an embossed pattern having an R _max value of 200 μm was used as the embossed roll 3.

Comparative Example 1 In Example 1, the upper end of the third roll 6 is located below the lower end of the embossed roll 3, that is, the third roll 6 is arranged at the position indicated by the imaginary line A in FIG. Example 1 except that the laminated sheet was brought into contact with a region of less than 1/4 along the circumferential direction of the outer peripheral surface of the Chevrolet roll 3.
A laminated sheet was obtained in the same manner as.

Comparative Example 2 The upper end of the third roll is located below the lower end of the embossing roll 3, that is, the position shown by the imaginary line A in FIG. 1, and the surface layer is in the circumferential direction of the outer peripheral surface of the embossing roll 3. Along 1
A laminated sheet was obtained in the same manner as in Example 2 except that it was brought into contact with the Chevrolet roll 3 in a region of less than / 4.

Evaluation of Examples and Comparative Examples The laminated sheets of Examples 1 and 2 and Comparative Examples 1 and 2 obtained as described above were molded using door-shaped molds attached to a stamping molding machine. After injecting polypropylene as a constituent resin, the laminated sheet obtained as described above was placed and stamped to obtain a molded product with a coating layer. The grain flow was evaluated by using the R _max value of the cross-section curve obtained by measuring the reference length 25 mm based on the surface roughness defined in JIS B0601 before and after the sheet stamping, and using the following equation as the grain flow rate. .

[0068]

[Equation 1]

The unevenness of the embossed pattern in the laminated sheet was cut in the thickness direction of each of the laminates of Examples 1 and 2 and Comparative Examples 1 and 2, and the cross section was observed with a 0.1 mm loupe. It was measured. The results are shown in Table 1 below.

The cross section of the laminate obtained in Example 1 and the cross section of the coating layer of the molded article with the coating layer obtained using the laminated sheet of Example 1 were observed with a loupe. The structure was as shown in FIGS. 2 and 3. That is, in FIG. 2, the unevenness X is formed so as to reach the skin layer 4 and the foam layer 5, and after the stamping molding, the unevenness as described above also reaches the foam layer 5. . Similar results were also observed in the case of the laminated sheet of Example 2.

4 and 5 show the cross section of the laminated sheet of Comparative Example 1 and the cross section of the coating layer of the molded article with the coating layer obtained using the laminated sheet of Comparative Example 1. As is apparent from FIG. 4, in the laminated sheet of Comparative Example 1, the unevenness Y exists only in the skin layer 11 and does not reach the foam layer 12. Further, it can be seen that after the sheet stamping molding, the unevenness X largely flows, and thus the wrinkle flow occurs at a considerable ratio. Even when the laminated sheet of Comparative Example 2 was used, the same results as in Comparative Example 1 were obtained.

[0072]

[Table 1]

As is clear from the results shown in FIGS. 2 to 5 and the results shown in Table 1, in Examples 1 and 2, the unevenness was formed so as to reach the foam layer, It can be seen that even if the product is stretched when applied to the surface of the product by the stamping molding method, a sufficiently uneven grain pattern is maintained. On the other hand, in the laminated sheets of Comparative Examples 1 and 2, by stretching during sheet stamping molding,
It can be seen that the grain pattern in the initial state flows significantly.

[0074]

As described above, in the laminated sheet according to the invention described in claim 1, the concavo-convex pattern formed from the surface layer side is formed so as to reach the foam layer. When it is used as a laminated sheet for forming a coating layer as described above, even if stretching is applied at the time of molding, it is difficult for a grain flow to occur. Therefore, it is possible to reliably provide a laminated sheet that has an excellent appearance and can give a good contact feeling.

Further, according to the manufacturing method of the present invention described in claim 4, after the skin layer is formed by coextrusion, the skin layer and the foam layer are laminated between the first and second rolls. 2. The invention according to claim 1, wherein the surface layer side is abutted in an area of at least ¼ or more along the circumferential direction of the outer circumferential surface of the second roll having the uneven surface provided on the outer circumferential surface. It is possible to easily and stably obtain the laminated sheet according to the above.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view for explaining an apparatus for manufacturing a laminated sheet in an example.

FIG. 2 is a cross-sectional view of the laminated body of Example 1.

FIG. 3 is a sectional view of a coating layer of a molded article with a coating layer obtained by using the laminated sheet of Example 1.

FIG. 4 is a sectional view of a laminated sheet obtained in Comparative Example 1.

FIG. 5 is a cross-sectional view of a coating layer of a molded article with a coating layer obtained by using the laminated sheet of Comparative Example 1.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Co-extrusion apparatus 1a-1c ... Extruder 2 ... Pinch roll as a 1st roll 3 ... Shibo roll as a 2nd roll 4 ... Skin layer 5 ... Foam layer 6 ... 3rd roll 7 ... Laminated sheet 11 ... Surface layer of the laminated sheet of Comparative Example 1 ... 12 Foam layer of the laminated sheet of Comparative Example 1

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location B32B 27/40 B32B 27/40

Claims (4)

[Claims] 1. A surface layer containing a thermoplastic resin elastomer as a main component, a base material layer containing a thermoplastic resin as a main component, and a foam layer containing a thermoplastic resin as a main component are laminated in this order. A laminated sheet having the above-mentioned surface layer side is provided with an uneven pattern, and the uneven pattern is formed so as to reach the foam layer. 2. The laminated sheet according to claim 1, wherein the laminated sheet is a coating laminated sheet for forming a coating on the surface of a molded article. 3. The laminated sheet according to claim 1, wherein the thermoplastic resin elastomer is a thermoplastic urethane elastomer, and the thermoplastic resin forming the base material layer is a thermoplastic elastomer. 4. A step of forming a skin layer by co-extruding a surface layer containing a thermoplastic resin elastomer as a main component and a base material layer containing a thermoplastic resin as a main component, a first roller, and an outer peripheral surface. The surface layer and a foam layer containing a thermoplastic resin as a main component are supplied between the second roll having irregularities formed on the surface, and the surface layer is laminated with the foam layer. A step of bringing the layer side into contact with at least a quarter or more portion of the outer peripheral surface of the second roll in the circumferential direction so as to impart an uneven pattern from the surface layer side to the foam layer. The method for manufacturing a laminated sheet according to claim 1, wherein the laminated sheet is manufactured.