JPH0957907A - Laminated sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated sheet on which a coating with a good soft touch effect and matte effect can be formed even when it is applied on the surface of a molded article by thermoforming and which can be relatively simply prepd. SOLUTION: A laminated sheet wherein a surface layer contg. a thermoplastic resin elastomer and elastic fine particles and a base material layer in which a thermoplastic resin is a main component are laminated and the elastic fine particles with a ratio of the thickness of the surface layer to the particle diameter of the elastic fine particles being smaller than 0.63 are compounded at a ratio of 15-30wt.% in the whole elastic fine particles, is provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a laminated sheet suitable for coating the surface of, for example, a plastic molded product or a metal molded product. The laminated sheet of the present invention includes, for example, interior materials for automobiles, housings for OA equipment and home appliances,
It is used to cover parts that may be touched by humans, such as stationery, sanitary products, daily necessities, or molded products used for interior decoration of building materials.

[0002]

2. Description of the Related Art Conventionally, a suede-like (soft touch) paint has been generally used in order to give a matte feeling or a suede feeling (soft touch feeling) to the surface of a plastic molded body or a metal molded body. ing. For example, JP-A-63
-199776, nylon powder and colorant,
Alternatively, a coating material is disclosed in which colored nylon powder is dispersed in a resin liquid containing a coating film-forming resin having an elongation of 60 to 700%.

However, Japanese Patent Laid-Open No. 63-199776.
When using the above paint described in the publication,
It was necessary to accurately adjust the viscosity and concentration of the paint, and the work was complicated. In addition, a paint using an organic solvent requires a booth for drying the solvent, and further tends to cause contamination of the work environment and safety and health problems.

In order to solve the above problems, for example, in Japanese Unexamined Patent Publication No. 6-246812, a surface layer containing a thermoplastic elastomer and elastic fine particles as main components, and a thermoplastic resin as a main component. A covering sheet having a base layer has been proposed. Here, the resin forming the surface layer and the base material layer is co-extruded to obtain the covering sheet.

[0005]

However, since the covering sheet described in JP-A-6-246812 is obtained by coextrusion, the material of each layer needs to be thermoplastic. Therefore, when the obtained covering sheet is applied to the surface of a plastic molded body by a molding method involving heating such as vacuum molding or stamping molding, the resin on the surface of the covering sheet tends to be softened by heating. there were. Especially, it tended to be remarkably softened in the low stretched portion. As a result, the gloss of the surface may be increased, the matte feeling may be impaired, or the feel may be deteriorated.
Further, if the molding temperature is lowered in order to suppress an increase in gloss, the sheet cannot be deep-drawn. Therefore, there are problems that the range of the molded product to be applied is limited and the molding temperature range is narrowed.

An object of the present invention is to reliably form a coating having a good soft touch feeling and a matte feeling even when it is applied to the surface of a plastic molded body or the like by thermoforming. (EN) Provided is a laminated sheet which can be simply manufactured and is less likely to cause environmental pollution during production and use.

[0007]

The present invention has been made to achieve the above object, and the invention as set forth in claim 1 is to form irregularities on the surface containing a thermoplastic resin elastomer and elastic fine particles. In a laminated sheet obtained by laminating a surface layer having the same and a base material layer containing a thermoplastic resin as a main component, the ratio of the thickness of the surface layer to the particle size of the elastic fine particles is 0.6.
The elastic fine particles of less than 3 are 15 to 30 in the total elastic fine particles.
It is a laminated sheet characterized by being blended in a weight percentage.

The laminated sheet of the present invention is preferably used as a covering laminated sheet as described in claim 2. In a specific aspect of the present invention, claim 3
The thermoplastic resin elastomer comprises a thermoplastic urethane elastomer.

Further, in another specific aspect of the present invention, as described in claim 4, the thermoplastic resin forming the base material layer is formed of a thermoplastic olefin elastomer.

The details of the laminated sheet of the present invention will be described below. 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 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 JIS 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 a hard segment and ethylene, ethylene and a small amount of a diene component as a 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).

The above-mentioned polyester type thermoplastic resin elastomer includes polyester as a hard segment,
Examples of the soft segment include a copolymer having a polyether.

As the above polyvinyl chloride 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 polyamide-based thermoplastic resin 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.

According to a third aspect of the invention, 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.

Elastic Fine Particles The laminated sheet of the present invention contains elastic fine particles 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, and are melted at the time of melt-kneading and molding of the thermoplastic resin elastomer. Those that do not are used. When elastic fine particles are melt-integrated with the thermoplastic resin elastomer when mixed with the thermoplastic resin elastomer and extruded into a sheet form from the extruder, a surface layer having good unevenness even if extended later is formed. Because it becomes difficult.

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. The particle size distribution ratio of the elastic fine particles is a ratio of the thickness of the surface layer and the particle size of the elastic fine particles, that is, the thickness of the surface layer / the particle size of the elastic fine particles (hereinafter, this ratio is referred to as a particle size distribution ratio).
However, as if less than 0.63 is blended in a proportion of 15 to 30% by weight in the total elastic fine particles, therefore, the elastic fine particles having a particle size distribution ratio of 0.63 or more are 70% of the total elastic fine particles.
It is necessary to be blended so as to occupy ˜85% by weight. The reason is as follows.

When the laminated sheet is applied to the surface of a plastic molding or the like and thermoformed, the concave portion of the unevenness formed on the surface of the sheet is stretched to increase the matte feeling and the soft touch feeling. Will occur. However, when the ratio of the elastic fine particles having the value of the particle size distribution ratio of less than 0.63 is less than 15% by weight in the total elastic fine particles, a greater matte feeling is obtained in the flat portion which is difficult to be stretched during the stretching process by heating. The ratio of the elastic fine particles having a large particle diameter that gives the above-mentioned effect decreases, and the matte feeling of the flat portion is impaired.
Therefore, in the present invention, elastic fine particles having a particle size distribution ratio of less than 0.63 are blended in a proportion of 15% by weight or more based on the total elastic fine particles.

On the other hand, when elastic fine particles having a particle size distribution ratio of less than 0.63 are mixed in a proportion of more than 30% by weight, there are many elastic fine particles having a large particle size even in the recesses stretched by heating. Therefore, by the above stretching, the recesses are stretched more, and the gloss of the recesses is increased. Therefore, in order to suppress an increase in the gloss of the concave portion, it is necessary that elastic fine particles having a small particle size be present in the concave portion at a certain ratio. When the elastic fine particles having a small particle size are present in the recesses to a certain extent, the elastic fine particles having a small particle size are projected on the surface, whereby the increase in gloss of the surface can be suppressed. Therefore, in the present invention, the above-mentioned particle size distribution ratio is less than 0.
Elastic fine particles of less than 63 are blended in a proportion of 30% by weight or less based on the total elastic fine particles.

It is preferable that the particle size distribution ratio is 0.
The elastic fine particles of less than 63 are blended in a proportion of 18 to 25% by weight in the total elastic fine particles for the above reason. 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 diameter of the elastic fine particles is 1 to 50 μm.
The range is preferably m, and more preferably 5 to 4.
The range is 0 μm.

When the content of the elastic fine particles is small, it is difficult to give a good matte feeling to the surface of the surface layer, and when the content is large, the surface layer is extruded and spread on the surface when the surface layer is extruded and spread. Cracks are likely to occur. Therefore, the elastic fine particles are 8 parts with respect to 100 parts by weight of the thermoplastic resin elastomer.
It is preferably contained in the range of 0 to 130 parts by weight,
More preferably, it is contained in the range of 80 to 120 parts by weight.

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. The thermoplastic resin forming the base material layer is preferably formed of a thermoplastic olefin elastomer when the foam layer described later is formed of an olefin material. When the foam layer is made of an olefin material, the base layer is made of a thermoplastic olefin elastomer so that the base layer can be laminated on the foam layer without using an adhesive layer by a heat lamination method or the like. You can

The thermoplastic resin elastomer used to form the surface layer can also be used as the thermoplastic resin elastomer to form the base layer. However, as the thermoplastic resin elastomer constituting the base material layer, a thermoplastic olefin 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.

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

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

As the thermoplastic olefin elastomer used for the base material layer, in addition to the above materials, for example, the resin elution amount at 0 ° C. by the cross fractionation method is 25 to 75% by weight of the total olefin elastomer, and 80 to 80%. An olefin elastomer whose resin elution amount at 100 ° C. is in the range of 1 to 45% by weight of the total olefin elastomer amount, and resin elution amount at 100 to 125 ° C. is in the range of 1 to 40% by weight of the total olefin elastomer amount The thing which consists of a composition which has a main component is also used preferably.

The amount of resin eluted by the cross fractionation method is measured by the following procedure. That is, resin 14
A solution was obtained by dissolving it in o-dichlorobenzene at a temperature of 0 ° C. or a temperature at which the resin completely melts, and the obtained solution was 1 ° C. /
Cool at a rate of minutes to form a thin polymer layer on the surface of the previously prepared inert carrier. At this time, the resin components are generated in the order of higher crystallinity and in the order of higher molecular weight.
Thereafter, the temperature is raised continuously or stepwise, and the concentration of the resin component eluted sequentially is detected, and the composition distribution (crystallinity distribution) is detected.
(Temperature rise elution fractionation). At the same time, the molecular weight and molecular weight distribution (weight average molecular weight / number average molecular weight) of the eluted components are measured by high temperature GPC (GASPhase Chromatograph).

The reason why the resin elution amount by the cross fractionation method of the above-mentioned specific thermoplastic olefin elastomer constituting the base material layer is preferably within the above range is as follows.

That is, when the resin elution amount at 0 ° C. decreases, the obtained laminated sheet becomes hard and the soft touch feeling deteriorates, and when the resin elution amount increases at 0 ° C., the heat resistance of the base material layer deteriorates. The amount is 25 to 75% by weight, preferably 30 to 70% by weight of the amount of elastomer.

When the resin elution amount at 80 to 100 ° C. decreases, the stretchability of the obtained laminated sheet decreases, and
If the amount is too large, the soft touch feeling of the obtained laminated sheet is deteriorated.
%, Preferably 1 to 40% by weight.

When the resin elution amount at 100 to 125 ° C. decreases, the stretchability of the obtained laminated sheet decreases, and when the resin elution amount increases, the soft touch feeling of the obtained laminated sheet deteriorates. 1 to 1
It is 40% by weight, preferably 1 to 35% by weight.

The method for producing the thermoplastic olefin-based elastomer having the above-mentioned predetermined resin elution amount is not particularly limited, but, for example, JP-A-4-96912 and JP-A-4-96912.
96907, JP-A-3-174410, JP-A-2-170803, and JP-A-2-170802.
JP-A-61-42553, JP-A-3-2
No. 05439 and Japanese Patent Laid-Open No. 3-97747 may be mentioned, and trade name "PE
R "and is marketed by Highmont under the trade name" Cataloy ".

The base material layer may be composed of a plurality of thermoplastic resin layers. When the base material layer is one layer, the thermoplastic olefin elastomer having the above specific resin elution amount distribution is the main component, and when it is two or more layers, at least one layer is the thermoplastic olefin elastomer main component. It is preferable to be made of one because it can enhance the stretchability and soft touch feeling of the obtained laminated sheet.

Foam layer In the laminated sheet of the present invention, a foam layer may be further laminated on the base material layer side, whereby the cushioning property and soft touch feeling can be further enhanced. 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 foamable thermoplastic resin materials such as a plastic elastomer can be used. If the expansion ratio of the foam is low, it may not be possible to obtain good cushioning properties and soft touch feeling, and if it is too high, the foam cells will easily collapse,
It is preferably 5 to 50 times, and particularly preferably 10 to 40 times.

Adhesive Layer In the laminated 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.

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 (weight average molecular weight) is not particularly limited, but it is generally about 0.2 to 500,000. In addition, the softening point of the resin forming the adhesive layer is preferably higher than the thermoforming temperature, whereby the gloss increase during thermoforming can be suppressed.

When a thermoplastic polyolefin-based 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.

Other Components that can be Added The laminated sheet of the present invention comprises the above-mentioned surface layer and base material layer, and optionally a foam layer and an adhesive layer, which are necessary for each layer. Depending on the purpose, 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 are used for the purpose of the present invention. You may make it contain in the range which does not inhibit.

As the above-mentioned colorant, any suitable pigment or dye used in paints can be used. As a pigment,
Examples thereof include titanium oxide, iron oxide, carbon black, cyanine pigments, quinacridone pigments, and the like. Examples of the dyes include azo dyes, anthraquinone dyes, indigoid dyes, and stilbenzene dyes. Further, aluminum flakes, metal powder such as nickel powder, gold powder, silver powder and the like may be used as the colorant. It is preferable that these colorants are fine particles. However, when a coloring agent is added, the soft touch feeling and matte feeling imparted by the elastic fine particles may fluctuate. Therefore, in the system to which the coloring agent is added, the appropriate amount of elastic fine particles may be different. .

Further, the laminated sheet of the present invention may be subjected to patterning such as printing in order to improve the design. In such a case, printing is preferably provided on the back surface of the surface layer, that is, the surface of the surface layer on the side of the base material layer.

Production of Laminated Sheet The method for producing the laminated sheet of the present invention is not particularly limited, but preferably, the surface layer and the base material layer or the surface layer, the adhesive layer and the base material layer are coextruded. Can be obtained by

The co-extrusion method is a method in which two or more extruders are used and the resins extruded from each extruder are merged 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,
Different coextrusion methods may be used in combination, such as the feed block method and the multi-manifold method.

The thermoplastic elastomer and the elastic fine particles constituting the surface layer are mixed and then melt-kneaded and extruded by using a twin-screw type extruder, and the resin is mixed with a resin to be a base material layer extruded from another extruder. Extruding or kneading the thermoplastic elastomer and elastic fine particles in advance to form pellets, and extruding the pellets with a commonly used extruder to co-extrude with the resin to be the base material layer extruded from another extruder. You can

When the thermoplastic elastomer and the elastic fine particles are kneaded and pelletized in advance, the thermoplastic elastomer and the elastic fine particles can be mixed with a Banbury mixer or the like.

The extrusion temperature conditions are, for example, 150 to 150 in the case of a surface layer composition using a thermoplastic urethane elastomer.
215 ° C. In the method for producing a thermoforming sheet of the present invention, elongation after coextrusion of the above composition into a sheet form from an extruder may be performed in the solid state of the sheet form body (in this case, in this case). (Generally called stretching)
However, the present invention is not limited to this case, and may be carried out in a semi-solid state immediately after extrusion as long as the sheet-like form is substantially retained.

Specifically, the composition may be stretched by a take-up roll or the like immediately after being co-extruded by an extruder, or may be sufficiently cooled and shaped so that the sheet can be wound, and then stretched. Good.

In the case of stretching, usually, after the temperature of the sheet falls below the softening temperature of the thermoplastic elastomer used, the cooled roll is brought into contact with the sheet, and the take-up roll is rotated at a speed higher than the resin discharge speed. Will be held at. When a cooled rubber roll or the like having a roughened surface is used, it may be near the softening temperature. Also,
A tenter stretching method or the like may be adopted.

The extension ratio varies depending on the compatibility between the thermoplastic elastomer and the elastic fine particles to be used, but is preferably 1.2 times or more, more preferably 2 times or more. By being stretched in this way, fine irregularities are formed on the surface of the obtained soft touch sheet, and a soft touch feeling is exhibited.

Further, the soft touch sheet thus obtained is annealed if necessary. A soft touch sheet obtained by coextrusion as described above,
As a method for laminating a synthetic resin foam to be a foam layer, there is, for example, co-extrusion, or a method of laminating a mixture in a molten state immediately after stretching on the base material layer side of a soft touch sheet (extrusion lamination). .

At this time, the surface of the laminating roll may be embossed, and the surface may be embossed simultaneously with the laminating. When the adhesion between the surface layer and the base material layer is poor at the time of the coextrusion, it is preferable to provide the above-mentioned adhesive layer by coextrusion between both layers, but as an alternative method, the surface layer or The material forming the base material layer may be acid-modified or graft-modified.

Similarly, even when the foam layer is laminated on the base material layer side and the adhesion between the base material layer and the foam material layer is poor, a primer layer or an adhesive is attached to the surface of the base material layer of the foam material layer. An agent layer may be provided in advance, or a primer layer or an adhesive layer may be provided on the foam layer side surface of the base material layer.

As a material for forming the primer layer, for example, when a base layer made of a thermoplastic elastomer is laminated on a polyolefin foam layer, a chlorinated polyolefin layer or an acid-modified SEBS (styrene-
Ethylene-butylene-styrene copolymer) or the like can be used.

Thickness of Laminated Sheet The thickness of the laminated sheet of the present invention obtained as described above varies depending on the constitution of the laminated sheet, but in consideration of soft touch feeling and moldability, etc., it is generally a surface layer. Is 5 to 100 μm, and the base material layer is 200 to 3000 μm
Is the thickness of. Further, the foam layer provided as necessary has a thickness of 1000 to 4000 μm, and the adhesive layer or the primer layer has a thickness of about 5 to 150 μm. When the base material layer is composed of two or more layers, the thickness of the base material layer means the total thickness of the layers constituting the base material layer.

Manufacturing method of products using the laminated sheet of the present invention
Method The production of a molded article using the laminating sheet of the present invention is carried out, for example, as follows.

1) The sheet is introduced into the mold in advance so that the surface layer becomes the surface, and the molding resin to be the molded article body is molded by injection molding or stamping molding, and at the same time, the sheet is attached to the molded article body surface. That is, after introducing into the mold so that the surface layer of the sheet faces the surface side of the obtained molded product, in the case of stamping molding, the mold resin is introduced into the mold and then the mold is closed, and in the case of injection molding, the mold is closed. After closing the mold, the resin is introduced to obtain a molded product.

2) The sheet is preformed by thermoforming in advance, and the preformed product is introduced into the mold so as to face the surface side of the molded product from which the soft touch layer is obtained, and then the molded resin to be the molded product main body. At the same time as molding by injection molding or stamping molding, the sheet is attached to the surface of the molded product body. That is, in stamping molding, a molding resin is introduced into the mold and then the mold is closed, and in injection molding, the mold is closed and then the resin is introduced to obtain a molded product.

3) The sheet is molded by thermoforming and then attached to a molded product made of resin or the like to obtain a molded product. The thermoforming broadly includes a method of performing vacuum forming, pressure forming or press forming after heating.

The pre-molding may be carried out using a mold for molding a resin such as injection molding, or may be carried out using another mold for sheet molding. As the resin for the molded product, any material can be used as long as it is a usual molding material. For example, ABS (acrylonitrile-butadiene-styrene copolymer), polyethylene, polypropylene, polyvinyl chloride, polystyrene, polycarbonate, acrylic resin, polyetherimide, polyphenylene sulfide, nylon, the above-mentioned thermoplastic elastomer, and these materials Examples include a mixture of glass fiber and an inorganic filler.

Since the laminated sheet of the present invention imparts a soft touch feeling and a matte feeling to the surface of the product, it can be suitably used in a place where a person can easily touch it, and further suitable for a portion to which heat is applied. Used for.

Therefore, for example, automobile interior members such as door panels, instrument panels, handles, gear lever knobs, door knobs, and various switches; portable products (telephones, cassette tape recorders, compact discs,
Televisions, etc.); refrigerators, housings for home electric appliances such as TVs, switches, etc .; housings for office automation products such as personal computers, printers, keyboards; sanitaries such as stools for Western toilets, bath tubs, chairs, mats, shelves, etc. Products and bathroom products; sports equipment such as grips for bats, rackets and clubs; cases,
It can be used for everyday goods such as containers and housings for stationery products; and also for benches, chairs, pedestals, sofas and the like.

[0069] In effect the present invention has the surface layer is configured to include the aforementioned thermoplastic resin elastomer and elastic fine particles, moreover,
Since the elastic fine particles having a ratio (thickness of surface layer / particle diameter of elastic fine particles) of less than 0.63 account for 15 to 30% by weight of the total elastic fine particles, small particles are formed in the recesses that are easily stretched during thermoforming. Since the elastic fine particles having a diameter are present in a certain ratio, it is possible to suppress the elongation in the recess,
Further, even if the elastic fine particles having a large particle size are reduced in density by being extended, the elastic fine particles having a small particle size project from the inside to form unevenness at that portion, which increases gloss. Can be suppressed, while
Since the elastic fine particles having a small particle size do not exist so much in the flat surface portion which is difficult to be stretched during the stretching process, the glossiness in the flat surface portion is unlikely to occur. Therefore, even if it is subjected to thermoforming, it is possible to obtain a laminated sheet in which the matte feeling and the soft touch feeling do not easily deteriorate.

Furthermore, since it is not necessary to provide a solvent-based top coat layer, safety and working environment problems are unlikely to occur.

[0071]

EXAMPLES The present invention will be made clear by describing non-limiting examples and comparative examples of the present invention.

In the following, parts are parts by weight of solid content unless otherwise specified. Example 1 Surface layer constituent material: thermoplastic urethane elastomer resin (manufactured by Nippon Miractolan Co., E990P non-yellowing, JIS
Elastic beads consisting of 100 parts of A hardness 90) and urethane resin as elastic fine particles (manufactured by Dainippon Ink and Chemicals, Inc., trade name:
Burnock CFB101-620-40 (clear),
90 parts with an average particle size of 10 μm (the particle size distribution ratio is 0.6
80% by weight for 3 or more, 20 for less than 0.63
It was blended in a weight percentage. ) And were extruded with a twin-screw kneading extruder, cooled, and then pelletized with a soft cutter.

Adhesive layer: Acid-modified polyolefin resin (manufactured by Mitsui Petrochemical Co., Ltd., trade name: Admer QF55
0). Base material layer: Olefin-based elastomer (manufactured by Highmont,
Product name: Catalloy NKS052P, resin elution amount at 0 ° C by cross fractionation method is 49.5% by weight of total olefin elastomer, resin elution amount at 80 to 100 ° C is 20.0% by total olefin elastomer amount. %, 100
The resin elution amount at ˜125 ° C. is 5.5% by weight of the total amount of the olefin elastomer) A laminated sheet was produced using the above materials and the three-layer coextrusion device shown in FIG. The three-layer coextrusion device 1 shown in FIG.
mm, 40 mm and 40 mm diameter extruders 1a to 1c
And a feedblock type die 2. In the extruder 1a, the surface layer material described above is added to the extruder 1b.
To the extruder 1c, and the adhesive layer material to the extruder 1c. Each resin temperature is 1 for surface layer material
80 ℃, 210 ℃ for base material, 200 for adhesive material
C. and the die 2 temperature was 190.degree.

Under the above conditions, the laminated sheet 3 was extruded from the coextrusion device 1. In the apparatus shown in FIG. 1, the laminated sheet 3 having a temperature of about 170 ° C. is rotated at a speed about 15 cm directly below the mold lip (width 2 mm, length 1 m) at a speed higher than the resin discharge speed. It was taken out while being stretched by the cooling take-up roll 4 having a temperature of 40 ° C. Thus, the laminated sheet 3 was obtained. In addition, in FIG. 1, 5, 6
Indicates rolls, respectively.

When the surface layer of the laminated sheet obtained as described above was observed with an electron microscope, fine irregularities were formed on the surface. The thickness of the surface layer, the adhesive layer and the base material layer of the obtained laminated sheet are respectively surface layer = 18 μm, adhesive layer = 10 μm and base material layer = 400 μm, and the lip cross-section area / the obtained laminated sheet The cross-sectional area = 4.

Example 2 Except that elastic fine particles having a particle size distribution ratio of 0.63 or more at a ratio of 75% by weight and less than 0.63 at a ratio of 25% by weight were used. A laminated sheet was obtained in the same manner as in Example 1.

Example 3 Other than using elastic fine particles having a particle size distribution ratio of 0.63 or more in an amount of 71% by weight and less than 0.63 in an amount of 29% by weight. A laminated sheet was obtained in the same manner as in Example 1.

Comparative Example 1 Other than using elastic fine particles having a particle size distribution ratio of 0.63 or more in an amount of 90% by weight and less than 0.63 in an amount of 10% by weight. Example 1
A laminated sheet was obtained in the same manner as.

Comparative Example 2 The same as Example 1 except that 65% by weight of elastic fine particles having a particle size distribution ratio of 0.63 or more and 35% by weight of less than 0.63 were used. A laminated sheet was obtained in the same manner.

The average particle size of the elastic fine particles in the surface layer of the laminated sheets obtained in Examples 1 to 3 and Comparative Examples 1 and 2 above, the thickness of the surface layer, the particle size distribution ratio, and the addition amount of the elastic fine particles were as follows. It is also shown in Table 1.

The laminated sheets of Examples 1 to 3 and Comparative Examples 1 and 2 were placed in an initial state at 120 ° C. in an oven.
The gloss and the appearance of the sheet surface after molding after heating for 30 minutes at the temperature of 30 minutes (after heating) and after heating vacuum molding performed in the following manner were measured by the following methods. The results are shown in Table 1 below.

Heating vacuum forming: The far-infrared heater is used to heat the front and back surfaces of the laminated sheet to temperatures of 115 ° C. and 140 ° C., and the cylindrical vacuum forming die 1 shown in FIG.
1 was used for vacuum forming. The vacuum forming die 11 has a vacuum hole 12, and has a cylindrical forming space 11a having an inner diameter of the bottom surface of 100 mm and an inner height of 20 mm. FIG. 3 shows a cross section of a cylindrical molded product formed using the vacuum molding die 28. That is, the laminated sheet 3 was molded, and the molded product 13 shown in FIG. 3 was obtained.

Gloss measurement: According to JIS K7105, 60 ° specular gloss was measured. In addition, the conditions of the initial state and the surface of the laminated sheet after heat-vacuum forming were visually observed and evaluated. The results are shown in Table 1 below. The meanings of the evaluation symbols in Table 1 are as follows.

Good ... No cracks in the surface layer Good ... Slight cracks in the surface layer but not noticeable Poor ... Many cracks in the surface layer

[0085]

[Table 1]

As is clear from Table 1, Comparative Example 2
It can be seen that the laminated sheet of No. 1 has a good appearance, but has a high gloss, and therefore the matte feeling is greatly impaired. In addition, the laminated sheet of Comparative Example 1 had not only high gloss, but also poor appearance after vacuum forming.

On the other hand, in Examples 1 to 3, elastic fine particles having a particle size distribution ratio of less than 0.63 were blended at a ratio of 15 to 30% by weight as elastic fine particles. Therefore, it can be seen that a laminated sheet which is excellent in matt feeling and has good appearance properties both in the initial state and after vacuum forming can be obtained.

[0088]

As described above, in the laminated sheet of the present invention, the elastic fine particles having a particle size distribution ratio of less than 0.63 among the elastic fine particles contained in the surface layer are included in all the elastic fine particles.
Since it is blended in a ratio of 5 to 30% by weight, even if it is used for molding with heating, it is possible to effectively suppress the increase in gloss of the surface layer, and it is also effective in generating cracks and reducing the feel. Can be suppressed. Therefore, when the laminated sheet of the present invention is used for coating the surface of a molded product such as a synthetic resin or a metal, it is possible to give the surface of the molded product a good soft touch feeling and matte feeling.

Therefore, since the laminated sheet of the present invention can be applied to the molded article body by a molding method involving heating such as vacuum molding, injection molding or stamping molding, the above-mentioned good matte feeling and softness are obtained. It is possible to provide a product having a touch feeling at low cost and easily.

[Brief description of drawings]

FIG. 1 is a sectional view for explaining an example of an apparatus for producing a laminated sheet of the present invention.

FIG. 2 is a cross-sectional view of a vacuum molding die used for evaluation of the laminated sheets obtained in Examples and Comparative Examples.

FIG. 3 is a cross-sectional view of a laminated sheet after being formed using the vacuum forming die shown in FIG.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Three-layer co-extrusion apparatus 1a-1c ... Extruder 2 ... Die 3 ... Laminated sheet 4 ... Cooling take-up roll 5,6 ... Roll 11 ... Vacuum forming die 12 ... Vacuum hole 13 ... Formed body consisting of laminated sheet

Claims (4)

[Claims] 1. A laminated sheet in which a surface layer having irregularities on a surface containing a thermoplastic resin elastomer and elastic fine particles and a base material layer containing a thermoplastic resin as a main component are laminated, and the thickness of the surface layer. Elastic fine particles having a ratio (surface layer thickness / elastic fine particle diameter) of less than 0.63 to the particle diameter of the elastic fine particles are blended in a proportion of 15 to 30% by weight based on the total elastic fine particles. Laminated sheet characterized by. 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. 4. The thermoplastic resin forming the base material layer is a thermoplastic olefin elastomer.
The laminated sheet according to any one of 3 above.