JPH0858004A - Cover sheet and production thereof - Google Patents

Abstract

PURPOSE: To obtain a cover sheet capable of easily forming a molded product the surface of which has a soft touch feeling by covering the surface of the molded product by a simple manufacturing method. CONSTITUTION: A cover sheet is constituted by successively lamainating a surface layer based on a thermoplastic elastomer and elastic fine particles to a base material layer based on an olefinic elastomer characterized by that a resin elution amt. due to a cross fractionation method with respect to all amt. of the olefinic elastomer is 25-75wt.% at 0 deg.C, l-45wt.% at 80-100 deg.C and 1-40wt.% at 100-120 deg.C and a foam layer.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is likely to be touched by humans for automobile interiors, housings for office automation (OA) equipment and home appliances, stationery, sanitary products, daily necessities, interior materials for building materials, etc. The present invention relates to a coating sheet that can impart good contact feeling and matte feeling to a molded article by coating the area, and a method for producing the same.

[0002]

2. Description of the Related Art In order to impart a suede feeling (soft touch feeling) to the surface of a plastic molded body or a metal molded body, a suede tone (soft touch) paint has been generally used. For example, JP-A-63-199776 discloses a nylon powder and a coloring agent or a colored nylon powder,
A coating composition is disclosed which 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 coating with a paint as in Japanese Patent Laid-Open Publication No. 2004-242, it is necessary to adjust the viscosity and concentration of the paint, which complicates the work. In addition, a paint using an organic solvent requires a booth for drying the solvent, which causes contamination of the work environment and safety and health problems. In order to solve these problems, for example, in JP-A-2-41243, a matte paint obtained by adding a bead pigment to a vehicle of an ionizing radiation curable resin is applied on a base film having good moldability, A suede-like sheet that has been cross-linked and cured by an electron beam has been proposed as an alternative to paint. An apparatus for decorating a sheet using injection molding is disclosed in, for example, Japanese Patent Laid-Open No. 59-20.
No. 2830 is proposed.

[0004]

However, Japanese Patent Laid-Open No. 2-4
The sheet described in Japanese Patent No. 1243 is inferior in the spreadability of the entire sheet because the coating film of the sheet is made of a resin cross-linked and cured by an electron beam. Therefore, when an attempt is made to obtain a molded article having a soft touch feeling and a matte feeling on the surface using this sheet and the apparatus proposed in Japanese Patent Laid-Open No. 59-202830, the following is obtained. There's a problem.

That is, when an attempt is made to attach a sheet to the surface of an adherend having irregularities or curved surfaces, the sheet may be torn due to the poor spreadability of the sheet. It was difficult to impart a matte feeling. Further, a method of laminating a foam on the sheet is also conceivable in order to give a soft touch feeling.
In such a case, it may be laminated via a base material, and as the base material, a polyolefin elastomer having good recyclability and incineration property is considered. However, the olefin elastomer has a problem that the dispersibility of the olefin resin and the rubber component is low, and it is difficult to form a sheet by extrusion unless the other resin is blended, and the stretchability is poor.

The present invention solves the above-mentioned problems and is capable of forming a coating having a soft touch feeling and a matte feeling, and a covering sheet excellent in soft touch (suede tone) and matte feeling, and a covering sheet for the covering. It is an object of the present invention to provide a manufacturing method capable of easily manufacturing a sheet.

[0007]

The thermoplastic elastomer resin used for the surface layer of the covering sheet obtained in the present invention has rubber elasticity at room temperature and is plasticized at high temperature to be subjected to various molding processes. Possible polymer materials are classified into 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, It is classified into 4 polyisoprene type.

In general, these thermoplastic elastomers often share a rubber component (soft segment) having entropy elasticity in the molecule and a molecular constraining component (hard segment) for preventing plastic deformation,
Although it may partially have a crosslinked structure in a moldable range, it does not have a wide range of three-dimensional stitch structures. The hardness of these thermoplastic elastomers varies depending on the feel to be obtained and the hardness of the elastic fine particles (elastic beads are often used) to be used, but generally JISK 6301 is used.
A hardness of 50 to 98 is preferable.

Examples of the thermoplastic elastomer include polyurethane-based block copolymers having polyurethane as a hard segment and polyether, polyester, polycarbonate, etc. as a soft segment. In the polystyrene type, there are a block copolymer having polystyrene as a hard segment and polybutadiene, polyisoprene, and polyethylene-polybutylene as a soft segment, and a block copolymer having hydrogenation or a functional group added thereto.

Among the polyolefin type, those having polypropylene as a hard segment and ethylene as a soft segment, those having a small amount of a diene component together with ethylene (EPM (ethylene-propylene-methylene bond) and EPDM (ethylene-ethylene in order) Propylene-diene methylene bond), generically EPR (ethylene-
Propylene rubber)), those obtained by blending these, those partially crosslinked by the addition of organic peroxides to these, and graft modification with unsaturated hydroxy monomers and unsaturated carboxylic acid derivatives. And other products such as butyl rubber grafted polyethylene.

In the polyester type, there are polyesters as the hard segment and copolymers having a polyether as the soft segment. In the case of polyvinyl chloride type, there are a method obtained by extremely increasing the polymerization degree of polyvinyl chloride, a method of introducing a three-dimensional crosslinked structure into a part of polyvinyl chloride, a method of introducing an ionic crosslinked structure, and the like. is there.

Among the polyamide-based materials, there are those using polyamide as the hard segment and polyether as the soft segment. Further, in selecting the type of the thermoplastic elastomer, in consideration of the performance desired to be obtained as the soft touch sheet, for example, when scratch resistance and abrasion resistance are required, a urethane type thermoplastic elastomer is preferably used.

The elastic fine particles have a property of elastically recovering when they are released after being pressed until their shape is deformed. For example, polyurethane, acrylic-urethane copolymer, polystyrene, styrene-isoprene copolymer are used. Examples thereof include those made of polymers and the like, and those which do not melt under the extrusion conditions of the thermoplastic elastomer are used. The reason is that when the elastic fine particles are melt-integrated with the thermoplastic elastomer when being extruded into a sheet form from an extruder by mixing with the thermoplastic elastomer, it is difficult to form a good surface layer even after the elongation. Because it will be.

These elastic fine particles having a maximum particle size distribution in the range of 1 to 50 μm are preferably 20 to 200 parts, preferably 100 parts by weight of the thermoplastic elastomer resin (hereinafter referred to as “parts”). Is preferably added in an amount of 50 to 150 parts. That is, if the particle size is less than 1 μm, the obtained sheet does not have sufficient soft touch feeling or matte feeling, and depending on the film thickness of the sheet, if the particle size exceeds 50 μm, the sheet is spread or stretched. Then, when the sheet is stretched, cracks are likely to occur on its surface. Further, if the addition amount is less than 20 parts, sufficient unevenness cannot be obtained and soft touch feeling and matte feeling are deteriorated, and if the addition amount is more than 200 parts, when the sheet is stretched by stretching or stretching, Cracks are likely to occur on the surface.

The elastic fine particles are not limited to one kind, but two kinds.
You may use together 1 or more types. Also, when using a flexible thermoplastic elastomer, or when a slightly hard feel is acceptable,
For example, crosslinked polymethylmethacrylate or hard particles made of an inorganic material may be used. When the base material layer is composed of one layer, the base material layer has a resin elution amount by the cross fractionation method at 0 ° C. of 25 to 75% by weight of the total amount of the olefin elastomer and a resin elution amount at 80 to 100 ° C. 1 to 45% by weight of the total olefinic elastomer amount, and the resin elution amount at 100 to 125 ° C. is 1 to 40% of the total olefinic elastomer amount.
It is composed of a composition containing an olefin-based elastomer as a main component in a range of weight%.

The amount of resin eluted by the cross fractionation method is measured by the following operation. That is, 1 resin
A solution was obtained by dissolving in o-dichlorobenzene at a temperature of 40 ° C. or a temperature at which the resin completely melts, and the obtained solution was 1 ° C. /
It is cooled at a rate of min to form a thin polymer layer on the surface of an inert carrier prepared in advance. At this time, the resin components are generated in the order of high crystallinity and high molecular weight. Then, the temperature is raised continuously or stepwise, the concentration of the resin component that is eluted sequentially is detected, and the composition distribution (crystallinity distribution) is measured (temperature rising 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 (GAS Phase Chromatograph).

The method for producing the olefinic elastomer having the above-mentioned predetermined resin elution amount is not particularly limited, but for example, JP-A-4-96912, JP-A-4-96907, JP-A-3-174410, JP-A-2-170803, Examples include the methods described in Kaihei 2-170802, JP-A-61-42553, JP-A-3-205439, and JP-A-3-97747, and the trade name "P
ER "and is marketed by Highmont under the trade name" Cataloy ".

When the base material layer is composed of two or more layers, the base material layer contains a thermoplastic resin as a main component, and at least one of the base material layers has a resin elution amount at 0 ° C. by the cross fractionation method of all olefins. 25 to 75% by weight of the system elastomer,
Olefin-based resin elution amount at 80 to 100 ° C is in the range of 1 to 45% by weight of the total olefinic elastomer amount, and resin elution amount at 100 to 125 ° C is in the range of 1 to 40% by weight of the total olefinic elastomer amount. It is composed of a composition containing an elastomer as a main component.

As described above, when the base layer is one layer, the predetermined olefin-based elastomer is the main component, and when it is two or more layers, at least one layer is the main olefin-based elastomer as the main component. When the above, the obtained covering sheet has excellent stretchability and soft touch feeling.

Further, it is preferable that the other layer is made of an olefin elastomer having good adhesion to the olefin elastomer having the above-mentioned predetermined resin elution amount, since the uniform stretching property of the obtained covering sheet is improved. Furthermore, it has polypropylene as a hard segment, and as a soft segment,
Ethylene or a blend of ethylene with a small amount of diene component, further partially crosslinked, for example,
It is preferable to use an olefin elastomer obtained by blending a partially cross-linked product of a polyolefin resin and an ethylene / α-olefin copolymer rubber because the uniform stretchability is further improved.

The reason why the resin elution amount of the olefinic elastomer constituting the base material layer by the cross fractionation method is limited as described above is as follows. That is, when the resin elution amount at 0 ° C. decreases, the obtained coating 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 decreases. Of 25 to 75% by weight, preferably 30 to 70% by weight.

When the resin elution amount at 80 to 100 ° C. decreases, the stretchability of the obtained covering sheet decreases, and
If the amount is large, the soft touch feeling of the obtained covering sheet is deteriorated.
It is set to 5% by weight, preferably 1 to 40% by weight.

When the resin elution amount at 100 to 125 ° C. is small, the stretchability of the obtained covering sheet is lowered,
Further, if the amount is large, the soft touch feeling of the obtained covering sheet is deteriorated, and the total amount of the olefin elastomer is 1 to 40.
%, And preferably 1 to 35% by weight.

The thermoplastic resin is, for example, the thermoplastic elastomer, polystyrene, acrylic polymer, polycarbonate, polyvinyl chloride, polyethylene, polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer), modified polyphenylene oxide or polyphenylene. Examples thereof include sulfide, polyetherimide, polyetheretherketone, and ionomer, but it is preferable to adopt a thermoplastic elastomer in order to impart a softer soft touch feeling.

Examples of the material forming 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 the like. Examples of foamable resin materials include various thermoplastic elastomer resins. Further, when the expansion ratio of these foams is low, the soft touch feeling of the obtained covering sheet is deteriorated, and when the expansion ratio is high, the strength of the obtained covering sheet is decreased, and during stretch forming such as vacuum forming. Since the foamed layer is easily broken and the foamed cells are easily crushed, it is preferably about 5 to 50 times, more preferably 10 to 40 times. The material forming the foam layer is preferably partially crosslinked from the viewpoint of improving foamability.

The method for producing the covering sheet is not particularly limited, but for example, a sheet-like laminate obtained by coextrusion of the composition constituting the surface layer and the composition constituting the base material layer is stretched. Then, a method of laminating a foam layer on the base material layer side can be mentioned.

Coextrusion molding refers to a method in which two or more extruders are used to combine each extruded resin into a single product having a multilayer structure. The merging method by this co-extrusion is roughly classified into a feed block method, a multi-manifold method, and a multi-throttle die method. The feed block method joins with a special block installed just before entering the die, and is also called a black box method. The multi-manifold method has as many manifolds as there are layers in the die. The multi-throttle die method is a method in which separate flows are made in the die and they are bonded immediately after leaving the die.

Although the sheet-like laminate of the present invention can be produced by any of these methods, the multi-manifold method is preferable in order to improve the thickness accuracy of each layer and the adhesion of each layer. Further, different coextrusion molding methods such as the feed block method and the multi-manifold method may be combined.

The thermoplastic elastomer and the elastic fine particles constituting the surface layer are mixed, then melt-kneaded and extruded by using a twin-screw type extruder, and co-extruded 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 condition is, for example, 150 to 215 ° C. in the case of a surface layer composition using a thermoplastic urethane elastomer.

In the method for producing a covering sheet according to the present invention, the sheet-shaped laminate may of course be stretched in the solid state after the composition is coextruded into a sheet by an extruder (this). However, the present invention is not limited to this case, and may be performed in a semi-solid state immediately after extrusion as long as the sheet-like form is substantially retained.

Specifically, the above composition may be stretched by a take-up roll or the like immediately after coextruding from the extruder, or may be stretched after sufficiently cooling and shaping the sheet so that the sheet can be wound. Good. In the case of stretching, usually, after the temperature of the sheet becomes equal to or lower than the softening temperature of the used thermoplastic elastomer, a cooled roll is brought into contact with the sheet, and further, it is taken up by a take-up roll rotating at a higher speed than the discharge speed of the resin. Done. When a cooled rubber roll or the like having a roughened surface is used, it may be near the softening temperature.
Alternatively, a tenter stretching method or the like may be adopted.

The elongation 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.

As a method for laminating the soft touch sheet obtained by coextrusion as described above and the synthetic resin foam to be the foam layer, for example, immediately after coextrusion and stretching,
There is a method of laminating the mixture in a molten state on the base material layer side of the soft touch sheet (extrusion lamination). At this time, the surface of the laminating roll may be embossed, and the surface layer may be embossed simultaneously with the laminating.

When the surface layer and the base material layer are not in close contact with each other during the coextrusion, an adhesive layer may be provided between the two layers by coextrusion (three-layer extrusion) to form the surface layer or the base material layer. The material may be acid-modified or graft-modified. As a material forming the adhesive layer, an adhesive polymer compatible with the resin forming the base layer is used. Such a polymer is a polymer 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 the main chain or a side chain, for example,
Acid-modified SBS (styrene-butadiene-styrene copolymer) and acid-modified SEBS (styrene-
(Ethylene-butylene-styrene copolymer), acid-modified polypropylene, polyethylene and the like. These acid modifications are generally carried out with maleic anhydride, fumaric acid, itaconic acid, tetrahydrophthalic anhydride and the like. Further, the acid value of the polymer is 1 as the amount of carboxylic acid.
-30 mg KOH / g is preferred.

Similarly, when the adhesiveness between the base material layer and the foam layer is poor, a primer layer or an adhesive layer may be provided in advance on the surface of the foam layer (the surface on the base material layer side), or the base material A primer layer or an adhesive layer may be provided on the layer side by coextrusion (four-layer extrusion).

As a material for forming the primer layer, for example, when a foam made of a thermoplastic polyurethane elastomer is laminated on a polyolefin base layer, a chlorinated polyolefin layer or acid-modified SEBS is used.
(Styrene-ethylene-butylene-styrene copolymer)
And the like. Examples of the material forming the adhesive layer include pressure-sensitive adhesives such as rubber-based, acrylic-based, urethane-based, and silicone-based adhesives, solvent-based adhesives, ethylene-vinyl acetate-based copolymer (EVA) -based, styrene-based adhesives. There are hot melt adhesives such as isobrene-styrene block copolymer (SIS) adhesives. Further, for example, a post-curing type adhesive agent of the curing type of micule capsule can also be used. The post-curing adhesive includes, for example, an uncrosslinked unsaturated polyester adhesive, an uncrosslinked acrylic adhesive, and the like.

The coating sheet used in the present invention may further contain a colorant such as a pigment or dye, an antioxidant, if necessary.
Materials such as UV absorbers and UV stabilizers (eg hindered amines) can be added. As the colorant, pigments and dyes used in paints can be used. Examples of pigments include titanium oxide, iron oxide, carbon black, cyanine pigments, and quinacridone pigments. Examples of the dye 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. These materials are preferably fine particles as much as possible.
However, when these coloring agents are added, the soft touch feeling and the matte feeling imparted by the elastic fine particles may be different, so that the appropriate amount of the elastic fine particles may change in the system in which the coloring agent is added.

Various functionalizing agents may be added to impart various functions to the covering sheet used in the present invention. Examples of the functionalizing agent include conductive materials, anti-condensation agents, photochromic compounds, and the like. Further, patterning such as printing may be performed on the above-mentioned sheet in order to improve the design. In this case, printing is preferably provided on the back surface of the surface layer (on the base material layer).

The thickness of the covering sheet used in the present invention thus obtained varies depending on the sheet structure.
Considering the soft touch feeling, moldability, etc. of the covering sheet, generally, the surface layer has a thickness of 5 to 500 μm and the base material layer has a thickness of 2 μm.
00-3000 μm, foam layer is 1000-4000 μm
m, the adhesive layer or the primer layer is preferably 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 forming the base material layer.

[One Example of Method for Producing Molded Article Using Covering Sheet Obtained in Present Invention] A molded article is produced using the covering sheet obtained in the present invention, for example, as follows.

1) The coating sheet is previously introduced into the mold so that the surface layer is on 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 coated on the molded article body surface. Attach a sheet for use. That is, after introducing into the mold so that the surface layer of the sheet faces the surface side of the obtained molded product, during stamping molding, the molding resin is introduced into the mold and then the mold is closed, and during injection molding, the mold is closed. After closing the mold, the resin is introduced to obtain a molded product.

2) The coating sheet is preliminarily preformed by pneumatic molding, and the preformed product is introduced into the mold so as to face the surface side of the molded product from which the softouch layer is obtained, and then the molded product is formed into a main body. The resin is molded by injection molding or stamping molding, and at the same time, the sheet is attached to the surface of the molded product body with the covering sheet. 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) After forming the covering sheet by pneumatic molding, it is attached to a molded product made of resin or the like to obtain a molded product.

The pneumatic forming means vacuum forming, pressure forming and the like. The pre-molding may be performed using a mold for molding a resin such as injection molding, or a mold for sheet molding different from that may be used.

As the molding resin used above, any material can be used as long as it is a material that is usually molded. For example, ABS (acrylonitrile-butadiene-styrene copolymer), polyethylene, polypropylene, polyvinyl chloride, polystyrene, polycarbonate, acrylic resin, polyetherimide, polyphenylene sulfide, nylon, and the above thermoplastic elastomers,
Further, these materials include those having glass fiber or an inorganic filler.

The molded article obtained by the method for producing a molded article of the present invention has a soft touch feeling and a matte feeling on the surface of the product, and thus can be suitably used in a place where people can easily touch it. That is, for example, interior materials such as door panels, instrument panels, handles, gear lever knobs, door knobs, various switches as automobiles, portable products (phones, cassette tape recorders, compact discs, TVs, etc.), refrigerators, TVs, etc. Household appliances, housings for switches, personal computers, printers, keyboards, and other office automation products, Western-style toilet seats, bath tubs, chairs,
Sanitary products such as mats and shelves, melting chamber products, sports goods such as grips such as bats, rackets and clubs, daily necessities such as cases and containers, housings for stationery products, etc.
It can be used for benches, chairs, pedestals, sofas, etc.

[0048]

The covering sheet of the present invention has the above-mentioned constitution,
When the base material layer is one layer, the base material layer is mainly composed of an olefin-based elastomer having a predetermined resin elution amount, and since such an olefin-based elastomer has excellent dispersibility of a rubber component, extrusion moldability in the case of manufacturing Excellent stretchability.

Further, when the base material layer has two or more layers, at least one of the base material layers is mainly composed of an olefin elastomer having a predetermined resin elution amount, and the other layers are mainly composed of a thermoplastic resin. Since it is a component, it has excellent uniform stretchability as compared with the case where the base layer is a single layer.

Further, the method for producing the covering sheet of the present invention comprises:
In the above structure, the composition containing the thermoplastic elastomer as the surface layer and the elastic fine particles as main components, and the thermoplastic resin as the base layer are laminated by coextrusion,
The layers can be easily laminated without entraining air between both layers.

Since the obtained sheet-shaped laminate is stretched, even if the surface layer has such a thinness that it is difficult to stretch with only one surface layer, the surface layer has a base layer. And can be easily extended.

EXAMPLES The present invention will be described in detail below by comparing Examples with Comparative Examples. In the following, "part"
Indicates parts by weight in terms of solid content.

(Example 1) a) Surface layer material Thermoplastic urethane elastomer resin (manufactured by Nippon Miractolan Co., Ltd., E375MNAT, JIS-A hardness 75) 1
00 parts Elastic beads (Sekisui Plastics Co., Ltd., UB15 (black), crosslinked polyurethane elastic beads, average particle size 24 μm) 120 parts The above thermoplastic elastomer and elastic beads are extruded with a biaxial kneading extruder, After cooling, it was pelletized with a soft cutter.

The set temperature of each part in the extruder was set under the following conditions. Screw rear 140 ° C, middle 160
C, front 170 ° C, die 170 ° C. b) Substrate layer material Olefin-based elastomer (manufactured by Himont Co., Ltd., Catalloy NKS052P, resin elution amount by cross fractionation method at 0 ° C. is 49.5% by weight of total olefin-based elastomer amount, resin at 80 to 100 ° C.) The elution amount is 20.0% by weight of the total olefin elastomer, and the resin elution amount at 100 to 125 ° C. is 5.5 of the total olefin elastomer amount.
% By weight) c) Adhesive layer Acid-modified SEBS (manufactured by Asahi Kasei Kogyo Co., Ltd., Tuftec M1943) The above three layers a), b) and c) are respectively manufactured by the Plastic Engineering Laboratory as shown in FIG. 50φ, 40φ, 40
The extrusion was performed downward from a three-layer coextrusion device 2 equipped with φ extruders 1a, 1b, 1c and a multi-manifold type die. Each resin temperature is 180 ℃ for a) and 2 for b).
10 ° C, c) was 210 ° C, and the die temperature was 190 ° C.

The mold lip (width 2
mm, length 1m), temperature is about 170 cm
The sheet-shaped laminated body 4 at a temperature of 40 ° C. is drawn while being stretched by a cooling take-up roll 3 at a temperature of 40 ° C. which is rotating at a higher speed than the discharge speed of the resin, while a foamed polypropylene sheet (foaming ratio of 15 times) 6 is taken up by cooling. By introducing and pressurizing between the roll 3 and the laminating roll 8, the laminate 4 and the sheet 6 were laminated and integrated to obtain a covering sheet 7.

The thickness of the surface layer, the adhesive layer, the base material layer and the foam layer of the obtained laminating sheet 7 is 50 for each surface layer.
μm, the adhesive layer was 30 μm, the substrate layer was 400 μm, the foam layer was 3000 μm, and the lip cross-sectional area / the cross-sectional area of the obtained sheet = 5.

(Example 2) a) Surface layer material Thermoplastic urethane elastomer resin (manufactured by Asahi Glass Co., Ltd.,
PN3429-215, JIS-A hardness 85) 100 parts Elastic beads (UB15 (black) manufactured by Sekisui Plastics Co., Ltd., elastic beads of cross-linked polyurethane, average particle size 24 μm) 120 parts The above thermoplastic elastomer and elasticity The beads were extruded with a biaxial kneading extruder, cooled, and then pelletized with a soft cutter.

The set temperature of each part of the extruder was set under the following conditions. Screw rear part 150 ° C, middle part 165
C., front 175.degree. C., die 175.degree. b) Base material layer material Olefin-based elastomer (manufactured by Himont Co., Ltd., NK
S052P, resin elution amount at 0 ° C. by the cross fractionation method is 49.5% by weight of the total olefin elastomer amount, 80
The resin elution amount at 100 ° C to 100 ° C is 20.0% by weight of the total olefin elastomer, and the resin elution amount at 100 to 125 ° C is 5.5% by weight of the total olefin elastomer) c) Adhesive layer Acid modification Polypropylene (Mitsui Petrochemical Industry Co., Ltd.)
Manufactured by Admer QF551) The above three layers a), b) and c) were coextruded downward in the same manner as in Example 1. Each resin temperature is a) 180
℃, b) 210 ℃, c) 210 ℃, die temperature 19
It was 0 ° C. The apparatus used and other conditions were the same as in Example 1, but the temperature of the sheet-shaped laminate 4 was about 180 ° C. at a position about 15 cm directly below the mold lip.

The sheet-shaped laminate 4 is formed by the take-up roll 3.
Was expanded, and a foamed polypropylene sheet (foaming ratio 25 times) 6 was laminated in the same manner as in Example 1 to obtain a covering sheet 7. Surface layer 5 of the obtained covering sheet 7
When confirmed with an electron microscope, fine irregularities were obtained on the surface. The thickness of the surface layer, the adhesive layer, the base material layer, and the foam layer of the obtained covering sheet 7 is 30 μm for the surface layer, 10 μm for the adhesive layer, and 500 μm for the base material layer.
The foam layer was 2000 μm and the lip cross-sectional area / obtained sheet cross-sectional area = 7.

(Example 3) Thermoplastic urethane elastomer resin (manufactured by Nippon Miractolan Co., Ltd., E375MNAT, JIS-A hardness 75) 1
00 parts Elastic beads (Burnock CFB manufactured by Dainippon Ink Co., Ltd.)
101-40, polyurethane elastic beads, average particle size 8
μm) 60 parts The above thermoplastic elastomer and elastic beads were extruded by a biaxial kneading extruder, cooled, and then pelletized by a soft cutter.

The set temperature of each part of the extruder was set under the following conditions. Screw rear 140 ° C, middle 160
C, front 170 ° C, die 170 ° C. b) Base material layer material Olefin-based elastomer (manufactured by Himont Co., Ltd., NK
S025P, the resin elution amount at 0 ° C. by the cross fractionation method is 39.2% by weight of the total amount of the olefin elastomer, 80
Resin elution amount at -100 ° C is 8.4% by weight of total olefin elastomer, resin elution amount at 100-125 ° C is 32.3% by weight of total olefin elastomer) c) Adhesive layer Acid modification The thus-obtained SEBS (Tuftec M1943 manufactured by Asahi Kasei Kogyo Co., Ltd.) a), b) c) 3 layers were coextruded downward in the same manner as in Example 1. Each resin temperature is a) 180 ℃,
b) is 210 ° C, c) is 210 ° C, and die temperature is 190 ° C.
Met.

The sheet-like laminate thus obtained was stretched twice at 140 ° C. by a tenter stretching device to obtain a soft touch sheet. The surface layer of the obtained soft touch sheet was confirmed with an electron microscope, and fine irregularities were formed on the surface. Next, the base material layer surface of the soft touch sheet was heated to 150 ° C. and laminated on a foamed polypropylene sheet (foaming ratio 25 times) whose surface was heated to 170 ° C. to obtain a covering sheet.

The surface layer of the obtained covering sheet, the base material layer,
The thickness of the adhesive layer and the foam layer is 50μ for each surface layer.
m, the adhesive layer was 80 μm, the base material layer was 300 μm, and the foam layer was 2000 μm.

(Example 4) Thermoplastic urethane elastomer resin (manufactured by Asahi Glass Co., Ltd.,
PN3429-215, JIS-A hardness 85) 100 parts Elastic beads (UB15 (black) manufactured by Sekisui Plastics Co., Ltd., elastic beads of cross-linked polyurethane, average particle size 24 μm) 120 parts The above thermoplastic elastomer and elasticity The beads were extruded with a biaxial kneading extruder, cooled, and then pelletized with a soft cutter.

The set temperature of each part of the extruder was set under the following conditions. Screw rear 200 ° C, middle 210
C, front 210 ° C., die part 205 ° C. b) Base material layer-A material Olefin-based elastomer (Mitsui Petrochemical Industry Co., Ltd.)
Made by MILASTOMER 8030N) 80 parts of low density polyethylene pellet blended. b ') Base material layer-B material Olefin-based elastomer (manufactured by Highmont Co., Ltd., NK
S052P, resin elution amount at 0 ° C. by the cross fractionation method is 49.5% by weight of the total olefin elastomer amount, 80
The resin elution amount at 100 ° C to 100 ° C is 20.0% by weight of the total olefin elastomer, and the resin elution amount at 100 to 125 ° C is 5.5% by weight of the total olefin elastomer) c) Adhesive layer Acid modification Polypropylene (Mitsui Petrochemical Industry Co., Ltd.)
Manufactured by Admer QF551) 4 layers of the above a), b), b ′) and c) were coextruded. The temperature of each resin is 210 ℃ for a) and 210 ℃ for b).
b ') is 210 ℃, c) is 210 ℃, die temperature 190
° C. The apparatus used and other conditions were the same as in Example 1, but the temperature of the sheet-like laminate 4 at a position of about 15 cm just below the mold lip was about 160 ° C.

The sheet-shaped laminated body 4 by the take-up roll 3.
Was expanded, and a foamed polypropylene sheet (foaming ratio 25 times) 6 was laminated in the same manner as in Example 1 to obtain a covering sheet 7. Surface layer 5 of the obtained covering sheet 7
When confirmed with an electron microscope, fine irregularities were obtained on the surface. The thicknesses of the surface layer, the adhesive layer, the base material layer-A, the base material layer-B, and the foam layer of the obtained covering sheet 7 were 30 μm for the surface layer, 10 μm for the adhesive layer, and the base material layer, respectively.
A was 100 μm, base material layer-B was 400 μm, and foam layer was 2000 μm, and lip cross-sectional area / obtained sheet cross-sectional area = 7.

(Comparative Example 1) As a material constituting the surface layer, a thermoplastic urethane elastomer resin (manufactured by Nippon Miractolan Co., Ltd., E375MNAT, JIS-A hardness 7)
5) A covering sheet was obtained in the same manner as in Example 2 except that 100 parts were used. The obtained coating sheet had a lip cross-sectional area / sheet cross-sectional area = 10, and the elastomer sheet was stretched by the take-up roll, but it was confirmed by an electron microscope that no fine unevenness was obtained on the sheet surface. .

Comparative Example 2 a) Surface layer material Thermoplastic urethane elastomer resin (manufactured by Asahi Glass Co., Ltd.,
PN3429-215, JIS-A hardness 85) 100 parts Elastic beads (UB15 (black) manufactured by Sekisui Plastics Co., Ltd., elastic beads of cross-linked polyurethane, average particle size 24 μm) 120 parts The above thermoplastic elastomer and elasticity The beads were extruded with a biaxial kneading extruder, cooled, and then pelletized with a soft cutter.

The set temperature of each part in the extruder was set under the following conditions. Screw rear part 150 ° C, middle part 165
C., front 175.degree. C., die 175.degree. b) Substrate layer material Olefin-based elastomer (manufactured by Himont Co., Ltd., Catalloy KT-011P, resin elution amount by cross fractionation method at 0 ° C. is 2.5% by weight of total olefin-based elastomer amount, at 80 to 100 ° C. Resin elution amount is 67.6% by weight of the total olefin elastomer, resin elution amount at 100 to 125 ° C is 0% by weight of the total olefin elastomer) c) Adhesive layer Acid-modified polypropylene (Mitsui Petrochemical Industry Co., Ltd.
Manufactured by Admer QF551) The above three layers a), b) and c) were coextruded downward in the same manner as in Example 1. Each resin temperature is a) 180
℃, b) 210 ℃, c) 210 ℃, die temperature 19
It was 0 ° C. The apparatus used and other conditions were the same as in Example 1, but the temperature of the sheet-shaped laminate 4 was about 180 ° C. at a position about 15 cm directly below the mold lip.

The sheet-shaped laminate 4 is produced by the take-up roll 3.
Was expanded, and a foamed polypropylene sheet (foaming ratio: 15 times) 6 was laminated in the same manner as in Example 1 to obtain a covering sheet 7. Surface layer 5 of the obtained covering sheet 7
When confirmed with an electron microscope, fine irregularities were obtained on the surface. The thickness of the surface layer, the adhesive layer, the base material layer, and the foam layer of the obtained covering sheet 7 is 30 μm for the surface layer, 10 μm for the adhesive layer, and 500 μm for the base material layer.
The foam layer was 2000 μm and the lip cross-sectional area / obtained sheet cross-sectional area = 7.

The stretchability, uniform stretchability and gloss of the coating sheets obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were measured by the methods described below, and the results are shown in Table 1.

(Stretchability) 1 according to JIS K6301
The maximum elongation at 20 ° C was measured. (Uniform Stretchability) As shown in FIG. 11, vacuum molding is performed using a cylindrical vacuum molding die 28 having a vacuum hole 29, an inner diameter of the bottom surface of 100 mm, and an internal height of 40 mm, and the molded coating. Sheet 30 was obtained, and (the thickness A of the covering sheet at the bottom surface / the thickness B of the covering sheet at the corner portion) was measured to obtain uniform stretchability. (Gloss) According to JIS K7105, 60 ° specular gloss was measured.

[0072]

[Table 1]

(A) Method of Manufacturing Molded Article (A) -1 Injection Molding Using the coating sheets obtained in the above Examples 2 to 4 and Comparative Example 1, an injection molding machine shown in FIGS. Injection molding was carried out according to the method shown in (1) to obtain a molded product.

As shown in FIG. 2, this injection molding machine has a moving mold 10 having a molding recess 10a and a vent 10b for drawing a vacuum, and a fixed mold 12 having a projection 12a.
And the two dies 1 and 2 are arranged between the two dies 10, 12.
It is equipped with a hot platen 14 having holes for vacuum and compressed air and a resin injection machine 15 which can be moved from between 0 and 12 to the outside.

First, as shown in FIG. 3, the covering sheet 13 is arranged between the movable mold 10 and the heating plate 14, and the sheet 13 is heated while being sucked by the heating plate 14, The sheet 13 was vacuum-molded and / or pressure-molded and brought into close contact with the inner surface of the recess 10a of the mold 10 as shown in FIG. next,
The hot platen 14 was moved to the outside from between the molds 10 and 12, and then the moving mold 10 was moved to the fixed mold 12 side to close the molds, as shown in FIG. Next, the molding resin was injected from the resin injection machine 15 into the cavity formed by both molds 10 and 12 at a nozzle tip temperature of 230 ° C. The resin used is polypropylene (BC3, manufactured by Mitsubishi Petrochemical Co., Ltd.). After molding, the molded product was taken out of the mold to obtain an injection molded product. Table 2 shows the molding temperature of the sheet of each Example or Comparative Example, the appearance of the obtained molded product, and the soft touch feeling.

[0076]

[Table 2]

Soft touch feeling evaluation: 1 point: not soft touch: 2 points: slightly soft touch: 3 points: soft touch: 10 people evaluated, a total of 25 points or more was good, A score of 15 or less was considered as a defect.

Appearance evaluation Good ・ ・ ・ ・ Molding resin could not be seen through the covering sheet in the corners of the molded product Poor ・ ・ ・ ・ ・ ・ Molding resin was visible through the covering sheet in the corners of the molded product

(A) -2 Stamping Molding Using the coating sheets obtained in Example 1 and Comparative Example 2, stamping molding was carried out by the stamping molding apparatus shown in FIGS. 6 to 9 according to the following method. As shown in FIG. 6, this molding machine has an upper mold 20, a lower mold 21, and a resin injection machine 22. A convex portion 20a is provided on the lower surface of the upper die 20, and a concave portion 21a is provided on the upper surface of the lower die 21 at a position corresponding to the convex portion 20a. Further, a resin injection passage 21b is formed in the center of the lower mold 21, and the nozzle 22a of the resin injection machine 22 is adjacent to the resin injection passage 21b.

Then, first, as shown in FIG.
Between the upper mold 20 and the lower mold 21 which are heated at a time
The lower edge of the lower die 21 and the periphery of the sheet 23.
The enclosure was fixed with fixing pins 24. Then, as shown in FIG.
The molding resin 25 from the nozzle 22a of the resin injection machine 22
It was injected into the mold 21 at a nozzle tip temperature of 230 ° C. Molded tree
Polypropylene (Sumitomo Chemical Co., Ltd.) as the fat 25
Manufactured by AZ564) was used. Then, as shown in FIG.
Shape the sheet 23 by closing the mold 20 with a predetermined pressure
At the same time, the resin 25 is stamped and molded.
A molded product 27 having the shape shown was obtained. 9 and 10 L₁Is 20
0 mm, L₂Is 300 mm, L₃Is 30 mm, L _FourIs 150m
m, L_FiveIs 280 mm, L₆Is 60 mm, L₇Is 500 mm
is there. Preheating temperature of the sheet of each Example or Comparative Example,
Table 3 shows the appearance and soft touch feeling of the obtained molded product.

[0081]

[Table 3]

Soft Touch Feeling Evaluation 1 point ... No soft touch 2 points ... Somewhat soft touch 3 points ... Soft touch 10 people evaluated, and a total of 25 points or more was good, A score of 15 or less was considered as a defect.

Appearance evaluation: Good: Molding resin was not visible through the covering sheet at the corners of the molded product Poor: Molding resin was visible through the covering sheet at the corners of the molded product

[0084]

The coating sheet of the present invention has a base material layer, or at least one of two or more base material layers, which is an olefin elastomer having a predetermined resin elution amount. Has excellent stretchability, and particularly in the latter case, it has excellent uniform stretchability. Since the method for producing a molded article according to the present invention is configured as described above, only by coating the surface of the molded article, a soft touch feeling when touched and a matte appearance on the touch are imparted to the molded article. It is possible to easily obtain a covering sheet that can be obtained. When the coating sheet of the present invention is used, a molded product having a soft touch (suede) feel can be easily and inexpensively obtained by a molding method such as injection molding or stamping molding.

[0085]

[Brief description of drawings]

FIG. 1 is an explanatory view showing an example of an apparatus for carrying out a method for manufacturing a covering sheet according to the present invention.

FIG. 2 is an explanatory diagram of an injection molding machine used when a molded product is manufactured using the covering sheets obtained in Examples 1 to 4 and Comparative Examples 1 and 2.

FIG. 3 is an explanatory view illustrating a state before preforming a covering sheet by the injection molding machine of FIG.

FIG. 4 is an explanatory view illustrating a state in which a covering sheet is preformed by the injection molding machine of FIG.

FIG. 5 is an explanatory view illustrating a state in which a molding resin that will be a molded article body is injection molded.

FIG. 6 is an explanatory diagram of a stamping molding device used when a molded product is manufactured using the covering sheets obtained in Examples 1 to 4 and Comparative Examples 1 and 2.

7 is an explanatory view illustrating a state in which a covering sheet is set in a lower mold of the stamping molding device of FIG.

8 is an explanatory view illustrating a state in which a molding resin to be a molded product body is injected into a lower mold of a stamping molding device in which the covering sheet of FIG. 7 is set.

FIG. 9 is an explanatory view illustrating a state where the upper mold is closed with the lower mold injected with the molding resin of FIG. 8 and the stamping molding is performed.

FIG. 10 is a cross-sectional view of a molded product obtained by stamping molding.

FIG. 11 is a schematic cross-sectional view of a vacuum forming mold used when measuring the uniform stretchability of the coating sheets obtained in Examples 1 to 4 and Comparative Examples 1 and 2.

FIG. 12 is a schematic cross-sectional view of a covering sheet after being molded using a vacuum molding die.

[Explanation of symbols] 4 sheet-like laminate 5 surface layer 6 expanded polypropylene sheet (foam layer) 7 covering sheet

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location B29K 105: 16 B29L 9:00

Claims (4)

[Claims] 1. A surface layer comprising a thermoplastic elastomer and elastic fine particles as main components, and a resin elution amount by a cross fractionation method at 0 ° C. is 25 to 75% by weight of the total amount of olefinic elastomer, and a resin at 80 to 100 ° C. The elution amount is 1 to 45% by weight of the total olefin elastomer, and the resin elution amount at 100 to 125 ° C. is 1 to 4 of the total olefin elastomer.
A covering sheet comprising a base material layer containing an olefin-based elastomer as a main component and a foam layer in the range of 0% by weight, which are sequentially laminated. 2. A covering sheet comprising a surface layer mainly composed of a thermoplastic elastomer and elastic fine particles, a base material layer composed mainly of a thermoplastic resin and comprising two or more layers, and a foam layer, which are sequentially laminated. At least one layer constituting the base material layer has a resin elution amount at 0 ° C. by the cross fractionation method of 25 to 75% by weight of the total olefinic elastomer amount, and a resin elution amount at 80 to 100 ° C. 1 to 45% by weight of the amount of the olefin-based elastomer, and the resin elution amount at 100 to 125 ° C. is 1 to 40 of the amount of the total olefin-based elastomer.
A coating sheet comprising a composition containing an olefin-based elastomer as a main component in a range of weight%. 3. A composition constituting a surface layer containing a thermoplastic elastomer and elastic fine particles as main components, and the resin elution amount at 0 ° C. by the cross fractionation method is 25 to 75% by weight of the total olefinic elastomer amount, 80 The resin elution amount at ~ 100 ° C is 1 to 45% by weight of the total amount of the olefin elastomer,
The resin elution amount at 100 to 125 ° C. was in the range of 1 to 40% by weight based on the total amount of the olefin elastomer, and was obtained by coextrusion with the composition constituting the base material layer containing the olefin elastomer as the main component. The method for producing a covering sheet according to claim 1, wherein the foam layer is laminated on the base material layer side after stretching the sheet-shaped laminate. 4. A composition comprising a surface layer containing a thermoplastic elastomer and elastic fine particles as main components, and a composition comprising a thermoplastic resin as a main component and a base layer consisting of two or more layers. A method for producing a covering sheet, comprising: stretching a sheet-shaped laminate obtained by extrusion; and then laminating a foam layer on the base material layer side, wherein at least one layer constituting the base material layer is a cross fractionation method. The resin elution amount at 0 ° C. is 25 to 75% by weight of the total olefinic elastomer, and 80 to 10% by weight.
An olefin elastomer whose resin elution amount at 0 ° C. is in the range of 1 to 45% by weight of the total olefin elastomer, and resin elution amount at 100 to 125 ° C. is in the range of 1 to 40% by weight of the total olefin elastomer The method for producing a covering sheet according to claim 2, wherein the method comprises a composition containing the main component.