JPH09295377A - Laminate - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide a laminate which can be produced by co-extrusion, has excellent surface appearance, and has excellent appearance even after molding. SOLUTION: A surface layer containing a thermoplastic resin elastomer and elastic fine particles, an adhesive layer containing a thermoplastic resin as a main component, and a base material layer containing a thermoplastic resin as a main component are laminated by coextrusion. In the laminate, the elastic fine particles having a ratio of the particle diameter of the elastic fine particles to the thickness of the surface layer (particle diameter of the elastic fine particles / surface layer thickness) in the range of 0.1 to 1 are 50% of all the elastic fine particles. A layered product characterized by being blended in a proportion of at least% by weight.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate suitable for coating the surface of, for example, a plastic molding or a metal molding. INDUSTRIAL APPLICABILITY The layered product of the present invention is, for example, an interior material for automobiles, a housing for OA equipment / home appliances, a stationery, a sanitary article, a daily article or a molded article used for building material interior, etc. Used for coating.

[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, paints that use organic solvents require a booth to dry the solvent, the cost of electricity and fuel required for drying is high, and the work environment is prone to pollution and safety and health problems. there were.

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, in the covering sheet described in JP-A-6-246812, when the film is formed by coextrusion, the outer surface of the surface layer is scratched or the surface layer has a thickness. There is a problem that unevenness occurs and the appearance quality deteriorates. Further, when the surface of the coating sheet is embossed, the outer surface is not noticeable due to the formation of the embossed pattern, but when the coating sheet is further post-processed, particularly when heated and vacuum formed. However, there is a problem that the appearance of the surface is deteriorated.

The object of the present invention is to produce by coextrusion,
Another object of the present invention is to provide a laminate which is less likely to cause scratches and uneven thickness in the surface layer and has excellent appearance even after the post-processing molding.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, the deterioration of the appearance property of the surface of the laminate obtained by coextrusion is caused by the portion where each layer joins during coextrusion. From the to the lip portion of the mold, local elongation occurs between the elastic fine particles in the surface layer due to the shear rate of the base material layer, and it is considered that it may be because the thermoplastic elastomer becomes a thin film. As a result of various studies on methods for suppressing local elongation, the present invention has been accomplished.

That is, the invention according to claim 1 is a surface layer containing a thermoplastic resin elastomer and elastic fine particles,
In a laminate in which an adhesive layer containing a thermoplastic resin as a main component and a base material layer containing a thermoplastic resin as a main component are laminated by coextrusion, the particle diameter of the elastic fine particles and the thickness of the surface layer Ratio (particle size of elastic fine particles / thickness of surface layer) is 0.1
The elastic fine particles in the range of 1 to 1 are blended in a proportion of 50% by weight or more in the total elastic fine particles.

Further, according to the present invention, as described in claim 2, a foam layer may be further laminated on the side of the base material layer of the laminated body, whereby the cushioning property and the soft touch feeling are effective. Can be raised to

The details of the laminate 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 the laminate of the present invention is used as a covering sheet having an excellent soft touch feeling, and when scratch resistance and abrasion resistance are more strongly required, 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.

The above-mentioned thermoplastic urethane elastomer generally has polyether, polyester or polycarbonate as a soft segment having entropy elasticity in the molecule, and is constituted by a urethane bond as a hard segment for preventing plastic modification. Have segments. The thermoplastic urethane elastomer provides the surface layer with excellent scratch resistance. 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
It is preferably in the range of 0. 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 laminate 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 polyurethane, acrylic resin, acrylic-
Examples thereof include those made of urethane resin, polystyrene, styrene-isoprene copolymer and the like, and those which do not melt at the time of melt kneading and molding of the thermoplastic resin elastomer 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.

In the present invention, the ratio of the diameter of the elastic fine particles to the thickness of the surface layer (hereinafter referred to as particle diameter ratio) is 0.1 to 0.1.
Elastic fine particles in the range of 1 are 50% by weight in all elastic fine particles.
It is mixed in the above proportions. When 50% by weight or more of the particles having a particle diameter ratio of less than 0.1 is included, the soft touch feeling is not sufficiently exhibited by the surface layer, and a good contact feeling cannot be provided. This is not necessarily clear, but the elastic fine particles form irregularities on the surface of the thermoplastic elastomer, and the presence of the elastic fine particles imparts a soft touch feeling.
It is considered that it is difficult to give a good soft touch feeling.

On the other hand, when 50% by weight or more of the elastic fine particles having the particle diameter ratio of more than 1 are blended, the above-mentioned scratches are likely to occur on the surface. Further, when the content of the particle diameter ratio is less than 50% by weight in the elastic fine particles, the elongation of the thermoplastic elastomer between the elastic fine particles becomes large, and the laminate and the laminate are post-processed. Especially, after the vacuum forming, the surface is easily scratched. Preferably, the elastic fine particles having the particle diameter ratio in the range of 0.1 to 1 are blended so as to account for 60% by weight of the total elastic fine particles.

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 contrary, when the average particle size of the elastic fine particles is large, the surface layer is liable to be scratched, and the appearance of the laminate or after post-processing, especially after vacuum forming may be deteriorated. 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 3.
The range is 0 μm.

Further, when the content of the elastic fine particles is small, it becomes difficult to give a good soft touch feeling to the surface of the surface layer, and conversely, when the content is large, the spreadability of the surface layer during co-extrusion is poor. And the surface layer may be broken.
Therefore, the elastic fine particles are the thermoplastic resin elastomer 10
The content is preferably 80 to 130 parts by weight, more preferably 80 to 120 parts by weight, based on 0 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

As the thermoplastic resin elastomer forming the base layer, the thermoplastic resin elastomer used for forming the surface layer can be used. However, as the thermoplastic resin elastomer constituting the base material layer, a thermoplastic 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 thermoplastic olefin-based 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-based 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-based elastomer, and 80 to 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 layer is preferably within the above range is as follows.

That is, when the resin elution amount at 0 ° C. is small, the obtained laminated sheet is hard and the soft touch feeling is deteriorated, and when it is large, the heat resistance of the base material layer is deteriorated. 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. is small, the stretchability of the obtained laminated sheet is lowered, 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 ".

Further, 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, since the stretchability and soft touch feeling of the obtained laminate can be enhanced.

Adhesive Layer In the laminate of the present invention, an adhesive layer for adhering the surface layer and the base material layer is provided between the surface layer and the base material layer.

As the resin constituting the adhesive layer, a polymer or oligomer having compatibility with the resin constituting 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.

The resin constituting the adhesive layer is preferably a resin having a carboxylic acid group among the above functional groups, and the acid value of the polymer or oligomer is 1 to 30 mgKOH / g as the amount of carboxylic acid. Is preferred.
When the resin constituting the adhesive layer is a polymer, its molecular weight (weight average molecular weight) is not particularly limited,
Generally, it is 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, which can suppress an increase in gloss during thermoforming.

When a thermoplastic polyolefin elastomer is used as the base material layer, the resin constituting the adhesive layer is chlorinated polyolefin, ionomer resin, acid-modified polyolefin resin, acid-modified styrene- A butadiene-styrene copolymer, an acid-modified styrene-ethylene / butylene-styrene copolymer, or the like is used, and in particular, a polymer which itself exhibits properties as an elastomer (for example, JISA hardness of about 50 to 98) is preferable. .

Foam layer As described in claim 2, a foam layer may be further laminated on the base material layer side in the laminate of the present invention, whereby a foam layer is formed.
Cushioning 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, good cushioning properties and soft touch feeling may not be obtained, and if it is too high, the foam cells are likely to be crushed.
0-40 times is desirable.

Other Addable Components The laminate of the present invention comprises the above surface layer, base material layer, and adhesive layer,
Although it includes a foam layer added as necessary,
In each of these layers, various kinds of colorants, antioxidants, ultraviolet absorbers, antistatic agents, conductive materials, anti-condensation agents, photochromic compounds, rust preventives, deodorants, fungicides, etc. can be added as necessary. The additive may be contained in a range that does not impair the object of the present invention.

As the 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 laminate of the present invention may be subjected to patterning such as printing in order to enhance 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 Laminate The laminate of the present invention can be obtained by coextruding the surface layer, the adhesive layer and the base material layer.

The coextrusion 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. Examples of the resin joining method in this coextrusion molding include a feed block method, a multi-manifold method, and a method in which both of them are combined. 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. As a mold used for film formation, a T-die method or a ○ die used for inflation molding can be used. That is, a die that can stack the surface layer, the adhesive layer, and the base material layer in the mold can be used.

The thermoplastic elastomer constituting the surface layer and the elastic fine particles are mixed, then melt-kneaded and extruded by using a twin-screw type extruder, and then extruded from another extruder together with the resin to be the base material layer. 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 present invention, as described in claim 2, a foam layer may be laminated on the laminate obtained as described above and having an excellent soft touch feeling. In this case, the foam is laminated on the laminate. As a method for laminating a synthetic resin foam to be a layer, there is, for example, coextrusion, 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, embossing may be provided on the surface of the laminating roll, and the surface may be embossed simultaneously with the laminating.

When the foam layer is laminated by extrusion laminating and the adhesion between the base material layer and the foam layer is not sufficient, the surface of the foam layer is heated by a far infrared heater, or the foam layer is previously prepared. It is preferable to provide a primer layer or an adhesive layer on the surface of the layer, or to provide an adhesive layer by coextrusion on the side on which the foam layer is further laminated on the base material layer.

As a material for forming the primer layer, for example, when a base material 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. The adhesive layer may be made of the same material as the above-mentioned adhesive layer.

Thickness of Laminate The thickness of the laminate of the present invention obtained as described above varies depending on the constitution of the laminate, but in consideration of the soft touch feeling, generally, the surface layer and the adhesive layer are 5-100μ
m, and the base material layer has a thickness of 100 to 3000 μm. In addition, the foam layer provided as necessary is 1000
~ 4000 μm, adhesive layer or primer layer is 5 ~
It is set to about 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 Product Using Laminate of the Present Invention A molded product using the laminate of the present invention is produced, for example, as follows. 1) The laminate 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 laminated body is attached to the surface of the molded article body. That is, the surface layer of the laminate is introduced into the mold so as to face the surface side of the obtained molded product, and in the case of stamping molding, the mold resin is introduced into the mold and then the mold is closed. After closing the mold, the resin is introduced to obtain a molded product.

2) The laminate 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 can be obtained, and then the molded product body is formed. The resin is molded by injection molding or stamping molding, and at the same time, the laminate is attached to the surface of the molded article 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) After forming the laminate by thermoforming, it is 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 performed using a mold for molding a resin such as injection molding, or may be performed using another mold for sheet molding.

As the resin for the above-mentioned molded article, any material can be used as long as it is a usual molding material. For example, AB
S (acrylonitrile-butadiene-styrene copolymer), polyethylene, polypropylene, polyvinyl chloride, polystyrene, polycarbonate, acrylic resin,
Examples thereof include polyether imide, polyphenylene sulfide, nylon, the above-mentioned thermoplastic elastomer, and a material obtained by mixing these materials with glass fiber or an inorganic filler.

Since the laminate of the present invention imparts a soft touch feeling and a matte feeling to the product surface, it can be suitably used in a place where a person can easily touch it, and is also 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.

Action In the present invention, the surface layer is constituted so as to include the thermoplastic resin elastomer and the elastic fine particles, and the elastic fine particles having the particle diameter ratio in the range of 0.1 to 1 have the total elasticity. Since it is blended in a proportion of 50% by weight or more in the fine particles, elastic fine particles capable of expressing a soft touch feeling are present on the surface of the surface layer in an appropriate proportion. Therefore, when the laminate is obtained by coextrusion, the surface layer is less likely to be scratched and is excellent in soft touch feeling. Furthermore, the above-mentioned laminated body also maintains good appearance properties after vacuum forming.

Further, since the above-mentioned laminate is obtained by coextrusion, it is not necessary to provide a solvent type top coat layer, and it is difficult for the working environment to be contaminated.

[0063]

EXAMPLES The present invention will be made clear by describing non-limiting examples and comparative examples of the present invention. In addition,
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 (average particle size 10 μm)
Those in the range of 1 to 1 were 68% by weight of the whole, and those in excess of 1 were blended in the ratio of 32% by weight. ) And 2
The mixture was extruded with a shaft 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
Resin elution amount at ~ 125 ° C is 5.5% by weight of the total olefin elastomer amount)

A laminate sheet was prepared using the above materials and the three-layer coextrusion apparatus shown in FIG. The three-layer coextrusion apparatus 1 shown in FIG. 1 is equipped with 50 mm diameter, 40 mm diameter and 40 mm diameter extruders 1a to 1c manufactured by Plastic Engineering Laboratory Co., Ltd., and a feed block type die 2, respectively. . The surface layer material was supplied to the extruder 1a, the substrate layer material was supplied to the extruder 1b, and the adhesive layer material was supplied to the extruder 1c. The respective resin temperatures were 180 ° C. for the surface layer material, 210 ° C. for the base material layer, 200 ° C. for the adhesive layer material, and 190 ° C. for the die 2.

Under the above conditions, the laminate sheet 3 was extruded from the coextrusion device 1. Next, it was passed through an embossing roll 5 and a pinch roll 6 and cooled to obtain a pinched laminate sheet and an unpinched laminate sheet.

When the surface layer of the non-pinch laminate sheet obtained as described above was observed with an electron microscope,
Fine irregularities were formed on the surface. The thicknesses of the surface layer, the adhesive layer and the base material layer of the obtained unpinched laminate sheet were as follows: surface layer = 10 μm, adhesive layer = 20 μm, respectively.
m, substrate layer = 400 μm, and (lip cross-sectional area / obtained laminate sheet cross-sectional area) = 4.

Example 2 As the elastic fine particles, those having the above-mentioned particle diameter ratio in the range of 0.1 to 1 in an amount of 89% by weight, and those containing more than 1 in the ratio of 11% by weight were used, and the thickness of the surface layer. Is 16 μm,
Further, a laminate sheet was obtained in the same manner as in Example 1 except that a polypropylene foam layer (manufactured by Sekisui Chemical Co., Ltd., trade name: Softlon SPH2703) was laminated on the base material layer side by thermal lamination. .

Example 3 As the elastic fine particles, those having the above-mentioned particle diameter ratio in the range of 0.1 to 1 were blended in a proportion of 52% by weight, and those having a particle diameter ratio of more than 1 in the ratio of 48% by weight were used. Layer thickness 8 μm
A laminate sheet was obtained in the same manner as in Example 2 except for the above.

Example 4 As elastic fine particles, 90 parts of elastic beads made of urethane resin (manufactured by Sekisui Plastics Co., Ltd., trade name: UB102, average particle diameter 26 μm) (where the particle diameter ratio is 0.1 to 1)
58% by weight in the range of 1 and 42 in excess of 1
A laminate sheet was obtained in the same manner as in Example 2 except that the mixture was used in the proportion of 1% by weight) and the thickness of the surface layer was 30 μm.

Example 5 As elastic fine particles, 90 parts of elastic beads made of acrylic resin (manufactured by Sekisui Plastics Co., Ltd., trade name: BM30X-5, average particle diameter 5 μm) (where the particle diameter ratio is 0.1 ~
84% by weight in the range of 1 and 1 in the range of more than 1
A laminate sheet was obtained in the same manner as in Example 2 except that the mixture was added at a ratio of 6% by weight) and the thickness of the surface layer was 8 μm.

Comparative Example 1 As the elastic fine particles, those having the above-mentioned particle diameter ratio in the range of 0.1 to 1 were blended in a proportion of 39% by weight, and those exceeding 1 were blended in a ratio of 61% by weight, and A laminate sheet was obtained in the same manner as in Example 2 except that the thickness of the surface layer was 8 μm.

Comparative Example 2 As elastic fine particles, those having the above-mentioned particle diameter ratio in the range of 0.1 to 1 were blended in a proportion of 20% by weight, and those exceeding 1 were blended in a proportion of 80% by weight, and A laminate sheet was obtained in the same manner as in Example 2 except that the thickness of the surface layer was 6 μm.

Comparative Example 3 As the elastic fine particles, those having the above particle diameter ratio in the range of 0.1 to 1 are 37% by weight, and those having the particle diameter ratio less than 0.1 are 63% by weight.
A laminate sheet was obtained in the same manner as in Example 5, except that the mixture was used in the proportion of 1 and the surface layer had a thickness of 50 μm.

In the above Examples 1 to 5 and Comparative Examples 1 to 3, the unpinched laminate sheet and the appearance, soft-touch feeling and heating vacuum formability after heating and vacuum forming using the laminate sheet are described below. It evaluated by the method. The results are shown in Table 1 below together with the average particle size of the elastic fine particles in the surface layer of each laminate sheet, the thickness of the surface layer, and the above particle size ratio.

(1) The appearance (dullness) was evaluated based on the following evaluation symbols. Good ... No scratches on the surface layer. Good: Slight scratches are present on the surface layer, but not noticeable. Poor ... Scratch is clearly seen in the surface layer.

(2) Regarding the soft touch feeling,
It was evaluated by a sensory test based on the feeling when the following panelists touched the surface layer of the laminate with their hands. Panelists: 20 men and women aged 15-40 years. Evaluation point: 3 A soft feel is obtained. 2 ... Slightly soft feel is obtained. 1 ... Soft feel cannot be obtained. A panel having a total of 50 or more evaluation points was rated as good, and a panel with a total rating of 50 or less was rated as bad, and the results are shown in Table 1 below.

(3) Heating vacuum forming ... The front and back surfaces of the laminated body are heated to a temperature of 120 ° C. by a far infrared heater, and vacuum forming is performed using a cylindrical vacuum forming die 11 shown in FIG. It was 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. The above vacuum forming mold 28
FIG. 3 shows a cross section of a cylindrical molded product formed by using. That is, the laminate sheet 3 was molded to obtain the molded product 13 shown in FIG.

The appearance properties (presence or absence of scratches) were evaluated in the same manner as above, even after the above heating vacuum forming.

[0081]

[Table 1]

As is apparent from Table 1, in Comparative Examples 1 and 2, the elastic fine particles having a particle diameter ratio of 0.1 to 1 were as low as 39% by weight and 20% by weight. The appearance of the sheet was poor, and the appearance was poor even after heating and vacuum forming.

In Comparative Example 3, the particle size ratio is 0.1 to 0.1.
Since the elastic fine particles in the range of 1 were 37% by weight and the content of less than 0.1 was 63% by weight, the appearance was good, but the soft touch feeling was poor.

On the other hand, in Examples 1 to 5, the elastic fine particles having a particle diameter ratio in the range of 0.1 to 1 accounted for 5 of the entire elastic fine particles.
Since it was blended in an amount of 2% by weight or more, the appearance was good and the soft touch feeling was good both at the stage of the laminate sheet and after vacuum forming.

[0085]

As described above, in the layered product of the present invention, in the elastic fine particles blended in the surface layer, the elastic fine particles having a particle diameter ratio in the range of 0.1 to 1 are included in the total elastic fine particles.
Since it is blended in an amount of 0% by weight or more, it is possible to provide a laminate that not only has less scratches on the surface layer of the laminate during coextrusion film formation, but also has a good appearance even after heating and vacuum forming. . Therefore, when the laminate of the present invention is used for coating the surface of a product such as a synthetic resin or a metal, it becomes possible to provide the surface of the molded product with a good soft touch feeling and appearance.

Further, since the laminate of the present invention is manufactured by the coextrusion method, the steps in manufacturing can be simplified and there is no fear of contaminating the working environment. Therefore, it is possible to inexpensively supply a product excellent in soft touch feeling and appearance.

When the foam layer is further laminated on the base material layer as described in claim 2, it is possible to obtain a laminate excellent in cushioning property and soft touch feeling.

[Brief description of drawings]

FIG. 1 is a sectional view for explaining an example of an apparatus for manufacturing a laminate of the present invention.

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

FIG. 3 is a cross-sectional view of a laminated body 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 ... Laminate sheet 4 ... Cooling take-up roll 5,6 ... Roll 11 ... Vacuum forming die 12 ... Vacuum hole 13 ... Formed body made of laminated sheet

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Claims (2)

[Claims] 1. A surface layer containing a thermoplastic resin elastomer and elastic fine particles, an adhesive layer containing a thermoplastic resin as a main component, and a base material layer containing a thermoplastic resin as a main component are laminated by coextrusion. In the laminated body, the elastic fine particles having a ratio of the particle diameter of the elastic fine particles to the thickness of the surface layer (particle diameter of the elastic fine particles / surface layer thickness) in the range of 0.1 to 1 are all elastic fine particles. A laminated body characterized by being mixed in a proportion of 50% by weight or more. 2. The laminate according to claim 1, further comprising a foam layer laminated on the base material layer side.