JP3260221B2 - Molded article covering sheet for stretch molding - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a formed feature cover sheet for stretching.

[0002]

2. Description of the Related Art A molded article covering sheet used for covering molded articles such as automobile interiors, office automation equipment, home appliances, stationery, sanitary goods, daily necessities, interior building materials, and the like has flexibility, abrasion resistance, and high feel. Need.

Heretofore, as a molded article covering sheet, a sheet obtained by laminating a foam as required on a polyvinyl chloride layer having a textured surface has been used, but there is a problem that the sheet lacks flexibility. .

Japanese Patent Publication No. 14023/1989 discloses a textured surface layer made of a blend of a polyolefin resin and a partially crosslinked product of an ethylene-α-olefin copolymer rubber made of polyethylene or polypropylene. There is disclosed a molded article covering sheet on which a foam is laminated. However, the molded article-covered sheet has a problem that it has flexibility but lacks abrasion resistance.

On the other hand, JP-A-2-41243 discloses that
There is disclosed a molded article-covered sheet comprising a base film having good moldability, and a coating of a mat paint obtained by adding a bead pigment to a vehicle of an ionizing radiation-curable resin.

However, since the surface layer is obtained by curing the ionizing radiation-curable resin by irradiation with an electron beam or ultraviolet rays, the surface layer lacks flexibility and does not have sufficient touch. Furthermore, since an organic solvent is used, there is a problem in hygiene.

[0007]

Formed <br/> form cover sheet for stretch forming of the 0008] The present invention has excellent flexibility, provides scuff resistance and excellent growth form cover sheet for stretching a high feeling of Is to do.

[0008]

The surface layer comprises a thermoplastic urethane elastomer and elastic fine particles. The thermoplastic urethane elastomer is not particularly limited, and a general one is used. Thermoplastic urethane elastomers exhibit rubber elasticity at room temperature, are plasticized at high temperatures, and can be subjected to various molding processes. In general, a rubber component (soft segment) having entropic elasticity in a molecule includes:
It is composed of polyether, polyester, or polycarbonate, and has a molecular constraint component (hard segment) for preventing plastic deformation composed of urethane bonds. The thermoplastic urethane elastomer may have a partial crosslink in the molecule as long as the thermoplastic urethane elastomer can be molded.

When the glass transition point of the thermoplastic urethane elastomer is low, the abrasion resistance of the obtained molded article-coated sheet is lowered, and when the glass transition point is high, the feel of the obtained molded article-coated sheet is lowered. Those having a temperature of 50 to 20 ° C are preferred.

On the other hand, if the weight average molecular weight of the thermoplastic urethane elastomer is large, the feel of the obtained molded article coated sheet is reduced, and if the weight average molecular weight is small, the abrasion resistance of the obtained molded article coated sheet is reduced. , 20,000-3,
M00000 is preferred.

Further, if the hardness of the thermoplastic urethane elastomer is low, the abrasion resistance of the obtained molded article-coated sheet is lowered, and if the hardness is high, the feel of the obtained molded article-coated sheet is lowered, and the JIS In A hardness, 50-98 is preferable.

[0012] As the thermoplastic urethane elastomer,
For example, from Japan Milactolan Co., Ltd.
375, sold by Asahi Glass Co., Ltd. under the trade name PN3429, and Dainippon Ink and Chemicals, Inc. under the trade name T7890.

The elastic fine particles are not particularly limited, as long as they are elastically recovered by pressing until the shape is deformed and then decompressed, and retain the original shape. Examples include elastic fine particles made of a urethane copolymer, polystyrene, a styrene-isoprene copolymer, and the like, and when the obtained molded article covering sheet may have a hard feel, a crosslinked polymethyl methacrylate or the like may be used. Elastic fine particles made of an inorganic material such as silica and mica are exemplified.

When the particle size of the elastic fine particles is large, it depends on the thickness of the surface layer.
Cracks may occur in the surface layer, and if the size is small, the feel of the obtained molded article-covered sheet may not be improved.

As used herein, the term “stretching” refers to stretching a molded article-covered sheet obtained by stretching.

On the other hand, if the amount of the elastic fine particles is large, cracks are generated in the surface layer when the sheet is stretched, and if the amount is small, the feel of the molded article-covered sheet obtained is not improved. The amount is limited to 15 to 150 parts by weight, preferably 30 to 150 parts by weight, based on 100 parts by weight of the urethane elastomer. Only one kind may be added, or two or more kinds may be mixed and added.

[0017] The surface layer composed of a thermoplastic urethane elastomer thickness may vary depending on the thickness of each layer, scuff resistance of <br/> formed form the covering sheet obtained, feel properties, considering the moldability, in general, 5 to 100 μm is preferred.

It is preferred that the surface layer is subjected to graining, since a leather pattern or the like is imparted to the obtained molded article-covered sheet and the appearance is improved.

The adhesive layer comprises an adhesive polymer and elastic fine particles. The adhesive polymer is not particularly limited, for example, chlorinated polyolefin, acid-modified styrene-butadiene-styrene copolymer, acid-modified styrene-
Examples include an ethylene-styrene copolymer, acid-modified polyethylene, and acid-modified polypropylene.

The elastic fine particles are not particularly limited, and the same fine particles as those used for the surface layer are used. Also, even if the same elastic fine particles used for the surface layer are used,
Different types may be used. The addition amount of the elastic fine particles is 1
If the amount is more than 50 parts by weight, when the molded article-covered sheet is stretched, a crack is generated in the adhesive layer, and a crack on the sheet surface or separation of the adhesive layer from the surface layer may occur.
On the other hand, if the amount is less than 15 parts by weight, the feel of the resulting molded article-covered sheet is not improved, so the amount is limited to 15 to 150 parts by weight based on 100 parts by weight of the adhesive polymer.

[0021] The thickness of the adhesive layer may vary depending on the thickness of each layer, scuff resistance of the formed features to be covered sheet obtained, feel properties, considering the moldability, in general, 5 to 100 [mu] m is preferred. Further, the resulting total thickness of the molded article coated surface layer of the sheet <br/> after enlargement extending the and adhesive layer, unevenness due to the elastic fine particles contained in the adhesive layer is obtained moldings cover sheet The particle size of the elastic fine particles contained in the adhesive layer is preferably equal to or smaller than the particle size, and particularly preferably equal to or smaller than 1/2 of the particle size, so as to be exhibited in the surface layer.

The base layer is made of a thermoplastic elastomer. The thermoplastic elastomer is not particularly limited, and a general one is used.

The thermoplastic elastomer exhibits rubber elasticity at normal temperature, and is plasticized at high temperature to enable various molding processes. Examples of the thermoplastic elastomer include polystyrene, polyvinyl chloride, and polyolefin elastomers. For example, in a polyolefin-based thermoplastic elastomer, a rubber component (soft segment) having entropy elasticity in a molecule includes polyethylene,
It is composed of a copolymer of ethylene and a small amount of a diene, or a partially crosslinked product thereof, and a molecular constraint component (hard segment) for preventing plastic deformation composed of polypropylene.

Further, the hardness of the thermoplastic elastomer varies depending on the feeling to be obtained, but is generally 50 to 98 in JIS A hardness.

[0025] The thickness of the base layer, varies depending on the thickness of each layer, scuff resistance of the formed features to be covered sheet obtained, feel properties, considering the moldability, in general, 200-300
0 μm is preferred.

The addition of a polyolefin-based resin such as polypropylene or linear low-density polyethylene to the base layer made of a thermoplastic elastomer can reduce the extrudability of the base layer and the formability of the resulting molded article-coated sheet. Is improved, which is preferable.

If the amount of the polyolefin-based resin is large, the rubber elasticity of the thermoplastic elastomer is reduced. If the amount is small, the moldability of the obtained molded article-covered sheet is reduced. Ten
~ 70 parts by weight are preferred.

The molded article-coated sheet is obtained by sequentially laminating a surface layer, an adhesive layer and a base material layer. Further, it is necessary to laminate a foam layer on the base material layer side of the molded article-coated sheet. This is suitable because the feel of the molded article-coated sheet is improved. The resin forming the foam layer is not particularly limited as long as it can be foamed. For example, phenol resin, polyimide, epoxy resin, polyurethane, polypropylene, polyolefin resin such as polyethylene, polystyrene, styrene-maleic anhydride Polystyrene resins such as copolymers, polyurethane resins such as polyurethane and polyether urethane, polyvinyl chloride resins such as soft polyvinyl chloride,
Thermoplastic polyurethane elastomers such as block copolymers with polyurethane as the hard segment and polyether, polyester, polycarbonate etc. as the soft segment, polypropylene with the hard segment and ethylene with the soft segment, and a small amount of diene component with ethylene (In order, EPM (ethylene-propylene-methylene bond), EP
DM (ethylene-propylene-diene methylene bond),
EPR (ethylene-propylene rubber)), those obtained by blending them, those partially cross-linked by further adding an organic peroxide, unsaturated hydroxy monomers, unsaturated Those graft-modified with carboxylic acid derivatives, other polyolefin thermoplastic elastomers such as butyl rubber-grafted polyethylene, polyester thermoplastic elastomers such as copolymers having polyester as a hard segment and polyether as a soft segment, and crosslinked And the like.

If the foaming ratio of the foam forming the foam layer is low, the cushioning property of the foam is not improved, and the feel of the molded article-covered sheet obtained is reduced. Is preferably 5 to 50 times.

[0030] The thickness of the foam varies depending on the thickness of each layer, scuff resistance of the formed features to be covered sheet obtained, feel properties, considering the moldability, in general, from 1000 to 300
0 μm is preferred.

When the adhesion between the base material layer and the foam layer is poor, an adhesive layer may be provided between the base material layer and the foam layer. As a polymer constituting such an adhesive layer,
For example, acid modification of the resin constituting the base layer or the foam layer,
Alternatively, a graft-modified polymer or the like may be used.

The surface layer, the base material layer, and the foam layer may include, if necessary, a colorant such as a pigment or a dye, an antioxidant, an ultraviolet absorber, or an ultraviolet light such as a hindered amine, as long as the physical properties are not impaired. You may add a stabilizer etc.

The colorant is not particularly restricted but includes, for example, titanium oxide, iron oxide, carbon black, pigments such as cyanine pigments and quinacridone pigments, azo dyes, anthraquinone dyes, indigoid dyes, and stilbene dyes. Dyes such as dyes, aluminum powder, nickel powder, gold powder, metal powder and the like.

The colorant varies depending on the use of the molded article-covered sheet, but is generally added in an amount of 2 to 100 parts by weight based on 100 parts by weight of the elastomer or resin constituting each layer.

In order to impart various functions to the obtained molded article-covered sheet, the surface layer, the base material layer, and the foam layer may be provided with a conductive material, if necessary, as long as the physical properties are not impaired. , Anti-condensation agent, photochromic compound, rust inhibitor,
A function-imparting agent such as an antibacterial agent, a fungicide, or a matting agent may be added.

The method for producing the molded article-coated sheet of the present invention is not particularly limited, and an example of the production method will be described below. It can be manufactured by stretching and cooling the laminated sheet obtained by the co-extrusion molding method. The co-extrusion molding method uses two or more extruders and merges the extruded resins into one. This is a method for producing a laminate. Such a method includes, for example, a multi-manifold method and a multi-throttle die method, and is not particularly limited.

The multi-manifold method is a method in which a plurality of manifolds are provided in a die and the respective layers are stacked in the die. With the multi-throttle die method, each layer is made to flow separately in the die, immediately after leaving the die,
This is a method of laminating each layer.

When two or more additives such as a surface layer are contained, they may be extruded while kneading with a twin-screw extruder, or may be separately melt-kneaded with a Banbury mixer or the like.
What was pelletized by a pelletizer or the like may be extruded by a single screw extruder.

In addition to the coextrusion molding method, a method in which a sheet-like material is manufactured for each layer, and this is pressure-bonded and integrated by a roll to manufacture a laminated sheet may be used.

Here, elongation means elongation of the laminated sheet in a molten state. By stretching the laminated sheet, fine irregularities are formed on the surface layer of the obtained molded article-covered sheet, and a high tactile sensation is exhibited.

If the elongation ratio is low, no irregularities will be formed on the surface, and the resulting molded article-coated sheet will have a reduced feel.
On the other hand, if it is too high, the laminated sheet may be damaged.
It is preferably 1 to 1.5 times.

The method of extending the molded article-covered sheet is not particularly limited, and includes, for example, a method in which a laminated sheet in a molten state is taken up by a take-up roll and extended.

The method of cooling is not particularly limited, and examples thereof include a method of cooling with a water-cooled take-off roll, a press with a cooled plate, and a cooling. The cooling temperature is usually lower than the softening temperature of the thermoplastic elastomer constituting the base material layer.

When the foam layer is laminated on the base material layer side of the molded article-covered sheet, the method of laminating the foam layer is not particularly limited. For example, an adhesive layer is added to the obtained molded article-coated sheet. Alternatively, a method may be used in which a foam is laminated when the laminated sheet is in a molten state after elongation of the laminated sheet, passed between a pair of rolls, and fused and integrated.

The surface layer of the molded article covering sheet of the present invention includes:
Since a thermoplastic urethane elastomer is used, it is excellent in extensibility, and even in a molded article having irregularities or curved surfaces, it can be adhered along the shape, and after elongation,
Even when the film thickness is reduced, a decrease in scratch resistance does not occur.

Further, by dispersing the elastic fine particles not only in the surface layer but also in the adhesive layer, even if the space between the elastic fine particles in the surface layer becomes narrow due to sheet stretching, Due to the elastic fine particles contained in the adhesive layer, irregularities can be expressed in the surface layer where the elastic fine particles are sparse, and the feel of the molded article covering sheet can be maintained.

[0046]

EXAMPLES In Examples 1 to 4, the following compositions were used for the surface layer, adhesive layer and substrate layer. Surface layer: 100 parts by weight of a thermoplastic urethane elastomer (trade name: PN3429, JISA hardness: 85, manufactured by Asahi Glass Industry Co., Ltd.) and elastic fine particles composed of acrylic acid ester (trade name: EAX15, manufactured by Sekisui Plastics Co., Ltd., average particle size: 1)
(5 μm) 30 parts by weight supplied to a twin-screw extruder (trade name: PCM30 extruder manufactured by Ikegai Iron and Steel Co., Ltd.) and kneaded at 185 ° C.

Adhesive layer Acid-modified polyolefin (Mitsui Petrochemical Co., Ltd.)
100 parts by weight of trade name QF551) and 30 parts by weight of elastic fine particles comprising acrylic acid ester (trade name: EAX15, average particle size: 15 μm, manufactured by Sekisui Plastics Co., Ltd.) (PCM30 extruder) and kneaded at 185 ° C.

Base material layer: 80 parts by weight of thermoplastic olefin elastomer (trade name: Elastomer 8030N, manufactured by Mitsui Petrochemical Industry Co., Ltd.); 30 parts by weight of thermoplastic olefin elastomer (elastomer: 5030N, manufactured by Mitsui Petrochemical Co., Ltd.) Parts, linear low-density polyethylene 10 parts by weight, polypropylene (trade name: F650, manufactured by Mitsui Petrochemical Industries, Ltd.)
The tumbler (trade name Tumbler M, manufactured by Matsui Seisakusho Co., Ltd.)
What was supplied to T-50 and pellet-blended.

Example 1 Multi-manifold type die, 30 mm in diameter held at 180 ° C., 210 ° C.
A three-layer co-extrusion apparatus having three extruders (trade name: UT-40-T, manufactured by Plastics Engineering Laboratory Co., Ltd.) having a diameter of 30 mm and a diameter of 50 mm maintained at 210 ° C. was used. .

The composition constituting the surface layer, the adhesive layer and the base layer was successively applied to the composition having a diameter of 30 m maintained at 180 ° C.
m, diameter 30 mm maintained at 210 ° C., and 21
The extruder was fed to three extruders having a diameter of 50 mm maintained at 0 ° C., and the obtained laminated sheet in a molten state was further subjected to 40 extruders.
Using a roll held at a temperature of 1.5 ° C., stretched and cooled 1.5 times, the thickness of the surface layer, the adhesive layer and the base material layer was 10,
A molded article covering sheet of 10, 400 μm was obtained.

The resulting molded article coated sheet, and further, 14
Maintained at 0 ° C, inner diameter is 100mm, depth is 30m
m, the corner R was vacuum-formed using a vacuum forming die having a diameter of 5 mm, and the obtained coated sheet, which is a small piece with a diameter of 90 mm on the bottom surface, was subjected to the following methods to evaluate the scratch resistance, appearance, and feel of the sheet. The measurement was performed, and the results are shown in Table 1.

(Scratch resistance) Scratch tester (Co., Ltd.)
A scratch resistance test was performed using a Toyo Seiki Seisakusho Co., Ltd. product name (Tavers clutch tester), the load at which the surface layer was slightly scratched was measured, and the value was defined as the scratch resistance.

(Appearance) The surface layers of the obtained molded article-covered sheet and stretched molded article-covered sheet were visually inspected for cracks.
If not, it was determined to be good.

(Tactile Sensitivity) Twenty people evaluated the following criteria, and the total was evaluated as good when 55 points or more, good when 30 to 54, and poor when 20 to 29 points. There is almost no tactile feel 1 point There is a little tactile feel 2 points There is a tactile feel 3 points

Example 2 A surface layer and a surface layer were prepared in the same manner as in Example 1 except that a rubber roll whose surface was embossed was held at 50 ° C. instead of the roll held at 40 ° C. The thickness of the adhesive layer and the base material layer is 10, 10,
A 400 μm molded article covering sheet was obtained.

In the same manner as in the obtained molded article-coated sheet and Example 1, the abrasion resistance, appearance and feel of the stretched and stretched molded article-coated sheet were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 3) On the substrate layer side of the laminated sheet in the molten state after elongation obtained in the same manner as in Example 1,
After laminating a foam made of polypropylene having a thickness of 3 mm (trade name: Softlon SP-V, manufactured by Sekisui Chemical Co., Ltd.), the laminate was passed through a pair of rolls adjusted to have a linear pressure of 5 kg. The thicknesses of the surface layer, the adhesive layer, the base material layer, and the foam layer are 10 μm, 10 μm, and 4 μm, respectively.
A molded article covering sheet on which a foam of 00 μm and 3 mm was laminated was obtained.

In the same manner as in Example 1 and the molded article-covered sheet on which the obtained foam was laminated, the stretched and coated sheet was further evaluated for scratch resistance, appearance, and feel.
The measurement was carried out using the same method as described above, and the results are shown in Table 1.

(Example 4) On the base layer side of the laminated sheet in the molten state after elongation obtained in the same manner as in Example 2,
After laminating a foam made of polypropylene having a thickness of 3 mm (trade name: Softlon SP-V, manufactured by Sekisui Chemical Co., Ltd.), the laminate was passed through a pair of rolls adjusted to have a linear pressure of 5 kg. The thicknesses of the surface layer, the adhesive layer, the base material layer, and the foam layer are 10 μm, 10 μm, and 4 μm, respectively.
A molded article covering sheet on which a foam of 00 μm and 3 mm was laminated was obtained.

[0060] In the same manner as in Example 1 and the molded article-covered sheet on which the obtained foam was laminated, the stretched and stretched-molded article-coated sheet was further evaluated for scratch resistance, appearance, and feel.
The measurement was carried out using the same method as described above, and the results are shown in Table 1.

In Examples 5 to 8, the following compositions were used for the surface layer, the adhesive layer and the substrate layer. Surface layer: 100 parts by weight of a thermoplastic urethane elastomer (trade name: PN3429, JISA hardness: 85, manufactured by Asahi Glass Industry Co., Ltd.) and elastic fine particles composed of cross-linked urethane (trade name: UB15, average particle size 15 μm, manufactured by Sekisui Chemical Co., Ltd.)
m) A 20-screw extruder (trade name: PCM30 extruder manufactured by Ikegai Iron & Steel Co., Ltd.), which was kneaded at 185 ° C.

Adhesive layer Acid-modified polyolefin (Mitsui Petrochemical Industry Co., Ltd.)
100 parts by weight of trade name QF551) and 20 parts by weight of elastic fine particles composed of cross-linked urethane (trade name: UB15, average particle size: 15 μm, manufactured by Sekisui Plastics Co., Ltd.)
Twin screw extruder (PCM30 extruder manufactured by Ikegai Iron and Steel Company)
And kneaded at 185 ° C.

Base material layer: 80 parts by weight of thermoplastic olefin elastomer (trade name: Elastomer 8030N, manufactured by Mitsui Petrochemical Industry Co., Ltd.); 30 parts by weight of thermoplastic olefin elastomer (elastomer: 5030N, manufactured by Mitsui Petrochemical Industry Co., Ltd.) Parts, linear low-density polyethylene 10 parts by weight, polypropylene (trade name: F650, manufactured by Mitsui Petrochemical Industries, Ltd.)
The tumbler (trade name Tumbler M, manufactured by Matsui Seisakusho Co., Ltd.)
What was supplied to T-50 and pellet-blended.

Examples 5 to 8 Except that the compositions constituting the surface layer, the adhesive layer and the base material layer were changed to the above-mentioned compositions,
In the case of Example 5, it is the same as Example 1 in the case of Example 6, the example 2 in the case of Example 6, the example 3 in the case of Example 7, and the example 4 in the case of Example 8, in the same manner as in Example 4. Done,
The scratch resistance, appearance, and feel of the stretch-coated body-coated sheet were measured using the same methods as in Example 1, and the results are shown in Table 1.

Comparative Example 1 The three-layer co-extrusion apparatus used in Example 1 was used. The composition constituting the base material layer used in Example 1 was treated at a temperature of 210 ° C. with a diameter of 50 m.
m and extruded 1.5 times using a rubber roll whose surface is embossed, which was maintained at 50 ° C., and then melted. After laminating a foam (made of Sekisui Chemical Co., Ltd., trade name: Softlon SP-V) made of polypropylene with a thickness of 3 mm on the sheet-like material, the linear pressure was adjusted to 5 kg. The sheet was passed through a pair of rolls and fused and integrated to obtain a coated sheet having a thickness of 400 μm and a thickness of 3 mm, respectively, of the base material layer and the foam layer.

In the same manner as in the obtained coated sheet and Example 1, the stretched coated sheet was further subjected to abrasion resistance,
The appearance and feel were measured using the same method as in Example 1,
The results are shown in Table 1.

Comparative Example 2 The three-layer co-extrusion apparatus used in Example 1 was used. The composition constituting the base material layer used in Example 1 was treated at a temperature of 210 ° C. with a diameter of 50 m.
m, and the obtained sheet in the molten state is further stretched 1.5 times using a rubber roll whose surface is embossed at 50 ° C., and cooled, On the base material layer, paint (Cenosoft Co., Ltd. product name Senosoft)
II) was applied so as to have a film thickness of 60 μm, and was heated and cured at 80 ° C. for 30 minutes to obtain coated sheets having a coating film thickness and a substrate layer thickness of 6,400 μm, respectively.

[0068]

[Table 1]

[0069]

The structure of the molded article-covered sheet of the present invention is as described above, and the molded article-coated sheet is excellent in flexibility, scratch resistance and feel.

Claims (1)

(57) [Claims] [Claim 1] After the urethane elastomer 100 parts by weight及beauty shape is pressurized to be deformed when the pressure solutions based on
Surface layer made of elastic particles 15 to 150 parts by weight of the elasticity of the shape recovery, varying the adhesive polymer 100 parts by weight及beauty shape
After pressurizing until shape is released, elasticity recovers to the original shape when decompressed
Adhesive layer made of elastic particles 15 to 150 parts by weight,
And a base layer made of a thermoplastic elastomer, sequentially laminated, wherein the stretching molding formed form the cover sheet you by comprising.