JPH07304146A - Coating sheet - Google Patents

Abstract

PURPOSE:To provide a coating sheet which is comprised of non-PVC resin, superior in contact feeling having favorable soft touch of a suede tone and marring resistance and can be laminated beautifully even to the complicated surface of housing and others such as trim of a motor car or an office automation equipment or household appliance. CONSTITUTION:A surface layer which is constituted of 0.1-30 pts.wt. silicone resin and 30-150 pts.wt. elastic particles and a base layer consisting mainly of a thermoplastic elastomer is laminated to a 100 pts.wt. thermoplastic elastomer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a covering sheet.

[0002]

2. Description of the Related Art Conventionally, as such a covering sheet, a sheet in which a polyolefin resin foam sheet is laminated on a soft vinyl chloride resin sheet having a textured surface has been used.

However, the sheet using the above-mentioned soft vinyl chloride resin tends to lose its flexibility over time, and
The odor of the plasticizer contained in the material also impairs the feeling of comfort during use, and in addition, the complex of soft vinyl chloride resin and other materials requires complicated steps due to the difference in polarity between the resins. is there. Due to the above-mentioned reasons, recently, for example, a coating sheet in which a surface-textured polyolefin-based thermoplastic elastomer layer and a polyethylene or polypropylene foam layer described in JP-B-1-14023 is laminated. Proposed.

However, the sheet using the polyolefin resin elastomer described in JP-B-1-14023 impairs the scratch resistance due to the contact resistance imparted to the surface of the sheet to improve the feel. In addition, there is a mechanical limitation in giving the surface unevenness by embossing or the like, and it is difficult to give a sufficient matte or suede-like feel.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to eliminate the above-mentioned drawbacks of the conventional products, and has sufficient scratch resistance and suede-like touch, but also has excellent scratch resistance. Moreover, it is an object of the present invention to provide a covering sheet which can be attached beautifully along a curved surface or a complicated uneven portion along its shape.

[0006]

SUMMARY OF THE INVENTION The present invention provides a thermoplastic elastomer and a surface layer comprising 0.1 to 30 parts by weight of a silicone resin and 30 to 150 parts by weight of elastic fine particles to 100 parts by weight of a thermoplastic urethane elastomer. The gist of the present invention is a covering sheet having a base material layer as a main component laminated.

The thermoplastic urethane elastomer in the present invention has rubber-like elasticity at normal temperature and is plasticized at high temperature. Generally, as a rubber component (soft segment) having entropy elasticity in the molecule, polyether polyester, It has a segment composed of urethane bond as a segment of polycarbonate or the like, and a molecular restraint component (hard segment) for preventing plastic deformation. Although it may have a partially crosslinked structure in the molecule, it does not have a wide range of three-dimensional network structure.

The thermoplastic urethane elastomer having a glass transition point (Tg) in the range of -50 to 20 ° C can be preferably used. If the Tg is less than -50 ° C, the resulting sheet has insufficient scratch resistance, and if it exceeds 20 ° C, the sheet becomes hard and a soft feel cannot be obtained.

The thermoplastic urethane elastomer having a weight average molecular weight in the range of 20,000 to 3,000,000 can be preferably used. When the weight average molecular weight is less than 20,000, the rigidity of the obtained sheet decreases,
When it exceeds 3,000,000, the flexibility is impaired, and neither of them gives a desirable result. The above-described evaluation of flexibility is also made by the A hardness defined in JIS K7215, and the one having the A hardness in the range of 50 to 98 gives preferable performance. Examples of the thermoplastic urethane elastomer include U-fine P, manufactured by Asahi Glass Co., Ltd.
N3429, manufactured by Nippon Miractolan Co., Ltd., trade name Miractolan E990P, manufactured by Dainippon Ink and Chemicals, trade name T789
0 and the like.

The elastic fine particles in the present invention have the property of elastically recovering rapidly after being deformed under pressure at room temperature and then released, and are made of, for example, polyurethane, acrylic-urethane resin, styrene-isoprene copolymer and the like. Is mentioned. Further, the shape thereof may be a spherical shape, or may be a random shape obtained by means such as freeze pulverization.

With respect to the size of the elastic fine particles, the maximum value of the particle size distribution (hereinafter abbreviated as average particle size) is 1 to 100.
Those in the range of μm are desirable, and the average particle size is 1μ.
If it is less than m, fine irregularities generated on the surface of the obtained sheet do not clearly appear in a suede tone, and a so-called soft touch feeling cannot be obtained. Further, when the thickness exceeds 100 μm, the surface of the obtained sheet becomes a rough surface, and in particular, the sheet surface is likely to be cracked in the stretching process carried out to improve the surface property in the sheet manufacturing process. Is also not preferable.

Further, the blending amount thereof needs to be in the range of 30 to 150 parts by weight with respect to 100 parts by weight of the thermoplastic urethane elastomer. When the compounding amount is less than 30 parts by weight, the concavo-convex pattern generated on the surface of the obtained sheet does not appear clearly, and when it exceeds 150 parts by weight, the surface of the obtained sheet becomes a rough surface, and cracks are formed on the sheet surface in the stretching step described above. It is not preferable because it tends to occur.

The elastic fine particles may be used alone, or two or more kinds may be mixed and used. Further, in order to give a slightly hard feel, hard beads such as crosslinked polymethylmethacrylate or silk gel may be mixed and used with the elastic fine particles.

The silicone resin in the present invention has a viscosity of 1
Those in the range of 10,000 to 1,000,000 cps are preferable. When the viscosity is less than 10,000 cps, the thermoplastic urethane elastomer undergoes phase separation,
When it exceeds 1,000,000 cps, the kneading becomes difficult and neither gives a homogeneous composition. Further, the silicone resin has a hydroxyl group, an amino group,
It contains a modified silicone resin substituted with a functional group such as an epoxy group, a phenol group, a carboxyl group and a mercapto group, and is suitably used as a silicone resin having improved dispersibility.

The amount of the silicone resin compounded is 0.1 with respect to 100 parts by weight of the thermoplastic urethane elastomer.
-30 parts by weight, preferably 1 to 10 parts by weight. If the blending amount is less than 0.1 parts by weight, the lubricity of the surface of the obtained sheet will not be improved, and if it exceeds 30 parts by weight, uniform dispersion in the thermoplastic urethane elastomer cannot be obtained.

These silicone resins may be kneaded in advance with the thermoplastic urethane elastomer or the like in order to give a good mixed state with the respective components constituting the surface layer, and may be pelletized before use. A resin having good compatibility with each of the above components may be filled with a silicone resin at a high concentration and used as a pelletized concentrate.

If necessary, colorants such as dyes and pigments, antioxidants, ultraviolet absorbers, hindered amines, etc. may be added to the above-mentioned constituents constituting the surface layer of the coating sheet of the present invention.

The base material layer composed of the thermoplastic elastomer in the present invention is A specified in JISK7215.
Those having a hardness in the range of 50 to 98 give preferable performance. As the thermoplastic elastomer, for example, the thermoplastic urethane elastomer and other styrene-based, vinyl chloride-based, polyester-based, polyolefin-based elastomers can be appropriately selected and used, among others,
As a polyolefin elastomer excellent in moldability and cost, one having polypropylene as a hard segment and an ethylene component as a soft segment (EPM), one having a diene component together with this ethylene (EPDM), a mixture of the above two. The above compounds and those partially cross-linked with an organic peroxide are preferably used.

The above-mentioned thermoplastic elastomer is, for example, polypropylene or LLDP in order to improve the stretch formability of the sheet in the manufacturing process of the coating sheet of the present invention.
A polyolefin resin such as E (linear low-density polyethylene) may be added. The above-mentioned thermoplastic elastomer which is the main component of the base material layer of the coating sheet of the present invention further comprises, if necessary, a coloring agent such as a dye or pigment, an antioxidant, an ultraviolet absorber, and a hindered amine. It may be added.

The coating sheet of the present invention comprises a method of coating a surface layer on a base material layer obtained by an extrusion molding method or a calendar molding method, or a method of separately molding the above two layers and then laminating them with a laminator. However, it is preferable in terms of quality control that the two layers are produced by a coextrusion molding method. However, the above two layers may be laminated directly by coating or heat bonding, but an undercoat layer or an adhesive layer made of a solvent type adhesive or a hot melt adhesive may be provided.

As the material for forming the undercoat layer or the adhesive layer, the most suitable adhesive material is selected and used depending on the type of the base material layer. For example, when the base material layer is a polyolefin resin elastomer, Chlorinated polyolefins, ionomer resins such as ethylene methacrylic acid copolymer metal salts, acid-modified SBS (styrene-butadiene-styrene copolymer), acid-modified SEBS (styrene
An ethylene / butadiene / styrene copolymer) or the like is used.

In the covering sheet of the present invention, a foam layer having heat insulating properties and cushioning properties may be provided on the surface of the base material layer opposite to the surface layer laminated. Materials for forming the foam layer include polyolefin resins such as polypropylene and polyethylene, polystyrene, styrene resins such as styrene / maleic anhydride copolymers, polyurethane resins, polyvinyl chloride resins, and various other thermoplastic resins. Examples thereof include foams such as elastomers. In particular, when the foam has thermoformability, it can be used for a wider range of purposes.

The expansion ratio of the foam is desired to be selected according to the use of the covering sheet of the present invention, but in general use, it is about 5 to 50 times.
Further, the base material layer and the foam layer may be directly laminated by a thermal bonding method, but as in the case of laminating the surface layer and the base material layer described above, the undercoat layer or the adhesive layer is formed on the base material layer. It may be provided between two layers of the foam layer.

The thickness of the coating sheet of the present invention varies depending on its application, but in consideration of the appearance of a suede-like soft touch feeling and the sheet formability, the surface layer has a thickness of 5 to 100.
μm, base material layer 0.2 to 3 mm, foam layer 1 to 3 m
m, and the adhesive layer is preferably in the range of 5 to 50 μm.

When the surface layer of the coating sheet of the present invention is formed into a film or a sheet with the above-mentioned blending amount, a concavo-convex pattern giving a desired suede-like soft touch is formed. Alternatively, the feel of the surface layer can be further improved by performing stretching treatment after molding in a state of being laminated with the base material layer. Further, after the surface layer is molded in a single layer or in a state of being laminated with the base material layer, or after further stretching treatment, the thermoplastic urethane elastomer whose roll temperature is a constituent component of the surface layer is softened. The embossing roll set at a temperature below the point, preferably room temperature to 100 ° C., gives 10 to 10 to the surface layer.
It is also possible to form fine irregularities of about 0 μm for matte processing, or to emboss similar to various leathers for pseudo-leathering processing.

[0026]

The coating sheet of the present invention exhibits flexibility and scratch resistance by using the thermoplastic urethane elastomer in the surface layer together with the silicone resin and the elastic fine particles. By forming fine irregularities on the surface, giving a so-called suede-like feel,
The silicone resin improves the moderate surface lubricity by this formulation. The combination of these three effects makes it possible to give a good suede-like soft touch feeling very similar to natural leather.

[0027]

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited thereto.

In the following examples, appearance, matteness,
The scratch resistance and the coefficient of friction were tested and evaluated by the methods described below. 1. Appearance The produced coating sheet was visually observed and evaluated for scratches and distortion, and for surface unevenness.

2. Matting degree According to JIS Z 8741 (specular gloss measurement method),
A specular gloss of 60 degrees is 2.0 or less is good.

3. Scratch resistance A scratch resistance test with a Taber Scratch Tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), 5 rank, 5 rank,
A load of 500 g or more when in the class 4 state was evaluated as good. The display shows the applied load when in the 5th or 4th class.

4. Friction coefficient According to JIS K 7125 (Friction coefficient test method for plastic films and sheets), the determined static friction coefficient, dynamic friction coefficient and fluctuation range of dynamic friction force are measured, and static friction coefficient of 1.0 or less and dynamic friction coefficient of 0.6 or less are good. It was evaluated as giving a suede-like feel.

(Example 1) As a material for the surface layer, a thermoplastic urethane elastomer (made by Asahi Glass Co., Ltd., trade name Ufine PN3429; JIS A hardness 85, molecular weight 15)
50,000) 100 parts by weight, elastic fine particles (Sekisui Plastics Co., Ltd., urethane beads techpolymer UB15; average particle size 15 μm) 70 parts by weight, silicone resin (Toray Dow Corning Silicone, silicone resin)・ SH
200 high viscosity; dimethyl silicone, viscosity 100,00
2.5 parts by weight (0 cps) were kneaded in advance with a Banbury mixer and pelletized.

As the material of the base material layer, 50 parts by weight of a thermoplastic polyolefin-based elastomer (Mitsui Petrochemical Industry Co., Ltd., Mirastomer 8030N; JIS A hardness 85), a thermoplastic polyolefin-based elastomer (Mitsui Petrochemical Industry Co., Ltd., Mirastomer 5030N; JIS A hardness 5
0) 30 parts by weight, LLDPE (manufactured by Mitsui Petrochemical Industry Co.,
Ultzex 2021L) 10 parts by weight, polypropylene (Mitsui Petrochemical Co., Ltd., Hipol F650) 10
All parts by weight were pelletized and mixed with a blender.

As the material of the adhesive layer for adhering the above two layers,
A modified polyolefin (Admer QF551, manufactured by Mitsui Petrochemical Co., Ltd.) was prepared. Further, a foamed polypropylene sheet (manufactured by Sekisui Chemical Co., Ltd., Softlon SP) is used as a foam layer laminated on the surface opposite to the surface layer of the base material layer.
-V; thickness 2 mm, foaming ratio 25 times) was prepared.

Feed block type T-die (manufactured by Krollen Co., 500
mm width epoch 3201; clearance 0.8 mm) and caliber 30 mmφ 2 units, 40 mmφ 1 unit 3 extruders (all manufactured by Plastic Engineering Laboratory Co., UT40, G
T40, GT50) using a three-layer coextrusion device, the heating temperature of the extruder for forming the surface layer is 190 ° C, the heating temperature of the extruder for forming the adhesive layer is 190 ° C, and the extruder for forming the base material layer The heating temperature is set to 230 ° C. and the mold temperature is set to 200 ° C., the sheet is extruded, the sheet is stretched by a take-up roll, the surface layer is embossed, and the base material layer on the opposite side is foamed. The layers were laminated to give a matte coating sheet. The thickness of each layer of the obtained covering sheet was as follows: surface layer 60 μm, adhesive layer 20 μm, base layer 400 μm
m, and the foam layer was 2 mm. Table 1 shows the appearance, matteness (gloss), scratch resistance, and friction coefficient (dynamic friction coefficient, static friction coefficient) of the obtained coating sheet.

(Example 2) As a material for the surface layer, a silicone resin (manufactured by Toray Dow Corning Silicone, silicone resin SH200 high viscosity; dimethyl silicone, viscosity 100,000 cps) was used, except that 5 parts by weight was used. A coating sheet was obtained in the same manner as in Example 1. or,
Table 1 shows the appearance, matteness (gloss), scratch resistance, and friction coefficient (dynamic friction coefficient, static friction coefficient) of the obtained coating sheet.

(Example 3) As a material for the surface layer, 5 parts by weight of a silicone resin (manufactured by Toray Dow Corning Silicone, silicone resin BY16-872; amino-modified dimethyl silicone, viscosity 18,000 cps) was used. A covering sheet was obtained in the same manner as in Example 1 except for the above. Also, the appearance, matteness (gloss), scratch resistance, friction coefficient (dynamic friction coefficient, static friction coefficient) of the obtained coating sheet
Is shown in Table 1.

Example 4 As a material for the surface layer, a silicone resin (manufactured by Toray Dow Corning Silicone Co., Ltd., silicone resin concentrate BY27-001; base resin polypropylene, silicone amount 50% by weight) 1
A covering sheet was obtained in the same manner as in Example 1 except that the amount was 0 part by weight. Table 1 shows the appearance, matteness (gloss), scratch resistance, and friction coefficient (dynamic friction coefficient, static friction coefficient) of the obtained coating sheet.

(Example 5) As a material for the surface layer, a silicone resin (manufactured by Toray Dow Corning Silicone, silicone resin concentrate BY27-004; base resin polystyrene, amount of silicone 50% by weight) 10
A coating sheet was obtained in the same manner as in Example 1 except that the weight part was used. Table 1 shows the appearance, matteness (gloss), scratch resistance, and friction coefficient (dynamic friction coefficient, static friction coefficient) of the obtained coating sheet.

Comparative Example 1 A coating sheet was obtained in the same manner as in Example 1 except that the silicone resin was not added as the material for the surface layer. Table 1 shows the appearance, matteness (gloss), scratch resistance, and friction coefficient (dynamic friction coefficient, static friction coefficient) of the obtained coating sheet.

Comparative Example 2 A covering sheet was obtained in the same manner as in Example 1 except that the surface layer was composed of a thermoplastic urethane elastomer only. Table 1 shows the appearance, matteness (gloss), scratch resistance, and friction coefficient (dynamic friction coefficient, static friction coefficient) of the obtained coating sheet.

(Comparative Example 3) As a material for the surface layer, a silicone resin (manufactured by Toray Dow Corning Silicone Co., Ltd., silicone resin SH200 high viscosity; dimethyl silicone, viscosity 100,000 cps) was used in an amount of 50 parts by weight. A coating sheet was obtained in the same manner as in Example 1.
Also, the appearance, matteness (gloss) of the obtained covering sheet,
Table 1 shows scratch resistance and friction coefficient (dynamic friction coefficient, static friction coefficient)
It was shown to.

(Comparative Example 4) A covering sheet was obtained in the same manner as in Example 1 except that the base material layer was used as the surface layer, and only the base material layer and the foam layer according to the present invention were used. Table 1 shows the appearance, matteness (gloss), scratch resistance, and friction coefficient (dynamic friction coefficient, static friction coefficient) of the obtained coating sheet.

[0044]

[Table 1]

[0045]

According to the present invention, the thermoplastic urethane elastomer is used in the surface layer together with the silicone resin and the elastic fine particles so that flexibility and scratch resistance can be exhibited. By forming fine irregularities on the surface and forming fine bubbles in the layer, it gives a so-called suede-like feel, and the silicone resin improves the appropriate surface lubricity by this blending. . Due to the combination of these three actions, the covering sheet of the present invention is provided with a suede-like soft touch feeling which is very similar to natural leather and the like, and becomes a sheet excellent in scratch resistance.

Furthermore, according to the present invention, a layer containing a thermoplastic elastomer as a main component is integrally laminated on the base material layer, and if necessary, the surface layer of the base material layer is laminated. Since the foam layer having heat insulating properties and cushioning properties is provided on the opposite surface, the covering sheet of the present invention can further improve the contact feeling of the surface layer.

Claims (1)

[Claims] 1. A surface layer comprising 0.1 to 30 parts by weight of a silicone resin and 30 to 150 parts by weight of elastic fine particles to 100 parts by weight of a thermoplastic urethane elastomer, and a group containing a thermoplastic elastomer as a main component. A covering sheet having laminated material layers