JPH06116874A - Polyolefin sheet and its production - Google Patents

Abstract

PURPOSE:To provide a polyolefin sheet having excellent interlaminar peeling strength and abrasion resistance, i.e., excellent coating film durability without deteriorating the characteristic properties and feeling of an olefin resin sheet and to provide a process for stably producing the sheet. CONSTITUTION:The polyolefin sheet is a laminated sheet having a resin coating film laminated to at least one surface of an olefin elastomer coating film and has an interlaminar peeling strength of >=150g/inch. The polyolefin sheet can be produced by treating a surface of an olefin elastomer coating film by discharge treatment, ultraviolet treatment, ozone treatment or two or more kinds of the above treatments and applying a resin to the treated surface.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin sheet having excellent coating durability, for example, an olefin sheet used as an automobile interior skin material, a chair skin material and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a coating method has been widely used in which a thermoplastic resin is pressure-bonded in a molten state onto a base material such as a textile fabric such as a knitted woven fabric or a non-woven fabric or a polyethylene foam sheet. As a synthetic leather with a leather-like appearance,
From the viewpoint of low cost, moldability, etc., polyvinyl chloride resin is generally used, but it has a serious drawback that chlorine-containing gas and residues during combustion pollute the environment.
At present, new materials are required due to global environmental issues.

[0003] In order to solve this problem, studies have been made on olefin resins which also have the property of weight reduction, and in particular, olefin elastomers. However, such olefin resins have originally the same material as wax. Since it is a substance, it is said that the surface is inactive, the dyeability and the adhesiveness are not good, and it is considered to be a substance that is difficult to develop for purposes. On the other hand, an olefin elastomer has a leather-like texture and a warm feel, but since it does not have a polar group in the molecule, it still lacks surface activity (reactivity), and dyeing and other It has a drawback that the adhesiveness with a resin is poor.

In order to solve such a drawback, a method of applying a large amount of adhesive has hitherto been dealt with, but there is a drawback that the texture of the sheet becomes coarse and hard.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the drawbacks of the olefin resin, and the characteristics of the sheet,
It is intended to provide an olefin-based sheet which has improved peeling strength and abrasion resistance, that is, excellent coating durability, which improves surface activity without deteriorating the texture, and further stably manufactures such a sheet. It is intended to provide a method.

[0006]

The present invention has the following constitution in order to achieve such an object. That is, the olefin-based sheet of the present invention is a laminated sheet in which a resin coating is laminated on at least one surface of an olefin elastomer coating, and the delamination force of the laminated sheet is 150 g / in.
It is characterized by being more than ch.

Further, in the method for producing an olefin sheet according to the present invention, the surface of the olefin elastomer coating is subjected to discharge treatment, ultraviolet treatment or ozone treatment, or at least two treatments of discharge treatment, ultraviolet treatment and ozone treatment are carried out. The resin is applied after the process.

[0008]

The present invention has been earnestly studied in order to solve the problem of the surface inactivity of the olefin resin sheet,
As a result, it was clarified that, as the olefin resin, an olefin elastomer exhibits unexpected behavior with respect to a specific physical treatment. That is, it was clarified that when the olefin elastomer coating is subjected to a discharge treatment, an ultraviolet treatment or an ozone treatment, the delamination strength of the resin coating in the laminate is extremely improved.

According to the present invention, by using an olefin elastomer as an olefin resin, the surface activity is enhanced without impairing the texture of such a resin coating, and the peel strength (adhesion) with the resin is significantly enhanced, thereby providing coating durability. It has succeeded in providing an excellent olefin-based sheet.

The olefin elastomer used in the present invention has a mutual compatibility between a rubber component (soft segment) having rubber elasticity in the polymer chain and a crystalline or glassy component (hard segment) which prevents plastic deformation near room temperature. It does not have both components. Specifically, as the soft segment, butadiene rubber or ethylene / propylene rubber is used, and as the hard segment,
It is possible to use polyethylene, polypropylene, or finely dispersed polyethylene, polypropylene, etc. with natural rubber, synthetic rubber, etc., or a so-called alloyed polyolefin partially crosslinked between polymers. it can. In any case, as the olefin elastomer used in the present invention, those commercially available as olefin elastomers can be used.

Specifically, for example, Mirastomer (manufactured by Mitsui Petrochemical Co., Ltd.), Santoprene (manufactured by AES Japan Co., Ltd.), Nisseki Soft Rex (manufactured by Nippon Petrochemical Co., Ltd.), Oreflex (Showa Denko). Sumiflex (manufactured by Sumitomo Bakelite Co., Ltd.), Sumitomo TPE (manufactured by Sumitomo Chemical Co., Ltd.), Thermoran (manufactured by Mitsubishi Chemical Co., Ltd.) and the like can be used.

The olefin elastomer coating of the present invention comprises:
The olefin elastomer chips can be introduced into an extruder or the like, heated and melted, and then extruded into a sheet form on a cooling roll by a T die, a slit die or the like to form a film. When the coating is combined with a fiber cloth or a plastic substrate, the elastomer coating is extruded onto the substrate and press-pressed under pressure, specifically, with a cooling roll and a silicone rubber lining press roll. Can be crimped. These are so-called melt extrusion methods. Further, the olefin elastomer may be melt-kneaded between two heated metal rolls, and may be formed into a sheet having a predetermined thickness through a heating calender, so-called calendering method or the like. A method (including plastic molding) can be adopted and is not particularly limited. As a method for imparting a leather-like pattern to the surface of the olefin-based sheet of the present invention, for example, at the time of forming the olefin elastomer film, pressure is imparted by using an embossing roll or embossing release paper having a leather-like pattern, Alternatively, after the film is formed, the sheet can be applied by using the embossing roll or the release paper while heating the sheet. In any case, a pattern can be imparted by employing these known methods.

By imparting such a leather-like pattern to the surface of the sheet, it is possible to produce a sheet-like article having a natural leather-like appearance. It is possible to provide a leather-like sheet having excellent coating durability, and to provide a sheet having extremely excellent abrasion resistance of the pattern and durability of the coating.

Further, the olefin elastomer of the present invention and the resin described below may be added to other resins, coloring agents, flame retardants, antibacterial agents, moisture absorbing / releasing agents, within the range that does not deviate from the effects of the present invention.
You may mix a filler, an ultraviolet absorber, etc.

In the present invention, the surface of the olefin elastomer coating (sheet) is subjected to a specific physical treatment, that is,
At least one selected from discharge treatment, ozone treatment and ultraviolet treatment, and further two or more physical treatments are applied. Of course, such physical treatment can be further performed after laminating the resin coating film described later.

By the physical treatment of the present invention, the surface of the olefin elastomer coating is remarkably activated and the delamination strength from the resin (including the surface resin processing agent) is extremely improved.

The discharge treatment as referred to in the present invention is to generate by applying a high voltage between the electrodes, and such discharge treatment is generated in a vacuum chamber and a normal pressure plasma for generating plasma at atmospheric pressure. There is low-pressure plasma that causes it. As a power supply for applying a high voltage, either direct current or alternating current can be used.

In this discharge treatment, at least one of the electrodes is preferably covered with a dielectric material, and the shape of the electrode is
A plate shape or a roll shape can be used without any particular limitation. The distance between the electrodes is preferably 0.2-in the case of atmospheric plasma.
The thickness is 40 mm, more preferably 0.5 to 3 mm, and for low pressure plasma, it is preferably 0.2 to 100 mm, more preferably 10 to 50 mm.

As the discharge atmosphere for such discharge treatment, non-polymerizable gases such as air, oxygen, nitrogen, carbon monoxide, water, argon and helium are preferably used, but the effect of the present invention is not excluded. Within the range, a polymerizable gas such as methane, perfluoroethylene or silane can be mixed and used. .

The atmospheric pressure of the low-pressure plasma is preferably 0.001 to 50 Torr under the above-mentioned specific gas atmosphere.
The reduced pressure is r, more preferably 0.01 to 10 Torr, and particularly preferably 0.1 to 5 Torr.

The treatment time of the discharge treatment is not particularly limited, but it is preferably several seconds to several minutes and can be set according to the purpose.

In the ozone treatment of the present invention, a gas containing oxygen is used as a raw material, and ozone is supplied to a treatment chamber from an ozone production apparatus using a normal pressure plasma, a low pressure mercury lamp or the like to perform a predetermined treatment. A known apparatus can be used as the ozone production apparatus.

In this ozone treatment, for example, ozone is introduced into a stainless steel or glass treatment chamber to control the ozone concentration to a predetermined value, and then the sheet to be treated is introduced into the treatment chamber and treated for a predetermined time according to the purpose. Good.

The ozone concentration used in the present invention is as follows.
Preferably 50 to 100,000 ppm, more preferably 300
A treatment time of 0 to 100,000 ppm, preferably several seconds to several minutes, is used.

In this ozone treatment, the ozone treatment atmosphere can be heated, and preferably 60-18.
It is preferable to employ conditions (including treatment time) at 0 ° C., more preferably in the range of 100 to 150 ° C. and at which the olefin elastomer does not deform. For heating the processing atmosphere, a normal heating means such as a heater can be used outside or inside the processing chamber. Under such conditions, the ozone concentration, temperature and processing time are determined according to the purpose.

In the ultraviolet treatment of the present invention, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, a low pressure mercury lamp or the like is used as a light source, and ultraviolet rays containing a wavelength of 300 nm or less are preferably used because of their fast reaction rate. It Among them, especially 184.9 nm and 253.7 nm
Ultraviolet rays emitted from a low-pressure mercury lamp having a peak at 1 are preferably used.

Irradiation conditions for such ultraviolet treatment are preferably 3 mW / in the case of a gas atmosphere of air, oxygen, nitrogen, argon or the like, for example, at a wavelength of 253.7 nm.
A treatment time of preferably several seconds to several minutes is used under an illuminance condition of cm ² or more, more preferably 10 mW / cm ² or more, and particularly preferably 30 mW / cm ² or more. Such conditions are
The illuminance and the processing time can be determined according to the purpose.
Further, the atmospheric pressure for ultraviolet irradiation can be not only normal pressure but also any condition such as reduced pressure or increased pressure.

The physical treatments used in the present invention described above can be carried out alone or in combination of two or more. The step of performing such physical treatment may be before or after embossing as long as it is after extrusion film formation. Further, in some cases, after the resin coating is laminated on the olefin elastomer coating, it can be further applied. The present invention, after physical treatment, is subjected to surface resin processing with a resin, and such surface resin processing is generally used to improve abrasion resistance, surface touch, antifouling property, etc. of the sheet surface. As the resin, for example, a natural resin or a synthetic resin may be used, but it is preferable to use a resin soluble in a solvent such as an acrylic resin, a urethane resin, a silicone resin, a fluororesin or a resin dispersed in water. A known film such as a laminating process in which a solution or dispersion of the resin is applied by a gravure roll, a knife coater, a spray or the like in a predetermined amount and then dried or cured, or the resin is melted and the molten resin is laminated. A lamination method can be adopted.

[0029]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Examples 1 to 12 and Comparative Example 1 Mirastomer 5030N (olefin elastomer manufactured by Mitsui Petrochemical Industries, Ltd.) was extruded at a temperature of 230 ° C.
While extruding onto a cotton cloth with a discharge rate of 350 g / min (width of 85 g / cm ² ) from the die and laminating it, the laminated resin coating surface is applied to a metal cooling roll having a leather pattern, and a silicone rubber is applied. Press with a lining press roll, take it off at a speed of 1 m / min, and crimp
A synthetic leather-like sheet having a thickness of 0.4 mm was obtained. The surface of the laminated resin coating of the synthetic leather-like sheet was subjected to a physical surface treatment under the following conditions and then subjected to surface resin processing. The evaluation results are summarized in Table 1.

(Physical Surface Treatment) (A: Normal Pressure Plasma Treatment) Electrode: 3 rolls of metal rod coated with silicone rubber
Installed at mm distance Discharge frequency: 35 KHz Discharge power: 1200 W Treatment speed, Number of treatment: 5 m / min, 1 to 5 times Discharge atmosphere pressure, Gas: 700 Torr, Air (B: Low pressure plasma) Electrode: Parallel plate type Discharge frequency: 600 KHz Discharge power: 250 W Treatment time: 5-30 sec Discharge atmosphere pressure, gas, flow rate: 1 Torr, argon, 10
0cc / min (C: Ozone treatment) Ozone generator: Corona discharge method Raw material gas: Oxygen Ozone concentration: 8000ppm Treatment temperature: 150 ° C Treatment time: 0.5 to 5min (D: UV treatment) Irradiation device: Low pressure mercury lamp 253 .7 nm Illuminance: 38 mW / cm ² Atmosphere temperature: 140 ° C. Atmosphere gas: Air Treatment time: 10 to 120 sec (Surface resin processing) Crisbon NY361 (Dainippon Ink and Chemicals Co., Ltd. polycarbonate polyurethane resin) 100 parts and N, N A resin consisting of 50 parts of dimethylformamide was applied with a knife coater in an amount of 180 g / m ² , dried at 80 ° C., and heat-treated at 120 ° C.

(Film peeling strength) JIS K6328-19
Adhesion of the surface resin film was evaluated in accordance with Method 77 by using a strip-shaped sample having a width of 2.5 cm.

As a comparative example, surface resin processing was carried out without physical surface treatment.

[0034]

[Table 1] From Table 1, those according to the examples are compared with those according to the comparative examples.
It is generally confirmed that the layer shows an extraordinary delamination force of several times to several tens of times in proportion to the processing time.

Examples 13 to 16 and Comparative Example 2 Sumitomo TPE WT214C (manufactured by Sumitomo Chemical Co., Ltd.)
(Olefin elastomer resin) is extruded at a temperature of 200 ° C. from a T-die at a width of 50 cm at a discharge rate of 370 g / min onto a foamed polyethylene having a thickness of 2 mm, and a release paper having a leather pattern is formed between the extruded sheet and the metal cooling roll. Insert it and take it out at a speed of 3 m / min while pressing it with a silicone rubber lining press roll, and the thickness of the resin sheet is 0.13.
mm synthetic leather was obtained. The synthetic leather was subjected to a physical surface treatment under the following conditions, and the treated surface was subjected to surface resin processing.

The evaluation results are summarized in Table 2.

(Physical Surface Treatment) (B: Low Pressure Plasma) Electrode: Discharge Electrode with Stainless Steel Tube Covered with Glass Earth Electrode 200 mmφ Stainless Drum Discharge Frequency: 350 KHz Discharge Power: 400 W Treatment Speed, Number of Treatments: 20 cm / min, 3 times discharge atmosphere pressure, gas, flow rate: 1 Torr, nitrogen, 100cc
/ min (D: UV treatment) Irradiation device: Low-pressure mercury lamp 253.7nm Illuminance: 25 mW / cm ² Atmospheric temperature: 160 ° C Atmospheric gas: Air Treatment time: 1 min (Surface resin processing) HYCOPE EU743-6 (special color material) 50 g / of sprayed polyurethane resin manufactured by Co., Ltd.
An amount of m ² was applied, dried at 90 ° C, and heat-treated at 110 ° C.

(Number of Delamination of Film) The taper abrasion tester specified in ASTM D 1175 was used to perform abrasion with a load of 500 g using a CS # 10 abrasion wheel, and the number of treatments for delamination of the surface resin was measured to determine the surface resin. Determine the wear resistance of the coating,
The durability was evaluated.

[0039]

[Table 2] It is confirmed from Table 2 that the results of the examples are out of ten to several tens of times that of the comparative examples, which are out of order of magnitude. In particular, it can be seen that the combination of the two physical surface treatment methods achieves extremely high levels of performance.

[0040]

According to the present invention, it is possible to stably provide an olefin-based sheet having excellent film durability.

Claims (11)

[Claims] 1. An olefin-based sheet, which is a laminated sheet in which a resin coating is laminated on at least one surface of an olefin elastomer coating, and the delamination force of the laminated sheet is 150 g / inch or more. 2. The olefin-based sheet according to claim 1, wherein at least one surface of the olefin elastomer coating has a leather-like pattern. 3. The olefin-based sheet according to claim 1, wherein the resin coating is made of a resin selected from acrylic resin, urethane resin, silicone resin and fluorine resin. 4. A method for producing an olefin-based sheet, which comprises subjecting the surface of an olefin elastomer coating to electrical discharge treatment and then applying a resin to the treated surface. 5. A method for producing an olefin-based sheet, which comprises subjecting the surface of an olefin elastomer coating to ozone treatment and then applying a resin to the treated surface. 6. A method for producing an olefin-based sheet, which comprises subjecting the surface of an olefin elastomer coating to ultraviolet irradiation and then applying a resin to the treated surface. 7. A process for producing an olefin-based sheet, which comprises subjecting the surface of an olefin elastomer coating to two or more treatments selected from discharge treatment, ozone treatment and ultraviolet treatment and then applying a resin to the treated surface. Method. 8. The olefin elastomer coating has a leather pattern on at least one side.
The method for producing an olefin-based sheet according to 5, 6, or 7. 9. The method for producing an olefin-based sheet according to claim 4, wherein the discharge treatment is corona discharge treatment or low-temperature plasma treatment. 10. The method for producing an olefin-based sheet according to claim 6, wherein the ultraviolet rays have a wavelength of 300 nm or less. 11. The method for producing an olefin-based sheet according to claim 6, wherein the ultraviolet rays have a wavelength of 300 nm or less.