JPS61200133A - Surface modification of polyvinyl chloride resin molded article - Google Patents

Abstract

PURPOSE:To take off the surface luster of a PVC resin molded article without lowering the original characteristics of the resin nor deforming the article, by treating the surface with a low-temperature plasma and then heat-treating at a specific temperature. CONSTITUTION:The surface of a PVC resin molded article is treated with a low-temperature plasma and then heat-treated at 100-400 deg.C. The treatment with low-temperature plasma is carried out preferably under 0.1-10 Torr pressure in the presence of a gas free from plasma-polymerizability (preferably He, Ne, Ar, N2, nitrous oxide, NO2, O2, air, CO, CO2, H2, Cl2, halide or sulfide).

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a method for surface modification of polyvinyl chloride resin molded articles. More specifically, the present invention relates to a method for eliminating the luster on the surface of a polyvinyl chloride resin object or a molded article thereof without damaging its shape.

BACKGROUND OF THE INVENTION Polyvinyl chloride resins have good processability, high strength, and are inexpensive, so they are used in a wide range of applications. However, as polyvinyl chloride resin melts and gels due to heating, its surface has the unique luster of polyvinyl chloride.
So-called "shininess" occurs. Therefore, the actual situation is that its use is limited in applications such as high-end interiors.

Methods to solve these problems include sandblasting, etching with a 20 ml mixture, squeezing with a matting engraving roll, surface treatment with a resin containing a matting agent such as silica, and high-polymerization and low-polymerization methods. Methods of kneading and melting polymerized resins are known. However, each of these methods has major problems. For example, the sandblasting method not only requires a long treatment time to obtain a matte effect, but also leaves a large amount of sand attached and remaining on the surface, which is difficult to remove. Also, chromium mixture i/
(The etching method described above has the disadvantage that there is a delay in the treatment of the waste liquid, and that it induces bleeding of plasticizers, other fillers contained in the molded product. , the pattern patterns are limited, and the workmanship requires high costs.Furthermore, in the method using a surface treatment agent, if the treatment agent is water-based, the durability of the matte surface obtained is poor; When the agent is used together with an organic solvent, it has the disadvantage that the solvent odor remains in the product for a long time.Furthermore, the method of kneading and melting the low polymerization degree resin and the high polymerization degree resin has the disadvantage that the product is If the heating temperature is high, the matting effect will be lost, while if the heating temperature is low, the properties of the resin itself will be impaired.

Problems to be solved by the invention (a) The surface of the polyvinyl chloride resin molded product can be made matte, (01) the shape can be maintained without difficulty, and (0) chemical and physical properties To provide a surface treatment method that does not damage.

The method of the present invention is to treat the surface of a polyvinyl chloride resin molded product with low-temperature plasma, and then heat it at 100°C to 4°C after being heated.
It is characterized by heat treatment at a temperature of 00°C, which eliminates the surface luster without changing the chemical and physical properties of the molded product or its shape. can.

The polyvinyl chloride thread resins used in the method of the present invention include soft-membered polyvinyl chloride resins, hard polyhinyl chloride resins, and copolymers of vinyl chloride and 10,000 olefins such as Eva, ethylene, propylene, or isobutylene. Resin, copolymer resin of vinyl chloride and styrene, copolymer resin of vinyl chloride and dienes, such as butadiene, or isoprene, vinyl chloride and acrylic acid, olefin, or vinyl acetate. and copolymer resins with the above resins and modifying resins, such as ABS and SBR.
.

Alternatively, there are mixed resins with rubbers such as NBR.

Polyvinyl chloride resin is a plasticizer, stabilizer, filler, flame retardant, flame retardant, dredging inhibitor, ultraviolet absorber, anti-mold agent,
A lubricant, a pigment, etc. may be contained as appropriate depending on the purpose.

There are no particular limitations on the shape and dimensions of the molded product to which the method of the present invention is applied; films, sheets, tapes, etc. having desired dimensions,
Any other molded product may be used, and the molding method used heretofore may be any conventionally used method such as a calendar method, an extrusion method, a coating method, or a dipping method.

There are no particular restrictions on the shape of the surface of the molded product, and the surface may be treated with an engraved roll having a desired pattern.

In the method of the present invention, the polyvinyl chloride resin molded article is first subjected to low temperature plasma treatment. Low temperature plasma treatment is
This is generally carried out by exposing the fibrous base fabric to a low-temperature plasma of a gas that does not exhibit plasma polymerizability under a pressure of 0.01 to 10 Torr. The plasma processing time varies depending on the applied mixed pressure, but generally a range of several seconds to several minutes is sufficient. For low-temperature plasma treatment, for example, low frequency or microwave can be used as the discharge frequency band, and continuous flow can also be used, and the plasma generation mode can also be glow discharge, corona discharge, spark discharge 1, or silent discharge. You may use any of the following.

Gases that do not have plasma polymerizability include helium, neon, argon, nitrogen, and suboxide? *Nitrogen dioxide, oxygen, air, carbon monoxide, carbon dioxide, hydrogen, chlorine, hydrogen chloride, bromine chloride, tin bromide, etc., or sulfur, sulfur dioxide gas, hydrogen sulfide, etc. These gases, such as sulfides, can be used alone or in combination.

Such low-temperature plasma treatment alone is insufficient to achieve a matting effect on the surface of the molded product, but if the low-temperature plasma-treated surface is subjected to heat treatment at a temperature of 100°C to 400°C, The matte effect on the surface of the molded product clearly appears. Such a phenomenon was discovered for the first time in the present invention.

Therefore, in the method of the present invention, the polyvinyl chloride resin molded product treated with low-temperature plasma is treated at a temperature of 1°C. At heating temperatures below 100"C, no matting effect is observed, and at heating temperatures above 400"C, the surface roughness becomes too thick and the shape of the molded product is damaged.Heating The time varies depending on the heating temperature used, but generally a few seconds to an hour is sufficient.
For example, 120°C for about 50 minutes, 200°C for about 20 seconds, 3
At 00°C, a sufficient matting effect can be obtained by heat treatment for about 5 seconds, and the shape of the molded product and its surface will not be damaged.

It is not yet clear why the matting effect, which was unclear after low-temperature plasma treatment alone, is subsequently developed by heat treatment. However, this is probably due to the heat treatment causing a difference in thermal stress between the crosslinked part and the non-crosslinked part caused by the low temperature plasma, resulting in the formation of fine irregularities that produce a matting effect only in the very vicinity of the surface.

Example The present invention will be further explained below with reference to Examples.

Example 1 Polyvinyl chloride resin composition having the following composition; polyvinyl chloride (TS7NE VINYL S-1003) DOP
60 Epoxidized dog bean oil 3Ba-Zu stabilizer
2 to a heating temperature of 1i160°C using a heating roll.
Heat and knead with a mixing time of 10 minutes to a thickness of 0.3 m.
It was formed into a film. This is designated as sample 1 (untreated product).

The test piece taken from this polyvinyl chloride film sample 1 was placed in a predetermined position in a low-temperature plasma device, the pressure inside the device was evacuated to 10 Torr, and then CO gas was introduced into the device to reduce the pressure inside the device. It was trained to 0.2 Torr.

The low-temperature plasma treatment was performed using a high-frequency power source (manufactured by Nippon Koshuha Co., Ltd.) with a frequency of 13.56 MHz, and the power consumption was 100 watts. Changed.

The sample that had been subjected to the low-temperature plasma treatment was then subjected to a heat treatment. The heat treatment was carried out in a gear oven (manufactured by Toyo Seiki Seisakusho) at 180° C. for 30 seconds. The matting effect of the obtained product was determined by visual observation using a magnifying glass. Judgment was based on the following criteria. In addition, the wear resistance properties were compared by the amount of wear loss using a taper type wear tester (manufactured by Toyo Seiki Seisakusho). The results are shown in Table 1.

(Judgment criteria for matting effect) ○: Matting effect is observed uniformly on the entire surface Δ: Gloss remains in some areas (recesses) ×: Gloss is present on the entire surface (tapered abrasion test conditions) According to JISL-1096C method Load: 250gr, rotation speed: 5oo times worn wheel
H-18 Example 2 Polyester base of the following fiber wire: Polychloride and Nylsol of the following composition: Polyvinyl chloride (Zeon 121) 100 parts by weight DO
P60
Soak in epoxidized dog bean oil 3 Ba-Zu stabilizer 2 and squeeze with a mangle! The PVC resin was gelled and fixed by heat treatment at +190°C for 3 minutes. The amount of adhesion at this time is 2501 in terms of solid content.
It was 17n'. without letting this thing cool down.
It was passed between an engraved roll having a floral pattern and a back roll to form a so-called crimping pattern on the surface of the PVC molded product. This is designated as sample 2 (untreated product).

The test piece obtained as Sample 2 was treated with low-temperature plasma in the same manner as in Example 1. Here, Ar was used as the gas, the power consumption was 500 W, and the initial time was 30 seconds.

In the heat treatment, the temperature was increased to 70°C as shown in Table 2.
The temperature was varied between 0.degree. C. and 450.degree. C., and the treatment time was also varied from several seconds to 1 hour.

The results are shown in Table 2.

As is clear from Table 2, by appropriately selecting the heating temperature and time in the method of the present invention, it is possible to create grooves and a matte surface while maintaining the wrinkled pattern.

Effects of the Invention The method of the present invention can eliminate the unique luster of polyvinyl chloride resin molded articles without impairing their physical or chemical properties. In particular, it has become possible to erase the luster of molded products that have been drawn and pressed using engraved rolls with various Kasakaki patterns without losing the surface patterns.

This has made it possible to use jelly-vinyl chloride resin molded products in the interior design field and other applications, where PVCK's unique luster had previously limited its use.

Claims (1)

[Scope of Claims] 1. A polyvinyl chloride resin molded article characterized in that the surface of the polyvinyl chloride resin molded article is treated with low-temperature plasma, and then heat treated at a temperature of 100°C to 400°C. Method for surface modification of resin molded products. 2. The low temperature plasma treatment is performed at a temperature of 0.01 to 10 Torr.
2. The method according to claim 1, wherein the method is carried out using low-temperature plasma of a gas that does not have plasma polymerizability under a pressure of . 3. A patent in which the non-plasma polymerizable gas is selected from helium, neon, argon, nitrogen, nitrous oxide, nitrogen dioxide, oxygen, air, carbon monoxide, carbon dioxide, hydrogen, chlorine, halides, and sulfides. The method according to claim 1.