JPS5849294B2 - Plasma reaction treatment method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improvements in methods for treating surfaces of various materials with glow discharge plasma reactions.

More specifically, the present invention aims to prevent deterioration of the treated object itself or damage to the aluminum or surface due to excessive action when the surface of various materials is subjected to glow discharge plasma reaction treatment. , relates to an improved method that has a milder effect.

Conventionally, efforts have been made to improve or modify the surface properties of materials made of various materials, such as improving heat resistance, chemical resistance, corrosion resistance, adhesion, mechanical strength, abrasion resistance, and imparting bacterial resistance and stainability. As a method for quality control, a method is known in which a workpiece is placed in a glow discharge atmosphere and subjected to plasma treatment.

This method has the advantages of relatively easily obtaining a glow discharge atmosphere, simple processing operations, and short processing time, and is therefore widely used in various fields.

However, when applying glow discharge plasma reaction treatment to some sheet-like or fibrous materials, there is a drawback that the decomposition type reaction due to etching takes priority rather than surface modification, and the properties of the material itself are impaired. This was a major obstacle to practical application.

As a result of extensive research in order to overcome the drawbacks of the conventional methods, the inventors of the present invention inserted a filter between the object to be treated and the plasma during glow discharge plasma reaction treatment to improve its effect. It was discovered that the objective could be achieved by relaxing the temperature, and the present invention was completed based on this knowledge.

That is, the present invention provides a plasma reaction treatment method characterized in that when performing glow discharge plasma reaction treatment, the object to be treated is subjected to an action through a filter.

Glow discharge plasma reactions include those in which plasma is generated in the presence of polymerizable monomers to form a polymer coating on the surface of an object, and those in which plasma is generated in the presence of a polymerizable monomer to form a polymer coating on the surface of an object. There are methods that perform etching on the surface of the plasma, but in either case, active species such as various radicals, ions, electrons, and photons contained in the plasma play an important role.

The present invention eliminates high-energy active species such as activated radicals and ions contained in non-polymerizable gas plasma using a filter, and uses only ultraviolet photons to generate plasma under mild conditions. By carrying out the reaction, the desired surface treatment can be performed without altering the material itself or damaging the surface.

Materials that can be treated by the method of the present invention may be any materials that have been previously subjected to plasma reaction treatment, such as various plastics, natural polymers,
There are natural fibers.

Moreover, there is no particular restriction on the shape of these materials, and they may be film-like or fibrous.

Next, the filter used in the method of the present invention is not particularly limited as long as it can transmit ultraviolet light and withstand the reaction conditions, but quartz glass and heat-resistant glass are suitable.

This filter can be formed into a semi-cylindrical shape, a plate shape, a tubular shape, or any other shape suitable for the reaction tube.

In order to suitably carry out the method of the present invention, for example, a tubular filter such as a quartz tube or a heat-resistant glass tube having a diameter slightly smaller than that of the reaction tube is inserted into a reaction tube type plasma reactor that utilizes afterglow discharge. The object to be treated is placed in the gap between the reaction tube and the tubular filter and subjected to plasma treatment in the usual manner.

Furthermore, instead of using a tubular filter, the object to be treated may be sandwiched between two plate-shaped filters or a plate-shaped filter and a support, and then placed in a reaction tube and subjected to plasma treatment.

The processing conditions at this time are the same as those for conventional plasma processing.

Next, specific embodiments of the method of the present invention will be described with reference to the accompanying drawings.

The drawing is an explanatory diagram showing an example of a suitable apparatus for carrying out the method of the present invention, and the reaction apparatus is composed of a reaction tube 1 made of hard glass and a glow discharge tube 2 connected thereto.

A coil connected to an RF wave generating power source is wound around the outer periphery of the glow discharge tube.

The end of the reaction tube 1 opposite to the glow discharge connection port is formed into an exhaust port 4, and a gas inlet pipe 5 is provided therein almost coaxially.
It is equipped with

A filter tube 6 of a slightly smaller diameter than the reaction tube 1 is inserted into the reaction tube and is fixed by a ring 7.7.

The object to be processed A is attached to the space between the reaction tube 1 and the filter tube 6.

In such an apparatus, a non-polymerizable gas is introduced into the reaction tube 1 through the gas introduction tube 5 while adjusting its flow rate and pressure using a needle pulp, is sucked by a vacuum pump, and is then discharged from the exhaust port 4. be discharged.

The plasma generated in the reaction tube in this way acts on the object A through the filter 6 and undergoes the desired treatment.

At this time, the glow discharge passes through the inside of the filter 6,
A ring between it and the reaction tube 1, such as a Teflon ring 1
, 7 (therefore, direct bombardment of the object A by the plasma can be avoided).

According to the uninvented method, even film-like and fibrous materials can be
Since plasma reaction treatment can be performed without any problems, it has the advantage that it can be used over a very wide range.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 In the reaction apparatus shown in the drawings, the inner diameter was 4.4 cIrL, the length was about 40 CrrL, the winding diameter of the coil was about 4.5 CrrL,
Inside the glow discharge tube, which consists of a supply tube with a diameter of 2.4F and a supply gas tube, an outer diameter of 3.8CIfL and a length of 20CII1. ,
The outer periphery of a 7 mm thick Pyrex tube is coated with 25 μm thick, 10 CTLXIO (117+1 polyethylene (PE)
) A sheet was glued with vinyl tape and inserted, and this was fixed with a ring made of polyfluoroethylene.The type of gas supplied was changed, and the pressure was 50 μmHg and the discharge voltage was 20.
A glow discharge was caused with W, and the treatment was carried out in that atmosphere.

The treatment time was 10 minutes. In this way, the reason for the particularly long processing time is that once the material to be processed has been modified and reaches its peak state, it retains its properties and does not deteriorate, and the processing time exceeds the required processing time. This is to ensure completeness of the process, since the time taken will not have a negative effect on the evaluation of the method of the present invention.

For comparison, a similar sheet without using quartz glass or the like was directly treated in a glow discharge atmosphere generated under the same conditions as above.

The wetting properties of the thus obtained material with respect to water were investigated.

The results are shown in Table 1. Example 2 A reaction apparatus similar to that of Example 1 was used, and a 50 μm thick
1. A soft polyvinyl chloride (PVC) sheet with a size of 2.5 CrrL x 7.5CIIL was sandwiched between both sides of Pyrex slide glass with a thickness of LOtnm, and the sheets were placed in close contact and treated under the same conditions as in Example 1, We investigated its wetting properties.

We also investigated the case where it was mounted directly without being sandwiched between slide glasses.

These results are shown in Table 2.

[Brief explanation of the drawing]

The drawing is an explanatory diagram of an example of a reaction apparatus used to carry out the method of the present invention, in which 1 is a reaction tube, 2 is a glow discharge tube, 5 is a gas introduction tube, and 6 is a filter tube. .

Claims (1)

[Scope of Claims] 1. A plasma reaction treatment method characterized in that when performing glow discharge plasma reaction treatment, an object to be treated is subjected to an action through a filter. 2. The method according to claim 1, wherein the filter is made of quartz glass or heat-resistant glass.