JPS60248742A - Surface modification of polyvinyl chloride resin molded article - Google Patents

Abstract

PURPOSE:To prevent the migration and bleeding of the additive in a molded article to the surface, and to improve the stain-proofing property, weather resistance, oil and water repellency, etc. of the surface, by subjecting a molded resin article to a low-temperature plasma treatment in a gaseous mixture containing a fluorocarbon and hydrogen. CONSTITUTION:The surface of a molded article of a polyvinyl chloride resin is subjected to the low-temperature plasma treatment in a mixed gas atmosphere containing a fluorocarbon and hydrogen. The fluorocarbon is a perfluorocarbon of formula CnF2n+2 (n is 1, 2 or 3), and the volume ratios of hydrogen and fluorocarbon in the mixed gas are selected to satisfy the formula 0.2A<=B<2.0A (A is volume of fluorocarbon and B is that of hydrogen). The mixed gas may further contain an inorganic gas such as CO, Ar, He, CO2, N2 at a ratio of C>=50/B (C is volume of the inorganic gas). The plasma treatment is carried out in a vacuum of 0.05-10Torr.

Description

Detailed Description of the Invention Technical Field The present invention relates to a method C for surface treatment of polyvinyl chloride resin molded articles; more specifically, the present invention relates to surface treatment method C for polyvinyl chloride resin molded articles; Surface modification method for preventing

Conventional technology Soft polyvinyl chloride resin has good processability, high strength, and low price, so it is used in a wide range of applications. It contains plasticizers and fillers, which tend to migrate and ooze out from the surface of the molded product over time, resulting in unsatisfactory stain resistance and durability.

In order to solve the above problems (2. The surface of the soft polyvinyl chloride resin molded article (2. However, this method (-) has also been recognized to have various drawbacks. For example, when an acrylic resin film is used, the adhesion between the polyvinyl chloride resin molding and the acrylic resin film becomes excessive. Depending on how the stress is applied, cracks may occur on the polyvinyl chloride resin molded body side 1.Furthermore, if the front adhesive strength becomes too small, there will be a drawback that the two will peel off and the adhesion between the two will deteriorate. It is difficult to control the force.Also, when using polytetrafluoroethylene film, it is necessary to use an adhesive and a special bonding process, which increases raw material and process costs. A method has been developed in which polyvinyl chloride resin molded bodies are treated with low-temperature plasma in an inorganic/gas atmosphere. 0 However, since the treated surface is made excessively (dihydrophilic), moldings treated with this method are used in applications C2 where waterproofness, water repellency, or water stopping properties are required. The body has low durability and is inappropriate.

JP-A No. 56-118,430 (Secondly, the surface of a polyvinyl chloride resin molded article is subjected to radiation irradiation, ultraviolet irradiation, or low-temperature plasma treatment (-, forming a carbon crosslinked layer, and forming a part of this crosslinked layer. Fluorine gas ζ: How to make it more fluorinated,
However, a method is disclosed in which the surface of a polyvinyl chloride molded article is subjected to low-temperature plasma treatment in an atmosphere containing fluorine or Freon gas to form a partially fluorinated crosslinked layer. , these methods (
The formation of a partially fluorinated crosslinked layer by D is still unsatisfactory, and further improvements are desired.

OBJECTS OF THE INVENTION An object of the present invention is to provide a surface modification method that can efficiently partially fluorinate and crosslink the surface of a polyvinyl chloride resin molded article.

Another object of the present invention is to provide a surface modification method capable of preventing surface migration and exudation of additives such as plasticizers in polyvinyl chloride resin molded articles.

Further objects of the present invention are stain resistance, weather resistance, abrasion resistance,
and to provide a surface modification method capable of obtaining a polyvinyl chloride resin molding with excellent water and oil repellency (there are two methods).

Structure of the Invention The method for surface modification of a polyvinyl chloride resin molded article of the present invention comprises applying a low-temperature plasma treatment to the surface C2 of a polyvinyl chloride resin molding in a fluoridation treatment gas atmosphere. death,
The fluorination treatment gas is characterized in that a mixed gas containing at least 1 m of fluorocarbon and (-hydrogen) is used.

The fluorine treatment gas may contain at least one inorganic gas along with fluorocarbon and hydrogen.

3. Detailed Description of the Invention The polyvinyl chloride resin molded article processed by method C2 of the present invention has polyvinyl chloride as its main component, and contains vinyl chloride, an olefin, and an example of an additive resin component. Copolymers of ethylene, propylene or imbutylene, or styrene, etc.: vinyl chloride and diene compounds, such as butadiene.

Copolymers with isoprene, etc.; copolymers of vinyl chloride with acrylic acid, methacrylic acid, or halogenated olefins, ethylene-vinyl acetate copolymers; or rubbers, such as ABS.

May contain SBR or NBR, etc., and further (-1
Additives may include plasticizers, stabilizers, fillers, antioxidants, UV absorbers and/or colorants.

In general, soft polyvinyl chloride thread resin moldings are preferred, but are not limited thereto.

Shape and dimensions of the molded product (: There are no particular limitations, and the molded product may be any film, sheet, tape, or other molded product having desired dimensions.

The fluorination process gas of the method of the invention contains at least one fluorocarbon, hydrogen and at least one inorganic gas more than the required carbon.

Fluorocarbons can be selected from perfluorocarbons, unsaturated fluorocarbons, cyclic fluorocarbons, and substituted versions thereof, including perfluorocarbons such as tetrafluoromethane, hexafluoroethane, perfluoropropane, perfluoro-n-butane, perfluorocarbon Pentane and perfluoro-n-
Preferably, it is selected from hexane and the like. Preferred fluorocarbons according to the method of the present invention are perfluorocarbons represented by the general formula % (where nH1, 2, or 3 is represented in the above formula).

The content of fluorocarbon and hydrogen in the fluorination treatment gas (there is no particular limitation, but the effect of preventing additives such as plasticizers from migrating to the surface and oozing out, and the water repellency of the modified surface of the resulting molded product, etc.) Considering T, the fluorocarbon content and hydrogen content in the fluorination treatment gas are calculated by the following formula +1
1 relationship: 0.2 people≦B≦2. OA (11 [However, in the above formula, A represents the content (volume) of fluorocarbon, and B represents the content (volume) of hydrogen.) It is preferable to satisfy the following.

In the case of 0, 2 A > H, the modified surface of the molded body (2) may have an unsatisfactory effect of preventing additive migration and exudation (2). This phenomenon was discovered by the present inventors (2).As the water repellency of the modified surface of the molded body becomes larger, the water repellency of the modified surface of the molded body decreases, resulting in excessive hydrophilicity. Body surface contact angle meter (Kyowa Kagaku model CA-D) (2) water contact angle measurement, ESCA (Shimadzu Corporation ESCA-750) It was confirmed.

Method C of the present invention The fluorinated gas used in the two ingredients is adjusted as described above (2. fluorocarbon content A and hydrogen content B (2.) so that the water contact angle on the modified surface is approximately It is possible to control its hydrophilicity and water repellency in the range of 125-70 degrees.

However, in order to ensure that the resulting modified surface has suitable antifouling properties, abrasion resistance, water and oil repellency, and to completely prevent surface migration and oozing of additives such as plasticizers (secondly, the above-mentioned (It is preferable to adjust the content of fluorocarbon and hydrogen so as to satisfy the relationship of Equation 11.

The inorganic gases that can be added to the fluorination treatment gas preferably include tICo, Ar, He, CO2, and N2.
It is preferably selected from CCO and Ar.

The content of the inorganic gas (there is no particular limitation. However, the present inventors set the content of the inorganic gas to an appropriate value (-) in relation to the amount of hydrogen gas, so as to achieve the desired effect. In order to achieve this, we have found that it is possible to save the necessary hydrogen content, the power required for processing, and the processing time.

That is, the content of inorganic gas-produced hydrogen in the fluorination treatment gas is determined by the following formula (1): C≧50/B (Ml (However, in the above formula, B (4) (represents volume), and C represents the content (volume) of inorganic gas]. , it becomes possible to improve the safety and economic efficiency of the treatment process.

The method of the present invention (method 1 for generating low-temperature plasma in -) is not particularly limited, and may be a conventionally known glow discharge method.

Either a corona discharge method or a microwave discharge method may be used. Further, there is no particular limitation on the electrode type in the low-temperature plasma generator, and any of the conventionally used electrodeless type, parallel plate electrode type, internal electrode type, and external electrode type may be used.

In low-temperature plasma processing, the pressure inside the processing equipment is 0.05 to 1
This is done at a low pressure of 0 Torr. If the processing power UWC is not limited to extremely low C2, it will be difficult to discharge and form plasma, and if it is extremely high, the etching effect due to fluorine C2 on the surface of the molded product will be excessive, resulting in plasticity. The effect of preventing surface migration and exudation of additives such as additives tends to be insufficient.In addition, although the treatment time is not particularly limited, if the treatment time is too long, the surface of the molded product tends to yellow. Also, if the length is too short (:), the processing effect will be insufficient.

The method of the present invention will be explained below in 42. Example 1 Polyvinyl chloride resin having the following composition: 100 parts by weight of polyvinyl chloride (Kaneka S-1300) DOP 60, # Epoxidized soybean oil 3 # Ba - Zn-based stabilizer 2# heated roll (second roll, heating temperature 160℃, crosstalk time 1
A test piece taken from this polyvinyl chloride resin film was heated and kneaded for 0 minutes and then molded into a film with a thickness of 0.3 ffIm. Pressure T!0:], O-' Tarr (2 exhausts,
Is this hexafluoroethane gas Y? 4 people, pressure inside the device k0. It was adjusted to I Torr. Next (: Stop the introduction of hexafluoroethane gas and run the inside of the device again at 10-5
It was evacuated to Torr. Predetermined amounts of hydrogen gas and hexafluoroethane gas were each introduced into this reduced pressure apparatus to adjust the overall pressure to 0.15 Torr. In the fluorine treatment gas atmosphere prepared in this manner, the test piece was subjected to low-temperature plasma treatment under the following conditions.

High frequency power source: 13.56 MHz (manufactured by Nippon Koshushu Co., Ltd.) Power consumption = 100 W Treatment time = 10 minutes The water contact angle of the treated test piece obtained was
The measurements were made using a contact angle meter model CA-D, and the amount of plasticizer extracted from the surface was measured using the following method.

That is, a test piece was placed in the bottom of a Pelger-type extraction tester, and a 1:50 ratio of hexane was added thereto. The contact area between hexane and the test piece was Hz, 7=.

The test device was shaken for 5 hours at a temperature of 40°C. Next, DOP (dioctyl phthalate) extracted with C2 in hexane was measured by tv gas chromatography using dinonyl phthalate as an internal standard.

The above operation was repeated by varying the volume of hydrogen and hexafluoromothane in the fluorine treatment gas between 1'kO and 300% (-).

The relationship between the water X/hexafluoroethane volume ratio, the amount of plasticizer extracted from the modified molded product, and the water contact angle on the modified surface is shown in Figure 1 (2).

As is clear from Figure 1, C2, hexafluoroethane C
By adding dihydrogen, the amount of plasticizer extraction is significantly reduced and the water contact angle is also reduced.

In addition, Figure 1 shows that the hydrogen content is 20-20% of the hexafluoroethane content based on the plasticizer extraction amount and water contact angle.
00% range (indicates that two is preferable).

Implementation fI12 The same operation as in implementation fl11 was repeated 9 times. However, the amount of hexafluoroethane in the fluorination treatment gas was set to 20 sec, and the amount of hydrogen gas was changed to 4, 6, 6,
and 8 sec, and argon gas was further introduced, and the amount of argon gas introduced was varied within the range of θ to 20 sec. Further, in the low-temperature plasma treatment, the power consumption was 50 watts, and the treatment time was 5 minutes.

The amount of plasticizer extracted from the obtained modified molded body is shown in Figure 2.

FIG. 2 shows that the addition of a fluorinated treatment gas (=argon gas) can thereby reduce or increase the amount of plasticizer extracted.

Special C: In this implementation INC, low temperature plasma treatment (:
However, the amount of argon gas added was adjusted (secondarily, the amount of plasticizer extracted was made zero). In other words, when the hydrogen gas feed rate is 8 sec and B/A=0.4, the argon gas feed rate ftY is 8 sec or more - 2, then (C≧8)>(50/ 8=6.25)
+7) The relationship is established, and the amount of plasticizer extracted becomes zero.

In addition, when the amount of hydrogen gas fed is 6 seconds, B/A=0
．． 3, the amount of argon gas supplied is '&10105c or more (
: Then, the relationship (C200)>(50/6=8.33) is established, and the amount of plasticizer extracted becomes zero.

Furthermore, when the C1 hydrogen gas feed rate is 4 sec and B/A = 0.2, the argon gas feed rate is 14 sec or more (
Then, the relationship (C204)>(50/4=12.5) is established, and the amount of plasticizer extracted becomes zero.

As is clear from the above facts, increasing the amount of argon gas (and therefore reducing the amount of hydrogen gas used)
This makes it possible to reduce the amount of plasticizer extracted to zero.

Example 3 The operation was repeated under the same conditions as in Example 2. However, the amount k of hexafluoroethane fed in the fluorination treatment gas C-
30 s, ccm, and the amount of hydrogen gas fed was 10 and 20 sec, and further, carbon oxide was fed, and the feeding rate was changed in the range fBYO to 10 sec.

The amount of plasticizer extracted from the obtained modified molded body is shown in FIG.

Same as Example 2 (2. Hydrogen gas feed amount 20SCCil)
(C20)>(50/20=2.5) at l, and (C20)>(50/10 at hydrogen gas feed amount of 10 Seem).
=5) is established, and by increasing the amount of carbon oxide fed, it is possible to reduce the amount of hydrogen gas used and efficiently reduce the amount of plasticizer extracted to zero C2.

January ■ Ladder [The method of the present invention modifies the surface of polyvinyl chloride resin molded products to prevent surface migration and exudation of additives such as plasticizers, and improves weather resistance, stain resistance, abrasion resistance, and It is possible to obtain a modified polyvinyl chloride resin molded product with water and oil repellency.

The polyvinyl chloride resin molded article modified in this way is
Tents and awnings.

Containers, other industrial materials, and tablecloths, etc., which have a wide range of uses.

[Brief explanation of drawings]

Figure 1 shows the ratio of the hydrogen content to the fluorocarbon content C2 in the fluorinated gas and the plasticizer extraction of the obtained modified polyvinyl chloride resin molded body using the method of the present invention (-). Figure 2 and Figure 3 are factor graphs showing the relationship between the amount and the water contact angle, respectively, in the method of the present invention.
FIG. 1 is a graph illustrating the relationship between the hydrogen content and inorganic gas content in the fluorinated gas (-) and the amount of plasticizer extracted from the obtained modified polyvinyl chloride resin molded article. Hexafluoroethane volume ratio Figure 2 Amount of argon introduced (sccm) Figure 3 Amount of carbon monoxide introduced (sccm) Procedural amendment (voluntary) April 7, 1985 Manabu Shiga, Commissioner of the Japan Patent Office 1, Incident Indication 1982 Patent Application No. 102686 2 Name of the invention Method for surface modification of polyvinyl chloride resin molded articles 3 Relationship with the case of the person making the amendment Name of patent applicant (114) Director of the Agency of Industrial Science and Technology Kawa 1) Yutaka Department (1 other person) 4. Sub-agent address 5-8-1o Toranomon-chome, Minato-ku, Tokyo 105.
Subject of amendment A: drawings (second
(Figure, Figure 3) 6. Contents of the amendment (1) In the 8th line of page 4 of the specification, the "front adhesive force" is corrected to ``one side adhesive force J. (2) In the specification, page 10, line 14. In the second line, "hydrogen content" is corrected to "hydrogen content,". (3) Page 12, line 11, r1300J' 1
Corrected to 303 J. Correct the mouth, Figures 2 and 3 as shown in the attached sheet. 7. Inventory drawings of attached documents (Figures 2 and 3) 1 copy 020 Argon introduction amount (sccm) Figure 2

Claims (1)

[Claims] 1. The surface of a polyvinyl chloride resin molded article (2. A method of subjecting it to low-temperature plasma treatment in a fluorination treatment gas atmosphere (:
A method for surface modification of a polyvinyl chloride resin molded article, characterized in that a mixed gas containing at least one kind of fluorocarbon and hydrogen is used as the fluorination treatment gas. 2. The method according to claim 1, wherein the fluorocarbon is selected from perfluorocarbons of the general formula: % where n represents 1, 2 or 3. 3. The content (volume) of hydrogen and fluorocarbon in the processing gas (2) has the following relationship: 0.2 people ≦ B
<2. OA [However, in the above formula, A represents the content (volume) of fluorocarbon, and B represents the content (volume) of hydrogen.] The method according to claim 1, which satisfies the following. 4. The method according to claim 1, wherein the processing gas contains at least one inorganic gas in combination with the fluorocarbon and hydrogen. 5. The content (volume) of inorganic gas and hydrogen in the processing gas has the following relationship: C≧507B [However, in the above formula, B represents the content (volume) of hydrogen, and C
represents the content (volume) of the inorganic gas], wherein the inorganic gas is CoHAr, He#CO2
and N2, the method 07 according to claim 4, wherein the low temperature plasma treatment
The method according to claim 1, which is carried out under low pressure of rr.