JPS6314403B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for modifying vinyl chloride-based resin records, and its purpose is to improve antistatic properties, abrasion resistance, etc. by modifying the surface characteristics of the records. be. Currently, commercially available record discs have a problem in that they are highly electrostatically charged, attract dust and the like to the disc surface, and generate significant noise. As a method to improve this, methods have been proposed to incorporate or apply antistatic agents, but the former significantly impairs the molding processability of records and is less effective, and the latter is less effective. In addition to poor compatibility with records, it has the disadvantage of being difficult to apply evenly. If a certain amount of solvent or the like is mixed into the coating agent for the purpose of improving this familiarity, significant adverse effects on sound quality such as generation of noise will be brought about. The present inventors have been conducting research on modifying the surface of vinyl chloride resin molded products such as vinyl records by treating them with low-temperature plasma. When low-temperature plasma treatment is performed, the treatment effect tends to be uneven in some parts of the board surface, and if the treatment is performed strongly to achieve a sufficient treatment effect on the entire surface,
There is a problem in that excessive processing inevitably occurs, which in turn leads to an increase in noise generation. The present invention was completed as a result of repeated research in consideration of such technical problems, and consists of a plurality of electrodes arranged in two parallel rows, with each electrode of one row of electrodes connected to the high-frequency power input side. In an internal electrode discharge type low-temperature plasma generator in which each electrode of the other electrode row is connected to the ground side, a record made of vinyl chloride resin is moved between the electrode rows while rotating the axis for 10 minutes. The present invention relates to a method for modifying a record disc, which is characterized in that it is treated with low-temperature plasma of an inorganic gas of less than Torr. The method of the present invention is particularly effective in improving the antistatic properties and abrasion resistance of vinyl records. According to this method, the antistatic properties and abrasion resistance can be improved without adversely affecting the sound quality of vinyl records. Applied uniformly over the entire surface. Furthermore, this method has the remarkable effect that the low-temperature plasma treatment of records can be carried out more easily and reliably. The method of the present invention will be explained in detail below. The internal electrode discharge type low-temperature plasma generator used in the method of the present invention is a device consisting of the two electrode arrays described above installed in a container that can have a reduced pressure inside. FIG. 2 schematically shows a specific embodiment of this electrode array arrangement and means for moving the molded product (record disc) to be processed. Figure 1 shows a configuration in which a plurality of rod-shaped electrodes 1 are arranged in two rows of four electrodes approximately parallel to each other, and in each electrode row, the electrodes marked with and are on the high-frequency power input side, and those marked with and are on the ground side. Connect to each. As a result, one electrode row is on the high frequency power input side and the other electrode row is on the ground side, and the electrodes facing each other in both electrode rows are a combination of the input side and the ground side. The distance between the opposing electrodes between these two electrode rows is a distance that allows sufficient processing, and is determined through experiments.
On the other hand, it is desirable that the intervals between the electrodes arranged in a row in each electrode row be determined so that the entire length of the electrode row is a distance that allows the record to rotate (rotate) one or more times. Reference numeral 2 in FIG. 1 is a device for moving a record to be subjected to low-temperature plasma treatment between both electrode rows. 3 indicates a vinyl record. 4 is a drive motor, and 5 and 5' are power transmission mechanisms. The arm 6 provided in the power transmission mechanism 5' is driven to rotate to a position where the arm is approximately horizontal between the electrode rows, and as a result, the record disc 3 rotatably attached to the tip of the arm 6 is rotated between the electrode rows. move between.
This movement operation is repeated several times. Of course, this moving operation should be determined in relation to the plasma processing time (several seconds to several minutes). A belt 8 connects the power transmission mechanism 5' and the shaft 7 to which the record 3 is attached.
When the record is moved between electrode rows, it rotates on its own axis (rotates on its axis). By providing this rotation mechanism, records can be more uniformly treated with low-temperature plasma. The electrode is provided with an inlet 9 and an outlet 9' for a heat medium (water) to control its temperature. FIG. 2 shows another example of the shape of the electrode and the means for moving the record, in which 11 is a plate-shaped electrode provided with a plurality of holes, 12 is an insulating plate, 1
Reference numerals 3 and 13' denote rail mechanisms for moving the record 3 while rotating it. In this figure, the number of electrodes in each electrode row is five arranged with an insulating plate in between, and the electrodes marked with and are connected to the input side, and those marked with are connected to the ground side. As a result, the basic arrangement of the electrodes is the same as that shown in FIG. There is no particular problem with the material of the electrode used as long as it is electrically conductive, and examples include iron, stainless steel, copper, and aluminum. Various structures can be considered for the shape, such as a rod shape, a flat plate shape, a flat plate with holes, or a wire mesh shape, but a shape that allows gas to pass through and can be cooled is preferable. This cooling is done to ensure that the treatment effect is uniform and to prevent the molded product (record) from being deformed due to the heat generated in the electrodes, and must be cooled to below 60℃ using a cooling medium. is preferred. It is preferable that the electrodes, especially the input side electrodes, be coated with enamel or glass. If the metal is exposed, sparks and the like in this area will promote the generation of noise. The method proposed by the present invention imparts sufficient wettability and antistatic properties to the record, and more preferably the surface of the activated record after plasma treatment contains 0.001 to 50% surfactant. By post-treating with an aqueous solution to fix the surfactant on the surface of the record, it is possible to impart a permanent antistatic effect. The surfactant to be used may be cationic, anionic, nonionic, amphoteric, etc., but cationic surfactants are most preferred for their antistatic effect. As a post-treatment method, any method such as spraying, impregnation, brushing, etc. can be used, but spraying is most preferable from a practical standpoint. Furthermore, when coating, it is also possible to add a solvent such as methanol or ethanol to improve the wettability to the record. Since the vinyl record treated in this manner is sufficiently hydrophilic, the surfactant is uniformly distributed, exhibits permanent antistatic ability, and does not cause any adverse effects such as noise. The plasma generation conditions for low-temperature plasma processing are as follows: while flowing an inorganic gas of 10 torr or less into the low-temperature plasma generator, a power of 13.56 MHz and several watts to several kW may be applied between the electrodes, and the plasma processing time varies depending on the applied voltage, but generally a few seconds to several minutes is sufficient. In addition, there are various means for plasma treatment other than the above-mentioned methods. For example, low frequency, microwave, etc. can be used as the discharge frequency band, and the plasma generation mode includes not only glow discharge but also corona discharge,
Spark discharge, silent discharge, etc. can also be employed. Examples of inorganic gases (inorganic or inert gases) include helium, neon, argon, nitrogen, nitrous oxide, nitrogen dioxide, oxygen, air, chlorine, hydrogen chloride, carbon monoxide, carbon dioxide, hydrogen, etc. These gases may be used alone or in combination. By setting the pressure of these gases in the plasma generator to 0.001 to 10 torr (preferably 0.01 to 1 torr), the desired plasma can be generated satisfactorily. By performing plasma treatment in this way,
The surface of the record is made hydrophilic, and if an antistatic agent is used, a synergistic effect with it will provide a remarkable antistatic effect, and the surface crosslinked layer formed by plasma treatment is a stabilizer and antistatic agent. This has the advantage of suppressing surface oozing of internal additives, making the above effects permanent, improving wear resistance, and reducing noise. The purpose of the present invention is to improve the surface characteristics of records made of vinyl chloride resin, but the vinyl chloride resins used in the manufacture of vinyl records include polyvinyl chloride and various other vinyl chloride-based resins. Examples of the comonomer of this copolymer include vinyl acetate, ethylene, propylene, acrylic acid or methacrylic acid, or esters thereof. Incidentally, these copolymers include those in which two or more of the above comonomers are used at the same time, as well as various graft copolymers mainly composed of vinyl chloride. When producing records from these vinyl chloride resins, various additives such as plasticizers, antistatic agents, stabilizers, and lubricants are added as necessary.
Examples of plasticizers include phthalate esters, aliphatic dibasic acid esters, glycol esters, fatty acid esters, phosphate esters, citric ester plasticizers, as well as epoxy plasticizers, polyester plasticizers, urethane plasticizers, Examples of antistatic agents include primary amine compounds, tertiary amine compounds, quaternary ammonium compounds, cationic surfactants made of pyridine derivatives, soaps, sulfated oils, and sulfated esters. oil, sulfated amide oil, olefin sulfate ester salts, fatty alcohol sulfate ester salts, alkyl sulfate ester salts, fatty acid ethyl sulfonates,
Anionic surfactants consisting of alkyl sulfonates, alkylnaphthalene sulfonates, alkylbenzene sulfonates, succinate sulfonic acids, phosphate esters, etc., fatty acid esters of polyhydric alcohols, ethylene oxide adducts of aliphatic alcohols, fatty acids Ethylene oxide adducts of aliphatic amino compounds or aliphatic amide compounds, ethylene oxide adducts of alkylphenols, ethylene oxide adducts of alkylnaphthols, ethylene oxide adducts of partial fatty acid esters of polyhydric alcohols , nonionic surfactants such as polyethylene glycol, and amphoteric surfactants such as carboxylic acid derivatives and imidazoline derivatives. Furthermore, as stabilizers, metal soaps such as calcium stearate, zinc stearate, cadmium stearate, lead stearate, barium stearate, dibutyltin dilaurate, di-
Organotin compounds such as n-octyltin dimaleate, di-n-octyltin mercaptide, lead-based stabilizers such as tribasic sulfates, dibasic lead phosphite, and various composite stabilizers: Examples of lubricants include esters such as butyl stearate, aliphatic amides such as ethylene bisstearamide, higher fatty acids and their esters, and polyethylene wax. In addition, various other additives used in molding vinyl chloride resins such as fillers, antioxidants, ultraviolet absorbers, antistatic agents, anti-drop agents, pigments, dyes,
A crosslinking aid or the like may also be added. The vinyl record that has been given antistatic properties by the method of the present invention has no change in appearance and has excellent durability and durability of the treatment effect. Next, examples of the present invention and comparative examples will be given. Example 1 Vinyl chloride-vinyl acetate copolymer 100 parts by weight Epoxy-modified soybean oil 1.0〃 Dibutyltin mercaptide 1.0〃 Calcium stearate 0.3〃 Using a compound consisting of the above composition, preheating was performed at 140°C using a record molding machine at a pressing temperature.
A record was created at 165℃. This record was subjected to low-temperature plasma treatment in the internal electrode discharge type low-temperature plasma generator equipped with the electrode arrangement mechanism shown in FIG. 1 in the following manner. Adjust and maintain the pressure at 0.15 torr while venting argon gas into the plasma generator, and apply 500 W to the electrodes.
A low-temperature plasma was generated by applying high-frequency power to generate a discharge, and arm 6 was operated to move the record so that it remained between both electrode rows for 10 seconds for processing. Also, at this time, the record was rotated five times (rotated). Next, a dilute aqueous solution of a cationic surfactant was applied to the surface of this low-temperature plasma-treated record, washed with water, and air-dried. The results of measuring various physical properties of the thus treated record (Sample 1-3) are shown in Table 1 together with the results of the examination of Samples 1-1 and 1-2 below. Sample 1-1: A record obtained by press molding in the same manner as Sample 1-3 was treated only with a diluted aqueous solution of a cationic surfactant without undergoing low-temperature plasma treatment. Sample 1-2: A record obtained by press molding in the same manner as Sample 1-3 was fixed between the high-frequency power input side electrode and the earth side electrode, and the argon gas pressure and applied power were applied to Sample 1-3.
A low-temperature plasma treatment was performed for 10 seconds in the same manner as above, and a diluted aqueous solution treatment of a cationic surfactant was further performed in the same manner. However, samples 1-2 and 1 shown in Table 1
-3 data was measured on the input side of the record.

[Table] Example 2 A record obtained by press molding in the same manner as in Example 1 was subjected to low temperature plasma treatment under the following conditions using the internal electrode discharge type low temperature plasma generator shown in FIG. A diluted aqueous solution treatment of a surfactant was performed. Venting gas: Argon gas, 0.1 Torr Applied power: 1.0 KW Plasma treatment time: 5 seconds The record was passed between the two electrode rows using the rail mechanisms 13 and 13' for 5 seconds. Record treated in this way (Sample 2-
The results of measuring various physical properties of 2) are shown in Table 2 together with the results of examining Sample 2-1 below. Sample 2-1: A record obtained by press molding in the same manner as Sample 2-2 was fixed between the high-frequency power input side electrode and the earth side electrode, and the argon gas pressure and applied power were applied to Sample 2-2.
A low temperature plasma treatment was performed for 5 seconds in the same manner as above, and a diluted aqueous solution treatment of a cationic surfactant was further performed in the same manner. However, all the data shown in Table 2 were measured on the input side of the record.

[Table] Example 3 Low-temperature plasma treatment and treatment with a dilute aqueous cationic surfactant solution were performed in the same manner as in Example 1, except that the plasma generation conditions were as follows. Ventilation gas: Argon gas, 0.3 torr Applied power: 1.0KW Plasma treatment time: 3 seconds Record rotation speed: 5 times/5 seconds The results of measuring various physical properties of the record treated in this way (sample 3-2) are as follows: Sample 3 below
The results are shown in Table 3 along with the results of the investigation regarding No. 1. Sample 3-1: A record obtained by press molding in the same manner as Sample 3-2 was fixed between the high-frequency power input side electrode and the earth side electrode, and the argon gas pressure and applied power were applied to Sample 3-2.
A low-temperature plasma treatment was performed for 3 seconds in the same manner as above, and a dilute aqueous solution treatment of a cationic surfactant was further performed in the same manner. However, all the data shown in Table 1 were measured on the input side of the record.

[Table] Example 4 Low-temperature plasma treatment and treatment with a dilute aqueous cationic surfactant solution were performed in the same manner as in Example 1, except that the plasma generation conditions were as follows. Venting gas: Argon gas, 0.2 Torr Applied power: 500W Plasma treatment time: 20 seconds, 30 seconds, 1 minute, 3 minutes Rotation (rotation) of the record within the plasma treatment time: 5 times In this way When the various physical properties of the treated vinyl records were measured, the results shown in Table 4 were obtained.

[Table] Example 5 A record obtained by press molding in the same manner as in Example 1 was subjected to low temperature plasma treatment under the following conditions using the internal electrode discharge type low temperature plasma generator shown in FIG. A diluted aqueous solution treatment of a surfactant was performed. Ventilation gas...Argon gas, 0.2 Torr Applied power...500W Plasma treatment time...10 seconds Number of rotations (rotations) of the record within the plasma treatment time Sample 5-1...0 rotation Sample 5-2...1 rotation Sample 5-3...5 rotations Sample 5-4...10 rotations When various physical properties were measured for each record treated in this way, the results shown in Table 5 were obtained.

【table】

【table】 [Brief explanation of the drawing]

Figure 1 schematically shows the arrangement of electrodes and the means for moving the record in the internal electrode discharge type low temperature plasma generator used in the method of the present invention, and Figure 2 shows the arrangement of the electrodes and the means for moving the record. This figure shows another aspect of the means. 1, 11... Electrode, 2 ... Record moving means, 3
...Record, 4...Drive motor, 5,5'...Power transmission mechanism, 6...Arm, 12...Insulating plate, 13,
13'...Rail mechanism, 24...Suspension movement mechanism.

Claims (1)

[Claims] 1 Consisting of multiple electrodes arranged in two parallel rows,
In an internal electrode discharge type low temperature plasma generator in which each electrode of one electrode row is connected to the high-frequency power input side and each electrode of the other electrode row is connected to the ground side, a record made of vinyl chloride resin is A method for modifying a record, comprising treating it with low-temperature plasma of an inorganic gas of 10 torr or less while rotating and moving between the electrode rows.