JPS6338283B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for processing while maintaining processing effects and maintaining initial performance at any time, and particularly relates to a method for effectively utilizing low-temperature plasma processing effects even after a predetermined period of time has elapsed. . [Prior Art] Conventionally, various methods have been used to improve adhesion using low-temperature plasma treatment and to improve various performances by using low-temperature plasma treatment as an intermediate step. The inventor also applied for a patent application in 1983-
No. 208356 and other publications have proposed various improvement methods. However, if the next process is carried out immediately after low-temperature plasma treatment in such a method, excellent effects are recognized, but if the next process is carried out immediately after low-temperature plasma treatment, it may be necessary to The product is bought and sold in the form of a processed product, and the user who purchased it performs the final process again.
When trying to obtain a final product, there were problems as the desired effect was often not obtained. In addition, low-temperature plasma processing is currently still in the development stage both technically and in terms of equipment for long sheet-like objects, and it is difficult to process it in batches or at any time. In some cases, problems like the ones mentioned above are encountered. [Problems to be solved by the invention] Therefore, if such problems can be solved and the desired performance can be obtained by performing post-processing at any time after low-temperature plasma treatment, the industrial value will be increased. is extremely large. The inventors of the present invention were aware of this problem, and as a result of various studies, after low-temperature plasma treatment, the treated substrate is immediately stored in a shielded state from moisture, oxygen, or both, and then removed from storage when necessary. The present inventors have discovered that extremely favorable results can be obtained by immediately performing the desired post-processing, leading to the completion of the present invention. [Means for Solving the Problems] According to the present invention, a method for maintaining the treatment effect of a substrate subjected to low-temperature plasma treatment is provided.
This method uses a base material that has been subjected to low-temperature plasma treatment.
When storing it until it undergoes the desired post-processing,
After the surface of the base material is subjected to low-temperature plasma treatment, the base material is wrapped as soon as possible in a packaging material that has low moisture permeability, low oxygen permeability, or both, and is stored in that state. To explain the present invention in more detail, the present invention can be applied to wide sheet-like elongated objects. For the reasons mentioned above, wide sheet-like materials are very likely to suffer from performance deterioration after low-temperature plasma treatment. In the present invention, the sheet-like wide and elongated object has a width of about 30 cm, 50 cm, or 1 m or more, for example. This is also a problem for smooth sheet-like materials, such as films, film-like materials, and processed sheets, but especially for fibrous base fabrics, the gaps between the constituent fibers are porous, and there are many opportunities for moisture and oxygen to be contained. This often becomes a problem. A fibrous base fabric can also be used as the base material in the present invention. The fibrous base fabric includes natural fibers such as cotton and hemp, inorganic fibers such as glass fibers, carbon fibers, asbestos fibers, and metal fibers, recycled fibers such as viscose rayon, and semi-synthetic fibers such as Kyupura. For example, di- and tri-acetate fibers, and synthetic fibers such as nylon 6, nylon 66, polyester (such as polyethylene terephthalate) fibers, aromatic polyamide fibers, acrylic fibers, polyvinyl chloride fibers, polyolefin fibers, and water-insoluble or It is made of at least one kind selected from polyvinyl alcohol fibers that have been rendered difficult to dissolve. The fibers in the base fabric may be in any form such as short fiber spun yarn, long fiber yarn, split yarn, or tape yarn, and the base fabric may be a woven fabric, a knitted fabric, a nonwoven fabric, or a composite fabric thereof. Good too. The type and form of the fibers are not particularly limited. Of course, it may also be a coarse or dense fabric made of monofilaments. Further, these fiber base fabrics may be sheet-like materials coated with synthetic resin, synthetic rubber, or natural rubber, which are high molecular weight polymers. Examples of synthetic resins include polyvinyl chloride (PVC), polyurethane, ethylene-vinyl acetate copolymer, isotactic polypropylene, polyethylene, polyacrylonitrile, polyester, polyamide,
There are fluorine resins, silicone resins, and other known materials. Examples of preferable synthetic rubbers include styrene-butadiene rubber (SBR), chlorosulfonated polyethylene rubber, polyurethane rubber, butyl rubber, isoprene rubber, silicone rubber, fluorine rubber, and other known materials. These polymers may contain plasticizers, fillers, colorants, various stabilizers, flame retardants, and the like. Further, these polymers may be in the form of individual films or sheets. These sheet-like materials are subjected to low-temperature plasma treatment in order to improve post-processability. The low-temperature plasma treatment can be performed by exposing the fibrous base fabric or the like to low-temperature plasma of a gas that does not have plasma polymerizability under a pressure of 0.01 to 10 Torr. As the plasma generation conditions, for example, 13.56 MHz and 10 to 500 W power may be applied between the electrodes, and sufficient results can be obtained whether the discharge is a polar discharge or a non-polar discharge. The plasma processing time varies depending on the applied voltage, but generally a few seconds to several tens of minutes is sufficient. In addition, there are various methods for plasma processing other than the above-mentioned methods. For example, low frequency, microwave, direct current, etc. can be used as the discharge frequency band,
The plasma generation mode can be selected from glow discharge, corona discharge, spark discharge, silent discharge, etc. In addition to external electrodes, the electrodes may also be internal electrodes, coil types, etc., capacitively coupled or inductively coupled. However, no matter what method is used, care must be taken to ensure that the surface of the material is not altered by the discharge heat. Gases that do not have plasma polymerizability include helium, neon, argon, nitrogen, nitrous oxide,
These include nitrogen dioxide, oxygen, air, carbon monoxide, carbon dioxide, hydrogen, chlorine, halides such as hydrogen chloride, bromine cyanide, and tin bromide, and sulfides such as sulfur, sulfur dioxide gas, and hydrogen sulfide. These gases can be used alone or in combination. The sheet-like material treated in this manner is stored by wrapping it in a material having low moisture permeability, low oxygen permeability, or both, so as to block moisture and oxygen as soon as possible. In that case, it is preferable to continuously wind it up into a roll and quickly wrap it in a wrapping material, but other methods may also be used. It is preferable to carry out continuous work as soon as possible. Of course, it may be carried out in vacuum or inert gas. Moisture-blocking packaging materials include low-density polyethylene, high-density polyethylene, polypropylene, polyethylene terephthalate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, saponified ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer. When combined, other films or sheets are crushed, but at 40℃ and 90%RH, the weight is 50g/ ^m2 .
24hr/25μm or less, preferably 30g/ ^m2・24hr/
25μm or less, more preferably 10g/m ²・24hr/
It is preferable to have a diameter of 25 μm or less. Packaging materials with low oxygen gas permeability include polyvinylidene chloride, ordinary cellophane, polyethylene terephthalate, nylon, saponified ethylene-vinyl acetate copolymer, polyacrylonitrile, and others.
RH: 100 c.c./m ²・24 hr・atm/25 μm or less, preferably 30 c.c./m ²・24 hr・atm/25 μm or less, more preferably 10 c.c./m ²・24 hr・atm/25 μm The following are good. Of course, there is no problem in using packaging materials that are a combination of materials that have these properties and materials that do not.
PET/LDPE, PVDC coated nylon/LDPE,
PVDC coated PET/LDPE, PVDC coated cellophane/LDPE, PVDC coated cellophane/CPP,
PET/PVDC/LDPE, nylon/LDPE, nylon/EVA, nylon/ionomer,
LDPE/PVDC/LDPE, EVA/PVDC/EVA,
Nylon/EVAL/LDPE, PET EVAL/
LDPE, OPP/EVAL/LDPE, OPP/
There are PVDC/LDPE, PVDC coated OPP/LDPE, aluminum vapor deposited PET/LDPE, etc. It is preferable to store the product by wrapping it in a packaging material that satisfies both the moisture permeability and oxygen gas permeability conditions described above. In addition to satisfying the above-mentioned performance, the packaging material may be attached to a reinforcing base material, such as a film, paper, or cloth, for the purpose of reinforcing strength. The packaging material may be transparent or opaque;
Moreover, it may or may not be colored. It is even better if the packaging material contains an ultraviolet absorber, and it is particularly preferred if it is transparent. The method of wrapping with the packaging material may be, for example, wrapping a film made of these materials into a roll and thermally sealing it, adhesively sealing it with an adhesive tape, or any other method. In the case of fibrous base fabric, since there are many spaces between the fibers, it is better to perform vacuum packaging or inert gas filling packaging to remove the gas or moisture contained therein. Furthermore, even if the packaging material is selected, it is difficult to achieve zero moisture permeability and oxygen gas permeability, so if desired, a conventionally known desiccant such as silica may be used, but it is not limited to this. Not allowed. Furthermore, any conventionally known oxygen scavenger can be used as the oxygen scavenger, such as "Ageless" manufactured by Mitsubishi Gas Chemical Co., Ltd., and the like. By combining these methods, the intermediate products treated with low-temperature plasma can be stored while being shielded from moisture and oxygen. In this case, one method is to use a winding core with holes in the core wall and to put a desiccant, an oxygen absorber, etc. therein. The low-temperature plasma-treated intermediate products stored in this manner are then released from storage at a desired time and immediately subjected to processing for various purposes. By implementing the present invention, the effect of low-temperature plasma treatment can be recognized in conventional continuous processing, but since the final process cannot be carried out for a long period after treatment, the effect of low-temperature plasma treatment may disappear over time. Even in this case, the loss of such effects can be completely prevented, so the technical effects of the present invention are extremely large. Examples Hereinafter, the present invention will be further explained with reference to Examples. Example 1 Polyester fiber base fabric: 1000d x 1000d 32 pieces/inch x 32 pieces/inch plain weave, area weight 300 g/m ² thickness 0.35 mm, and Hobotex FTC (Ciba-
Geigy product, amino resin derivative water repellent) 4.5%
Treated with solution. Catalyzer RB (Ciba-Geigy product) was used as a reaction catalyst.
It was used at a ratio of 25% by weight relative to FTC. After soaking the base fabric in a water repellent bath, squeeze it with a mangle so that the wet adhesion amount is 100g/ ^m2 , and
It was pre-dried at 90°C and then baked at 150°C for 3 minutes to make it water repellent. The solid content of the water repellent was 1.5% owf. Furthermore, the sample obtained in this way was processed using a low-temperature plasma processing device at a vacuum level of 2 Torr, an oxygen gas flow rate of 100 ml/min, and a high frequency output of 4 KW (frequency
The sample was subjected to low-temperature plasma treatment for 2 seconds at 20KHz). The sample thus obtained was continuously wound up in 30 m increments, immediately wrapped tightly in polyvinylidene chloride coated biaxially stretched nylon film, and stored. The oxygen gas permeability of this film is ^10c.c./m2 .
24hr・atm/25μm (25℃, 50%RH),
Moisture permeability is 5g/ ^m2・24hr/25μm (40℃, 90%
RH). For comparison, unwrapped and paper-wrapped versions were made and stored in the same manner. Immediately after the low-temperature plasma treatment, and after being left for 3 months, 6 months, and 1 year, the following post-adhesion treatment process was performed to produce a final product as a waterproof sheet, and the peel strength of the film from the base material was measured. did. The post-adhesion treatment step was carried out as follows. That is, 100 parts of Nitsuporan was applied to both sides of each of the fibrous base fabrics obtained as described above.
3105 and 15 parts of Coronate L (both products of Nippon Polyurethane Industries Co., Ltd.: polyurethane adhesive)
diluted with ethyl acetate to make a 50% solution, and this
It was applied in an amount of g/m ² and dried. Next, a PVC film (0.1 mm) having the following composition was attached by heating. PVC 100 parts DOP (plasticizer) 75 parts Titanium dioxide 8 parts Antimony trioxide (flame retardant) 5 parts Zinc stearate (stabilizer) 3 parts The peeling strength of the film was measured for these waterproof sheets obtained. Measurement method Peeling strength: Compliant with JIS-K-6328-1977 5.3.7 peeling test. The results are shown in Table 1. Water pressure resistance is 2000mm for both
It was above the water column.

[Table] In the example of the present invention, appropriate amounts of a desiccant and an oxygen scavenger are further sealed in the hollow part of a core roll with small holes on the entire surface in the form of air-permeable pouches, and roll packaging is carried out. Most of the things I stored are still intact after a year.
It showed a peel strength of 9.6 to 9.8 Kg/3cm.

Claims (1)

[Scope of Claims] 1. When storing a base material that has been subjected to low-temperature plasma treatment until it is subjected to a desired post-processing, the surface of the base material is treated with low-temperature plasma, and as soon as possible after the low-temperature plasma treatment, 1. A method for maintaining the treatment effect of a substrate subjected to low-temperature plasma treatment, the method comprising wrapping the substrate in a packaging material having low oxygen permeability or both, and storing and maintaining the substrate in that state. 2 Claim 1 in which the base material is a fibrous base fabric
The method described in section. 3 Claim 1 in which the base material is a sheet-like material
The method described in section. 4. The method according to claim 1, wherein after the low-temperature plasma treatment, the substrate is wound up into a roll and then wrapped in a wrapping material. 5 The packaging material is low density polyethylene, high density polyethylene, polypropylene, polyethylene terephthalate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, saponified ethylene-vinyl acetate copolymer, cellophane, ethylene-vinyl alcohol copolymer, nylon , and a polyacrylonitrile film or sheet. 6. The method according to claim 1, wherein vacuum packaging is applied when wrapping with a packaging material. 7 Claim 1 or 6 in which inert gas is filled when wrapping with a packaging material
The method described in section. 8. The method according to claim 1, 6 or 7, wherein an oxygen absorber and/or desiccant agent is enclosed when wrapping with the packaging material.