JPH0643644B2 - Antifouling polyester monofilament - Google Patents
Antifouling polyester monofilamentInfo
- Publication number
- JPH0643644B2 JPH0643644B2 JP58185169A JP18516983A JPH0643644B2 JP H0643644 B2 JPH0643644 B2 JP H0643644B2 JP 58185169 A JP58185169 A JP 58185169A JP 18516983 A JP18516983 A JP 18516983A JP H0643644 B2 JPH0643644 B2 JP H0643644B2
- Authority
- JP
- Japan
- Prior art keywords
- antifouling
- polyester
- monofilament
- weight
- titanium oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/08—Filter cloth, i.e. woven, knitted or interlaced material
- B01D39/083—Filter cloth, i.e. woven, knitted or interlaced material of organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/02—Types of fibres, filaments or particles, self-supporting or supported materials
- B01D2239/0216—Bicomponent or multicomponent fibres
- B01D2239/0233—Island-in-sea
Description
【発明の詳細な説明】 本発明は、防汚性にすぐれ、とくに抄紙用、濾過布およ
びコンベアベルト用に適したポリエステルモノフィラメ
ントに関するものである。Description: TECHNICAL FIELD The present invention relates to a polyester monofilament which is excellent in antifouling properties and is particularly suitable for papermaking, filter cloths and conveyor belts.
ポリエステルモノフィラメントは、そのすぐれた特性か
ら種々の産業用用途に用いられている。とくにポリエス
テルモノフィラメントは、従来金属ワイヤーが使用され
ていた分野、たとえば抄紙装置用、濾過装置用、コンベ
アー用などの分野において、そのすぐれた強靭性、可撓
性、防錆性、耐薬品性および安定性などが注目され、金
属ワイヤーに代替するものとして、近年急速に需要が拡
大してきている。Polyester monofilaments are used in various industrial applications because of their excellent properties. In particular, polyester monofilaments have excellent toughness, flexibility, rust resistance, chemical resistance, and stability in fields where metal wires have been used in the past, such as paper machines, filtration machines, and conveyor fields. In recent years, the demand has rapidly expanded as a substitute for metal wires because of its excellent properties.
しかるに、このような用途に用いられるポリエステルモ
ノフィラメントには、とくに汚れが付着しにくい性質、
すなわち防汚性が要求され、従来からその防汚性改良の
ために種々の試みが行われてきた。たとえば、ポリエス
テルモノフィラメントの表面にシリコーンコーティング
を行い、撥油、溌水性と共に防汚性を持たせる方法およ
びポリアルキレンオキシド系化合物をポリエステルとの
共重合成分あるいはブレンド成分としてモノフィラメン
ト表面に含有または付着させて、一種の親水加工を行う
方法などが挙げられるが、いずれも十分満足すべき防汚
性の改良は得られていない。すなわち、前者の方法で
は、抄紙網として用いられたときに、汚れ除去のために
行う高圧水洗浄などによってコーティング被膜が容易に
剥離し、防汚性能が激減してしまうばかりか、抄紙時に
表面シリコーン層の一部が紙へ移行付着して、印刷性能
を阻害するなどの問題があった。また、後者の方法で
は、加水分解に対する耐久性に問題があり、蒸気洗浄や
アルカリ洗浄を行うと、防汚性能が急速に低下してしま
うという問題があった。However, the polyester monofilament used for such an application has a property that dirt is not easily attached,
That is, antifouling property is required, and various attempts have been made to improve the antifouling property. For example, a method of applying a silicone coating to the surface of a polyester monofilament to impart oil repellency, water repellency and antifouling property, and a polyalkylene oxide compound as a copolymerization component or blending component with polyester are contained or adhered to the monofilament surface. There is a method of hydrophilic treatment, but none of them has sufficiently improved antifouling property. That is, in the former method, when used as a papermaking net, not only the coating film is easily peeled off by high-pressure water washing or the like performed to remove stains, but the antifouling performance is drastically reduced, and the surface silicone is used during papermaking. There is a problem that a part of the layer moves to the paper and adheres to the paper to impair the printing performance. In addition, the latter method has a problem in durability against hydrolysis, and there is a problem that the antifouling performance is rapidly deteriorated when steam cleaning or alkali cleaning is performed.
そこで本発明者らは、上述の従来技術における欠点を改
良し、防汚性にすぐれたポリエステルモノフィラメント
の取得を目的として種々検討した結果、溶融混練によっ
てモノフィラメントに練り込まれたポリシロキサンは、
表面コーティングされたシリコーン層とは異なり、高圧
水洗浄、蒸気洗浄およびアルカリ洗浄などに対する耐久
性が良好であり、かつ抄紙網として用いる場合に紙へ移
行付着して印刷性能を阻害することがなく、しかもさら
に糸の表層部に少なくとも０．３重量％の酸化チタン粉
末を含有させることによって、防汚性能が一層増大する
ことを見出し、本発明に到達した。Therefore, the present inventors have improved the above-mentioned drawbacks in the prior art, and as a result of various studies for the purpose of obtaining a polyester monofilament having excellent antifouling properties, the polysiloxane kneaded into the monofilament by melt kneading,
Unlike the surface-coated silicone layer, it has good durability against high-pressure water cleaning, steam cleaning, alkali cleaning, etc., and when used as a paper making net, does not migrate to paper and impair printing performance, Moreover, the inventors have found that the antifouling performance is further increased by further containing at least 0.3% by weight of titanium oxide powder in the surface layer of the yarn, and arrived at the present invention.
すなわち本発明は、少なくとも糸の表層部に、溶融混練
されたポリシロキサンを０．３〜３重量％および酸化チ
タン粉末を０．３〜１．６重量％含有することを特徴と
する防汚性ポリエステルモノフィラメント、とくに抄紙
用、濾過布およびコンベアベルト用途に用いられること
を特徴とする防汚性ポリエステルモノフィラメントを提
供するものである。That is, the present invention is characterized by containing 0.3 to 3% by weight of melt-kneaded polysiloxane and 0.3 to 1.6% by weight of titanium oxide powder in at least the surface layer portion of the yarn. Provided is a polyester monofilament, particularly an antifouling polyester monofilament which is used for papermaking, filter cloth and conveyor belt applications.
本発明でいうポリエステルモノフィラメントとは、ポリ
アルキレンテレフタレートまた主としてポリアルキレン
テレフタレートよりなるもの、たとえばポリエチレンテ
レフタレート、ポリブチレンテレフタレートおよびポリ
プロピレンテレフタレートなどであり、共重合体をも包
含する。The polyester monofilament referred to in the present invention is polyalkylene terephthalate or one mainly composed of polyalkylene terephthalate, such as polyethylene terephthalate, polybutylene terephthalate and polypropylene terephthalate, and also includes a copolymer.
本発明において、少なくとも糸の表層部に、溶融混練さ
れたポリシロキサンおよび酸化チタン粉末を含有させる
方法は任意であるが、たとえば次のような方法が実用上
有利に実施できる。In the present invention, the method of incorporating the melt-kneaded polysiloxane and the titanium oxide powder into at least the surface layer portion of the yarn is arbitrary, but the following method can be practically carried out advantageously.
第一の方法は、あらかじめポリシロキサンをポリエステ
ルに溶融混練した高濃度のマスターペレットを作成して
おき、このマスターペレットと酸化チタン粉末を含有す
るポリエステルとを所定の比率で混合してブレンド紡糸
する方法である。この方法によると、任意の濃度のポリ
シロキサンおよび酸化チタン粉末が、表層を含むポリエ
ステルモノフィラメント全体にわたってほぼ均一に分散
したものが得られる。The first method is to prepare high-concentration master pellets by melt-kneading polysiloxane with polyester in advance, and mix the master pellets and polyester containing titanium oxide powder at a predetermined ratio to perform blend spinning. Is. According to this method, a polysiloxane and a titanium oxide powder having arbitrary concentrations are almost uniformly dispersed throughout the polyester monofilament including the surface layer.
第二の方法は、第一の方法と同様に、高濃度のポリシロ
キサンおよび酸化チタン粉末を含有するポリエステルマ
スターペレットあるいはこれを所定比率でポリエステル
に混合したものを鞘成分とし、ポリシロキサンおよび酸
化チタン粉末を含有しないポリエステルを芯成分とした
複合糸を作成する方法である。この方法によると、任意
の濃度のポリシロキサンおよび酸化チタン粉末を含有
し、かつ所定の厚さを有する表層部を設けることができ
る。The second method is similar to the first method, in which polyester master pellets containing a high concentration of polysiloxane and titanium oxide powder or a mixture of the polyester master pellets in a predetermined ratio with polyester is used as a sheath component, and polysiloxane and titanium oxide are used. This is a method for producing a composite yarn containing a powder-free polyester as a core component. According to this method, it is possible to provide the surface layer portion which contains the polysiloxane and the titanium oxide powder in arbitrary concentrations and has a predetermined thickness.
本発明で使用するポリシロキサンは、次式 （式中、Ｒ１、Ｒ２はＨあるいはアルキル基、シクロア
ルキル基、アリール基を示す）の化学構造を有するもの
が好適であり、トーレ・シリコーン（株）製ＳＨ２００
のポリジメチルシロキサンや、同じくＳＨ５１０のポリ
フェニルメチルシロキサンなどが挙げられる。The polysiloxane used in the present invention has the following formula (Wherein R 1 and R 2 represent H or an alkyl group, a cycloalkyl group, or an aryl group) are preferable, and SH200 manufactured by Torre Silicone Co., Ltd.
And polyphenylmethylsiloxane of SH510.
ポリシロキンサンの添加量は、ポリシロキサンを含有す
る層のポリエステルに対し０．３〜３重量％の範囲が適
当である。０．３重量％よりも少ないと防汚性能が不十
分であり、高濃度になるにつれて性能は良くなるが、３
重量％を越えると、モノフィラメントの物性および製糸
性が低下するため好ましくない。The addition amount of polysiroquinsan is appropriately in the range of 0.3 to 3% by weight based on the polyester of the layer containing polysiloxane. If it is less than 0.3% by weight, the antifouling performance is insufficient, and the performance becomes better as the concentration becomes higher.
If the content exceeds 10% by weight, the physical properties of the monofilament and the spinnability are deteriorated, which is not preferable.
また、糸の表層部に、さらに０．３〜１．６重量％の酸
化チタン粉末を含有させることにより、本発明の防汚性
改良効果がさらに増大する。ここで、酸化チタン粉末の
添加量が０．３重量％より少ないと、防汚性能の増大効
果が十分でなく、１．６重量％を越えると、糸の物性や
製糸性が阻害されることになるため好ましくない。Further, by further adding 0.3 to 1.6% by weight of titanium oxide powder in the surface layer portion of the yarn, the antifouling property improving effect of the present invention is further increased. Here, if the addition amount of the titanium oxide powder is less than 0.3% by weight, the effect of increasing the antifouling performance is not sufficient, and if it exceeds 1.6% by weight, the physical properties of the yarn and the spinnability are impaired. Is not preferable.
なお、酸化チタン粉末は、ポリエステルの重合時に添加
されることが、製糸性および経済性などの点からとくに
有利である。In addition, it is particularly advantageous to add the titanium oxide powder at the time of polymerization of polyester from the viewpoints of spinnability and economy.
しかして、本発明のポリエステルモノフィラメントは、
防汚性能がすぐれ、しかもその耐久性が良好であるた
め、主として抄紙網などの抄紙用、一般濾過布用および
コンベアベルト用の素材として有用である。Then, the polyester monofilament of the present invention,
Since it has excellent antifouling performance and good durability, it is mainly useful as a material for papermaking such as papermaking nets, general filter cloths, and conveyor belts.
以下に、実施例を挙げて本発明をさらに詳細に説明する
が、実施例および比較例に示す防汚性能の評価は次のよ
うにして行った。Hereinafter, the present invention will be described in more detail with reference to Examples. The evaluation of the antifouling performance shown in Examples and Comparative Examples was performed as follows.
直径０．２０mmのモノフィラメントを、タテ、ヨコ４２
本／cmの平織とし、５cm角に切断して試験片とした。水
２００ccを入れたビーカーに汚染液（大京化学製）５cc
を分散させ、さらに水に濡らした試験片を入れ１分間ガ
ラス棒で攪拌する。その後試験片を引き上げ、軽く水洗
し、乾燥した後、分光光度計により４３２nmにおける反
射率を測定し、未汚染片に対する百分比で汚染度を比較
した。A vertical and horizontal 42 mm diameter monofilament
A plain weave of books / cm was cut into 5 cm squares to give test pieces. 5cc of contaminated liquid (manufactured by Daikyo Kagaku) in a beaker containing 200cc of water
Is dispersed, and a test piece moistened with water is added, and the mixture is stirred for 1 minute with a glass rod. After that, the test piece was pulled up, lightly washed with water, and dried, and then the reflectance at 432 nm was measured by a spectrophotometer, and the contamination degree was compared in percentage to the uncontaminated piece.
反射率比（％）＝（汚染片の反射率／未汚染片の反射
率）×１００ なお、実施例および比較例において、反射率比以外の％
はいずれも重量％を意味する。Reflectance ratio (%) = (reflectance of contaminated pieces / reflectance of uncontaminated pieces) × 100 In the examples and comparative examples,% other than the reflectance ratio
Means% by weight.
［実施例１乃至４、比較例１乃至６］ 固有粘度０．６のポリエチレンテレフタレート（Ｂ）
に、２５℃における粘度３０，０００ポイズのポリジメ
チルシロキサンを１５重量％添加し、二軸エクストルー
ダを用いて混練押出を行い、カッティングしてマスター
ペレット（Ａ）を得た。[Examples 1 to 4 and Comparative Examples 1 to 6] Polyethylene terephthalate (B) having an intrinsic viscosity of 0.6
Then, 15% by weight of polydimethylsiloxane having a viscosity of 30,000 poise at 25 ° C. was added, kneading and extruding was performed using a twin-screw extruder, and cutting was performed to obtain master pellets (A).
酸化チタン粉末０．４重量％を重合時添加した固有粘度
０．７０のポリエチレンテレフタレートペレット（Ｃ）
または酸化チタン２重量％を重合時添加した固有粘度
０．７０のポリエチレンテレフタレートペレット（Ｄ）
と、上記マスターペレット（Ａ）とを、それぞれ乾燥し
た後、上記（Ｃ）／（Ａ）または（Ｄ）／（Ａ）を所定
の割合で混合することにより、表１に示したポリジメチ
ルシロキサン濃度および酸化チタン含有量を有する混合
ペレットを得た。Polyethylene terephthalate pellets (C) having an intrinsic viscosity of 0.70 added with 0.4% by weight of titanium oxide powder during polymerization
Alternatively, polyethylene terephthalate pellets (D) having an intrinsic viscosity of 0.70 added with 2% by weight of titanium oxide during polymerization
And the above master pellets (A) are respectively dried, and then the above (C) / (A) or (D) / (A) is mixed at a predetermined ratio to obtain the polydimethylsiloxane shown in Table 1. Mixed pellets having a concentration and a titanium oxide content were obtained.
これらの混合ペレットをスクリュー径４０mmのエクスト
ルーダーを用い、２９０℃の紡糸温度で溶融紡糸した。
紡出後水冷固化し、引き続き５倍に延伸して直径０．２
０mmのモノフィラメントを得た。These mixed pellets were melt-spun at a spinning temperature of 290 ° C. using an extruder having a screw diameter of 40 mm.
After spinning, it is solidified by cooling with water and then stretched 5 times to have a diameter of 0.2.
A 0 mm monofilament was obtained.
得られた各モノフィラメントを織物試験片とし、防汚性
能を評価した結果をまとめて表１に示す。Each of the obtained monofilaments is used as a woven fabric test piece, and the results of evaluation of antifouling performance are summarized in Table 1.
［実施例５乃至８、比較例７乃至１２］ 実施例１乃至４、比較例１乃至６で使用した各混合ペレ
ットを鞘成分とし、上記ポリエチレンテレフタレート
（Ｂ）を芯成分とした複合糸を製造した。 [Examples 5 to 8 and Comparative Examples 7 to 12] Composite yarns having the mixed pellets used in Examples 1 to 4 and Comparative Examples 1 to 6 as the sheath component and the polyethylene terephthalate (B) as the core component were produced. did.
すなわち、芯／鞘複合比を８０／２０として紡糸温度２
９０℃で溶融紡出した後、水冷固化し、引き続き４．７
５倍に延伸して、糸直径０．２０mmの複合モノフィラメ
ントを得た。That is, with a core / sheath composite ratio of 80/20, a spinning temperature of 2
After melt-spinning at 90 ° C, solidified by water cooling and then 4.7
It was drawn 5 times to obtain a composite monofilament having a yarn diameter of 0.20 mm.
得られた各モノフィラメントを同様に織物試験片とし、
防汚性能を評価した結果をまとめて表２に示す。Each monofilament obtained was similarly used as a fabric test piece,
The results of evaluating the antifouling performance are summarized in Table 2.
［実施例９、比較例１３］ 比較例１で紡糸したモノフィラメントの織物を、ポリエ
チレングリコール、ポリエチレンテレフタレートのブロ
ック共重合ポリエステルを主成分とする防汚加工剤（た
とえばPermalose Ｔ）で処理して試験片を作成し、実施
例２による試験片と、アルカリ洗浄による防汚効果の耐
久性を比較した。 [Example 9, Comparative Example 13] The monofilament woven fabric spun in Comparative Example 1 was treated with an antifouling agent (for example, Permalose T) containing a block copolymerized polyester of polyethylene glycol and polyethylene terephthalate as a main component, and a test piece. Was prepared, and the durability of the antifouling effect by alkali cleaning was compared with the test piece of Example 2.
すなわち、５％苛性ソーダ水溶液を用いて、常温で２０
時間試験片を洗浄し、この洗浄前後の試験片について、
上記と同様の方法で汚染して反射率を測定したところ、
前者は洗浄前の反射率６５％が、洗浄後には３４％に低
下した。これに対し、本発明による後者は、洗浄前反射
率比６８％が、洗浄後６６％であり、ほとんど低下が認
められなかった。That is, using a 5% caustic soda solution at room temperature,
Time to wash the test piece, for the test piece before and after this washing,
When the reflectance was measured after contamination by the same method as above,
The former had a reflectance of 65% before washing, but decreased to 34% after washing. On the other hand, in the latter according to the present invention, the reflectance ratio before washing was 68% and the reflectance ratio after washing was 66%, and almost no decrease was observed.
［実施例１０、比較例１４］ 比較例１で紡糸したモノフィラメントと織物を、シリコ
ーンエマルジョン（トーレ・シリコーン（株）製ＳＨ８
２００）で処理して試験片を作成し、実施例２による試
験片と、５０kg／cm2の高圧水洗浄による防汚効果の耐
久性を比較した。[Example 10 and Comparative Example 14] The monofilament and the woven fabric spun in Comparative Example 1 were treated with a silicone emulsion (SH8 manufactured by Toray Silicone Co., Ltd.).
200) to prepare a test piece, and the endurance of the antifouling effect by washing with high-pressure water of 50 kg / cm 2 was compared with the test piece according to Example 2.
この結果、前者は洗浄前の反射率比５９％が、洗浄後に
は２８％に低下した。これに対し、本発明による後者
は、洗浄前反射率比６８％が、洗浄後６９％であり、全
く低下が認められなかった。As a result, the former had a reflectance ratio of 59% before washing and 28% after washing. On the other hand, in the latter according to the present invention, the reflectance ratio before washing was 68%, and the reflectance ratio after washing was 69%, and no decrease was observed.
フロントページの続き (72)発明者 吉村 英良 愛知県岡崎市昭和町字河原１番地 東レ・ モノフイラメント株式会社内 (56)参考文献 特開 昭57−171790（ＪＰ，Ａ) 特開 昭50−90715（ＪＰ，Ａ) 特開 昭53−103043（ＪＰ，Ａ) 特開 昭58−18497（ＪＰ，Ａ) 特公 昭57−14372（ＪＰ，Ｂ１)Front page continuation (72) Inventor Hideyoshi Yoshimura 1 Kawahara, Showa-cho, Okazaki-shi, Aichi Toray Monofilament Co., Ltd. (56) References JP-A-57-171790 (JP, A) JP-A-50- 90715 (JP, A) JP 53-103043 (JP, A) JP 58-18497 (JP, A) JP 57-14372 (JP, B1)
Claims (2)
ポリシロキサンを０．３〜３重量％および酸化チタン粉
末を０．３〜１．６重量％含有することを特徴とする防
汚性ポリエステルモノフィラメント。1. An antifouling property, characterized in that at least the surface layer of the yarn contains 0.3 to 3% by weight of melt-kneaded polysiloxane and 0.3 to 1.6% by weight of titanium oxide powder. Polyester monofilament.
用、濾過布およびコンベアベルト用途に用いられること
を特徴とする特許請求の範囲第（１）項記載の防汚性ポ
リエステルモノフィラメント。2. The antifouling polyester monofilament according to claim (1), which is used for papermaking, filter cloth and conveyor belt applications.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58185169A JPH0643644B2 (en) | 1983-10-05 | 1983-10-05 | Antifouling polyester monofilament |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58185169A JPH0643644B2 (en) | 1983-10-05 | 1983-10-05 | Antifouling polyester monofilament |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6081313A JPS6081313A (en) | 1985-05-09 |
| JPH0643644B2 true JPH0643644B2 (en) | 1994-06-08 |
Family
ID=16166036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58185169A Expired - Lifetime JPH0643644B2 (en) | 1983-10-05 | 1983-10-05 | Antifouling polyester monofilament |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0643644B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62231094A (en) * | 1986-03-07 | 1987-10-09 | 大和紡績株式会社 | Dryer canvas for papermaking |
| JP2912627B2 (en) * | 1989-04-07 | 1999-06-28 | 株式会社ボナンザ | Method for producing modified monofilament for fishing line |
| US5759685A (en) * | 1993-07-02 | 1998-06-02 | Rhone-Poulenc Viscosuisse S.A. | Soil-repellent and abrasion-resistant monofilaments and methods of making and using same |
| WO1995004847A1 (en) * | 1993-08-06 | 1995-02-16 | Rhone-Poulenc Viscosuisse S.A. | Monofilaments with improved weavability and use of the fabrics produced therewith |
| JP2008279339A (en) * | 2007-05-09 | 2008-11-20 | Jfe Engineering Kk | Solid/liquid separation apparatus |
| US20120214374A1 (en) * | 2011-02-21 | 2012-08-23 | Chaitra Mahesha | Paper machine clothing having monofilaments with lower coefficient of friction |
| MX2016013096A (en) * | 2014-04-07 | 2017-04-27 | Trevira Gmbh | Polymer fibre having improved dispersibility. |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5090715A (en) * | 1973-12-20 | 1975-07-21 | ||
| JPS53103043A (en) * | 1977-02-18 | 1978-09-07 | Kanebo Ltd | Sewing yarn and method of manufacture thereof |
| JPS5834156B2 (en) * | 1980-06-30 | 1983-07-25 | 松下電工株式会社 | Manufacturing method for inner blades for electric razors |
| JPS57171790A (en) * | 1980-12-06 | 1982-10-22 | Nihon Felt Kk | Papermaking cloth having anti-stain property |
| JPS5818497A (en) * | 1981-07-17 | 1983-02-03 | イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− | Papermaking belt |
-
1983
- 1983-10-05 JP JP58185169A patent/JPH0643644B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6081313A (en) | 1985-05-09 |
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