JPH02135297A - Fluorinated hydrocarbon-based azeotropic mixture - Google Patents
Fluorinated hydrocarbon-based azeotropic mixtureInfo
- Publication number
- JPH02135297A JPH02135297A JP63288795A JP28879588A JPH02135297A JP H02135297 A JPH02135297 A JP H02135297A JP 63288795 A JP63288795 A JP 63288795A JP 28879588 A JP28879588 A JP 28879588A JP H02135297 A JPH02135297 A JP H02135297A
- Authority
- JP
- Japan
- Prior art keywords
- mixture
- methanol
- azeotropic mixture
- solvent
- fluorinated hydrocarbon
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 6
- 229930195733 hydrocarbon Natural products 0.000 title claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 claims abstract description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 abstract description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 7
- 230000004907 flux Effects 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000976 ink Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 239000001993 wax Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract 1
- 239000003599 detergent Substances 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 239000010721 machine oil Substances 0.000 description 3
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- ZKVMMSGRDBQIOQ-UHFFFAOYSA-N 1,1,2-trichloro-1-fluoroethane Chemical compound FC(Cl)(Cl)CCl ZKVMMSGRDBQIOQ-UHFFFAOYSA-N 0.000 description 1
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- 240000000220 Panda oleosa Species 0.000 description 1
- 235000016496 Panda oleosa Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 125000004971 nitroalkyl group Chemical group 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000013020 steam cleaning Methods 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 239000005436 troposphere Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Detergent Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、代替フロンとして使用できるとともに溶剤等
として優れた特性を有する新規なフッ素化炭化水素系共
沸様混合物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel fluorinated hydrocarbon azeotrope-like mixture that can be used as a CFC substitute and has excellent properties as a solvent and the like.
［従来の技術］
フッ素化炭化水素系化合物（以下単にフロンという）は
、毒性が少なく不燃で化学的に安定なものが多く、標準
沸点の異なる各種フロンが入手できることから、これら
の特性を生かして溶剤、発泡剤、プロペラントあるいは
冷媒等として種々のフロンが使われている。例えば、溶
剤として１，１．２−１−リクロロー１．２．２− ト
リフルオロエタン（Ｒ１１３）が、発泡剤としてトリク
ロロモノフルオロメタン（１１１１）が、プロペラント
や冷媒としてジクロロジフルオロメタン（ｒｔ１２）が
使われている。[Prior art] Fluorinated hydrocarbon compounds (hereinafter simply referred to as fluorocarbons) are mostly non-toxic, non-flammable, and chemically stable, and various fluorocarbons with different standard boiling points are available, so they can be used to take advantage of these characteristics. Various types of fluorocarbons are used as solvents, blowing agents, propellants, refrigerants, etc. For example, 1,1,2-1-lichloro-1,2,2-trifluoroethane (R113) is used as a solvent, trichloromonofluoromethane (1111) is used as a blowing agent, and dichlorodifluoromethane (rt12) is used as a propellant or refrigerant. is used.
［発明が解決しようとする課題］
化学的に特に安定なＲ１１，Ｒ１２，ｌ’ｔｌ１３は対
流圏内での寿命が長く、拡散して成層圏に達し、ここで
太陽光線により分解して発生する塩素ラジカルがオゾン
と連鎖反応を起こし、オゾン層を破壊するとのことから
、これら従来のフロンの使用を規制する動きがある。こ
のため、これらの従来のフロンに替わり、オゾン層を破
壊しに（い代替フロンの探索が活発に行なわれている。[Problem to be solved by the invention] R11, R12, and l'tl13, which are particularly chemically stable, have a long life in the troposphere and diffuse into the stratosphere, where they are decomposed by sunlight and generate chlorine radicals. There is a movement to restrict the use of these conventional fluorocarbons because they are said to cause a chain reaction with ozone and destroy the ozone layer. Therefore, in place of these conventional fluorocarbons, there is active search for alternative fluorocarbons that do not destroy the ozone layer.
本発明は、従来のフロンの使用量を低減し、且つ該フロ
ンが有している優れた特性を満足しながら代替フロンと
して使用できる新規なフロン混合物を提供することを目
的とするものである。An object of the present invention is to provide a new fluorocarbon mixture that can be used as a fluorocarbon substitute while reducing the amount of conventional fluorocarbons used and satisfying the excellent properties of the fluorocarbons.
［課題を解決するための手段］
本発明は１，１．２−トリクロロフルオロエタン（Ｒ１
１３）及びメタノールと１−ヘキセンの２成分共沸混合
物からなるフッ素化炭化水素系共沸様混合物に関するも
のである。本発明の混合物は不燃又は難燃性であるとと
もに、特に洗浄溶剤として従来のＲ１１３単体よりも洗
浄力が高いため、Ｒ１１３の代替として極めて有用なも
のである。[Means for solving the problems] The present invention provides 1,1,2-trichlorofluoroethane (R1
13) and a fluorinated hydrocarbon azeotrope-like mixture consisting of a binary azeotrope of methanol and 1-hexene. The mixture of the present invention is non-flammable or flame-retardant and has higher cleaning power than conventional R113 alone as a cleaning solvent, so it is extremely useful as a substitute for R113.
更にリサイクルしても組成の変動が少ないこと、又従来
の単一フロンと同じ使い方ができ、従来技術の大幅な変
更を要しないこと等の利点があることから、本発明の混
合物としてはＲ１１３が９５〜２０重量％及びメタノー
ルと１−ヘキセンの２成分共沸混合物が５〜８０重量％
、好ましくはＲ１１３が８０〜４０重量％及びメタノー
ルと１−ヘキセンの２成分共沸混合物が２０〜６０重量
％であり、さらに好ましくはＲ１１３が約５０１１％と
メタノールと１−ヘキセンの２成分共？Ｊｌ混合物の約
５０重量％からなる共沸様混合物である。本発明の混合
物には、用途に応じてその他の成分をさらに添加混合す
ることができる。例えば、溶剤としての用途においては
、ペンタン、イソペンタン、ヘキサン、イソヘキサン、
ヘプタン、イソへブタン等の炭化水素類、ニトロメタン
、ニトロエタン、ニトロプロパン等のニトロアルカン類
、ジエチルアミン、トリエチルアミン、イソプロピルア
ミン、ブチルアミン、イソブチルアミン、等のアミン類
、エタノール、ｎ−プロピルアルコール、ｉ−プロピル
アルコール、ｎ−ブタノール、ｉ−ブタノール、等のア
ルコール類、メチルセロソルブ、テトラヒドロフラン、
１．４−ジオキサン等のエーテル！ｎ、アセトン、メチ
ルエチルケトン、メチルブチルケトン等のケトン類、酢
酸エチル、酢酸プロピル、酢酸ブチル等のエステル類等
から選ばれる１種又は２種以上を添加混合することがで
きる。Furthermore, R113 is suitable for the mixture of the present invention because it has the advantage that there is little change in composition even when recycled, it can be used in the same way as conventional single CFCs, and it does not require major changes to the conventional technology. 95-20% by weight and 5-80% by weight of a binary azeotrope of methanol and 1-hexene.
, preferably 80 to 40% by weight of R113 and 20 to 60% by weight of a binary azeotrope of methanol and 1-hexene, more preferably about 5011% of R113 and a binary azeotrope of methanol and 1-hexene. It is an azeotrope-like mixture consisting of about 50% by weight of the Jl mixture. Other components may be further added to the mixture of the present invention depending on the intended use. For example, when used as a solvent, pentane, isopentane, hexane, isohexane,
Hydrocarbons such as heptane and isohbutane, nitroalkanes such as nitromethane, nitroethane, and nitropropane, amines such as diethylamine, triethylamine, isopropylamine, butylamine, isobutylamine, ethanol, n-propyl alcohol, i-propyl Alcohol, alcohols such as n-butanol, i-butanol, methyl cellosolve, tetrahydrofuran,
1. Ethers such as 4-dioxane! One or more selected from the group consisting of ketones such as n, acetone, methyl ethyl ketone, and methyl butyl ketone, and esters such as ethyl acetate, propyl acetate, and butyl acetate can be added and mixed.
本発明の共沸様混合物は、従来のフロンと同様、熱媒体
、ドライクリーニング等の各種用途に使用でき、特に溶
剤として用いた場合、従来のＲ１１３に比べ溶解力が高
いため好適である。溶剤の具体的な用途としては、フラ
ックス、グリース、油、ワックス、インキ等の除去剤、
塗料用溶剤、抽出剤、シミ抜き剤、ガラス、セラミック
ス、プラスチック、ゴム、金属製各種物品、特にＩＣ部
品、電気機器、精密機械、光学レンズ等の洗浄剤や水切
り剤等を挙げることができる。洗浄方法としては、手拭
き、浸漬、スプレー、揺動、超音波洗浄、蒸気洗浄等を
採用すればよい。The azeotrope-like mixture of the present invention can be used in various applications such as heat transfer, dry cleaning, etc., like conventional fluorocarbons, and is particularly suitable when used as a solvent because it has a higher dissolving power than conventional R113. Specific uses of solvents include removers for flux, grease, oil, wax, ink, etc.
Examples include solvents for paints, extractants, stain removers, cleaning agents and draining agents for various articles made of glass, ceramics, plastics, rubber, and metals, especially IC parts, electrical equipment, precision instruments, optical lenses, etc. As the cleaning method, hand wiping, dipping, spraying, shaking, ultrasonic cleaning, steam cleaning, etc. may be employed.
［実施例］
実施例１
本発明の混合物（Ｒ−１１３／メタノール／ｌ−ヘキセ
ン＝ ５０．０／１５．２／３４．８重量％）を用いて
フラックスの洗浄試験を行なった。[Examples] Example 1 A flux cleaning test was conducted using the mixture of the present invention (R-113/methanol/l-hexene = 50.0/15.2/34.8% by weight).
プリント基板全面にフラックスを塗布し、２００℃の電
気炉で２分間焼成後、本発明の前記混合物に１分間浸漬
した。比較例としてＲ１１３についても同様の試験を行
なった。フラックスの除去の度合いを第１表に示す。Flux was applied to the entire surface of the printed circuit board, baked in an electric furnace at 200° C. for 2 minutes, and then immersed in the mixture of the present invention for 1 minute. A similar test was also conducted for R113 as a comparative example. Table 1 shows the degree of flux removal.
第１表
０：良好に除去できる ○；はぼ良好△：微量残存
×：かな、り残存実施例２
本発明の混合物（Ｒ−１１３／メタノール／１−ヘキセ
ン＝ ５０．０／１５．２／３４．８重量％）を用いて
機械油の洗浄試験を行なった。Table 1 0: Can be removed well ○; Good △: Trace amount remains
x: Kana, resin remaining Example 2 A machine oil cleaning test was conducted using the mixture of the present invention (R-113/methanol/1-hexene = 50.0/15.2/34.8% by weight).
５ＯＳ−３０４のテストピース（２５ｍｍＸ ３０ｍｍ
Ｘ ２ ｍｍ厚）を機械油中に浸漬した後、本発明の前
記混合物に５分間浸漬した。比較例としてＲ１１３につ
いても同様の試験を行なった。機械油の除去の度合いを
第２表に示す。5OS-304 test piece (25mm x 30mm
X 2 mm thick) was immersed in machine oil and then immersed in the mixture of the present invention for 5 minutes. A similar test was also conducted for R113 as a comparative example. Table 2 shows the degree of machine oil removal.
第２表
０：良好に除去できる ○：はぼ良好△：微量残存
×：かなり残存［発明の効果］Table 2 0: Can be removed well ○: Good △: Trace amount remains
×: Significantly remaining [effect of invention]
Claims (1)
タノールと１−ヘキセンの２成分共沸混合物とからなる
フッ素化炭化水素系共沸様混合 物。 ２、１，１，２−トリクロロトリフルオロエタン９５〜
２０重量％及びメタノールと１−ヘキセンの２成分共沸
混合物５〜８０重量％からなる請求項１記載の混合物。[Scope of Claims] A fluorinated hydrocarbon azeotrope-like mixture comprising 1,1,1,2-trichlorotrifluoroethane and a binary azeotrope of methanol and 1-hexene. 2,1,1,2-trichlorotrifluoroethane 95~
2. A mixture according to claim 1, comprising 20% by weight and 5 to 80% by weight of a binary azeotrope of methanol and 1-hexene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63288795A JPH02135297A (en) | 1988-11-17 | 1988-11-17 | Fluorinated hydrocarbon-based azeotropic mixture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63288795A JPH02135297A (en) | 1988-11-17 | 1988-11-17 | Fluorinated hydrocarbon-based azeotropic mixture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02135297A true JPH02135297A (en) | 1990-05-24 |
Family
ID=17734829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63288795A Pending JPH02135297A (en) | 1988-11-17 | 1988-11-17 | Fluorinated hydrocarbon-based azeotropic mixture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02135297A (en) |
-
1988
- 1988-11-17 JP JP63288795A patent/JPH02135297A/en active Pending
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