JPH037702A - Reactive vinyl chloride polymer and production thereof - Google Patents
Reactive vinyl chloride polymer and production thereofInfo
- Publication number
- JPH037702A JPH037702A JP3283690A JP3283690A JPH037702A JP H037702 A JPH037702 A JP H037702A JP 3283690 A JP3283690 A JP 3283690A JP 3283690 A JP3283690 A JP 3283690A JP H037702 A JPH037702 A JP H037702A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- polymerization
- amino group
- polymer
- chloride polymer
- 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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229920000642 polymer Polymers 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 125000003277 amino group Chemical group 0.000 claims abstract description 30
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 13
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 abstract description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005977 Ethylene Substances 0.000 abstract description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract description 2
- QBKALCIQIBIEFY-UHFFFAOYSA-N 2-[(1-amino-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidamide;dihydrate Chemical compound O.O.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N QBKALCIQIBIEFY-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- -1 vinyl acetate Chemical compound 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000004684 trihydrates Chemical class 0.000 description 2
- 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
- CCTFAOUOYLVUFG-UHFFFAOYSA-N 2-(1-amino-1-imino-2-methylpropan-2-yl)azo-2-methylpropanimidamide Chemical compound NC(=N)C(C)(C)N=NC(C)(C)C(N)=N CCTFAOUOYLVUFG-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- JMQWYNRFGWFWBU-UHFFFAOYSA-N 2-[[1-amino-1-(4-aminophenyl)imino-2-methylpropan-2-yl]diazenyl]-n'-(4-aminophenyl)-2-methylpropanimidamide Chemical compound C=1C=C(N)C=CC=1N=C(N)C(C)(C)N=NC(C)(C)C(N)=NC1=CC=C(N)C=C1 JMQWYNRFGWFWBU-UHFFFAOYSA-N 0.000 description 1
- MERLDGDYUMSLAY-UHFFFAOYSA-N 4-[(4-aminophenyl)disulfanyl]aniline Chemical compound C1=CC(N)=CC=C1SSC1=CC=C(N)C=C1 MERLDGDYUMSLAY-UHFFFAOYSA-N 0.000 description 1
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、塩化ビニル系樹脂の改質に好適に用いられる
反応性塩化ビニル系重合体及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a reactive vinyl chloride polymer suitably used for modifying vinyl chloride resins and a method for producing the same.
（従来の技術）
塩化ビニル樹脂は、剛性及び引張強度が高く、難燃性、
耐候性、耐薬品性に優れており、パイプ、プレート、フ
ィルム、シートなどに広く用いられている。しかし、欠
点もある。例えば、耐熱性、熱安定性、成形時の流動性
、耐衝撃性が充分でない。(Prior art) Vinyl chloride resin has high rigidity and tensile strength, and is flame retardant.
It has excellent weather resistance and chemical resistance, and is widely used in pipes, plates, films, sheets, etc. However, there are also drawbacks. For example, heat resistance, thermal stability, fluidity during molding, and impact resistance are insufficient.
このような欠点の改善方法として、従来、主として後塩
素化法、共重合法、ブレンド法による塩化ビニル樹脂の
改質が行なわれている。ところが、反応性を有する塩化
ビニル系重合体を原料として使用することは知られてい
ない。Conventionally, as a method for improving such defects, vinyl chloride resins have been modified mainly by a post-chlorination method, a copolymerization method, and a blending method. However, it is not known to use a reactive vinyl chloride polymer as a raw material.
（発明が解決しようとする課題）
本発明の目的とするところは、塩化ビニル系樹脂の改質
に好適に用いられる新規な反応性塩化ビニル系重合体及
びその製造方法を提供することにある。(Problems to be Solved by the Invention) An object of the present invention is to provide a novel reactive vinyl chloride polymer suitable for use in modifying vinyl chloride resins and a method for producing the same.
（課題を解決、するための手段）
本発明の反応性塩化ビニル系重合体は、分子の一端又は
両末端にアミノ基を導入してなる。(Means for solving the problems) The reactive vinyl chloride polymer of the present invention has an amino group introduced at one or both ends of the molecule.
また、本発明の反応性塩化ビニル系重合体の製造方法は
、塩化ビニルを主成分とする単量体をラジカル重合する
に際し、重合時の分解で二つのラジカルが生成し双方の
ラジカルにアミノ基が配分されるような重合開始剤を用
いることにより、分子の一端又は両末端にアミノ基を導
入することを特徴とする。以上の構成により」２記の目
的が達成される。In addition, in the method for producing a reactive vinyl chloride polymer of the present invention, when a monomer containing vinyl chloride as a main component is radically polymerized, two radicals are generated by decomposition during polymerization, and both radicals have amino groups. It is characterized in that an amino group is introduced at one or both ends of the molecule by using a polymerization initiator that distributes . With the above configuration, the purpose stated in item 2 is achieved.
本発明において、塩化ビニルを主成分とする単量体とし
ては、塩化ビニルのみからなる単量体をはじめ、この塩
化ビニルを主成分としこれに、エチレンなどのオレフィ
ン類、酢酸ビニルなどのビニルエステル類、（メタ）ア
クリル酸メチルなどのアクリレート類、ビニルエーテル
類、塩化ビニリデン等の塩化ビニルと共重合可能な他の
単量体を併用してなる単量体が用いられる。In the present invention, monomers containing vinyl chloride as a main component include monomers containing only vinyl chloride, olefins such as ethylene, vinyl esters such as vinyl acetate, etc. Monomers such as acrylates such as methyl (meth)acrylate, vinyl ethers, and other monomers copolymerizable with vinyl chloride such as vinylidene chloride are used.
また、重合開始剤としては、重合時の分解で二つのラジ
カルが生成し双方のラジカルにアミノ基が配分されるよ
うなラジカル重合開始剤が用いられる。かかる重合開始
剤には、例えば、２．２′−アゾビス−（Ｎ−（４−ア
ミノフェニル）−２メチル−プロピオンアミジン〕四基
酸塩：２．２゛−アゾビス−（２−メチルプロピオンア
ミジン）三水和物；
などがある。Further, as the polymerization initiator, a radical polymerization initiator is used which generates two radicals by decomposition during polymerization and an amino group is distributed to both radicals. Such polymerization initiators include, for example, 2,2'-azobis-(N-(4-aminophenyl)-2methyl-propionamidine] tetrabasic acid salt: 2,2'-azobis-(2-methylpropionamidine) ) trihydrate; etc.
かような重合開始剤を用いて、上記の塩化ビニルを主成
分とする単量体をラジカル重合するには、通常、懸濁重
合法、溶液重合法が採用される。特に、連鎖移動の少な
い水懸濁重合が最適である。溶液重合法を採用する場合
は、連鎖移動効果の小さい溶媒を使用するのが好ましい
。In order to radically polymerize the above-mentioned monomer mainly composed of vinyl chloride using such a polymerization initiator, a suspension polymerization method or a solution polymerization method is usually employed. In particular, water suspension polymerization with less chain transfer is most suitable. When a solution polymerization method is employed, it is preferable to use a solvent with a small chain transfer effect.
連鎖移動効果の大きい溶媒を使用すると、得られる塩化
ビニル系重合体の分子末端にアミノ基が導入されない恐
れがある。If a solvent with a large chain transfer effect is used, there is a possibility that an amino group will not be introduced at the molecular end of the resulting vinyl chloride polymer.
また、上記の重合開始剤は、塩化ビニルを主成分とする
単量体１モルに対し０．０３モル以上使用するのが好ま
しい。０．０３モルを下まわると、得られる塩化ビニル
系重合体の分子両末端にアミノ基が充分に導入されず、
分子の一端のみにアミノ基が導入された重合体が多くな
り、その分だけ塩化ビニル系重合体の反応性が低下する
。Moreover, it is preferable to use the above-mentioned polymerization initiator in an amount of 0.03 mol or more per 1 mol of the monomer whose main component is vinyl chloride. If it is less than 0.03 mol, amino groups will not be sufficiently introduced at both ends of the molecule of the vinyl chloride polymer obtained,
The number of polymers in which an amino group is introduced only at one end of the molecule increases, and the reactivity of the vinyl chloride polymer decreases accordingly.
重合温度は、製造しようとする重合体の重合度によって
決まるが、好ましくは用いる重合開始剤が分解によって
、１０時間で半減する温度以上である。通常は４０〜９
０°Ｃで行なわれる。重合度は、一般に５０〜１０００
の範囲で用途によって適当な値に設定される。The polymerization temperature is determined by the degree of polymerization of the polymer to be produced, but is preferably at least the temperature at which the polymerization initiator used is reduced by half in 10 hours due to decomposition. Usually 40-9
Performed at 0°C. The degree of polymerization is generally 50 to 1000
It is set to an appropriate value depending on the purpose within the range of .
また、本発明においては、ラジカル重合の際に、重合度
調節のための連鎖移動剤を用いてもよい。連鎖移動剤を
用いると重合度を低下させることができる。このような
連鎖移動剤としては、連鎖移動したときにアミノ基を含
むメルカプト化合物やジスルフィド化合物、例えば、ｐ
アミノチオフェノール、４，４゛−ジチオジアニリンな
どが好適に用いられる。Furthermore, in the present invention, a chain transfer agent may be used to adjust the degree of polymerization during radical polymerization. The degree of polymerization can be lowered by using a chain transfer agent. Examples of such chain transfer agents include mercapto compounds and disulfide compounds that contain an amino group when chain transfer occurs, such as p
Aminothiophenol, 4,4'-dithiodianiline, etc. are preferably used.
（作用）
本発明方法によれば、重合開始剤により塩化ビニルを主
成分とする単量体がラジカル重合し塩化ビニル系重合体
が得られる。また、上記のラジカル重合時に上記の重合
開始剤が分解し、（アゾビス化合物の場合は窒素が離脱
する）二つのラジカルが生成し、双方のラジカルにアミ
ノ基が配分される。そして、このアミノ基を含有するラ
ジカルが塩化ビニルを主成分とする単量体と反応して遊
離基重合体が生長し、その結果、得られる塩化ビニル系
重合体の分子の一端又は両末端にアミノ基が導入される
。(Function) According to the method of the present invention, a monomer containing vinyl chloride as a main component undergoes radical polymerization using a polymerization initiator to obtain a vinyl chloride polymer. Further, during the radical polymerization, the polymerization initiator is decomposed to generate two radicals (nitrogen is eliminated in the case of an azobis compound), and amino groups are distributed to both radicals. Then, this amino group-containing radical reacts with a monomer whose main component is vinyl chloride to grow a free radical polymer, and as a result, one or both ends of the molecule of the vinyl chloride polymer obtained An amino group is introduced.
なお、アミノ基を含有するメルカプト化合物やジスルフ
ィド化合物を連鎖移動剤として用いた場合は、この連鎖
移動剤分子のメルカプト結合又はジスルフィド結合で切
れ、これが遊離基重合体と反応し、その結果、得られる
塩化ビニル系重合体の分子の一端又は両末端に上記連鎖
移動剤に由来するアミノ基も一部導入される。In addition, when a mercapto compound or a disulfide compound containing an amino group is used as a chain transfer agent, the mercapto bond or disulfide bond of this chain transfer agent molecule is cut, and this reacts with the free radical polymer, resulting in the A portion of amino groups derived from the chain transfer agent are also introduced into one or both ends of the vinyl chloride polymer molecule.
（実施例） 以下、本発明の実施例を示す。(Example) Examples of the present invention will be shown below.
実施孤１
２０Ｉ！、の撹拌機付き耐圧重合器にイオン交換水１２
ｋｇ、部分ケン化ポリビニルアルコール５ｇ。Implementation song 1 20I! 12 ion-exchanged water was added to a pressure-resistant polymerization vessel equipped with a stirrer.
kg, partially saponified polyvinyl alcohol 5g.
重合開始剤として２，２゛−アゾビス−（Ｎ−（４−ア
ミノフェニル）−２−メチル−プロピオンアミジン〕四
基酸塩３３７ｇを入れ（これは塩化ビニル１モルに対し
て０．０４モルに相当する）、器内を真空にした後、塩
化ビニル１０００ ｇを入れ、内温を７５°Ｃに上昇さ
せ、５時間重合を行なった。得られた塩化ビニル重合体
をテトラヒドロフランに溶解し、メタノールで析出させ
、これを５０°Ｃのメタノール中で４時間撹拌し精製し
た。337 g of 2,2'-azobis-(N-(4-aminophenyl)-2-methyl-propionamidine) tetrabasic acid salt was added as a polymerization initiator (this amounted to 0.04 mole per mole of vinyl chloride). After evacuating the inside of the vessel, 1000 g of vinyl chloride was added, the internal temperature was raised to 75°C, and polymerization was carried out for 5 hours.The obtained vinyl chloride polymer was dissolved in tetrahydrofuran, and then dissolved in methanol. This was purified by stirring in methanol at 50°C for 4 hours.
この重合体について、ＪＩＳ Ｋ ６７２１により平均
重合度を測定したところ、その平均重合度は１２０であ
った。また、この重合体について、水素核磁気共鳴スペ
クトルにより、アミノ基の含有量を定量（アミノ基に由
来する３、５６ｐｐｍのピークを定量）したところ、そ
の含有量は０．４３重景％であった。この含有量及び平
均重合度から、塩化ビニル重合体１分子当り約２個のア
ミノ基、即ち塩化ビニル重合体のほぼ分子両末端にアミ
ノ基が導入されていることがわかる。The average degree of polymerization of this polymer was measured according to JIS K 6721, and the average degree of polymerization was 120. In addition, when the content of amino groups in this polymer was determined by hydrogen nuclear magnetic resonance spectroscopy (quantification of the peak at 3.56 ppm derived from amino groups), the content was found to be 0.43% by weight. Ta. From this content and average degree of polymerization, it can be seen that about two amino groups are introduced per molecule of the vinyl chloride polymer, that is, amino groups are introduced almost at both ends of the vinyl chloride polymer.
実施例１
重合開始剤として２．２°−アゾビス−（２−メチルプ
ロピオンアミジン）三水和物１７４ｇ （これは塩化
ビニル１モルに対して０．０４モルに相当スる）に替え
、それ以外は実施例１と同様に行って塩化ビニル重合体
を得た。この重合体の平均重合度は１１０、アミノ基の
含有量は０．４６重景％であった。この含有量及び平均
重合度から、塩化ビニル重合体１分子当り約２個のアミ
ノ基が、即ち塩化ビニル重合体のほぼ分子両末端にアミ
ノ基が導入されていることがわかる。Example 1 The polymerization initiator was replaced with 174 g of 2.2°-azobis-(2-methylpropionamidine) trihydrate (this corresponds to 0.04 mol per 1 mol of vinyl chloride), and other A vinyl chloride polymer was obtained in the same manner as in Example 1. The average degree of polymerization of this polymer was 110, and the content of amino groups was 0.46%. From this content and average degree of polymerization, it can be seen that about two amino groups are introduced per molecule of the vinyl chloride polymer, that is, amino groups are introduced almost at both ends of the vinyl chloride polymer.
（発明の効果）
上述の通り、本発明方法によれば、塩化ビニルを主成分
とする単量体をラジカル重合するとともに、得られる塩
化ビニル系重合体の分子の一端又は両末端にアミノ基が
導入される。(Effects of the Invention) As described above, according to the method of the present invention, a monomer containing vinyl chloride as a main component is radically polymerized, and an amino group is added to one or both ends of the molecule of the resulting vinyl chloride polymer. be introduced.
このようにアミノ基が導入された塩化ビニル系重合体は
、アミノ基に基づいて反応性を有する。それゆえ、かか
る本発明の反応性塩化ビニル系重合体を用い、そのアミ
ノ基に他の化合物の反応基、例えばカルボキシル基など
を反応させ、その性能が種々改質された塩化ビニル系樹
脂を製造することができる。The vinyl chloride polymer into which amino groups have been introduced in this way has reactivity based on the amino groups. Therefore, using the reactive vinyl chloride polymer of the present invention, the amino group is reacted with a reactive group of another compound, such as a carboxyl group, to produce a vinyl chloride resin whose performance is variously modified. can do.
Claims (1)
応性塩化ビニル系重合体。 ２、塩化ビニルを主成分とする単量体をラジカル重合す
るに際し、重合時の分解で二つのラジカルが生成し双方
のラジカルにアミノ基が配分されるような重合開始剤を
用いることにより、分子の一端又は両末端にアミノ基を
導入することを特徴とする反応性塩化ビニル系重合体の
製造方法。[Scope of Claims] 1. A reactive vinyl chloride polymer having an amino group introduced at one or both ends of the molecule. 2. When performing radical polymerization of a monomer whose main component is vinyl chloride, by using a polymerization initiator that generates two radicals during decomposition during polymerization and distributes amino groups to both radicals, the molecule can be A method for producing a reactive vinyl chloride polymer, which comprises introducing an amino group into one or both ends of the polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3283690A JPH037702A (en) | 1989-03-14 | 1990-02-14 | Reactive vinyl chloride polymer and production thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6301289 | 1989-03-14 | ||
| JP1-63012 | 1989-03-14 | ||
| JP3283690A JPH037702A (en) | 1989-03-14 | 1990-02-14 | Reactive vinyl chloride polymer and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH037702A true JPH037702A (en) | 1991-01-14 |
Family
ID=26371421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3283690A Pending JPH037702A (en) | 1989-03-14 | 1990-02-14 | Reactive vinyl chloride polymer and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH037702A (en) |
-
1990
- 1990-02-14 JP JP3283690A patent/JPH037702A/en active Pending
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