JPS63277205A - Production of polystyrene - Google Patents
Production of polystyreneInfo
- Publication number
- JPS63277205A JPS63277205A JP11177387A JP11177387A JPS63277205A JP S63277205 A JPS63277205 A JP S63277205A JP 11177387 A JP11177387 A JP 11177387A JP 11177387 A JP11177387 A JP 11177387A JP S63277205 A JPS63277205 A JP S63277205A
- Authority
- JP
- Japan
- Prior art keywords
- polystyrene
- catalyst
- molecular weight
- styrene
- sulfonic acid
- 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
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 28
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims abstract description 22
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 9
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 238000009826 distribution Methods 0.000 claims description 8
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 4
- 239000000178 monomer Substances 0.000 abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000704 physical effect Effects 0.000 abstract description 3
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000006277 sulfonation reaction Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】 （ｉ）発明の目的 〔産業上の利用分野〕 本発明は、ポリスチレンの製造法に関するものである。[Detailed description of the invention] (i) Purpose of the invention [Industrial application field] The present invention relates to a method for producing polystyrene.
詳しくは、本発明は、ハロゲン化炭化水素の存在下でポ
リスチレンスルホン酸を触媒としてスチレンを重合する
ことを特徴とするポリスチレンの製造法に関するもので
ある。Specifically, the present invention relates to a method for producing polystyrene, which comprises polymerizing styrene using polystyrene sulfonic acid as a catalyst in the presence of a halogenated hydrocarbon.
従来、スチレンの重合には種々の方法が知られている。 Conventionally, various methods are known for polymerizing styrene.
特に重量平均分子１５００００以下のポリスチレンの製
造法としては、１）ラジカル開始剤を多量に加えて加熱
する方法、２）γ線などの高エネルギー放射線の照射す
る方法、３）硫酸などの酸触媒により重合する方法、４
） １．２−ジクロロエタン中、クロロ硫酸を触媒とし
て重合する方法（特開昭４８−５４１８９号公報）、等
が提案されている。In particular, methods for producing polystyrene with a weight average molecular weight of 150,000 or less include 1) adding a large amount of radical initiator and heating, 2) irradiating with high-energy radiation such as gamma rays, and 3) using an acid catalyst such as sulfuric acid. Method of polymerizing, 4
) 1. A method of polymerizing in 2-dichloroethane using chlorosulfuric acid as a catalyst (Japanese Unexamined Patent Publication No. 48-54189) has been proposed.
ポリスチレンをスルホン化する場合、ポリスチレンの分
子量およびその分子量分布、残存モノマー、２．３量体
、残存した重合溶媒などの低分子量成分、触媒などが、
反応や中和後のポリスチレンスルホン酸塩の物性に悪影
響を与える。When polystyrene is sulfonated, the molecular weight of polystyrene and its molecular weight distribution, residual monomers, 2.3-mers, low molecular weight components such as residual polymerization solvent, catalyst, etc.
It has a negative effect on the physical properties of polystyrene sulfonate after reaction and neutralization.
上記の方法１）、 ２）、 ３）においては、重合溶媒
として芳香族炭化水素、脂肪族炭化水素が使用されるが
、これらの溶媒はスルホン化反応に使用できない。その
ため、スチレンを重合し、更に生成したポリスチレンを
スルホン化するにあたり、重合反応後説溶媒し、樹脂と
して回収後再び溶解という工程が必要となり、操作上、
及びエネルギー的に不利となる。更に１）の方法では、
高価な過酸化物を多量に使うため経済的でない。２）の
方法では、放射線源を取り扱う、装置が高価である。In the above methods 1), 2), and 3), aromatic hydrocarbons and aliphatic hydrocarbons are used as polymerization solvents, but these solvents cannot be used in the sulfonation reaction. Therefore, when styrene is polymerized and the resulting polystyrene is sulfonated, it is necessary to use a solvent after the polymerization reaction, recover the resin, and then dissolve it again.
and energetically disadvantageous. Furthermore, in method 1),
It is not economical because a large amount of expensive peroxide is used. In method 2), the equipment for handling the radiation source is expensive.
などの問題点があり、コスト的にも不利である。There are problems such as these, and it is disadvantageous in terms of cost.
また、４）の方法でも脱触媒が必要となる、残存モノマ
ー量が多くモノマーの除去が必要となる、など、工程上
の問題点があり、何れも満足できるものではない。In addition, method 4) also has problems in the process, such as decatalyst removal being required, and the amount of residual monomer being large, making it necessary to remove the monomer, and neither of these methods is satisfactory.
（ｉｉ）発明の構成
〔問題点を解決するための手段〕
本発明者等は、前記の問題点を解決するために鋭意検討
を重ねた結果、１，２−ジクロロエタンのようなハロゲ
ン化炭化水素溶媒中でポリスチレンスルホン酸を触媒と
してスチレンの重合を行なったところ、これらの問題点
の解決が可能であることを見い出し本発明を完成するに
至った。(ii) Structure of the Invention [Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors have discovered that halogenated hydrocarbons such as 1,2-dichloroethane When styrene was polymerized in a solvent using polystyrene sulfonic acid as a catalyst, it was discovered that these problems could be solved, and the present invention was completed.
即ち、本発明のポリスチレンの製造法は、ｌ）重量平均
分子量５００〜５００００のポリスチレンの製造法にお
いて、ハロゲン化炭化水素の存在下でポリスチレンスル
ホン酸を触媒としてスチレンを重合することを特徴とす
るポリスチレンの製造法。That is, the method for producing polystyrene of the present invention is l) a method for producing polystyrene having a weight average molecular weight of 500 to 50,000, which comprises polymerizing styrene using polystyrene sulfonic acid as a catalyst in the presence of a halogenated hydrocarbon; manufacturing method.
２）触媒がポリスチレン中のベンゼン環のうち１〜９０
％がスルホン化されたポリスチレンスルホン酸である特
許請求の範囲第１項記載の方法。2) The catalyst is 1 to 90 of the benzene rings in polystyrene.
% is sulfonated polystyrene sulfonic acid.
３）触媒が製造するポリスチレンと分子量分布が近似す
るポリスチレンをスルホン化したポリスチレンスルホン
酸である特許請求の範囲第１〜２項のいずれか１項に記
載の方法。3) The method according to any one of claims 1 to 2, wherein the catalyst is polystyrene sulfonic acid obtained by sulfonating polystyrene having a molecular weight distribution similar to that of the polystyrene produced.
である。It is.
（発明の詳細な説明）
ハロゲンヒ・ヒ、工
本発明の製造法に用いられる溶媒のハロゲン化炭化水素
としては、例えば塩化メチレン、クロロホルム、四塩化
炭素、ジクロルエタン、トリクロルエタン、テトラクロ
ルエタン、テトラクロルエチレン等が挙げられる。(Detailed Description of the Invention) Halogenated hydrocarbons as solvents used in the production method of the present invention include, for example, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, and tetrachloroethylene. etc.
放−一裸
本発明の製造法において触媒として用いられるポリスチ
レンスルホン酸は重量平均分子量が５００〜５ｏｏｏｏ
のポリスチレンを常法によりスルホン化して得られるも
ので、そのポリスチレンのベンゼン環のうち１〜９０％
、好ましくは５〜５０％がスルホン化されたポリスチレ
ンスルホン酸が適当である。スルホン化率が９０％を越
えるとスチレンを加えた時、触媒のポリスチレンスルホ
ン酸が析出するので好ましくない。又、スルホン化率が
１％未満の場合には触媒の効率が悪く好ましくない。ま
た、触媒として使用するポリスチレンスルホン酸の分子
量分布は本発明の方法により製造されるポリスチレンの
分子量分布と近似しているものが好ましく、その分布が
実質的に等しいものが特に好ましい。仮にその分子量分
布が著しく異なっている場合、生成したポリスチレンを
スルホン化したときのポリスチレンスルホン酸の分子量
分布を変化させてしまうので好ましくない。なお、触媒
の使用量は通常、スチレンに対して０．０１〜５モル％
、好ましくは、０．０４〜１モル％である。The polystyrene sulfonic acid used as a catalyst in the production method of the present invention has a weight average molecular weight of 500 to 5oooo
It is obtained by sulfonating polystyrene by a conventional method, and 1 to 90% of the benzene rings of the polystyrene are
, preferably 5 to 50% sulfonated polystyrene sulfonic acid. If the sulfonation rate exceeds 90%, the polystyrene sulfonic acid catalyst will precipitate when styrene is added, which is not preferable. Furthermore, if the sulfonation rate is less than 1%, the efficiency of the catalyst will be poor, which is not preferable. Further, the molecular weight distribution of polystyrene sulfonic acid used as a catalyst is preferably similar to the molecular weight distribution of polystyrene produced by the method of the present invention, and it is particularly preferable that the distribution is substantially the same. If the molecular weight distributions are significantly different, this is not preferable because the molecular weight distribution of polystyrene sulfonic acid when the produced polystyrene is sulfonated will change. The amount of catalyst used is usually 0.01 to 5 mol% based on styrene.
, preferably 0.04 to 1 mol%.
反−一息
本発明の重合反応において用いるハロゲン化炭化水素溶
媒とスチレンの比率については特に制限はないが、溶媒
に対するスチレンの比率が１０〜３００重量％であるこ
とが好ましく、更に好ましくは２０〜２００重量％であ
る。そして、反応は予じめ溶媒に溶解したスチレンを触
媒の存在下で重合させるのが通常であるが、スチレンを
滴下しながら重合を行なってもよい。また、重合反応温
度については、通常、常温〜１００℃の範囲が適当であ
るが、５０〜７５℃の範囲が好ましい。なお、重合反応
時間については、通常５分〜５時間、好ましくはｌＯ分
〜２時間が適当である。There is no particular restriction on the ratio of styrene to the halogenated hydrocarbon solvent used in the polymerization reaction of the present invention, but the ratio of styrene to the solvent is preferably 10 to 300% by weight, more preferably 20 to 200% by weight. Weight%. In the reaction, styrene dissolved in a solvent in advance is usually polymerized in the presence of a catalyst, but the polymerization may be performed while dropping styrene. Regarding the polymerization reaction temperature, a range of normal temperature to 100°C is usually appropriate, but a range of 50 to 75°C is preferable. The polymerization reaction time is usually 5 minutes to 5 hours, preferably 10 minutes to 2 hours.
ス土土ヱ■笠
本発明の製造法により得られたポリスチレンは、所望に
より、触媒及び溶媒を除去することなく、そのまま或い
は更に溶媒で希釈の上スルホン化工程に付すことが出来
る。そしてこの際、触媒として使用したポリスチレンス
ルホン酸もポリスチレンと同時にスルホン化されるので
、これをそのまま触媒として使用する場合には触媒コス
トも殆んどかからず、又、生成したポリスチレンスルホ
ン酸の物性等に悪影響を及ぼすことがない。If desired, the polystyrene obtained by the production method of the present invention can be subjected to the sulfonation step without removing the catalyst and solvent, or as it is or after further dilution with a solvent. At this time, the polystyrene sulfonic acid used as a catalyst is also sulfonated at the same time as the polystyrene, so if it is used as a catalyst as it is, there is almost no catalyst cost, and the physical properties of the produced polystyrene sulfonic acid are has no adverse effect on
実施例１
ポリスチレンスルホン酸（スルホン化する前の重量平均
分子１６６００、スルホン化率２５％）１．８ｇを１，
２−ジクロロエタン２４０ｇに溶かし、スチレン６０ｇ
を加えて５０℃で２時間重合させ、７０℃で更に２時間
重合させた。重合後の残存モノマー量はガスクロマトグ
ラフィーで測定したところ０．７％であった。また重量
平均分子量はゲルバーミエイシ；ンクロマトグラフィー
で測定した結果５５００であった。Example 1 1.8 g of polystyrene sulfonic acid (weight average molecule 16600 before sulfonation, sulfonation rate 25%) was
Dissolved in 240g of 2-dichloroethane, 60g of styrene
was added, polymerized at 50°C for 2 hours, and further polymerized at 70°C for 2 hours. The amount of monomer remaining after polymerization was determined by gas chromatography to be 0.7%. The weight average molecular weight was 5500 as measured by gel vermicin chromatography.
実施例２
ポリスチレンスルホン酸（スルホン化する前の重量平均
分子１ｔ６６００、スルホン化率８％）３．０ｇを１．
２−ジクロロエタン１２０ｇに溶かし、この溶液を５０
℃に加熱し、スチレン６０ｇを２５分で滴下した。溶液
の温度を３０分で７０℃まで上げ、そのまま６０分重合
させた。反応後の残存モノマーは１゜０％、重量平均分
子量は２１００であった。Example 2 3.0 g of polystyrene sulfonic acid (weight average molecular weight before sulfonation 1t6600, sulfonation rate 8%) was added to 1.
Dissolve in 120 g of 2-dichloroethane, and add 50 g of this solution.
The mixture was heated to 0.degree. C., and 60 g of styrene was added dropwise over 25 minutes. The temperature of the solution was raised to 70° C. over 30 minutes, and polymerization was continued for 60 minutes. The residual monomer content after the reaction was 1.0%, and the weight average molecular weight was 2100.
実施例３
ポリスチレンスルホン酸（スルホン化する前の重量平均
分子１６６００、スルホン化率２５％）１８５ｇを１，
２−ジクロロエタン１００ｇに溶かし、この溶液を５０
℃に加熱し、スチレン３００ｇを加えた。溶液の温度を
５５℃まで上げ、そのまま２時間重合させた。反応後の
残存モノマーは１．０％、重量平均分子量は２３００で
あった。Example 3 185 g of polystyrene sulfonic acid (weight average molecule 16600 before sulfonation, sulfonation rate 25%) was
Dissolve in 100 g of 2-dichloroethane, and add 50 g of this solution.
It was heated to 0.degree. C. and 300 g of styrene was added. The temperature of the solution was raised to 55° C., and polymerization was continued for 2 hours. The residual monomer content after the reaction was 1.0%, and the weight average molecular weight was 2,300.
比較例１
１．２−ジクロロエタン２４０ｇに、スチレン６０ｇ、
クロル硫酸０．３ｇを加え、３５℃で１時間重合させた
０反応後の残存モノマーは２２％であった。Comparative Example 1 240 g of 1,2-dichloroethane, 60 g of styrene,
After adding 0.3 g of chlorosulfuric acid and polymerizing at 35° C. for 1 hour, the remaining monomer was 22%.
応用例
実施例１で得られた溶液２２５ｇに、１．２−ジクロロ
エタン６７５ｇを加え撹拌しながら窒素で８％に希釈し
た５０３ガス４４ｇを３３分間で吹き込み、さらに２０
分間撹拌を続けた。反応温度は３３〜３７℃であった。Application Example 675 g of 1,2-dichloroethane was added to 225 g of the solution obtained in Example 1, and while stirring, 44 g of 503 gas diluted to 8% with nitrogen was blown in over 33 minutes.
Stirring was continued for a minute. The reaction temperature was 33-37°C.
得られたスルホン化物のスルホン化率は９３％であった
。The sulfonation rate of the obtained sulfonated product was 93%.
（ｉｉｉ ）発明の効果
本発明の製造法によれば、残存モノマー量の少ない、重
量平均分子量５００〜５００００のポリスチレンを有利
に製造することが出来る。そして、得られたポリスチレ
ン溶液は、触媒を除去することなく、そのままスルホン
化工程に付することが出来るので、この方法はポリスチ
レンスルホン酸の製造にも有利である。(iii) Effects of the Invention According to the production method of the present invention, polystyrene having a weight average molecular weight of 500 to 50,000 and having a small amount of residual monomer can be advantageously produced. Since the obtained polystyrene solution can be directly subjected to the sulfonation step without removing the catalyst, this method is also advantageous for producing polystyrene sulfonic acid.
Claims (1)
の製造法において、ハロゲン化炭化水素の存在下でポリ
スチレンスルホン酸を触媒としてスチレンを重合するこ
とを特徴とするポリスチレンの製造法。 ２）触媒がポリスチレン中のベンゼン環のうち１〜９０
％がスルホン化されたポリスチレンスルホン酸である特
許請求の範囲第１項記載の方法。 ３）触媒が製造するポリスチレンと分子量分布が近似す
るポリスチレンをスルホン化したポリスチレンスルホン
酸である特許請求の範囲第１〜２項のいずれか１項に記
載の方法。Claims: 1) A method for producing polystyrene having a weight average molecular weight of 500 to 50,000, which comprises polymerizing styrene using polystyrene sulfonic acid as a catalyst in the presence of a halogenated hydrocarbon. 2) The catalyst is 1 to 90 of the benzene rings in polystyrene.
% is sulfonated polystyrene sulfonic acid. 3) The method according to any one of claims 1 to 2, wherein the catalyst is polystyrene sulfonic acid obtained by sulfonating polystyrene having a molecular weight distribution similar to that of the polystyrene produced.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11177387A JPS63277205A (en) | 1987-05-08 | 1987-05-08 | Production of polystyrene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11177387A JPS63277205A (en) | 1987-05-08 | 1987-05-08 | Production of polystyrene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63277205A true JPS63277205A (en) | 1988-11-15 |
Family
ID=14569801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11177387A Pending JPS63277205A (en) | 1987-05-08 | 1987-05-08 | Production of polystyrene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63277205A (en) |
-
1987
- 1987-05-08 JP JP11177387A patent/JPS63277205A/en active Pending
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