JP3248979B2 - Coagulant for deproteinized natural rubber latex and method for producing raw rubber using the same - Google Patents
Coagulant for deproteinized natural rubber latex and method for producing raw rubber using the sameInfo
- Publication number
- JP3248979B2 JP3248979B2 JP11176693A JP11176693A JP3248979B2 JP 3248979 B2 JP3248979 B2 JP 3248979B2 JP 11176693 A JP11176693 A JP 11176693A JP 11176693 A JP11176693 A JP 11176693A JP 3248979 B2 JP3248979 B2 JP 3248979B2
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- JP
- Japan
- Prior art keywords
- latex
- natural rubber
- rubber
- coagulant
- deproteinized natural
- Prior art date
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- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は脱蛋白天然ゴムラテック
スから効率よく生ゴムを得るための凝固剤およびこれを
用いる生ゴムの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coagulant for efficiently obtaining raw rubber from deproteinized natural rubber latex and a method for producing raw rubber using the same.
【０００２】[0002]
【従来の技術】従来より、天然ゴムは、自動車用タイ
ヤ、ベルト、粘接着剤などの工業用品から手袋などの家
庭用品まで幅広く利用されている。これらの天然ゴム製
品は、通常、天然ゴムラテックスからゴム分を凝固させ
て生ゴム（クレープゴムまたはスモークドシートゴム）
を得、この生ゴムから素練り、配合剤の配合、成形、加
硫の各工程を経て製造される。2. Description of the Related Art Conventionally, natural rubber has been widely used from industrial products such as automobile tires, belts and adhesives to household products such as gloves. These natural rubber products are usually made from raw rubber (crepe rubber or smoked sheet rubber) by coagulating the rubber component from natural rubber latex.
The raw rubber is manufactured through the steps of mastication, compounding of compounding agents, molding and vulcanization.
【０００３】ところが、近時、天然ゴム製品を使用した
手術用手袋や各種カテーテル、麻酔用マスク等の医療用
具が原因で患者が呼吸困難、アナフィラキシー様症状
（血管性浮腫、じんましん、虚脱、チアノーゼ等）を起
こすことが米国で報告された。また、アレルギーの既往
症をもつ女性が天然ゴムからつくった家庭用ゴム手袋を
使用した際、手の痛み、じんましん、眼の周囲の血管性
浮腫が現れた等の症例も報告されている。Recently, however, medical devices such as surgical gloves, various catheters, and anesthesia masks using natural rubber products have caused patients to have difficulty breathing and anaphylaxis-like symptoms (angioedema, urticaria, collapse, cyanosis, etc.). ) Was reported in the United States. In addition, there have been reports of cases in which women with a history of allergies used home rubber gloves made of natural rubber, showing pain in the hands, hives, and angioedema around the eyes.
【０００４】その原因としては、天然ゴム中の蛋白質で
あろうと推測されており、米国の食品医薬品局（ＦＤ
Ａ）は天然ゴム製品の製造業者に蛋白質量を少なくする
よう働きかけている。従って、天然ゴム中の蛋白質量を
除去することが必要であった。天然ゴムは、ヘビア樹の
樹液として、ゴム分のほか、水、蛋白質、無機塩類など
を含むラテックスとして得られる。ヘビア樹をタッピン
グして出てくる生ラテックスをカップに受け、それを集
荷し精製工場で凝固して生ゴム（クレープゴムまたはス
モークドシートゴム）とするか、あるいは遠心分離法に
よって濃縮した精製ラテックスを製造する。[0004] The cause is presumed to be proteins in natural rubber, and the US Food and Drug Administration (FD)
A) urges natural rubber product manufacturers to reduce protein content. Therefore, it was necessary to remove the protein content in natural rubber. Natural rubber is obtained as a sap of a heavy tree, and as a latex containing water, proteins, inorganic salts, and the like in addition to the rubber component. Tapping a heavy tree and receiving the raw latex that comes out into a cup, collecting it and coagulating it at a refinery to produce raw rubber (crepe rubber or smoked sheet rubber), or manufacturing concentrated latex by centrifugation I do.
【０００５】ところで、天然ゴムの蛋白質含有率は、通
常ケルダール法によって、決定される窒素含有率（Ｎ
％）の６．３倍量で表されてきた。本発明者らは、天然
ゴムラテックスから得られる生ゴム中の蛋白質が生ゴム
フィルムの赤外線吸収スペクトルにおいて３２８０ｃｍ
ー1のポリペプチド特有な吸収で確認されることを見いだ
した。The protein content of natural rubber is usually determined by the Kjeldahl method.
%). The present inventors have found that the protein in raw rubber obtained from natural rubber latex has an infrared absorption spectrum of a raw rubber film of 3280 cm.
-1 was confirmed by the absorption characteristic of the polypeptide.
【０００６】そして、本発明者らは、さきに蛋白質分解
酵素と界面活性剤とで天然ゴムラテックスを同時又は順
次処理し一定時間放置後、遠心分離によりゴム分を回収
することにより、その生ゴムフィルムに前記した３２８
０ｃｍー1に吸収が認められない脱蛋白天然ゴムラテック
スが得られることを見出し、特許出願を行った（特願平
４ー２０８７５４〜特願平４ー２０８７５８号）。The inventors of the present invention have previously treated natural rubber latex simultaneously or sequentially with a protease and a surfactant, allowed it to stand for a certain period of time, and then recovered the rubber component by centrifugation to obtain the raw rubber film. 328 described above
They found that a deproteinized natural rubber latex having no absorption at 0 cm -1 was obtained, and filed a patent application (Japanese Patent Application Nos. 4-208754 to 4-208758).
【０００７】[0007]
【発明が解決しようとする課題】一般に天然ゴムラテッ
クスから生ゴムを得る方法としてはギ酸や酢酸等の酸を
添加して回収する方法と、塩化カルシウム、硫酸アルミ
ニウム、硝酸カルシウム等の無機塩を添加する方法とが
知られている。例えば、ラテックスを固形分約１５〜２
０重量％に希釈し、ついでギ酸を０．１〜１重量％添加
してゴム分を凝集させ、分離洗浄後、乾燥して生ゴムを
得る方法が用いられている。Generally, as a method for obtaining raw rubber from natural rubber latex, a method for recovering by adding an acid such as formic acid or acetic acid and a method for adding an inorganic salt such as calcium chloride, aluminum sulfate or calcium nitrate are used. Methods and methods are known. For example, latex is used for a solid content of about 15 to 2
A method of diluting to 0% by weight, then adding 0.1 to 1% by weight of formic acid to coagulate a rubber component, separating and washing, and then drying to obtain a raw rubber is used.
【０００８】しかしながら、前述のような脱蛋白天然ゴ
ムラテックスでは、通常の市販ラテックスと違い一般の
酸添加による凝集がほとんど起こらないため生ゴムの生
成が困難であるという問題が生じている。また、前記無
機塩の添加により凝固させる方法では、得られた固形ゴ
ム分中に金属イオンが含有されるため、吸湿による物性
低下、ブルーミング、加硫の遅延、耐老化性の低下など
の問題が生じる。However, in the case of the above-described deproteinized natural rubber latex, unlike the conventional commercially available latex, there is a problem that it is difficult to produce a raw rubber because aggregation due to addition of a general acid hardly occurs. Further, in the method of coagulation by the addition of the inorganic salt, since metal ions are contained in the obtained solid rubber component, there are problems such as deterioration in physical properties due to moisture absorption, blooming, delay in vulcanization, deterioration in aging resistance, and the like. Occurs.
【０００９】従って、本発明の主たる目的は脱蛋白天然
ゴムラテックスからの生ゴムの生成効率を高めるための
脱蛋白天然ゴムラテックスの凝固剤およびこれを用いる
生ゴムの製造方法を提供することである。本発明の他の
目的は、生成した生ゴムに金属イオンが含有されない脱
蛋白天然ゴムラテックスの凝固剤およびこれを用いる生
ゴムの製造方法を提供することである。Accordingly, it is a primary object of the present invention to provide a coagulant for a deproteinized natural rubber latex for improving the production efficiency of a raw rubber from a deproteinized natural rubber latex and a method for producing a raw rubber using the same. Another object of the present invention is to provide a coagulant for a deproteinized natural rubber latex containing no metal ions in the produced raw rubber and a method for producing raw rubber using the same.
【００１０】[0010]
【課題を解決するための手段および作用】本発明者らは
前記の課題を解決するために鋭意研究を重ねた結果、脱
蛋白天然ゴムラテックスから生ゴムを分離する際に酸や
無機塩等を用いずに、２０〜１００℃の曇点を有しかつ
分子量が３００以上の非イオン界面活性剤を用いること
によって脱蛋白天然ゴムラテックスより金属イオンを含
有しない生ゴムを高効率で回収できるという新たな事実
を見出し、本発明を完成するに至った。The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that when raw rubber is separated from deproteinized natural rubber latex, acid or inorganic salt is used. New fact that raw rubber containing no metal ions can be efficiently recovered from deproteinized natural rubber latex by using a nonionic surfactant having a cloud point of 20 to 100 ° C and a molecular weight of 300 or more. And completed the present invention.
【００１１】すなわち、本発明の凝固剤は、２０〜１０
０℃の曇点を有しかつ分子量が３００以上の非イオン界
面活性剤からなることを特徴とする。また、本発明の生
ゴムの製造方法は、前記凝固剤を脱蛋白天然ゴムラテッ
クスに加えて、該ラテックスを前記凝固剤を構成する非
イオン界面活性剤の曇点以上の温度に加熱して脱蛋白質
天然ゴムラテックス中のゴム分を凝固させることを特徴
とする。That is, the coagulant of the present invention contains 20 to 10
It is characterized by comprising a nonionic surfactant having a cloud point of 0 ° C. and a molecular weight of 300 or more. Further, the method for producing a raw rubber according to the present invention comprises the steps of: adding the coagulant to a deproteinized natural rubber latex; and heating the latex to a temperature equal to or higher than the cloud point of the nonionic surfactant constituting the coagulant. The rubber component in natural rubber latex is coagulated.
【００１２】本発明に用いる非イオン界面活性剤は２０
〜１００℃の曇点を有しかつ分子量が３００以上であ
り、好ましくは２０〜１００℃の曇点を有しかつ分子量
が１０００以上のもの、より好ましくは２０〜８０℃の
曇点を有しかつ分子量が１０００以上のものである。使
用する非イオン界面活性剤の曇点が２０℃未満だと室温
での取扱いが難しくなり、他方１００℃を越えると凝固
効果を得ることが困難になる。さらに分子量が３００未
満の非イオン界面活性剤ではゴム分を効率よく凝固させ
ることが難しくなる。The nonionic surfactant used in the present invention is 20
It has a cloud point of -100 ° C and a molecular weight of 300 or more, preferably has a cloud point of 20-100 ° C and a molecular weight of 1000 or more, more preferably has a cloud point of 20-80 ° C. And it has a molecular weight of 1,000 or more. If the cloud point of the nonionic surfactant used is less than 20 ° C., it is difficult to handle at room temperature, and if it exceeds 100 ° C., it is difficult to obtain a coagulation effect. Further, with a nonionic surfactant having a molecular weight of less than 300, it is difficult to efficiently coagulate the rubber component.
【００１３】本発明に用いる非イオン界面活性剤の添加
量は一般に脱蛋白天然ゴムラテックスの固形分に対し
０．０１〜１０重量％、好ましくは０．１〜５重量％の
範囲である。添加量が０．０１重量％未満ではゴム分を
凝固する効果が乏しく、他方１０重量％を超えるとコス
トアップになり、また回収したゴム分に残存する界面活
性剤の量も多くなり好ましくない。The amount of the nonionic surfactant used in the present invention is generally in the range of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the solid content of the deproteinized natural rubber latex. If the addition amount is less than 0.01% by weight, the effect of coagulating the rubber component is poor, while if it exceeds 10% by weight, the cost increases and the amount of the surfactant remaining in the recovered rubber component increases, which is not preferable.
【００１４】本発明に用いられる非イオン界面活性剤と
しては、例えばポリオキシアルキレンエステル系、ポリ
オキシアルキレンエーテル系、ポリオキシアルキレン多
価アルコールエステル、ポリオキシアルキレン糖脂肪酸
エステル、オルガノポリシロキサンーポリオキシアルキ
レン共重合体、フェノール又はアルキルフェノールのホ
ルマリン縮合物のポリオキシアルキレン付加物、ビスフ
ェノールＡもしくはビスフェノールＳのポリオキシアル
キレン付加物などを挙げることができる。The nonionic surfactants used in the present invention include, for example, polyoxyalkylene esters, polyoxyalkylene ethers, polyoxyalkylene polyhydric alcohol esters, polyoxyalkylene sugar fatty acid esters, organopolysiloxane-polyoxy Examples include an alkylene copolymer, a polyoxyalkylene adduct of a formalin condensate of phenol or alkylphenol, and a polyoxyalkylene adduct of bisphenol A or bisphenol S.
【００１５】ここで、ポリオキシアルキレン基として
は、炭素数２〜４のアルキレン基を有するものがあげら
れ、例えば酸化エチレンの付加モル数が１〜３００モ
ル、好ましくは５〜３００モル程度のものが挙げられ
る。また、これらの界面活性剤は一種または二種以上を
併用してもよく、その種類は適宣選択される。The polyoxyalkylene group includes those having an alkylene group having 2 to 4 carbon atoms. For example, the polyoxyalkylene group has an addition mole number of ethylene oxide of 1 to 300 mol, preferably about 5 to 300 mol. Is mentioned. These surfactants may be used alone or in combination of two or more, and the type is appropriately selected.
【００１６】本発明に用いる非イオン界面活性剤は、脱
蛋白天然ゴムラテックスの製造後に添加してもよく、或
いは脱蛋白天然ゴムラテックスの製造前に添加してもよ
い。通常は前者の方が好ましい。本発明において天然ゴ
ムを凝固させる際には、凝固剤として非イオン界面活性
剤を含有する脱蛋白天然ゴムラテックスを、その非イオ
ン界面活性剤の曇点以上の温度に加熱する。非イオン界
面活性剤の添加と加熱の順序はとくに制限されるもので
はなく、非イオン界面活性剤を添加する前に予めラテッ
クスを加熱してもよく、あるいはラテックスに非イオン
界面活性剤を添加した後に加熱してもよい。The nonionic surfactant used in the present invention may be added after the production of the deproteinized natural rubber latex, or may be added before the production of the deproteinized natural rubber latex. Usually, the former is preferred. In coagulating natural rubber in the present invention, a deproteinized natural rubber latex containing a nonionic surfactant as a coagulant is heated to a temperature equal to or higher than the cloud point of the nonionic surfactant. The order of addition and heating of the nonionic surfactant is not particularly limited, and the latex may be heated before adding the nonionic surfactant, or the nonionic surfactant is added to the latex. It may be heated later.
【００１７】凝固後はラテックスより分離したゴムを十
分水洗し乾燥すればよい。なお、水洗時のゴム分および
水の温度は曇点以下にするほうがより非イオン界面活性
剤および他の界面活性剤の除去効果が高い。前記のよう
に本発明の非イオン界面活性剤を用いてラテックスから
回収したゴム分は、凝固剤として金属塩を用いて回収し
たゴム分と比べて、金属イオン及び界面活性剤の含有量
が極めて微量である。After coagulation, the rubber separated from the latex may be sufficiently washed with water and dried. The effect of removing the nonionic surfactant and other surfactants is higher when the temperature of the rubber component and water during washing with water is lower than the cloud point. As described above, the rubber component recovered from the latex using the nonionic surfactant of the present invention has a very high content of metal ions and surfactant compared to the rubber component recovered using a metal salt as a coagulant. Trace amount.
【００１８】また、上記方法は、従来の酸を添加して凝
集させる生ゴムの製造方法と併用することも可能であ
る。The above method can be used in combination with a conventional method for producing a raw rubber in which an acid is added to cause coagulation.
【００１９】[0019]
【実施例】次に実施例を挙げて本発明を詳細に説明する
が、本発明はこれらの実施例のみに限定されるものでは
ない。なお、以下において、部及び％はそれぞれ重量部
及び重量％を意味する。 実施例１〜６ 天然ゴムのハイアンモニアラテックスを蛋白分解酵素
（アルカリプロテアーゼ）と界面活性剤〔ドデシルベン
ゼンスルホン酸ナトリウムとポリオキシエチレン(9モ
ル) ラウリルエーテルとの混合物（６０：４０）〕で処
理し赤外線スペクトルにおいて３２８０ｃｍ-1にポリペ
プチドの吸収が見られない脱蛋白天然ゴムラテックスを
調製した。試験管中で、得られた脱蛋白天然ゴムラテッ
クス（固形分３０％）１００部に表１に示す非イオン界
面活性剤の１０％水溶液１部を混合した後、９０℃の水
浴中で５分間加熱した。加熱後の凝固状態を目視判定に
より評価した。その結果を表１に示す。なお、表におい
て評価基準は次の通りである。Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In the following, parts and% mean parts by weight and% by weight, respectively. Examples 1 to 6 Natural rubber high ammonia latex was treated with a protease (alkali protease) and a surfactant [a mixture of sodium dodecylbenzenesulfonate and polyoxyethylene (9 mol) lauryl ether (60:40)]. Then, a deproteinized natural rubber latex having no absorption of the polypeptide at 3280 cm -1 in the infrared spectrum was prepared. In a test tube, 1 part of a 10% aqueous solution of a nonionic surfactant shown in Table 1 was mixed with 100 parts of the obtained deproteinized natural rubber latex (solid content: 30%), and then mixed in a water bath at 90 ° C. for 5 minutes. Heated. The solidification state after heating was evaluated by visual judgment. Table 1 shows the results. The evaluation criteria in the table are as follows.
【００２０】○…ゴム分が凝固する ×…ゴム分が凝固しない また、第１表において、ｎはフェノール又はアルキルフ
ェノールのホルマリン縮合物の平均縮合度を、またＥＯ
及びＰＯはそれぞれ酸化エチレン及び酸化プロピレンを
表し、括弧内の数字は共付加物１分子当たりのそれぞれ
の平均付加モル数を示す。 比較例１〜２ 凝固剤として、表１に示す曇点および分子量を有する非
イオン界面活性剤を使用したほかは実施例１〜６と同様
にして凝固させた。…: Rubber component coagulates X: rubber component does not coagulate In Table 1, n is the average degree of condensation of formalin condensate of phenol or alkylphenol, and EO
And PO represent ethylene oxide and propylene oxide, respectively, and the numbers in parentheses indicate the respective average moles added per molecule of the co-adduct. Comparative Examples 1-2 Coagulation was carried out in the same manner as in Examples 1-6, except that a nonionic surfactant having a cloud point and a molecular weight shown in Table 1 was used as a coagulant.
【００２１】なお、対照として、凝固剤を添加しない脱
蛋白天然ゴムラテックスについても同様にして試験し、
凝固状態を観察した。それらの結果も表１に併せて示
す。As a control, a deproteinized natural rubber latex to which no coagulant was added was also tested in the same manner.
The coagulation state was observed. The results are also shown in Table 1.
【００２２】[0022]
【表１】 [Table 1]
【００２３】表１から、非イオン界面活性剤の曇点が２
０〜１００℃の範囲外でかつ分子量が３００未満の比較
例２では、非イオン界面活性剤の添加による効果が発現
しない。また、比較例１のように分子量が３００以上で
も曇点が２０〜１００℃外のものであれば凝固効果を示
さない。これに対して、実施例１〜６では、曇点が２０
〜１００℃の範囲内でかつ分子量が３００以上の非イオ
ン界面活性剤を使用しているため、良好な凝固効果を示
している。From Table 1, it can be seen that the cloud point of the nonionic surfactant is 2
In Comparative Example 2 in which the molecular weight is outside the range of 0 to 100 ° C. and the molecular weight is less than 300, the effect of adding the nonionic surfactant does not appear. Further, even if the molecular weight is 300 or more as in Comparative Example 1, if the cloud point is outside the range of 20 to 100 ° C., no coagulation effect is exhibited. In contrast, in Examples 1 to 6, the cloud point was 20
Since a nonionic surfactant having a molecular weight in the range of １００100 ° C. and a molecular weight of 300 or more is used, a good coagulation effect is exhibited.
【００２４】[0024]
【発明の効果】以上のように本発明の凝固剤は、これを
脱蛋白天然ゴムラテックスに添加してゴム分を凝固させ
ることにより、金属イオンを含有しない生ゴムを高効率
で得ることができるという効果がある。As described above, the coagulant of the present invention can obtain a raw rubber containing no metal ions with high efficiency by adding the coagulant to the deproteinized natural rubber latex to coagulate the rubber component. effective.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 林 正治 和歌山県和歌山市榎原133−５ (72)発明者 市川 直哉 兵庫県明石市魚住町清水41番地の１ 住 友ゴム魚住寮 (72)発明者 榊 俊明 兵庫県加古川市尾上町養田1314番地の１ (56)参考文献 特開 平６−56902（ＪＰ，Ａ) 特開 平６−56903（ＪＰ，Ａ) 特開 平６−56904（ＪＰ，Ａ) 特開 平６−56905（ＪＰ，Ａ) 特開 平６−56906（ＪＰ，Ａ) 英国特許出願公開309245（ＧＢ，Ａ) 英国特許出願公開1192407（ＧＢ，Ａ) 英国特許出願公開2098222（ＧＢ，Ａ) 米国特許出願公開2097481（ＵＳ，Ａ) 米国特許出願公開2399156（ＵＳ，Ａ) 米国特許出願公開4379095（ＵＳ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08C 1/14 C08L 7/02 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masaharu Hayashi 133-5 Enohara, Wakayama-shi, Wakayama Prefecture (72) Inventor Naoya Ichikawa 41-1, Shimizu, Uozumi-cho, Akashi-shi, Hyogo Prefecture Toshiaki Sakaki 1314, Yoda, Onoe-cho, Kakogawa-shi, Hyogo (56) References JP-A-6-56902 (JP, A) JP-A-6-56903 (JP, A) JP-A-6-56904 (JP, A) JP-A-6-56905 (JP, A) JP-A-6-56906 (JP, A) UK Patent Application Publication 309245 (GB, A) UK Patent Application Publication 1192407 (GB, A) UK Patent Application Publication 2098222 (GB) U.S. Patent Application Publication No. 2097481 (US, A) U.S. Patent Application Publication No. 2399156 (US, A) U.S. Patent Application Publication No. 4379095 (US, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08C 1/14 C08L 7/02
Claims (3)
３００以上の非イオン界面活性剤からなることを特徴と
する脱蛋白天然ゴムラテックスの凝固剤。1. A coagulant for a deproteinized natural rubber latex, comprising a nonionic surfactant having a cloud point of 20 to 100 ° C. and a molecular weight of 300 or more.
テックスに加えて、該ラテックスを前記凝固剤を構成す
る非イオン界面活性剤の曇点以上の温度に加熱して脱蛋
白質天然ゴムラテックス中のゴム分を凝固させることを
特徴とする生ゴムの製造方法。2. A deproteinized natural rubber obtained by adding the coagulant according to claim 1 to a deproteinized natural rubber latex, and heating the latex to a temperature higher than the cloud point of the nonionic surfactant constituting the coagulant. A method for producing raw rubber, comprising coagulating a rubber component in latex.
スの固形分に対して請求項１記載の凝固剤を０．０１〜
１０重量％の割合で添加する請求項２記載の生ゴムの製
造方法。3. A coagulant according to claim 1, which is added to the deproteinized natural rubber latex in an amount of 0.01 to 3% based on the solid content of the latex.
The method for producing raw rubber according to claim 2, wherein the raw rubber is added at a ratio of 10% by weight.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11176693A JP3248979B2 (en) | 1993-05-13 | 1993-05-13 | Coagulant for deproteinized natural rubber latex and method for producing raw rubber using the same |
| ES94107308T ES2106404T3 (en) | 1993-05-13 | 1994-05-10 | GROSS RUBBER PRODUCTION METHOD. |
| EP94107308A EP0624601B1 (en) | 1993-05-13 | 1994-05-10 | Process for producing raw rubber |
| DE69404740T DE69404740T2 (en) | 1993-05-13 | 1994-05-10 | Process for the production of raw rubber |
| AU63070/94A AU666267B2 (en) | 1993-05-13 | 1994-05-12 | Process for producing raw rubber |
| US08/241,714 US5585459A (en) | 1993-05-13 | 1994-05-12 | Process for producing raw rubber |
| TW083104280A TW321652B (en) | 1993-05-13 | 1994-05-12 | |
| KR1019940010459A KR100316115B1 (en) | 1993-05-13 | 1994-05-13 | Manufacturing method of raw rubber |
| CN94106007A CN1065539C (en) | 1993-05-13 | 1994-05-13 | Process for producing raw rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11176693A JP3248979B2 (en) | 1993-05-13 | 1993-05-13 | Coagulant for deproteinized natural rubber latex and method for producing raw rubber using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06322004A JPH06322004A (en) | 1994-11-22 |
| JP3248979B2 true JP3248979B2 (en) | 2002-01-21 |
Family
ID=14569644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11176693A Expired - Fee Related JP3248979B2 (en) | 1993-05-13 | 1993-05-13 | Coagulant for deproteinized natural rubber latex and method for producing raw rubber using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3248979B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4179793B2 (en) * | 2002-04-23 | 2008-11-12 | 株式会社ブリヂストン | Natural rubber mixture, rubber composition and method for producing natural rubber mixture |
| US20050256250A1 (en) * | 2002-04-23 | 2005-11-17 | Seiichiro Iwafune | Rubber compositions containing rubber-containing coagulums and processes for production of the coagulums |
| JP6215606B2 (en) * | 2013-07-22 | 2017-10-18 | 住友ゴム工業株式会社 | Process for producing epoxidized natural rubber, epoxidized natural rubber, rubber composition for tire and pneumatic tire |
| US10647842B2 (en) | 2013-12-23 | 2020-05-12 | Arlanxeo Singapore Pte. Ltd. | Anti-agglomerants for elastomeric ethylene/A-olefin copolymers |
| JP6328773B2 (en) | 2013-12-23 | 2018-05-23 | アランセオ・シンガポール・プライヴェート・リミテッド | High purity halogenated rubber |
| EP3087140B1 (en) * | 2013-12-23 | 2019-05-22 | Arlanxeo Singapore Pte. Ltd. | Novel anti-agglomerants for the rubber industry |
| CN106032394B (en) * | 2015-03-17 | 2017-08-22 | 中国石油化工股份有限公司 | The production method and isoprene rubber of a kind of isoprene rubber and its application |
| CN112592417B (en) * | 2020-12-09 | 2023-03-28 | 中国化工集团曙光橡胶工业研究设计院有限公司 | Aircraft tire natural rubber solidification system, application method thereof and aircraft tire natural rubber |
-
1993
- 1993-05-13 JP JP11176693A patent/JP3248979B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06322004A (en) | 1994-11-22 |
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