JPH0656906A - Deproteinizing agent for natural rubber and production of deproteinized natural rubber using same - Google Patents
Deproteinizing agent for natural rubber and production of deproteinized natural rubber using sameInfo
- Publication number
- JPH0656906A JPH0656906A JP4208758A JP20875892A JPH0656906A JP H0656906 A JPH0656906 A JP H0656906A JP 4208758 A JP4208758 A JP 4208758A JP 20875892 A JP20875892 A JP 20875892A JP H0656906 A JPH0656906 A JP H0656906A
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- JP
- Japan
- Prior art keywords
- natural rubber
- deproteinizing agent
- latex
- fatty acid
- protease
- 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.)
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Abstract
(57)【要約】
【構成】 プロテアーゼと、この酵素の活性を弱める事
が少なくかつ分散能が高い特定の非イオン界面活性剤と
を有効成分として含有する天然ゴム用脱蛋白処理剤であ
り、この脱蛋白処理剤を天然ゴムラテックスに添加し、
ラテックス粒子を洗浄して、脱蛋白天然ゴムを得る。
【効果】 天然ゴム中の蛋白質を効率よく簡単に除去す
ることができ、しかも高い生産性で脱蛋白天然ゴムを製
造できる。(57) [Summary] [Structure] A deproteinizing agent for natural rubber, which contains a protease and a specific nonionic surfactant which does not weaken the activity of this enzyme and has high dispersibility as an active ingredient, Add this deproteinizing agent to natural rubber latex,
The latex particles are washed to obtain deproteinized natural rubber. [Effect] Proteins in natural rubber can be efficiently and easily removed, and deproteinized natural rubber can be produced with high productivity.
Description
【0001】[0001]
【産業上の利用分野】本発明は、天然ゴム中の蛋白質を
除去する為の脱蛋白処理剤及びそれを用いた脱蛋白天然
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 deproteinizing agent for removing proteins in natural rubber and a method for producing deproteinized natural rubber using the same.
【0002】[0002]
【従来の技術及び発明が解決しようとする課題】一般
に、天然ゴムの原料であるフィ−ルドラテックス中に
は、ゴム成分の以外に蛋白質等の成分が混在しており、
最終製品を使用した人に対して強いアレルギ−反応を引
き起こす等の問題が生じている。また、天然ゴムは、生
産される地域や時期、気候の違いにより混在するタンパ
ク質の量や種類が異なることから、最終ゴム製品の品質
が悪くなる等の問題が発生している。2. Description of the Related Art Generally, a field latex, which is a raw material of natural rubber, contains components such as proteins in addition to the rubber component.
Problems such as causing a strong allergic reaction to the person who uses the final product have occurred. In addition, since the amount and type of proteins that are mixed in natural rubber differ depending on the region, time of production, and climate, problems such as poor quality of the final rubber product occur.
【0003】これらの問題に対して、フィ−ルドラテッ
クスを水で洗浄した後に濃縮したり、界面活性剤を加え
て洗浄後濃縮する等の方法を用いて蛋白質の洗浄除去を
行っているが、混在する蛋白質を十分除去することは困
難である。また、脂肪酸石鹸とプロテア−ゼ及び特定の
非イオン界面活性剤とプロテア−ゼによりフィ−ルドラ
テックスを処理する技術では、充分な除去効果は得られ
ていない。To solve these problems, the protein is washed and removed by a method such as washing the field latex with water and then concentrating it, or adding a surfactant and washing and concentrating it. It is difficult to sufficiently remove the mixed proteins. Further, the technique of treating the field latex with a fatty acid soap and protease and a specific nonionic surfactant and protease does not provide a sufficient removal effect.
【0004】従って、本発明の主たる目的は、天然ゴム
中の蛋白質を簡単にかつ効率よく取り除くことができ、
その結果蛋白質によるアレルギ−を引き起こす心配のな
い天然ラテックス及びゴムを得ることができ、しかも天
然ゴム中の不純物を取り除くことにより品質の安定した
ゴム製品を得ることができる天然ゴム用脱蛋白処理剤を
提供することである。Accordingly, the main object of the present invention is to remove proteins in natural rubber easily and efficiently,
As a result, a natural protein deproteinizing agent for natural rubber and rubber can be obtained which does not cause allergies due to proteins, and a rubber product of stable quality can be obtained by removing impurities in the natural rubber. Is to provide.
【0005】本発明の他の目的は、高い生産性で脱蛋白
天然ゴムを製造することができる脱蛋白天然ゴムの製造
方法を提供することである。Another object of the present invention is to provide a method for producing deproteinized natural rubber which is capable of producing deproteinized natural rubber with high productivity.
【0006】[0006]
【課題を解決するための手段および作用】本発明者ら
は、蛋白分解酵素と、この酵素の活性を弱める事が少な
くかつ分散能が高い特定の非イオン界面活性剤とを用い
て洗浄することにより、簡単にかつ効率良く天然ゴム中
の蛋白質を取り除くことが可能であることを見い出し、
本発明を完成した。Means and Actions for Solving the Problems The inventors of the present invention wash with a proteolytic enzyme and a specific nonionic surfactant which is less likely to weaken the activity of this enzyme and has high dispersibility. Found that it is possible to remove proteins in natural rubber easily and efficiently,
The present invention has been completed.
【0007】すなわち、本発明は、プロテア−ゼと、ポ
リオキシアルキレンエステル系,多価アルコ−ル脂肪酸
エステル系,糖脂肪酸エステル系,アルキルポリグリコ
シド系およびポリオキシアルキレン多価アルコ−ルエー
テル系の非イオン界面活性剤よりなる群から選ばれた一
種以上の界面活性剤とを有効成分として含有することを
特徴とする天然ゴム用脱蛋白処理剤を提供するものであ
る。That is, according to the present invention, a protease, a polyoxyalkylene ester type, a polyvalent alcohol fatty acid ester type, a sugar fatty acid ester type, an alkyl polyglycoside type and a polyoxyalkylene polyvalent alcohol ether type are used. It is intended to provide a deproteinizing agent for natural rubber, which comprises, as an active ingredient, one or more surfactants selected from the group consisting of ionic surfactants.
【0008】本発明の脱蛋白処理剤による蛋白質除去の
メカニズムについては、必ずしも明らかではないが、プ
ロテア−ゼにより蛋白質がゴム成分から脱離されると同
時に、低分子化され、非イオン界面活性剤により蛋白質
が分散し易い形状に変性されることにより効率よく洗浄
除去されるためと考えられる。本発明における前記非イ
オン界面活性剤としては、ポリオキシアルキレンエステ
ル系,多価アルコ−ル脂肪酸エステル系,糖脂肪酸エス
テル系,アルキルポリグリコシド系またはポリオキシア
ルキレン多価アルコ−ルエーテル系があげられる。Although the mechanism of protein removal by the deproteinizing agent of the present invention is not necessarily clear, the protein is desorbed from the rubber component by the protease, and at the same time the protein is depolymerized and the nonionic surfactant is used. It is considered that the protein is efficiently washed and removed by denaturing the protein into a form in which it can be easily dispersed. Examples of the nonionic surfactant in the present invention include polyoxyalkylene ester type, polyhydric alcohol fatty acid ester type, sugar fatty acid ester type, alkyl polyglycoside type and polyoxyalkylene polyhydric alcohol ether type.
【0009】前記ポリオキシアルキレンエステル系の非
イオン界面活性剤としては、例えばポリオキシアルキレ
ン脂肪酸エステルなどが挙げられる。多価アルコ−ル脂
肪酸エステル系の非イオン界面活性剤としては、炭素数
2〜12の多価アルコ−ルの脂肪酸エステルまたはポリ
オキシアルキレン多価アルコ−ルの脂肪酸エステルがあ
げられる。より具体的には、例えばソルビトール脂肪酸
エステル、ソルビタン脂肪酸エステル、脂肪酸モノグリ
セライド、脂肪酸ジグリセライド、ポリグリセリン脂肪
酸エステルなどが挙げられる。また、これらのポリアル
キレンオキサイド付加物(例えばポリオキシアルキレン
ソルビタン脂肪酸エステル、ポリオキシアルキレングリ
セリン脂肪酸エステルなど)も使用可能である。Examples of the polyoxyalkylene ester-based nonionic surfactants include polyoxyalkylene fatty acid esters. Examples of the polyvalent alcohol fatty acid ester-based nonionic surfactant include polyvalent alcohol fatty acid esters having 2 to 12 carbon atoms and polyoxyalkylene polyvalent alcohol fatty acid esters. More specifically, examples thereof include sorbitol fatty acid ester, sorbitan fatty acid ester, fatty acid monoglyceride, fatty acid diglyceride, and polyglycerin fatty acid ester. Further, these polyalkylene oxide adducts (for example, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycerin fatty acid ester, etc.) can also be used.
【0010】糖脂肪酸エステル系の非イオン界面活性剤
としては、例えばショ糖、グルコース、マルトース、フ
ラクトース、多糖類の脂肪酸エステルなどが挙げられ、
これらのポリアルキレンオキサイド付加物も使用可能で
ある。アルキルポリグリコシド系の非イオン界面活性剤
としては、例えばアルキルグルコシド、アルキルポリグ
ルコシド、ポリオキシアルキレンアルキルグルコシド、
ポリオキシアルキレンアルキルポリグルコシドなどが挙
げられ、これらの脂肪酸エステル類も挙げられる。ま
た、これらのポリアルキレンオキサイド付加物も使用可
能である。Examples of sugar fatty acid ester-based nonionic surfactants include sucrose, glucose, maltose, fructose, and fatty acid esters of polysaccharides.
These polyalkylene oxide adducts can also be used. Examples of the alkyl polyglycoside nonionic surfactant include, for example, alkyl glucoside, alkyl polyglucoside, polyoxyalkylene alkyl glucoside,
Examples thereof include polyoxyalkylene alkyl polyglucosides, and fatty acid esters thereof. Also, these polyalkylene oxide adducts can be used.
【0011】多価アルコールエーテル系の非イオン界面
活性剤としては、例えばポリオキシエチレン多価アルコ
ールアルキルエーテルが挙げられ、多価アルコールとし
ては、炭素数2〜12のポリオールがあげられ、例えば
プロピレングリコール、グリセリン、ソルビトール、シ
ュクロース、ペンタエリスリトール、ソルビタンなどが
挙げられる。Examples of polyhydric alcohol ether type nonionic surfactants include polyoxyethylene polyhydric alcohol alkyl ethers, and examples of polyhydric alcohols include polyols having 2 to 12 carbon atoms, such as propylene glycol. , Glycerin, sorbitol, sucrose, pentaerythritol, sorbitan and the like.
【0012】これらの界面活性剤におけるアルキル基と
しては、例えば炭素数4〜30のアルキル基があげられ
る。また、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1〜50モル程度のものがあ
げられる。また、前記脂肪酸としては、例えば炭素数4
〜30の直鎖または分岐した飽和または不飽和脂肪酸が
挙げられる。Examples of the alkyl group in these surfactants include alkyl groups having 4 to 30 carbon atoms. The polyoxyalkylene group has 2 carbon atoms.
Examples thereof include those having an alkylene group of 4 to 4, and examples thereof include those having an addition mole number of ethylene oxide of about 1 to 50 moles. The fatty acid has, for example, 4 carbon atoms.
-30 straight or branched, saturated or unsaturated fatty acids are mentioned.
【0013】また、これらの酵素及び界面活性剤を用い
るにあたり、他の添加剤、即ちpH調整剤としてリン酸
第一カリウム、第二カリウム、ナトリウム等の燐酸塩や
酢酸カリウム、酢酸ナトリウム等の酢酸塩、さらに硫
酸、酢酸、塩酸、硝酸、クエン酸、琥珀酸等の酸類とそ
の塩、あるいはアンモニア、水酸化ナトリウム、水酸化
カリウム、炭酸ナトリウム、炭酸水素ナトリウム等を併
用しても構わない。また、酵素としてリパ−ゼ、エステ
ラ−ゼ、アミラ−ゼ、ラッカ−ゼ、セルラ−ゼ等の酵素
と併用することもできる。When using these enzymes and surfactants, other additives such as phosphates such as potassium phosphate dibasic, sodium phosphate and acetic acid such as potassium acetate and sodium acetate are used as pH adjusters. A salt, an acid such as sulfuric acid, acetic acid, hydrochloric acid, nitric acid, citric acid, and succinic acid and a salt thereof, or ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, or the like may be used in combination. Further, the enzyme may be used in combination with an enzyme such as lipase, esterase, amylase, laccase, and cellulase.
【0014】さらに、必要に応じてスチレンスルホン酸
共重合物、ナフタレンスルホン酸ホルマリン縮合物、リ
グニンスルホン酸、多環型芳香族スルホン酸共重合物、
アクリル酸及び無水マレイン酸ホモポリマ−及び共重合
物、イソブチレン−アクリル酸及びイソブチレン−無水
マレイン酸共重合物等の分散剤を併用することができ
る。Further, if necessary, a styrene sulfonic acid copolymer, a naphthalene sulfonic acid formalin condensate, a lignin sulfonic acid, a polycyclic aromatic sulfonic acid copolymer,
Dispersants such as acrylic acid and maleic anhydride homopolymers and copolymers, isobutylene-acrylic acid and isobutylene-maleic anhydride copolymers can be used in combination.
【0015】本発明の脱蛋白処理剤中のプロテア−ゼと
陰イオン界面活性剤の配合比率は特に限定されないが、
重量比で1/(1〜200)、好ましくは、1/(1〜
100)である。プロテア−ゼの量が1/200未満で
は、充分な効果を発揮出来ず、1/1を超えるとコスト
がアップする。本発明の脱蛋白処理剤を用いて脱蛋白天
然ゴムを製造するにあたっては、フィ−ルドラテックス
及びアンモニア処理ラテックスに本発明の脱蛋白処理剤
を添加し、ラテックス粒子を洗浄するゴム処理方法が好
適に採用される。The mixing ratio of the protease and the anionic surfactant in the deproteinizing agent of the present invention is not particularly limited,
The weight ratio is 1 / (1-200), preferably 1 / (1-
100). If the amount of protease is less than 1/200, sufficient effect cannot be exhibited, and if it exceeds 1/1, the cost increases. In producing a deproteinized natural rubber using the deproteinizing agent of the present invention, a rubber treatment method of adding the deproteinizing agent of the present invention to a field latex and an ammonia-treated latex and washing latex particles is preferable. Adopted by.
【0016】その際、脱蛋白処理剤の添加量がラテック
ス分散液に対して0.001〜10重量%、好ましくは
0.1〜3重量%である。添加量が0.001重量%未
満の場合は添加量が少なすぎて十分な効果が得られず、
10重量%を超えると量が多すぎてコストアップにつな
がると共に、酵素の活性も低下する。脱蛋白処理剤の処
理時間は特に限定されないが、数分から1週間程度処理
を行うことが好ましい。ラテックスの処理においては攪
拌しても良いし、静置でもかまわない。また、必要に応
じて温度調節を行っても良く、適当な温度としては、5
℃〜90℃、好ましくは20℃〜60℃ある。90℃を
超えると酵素の失活が早く、5℃未満では酵素の反応が
進行し難くなる。At this time, the amount of the deproteinizing agent added is 0.001 to 10% by weight, preferably 0.1 to 3% by weight, based on the latex dispersion. If the addition amount is less than 0.001% by weight, the addition amount is too small to obtain a sufficient effect,
If it exceeds 10% by weight, the amount is too large, which leads to an increase in cost and the activity of the enzyme is also reduced. The treatment time of the deproteinizing agent is not particularly limited, but it is preferable to perform the treatment for several minutes to about one week. The latex may be treated with stirring or may be left standing. In addition, the temperature may be adjusted if necessary, and an appropriate temperature is 5
C. to 90.degree. C., preferably 20.degree. C. to 60.degree. If the temperature exceeds 90 ° C, the enzyme is rapidly deactivated, and if the temperature is lower than 5 ° C, the enzyme reaction is difficult to proceed.
【0017】ラテックス粒子の洗浄方法としては、特に
限定されないがラテックス粒子と洗浄液を遠心分離法に
より分離することもできるし、ラテックス粒子を凝集さ
せて分離することもできる。また、天然ゴムを洗浄する
際に、合成ゴムまたは合成ゴムラテックスを組み合わせ
て用いることができる。本発明のプロテア−ゼは一般公
知のものが使用でき特に限定されないが、アルカリプロ
テア−ゼが好ましい。プロテア−ゼの由来としては、細
菌由来のもの、糸状菌由来のもの酵母由来のものいずれ
でも構わないが、これらの中では細菌由来のプロテア−
ゼを使用するのが好ましい。The method for washing the latex particles is not particularly limited, but the latex particles and the washing liquid can be separated by a centrifugal separation method, or the latex particles can be aggregated and separated. Further, when washing the natural rubber, a synthetic rubber or a synthetic rubber latex can be used in combination. The protease of the present invention may be any known one and is not particularly limited. Alkaline protease is preferred. The origin of the protease may be either a bacterial origin, a filamentous fungus origin or a yeast origin, and among these, a bacterial origin
It is preferable to use ze.
【0018】本発明における天然ゴムとは、天然のゴム
の木から得られたフィ−ルドラテックス及び固形ゴムを
意味し、ラテックスは熟成したものでもハイアンモニア
ラテックスでも新鮮なフィ−ルドラテックスのいずれで
も用いることができる。本発明により得られた蛋白質を
高レベルに除去した天然ゴムは、例えば手袋、避妊具、
医療器具、引き糸、固形ゴム製品、スポ−ツ用品、タイ
ヤ等の分野に用いる事が可能と考えられる。The term "natural rubber" as used in the present invention means a field latex and a solid rubber obtained from a natural rubber tree, and the latex may be aged one, a high ammonia latex or a fresh field latex. Can be used. The natural rubber from which the protein obtained by the present invention has been removed to a high level is, for example, gloves, contraceptives,
It is considered that it can be used in the fields of medical equipment, drawing thread, solid rubber products, sports goods, tires and the like.
【0019】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に限定されるもので
はない。Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
【0020】[0020]
実施例1〜5 天然ゴムのハイアンモニアラテックスをゴム分で30重
量%になるように希釈し、H3 PO4 でpHを9に調整
後、表1に示す処方の脱蛋白処理剤を1重量%添加し
た。ついで、30℃で24時間静置し、13000rp
mで30分遠心分離した後、分離してくる上層のクリ−
ム部分を取り出して同量の水に再分散した。2回及び3
回遠心分離したものは、1回目の遠心分離後、クリ−ム
部分を界面活性剤1%溶液(プロテア−ゼを含まないも
の)で洗浄し、13000rpmで30分遠心分離を行
い以下1回目と同様の作業を繰り返した。これを少量の
CaCl2 を含むメタノ−ル中に注いでゴムを沈澱さ
せ、一夜減圧乾燥した。その後、ケルダ−ル法により窒
素含有率を求めて残存する蛋白分とした。尚、窒素含有
量の測定精度は±0.0001%である。Examples 1 to 5 Natural ammonia high ammonia latex was diluted to a rubber content of 30% by weight, the pH was adjusted to 9 with H 3 PO 4 , and 1% by weight of a deproteinizing agent having the formulation shown in Table 1 was used. % Added. Then, let stand at 30 ℃ for 24 hours, 13000 rp
After centrifuging at m for 30 minutes, the upper layer clear
The water portion was taken out and redispersed in the same amount of water. 2 times and 3
After centrifugation for the first time, the cream portion was washed with a 1% solution of a surfactant (without protease) after the first centrifugation, and then centrifuged at 13000 rpm for 30 minutes. The same work was repeated. This was poured into methanol containing a small amount of CaCl 2 to precipitate the rubber, which was dried under reduced pressure overnight. Then, the nitrogen content was determined by the Kjeldahl method to obtain the remaining protein. The measurement accuracy of the nitrogen content is ± 0.0001%.
【0021】[0021]
【表1】 [Table 1]
【0022】比較例1〜3 表2に示す処方の脱蛋白処理剤を使用したほかは実施例
1〜5と同様に処理し、残存する蛋白分を求めた。Comparative Examples 1 to 3 The same procedure was performed as in Examples 1 to 5 except that the deproteinizing agent having the formulation shown in Table 2 was used, and the residual protein content was determined.
【0023】[0023]
【表2】 [Table 2]
【0024】これらの処理条件および試験結果を表3に
示す。なお、同表中、「蒸留水」とあるのは、ブランク
として蒸留水のみで処理した場合の窒素含有量を示した
ものである。また、実施例2は洗浄回数が1回の場合と
2回の場合のそれぞれの窒素含有量を求めた。Table 3 shows these processing conditions and test results. In addition, in the same table, "distilled water" indicates the nitrogen content when treated with only distilled water as a blank. In addition, in Example 2, the nitrogen content was determined when the number of times of cleaning was once and twice.
【0025】[0025]
【表3】 [Table 3]
【0026】表3から、本発明の脱蛋白処理剤を用いて
天然ゴムラテックスを処理することにより、天然ゴムか
ら蛋白質を効率よく簡単に除去できることがわかる。From Table 3, it can be seen that the protein can be efficiently and easily removed from the natural rubber by treating the natural rubber latex with the deproteinizing agent of the present invention.
【0027】[0027]
【発明の効果】以上のように、本発明の脱蛋白処理剤
は、プロテア−ゼと、酵素にマイルドな非イオン界面活
性剤とを有効分として含有するため、天然ゴム中のタン
パク質を効率よく簡単に除去することができ、従ってア
レルギ−対策として有用であり、かつ品質の安定した脱
蛋白天然ゴムを簡単に製造できるという効果がある。INDUSTRIAL APPLICABILITY As described above, the deproteinizing agent of the present invention contains protease and a nonionic surfactant mild to the enzyme as effective components, so that the protein in natural rubber can be efficiently treated. Since it can be easily removed, it is useful as a countermeasure against allergies, and deproteinized natural rubber of stable quality can be easily produced.
【0028】また、本発明の脱蛋白天然ゴムの製造方法
は、上記脱蛋白処理剤を天然ゴムラテックスに添加して
ラテックス粒子を洗浄するだけであるから、高い生産性
を有するという効果がある。In addition, the method for producing deproteinized natural rubber of the present invention has an effect of having high productivity because the above deproteinizing agent is simply added to the natural rubber latex to wash the latex particles.
Claims (5)
ステル系,多価アルコ−ル脂肪酸エステル系,糖脂肪酸
エステル系,アルキルポリグリコシド系およびポリオキ
シアルキレン多価アルコ−ルエーテル系の非イオン界面
活性剤よりなる群から選ばれた一種以上の界面活性剤と
を有効成分として含有することを特徴とする天然ゴム脱
蛋白処理剤。1. A nonionic surfactant of proteases, polyoxyalkylene ester type, polyhydric alcohol fatty acid ester type, sugar fatty acid ester type, alkyl polyglycoside type and polyoxyalkylene polyhydric alcohol ether type. A natural rubber deproteinizing agent comprising as an active ingredient one or more surfactants selected from the group consisting of:
ゼであることを特徴とする請求項1記載の天然ゴム脱蛋
白処理剤。2. The alkaline protease is an alkaline protease.
The natural rubber deproteinizing agent according to claim 1, which is Z.
が重量比で1/(1〜200)であることを特徴とする
請求項1叉は2記載の天然ゴム脱蛋白処理剤。3. The natural rubber deproteinizing agent according to claim 1 or 2, wherein the weight ratio of the protease to the nonionic surfactant is 1 / (1 to 200).
理剤をフィ−ルドラテックスまたはアンモニア処理ラテ
ックスに添加しラテックス粒子を処理することを特徴と
する脱蛋白天然ゴムの製造方法。4. A process for producing deproteinized natural rubber, which comprises adding the deproteinizing agent according to claim 1 to a field latex or an ammonia-treated latex to treat latex particles.
に対して0.001〜10重量%であることを特徴とす
る請求項4記載の脱蛋白天然ゴムの製造方法。5. The method for producing deproteinized natural rubber according to claim 4, wherein the deproteinizing agent is added in an amount of 0.001 to 10% by weight based on the latex dispersion.
Priority Applications (17)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20875892A JP3150434B2 (en) | 1992-08-05 | 1992-08-05 | Deproteinizing agent for natural rubber |
| MYPI93001509A MY137284A (en) | 1992-08-05 | 1993-07-30 | Deproteinized natural rubber and process for producing the same |
| MYPI20064692A MY137265A (en) | 1992-08-05 | 1993-07-30 | Methods for elevating or lowering the green strength of a natural rubber |
| AU44456/93A AU663396B2 (en) | 1992-08-05 | 1993-08-04 | Deproteinized natural rubber and process for producing the same |
| DE69333308T DE69333308T2 (en) | 1992-08-05 | 1993-08-04 | Process for increasing or reducing the raw tensile strength of natural rubber |
| ES97111932T ES2210423T3 (en) | 1992-08-05 | 1993-08-04 | PROCEDURE TO INCREASE OR DECREASE THE RESISTANCE IN THE UNVULCANIZED STATE OF NATURAL RUBBER. |
| ES93112501T ES2116374T3 (en) | 1992-08-05 | 1993-08-04 | DEPROTEINIZED NATURAL RUBBER AND PROCEDURE FOR ITS PRODUCTION. |
| DE69318492T DE69318492T2 (en) | 1992-08-05 | 1993-08-04 | Deproteinized natural rubber and process for its manufacture |
| EP97111932A EP0805163B1 (en) | 1992-08-05 | 1993-08-04 | Methods for elevating or lowering the green strength of a natural rubber |
| EP93112501A EP0584597B1 (en) | 1992-08-05 | 1993-08-04 | Deproteinized natural rubber and process for producing the same |
| CNB001049666A CN1163517C (en) | 1992-08-05 | 1993-08-05 | Deproteinized natural rubber and method for producing it |
| CN93117657A CN1061993C (en) | 1992-08-05 | 1993-08-05 | Deproteinized natural rubber and process for producing the same |
| KR1019930015167A KR100269837B1 (en) | 1992-08-05 | 1993-08-05 | Methods for elevating or lowering the green strength of a na |
| TW082107616A TW301665B (en) | 1992-08-05 | 1993-09-16 | |
| US08/799,363 US6335407B1 (en) | 1992-08-05 | 1997-02-14 | Deproteinized natural rubber and process for producing the same |
| US09/357,077 US6204358B1 (en) | 1992-08-05 | 1999-07-19 | Process for producing deproteinized natural rubber using protease and anionic surfactant |
| US09/356,523 US6239253B1 (en) | 1992-08-05 | 1999-07-19 | Deproteinized natural rubber and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20875892A JP3150434B2 (en) | 1992-08-05 | 1992-08-05 | Deproteinizing agent for natural rubber |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000335817A Division JP3286635B2 (en) | 2000-11-02 | 2000-11-02 | Method for producing deproteinized natural rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0656906A true JPH0656906A (en) | 1994-03-01 |
| JP3150434B2 JP3150434B2 (en) | 2001-03-26 |
Family
ID=16561599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20875892A Expired - Lifetime JP3150434B2 (en) | 1992-08-05 | 1992-08-05 | Deproteinizing agent for natural rubber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3150434B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6265479B1 (en) | 1999-09-10 | 2001-07-24 | Sumitomo Rubber Industries, Ltd. | Deproteinizing agent and method of preparing cationic deproteinized natural rubber latex using the same |
| US6462159B1 (en) | 1999-09-10 | 2002-10-08 | Sumitomo Rubber Industries, Ltd | Cationic deproteinized natural rubber latex, method of preparing the same, and treating agent used in the method |
| JP2003002902A (en) * | 2001-06-18 | 2003-01-08 | Sumitomo Rubber Ind Ltd | Natural rubber, method for producing the same, and rubber composition |
| JP2003020301A (en) * | 2001-07-06 | 2003-01-24 | Sumitomo Rubber Ind Ltd | Method for producing hypoallergenic natural rubber latex |
| JP2004197052A (en) * | 2002-12-20 | 2004-07-15 | Sumitomo Rubber Ind Ltd | Method for producing deproteinized natural rubber latex |
| JP2005281681A (en) * | 2004-03-05 | 2005-10-13 | Toyota Motor Corp | Method for producing deproteinized natural rubber latex |
| WO2008107155A1 (en) | 2007-03-07 | 2008-09-12 | Beneo-Orafti S.A. | Natural rubber latex preservation |
| US7825185B2 (en) | 2002-12-06 | 2010-11-02 | Bridgestone Corporation | Natural rubber latex, natural rubber, rubber composition, and tire using the same |
| US7825175B2 (en) | 2002-12-06 | 2010-11-02 | Bridgestone Corporation | Natural rubber latex, natural rubber, rubber composition and tire using the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2098222B (en) | 1981-05-07 | 1984-08-15 | Malaysia Rubber Res Inst | Processing of hevea latex |
-
1992
- 1992-08-05 JP JP20875892A patent/JP3150434B2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6265479B1 (en) | 1999-09-10 | 2001-07-24 | Sumitomo Rubber Industries, Ltd. | Deproteinizing agent and method of preparing cationic deproteinized natural rubber latex using the same |
| US6462159B1 (en) | 1999-09-10 | 2002-10-08 | Sumitomo Rubber Industries, Ltd | Cationic deproteinized natural rubber latex, method of preparing the same, and treating agent used in the method |
| JP2003002902A (en) * | 2001-06-18 | 2003-01-08 | Sumitomo Rubber Ind Ltd | Natural rubber, method for producing the same, and rubber composition |
| JP2003020301A (en) * | 2001-07-06 | 2003-01-24 | Sumitomo Rubber Ind Ltd | Method for producing hypoallergenic natural rubber latex |
| US7825185B2 (en) | 2002-12-06 | 2010-11-02 | Bridgestone Corporation | Natural rubber latex, natural rubber, rubber composition, and tire using the same |
| US7825175B2 (en) | 2002-12-06 | 2010-11-02 | Bridgestone Corporation | Natural rubber latex, natural rubber, rubber composition and tire using the same |
| JP2004197052A (en) * | 2002-12-20 | 2004-07-15 | Sumitomo Rubber Ind Ltd | Method for producing deproteinized natural rubber latex |
| JP2005281681A (en) * | 2004-03-05 | 2005-10-13 | Toyota Motor Corp | Method for producing deproteinized natural rubber latex |
| WO2008107155A1 (en) | 2007-03-07 | 2008-09-12 | Beneo-Orafti S.A. | Natural rubber latex preservation |
| US7989546B2 (en) | 2007-03-07 | 2011-08-02 | Beneo-Orafti S.A. | Natural rubber latex preservation |
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| Publication number | Publication date |
|---|---|
| JP3150434B2 (en) | 2001-03-26 |
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