JPH0367543B2 - - Google Patents
Info
- Publication number
- JPH0367543B2 JPH0367543B2 JP60162335A JP16233585A JPH0367543B2 JP H0367543 B2 JPH0367543 B2 JP H0367543B2 JP 60162335 A JP60162335 A JP 60162335A JP 16233585 A JP16233585 A JP 16233585A JP H0367543 B2 JPH0367543 B2 JP H0367543B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- natural rubber
- weight
- latex
- natural
- 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.)
- Expired
Links
- 229920001971 elastomer Polymers 0.000 claims description 94
- 244000043261 Hevea brasiliensis Species 0.000 claims description 65
- 229920001194 natural rubber Polymers 0.000 claims description 64
- 229920003052 natural elastomer Polymers 0.000 claims description 63
- 229920006173 natural rubber latex Polymers 0.000 claims description 35
- 210000002966 serum Anatomy 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000001694 spray drying Methods 0.000 claims description 6
- 230000000704 physical effect Effects 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- 238000004073 vulcanization Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229920000126 latex Polymers 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- 239000004636 vulcanized rubber Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000001112 coagulating effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 210000004911 serous fluid Anatomy 0.000 description 3
- 101100533729 Arabidopsis thaliana SMR5 gene Proteins 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 150000008163 sugars Chemical class 0.000 description 2
- LOVYCUYJRWLTSU-UHFFFAOYSA-N 2-(3,4-dichlorophenoxy)-n,n-diethylethanamine Chemical compound CCN(CC)CCOC1=CC=C(Cl)C(Cl)=C1 LOVYCUYJRWLTSU-UHFFFAOYSA-N 0.000 description 1
- 101100148545 Caenorhabditis elegans snr-5 gene Proteins 0.000 description 1
- 101100538857 Caenorhabditis elegans ttr-5 gene Proteins 0.000 description 1
- 241001495453 Parthenium argentatum Species 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000005314 correlation function Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
- C08C1/04—Purifying; Deproteinising
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L89/00—Compositions of proteins; Compositions of derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Description
＜技術分野＞
本発明は、天然ゴムに関し、特に未加硫の天然
ゴムの粘度を低下させると同時に、混合時の粘度
も下げることによつて、加工性を改良し、しかも
加硫後のゴム物性も強化した新規な強化天然ゴム
およびその製造方法に関する。
＜従来技術＞
従来の天然ゴム（一般にRSS：Ribbed
Smoked Sheet，SNR5：Standard Malaysian
Rubber5）等の製法は約35重量％のゴム成分と約
５重量％の非ゴム成分（例えば蛋白質、アミノ
酸、樹脂分、糖分等）を含む天然ゴムラテツクス
を一旦ゴム成分約15〜20重量％の一定濃度に希釈
し、蟻酸等の凝固剤を添加し、ゴム成分を凝固す
る。この時凝固したゴム成分を取除いた残りが漿
液（Serum）と呼ばれる水溶液である。得られた
凝固ゴム成分は、絞りロールで型付け（シート
状）脱水し、70〜80℃で７〜８日間燻煙（スモー
クド）、乾燥後、パツキングして天然ゴム製品
（ベール）とする。
現在、特にスモールホルダー（小農園）では、
漿液をそのまま廃棄するケースがほとんどであ
る。この漿液中には約0.5重量％の凝固しきれな
いゴム成分の他約３〜５重量％の非ゴム成分が含
有されており、漿液をそのまま廃棄する場合、腐
敗臭、河川の汚染等の公害が最近とみに問題とな
つている。
また、エステート（大農園）では、この公害対
策として、多額の金を投入して汚染処理装置等を
設置し、大々的に対策を講じてはいるものの効果
は少なく、異臭や発生ガス等の多くの問題があい
変らず残つていた。
一方、このようにして作られる天然ゴム（一般
にRSSおよびSMR5等で天然ゴムラテツクスを凝
固して作るもの）は、凝固の際に非ゴム成分（蛋
白質、糖分、樹脂等）が一部流出することにな
る。従つて、この天然ゴムでは一般に非ゴム成分
含有量は1.5〜４重量％程度であり、非ゴム成分
が流出しない状態での天然ゴムの非ゴム成分含有
量約９〜11重量％に比較して、かなり低くなり、
天然ゴム本来の未加硫ゴムおよび加硫ゴム物性を
発現するに至らなかつた。
従来、これらの問題点を解消するために天然ゴ
ムラテツクスをそのままスプレードライ装置を用
いて脱水、凝固して天然ゴムを製造する方法等も
試みられているが、価格の点および酸化珪素（シ
リカ）を混入せしめる必要がある等の物性の面で
汎用化には至つていない。また、ICR（Initial
Concentrated Natural Rubber）と称し、天然
ゴムラテツクスを原濃度約35重量％（ゴム分）の
まま酸凝固することによつて製品の天然ゴム中の
非ゴム成分の含有量を高める製法もあるが、これ
では非ゴム成分含有量が４〜６重量％程度にしか
ならず、天然ゴム製品中に非ゴム成分を含む効果
が顕著に表われないという欠点があつた。
＜発明の目的＞
本発明の目的は、前述した問題点を改善し、
１） 従来の天然ゴムの未加硫時の加工性を改良
し、加硫後のゴム物性を強化した強化天然ゴム
を得る、
２） 上記強化天然ゴムを製造することによつ
て、天然ゴムラテツクス漿液の廃棄による公害
を解消する、
ことのできる強化天然ゴムおよびその製造方法を
提供することにある。
＜発明の構成＞
第１の発明は、天然ゴムに、天然ゴムラテツク
ス漿液から得られる非ゴム成分を添加してなる強
化天然ゴムであつて、非ゴム成分総含有量が3.5
〜12.0重量％であることを特徴とする強化天然ゴ
ムである。
第２の発明は、天然ゴムラテツクス漿液非ゴム
成分を30重量％以上含む水溶液を用いて、天然ゴ
ム中の前記非ゴム成分の含有量を3.5〜12.0重量
％とすることを特徴とする強化天然ゴムの製造方
法である。
第３の発明は、天然ゴムに、天然ゴムラテツク
ス漿液からスプレードライ方法によつて得られる
10〜100μmの粉末状非ゴム成分を混練し、天然ゴ
ム中の非ゴム成分の含有量を3.5〜12.0重量％と
することを特徴とする強化天然ゴムの製造方法で
ある。
本発明者は、天然ゴムラテツクスからゴム成分
を除いた残りの従来は無用のものであつた漿液中
に、天然ゴムの物性を改善することのできる有効
成分が存在することを知見し、本発明に至つたも
のである。
以下に、本発明をさらに詳細に説明する。
本発明の強化天然ゴムに用いるラテツクスとし
ては、ゴム樹と呼ばれるヘベアブラジリエンシス
から得られる白色の乳状液（ラテツクス）のみな
らず、グアユール（guayule）等から得られる天
然ポリイソプレン重合体主体の白色の乳状液（ラ
テツクス）も用いると良い。このラテツクスを水
で希釈し、ごみを除去した後、凝固剤として蟻
酸、硝酸、硫酸等を添加して、ゴム分を凝固し漿
液（Serum）を絞り出し除去し、絞りロールで脱
水したものを天然ゴムとして用いる。
上記の天然ゴムに、天然ゴムラテツクス漿液中
に含有される非ゴム成分を添加し、その後含有量
を3.5〜12.0重量％としたものが本発明の強化天
然ゴムである。
ここで、天然ゴムラテツクス漿液とは、原料の
天然ゴムラテツクスから凝固剤として蟻酸、硝
酸、硫酸等を用いてゴム分を凝固し、取り除いた
残りの水溶液である。
天然ゴムラテツクスは、ゴム樹の種類によつて
組成が異なるが、１例を示すと第１表に示す組成
である。
<Technical Field> The present invention relates to natural rubber, and in particular, the present invention improves the processability of natural rubber by reducing the viscosity of unvulcanized natural rubber and also lowering the viscosity during mixing. This invention relates to a new reinforced natural rubber with enhanced physical properties and a method for producing the same. <Conventional technology> Conventional natural rubber (generally RSS: Ribbed
Smoked Sheet，SNR5：Standard Malaysian
The manufacturing method for Rubber5) is to first mix natural rubber latex containing approximately 35% by weight of rubber components and approximately 5% by weight of non-rubber components (e.g. proteins, amino acids, resins, sugars, etc.) with a constant rubber component of approximately 15 to 20% by weight. Dilute to a specific concentration and add a coagulant such as formic acid to coagulate the rubber component. What remains after removing the coagulated rubber component is an aqueous solution called serum. The obtained coagulated rubber component is shaped (sheet-shaped) and dehydrated using squeeze rolls, smoked at 70 to 80°C for 7 to 8 days, dried, and packed to form a natural rubber product (veil). Currently, especially in smallholders,
In most cases, the serum is discarded as is. This serum contains approximately 0.5% by weight of rubber components that have not yet coagulated, as well as approximately 3-5% by weight of non-rubber components, and if the serum is disposed of as is, it will cause pollution such as putrid odor and river pollution. has become a problem recently. In addition, estates (large farms) have invested a large amount of money to install pollution treatment equipment, etc. as a countermeasure against pollution, and although they have taken extensive measures, the effects have been small and many problems such as strange odors and gases have been taken. The problem remained unchanged. On the other hand, natural rubber made in this way (generally made by coagulating natural rubber latex using RSS and SMR5, etc.) has a tendency for some non-rubber components (proteins, sugars, resins, etc.) to flow out during coagulation. Become. Therefore, the non-rubber component content of this natural rubber is generally about 1.5 to 4% by weight, compared to the non-rubber component content of natural rubber of about 9 to 11% by weight in a state where the non-rubber components do not flow out. , becomes considerably lower;
The physical properties of unvulcanized rubber and vulcanized rubber, which are original to natural rubber, could not be expressed. In order to solve these problems, attempts have been made to produce natural rubber by directly dehydrating and coagulating natural rubber latex using a spray-drying device, but due to the cost and the use of silicon oxide (silica), attempts have been made to produce natural rubber. It has not been widely used due to physical properties such as the need to mix it in. In addition, ICR (Initial
There is also a manufacturing method known as Concentrated Natural Rubber that increases the content of non-rubber components in the natural rubber of the product by acid coagulating natural rubber latex at an original concentration of approximately 35% by weight (rubber content), but this method The non-rubber component content was only about 4 to 6% by weight, and the disadvantage was that the effect of including the non-rubber component in natural rubber products was not noticeable. <Objective of the Invention> The object of the present invention is to improve the above-mentioned problems and to: 1) improve the processability of conventional natural rubber when it is not vulcanized, and create a reinforced natural rubber that has enhanced rubber physical properties after vulcanization; 2) An object of the present invention is to provide a reinforced natural rubber and a method for producing the same, which can eliminate pollution caused by disposal of natural rubber latex serum by producing the above-mentioned reinforced natural rubber. <Structure of the Invention> The first invention is a reinforced natural rubber obtained by adding a non-rubber component obtained from natural rubber latex serum to natural rubber, wherein the total content of the non-rubber component is 3.5.
It is a reinforced natural rubber characterized by ~12.0% by weight. A second invention is a reinforced natural rubber characterized in that the content of the non-rubber component in the natural rubber is adjusted to 3.5 to 12.0% by weight using an aqueous solution containing 30% by weight or more of the non-rubber component of natural rubber latex serum. This is a manufacturing method. The third invention is to obtain natural rubber from natural rubber latex serum by a spray drying method.
This is a method for producing reinforced natural rubber characterized by kneading powdered non-rubber components with a size of 10 to 100 μm so that the content of the non-rubber components in the natural rubber is 3.5 to 12.0% by weight. The present inventor discovered that an active ingredient capable of improving the physical properties of natural rubber exists in the serous fluid remaining after removing the rubber component from natural rubber latex, which was previously useless. It has been reached. The present invention will be explained in more detail below. The latex used in the reinforced natural rubber of the present invention is not only a white emulsion (latex) obtained from the rubber tree Hevea brasiliensis, but also a latex mainly composed of natural polyisoprene polymers obtained from guayule and the like. It is also a good idea to use a white emulsion (latex). After diluting this latex with water and removing dust, formic acid, nitric acid, sulfuric acid, etc. are added as a coagulant to coagulate the rubber content, and the serum is squeezed out and removed. Used as rubber. The reinforced natural rubber of the present invention is obtained by adding a non-rubber component contained in natural rubber latex serum to the above natural rubber, and then adjusting the content to 3.5 to 12.0% by weight. Here, the natural rubber latex serum is an aqueous solution remaining after coagulating and removing the rubber component from the natural rubber latex as a raw material using formic acid, nitric acid, sulfuric acid, etc. as a coagulant. The composition of natural rubber latex varies depending on the type of rubber tree, but one example is the composition shown in Table 1.
【表】
この天然ゴムラテツクスからゴム炭化水素を除
いたものを漿液といい、これは一般的には約0.5
重量％のゴム成分と非ゴム成分約2.0重量％を含
む。本発明の強化天然ゴムは、後に製造方法にお
いて詳述するように、この漿液をそのまま、また
は濃縮して、あるいは漿液を粉末状非ゴム成分と
して、前述した天然ゴムに所定量含有せしめたも
のである。
非ゴム分の総計が3.5重量％未満であると、本
発明の効果が顕著にみられず12重量％を超えると
逆に加硫後の物性を損なうこととなる。
添加すべき非ゴム分の量は、天然ゴムのグレー
ドによつて適量が異なる。上質の天然ゴム、たと
えばRSSNo.１，No.２，ブラウンクレープNo.１，
SMR5，TTR5では、原料ゴム中に含有される非
ゴム分は比較的多く、2.5〜3.5重量％のものが多
い。このようなゴムに対して添加する非ゴム分
は、ゴム中の非ゴム分が、もともと含有されてい
たものと、添加したものと合せて総計10重量％〜
12重量％となるまで添加することが良い。これに
対し、品質の低い天然ゴム、たとえばブラウンク
レープ2X，TTR20，SMR20等の原料ゴム中に
含有される非ゴム分は、製造の過程で水洗を繰返
されるため少なく、1.5〜2.5％程度である。この
ような低質天然ゴムに非ゴム分を多量に加える
と、（もともと過度にロール練りされ、分子量が
低くなつているため）加硫後の物性が低くなる。
これに添加する非ゴム分は、総計で3.5〜４重量
％となる量以上添加出来ない。本発明の強化天然
ゴムの物性は、後に実施例で詳述するように、レ
オメーター加硫曲線から従来の天然ゴムに比して
以下の特性を有する。
１） 最大トルクが大きい。加硫ゴム物性、特に
引張応力、引張強さ、反発弾性が良好である。
２） 最小トルクおよび初期トルクが小さい（ゴ
ム粘度が低く、加工性が良好）。
３） グリーンストレングスおよび伸びが大き
い。未加硫時特性（タツキネス等）が向上して
いる。
以上の強化天然ゴムの製造方法すなわち天然ゴ
ム中の非ゴム成分を増加させるのに、
(1) 天然ゴムラテツクス漿液から得られる非ゴム
成分を含む水溶液を用いる方法（以下、溶液法
という）
(2) 天然ゴムラテツクス漿液からスプレードライ
方法によつてられる10〜100μmの粉末状非ゴム
成分を混練する方法（以下、粉末法という）が
ある。
これらについて以下に詳細に説明する。
(1) 溶液法
天然ゴムラテツクスから、酸凝固法によつて
ゴム成分を凝固させ、漿液を絞り出し除去し、
絞りロールで脱水し、シート状またはクラム状
とする。
本発明では天然ゴムラテツクス漿液中の、あ
るいは漿液から得られる非ゴム成分濃度を30重
量％以上とした水溶液を用いるのがよい。非ゴ
ム成分濃度を30重量％以上とするのは、30重量
％未満の濃度では浸漬によりゴムに含有させる
のが困難だからである。
非ゴム成分濃度30重量％以上の溶液を得るに
は、天然ゴムラテツクス漿液を多重効用型濃縮
装置を用いて、加熱によつて濃縮することがよ
い。また、後に粉末法で詳述する天然ゴムラテ
ツクス漿液からスプレードライ方法によつて得
られる10〜100μmの粉末状非ゴム成分を水に溶
解して非ゴム成分濃度30重量％以上の溶液とし
てもよい。
この非ゴム成分30重量％以上の溶液に、前記
シート状またはクラム状のゴムを浸漬し、脱水
乾燥後天然ゴム中の非ゴム成分濃度を3.5〜
12.0重量％とする。
また別の製法では、非ゴム成分30重量％以上
の溶液をスプレー装置を用いて、前記シート状
またはクラム状のゴムにスプレーし、脱水乾燥
後、天然ゴム中の非ゴム成分濃度を3.5〜12.0
重量％とする。
さらに他の方法として、非ゴム成分濃度が30
重量％以上の溶液を天然ゴムラテツクスに添加
し、非ゴム成分濃度の高い天然ゴムラテツクス
を得、これに酸を加えてゴム分等を凝固させ、
非ゴム成分濃度が3.5〜12.0重量％の強化天然
ゴムを得る方法も挙げられる。
(2) 粉末法
天然ゴムラテツクス漿液から得られる10〜
100μmの粉末状非ゴム成分を、脱水後シート状
またはクラム状とした天然ゴム、又はこれを乾
燥した天然ゴムにロール装置を用いて混練し、
天然ゴム中の非ゴム成分濃度を3.5〜12.0重量
％とする。
ここで、天然ゴムラテツクス漿液から得られ
る10〜100μmの粉末状非ゴム成分とは、以下の
ようにして製造される粉末である。
天然ゴムラテツクスのゴム成分を凝固除去
し、残りの漿液を150〜250℃の高温雰囲気中
へ、ノズルまたはデイスク回転体を用いてスプ
レードライし、水分を蒸発させて平均粒径10〜
100μmの粉末とする。
（詳細は、本出願人の昭和60年６月22日出願
の特許明細書参照）
＜実施例＞
以下に、実施例と比較例を用いて、本発明を具
体的に説明する。
実施例 １
天然ゴムラテツクスを酸凝固し、脱水後に約１
cm角の小片に切断し、天然ゴムラテツクスから得
られた漿液を濃縮して、非ゴム成分の含有量を80
重量％とした水溶液に10時間浸漬後、脱水、乾燥
（110℃×20分）し、天然ゴム中の非ゴム成分含有
量を7.5重量％とした強化天然ゴムを作製した
（第２表 実施例１）。
実施例 ２
天然ゴムラテツクスを酸凝固し、脱水後に約１
cm角の小片に切断し、天然ゴムラテツクス漿液か
らスプレードライ法によつて作つた粒径60μmの
非ゴム成分の粉末を水にとかし、その濃度を80重
量％とした水溶液に10時間浸漬し、脱水、乾燥
（110℃×20分）し、天然ゴム中の非ゴム成分含有
量10.4重量％とした強化天然ゴムを作製した（第
２表、実施例２）。
比較例 １
天然ゴムラテツクスを酸凝固、脱水乾燥して得
られるリブド・スモークド・シート（従来の市販
品天然ゴムRSS No.１）をそのまま用い比較例１
とした。非ゴム物質の含有量は3.3重量％であつ
た。
比較例 ２
天然ゴムラテツクスを酸凝固し、脱水後に約１
cm角の小片に切断し、実施例１で用いたと同様の
非ゴム成分含有量80重量％とした水溶液に30時間
浸漬し、脱水、乾燥（110℃×20分）後、天然ゴ
ム中の非ゴム成分含有量12.6重量％としたものを
比較例２として作製した。[Table] The product from which rubber hydrocarbons are removed from this natural rubber latex is called serous fluid, which is generally about 0.5
Contains % rubber components by weight and approximately 2.0% non-rubber components by weight. The reinforced natural rubber of the present invention is obtained by adding a predetermined amount of this serum directly or as a concentrated non-rubber component to the above-mentioned natural rubber as a powdered non-rubber component, as detailed later in the manufacturing method. be. If the total non-rubber content is less than 3.5% by weight, the effects of the present invention will not be noticeable, and if it exceeds 12% by weight, the physical properties after vulcanization will be impaired. The appropriate amount of the non-rubber component to be added varies depending on the grade of natural rubber. High-quality natural rubber, such as RSS No.1, No.2, Brown Crepe No.1,
In SMR5 and TTR5, the non-rubber content contained in the raw rubber is relatively large, often 2.5 to 3.5% by weight. The non-rubber content added to such rubber is 10% by weight or more, including the non-rubber content originally contained in the rubber and the added content.
It is preferable to add up to 12% by weight. On the other hand, the non-rubber content contained in the raw material rubber of low-quality natural rubber, such as Brown Crepe 2X, TTR20, SMR20, etc., is small, at around 1.5 to 2.5%, because it is repeatedly washed with water during the manufacturing process. . If a large amount of non-rubber components are added to such low-quality natural rubber, the physical properties after vulcanization will deteriorate (because it has been roll-kneaded excessively and has a low molecular weight).
The non-rubber component added to this cannot exceed a total amount of 3.5 to 4% by weight. The reinforced natural rubber of the present invention has the following physical properties compared to conventional natural rubber based on the rheometer vulcanization curve, as will be explained in detail later in Examples. 1) Maximum torque is large. Vulcanized rubber has good physical properties, especially tensile stress, tensile strength, and impact resilience. 2) Small minimum torque and initial torque (low rubber viscosity, good workability). 3) High green strength and elongation. Improved unvulcanized properties (tackiness, etc.). The above method for producing reinforced natural rubber, that is, increasing the non-rubber components in natural rubber, includes (1) a method using an aqueous solution containing non-rubber components obtained from natural rubber latex serum (hereinafter referred to as solution method); (2) There is a method (hereinafter referred to as the powder method) in which a powdered non-rubber component of 10 to 100 μm is kneaded from natural rubber latex serum by a spray drying method. These will be explained in detail below. (1) Solution method The rubber component is coagulated from natural rubber latex using the acid coagulation method, and the serous fluid is squeezed out and removed.
Dehydrate with squeeze rolls and form into sheets or crumbs. In the present invention, it is preferable to use an aqueous solution in which the concentration of non-rubber components in or obtained from the serum of natural rubber latex is 30% by weight or more. The reason why the concentration of non-rubber components is set to 30% by weight or more is because it is difficult to incorporate the non-rubber component into rubber by dipping at a concentration of less than 30% by weight. In order to obtain a solution with a non-rubber component concentration of 30% by weight or more, natural rubber latex serum may be concentrated by heating using a multi-effect concentrator. Alternatively, a powdery non-rubber component of 10 to 100 μm obtained by a spray drying method from natural rubber latex serum, which will be described in detail later in the powder method, may be dissolved in water to form a solution having a non-rubber component concentration of 30% by weight or more. The sheet-like or crumb-like rubber is immersed in this solution containing 30% or more of non-rubber components, and after dehydration and drying, the concentration of non-rubber components in the natural rubber is 3.5 to 3.5%.
12.0% by weight. In another manufacturing method, a solution containing 30% by weight or more of non-rubber components is sprayed onto the sheet-like or crumb-like rubber using a spray device, and after dehydration and drying, the concentration of non-rubber components in natural rubber is reduced to 3.5 to 12.0%.
Weight%. In yet another method, the non-rubber component concentration is 30
A solution of more than % by weight is added to natural rubber latex to obtain a natural rubber latex with a high concentration of non-rubber components, and an acid is added to this to coagulate the rubber components, etc.
Also included is a method for obtaining reinforced natural rubber having a non-rubber component concentration of 3.5 to 12.0% by weight. (2) Powder method 10~ obtained from natural rubber latex serum
A powdered non-rubber component of 100 μm is kneaded with dehydrated natural rubber in the form of a sheet or crumb, or dried natural rubber using a roll device,
The concentration of non-rubber components in natural rubber is 3.5 to 12.0% by weight. Here, the powdered non-rubber component of 10 to 100 μm obtained from natural rubber latex serum is a powder produced as follows. The rubber components of natural rubber latex are coagulated and removed, and the remaining serum is spray-dried in a high-temperature atmosphere of 150 to 250 degrees Celsius using a nozzle or disc rotator to evaporate the moisture and reduce the average particle size to 10 to 250 degrees Celsius.
Make a powder of 100μm. (For details, refer to the patent specification filed by the present applicant on June 22, 1985) <Examples> The present invention will be specifically described below using Examples and Comparative Examples. Example 1 Natural rubber latex was coagulated with acid, and after dehydration, about 1
The serum obtained from natural rubber latex was cut into small pieces of cm square and concentrated to reduce the content of non-rubber components to 80%.
After immersing in an aqueous solution with a concentration of 7.5% by weight, it was dehydrated and dried (110°C x 20 minutes) to produce reinforced natural rubber with a non-rubber component content of 7.5% by weight (Table 2 Examples) 1). Example 2 Natural rubber latex was coagulated with acid, and after dehydration, about 1
A non-rubber component powder with a particle size of 60 μm made by spray drying from natural rubber latex serum was cut into cm square pieces, dissolved in water, immersed in an aqueous solution with a concentration of 80% by weight for 10 hours, and dehydrated. and dried (110°C x 20 minutes) to produce reinforced natural rubber with a non-rubber component content of 10.4% by weight (Table 2, Example 2). Comparative Example 1 Comparative Example 1 Using a ribbed smoked sheet (conventional commercial product natural rubber RSS No. 1) obtained by acid coagulation and dehydration drying of natural rubber latex as it was
And so. The content of non-rubber material was 3.3% by weight. Comparative Example 2 Natural rubber latex was coagulated with acid, and after dehydration, approximately 1
It was cut into small pieces of cm square, immersed in an aqueous solution with a non-rubber content of 80% by weight similar to that used in Example 1 for 30 hours, dehydrated and dried (110°C x 20 minutes). Comparative Example 2 was prepared with a rubber component content of 12.6% by weight.
【表】
以上の実施例１，２および比較例１，２を用い
て、第３表に示す、ACS（American Chemical
Society）のNo.１純ゴム配合のゴム組成物を作製
し、以下の物性試験を行つた。
Monsanto Rheometer Tp−100型、温度
140℃、ARC±3゜LPC用ローターを用いて、加
硫曲線を測定し第１図に示した。
未加硫時のゴム組成物を厚さ２mmに冷プレス
（100℃×５分）し、JIS3号ダンベルに打抜き、
オートグラフ（Ｐ−500）で未加硫ゴムのグリ
ーンストレングスを評価し、第２図に示した。
また、第１図、第２図の測定結果からゴム組成
物の物性値を算出し、第２表に示した。
第１図から、本発明の強化天然ゴムは最大トル
クが大きく、最小トルクおよび初期トルクが小さ
いことがわかる。
第２図から、本発明の強化天然ゴムは、グリー
ンストレングスおよび伸びが大きいことがわか
る。[Table] Using the above Examples 1 and 2 and Comparative Examples 1 and 2, ACS (American Chemical
A rubber composition with the No. 1 pure rubber formulation was prepared by the Society) and the following physical property tests were conducted. Monsanto Rheometer Tp−100, temperature
The vulcanization curve was measured at 140°C using an ARC±3° LPC rotor and is shown in Figure 1. The unvulcanized rubber composition was cold pressed to a thickness of 2 mm (100°C x 5 minutes) and punched into JIS No. 3 dumbbells.
The green strength of the unvulcanized rubber was evaluated using Autograph (P-500) and is shown in FIG. Further, the physical property values of the rubber composition were calculated from the measurement results shown in FIGS. 1 and 2, and are shown in Table 2. From FIG. 1, it can be seen that the reinforced natural rubber of the present invention has a large maximum torque and a small minimum torque and initial torque. From FIG. 2, it can be seen that the reinforced natural rubber of the present invention has high green strength and elongation.
【表】
アゾール
なお、物性試験に用いたレオメーターによる測
定結果と通常の加硫ゴムシート（加硫140℃×40
分）を用いて測定した加硫ゴム物性との相関関数
は、次のとおりであつた。ここで用いたゴム組成
物はACSNo.１配合である。
加硫後の引張強さTB （Kg／cm2），Ｙ
と 最大トルク（Kg−cm），Ｘの関係は、危険率
１％で有意であつた。Ｙ＝12X−70、相関係数Ｒ
＝0.67。
加硫後の引張応力600％モジユラス（Kg／cm2），
Ｙと最大トルク（Kg−cm），Ｘの関係は、危険率
１％で有意であつた。Ｙ＝6.1X−68、相関係数
Ｒ＝0.87。
加硫後のリユプケ反発弾性（％），Ｙと、最大
トルク（Kg−cm），Ｘの関係は、危険率１％で有
意であつた。Ｙ＝0.8X＋60，相関係数Ｒ＝0.75。
最小トルク（Kg−cm），Ｘと粘度（ML+4 100
℃），Ｙの関係は、危険率５％で有意であつた。
Ｙ＝3.5X＋36，相関係数Ｒ＝0.41。
＜発明の効果＞
本発明の強化天然ゴムは、ゴム組成物として用
いた場合に以下の特性を有する。
１ 最大トルクが大きい。即ち加硫ゴム物性（特
に引張応力、引張強さ、反発弾性）が良好であ
る。
２ 最小トルク及び初期トルクがいづれも小さ
い。即ち混合が容易となり、混合時の消費エネ
ルギーの節約となる。
３ グリーンストレングス及び伸びが大きく、従
つて、未加硫ゴム時のタツキネス等の特性が向
上している。
４ 加硫速度が早くなる（加硫促進剤の節減が可
能）。
また、本発明の強化天然ゴムの製造方法は、強
化天然ゴムの製造に際し、従来は廃棄され、公害
問題の原因となつていた天然ゴムラテツクス漿液
を副生しないため、公害問題を解消できる。[Table] Azole In addition, the measurement results with the rheometer used for the physical property test and the normal vulcanized rubber sheet (vulcanized at 140℃
The correlation function with the physical properties of vulcanized rubber measured using The rubber composition used here was ACS No. 1 formulation. The relationship between the tensile strength after vulcanization T B (Kg/cm 2 ), Y and the maximum torque (Kg-cm), X was significant at a criticality rate of 1%. Y=12X−70, correlation coefficient R
=0.67. Tensile stress after vulcanization 600% modulus (Kg/cm 2 ),
The relationship between Y, maximum torque (Kg-cm), and X was significant at a risk rate of 1%. Y=6.1X−68, correlation coefficient R=0.87. The relationship between the Ryupke impact resilience (%), Y, and the maximum torque (Kg-cm), X after vulcanization was significant at a risk rate of 1%. Y=0.8X+60, correlation coefficient R=0.75. Minimum torque (Kg-cm), X and viscosity (M L+4 100
℃), Y was significant at a significance level of 5%.
Y=3.5X+36, correlation coefficient R=0.41. <Effects of the Invention> The reinforced natural rubber of the present invention has the following properties when used as a rubber composition. 1 Maximum torque is large. That is, the physical properties of the vulcanized rubber (particularly tensile stress, tensile strength, and impact resilience) are good. 2. Both the minimum torque and initial torque are small. That is, mixing becomes easier and energy consumption during mixing can be saved. 3. Green strength and elongation are large, and therefore properties such as tackiness of unvulcanized rubber are improved. 4. Vulcanization speed becomes faster (vulcanization accelerator can be saved). In addition, the method for producing reinforced natural rubber of the present invention eliminates the problem of pollution because natural rubber latex serum, which was conventionally discarded and caused pollution problems, is not produced as a by-product during the production of reinforced natural rubber.
第１図は、本発明の実施例１，２および比較例
１，２を用いたゴム組成物の加硫曲線を示すグラ
フである。第２図は、本発明の実施例２および比
較例１を用いたゴム組成物のエロンゲイシヨン−
グリーンストレングス測定曲線である。
FIG. 1 is a graph showing vulcanization curves of rubber compositions using Examples 1 and 2 of the present invention and Comparative Examples 1 and 2. FIG. 2 shows the elongation of rubber compositions using Example 2 of the present invention and Comparative Example 1.
This is a green strength measurement curve.
Claims (1)
られる非ゴム成分を添加してなる強化天然ゴムで
あつて、非ゴム成分総含有量が3.5〜12.0重量％
であることを特徴とする強化天然ゴム。 ２ 天然ゴムラテツクス漿液から得られる非ゴム
成分を30重量％以上含む水溶液を用いて、天然ゴ
ム中の前記非ゴム成分の含有量を3.5〜12.0重量
％とすることを特徴とする強化天然ゴムの製造方
法。 ３ 天然ゴムに、天然ゴムラテツクス漿液からス
プレードライ方法によつて得られる10〜100μmの
粉末状非ゴム成分を混練し、天然ゴム中の非ゴム
成分の含有量を3.5〜12.0重量％とすることを特
徴とする強化天然ゴムの製造方法。[Scope of Claims] 1. Reinforced natural rubber obtained by adding non-rubber components obtained from natural rubber latex serum to natural rubber, wherein the total content of non-rubber components is 3.5 to 12.0% by weight.
Reinforced natural rubber characterized by: 2. Production of reinforced natural rubber characterized in that the content of the non-rubber component in the natural rubber is 3.5 to 12.0% by weight using an aqueous solution containing 30% by weight or more of the non-rubber component obtained from natural rubber latex serum. Method. 3. A powdered non-rubber component of 10 to 100 μm obtained from natural rubber latex serum by a spray drying method is kneaded into natural rubber, so that the content of the non-rubber component in the natural rubber is 3.5 to 12.0% by weight. A unique method for producing reinforced natural rubber.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60162335A JPS6222837A (en) | 1985-07-23 | 1985-07-23 | Reinforced natural rubber and production thereof |
| GB08617959A GB2178044B (en) | 1985-07-23 | 1986-07-23 | Reinforced natural rubbers and processes for their production |
| MYPI87000119A MY101145A (en) | 1985-07-23 | 1987-02-10 | Reinforced natural rubbers and processes for their production. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60162335A JPS6222837A (en) | 1985-07-23 | 1985-07-23 | Reinforced natural rubber and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6222837A JPS6222837A (en) | 1987-01-31 |
| JPH0367543B2 true JPH0367543B2 (en) | 1991-10-23 |
Family
ID=15752591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60162335A Granted JPS6222837A (en) | 1985-07-23 | 1985-07-23 | Reinforced natural rubber and production thereof |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS6222837A (en) |
| GB (1) | GB2178044B (en) |
| MY (1) | MY101145A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2613068B2 (en) * | 1987-12-22 | 1997-05-21 | 横浜ゴム株式会社 | Rubber composition for tire tread |
| JPH01165637A (en) * | 1987-12-22 | 1989-06-29 | Yokohama Rubber Co Ltd:The | Rubber composition for tire tread |
| JP2839193B2 (en) * | 1989-08-10 | 1998-12-16 | ザ ボード オブ ザ ラバー リサーチ インスティテュート オブ マレーシア | Concentrate of natural rubber serum |
| WO2003091326A1 (en) * | 2002-04-23 | 2003-11-06 | Bridgestone Corporation | Rubber compositions containing rubber-containing coagulums and processes for production of the coagulums |
| JP2006328142A (en) * | 2005-05-24 | 2006-12-07 | Yokohama Rubber Co Ltd:The | Natural rubber composition compounded of silica and pneumatic tire given by using the same |
| JP2009178854A (en) * | 2008-01-29 | 2009-08-13 | Daikin Ind Ltd | Method for manufacturing lengthy rubber-coagulated product and method for manufacturing sheet-shaped rubber-coagulated product |
-
1985
- 1985-07-23 JP JP60162335A patent/JPS6222837A/en active Granted
-
1986
- 1986-07-23 GB GB08617959A patent/GB2178044B/en not_active Expired
-
1987
- 1987-02-10 MY MYPI87000119A patent/MY101145A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6222837A (en) | 1987-01-31 |
| GB2178044A (en) | 1987-02-04 |
| GB8617959D0 (en) | 1986-08-28 |
| GB2178044B (en) | 1988-11-09 |
| MY101145A (en) | 1991-07-31 |
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