WO2012105681A1 - 天然ゴム及びそれを用いたゴム組成物並びにタイヤ - Google Patents
天然ゴム及びそれを用いたゴム組成物並びにタイヤ Download PDFInfo
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- WO2012105681A1 WO2012105681A1 PCT/JP2012/052476 JP2012052476W WO2012105681A1 WO 2012105681 A1 WO2012105681 A1 WO 2012105681A1 JP 2012052476 W JP2012052476 W JP 2012052476W WO 2012105681 A1 WO2012105681 A1 WO 2012105681A1
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- natural rubber
- rubber
- preservative
- latex
- natural
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C3/00—Treatment of coagulated rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
Definitions
- the present invention relates to natural rubber, a rubber composition using the same, and a tire, and more particularly, natural rubber coagulation with little change with time in a standing process (aging or aging) including moisture after coagulation of natural rubber latex.
- the present invention relates to a natural rubber comprising a product, a rubber composition using the same, and a tire using the rubber composition. Aging here means leaving for a certain period of time in a moisture-containing state, and aging means changing the molecular weight of polyisoprene chains in natural rubber coagulum and the amount of non-rubber components such as proteins and lipids. To tell. Non-rubber components include proteins that have an anti-aging action and a vulcanization-accelerating action.
- a rubber composition using natural rubber obtained by washing and drying the non-rubber component by positively fixing the non-rubber component in the natural rubber coagulated product by aging to prevent the loss from the natural rubber coagulated product. Can be expected to improve aging resistance.
- a natural rubber coagulated product produced from a cup lamp contains moisture during the standing process.
- bacteria and microorganisms in the coagulum increase and become activated, and proteins and lipids that are non-rubber components in the natural rubber coagulum are decomposed.
- the polyisoprene chain itself of natural rubber is also affected, and the molecular weight is lowered during the standing process.
- the decrease in molecular weight of the natural rubber coagulated product containing moisture in the process of standing causes a significant decrease in physical properties such as modulus and fracture stress in the rubber composition.
- the natural rubber coagulated material varies greatly with time in the course of standing, and the desired physical properties may not be obtained in the rubber composition.
- the variation with time is a variation resulting from a variation with time of the natural rubber coagulated product itself in the same period and a difference in the leaving period.
- the object of the present invention is to solve the above-mentioned problems of the prior art and suppress variations by suppressing the decrease in molecular weight and the deterioration of non-rubber components even in the standing process (aging) of natural rubber coagulum.
- Another object of the present invention is to provide a natural rubber having a stable mechanical property, comprising a natural rubber coagulum, which stably contains a non-rubber component in the coagulum.
- Another object of the present invention is to provide a rubber composition using such natural rubber and a tire using the same.
- this invention achieves the said objective with the following structures or structures.
- (1) Obtained from a natural rubber latex to which a preservative has been added and / or obtained by washing and drying the water-containing solidified product obtained by adding a preservative to the natural rubber latex coagulated product for more than 3 days.
- Natural rubber (2) The natural rubber as described in (1) above, wherein the preservative is 1,2-benzisothiazolin-3-one.
- the standing time is preferably at least 3 days or more, more preferably 5 days or more.
- the natural rubber of the present invention is a natural rubber obtained by coagulating natural rubber latex, aging for a predetermined period, and drying, and the presence of a preservative in the water-containing coagulated product before aging causes the aging to occur.
- the non-rubber component is prevented from flowing without deterioration, the change with time is suppressed, and a natural rubber having stable mechanical properties is obtained after drying.
- microorganisms propagate and the non-rubber component is prevented from being decomposed or altered.
- the rubber composition of the present invention uses natural rubber made of the above natural rubber coagulum contained in a good state without altering the non-rubber component, so that mechanical properties such as modulus and fracture stress are increased, Improves aging resistance by improving vulcanization acceleration.
- the tire of the present invention can be expected to have good tire performance by using the rubber composition.
- the natural rubber and the rubber composition thereof according to the present invention are not limited to the following embodiments, and it goes without saying that various changes can be made without departing from the gist of the present invention.
- the natural rubber coagulated product in the present embodiment is obtained by leaving a hydrous coagulated product obtained from a natural rubber latex added with a preservative and / or by adding a preservative to the coagulated product of natural rubber latex for a predetermined time, This is washed and dried to obtain natural rubber.
- natural rubber has two typical production methods.
- RSS ribbed smoked sheet
- Green Book the international quality packaging standard (commonly known as the Green Book) of natural rubber grades
- natural rubber collected after tapping is collected.
- the rubber component is coagulated with an acid or the like in the latex
- the solid rubber is separated from the water-soluble non-rubber component with a roll, and the solid rubber is smoke dried at about 60 ° C. for 5 to 7 days.
- TSR technical rating rubber
- the rubber component of the natural rubber latex is naturally coagulated or acid coagulated (cup lamp), the solid rubber is pulverized, washed with water, dehydrated, and then the solid rubber is treated with 110%.
- a natural rubber latex that has been pre-coagulated with a preservative or a water-containing cup lamp with a preservative is allowed to stand (age) for a predetermined period of time and then washed and dried. This is a natural rubber obtained.
- the natural rubber latex includes, for example, a fresh latex that is used within 3 hours after being tapped from natural rubber wood, and a stabilizer that is stabilized by ammonia treatment or the like after the tapping latex, and preferably has a pH of 7.0 to The latex is about 11.0.
- the centrifuge latex which centrifuged these latexes with the centrifuge can be used.
- the solid component of the natural rubber latex used is preferably in the range of 10 to 80% by mass, particularly preferably in the range of 20 to 65% by mass.
- the coagulation treatment may be performed by the above-described natural coagulation, or may be performed by a chemical treatment using the following coagulation acid or the like.
- the coagulating acid in the chemical treatment may be an organic acid or an inorganic acid, and examples thereof include formic acid, citric acid, phosphoric acid, sulfuric acid and the like.
- a preservative is added and the above aging is performed.
- the aging time is preferably at least 3 days or more, more preferably 5 days or more and 60 days or less.
- the temperature at the time of aging is room temperature, but is not limited to this temperature, and may be a place where cooling and heating treatment is performed in the range of 5 to 40 ° C.
- the preservative in the present embodiment various preservatives that can suppress the activity of microorganisms can be used.
- 1,2-benzisothiazolin-3-one is particularly preferable because it has a high effect of suppressing the activity of microorganisms and has a low environmental load.
- 2-pyridinethiol-1-oxide sodium salt, 2-pyridinethiol-1-oxide zinc salt, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazoline-3- Further, ON, 3-iodo-2-propynylbutyl carbamate and the like can be mentioned.
- the amount of the preservative added to the natural rubber coagulated product is 0.01 to 1.00% by mass, preferably 0.1 to 0.8% by mass, particularly preferably based on the total amount of the natural rubber coagulated product. 0.2 to 0.5 mass%. If the addition amount of the preservative is less than 0.01% by mass, the desired antiseptic effect may not be exhibited. If it exceeds 1.00% by mass, the economic cost corresponding to the antiseptic effect may be exerted. May increase and may remain in the agglomerates and have an adverse effect.
- the crumb treatment is not necessarily required, but is performed for efficient drying.
- the crumb treatment can be performed through a creper process and / or a shredder process.
- a creper process for example, a creper sheet can be obtained by passing the coagulated material three times through a Creper Model CRC 14/28 manufactured by SPHERE.
- a shredder process for example, a Shredder Model CRC manufactured by SPHERE is used.
- the crumb can be obtained by charging this creper sheet on 14/28.
- the drying treatment of the solidified product can be performed using, for example, a bucket dryer or a belt dryer.
- the bucket dryer include a dryer used for normal TSR production, specifically, a Single Box Dryer Model CRDS manufactured by SPHERE.
- the belt-type dryer the thing provided with the conveyor-type dryer, for example, a far infrared ray apparatus, or a microwave apparatus, is mentioned.
- the dried solidified product is preferably dried until the moisture content of the natural rubber solidified product is 1.5% or less, more preferably 0.8% or less. It is desirable to do.
- a viscosity stabilizer may be added to the rubber latex together with the preservative or after aging.
- viscosity stabilizer examples include hydroxylamine sulfate, semicarbazide, dimedone (1,1-dimethylcyclohexane-3,5-dione), triazole compounds, hydrazide compounds, and the like.
- hydrazide compound examples include acetohydrazide, propionic acid hydrazide, butanoic acid hydrazide, lauric acid hydrazide, palmitic acid hydrazide, stearic acid hydrazide, cyclopropanecarboxylic acid hydrazide, cyclohexanecarboxylic acid hydrazide, cycloheptanecarboxylic acid hydrazide, and benzoic acid hydrazide.
- triazole compound examples include 1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, and 3-mercapto-1,2,4-triazole.
- the amount of the viscosity stabilizer added to natural rubber is 0.001 to 3% by mass, preferably 0.03 to 2.5% by mass, based on the total amount of natural rubber (raw rubber).
- the addition amount of the viscosity stabilizer is less than 0.001% by mass, the desired viscosity effect may not be exhibited.
- the amount exceeds 3% by mass it remains in the natural rubber, The low exothermic property and durability of the rubber composition used may be lowered. Moreover, the dispersibility of carbon black and other compounding chemicals may be lowered, which is not preferable.
- the rubber composition of the present embodiment is formed by blending a rubber component containing natural rubber, and the natural rubber is composed of the natural rubber coagulum.
- the rubber component in the rubber composition various synthetic rubbers can be used in addition to the natural rubber including the natural rubber. It is preferable to use a diene synthetic rubber from the viewpoint of polymer compatibility (uniform dispersion).
- the diene-based synthetic rubber that can be used include at least one selected from isoprene rubber, styrene-butadiene copolymer rubber, butadiene rubber, and styrene-isoprene copolymer rubber, particularly from the viewpoint of heat resistance.
- Desirable is at least one selected from isoprene rubber, styrene-butadiene copolymer rubber, and butadiene rubber.
- the content of the natural rubber obtained above is 5% by mass or more, preferably 10 to 70% by mass with respect to the total amount of all rubber components. If the content of the natural rubber is less than 5% by mass, the effect of improving viscosity and improving low heat build-up will not be obtained, which is not preferable.
- the rubber composition of the present invention configured as described above, a rubber composition containing a rubber component containing natural rubber having excellent heat aging resistance, having no increase in viscosity during storage, and having a stable quality can be obtained.
- the natural rubber production method of the present invention is excellent in dispersibility, exhibits an excellent constant viscosity effect, and always provides a homogeneous natural rubber.
- the rubber composition containing the natural rubber obtained in the above treatment step of the present invention includes a filler, a reinforcing agent, a softening agent, a vulcanizing agent, a vulcanization accelerator, and a vulcanization acceleration aid as necessary.
- An optional component such as an anti-aging agent can also be contained.
- Natural rubber is widely used in the rubber industry and the tire industry because of its excellent physical properties, and is particularly preferably used for tire rubber.
- a natural rubber latex added with 0.4% by mass of ammonia is concentrated by centrifuging using a continuous latex separator, and the resulting latex latex has a rubber latex solids (DRC) concentration of 40% by mass. Adjusted.
- DRC rubber latex solids
- Examples 1-6 0.5 parts by mass of 1,2-benzisothiazolin-3-one (preservative 1) as a preservative is added to the natural rubber latex with respect to 100 parts by mass of the rubber solid content, and this is naturally coagulated (cup lamp) And aging was performed at a temperature of 25 ° C. for a maximum of 35 days.
- Examples 7-8 0.1 parts by weight of preservative 1 as a preservative is added to the natural rubber latex with respect to 100 parts by weight of the rubber solid content, and this is naturally coagulated (cup lamp) at a temperature of 25 ° C. for 3 or 5 days. Aging was performed.
- Examples 9-10 To the natural rubber latex, 0.3 parts by mass of the preservative 1 as a preservative is added to 100 parts by mass of the rubber solid content, and this is naturally coagulated (cup lamp) at a temperature of 25 ° C. for 3 or 5 days. Aging was performed. Examples 11-12 To the natural rubber latex, 0.8 parts by mass of the preservative 1 as a preservative is added to 100 parts by mass of the rubber solid content, and this is naturally coagulated (cup lamp) at a temperature of 25 ° C. for 3 or 5 days. Aging was performed.
- Example 13 0.5 parts by mass of 5-chloro-2-methyl-4-isothiazolin-3-one (preservative 2) as a preservative is added to the natural rubber latex with respect to 100 parts by mass of the rubber solid content. The product was naturally coagulated (cup lamp) and aged at a temperature of 25 ° C. for 3 days.
- Example 14 0.8 parts by mass of preservative 2 as a preservative is added to the natural rubber latex with respect to 100 parts by mass of the rubber solid content, and this is naturally coagulated (cup lamp) and aged at a temperature of 25 ° C. for 3 days. went.
- Comparative Examples 1 to 4 The natural rubber latex was naturally coagulated (cup lamp) without adding a preservative, and aged at a temperature of 25 ° C. for a maximum of 35 days. Comparative Example 5 0.5 parts by mass of the preservative 1 was added to the natural rubber latex with respect to 100 parts by mass of the rubber solid content to allow natural coagulation (cup lamp). Aging was not performed.
- the natural rubber coagulated product (after aging) was pulverized (crumbized) by passing it through a crusher, a scraper 3 times and a shredder.
- the crushed solidified product was washed, dehydrated and dried to obtain natural rubber.
- Evaluation method (measurement method of nitrogen content) The total nitrogen content of natural rubber was measured by the Kjeldahl method and calculated as a ratio (mass%) to the total amount. (Measurement method of molecular weight Mw) Using gel permeation chromatography [GPC: HLC-8020 manufactured by Tosoh Corp., column: GMH-XL manufactured by Tosoh Corp., detector: differential refractive index (RI)], each natural rubber was determined based on standard polystyrene manufactured by Tosoh Corp. The weight average molecular weight in terms of polystyrene was determined.
- a rubber composition was prepared with the composition shown in Table 2, and vulcanized from the rubber composition at a temperature of 145 ° C. for 33 minutes to obtain a sheet-like prototype rubber. After punching this out into a ring shape, the stress at break was measured with a tensile tester. Comparative example 1 was taken as 100 and displayed as an index. It shows that it is so favorable that a numerical value is high.
- (Measurement method for aging resistance) A prototype rubber deteriorated by placing the prototype rubber in an oven at 100 ° C. for 48 hours was obtained. After punching this out into a ring shape, 300% modulus was measured with a tensile tester to measure aging resistance.
- Comparative example 1 was taken as 100 and displayed as an index. It shows that it is so favorable that a numerical value is high.
- the evaluation results of Examples and Comparative Examples are shown in Table 1 above. However, the molecular weight is a numerical value of ⁇ 10 ⁇ 4 .
- the nitrogen content (% by mass) after standing for a predetermined period was remarkably reduced when the additive was not added, but the nitrogen amount was not decreased when the preservative was added, and the decomposition and loss of non-rubber components were suppressed. Especially for those stored for a long time, the nitrogen content increased due to improved uptake of non-rubber components.
- the weight average molecular weight (x10 4 [Da]) of natural rubber after standing for a predetermined period was significantly reduced when left unadded, but the reduction was significantly suppressed when left as a preservative.
- the fracture characteristics of the rubber composition containing natural rubber after standing for a predetermined period of time were significantly reduced when the additive was not added, but the reduction was significantly suppressed when the preservative was added.
- the aging resistance of the rubber composition containing natural rubber after standing for a predetermined period of time was remarkably reduced when the additive was not added, but the decrease was significantly suppressed when the preservative was added.
- the natural rubber of the present invention has stable mechanical properties, and the rubber composition is industrially capable of using the above-mentioned natural rubber containing the non-rubber component in a good state while suppressing runoff without altering the non-rubber component. There is a possibility of use.
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Abstract
Description
ここでの熟成とは、水分を含んだ状態での一定期間放置することで、経時変化とは、天然ゴム凝固物中のポリイソプレン鎖の分子量及びたんぱく質や脂質などの非ゴム成分量の変質を言う。非ゴム成分には、老化防止作用や加硫促進作用を有するたんぱく質が含まれる。これらの天然ゴム凝固物からの流亡を防ぎ、エージングにより積極的に非ゴム成分を天然ゴム凝固物中に固定化することにより、それを洗浄・乾燥して得た天然ゴムを用いたゴム組成物は耐老化性向上が期待できる。
(1)防腐剤を添加した天然ゴムラテックスより得られる及び/又は天然ゴムラテックスの凝固物に防腐剤を添加して得られる含水凝固物を3日以上放置した後に、洗浄・乾燥して得られる天然ゴム。
(2)防腐剤が1,2-ベンズイソチアゾリン-3-オンであることを特徴とする上記(1)に記載の天然ゴム。
(3)防腐剤の添加量が天然ゴム凝固物中0.01~1.0質量%である上記(1)又は(2)に記載の天然ゴム。
尚、上記放置時間は少なくとも3日以上が好ましく、より好ましくは、5日以上の範囲である。
(5)上記(4)に記載のゴム組成物を用いて製造したタイヤ。
また、本発明のゴム組成物は、非ゴム成分を変質させることなく、良好な状態で含んだ上記天然ゴム凝固物からなる天然ゴムを使用するので、モジュラス、破壊応力等の力学特性が高まり、加硫促進作用が良好となり、耐老化特性を向上する。本発明のタイヤは、上記ゴム組成物を使用することにより、良好なタイヤ性能が期待できる。
本実施形態における天然ゴム凝固物は、防腐剤を添加した天然ゴムラテックスより得られる及び/又は天然ゴムラテックスの凝固物に防腐剤を添加して得られる含水凝固物を所定時間放置したもので、これを洗浄・乾燥して天然ゴムが得られる。
本実施形態は、具体的に凝固前の天然ゴムラテックスに防腐剤を添加したもの、もしくは水分を含むカップランプに防腐剤を添加したものを、所定時間放置(エージング)して洗浄・乾燥して得られた天然ゴムである。
具体的に使用される天然ゴムラテックスの固形成分は、10~80質量%の範囲にあるものを使用することが好ましく、特に、20~65質量%の範囲にあるものを使用することが好ましい。
化学的処理における凝固酸は、有機酸又は無機酸でもよく、例えば、ギ酸、クエン酸、燐酸、硫酸等を代表として挙げることができる。
エージングに際しての温度は室温であるが、この温度に限ることはなく、5~40℃の範囲で冷暖処理した場所においても良い。
また、天然ゴム凝固物に対する防腐剤の添加量は、天然ゴム凝固物の全量に対して、0.01~1.00質量%、好ましくは、0.1~0.8質量%、特に好ましくは、0.2~0.5質量%である。防腐剤の添加量が0.01質量%未満であると、目的の防腐効果が発揮することができないことがあり、また、1.00質量%を越えると、防腐効果に対応する経済的なコストが上がり、また凝集物中に残留して悪影響を与える恐れがある。
恒粘度剤としては、例えば、硫酸ヒドロキシルアミン、セミカルバジド、ジメドン(1,1-ジメチルシクロヘキサン-3,5-ジオン)、トリアゾール化合物、ヒドラジド化合物などが挙げられる。ヒドラジド化合物としては、例えば、アセトヒドラジド、プロピオン酸ヒドラジド、ブタン酸ヒドラジド、ラウリン酸ヒドラジド、パルミチン酸ヒドラジド、ステアリン酸ヒドラジド、シクロプロパンカルボン酸ヒドラジド、シクロヘキサンカルボン酸ヒドラジド、シクロヘプタンカルボン酸ヒドラジド、安息香酸ヒドラジド、o-,m-,p-トルイル酸ヒドラジド、p-メトキシ安息香酸ヒドラジド、3,5-ジメチル安息香酸ヒドラジド、1-ナフトエ酸ヒドラジドが挙げられる。また、トリアゾール化合物としては、1,2,4-トリアゾール、3-アミノ-1,2,4-トリアゾール、4-アミノ-1,2,4-トリアゾール、3-メルカプト-1,2,4-トリアゾール、1,2,4-トリアゾール-3-オール、5-アミノ-3-メルカプト-1,2,4-トリアゾール、5-アミノ-1,2,4-トリアゾール、1,2,4-トリアゾール-3-カルボン酸、ベンゾトリアゾール、1-ヒドロキシベンゾトリアゾール(1水和物)などが挙げられる。
また、天然ゴムに対する恒粘度剤の添加量は、天然ゴム(生ゴム)全量に対して、0.001~3質量%、好ましくは、0.03~2.5質量%である。恒粘度剤の添加量が0.001質量%未満であると、目的の恒粘度効果が発揮することができないことがあり、また、3質量%を越えると、天然ゴム中に残留し、それを用いたゴム組成物の低発熱性及び耐久性を低下させることがある。また、カーボンブラック他配合薬品の分散性を低下させることがあり、好ましくない。
ゴム組成物におけるゴム成分には、上記天然ゴムを含む天然ゴムの他に、各種の合成ゴムを用いることができる。好ましくは、ポリマー相溶性(均一分散)の点からジエン系合成ゴムを用いることが好ましい。用いることができるジエン系合成ゴムとしては、例えば、イソプレンゴム、スチレン-ブタジエン共重合体ゴム、ブタジエンゴム、スチレン-イソプレン共重合体ゴムから選ばれる少なくとも一種が挙げられ、特に、耐熱性の点から、イソプレンゴム、スチレン-ブタジエン共重合体ゴム、ブタジエンゴムから選ばれる少なくとも一種が望ましい。本発明のゴム組成物において、上記で得られた天然ゴムの含有量は、全ゴム成分全量に対して、5質量%以上、好ましくは、10~70質量%とすることが望ましい。この天然ゴムの含有量が5質量%未満であると、粘度改良、低発熱性の改良効果がなく、好ましくない。
上記天然ゴムラテックスに、ゴム固形分100質量部に対して、防腐剤として1,2-ベンゾイソチアゾリンー3-オン(防腐剤1)を0.5質量部添加し、これを自然凝固(カップランプ)せしめ、温度25℃で、最大35日間エージングを行った。
実施例7~8
上記天然ゴムラテックスに、ゴム固形分100質量部に対して、防腐剤として防腐剤1を0.1質量部添加し、これを自然凝固(カップランプ)せしめ、温度25℃で、3または5日間エージングを行った。
上記天然ゴムラテックスに、ゴム固形分100質量部に対して、防腐剤として防腐剤1を0.3質量部添加し、これを自然凝固(カップランプ)せしめ、温度25℃で、3または5日間エージングを行った。
実施例11~12
上記天然ゴムラテックスに、ゴム固形分100質量部に対して、防腐剤として防腐剤1を0.8質量部添加し、これを自然凝固(カップランプ)せしめ、温度25℃で、3または5日間エージングを行った。
実施例13
上記天然ゴムラテックスに、ゴム固形分100質量部に対して、防腐剤として5-クロロ-2-メチル-4-イソチアゾリン-3-オン(防腐剤2)を0.5質量部添加し、これを自然凝固(カップランプ)せしめ、温度25℃で、3日間エージングを行った。
実施例14
上記天然ゴムラテックスに、ゴム固形分100質量部に対して、防腐剤として防腐剤2を0.8質量部添加し、これを自然凝固(カップランプ)せしめ、温度25℃で、3日間エージングを行った。
上記天然ゴムラテックスに、防腐剤を添加せずに自然凝固(カップランプ)せしめ、温度25℃で、最大35日間エージングを行った。
比較例5
上記天然ゴムラテックスに、ゴム固形分100質量部に対して、防腐剤1を0.5質量部添加し、自然凝固(カップランプ)せしめた。エージングは行わなかった。
(窒素量の測定方法)
ケルダール法によって天然ゴムの総窒素含有量を測定し、全量に対する割合(質量%)として算出した。
(分子量Mwの測定方法)
ゲルパーミエーションクロマトグラフィー〔GPC:東ソー社製HLC-8020、カラム:東ソー社製GMH-XL、検出器:示差屈折率(RI)〕を用いて東ソー社製の標準ポリスチレンを基準として各天然ゴムのポリスチレン換算の重量平均分子量を求めた。
(破壊特性の測定方法)
ゴム組成物を、表2に示す組成で調製を行い、ゴム組成物から温度145℃、33分間の条件で加硫し、シート状の試作ゴムを得た。これをリング状に打ち抜いた後、引張試験機にて、破断時の応力を測定した。比較例1を100として指数表示した。数値が高い程良好であることを示す。
(耐老化性の測定方法)
上記試作ゴムを、100℃のオーブンに48時間整置することで劣化した試作ゴムを得た。これをリング状に打ち抜いた後、引張試験機にて、300%モジュラスを測定し、耐老化性を測定した。比較例1を100として指数表示した。数値が高い程良好であることを示す。
以上、実施例及び比較例の評価結果を表1に示した。ただし、分子量は×10-4の 数値を示す。
Claims (5)
- 防腐剤を添加した天然ゴムラテックスより得られる及び/又は天然ゴムラテックスの凝固物に防腐剤を添加して得られる含水凝固物を3日以上放置した後に、洗浄・乾燥して得られる天然ゴム。
- 防腐剤がイソチアゾリン系化合物であることを特徴とする請求項1に記載の天然ゴム。
- 防腐剤の添加量が天然ゴム凝固物中0.01~1.0質量%である請求項1又は2に記載の天然ゴム。
- 請求項1~3の何れかに記載の天然ゴムを含むことを特徴とするゴム組成物。
- 請求項4に記載のゴム組成物を用いて製造したタイヤ。
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JP2012555969A JP5860416B2 (ja) | 2011-02-03 | 2012-02-03 | 天然ゴムの製造方法及び天然ゴムを用いたゴム組成物並びにタイヤの製造方法 |
US13/983,175 US8901206B2 (en) | 2011-02-03 | 2012-02-03 | Natural rubber, rubber composition using the same, and tire |
EP12742265.7A EP2671913B1 (en) | 2011-02-03 | 2012-02-03 | Natural rubber, rubber composition using the same, and tire |
CN201280016417.6A CN103476849B (zh) | 2011-02-03 | 2012-02-03 | 天然橡胶、使用其的橡胶组合物,和轮胎 |
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EP (1) | EP2671913B1 (ja) |
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Cited By (2)
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WO2016043056A1 (ja) * | 2014-09-18 | 2016-03-24 | 株式会社ブリヂストン | 天然ゴム、その製造方法、ゴム組成物及びそれを用いた空気入りタイヤ |
WO2021153415A1 (ja) * | 2020-01-27 | 2021-08-05 | 住友ゴム工業株式会社 | 改質天然ゴム及びゴム組成物 |
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US9941918B2 (en) * | 2015-01-07 | 2018-04-10 | Samsung Electronics Co., Ltd. | Bendable user terminal device and method for displaying contents based on bending status thereof |
JP6550870B2 (ja) * | 2015-04-02 | 2019-07-31 | 住友ゴム工業株式会社 | 天然ゴムの製造方法 |
FR3043678B1 (fr) * | 2015-11-17 | 2018-01-05 | Compagnie Generale Des Etablissements Michelin | Procede de preparation d'un caoutchouc naturel stabilise. |
FR3051795B1 (fr) * | 2016-05-31 | 2018-06-15 | Compagnie Generale Des Etablissements Michelin | Procede de sechage d'un caoutchouc naturel |
CN108424551B (zh) * | 2018-03-30 | 2020-12-01 | 云南滇源橡胶有限公司 | 一种复合橡胶 |
CN110091445A (zh) * | 2019-03-29 | 2019-08-06 | 昆明理工大学 | 一种微波加热联合真空干燥天然橡胶的方法及装置 |
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US20130303686A1 (en) | 2013-11-14 |
JPWO2012105681A1 (ja) | 2014-07-03 |
EP2671913A4 (en) | 2015-12-30 |
CN103476849B (zh) | 2016-01-13 |
EP2671913A1 (en) | 2013-12-11 |
US8901206B2 (en) | 2014-12-02 |
EP2671913B1 (en) | 2017-03-29 |
JP5860416B2 (ja) | 2016-02-16 |
CN103476849A (zh) | 2013-12-25 |
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