JP7532026B2 - Deproteinized natural rubber composition - Google Patents
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Description
本発明は、タンパク質除去天然ゴム組成物に関する。さらに詳しくは、水浸漬時の体積膨張および物性低下の少ない架橋物を与えるタンパク質除去天然ゴム組成物に関する。 The present invention relates to a protein-removed natural rubber composition. More specifically, the present invention relates to a protein-removed natural rubber composition that gives a crosslinked product that exhibits minimal volume expansion and loss of physical properties when immersed in water.
水廻りに使用されるゴム材料としては、EPDM、(水素化)NBR、フッ素ゴム等の合成ゴムが一般的であるが、資源の持続可能性などの観点から、植物由来の天然ゴムの使用が望まれる。 The rubber materials commonly used in wet areas are synthetic rubbers such as EPDM, (hydrogenated) NBR, and fluororubber, but from the perspective of resource sustainability, it is desirable to use plant-derived natural rubber.
しかしながら、天然ゴムは親水性のタンパク質をその構造中に含むため、使用時に体積が増大するという課題がみられる。 However, because natural rubber contains hydrophilic proteins in its structure, there is an issue that its volume increases during use.
天然ゴムからタンパク質を分離したタンパク質フリー天然ゴムが特許文献１に提案されているが、この場合にあってもそのような傾向は依然としてみられる。 Patent Document 1 proposes protein-free natural rubber, in which proteins are separated from natural rubber, but even in this case, such a tendency is still observed.
本発明の目的は、水浸漬時の体積膨張および物性低下の少ない架橋物を与え得るタンパク質除去天然ゴム組成物を提供することにある。 The object of the present invention is to provide a protein-removed natural rubber composition that can give a crosslinked product that undergoes minimal volume expansion and loss of physical properties when immersed in water.
かかる本発明の目的は、ISO 1407に対応するJIS K-6451で規定されるケルダール法で測定した窒素含有率が0.019重量％以下であるタンパク質除去天然ゴムのみからなるゴム、カーボンブラックおよび／または白色充填剤および有機過酸化物架橋剤を含有してなるタンパク質除去天然ゴム組成物によって達成される。 The object of the present invention is achieved by a protein-removed natural rubber composition which contains rubber consisting solely of protein-removed natural rubber having a nitrogen content of 0.019% by weight or less as measured by the Kjeldahl method defined in JIS K-6451, which corresponds to ISO 1407, carbon black and/or white filler, and an organic peroxide crosslinking agent.
ISO 1407に対応するJIS K-6451で規定されるケルダール法で測定した窒素含有率が0.019重量％以下であるタンパク質除去天然ゴムに有機過酸化物架橋剤を配合したタンパク質除去天然ゴム組成物は、物性低下を殆ど伴うことなく、水浸漬時の体積膨張を有効に防止する。 A protein-removed natural rubber composition prepared by blending an organic peroxide crosslinking agent with protein-removed natural rubber having a nitrogen content of 0.019% by weight or less, as measured by the Kjeldahl method specified in JIS K-6451, which corresponds to ISO 1407, effectively prevents volume expansion when immersed in water with almost no deterioration in physical properties.
本発明に係るタンパク質除去天然ゴム組成物は、ISO 1407に対応するJIS K-6451で規定されるケルダール法で測定した窒素含有率が0.019重量％以下であるタンパク質除去天然ゴムおよび有機過酸化物架橋剤を含有してなる。 The protein-depleted natural rubber composition according to the present invention contains protein-depleted natural rubber having a nitrogen content of 0.019% by weight or less, as measured by the Kjeldahl method defined in JIS K-6451, which corresponds to ISO 1407, and an organic peroxide crosslinking agent.
本発明においてタンパク質除去天然ゴムとは、ケルダール法(ISO 1407に対応するJIS K6451-2準拠；硫酸カリウムと硫酸銅(II)との混合触媒および硫酸を用いて試料を湿式分解し、試料中の窒素を硫酸アンモニウムに変換し、これに強アルカリを加えて遊離したアンモニアを水蒸気蒸留し、ほう酸水溶液に導入した後、硫酸または塩酸で滴定してアンモニア量を求め、その値から窒素含有率を算出する)で測定した窒素含有率が0.019重量％以下のタンパク質除去天然ゴムを指している。 In this invention, deproteinized natural rubber refers to deproteinized natural rubber having a nitrogen content of 0.019% by weight or less, as measured by the Kjeldahl method (based on JIS K6451-2, which corresponds to ISO 1407; a sample is wet-decomposed using a mixed catalyst of potassium sulfate and copper (II) sulfate and sulfuric acid, the nitrogen in the sample is converted to ammonium sulfate, a strong alkali is added to this and the liberated ammonia is subjected to steam distillation, introduced into an aqueous boric acid solution and then titrated with sulfuric acid or hydrochloric acid to determine the amount of ammonia, from which the nitrogen content is calculated).
このようなタンパク質除去天然ゴムは、天然ゴムラテックスに尿素系化合物、好ましくは一般式 RNHCONH2 (R：水素原子または炭素数1～5のアルキル基)で表される尿素またはその低級アルキル誘導体、アニオン系、ノニオン系またはカチオン系の界面活性剤および極性有機溶媒、好ましくは炭素数1～5のアルキル基を有する脂肪族アルコール、炭素数3～4のケトン、炭素数1～5の脂肪族カルボン酸、炭素数1～5のアルキル基を有するカルボン酸エステル等の水混和性極性有機溶媒を添加し、該ラテックス中のタンパク質を変性処理した後除去することにより得られる。 Such protein-removed natural rubber can be obtained by adding a urea compound, preferably urea represented by the general formula RNHCONH2 (R: hydrogen atom or an alkyl group having 1 to 5 carbon atoms) or a lower alkyl derivative thereof, an anionic, nonionic or cationic surfactant and a polar organic solvent, preferably a water-miscible polar organic solvent such as an aliphatic alcohol having an alkyl group having 1 to 5 carbon atoms, a ketone having 3 to 4 carbon atoms, an aliphatic carboxylic acid having 1 to 5 carbon atoms, or a carboxylate ester having an alkyl group having 1 to 5 carbon atoms, to natural rubber latex, and then denaturing and removing the proteins in the latex.
また、このようなタンパク質除去天然ゴムは、改良ローリー法により測定した固形ゴム中のタンパク質量が0.5μg/g以下のレベルである。 In addition, such protein-removed natural rubber has a protein content in the solid rubber of 0.5 μg/g or less as measured by the modified Lowry method.
ケルダール法(JIS K6451-2)：
ケルダールフラスコにゴム0.1g、触媒(硫酸カリウム：硫酸銅(II)・五水和物：セレン＝重量比 15：2：1)0.65g、濃硫酸2.5mlを計りとり、ガスバーナーで溶液の色が緑色になるまで30分間程度加熱した。水蒸気蒸留装置を組み立て、容量1Lのフラスコに蒸留水を適量入れ、オイルバスで加熱し、水蒸気で容量300mlの二口フラスコとリービッヒ冷却管を洗浄した。蒸留水20mlを用いて、ケルダールフラスコの中身を二口フラスコ内に移し、67w/v％水酸化ナトリウム水溶液10mlと蒸留水10mlとを二口フラスコ内に加えて蒸気を通し、2w/v％ホウ酸水溶液10mlを入れた三角フラスコを受器としてアンモニアを捕捉した。水蒸気蒸留装置の三角フラスコの内容量が20ml程度になったところで蒸留を止めた。リービッヒ冷却器内を蒸留水で洗い、洗浄液を三角フラスコに流して、メチルレッドを指示薬として0.005mol/L硫酸で滴定してゴム試料中の窒素含有率を求めた。
窒素含有率の算出には、以下の式を用いた。
窒素含有率(％)＝ V/1000(L)×N(molL-1)×14×2(gmol-1)×1/w(g-1)×100
ここで、Vは0.005mol/L硫酸の滴定量、wはゴムの質量、Nは滴定に用いた0.005mol/L硫酸の濃度にファクター(1.004)を掛け合わせた値である。
Kjeldahl method (JIS K6451-2):
0.1g of rubber, 0.65g of catalyst (potassium sulfate: copper (II) sulfate pentahydrate: selenium = weight ratio 15:2:1), and 2.5ml of concentrated sulfuric acid were weighed and placed in a Kjeldahl flask, and heated with a gas burner for about 30 minutes until the solution turned green. A steam distillation apparatus was assembled, and an appropriate amount of distilled water was placed in a 1L flask, which was then heated in an oil bath, and the 300ml two-neck flask and Liebig condenser were washed with steam. The contents of the Kjeldahl flask were transferred into the two-neck flask using 20ml of distilled water, and 10ml of 67w/v% sodium hydroxide aqueous solution and 10ml of distilled water were added to the two-neck flask, and steam was passed through. Ammonia was captured using an Erlenmeyer flask containing 10ml of 2w/v% boric acid aqueous solution as a receiver. The distillation was stopped when the content of the Erlenmeyer flask in the steam distillation apparatus reached about 20ml. The inside of the Liebig condenser was washed with distilled water, and the washings were poured into an Erlenmeyer flask. The nitrogen content in the rubber sample was determined by titration with 0.005 mol/L sulfuric acid using methyl red as an indicator.
The nitrogen content was calculated using the following formula.
Nitrogen content (%) = V/1000 (L) × N (molL -1 ) × 14 × 2 (gmol -1 ) × 1/w (g -1 ) × 100
Here, V is the titration amount of 0.005 mol/L sulfuric acid, w is the mass of rubber, and N is the concentration of 0.005 mol/L sulfuric acid used in the titration multiplied by a factor (1.004).
有機過酸化物架橋剤としては、例えばジクミルパーオキサイド、ジ第3ブチルパーオキサイド、2,5-ジメチル－2,5-ジ(第3ブチルパーオキシ)-3-ヘキシン、2,5-ジメチル-2,5-ジ(第3ブチルパーオキシ)ヘキサン、1,3-ビス(第3ブチルパーオキシイソプロピル)ベンゼン等のジアルキルパーオキサイド、ベンゾイルパーオキサイド等のジアシルパーオキサイド、2,5-ジメチル-2,5-ビス(ベンゾイルパーオキシ)ヘキサン、第3ブチルパーオキシイソプロピルカルボネート等のパーオキシエステル等が用いられ、好ましくはジクミルパーオキサイドが用いられる。 As organic peroxide crosslinking agents, for example, dialkyl peroxides such as dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 1,3-bis(tert-butylperoxyisopropyl)benzene, diacyl peroxides such as benzoyl peroxide, peroxy esters such as 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, and tert-butylperoxyisopropyl carbonate are used, and dicumyl peroxide is preferably used.
これらの有機過酸化物架橋剤は、タンパク質除去天然ゴム100重量部当り約0.1～10重量部、好ましくは約0.2～5重量部の割合で用いられる。 These organic peroxide crosslinking agents are used in a ratio of about 0.1 to 10 parts by weight, preferably about 0.2 to 5 parts by weight, per 100 parts by weight of protein-removed natural rubber.
有機過酸化物架橋剤と共に、トリアリルイソシアヌレート、トリアリルシアヌレート
トリメチロールプロパントリメタクリール等の多官能性不飽和化合物を、タンパク質除去天然ゴム100重量部当り約10重量部以下、好ましくは約0.2～5重量部を併用することもできる。
A polyfunctional unsaturated compound such as triallyl isocyanurate, triallyl cyanurate, trimethylolpropane trimethacrylate, etc. may be used in combination with the organic peroxide crosslinking agent in an amount of about 10 parts by weight or less, preferably about 0.2 to 5 parts by weight, per 100 parts by weight of the protein-removed natural rubber.
さらに、亜鉛華、酸化マグネシウム、リサージ等またはステアリン酸、ステアリン酸亜鉛等の架橋助剤を、タンパク質除去天然ゴム100重量部当り約0.1～10重量部、好ましくは約0.2～5重量部の割合で添加して用いることもできる。 In addition, crosslinking aids such as zinc oxide, magnesium oxide, litharge, stearic acid, zinc stearate, etc. can be added in a ratio of about 0.1 to 10 parts by weight, preferably about 0.2 to 5 parts by weight, per 100 parts by weight of protein-removed natural rubber.
また、N-イソプロピル-N′-フェニル-p-フェニレンジアミン、N-オクチル-N′-フェニル-p-フェニレンジアミン、N,N′-ジアリル-p-フェニレンジアミン、N-(1,3-ジメチルブチル)-N′-フェニル-p-フェニレンジアミン、N,N′-ジ(1,4-ジメチルペンチル)-p-フェニレンジアミン等のp-フェニレンジアミン系、6-エトキシ-2,2,4-トリメチル-1,2-ジヒドロキノリン等のケトン・アミン反応生成物などによって代表される老化防止剤、その他の任意成分も適宜配合して用いられる。 In addition, p-phenylenediamines such as N-isopropyl-N'-phenyl-p-phenylenediamine, N-octyl-N'-phenyl-p-phenylenediamine, N,N'-diallyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, and N,N'-di(1,4-dimethylpentyl)-p-phenylenediamine, as well as anti-aging agents such as ketone-amine reaction products such as 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, and other optional ingredients may be appropriately blended and used.
タンパク質除去天然ゴム組成物中には、各種の補強剤または充填剤をタンパク質除去天然ゴム100重量部当り約90重量部以下、好ましくは約35～60重量部配合して用いることもできる。補強剤または充填剤の割合は、架橋物の破断強度やモジュラスを改善させるが、これより多い割合での配合は破断伸びや圧縮永久歪特性を損なわせるおそれがある。 Various reinforcing agents or fillers can also be compounded in the protein-removed natural rubber composition in an amount of up to about 90 parts by weight, preferably about 35 to 60 parts by weight, per 100 parts by weight of protein-removed natural rubber. The proportion of reinforcing agent or filler improves the breaking strength and modulus of the crosslinked product, but compounding in a higher proportion may impair the breaking elongation and compression set properties.
補強剤または充填剤としては、一般に各種グレードのカーボンブラック、好ましくはFEFカーボンブラック、乾式法または湿式法で製造されたシリカ等の白色充填剤が用いられる。シリカが用いられた場合には、シランカップリング剤も併用されることが好ましい。 As reinforcing agents or fillers, generally various grades of carbon black, preferably FEF carbon black, and white fillers such as silica produced by the dry or wet process are used. When silica is used, it is preferable to use a silane coupling agent in combination.
タンパク質除去天然ゴム組成物の調製は、タンパク質除去天然ゴムおよび他の配合成分を密封型ニーダやオープンロールで混練することにより行われる。 The protein-removed natural rubber composition is prepared by kneading the protein-removed natural rubber and other compounding ingredients in a closed kneader or open roll.
タンパク質除去天然ゴム組成物の架橋は、用いられた架橋剤の種類に応じて約140～200℃の加熱プレスで約3～30分間加熱することにより行われる。 Crosslinking of the protein-removed natural rubber composition is carried out by heating in a hot press at approximately 140 to 200°C for approximately 3 to 30 minutes, depending on the type of crosslinking agent used.
得られたタンパク質除去天然ゴム組成物の架橋物よりなる天然ゴム架橋物は、水と接触して使用されるゴム製品、特に水系用シール材、例えば水道用シール材等として有効に用いられる。 The resulting crosslinked natural rubber composition is effectively used as a rubber product that is used in contact with water, particularly as a sealant for water systems, such as a sealant for water supply systems.
次に、実施例について本発明を説明する。 Next, the present invention will be explained using examples.
参考例
天然ゴムラテックス(マレーシアゴールデンホープ社製品、豊通ケミプラス輸入品；ゴム分濃度60.2重量％、アンモニア分0.7重量％)100重量部に、ドデシル硫酸ナトリウム1重量部および尿素0.1重量部を加え、室温条件下で90分間攪拌した。
Reference Example 100 parts by weight of natural rubber latex (product of Malaysia Golden Hope Pvt. Ltd., imported by Toyotsu Chemiplas; rubber content 60.2% by weight, ammonia content 0.7% by weight) was added with 1 part by weight of sodium dodecyl sulfate and 0.1 part by weight of urea and stirred at room temperature for 90 minutes.
その後、ラテックスを15℃、回転数9000rpmの条件下で30分間遠心分離し、上層のクリーム分を分離した。クリーム分に蒸留水を加え、ドデシル硫酸ナトリウム0.5重量部およびアセトン2.5重量部を添加し、1時間撹拌した。 The latex was then centrifuged at 15°C and 9000 rpm for 30 minutes to separate the upper cream layer. Distilled water was added to the cream layer, followed by the addition of 0.5 parts by weight of sodium dodecyl sulfate and 2.5 parts by weight of acetone, and the mixture was stirred for 1 hour.
この遠心分離と再分散(1％アニオン系界面活性剤－0.025％エタノール水溶液によりゴム分濃度を30重量％にする)の作業を合計3回くり返すことで、タンパク質除去天然ゴムラテックスを調製し、このラテックスを乾燥して、タンパク質除去天然ゴムを得た。 This centrifugation and redispersion process (rubber concentration is adjusted to 30% by weight using 1% anionic surfactant-0.025% ethanol aqueous solution) was repeated a total of three times to prepare protein-removed natural rubber latex, which was then dried to obtain protein-removed natural rubber.
得られた天然ゴム〔PFNR〕は、ケルダール法(JIS K-6451)で前記の条件に従い測定した窒素含有率が検出限界である0.001重量％以下のレベルであり、改良ローリー法により測定したタンパク質量が検出限界である0.5μg/g以下のレベルであった。 The resulting natural rubber (PFNR) had a nitrogen content of 0.001% by weight or less, which is the detection limit, as measured by the Kjeldahl method (JIS K-6451) under the above-mentioned conditions , and a protein content of 0.5 μg/g or less, which is the detection limit, as measured by the modified Lowry method.
実施例１
参考例で得られたPFNR 100重量部
FEFカーボンブラック 50 〃
ジクミルパーオキサイド 2.5 〃
架橋助剤亜鉛華 5 〃
架橋助剤ステアリン酸 1 〃
老化防止剤(川口化学工業製品アンテージRD) 2 〃
以上の各成分の内、PFNRを密封型ニーダで素練りした後、ジクミルパーオキサイド以外の配合成分を加えて120℃で混練した。さらに、オープンロールでジクミルパーオキサイドを添加、混練して、タンパク質除去天然ゴム組成物を得た。
Example 1
PFNR obtained in the reference example 100 parts by weight
FEF Carbon Black 50%
Dicumyl peroxide 2.5 〃
Crosslinking agent zinc oxide 5 〃
Crosslinking agent stearic acid 1 〃
Anti-aging agent (Kawaguchi Chemical Industry Products Antage RD) 2 Same
Of the above components, PFNR was masticated in a closed kneader, and then the compounding components other than dicumyl peroxide were added and kneaded at 120° C. Furthermore, dicumyl peroxide was added and kneaded using an open roll to obtain a protein-removed natural rubber composition.
得られたタンパク質除去天然ゴム組成物を、170℃、7分間加熱架橋し、加硫曲線のt90に該当する時間まで架橋し、厚さ2mmの架橋シートを得た。
架橋シートについて、次の各項目の試験を行った。
常態値(硬さ、引張強さ、破断時伸び)：JIS K-6253、K-6251準拠
水浸漬試験(JIS K-6258準拠)：80℃で140時間または500時間水浸漬後の常態値変化
および体積変化率を測定
JIS6号試験片および体積変化測定用2×5cmの試験片をゴムシートか
ら打ち抜き、それぞれ3個を1セットとした。試験管にゴムサンプルを
入れ、イオン交換水を100ml注ぎ入れてアルミニウムホイルで蓋をし
た後、試験管を所定の温度の恒温槽に放置した。試験後の試験片を水
より取り出して、不織布で水分をふき取った。体積は、試験片を水中
につるした時の重さからアルキメデスの原理を用いて算出し、試験前
の体積に対する変化率を算出した。
The resulting protein-removed natural rubber composition was heat-crosslinked at 170° C. for 7 minutes, and crosslinked until the time corresponding to t90 on the vulcanization curve, to obtain a crosslinked sheet having a thickness of 2 mm.
The crosslinked sheet was subjected to the following tests.
Normal values (hardness, tensile strength, elongation at break): Compliant with JIS K-6253 and K-6251 Water immersion test (Compliant with JIS K-6258): Change in normal values after immersion in water for 140 hours or 500 hours at 80°C
and volume change rate
JIS No. 6 test piece and 2 x 5 cm test piece for measuring volume change were placed on the rubber sheet.
The rubber samples were punched out from the test tubes, and three pieces were punched out from each set.
Add 100ml of ion-exchanged water and cover with aluminum foil.
After the test, the test tube was placed in a thermostatic chamber at a specified temperature.
The volume was measured by immersing the test piece in water.
The weight of the specimen was calculated using Archimedes' principle.
The rate of change in volume was calculated.
実施例２
実施例１において、参考例で得られたPFNRの代わりに、同量(100重量部)の脱タンパク質NR(豊通ケミプラス輸入品；窒素含有率0.019重量％)が用いられた。
Example 2
In Example 1, instead of the PFNR obtained in the Reference Example, the same amount (100 parts by weight) of deproteinized NR (imported by Toyotsu Chemiplas; nitrogen content 0.019% by weight) was used.
比較例
実施例１において、参考例で得られたPFNRの代わりに、同量(100重量部)の天然ゴム(豊通ケミプラス輸入品；窒素含有率0.480重量％)が用いられた。
Comparative Example In Example 1, the same amount (100 parts by weight) of natural rubber (imported by Toyotsu Chemiplas; nitrogen content 0.480% by weight) was used in place of the PFNR obtained in the Reference Example.
以上の各実施例および比較例で得られた結果は、次の表中に示される。
表
測定項目 実施例１ 実施例２ 比較例
〔常態値〕
硬さ(デュロメータA) 53 59 61
引張強さ (MPa) 20.3 23.4 24.5
破断時伸び (％) 340 380 350
〔80℃、500時間水浸漬後〕
硬さ変化率 (％) -6 -14 -10
引張強さ変化率 (％) -10 -16 -32
破断時伸び変化率 (％) +3 -8 -14
体積変化率 (％) +4.1 +4.3 +9.1
The results obtained in the above examples and comparative examples are shown in the following table.
table
Measurement items Example 1 Example 2 Comparative example
[Normal value]
Hardness (Durometer A) 53 59 61
Tensile strength (MPa) 20.3 23.4 24.5
Elongation at break (%) 340 380 350
[After immersion in water for 500 hours at 80℃]
Hardness change rate (%) -6 -14 -10
Tensile strength change rate (%) -10 -16 -32
Elongation change at break (%) +3 -8 -14
Volume change rate (%) +4.1 +4.3 +9.1
以上の結果から、天然ゴムに代えてPFNRあるいは脱タンパク質NRが用いられた場合には、80℃、500時間水浸漬後における体積変化率が小さく、特にPFNRについては、各種物性値の変化率も小さく抑えられることが分かる。 These results show that when PFNR or deproteinized NR is used instead of natural rubber, the volume change rate after immersion in water at 80°C for 500 hours is small, and in particular for PFNR, the rate of change in various physical properties is also kept small.
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| JP2003012736A (en) | 2001-04-25 | 2003-01-15 | Sumitomo Rubber Ind Ltd | Rubber product |
| JP2005126488A (en) | 2003-10-21 | 2005-05-19 | Sumitomo Rubber Ind Ltd | Method for producing hypoallergenic natural rubber products |
| WO2011027739A1 (en) | 2009-09-01 | 2011-03-10 | 国立大学法人長岡技術科学大学 | Protein-free natural rubber, latex thereof, and method for manufacturing said rubber and latex |
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| JP2905005B2 (en) * | 1992-08-05 | 1999-06-14 | 住友ゴム工業株式会社 | Deproteinized natural rubber |
| JP2717493B2 (en) * | 1993-01-11 | 1998-02-18 | 不二ラテックス株式会社 | Method for removing allergenic substance from natural rubber latex and method for producing natural rubber molded article |
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| JP5728297B2 (en) * | 2011-06-09 | 2015-06-03 | 白石カルシウム株式会社 | Crosslinked polymer composition and method for producing the same |
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| JP2005126488A (en) | 2003-10-21 | 2005-05-19 | Sumitomo Rubber Ind Ltd | Method for producing hypoallergenic natural rubber products |
| WO2011027739A1 (en) | 2009-09-01 | 2011-03-10 | 国立大学法人長岡技術科学大学 | Protein-free natural rubber, latex thereof, and method for manufacturing said rubber and latex |
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