JP7522549B2 - Cross-linked natural rubber - Google Patents
Cross-linked natural rubber Download PDFInfo
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- JP7522549B2 JP7522549B2 JP2019224478A JP2019224478A JP7522549B2 JP 7522549 B2 JP7522549 B2 JP 7522549B2 JP 2019224478 A JP2019224478 A JP 2019224478A JP 2019224478 A JP2019224478 A JP 2019224478A JP 7522549 B2 JP7522549 B2 JP 7522549B2
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- 244000043261 Hevea brasiliensis Species 0.000 title claims description 44
- 229920003052 natural elastomer Polymers 0.000 title claims description 44
- 229920001194 natural rubber Polymers 0.000 title claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 6
- 102000004169 proteins and genes Human genes 0.000 claims description 6
- 108090000623 proteins and genes Proteins 0.000 claims description 6
- 238000007696 Kjeldahl method Methods 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000003566 sealing material Substances 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 description 15
- 229920001971 elastomer Polymers 0.000 description 12
- 239000005060 rubber Substances 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000007654 immersion Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229920006173 natural rubber latex Polymers 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- 239000012763 reinforcing filler Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- -1 urea compound Chemical class 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- ZJNLYGOUHDJHMG-UHFFFAOYSA-N 1-n,4-n-bis(5-methylhexan-2-yl)benzene-1,4-diamine Chemical compound CC(C)CCC(C)NC1=CC=C(NC(C)CCC(C)C)C=C1 ZJNLYGOUHDJHMG-UHFFFAOYSA-N 0.000 description 1
- MINNIIWBFAPUKJ-UHFFFAOYSA-N 1-n-octyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NCCCCCCCC)=CC=C1NC1=CC=CC=C1 MINNIIWBFAPUKJ-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 229940096818 dipentamethylenethiuram disulfide Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- 235000019285 ethoxyquin Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- KNBRWWCHBRQLNY-UHFFFAOYSA-N piperidine-1-carbothioylsulfanyl piperidine-1-carbodithioate Chemical compound C1CCCCN1C(=S)SSC(=S)N1CCCCC1 KNBRWWCHBRQLNY-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Sealing Material Composition (AREA)
Description
本発明は、天然ゴム架橋物に関する。さらに詳しくは、水浸漬時の膨張およびブルーム(白色化)の度合いの小さい天然ゴム架橋物に関する。 The present invention relates to a cross- linked natural rubber product , and more particularly to a cross-linked natural rubber product that exhibits low levels of swelling and blooming (whitening) 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。また、配合物が水浸漬時にゴム表面に白く析出し、著しく外観を損ねるという課題もある。 However, natural rubber contains hydrophilic proteins in its structure, which causes the problem of its volume increasing during use. Another problem is that the compound precipitates as a white layer on the rubber surface when immersed in water, significantly impairing its appearance.
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、水浸漬時の膨張およびブルーム(白色化)の度合いの小さい天然ゴム架橋物を提供することにある。 An object of the present invention is to provide a cross-linked natural rubber product that exhibits small degrees of swelling and blooming (whitening) when immersed in water.
かかる本発明の目的は、ISO 1407に対応するJIS K-6451-2で規定されるケルダール法で測定した窒素含有率がその検出限界である0.001重量％以下であるタンパク質除去天然ゴムおよび硫黄系架橋剤を含有してなるタンパク質除去天然ゴム組成物の架橋物よりなる、水と接触して使用される水系用シール材として使用される、天然ゴム架橋物によって達成される。 The object of the present invention is achieved by a cross-linked natural rubber material for use as an aqueous sealing material which is used in contact with water and which comprises a cross-linked product of a protein-removed natural rubber composition which contains a protein-removed natural rubber having a nitrogen content of 0.001% by weight or less, which is the detection limit, as measured by the Kjeldahl method specified in JIS K-6451-2, which corresponds to ISO 1407, and a sulfur-based cross-linking agent.
本発明に係るタンパク質除去天然ゴムに硫黄系架橋剤を配合したタンパク質除去天然ゴム組成物の架橋物は、水浸漬時の膨張およびブルーム(白色化)の度合いの小さい水と接触して使用される水系用シール材等として使用される。 The cross-linked product of the protein-removed natural rubber composition according to the present invention , in which the protein-removed natural rubber is blended with a sulfur-based cross-linking agent, is used as an aqueous sealing material or the like which is used in contact with water and which has a small degree of swelling and blooming (whitening) when immersed in water.
タンパク質除去天然ゴム組成物は、タンパク質除去天然ゴムおよび硫黄系架橋剤を含有してなる。 The protein -removed natural rubber composition contains the protein-removed natural rubber and a sulfur-based 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0.05重量％以下、好ましくはその検出限界である0.001％以下の実質的にタンパク質がフリーの天然ゴムを指している。 In the present invention, deproteinized natural rubber refers to substantially protein-free natural rubber with a nitrogen content of 0.05% by weight or less, preferably 0.001% or less, which is the detection limit, 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 steam-distilled, 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).
硫黄系架橋剤としては、可溶性または不溶性の硫黄または含硫黄架橋促進剤が用いられる。硫黄としては、硫黄単体のみならず、高分子硫黄等も用いられる。 As the sulfur-based crosslinking agent, soluble or insoluble sulfur or a sulfur-containing crosslinking accelerator is used. As the sulfur, not only elemental sulfur but also polymeric sulfur, etc. are used.
含硫黄架橋促進剤としては、例えばテトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、ジペンタメチレンチウラムジスルフィド等のチウラム系を始め、チアゾール系、スルフェンアミド系、グアニジン系、ジチオカルバミン酸系、キサントゲン酸系等の各種含硫黄化合物が用いられる。 Examples of sulfur-containing crosslinking accelerators that can be used include thiuram-based compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, and dipentamethylenethiuram disulfide, as well as various sulfur-containing compounds such as thiazole-based compounds, sulfenamide-based compounds, guanidine-based compounds, dithiocarbamic acid-based compounds, and xanthogenic acid-based compounds.
硫黄または含硫黄架橋促進剤がそれ単独で用いられる場合には、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、両者が併用される場合には上記割合の範囲で任意の割合で用いられる。 When sulfur or a sulfur-containing crosslinking accelerator is used alone, it is 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, and when both are used in combination, they are used in any ratio within the above range.
さらに、この場合には、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, in this case, 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-6451-2)で測定した窒素含有率が検出限界である0.001％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 below 0.001%, which is the detection limit, as measured by the Kjeldahl method (JIS K- 6451-2 ), and a protein content below 0.5 μg/g, 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 〃
硫黄 1 〃
架橋促進剤(大内新興化学工業製品ノクセラーCZ) 1.25 〃
架橋促進剤(大内新興化学製品ノクセラーTT) 0.63 〃
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、加硫促進剤以外の配合成分を加えて120℃で混練した。さらに、オープンロールで加硫促進剤を添加、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%
Sulfur 1 〃
Crosslinking accelerator (Ouchi Shinko Chemical Industry Products Noccela CZ) 1.25 Same
Crosslinking accelerator (Ouchi Shinko Chemical Products Noccela TT) 0.63 Same
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 the vulcanization accelerator were added and kneaded at 120° C. Furthermore, the vulcanization accelerator 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、150℃の加熱プレスで架橋し、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。
体積変化率：JIS K6258(耐液性試験；180℃、40時間)準拠
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。
5％未満を合格、5％以上を不合格と判定
外観：第１図参照
外観明度：ゴム表面を撮影し、画像をHSV空間に分解したときの明度(V)によって
評価
上記耐液性試験で、浸漬前のブルームしていない状態を0、明度100
％を100とした
The resulting protein-removed natural rubber composition was crosslinked in a hot press at 150° C. 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.
Volume change rate: Compliant with JIS K6258 (liquid resistance test: 180℃, 40 hours)
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.
Less than 5% is judged as pass, and more than 5% is judged as fail. Appearance: See Figure 1. Appearance brightness: The rubber surface is photographed and the image is decomposed into HSV space, and the brightness (V) is used to determine the brightness.
evaluation
In the above liquid resistance test, the state without bloom before immersion is 0, and the brightness is 100.
% is set to 100
実施例２
実施例１において、硫黄および架橋促進剤ノクセラーCZは用いられなかった。また、架橋促進剤ノクセラーTTは、4重量部に変更された。
Example 2
In Example 1, sulfur and the crosslinking accelerator Noccelaer CZ were not used, and the crosslinking accelerator Noccelaer TT was changed to 4 parts by weight.
実施例３
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。ただし、架橋促進剤ノクセラーCZは1重量部、同ノクセラーTTは0.5重量部に変更された。
Example 3
In Example 1, the same amount (100 parts by weight) of deproteinized NR (imported by Toyotsu Chemiplus; nitrogen content 0.019% by weight) was used instead of the PFNR obtained in the Reference Example. However, the crosslinking accelerator Noccelaer CZ was changed to 1 part by weight, and the same Noccelaer TT was changed to 0.5 parts by weight.
実施例４
実施例３において、硫黄および架橋促進剤ノクセラーCZは用いられなかった。また、架橋促進剤ノクセラーTTは、4重量部に変更された。
Example 4
In Example 3, sulfur and the crosslinking accelerator Noccelaer CZ were not used, and the crosslinking accelerator Noccelaer TT was changed to 4 parts by weight.
比較例１
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％)が同量(100重量部)用いられた。ただし、架橋促進剤ノクセラーCZは0.88重量部、同ノクセラーTTは0.44重量部に変更された。
Comparative Example 1
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, except that the crosslinking accelerator Noccelaer CZ was changed to 0.88 parts by weight, and the same Noccelaer TT was changed to 0.44 parts by weight.
比較例２
比較例１において、硫黄および架橋促進剤ノクセラーCZは用いられなかった。また、架橋促進剤ノクセラーTTは4重量部に変更された。
Comparative Example 2
In Comparative Example 1, sulfur and the crosslinking accelerator Noccelaer CZ were not used, and the crosslinking accelerator Noccelaer TT was changed to 4 parts by weight.
以上の各実施例および比較例で得られた結果は、次の表に示される。
表
測定項目 実－１ 実－２ 実－３ 実－４ 比－１ 比－２
体積変化率(％) 2.1 2.1 3.6 2.8 6.0 5.6
同判定 ○ ○ ○ ○ × ×
外観 第１図 第２図 第３図 第４図 第５図 第６図
外観明度(％) 18 20 35 66 69 75
The results obtained in the above examples and comparative examples are shown in the following table .
table
Measurement item Fruit-1 Fruit-2 Fruit-3 Fruit-4 Ratio-1 Ratio-2
Volume change rate (%) 2.1 2.1 3.6 2.8 6.0 5.6
Same judgment ○ ○ ○ ○ × ×
Appearance Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Appearance brightness (%) 18 20 35 66 69 75
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| 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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