JP2006008923A - Resol-type alkylphenol-formaldehyde copolycondensated resin crosslinking agent - Google Patents
Resol-type alkylphenol-formaldehyde copolycondensated resin crosslinking agent Download PDFInfo
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- JP2006008923A JP2006008923A JP2004190978A JP2004190978A JP2006008923A JP 2006008923 A JP2006008923 A JP 2006008923A JP 2004190978 A JP2004190978 A JP 2004190978A JP 2004190978 A JP2004190978 A JP 2004190978A JP 2006008923 A JP2006008923 A JP 2006008923A
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- resin
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- alkylphenol
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- 239000011347 resin Substances 0.000 title claims abstract description 72
- 229920005989 resin Polymers 0.000 title claims abstract description 72
- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 44
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229920003987 resole Polymers 0.000 claims description 7
- 229920001971 elastomer Polymers 0.000 abstract description 23
- 239000005060 rubber Substances 0.000 abstract description 23
- 238000004132 cross linking Methods 0.000 abstract description 14
- 230000000903 blocking effect Effects 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000003921 oil Substances 0.000 description 18
- 235000019198 oils Nutrition 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- 239000013557 residual solvent Substances 0.000 description 9
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000010734 process oil Substances 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 235000005956 Cosmos caudatus Nutrition 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 235000014692 zinc oxide Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229940118056 cresol / formaldehyde Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- MMMNTDFSPSQXJP-UHFFFAOYSA-N orphenadrine citrate Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O.C=1C=CC=C(C)C=1C(OCCN(C)C)C1=CC=CC=C1 MMMNTDFSPSQXJP-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、フェノール類・ホルムアルデヒド共縮合樹脂からなるゴムの樹脂架橋剤に関するものであり、更に詳しくはオイルを含有したレゾール型アルキルフェノール・ホルムアルデヒド共縮合樹脂からなる樹脂架橋剤に関するものである。 The present invention relates to a rubber resin cross-linking agent comprising a phenol / formaldehyde co-condensation resin, and more particularly to a resin cross-linking agent comprising a resol-type alkylphenol / formaldehyde co-condensation resin containing oil.
樹脂架橋剤には従来からフレーク状または粒子状のレゾール型アルキルフェノール・ホルムアルデヒド共縮合樹脂が用いられているが、ゴムへの分散性が悪いことが知られている。樹脂架橋剤をゴムに充分分散させる為には、樹脂の軟化点以上の温度で混練するのが好ましいが、混練温度が１２０℃以上となるとゴムの架橋反応が開始しだし、均一なゴム組成物が得られなくなる。このため樹脂架橋剤は軟化点が１１５℃以下のものが一般的に用いられている。 Conventionally, flaky or particulate resol-type alkylphenol-formaldehyde cocondensation resin has been used as a resin crosslinking agent, but it is known that dispersibility in rubber is poor. In order to sufficiently disperse the resin cross-linking agent in the rubber, it is preferable to knead at a temperature equal to or higher than the softening point of the resin. However, when the kneading temperature is 120 ° C. or higher, the rubber cross-linking reaction starts and a uniform rubber composition is obtained. Cannot be obtained. For this reason, a resin crosslinking agent having a softening point of 115 ° C. or lower is generally used.
樹脂架橋剤を微粉末状にして用いるか、樹脂架橋剤の軟化点を低くすると分散性が改良されることが知られているが、微粉化したり、軟化点を下げると、保管中に樹脂同士の互着が生じて実使用に耐えられない。
樹脂架橋剤の計量、ゴムとの混練作業工程での粉塵防止と、樹脂架橋剤のゴムへの分散性を向上させる方法として、樹脂架橋剤とゴムとのマスターバッチを作成する方法が開示されている。（特許文献１）
It is known that the resin cross-linking agent is used in the form of fine powder or the softening point of the resin cross-linking agent is lowered, so that dispersibility is improved. Can not withstand actual use.
As a method of measuring the resin cross-linking agent, preventing dust in the kneading operation step with rubber, and improving the dispersibility of the resin cross-linking agent in rubber, a method of creating a master batch of the resin cross-linking agent and rubber is disclosed. Yes. (Patent Document 1)
一方において近年環境汚染防止が社会的課題となっており、製品中の不純物、残留原料、残留溶剤の削減が求められている。樹脂架橋剤の製造において、原料であるアルキルフェノールの残留量を分離削減するのはなかなか困難であり、縮合反応をできるだけ完結させる方法で残留量を削減するのが製造コスト的にも好ましい方法である。しかしながらこの方法では必然的に得られる樹脂架橋剤の軟化点が高くなり、上記特許文献１記載の方法では、上述したゴムへの分散性の低下が生じてしまう欠点がある。 On the other hand, prevention of environmental pollution has become a social issue in recent years, and reduction of impurities, residual raw materials and residual solvents in products has been demanded. In the production of a resin cross-linking agent, it is difficult to separate and reduce the residual amount of alkylphenol as a raw material, and reducing the residual amount by a method that completes the condensation reaction as much as possible is a preferable method in terms of manufacturing cost. However, this method inevitably increases the softening point of the resin cross-linking agent obtained, and the method described in Patent Document 1 has a drawback in that the dispersibility of the rubber described above is reduced.
本発明の目的は、軟化点がゴムの架橋反応温度より低く、かつ原料であるアルキルフェノールの残留量が低減された樹脂架橋剤を提供する事である。 An object of the present invention is to provide a resin crosslinking agent having a softening point lower than the crosslinking reaction temperature of rubber and a reduced residual amount of alkylphenol as a raw material.
本発明者らは課題解決に向けて鋭意検討した結果、レゾール型アルキルフェノール・ホルムアルデヒド共縮合樹脂にオイルを含有させる事で、本発明の目的が達成できる事を見出した。 As a result of intensive studies aimed at solving the problems, the present inventors have found that the object of the present invention can be achieved by adding oil to a resol-type alkylphenol-formaldehyde cocondensation resin.
以下本発明について詳細に説明する。
本発明の樹脂架橋剤は硫黄架橋可能な全てのゴムに適用可能であり、具体的ゴムとしては、天然ゴム、ＳＢＲ、イソプレンゴム、ＮＢＲ、ブチルゴム、ＥＰＤＭ、ＣＲ等が挙げられる。
The present invention will be described in detail below.
The resin crosslinking agent of the present invention can be applied to all rubbers capable of sulfur crosslinking, and specific rubbers include natural rubber, SBR, isoprene rubber, NBR, butyl rubber, EPDM, CR and the like.
本発明で使用されるレゾール型アルキルフェノール・ホルムアルデヒド共縮合樹脂は、プラスチック材料講座１５「フェノール樹脂」（日刊工業新聞社 刊）等に記載の公知の方法で合成可能であり、アルキル基の炭素数は１〜２０のものが好適に使用される。共縮合樹脂の分子量はポリスチレン換算重量平均分子量が２０００〜５０００のものが通常用いられる。また環境汚染防止の観点から、レゾール型アルキルフェノール・ホルムアルデヒド共縮合樹脂中には、原料であるアルキルフェノールの残留量及び反応等に用いる溶媒の残留量は少ない程好ましく、具体的にはそれぞれ１重量％未満が好ましい。 The resol-type alkylphenol-formaldehyde cocondensation resin used in the present invention can be synthesized by a known method described in Plastic Materials Course 15 “Phenolic Resin” (published by Nikkan Kogyo Shimbun), and the carbon number of the alkyl group is Those of 1 to 20 are preferably used. As the molecular weight of the cocondensation resin, those having a polystyrene equivalent weight average molecular weight of 2000 to 5000 are usually used. Also, from the viewpoint of preventing environmental pollution, it is preferable that the residual amount of alkylphenol as a raw material and the residual amount of solvent used for the reaction are smaller in the resol type alkylphenol / formaldehyde cocondensation resin, specifically less than 1% by weight respectively. Is preferred.
本発明に用いられるレゾール型アルキルフェノール・ホルムアルデヒド共縮合樹脂の具体的化合物としては、クレゾール・ホルムアルデヒド共縮合樹脂、エチルフェノール・ホルムアルデヒド共縮合樹脂、ブチルフェノール・ホルムアルデヒド共縮合樹脂、オクチルフェノール・ホルムアルデヒド共縮合樹脂、ブチルフェノール・オクチルフェノール・ホルムアルデヒド共縮合樹脂等が挙げられる。 Specific compounds of the resol type alkylphenol / formaldehyde cocondensation resin used in the present invention include cresol / formaldehyde cocondensation resin, ethylphenol / formaldehyde cocondensation resin, butylphenol / formaldehyde cocondensation resin, octylphenol / formaldehyde cocondensation resin, butylphenol. -Examples include octylphenol / formaldehyde co-condensation resin.
本発明のレゾール型アルキルフェノール・ホルムアルデヒド共縮合樹脂中のオイルの含有量は、１〜３０重量％が好ましく、２〜２５重量％が更に好ましい範囲である。該オイルの含有量が１重量％未満であれば軟化点の低減効果が認められず、３０重量％を超えると架橋ゴムの硬度の減少、圧縮永久歪の増大等を招き、好ましくない。 The oil content in the resol-type alkylphenol / formaldehyde cocondensation resin of the present invention is preferably 1 to 30% by weight, and more preferably 2 to 25% by weight. If the content of the oil is less than 1% by weight, the effect of reducing the softening point is not recognized, and if it exceeds 30% by weight, the hardness of the crosslinked rubber is decreased and the compression set is increased, which is not preferable.
本発明におけるオイルは、特に限定はないが、レゾール型アルキルフェノール・ホルムアルデヒド共縮合樹脂及びゴムの両方に相溶性の良いものが好ましく、ナフテン系オイルはどんなゴムにも比較的に相溶性が良く、本発明には特に好ましいオイルである。具体的には、パラフィン系オイルとしては、ダイアナプロセスオイルＰＷ−３２，ＰＷ−９０，ＰＷ−１５０，ＰＷ−３８０，ＰＳ−３２，ＰＳ−９０，ＰＳ−４３０，ＰＸ−３２，ＰＸ−９０（以上、出光興産株式会社製商品名）、スタノール４０，４３Ｎ，５２，６９，１４９，ＬＰ４０，ＬＰ６９，フレクソン８４５（以上、エッソ石油株式会社製商品名）、シンタックＰＡ−９５，ＰＡ−１００，ＰＡ−１４０（以上、神戸油化学工業株式会社製商品名）、コスモプロセス１０，４０，４０Ｃ（以上、コスモ石油株式会社製商品名）、ルブフレックス２６，１００，４００（以上、シェルジャパン株式会社製商品名）、共石プロセスＰ−２００，Ｐ−３００，Ｐ−５００（以上、日鉱共石株式会社製商品名）、サンパー（Sunper）１１０，１１５，１２０，１３０，１５０，１８０，２１００，２２１０，２２８０（以上、日本サンオイル株式会社製商品名）、フッコールＰ−２００，Ｐ−４００，Ｐ−５００（以上、富士興産株式会社製商品名）、三菱１０，三菱１２（以上、三菱製油株式会社製商品名）などが挙げられる。 The oil in the present invention is not particularly limited, but is preferably compatible with both the resol type alkylphenol-formaldehyde co-condensation resin and rubber, and the naphthenic oil is relatively compatible with any rubber. Particularly preferred oils for the invention. Specifically, as the paraffinic oil, Diana process oil PW-32, PW-90, PW-150, PW-380, PS-32, PS-90, PS-430, PX-32, PX-90 ( As mentioned above, Idemitsu Kosan Co., Ltd. product name), Stanol 40, 43N, 52, 69, 149, LP40, LP69, Flexon 845 (above, Esso Oil Co., Ltd. product name), Syntac PA-95, PA-100, PA -140 (above, product name manufactured by Kobe Oil Chemical Co., Ltd.), Cosmo Process 10, 40, 40C (above, product name manufactured by Cosmo Oil Co., Ltd.), Lubuflex 26,100,400 (above, manufactured by Shell Japan Co., Ltd.) Trade name), Kyoishi Process P-200, P-300, P-500 (above, trade name made by Nikko Kyoishi Co., Ltd.), Sunper 11 115, 120, 130, 150, 180, 2100, 2210, 2280 (Nippon Sun Oil Co., Ltd. trade name), Fukkor P-200, P-400, P-500 (Fuji Kosan Co., Ltd., trade name) Name), Mitsubishi 10, Mitsubishi 12 (and above, trade name of Mitsubishi Oil Co., Ltd.), and the like.
また、ナフテン系オイルとしては、ダイアナプロセスオイルＮＳ−２４，ＮＳ−１００，ＮＭ−２６，ＮＭ−６８，ＮＭ−１５０，ＮＭ−２８０，ＮＰ−２４，ＮＵ−８０，ＮＦ−９０（以上、出光興産株式会社製商品名）、エッソプロセスオイル７２５，７６５（以上、エッソ石油株式会社製商品名）、シンタックＮ−４０，Ｎ−６０，Ｎ−７０，Ｎ−７５，Ｎ−８５（以上、神戸油化学工業株式会社製商品名）、シェルフレックス３７１ＪＹ，３７１Ｎ，４５１，Ｎ−４０，２２，２２Ｒ，３２Ｒ，１００Ｒ，１００Ｓ，１００ＳＡ，２２０ＲＳ，２２０Ｓ，２６０，３２０Ｒ，６８０（以上、シェルジャパン株式会社製商品名）、共石プロセスＲ−５０，Ｒ−２００，Ｒ−１０００（日鉱共石株式会社製商品名）、サンセン（Sunthene）３１０，３８０，４１０，４１５，４２０，４３０，４５０，４８０，３２１５，４１３０，４２４０，Ciro Light R.P.O. （以上、日本サンオイル株式会社製商品名）、コウモレックス２号、コウモレックスＦ２２、（日本石油株式会社製商品名）、フッコール１１５０Ｎ，１４００Ｎ（以上、富士興産株式会社製商品名）、三菱２０（三菱石油株式会社製商品名）、ナプレックス３２，３８（以上、モービル石油株式会社製商品名）、ペトレックスＰＮ−３（山文油化株式会社製商品名）などが挙げられる。芳香族系オイルとしては、ダイアナプロセスオイルＡＣ−１２，ＡＣ−４６０，ＡＥ−２４，ＡＥ−５０，ＡＥ−２００，ＡＨ−１６，ＡＨ−５８（以上、出光興産株式会社製商品名）、エッソプロセスオイル１１０，１２０（以上、エッソ石油株式会社製商品名）、シンタックＨＡ−１０，ＨＡ−１５，ＨＡ−３０，ＨＡ−３５（以上、神戸油化学工業株式会社製商品名）、コスモプロセス４０Ａ（コスモ石油株式会社製商品名）、デュートレックス７２９ＵＫ，７３９（以上、シェルジャパン株式会社製商品名）、共石プロセスＸ１００−Ａ，Ｘ１００（以上、日鉱共石株式会社製商品名）、ＪＳＯ Ａｒｏｍａ７９０（日本サン石油株式会社製商品名）、コウモレックス３００，７００（以上、日本石油株式会社製商品名）、アロマックス＃１，＃３，＃５（以上、富士興産株式会社製商品名）ヘビープロセス油 三菱３４，三菱３８，三菱４４（以上、三菱石油株式会社製商品名）、モービルゾール Ｋ，２２，３０，１３０（以上、モービル石油株式会社製商品名）、ペトレックスＬＰＯ−Ｒ，ＬＰＯ−Ｖ，ＰＦ−１，ＰＦ−２（以上、山文油化株式会社製商品名）などが挙げられ、２種以上のオイルを同時に使用しても良い。 Naphthenic oils include Diana process oil NS-24, NS-100, NM-26, NM-68, NM-150, NM-280, NP-24, NU-80, NF-90 (above, Idemitsu Kosan Co., Ltd. product name), Esso Process Oil 725,765 (above, Esso Oil Co., Ltd. product name), SYNTAC N-40, N-60, N-70, N-75, N-85 (above, Kobe) Yuka Chemical Co., Ltd. trade name), shelf rex 371JY, 371N, 451, N-40, 22, 22R, 32R, 100R, 100S, 100SA, 220RS, 220S, 260, 320R, 680 (above, Shell Japan Co., Ltd.) Product name), Kyoishi Process R-50, R-200, R-1000 (product name made by Nikko Kyoishi Co., Ltd.), Sunthene 10, 380, 410, 415, 420, 430, 450, 480, 3215, 4130, 4240, Ciro Light RPO (Nippon Sun Oil Co., Ltd., trade name), Komolex No. 2, Komolex F22, (Japan Oil) Product name), Fukkor 1150N, 1400N (Fuji Kosan Co., Ltd. product name), Mitsubishi 20 (Mitsubishi Oil Co., Ltd. product name), Naplex 32, 38 (more, Mobil Oil Co., Ltd. product name) ), Petrex PN-3 (trade name, manufactured by Yamabun Oil Chemical Co., Ltd.) and the like. Aromatic oils include Diana Process Oil AC-12, AC-460, AE-24, AE-50, AE-200, AH-16, AH-58 (above, trade names made by Idemitsu Kosan Co., Ltd.), Esso Process oil 110, 120 (above, trade name made by Esso Oil Co., Ltd.), SYNTAC HA-10, HA-15, HA-30, HA-35 (above, trade name made by Kobe Oil Chemical Co., Ltd.), Cosmo Process 40A (Trade name made by Cosmo Oil Co., Ltd.), Dutrex 729UK, 739 (above, trade name made by Shell Japan Co., Ltd.), Kyoishi Process X100-A, X100 (above, trade name made by Nikko Kyoishi Corporation), JSO Aroma 790 (Nippon Sun Oil Co., Ltd. product name), Komolex 300,700 (above, Nippon Oil Co., Ltd. product name), Aroma # 1, # 3, # 5 (trade name, manufactured by Fujikosan Co., Ltd.) Heavy Process Oil Mitsubishi 34, Mitsubishi 38, Mitsubishi 44 (trade name, manufactured by Mitsubishi Oil Corporation), Mobilsol K, 22, 30 , 130 (above, trade name made by Mobile Oil Co., Ltd.), Petrex LPO-R, LPO-V, PF-1, PF-2 (above, trade name made by Yamabun Yuka Co., Ltd.), etc. More than one seed oil may be used simultaneously.
レゾール型アルキルフェノール・ホルムアルデヒド共縮合樹脂とオイルとの混合方法は、レゾール型アルキルフェノール・ホルムアルデヒド共縮合樹脂の有機溶剤溶液にオイルを均一に溶解させた後に有機溶剤を留去させる方法が最も簡便な方法であるが、樹脂の軟化点以上の温度でオイルと混合する方法も可能である。
本発明の樹脂架橋剤の軟化点は、縮合樹脂の分子量、残留アルキルフェノール量、残留溶媒量、オイルの添加量によって決まり、通常８５〜１１５℃の軟化点のものが使用され、９０〜１１０℃のものが好ましい。軟化点が８５℃より低いと保管中に樹脂同士の互着が生じやすくなるため、本発明の樹脂架橋剤を低温で保管する必要性が生じ、また１１５℃より高いとゴムのコンパウンド作成時の混練温度が高温となりゴムの架橋反応が部分的に開始されてコンパウンドの品質低下が生じる。
The simplest method for mixing the resole-type alkylphenol-formaldehyde cocondensation resin and oil is to dissolve the oil uniformly in the organic solvent solution of the resol-type alkylphenol-formaldehyde cocondensation resin and then distill off the organic solvent. However, a method of mixing with oil at a temperature higher than the softening point of the resin is also possible.
The softening point of the resin cross-linking agent of the present invention is determined by the molecular weight of the condensation resin, the amount of residual alkylphenol, the amount of residual solvent, and the amount of oil added. Usually, those having a softening point of 85 to 115 ° C are used. Those are preferred. If the softening point is lower than 85 ° C., mutual adhesion between the resins tends to occur during storage. Therefore, it becomes necessary to store the resin cross-linking agent of the present invention at a low temperature. The kneading temperature becomes high and the rubber cross-linking reaction is partially initiated, resulting in a deterioration in the quality of the compound.
本発明の樹脂架橋剤の使用量に特に制限は無いが、ゴム１００重量部に対して、１〜５０重量部、好ましくは３〜３０重量部使用される。
また本発明の樹脂架橋剤は、ＣＲ、塩化スズ、ベンゼンスルフォン酸、酸化カルシュウム、モレキュラーシーブ、といった架橋促進剤の併用も可能である。
Although there is no restriction | limiting in particular in the usage-amount of the resin crosslinking agent of this invention, 1-50 weight part with respect to 100 weight part of rubber | gum, Preferably 3-30 weight part is used.
The resin cross-linking agent of the present invention can be used in combination with a cross-linking accelerator such as CR, tin chloride, benzenesulfonic acid, calcium oxide, molecular sieve.
本発明の樹脂架橋剤を用いた時の架橋温度は、従来の樹脂架橋剤と同じ温度領域が適用可能である。具体的には１２０〜２３０℃において、ゴムの種類に応じた適切な温度が選択される。
本発明の樹脂架橋剤は、薬栓、ブラダー、コンデンサーパッキン、タイヤチューブ、インナーライナー、ホース、チューブ、ガスケット、自動車内装材、家電部品、等に使用されるゴム製品、ＴＰＥ製品に好適に使用される。
As the crosslinking temperature when the resin crosslinking agent of the present invention is used, the same temperature region as that of the conventional resin crosslinking agent can be applied. Specifically, an appropriate temperature according to the type of rubber is selected at 120 to 230 ° C.
The resin cross-linking agent of the present invention is suitably used for rubber products and TPE products used in medicine plugs, bladders, condenser packings, tire tubes, inner liners, hoses, tubes, gaskets, automobile interior materials, home appliance parts, etc. The
本発明により、分散性、樹脂架橋剤の保管、ゴムの架橋性能共に従来品と同等性能を有し、かつ、従来品より残留溶媒、残留未反応アルキルフェノールについて大幅に低減された樹脂架橋剤が得られる。 According to the present invention, a resin crosslinking agent having dispersibility, storage of a resin crosslinking agent, rubber crosslinking performance equivalent to that of a conventional product, and greatly reduced residual solvent and residual unreacted alkylphenol than the conventional product is obtained. It is done.
本発明の詳細を、実施例と比較例により本発明を具体的に説明する。本発明はこれらの例によって何ら限定されるものではない。 The details of the present invention will be described specifically by way of examples and comparative examples. The present invention is not limited by these examples.
下記の方法により樹脂架橋剤の評価をおこなった。
「残留溶剤、残留アルキルフェノ−ルの測定」
樹脂架橋剤１ｇに、内部標準物質としてアニソールを０．１ｇ加え、アセトン２０ｍｌに溶解させ、ガスクロマトグラフィーで測定した。
「軟化点の測定」
ＪＩＳ Ｋ２２０７準拠
「耐ブロッキング性の測定」
フレーク状の樹脂架橋剤を口径４cmの円筒に厚さ３cmになるように投入し、上部に厚さ１mm、径４cmのプラッスチック板と３６０gの荷重を載せ、４５℃のオーブン中で一週間静置後にフレーク同士のブロッキング状態の観察を行った。ブロッキング部分が５％以上のものを×とした。
「分散性の測定」
東洋精機ラボプラストミル・ローラーミキサー（チャンバー容量６０cc）を用いて、下記配合のゴムコンパウンド５０ｇを設定温度９０℃、１５分混練で作成した。得られたコンパウンドをロールで厚さ０．５mmにシート成形し、目視で凝集物の有無を観察した。凝集物の無い物を分散性〇とし、凝集物があるものを分散性×とした。
＜配合＞ポリサーブチル４０２ １００重量部
ＳＲＦカーボン ５０重量部
ステアリン酸 １重量部
亜鉛華 ５重量部
樹脂架橋剤 ４０重量部
「オシレーティング・レオメータによる架橋特性の測定」
(株)東洋精機製作所製ロータレスレオメータ使用。
測定温度１８０℃、振幅角度３°で測定。
The resin crosslinking agent was evaluated by the following method.
"Measurement of residual solvent and residual alkylphenol"
0.1 g of anisole as an internal standard substance was added to 1 g of a resin crosslinking agent, dissolved in 20 ml of acetone, and measured by gas chromatography.
"Measurement of softening point"
JIS K2207 compliant "Measurement of blocking resistance"
A flake-shaped resin cross-linking agent is put into a cylinder with a diameter of 4 cm so as to have a thickness of 3 cm. Later, the blocking state of flakes was observed. Those having a blocking portion of 5% or more were evaluated as x.
"Measurement of dispersibility"
Using a Toyo Seiki Lab Plast Mill roller mixer (chamber capacity 60 cc), 50 g of a rubber compound having the following composition was prepared by kneading at a set temperature of 90 ° C. for 15 minutes. The obtained compound was formed into a sheet having a thickness of 0.5 mm with a roll, and the presence or absence of aggregates was visually observed. The thing without an aggregate was made into dispersibility (circle), and the thing with an aggregate was made into dispersibility x.
<Formulation> Polycerbutyl 402 100 parts by weight SRF carbon 50 parts by weight Stearic acid 1 part by weight Zinc white 5 parts by weight Resin cross-linking agent 40 parts by weight "Measurement of cross-linking characteristics with an oscillating rheometer"
Uses a rotary rheometer manufactured by Toyo Seiki Seisakusho.
Measured at a measurement temperature of 180 ° C and an amplitude angle of 3 °.
公知の方法に従って、ホルムアルデヒドとアルキルフェノールの１種であるｐ−オクチルフェノールを原料とし、アルカリ触媒を用いてｐ−オクチルフェノールの残留量が１.０％未満のレゾール型樹脂を合成し、続いてその樹脂のトルエン溶液に、ナフテン系オイルであるコーモレックスＦ２２を樹脂１００重量部に対して１２重量部加えた。その後、減圧下にトルエンを留去して、樹脂架橋剤Ａを得た。
得られた樹脂架橋剤Ａの、残留溶剤量、残留ｐ-オクチルフェノール量、軟化点、ブロッキング性、分散性を測定して表１に記載した。
ポリサー・ブチル４０２（１００重量部）、ＳＲＦカーボン（５０重量部）、ステアリン酸（１重量部）、亜鉛華（５重量部）、樹脂架橋剤Ａ（１２重量部）の配合コンパウンドをロールを用いて通常の混練方法で作成した。得られたコンパウンドのオシレーティング・レオメータによる架橋特性を１８０℃、６０分の条件下に測定し、表２に記載した。
According to a known method, p-octylphenol, which is one of formaldehyde and alkylphenol, is used as a raw material, and a resole type resin having a residual amount of p-octylphenol of less than 1.0% is synthesized using an alkali catalyst. 12 parts by weight of Comolex F22, which is a naphthenic oil, was added to 100 parts by weight of the resin. Thereafter, toluene was distilled off under reduced pressure to obtain a resin crosslinking agent A.
The obtained resin cross-linking agent A was measured for residual solvent amount, residual p-octylphenol amount, softening point, blocking property, and dispersibility, and listed in Table 1.
Using a roll of compounded compound of Policer butyl 402 (100 parts by weight), SRF carbon (50 parts by weight), stearic acid (1 part by weight), zinc white (5 parts by weight), and resin cross-linking agent A (12 parts by weight) And prepared by a conventional kneading method. The resulting compound was measured for cross-linking properties with an oscillating rheometer at 180 ° C. for 60 minutes and listed in Table 2.
コーモレックスＦ２２の配合量を８重量部に変更する以外は実施例１と同様にして樹脂架橋剤Ｂを合成した。得られた樹脂Ｂの残留溶剤量、残留ｐ-オクチルフェノール量、軟化点、ブロッキング性、分散性、オシレーティング・レオメータによる架橋特性を実施例１と同様にして測定した結果を表１〜２に示した。 Resin crosslinking agent B was synthesized in the same manner as in Example 1 except that the amount of Comolex F22 was changed to 8 parts by weight. Tables 1 and 2 show the results of measuring the amount of residual solvent, the amount of residual p-octylphenol, the softening point, blocking properties, dispersibility, and crosslinking characteristics with an oscillating rheometer in the same manner as in Example 1. It was.
コーモレックスＦ２２の配合量を４重量部に変更する以外は実施例１と同様にして樹脂架橋剤Ｃを合成した。得られた樹脂Ｃの残留溶剤量、残留ｐ-オクチルフェノール量、軟化点、ブロッキング性、分散性、オシレーティング・レオメータによる架橋特性を実施例１と同様にして測定した結果を表１〜２に示した。 Resin crosslinking agent C was synthesized in the same manner as in Example 1 except that the amount of Comolex F22 was changed to 4 parts by weight. Tables 1 and 2 show the results of measuring the amount of residual solvent, the amount of residual p-octylphenol, the softening point, the blocking property, the dispersibility, and the crosslinking characteristics with an oscillating rheometer in the same manner as in Example 1. It was.
ポリサー・ブチル４０２（８０重量部）、ネオプレンＷＲＴ（２０重量部）、SRFカーボン（５０重量部）、ステアリン酸（１重量部）、亜鉛華（５重量部）、樹脂架橋剤Ｂ（１２重量部）のコンパウンドを実施例１と同様にして作成し、オシレーティング・レオメータによる架橋特性を実施例１と同様にして測定した結果を表２に示した。 Policer butyl 402 (80 parts by weight), neoprene WRT (20 parts by weight), SRF carbon (50 parts by weight), stearic acid (1 part by weight), zinc white (5 parts by weight), resin crosslinking agent B (12 parts by weight) ) Was prepared in the same manner as in Example 1, and the results of measuring the crosslinking characteristics with an oscillating rheometer in the same manner as in Example 1 are shown in Table 2.
（比較例１）
コーモレックスＦ２２を配合しない以外は実施例１と同様にして樹脂架橋剤Ｄを合成した。得られた樹脂Ｄの残留溶剤量、残留ｐ-オクチルフェノール量、軟化点、ブロッキング性、分散性を実施例１と同様にして測定した結果を表１に示した。
(Comparative Example 1)
Resin crosslinking agent D was synthesized in the same manner as in Example 1 except that Comorex F22 was not blended. Table 1 shows the results obtained by measuring the residual solvent amount, residual p-octylphenol amount, softening point, blocking property, and dispersibility of the obtained resin D in the same manner as in Example 1.
（比較例２）
コーモレックスＦ２２の配合量を２０重量部に変更する以外は実施例１と同様にして樹脂架橋剤Ｅを合成した。得られた樹脂Ｅの残留溶剤量、残留ｐ-オクチルフェノール量、軟化点、ブロッキング性、分散性、を実施例１と同様にして測定した結果を表１に示した。
(Comparative Example 2)
Resin crosslinking agent E was synthesized in the same manner as in Example 1 except that the amount of Comolex F22 was changed to 20 parts by weight. Table 1 shows the results obtained by measuring the residual solvent amount, residual p-octylphenol amount, softening point, blocking property, and dispersibility of the obtained resin E in the same manner as in Example 1.
（比較例３）
樹脂架橋剤Ａ（１２重量部）のかわりに田岡化学工業（株）製レゾール型アルキルフェノール・ホルムアルデヒド共縮合樹脂架橋剤であるＴＡＬ２０１（１２重量部）を用いること以外は実施例１と同様にしてオシレーティング・レオメータによる架橋特性を実施例１と同様にして測定した結果を表２に示した。
(Comparative Example 3)
In the same manner as in Example 1 except that TAL201 (12 parts by weight) which is a resol type alkylphenol-formaldehyde cocondensation resin crosslinking agent manufactured by Taoka Chemical Industries, Ltd. is used instead of the resin crosslinking agent A (12 parts by weight). Table 2 shows the results of measuring the cross-linking characteristics with a rating rheometer in the same manner as in Example 1.
Ｔ（１０）：加硫曲線から求められた、トルクの最大値と最小値との差の１０％に 達するまでの時間（分）
Ｔ（９０）：加硫曲線から求められた、トルクの最大値と最小値との差の９０％に
達するまでの時間（分）
ＭＬ ：加硫曲線から求められた、トルクの最小値（ｋｇ・ｃｍ）
ＭＨ ：加硫曲線から求められた、トルクの最大値（ｋｇ・ｃｍ）
T (10): Time (minutes) required to reach 10% of the difference between the maximum and minimum torque values obtained from the vulcanization curve
T (90): Time (minutes) required to reach 90% of the difference between the maximum and minimum torque values determined from the vulcanization curve
ML: Minimum torque value (kg · cm) obtained from the vulcanization curve
MH: Maximum value of torque (kg · cm) obtained from vulcanization curve
Claims (3)
3. The resin crosslinking agent according to claim 1, wherein the content of unreacted alkylphenol in the resol type alkylphenol / formaldehyde cocondensation resin is less than 1.0%.
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| JP2004190978A JP4408394B2 (en) | 2004-06-29 | 2004-06-29 | Resol type alkylphenol / formaldehyde co-condensation resin crosslinking agent for rubber |
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| JP2004190978A JP4408394B2 (en) | 2004-06-29 | 2004-06-29 | Resol type alkylphenol / formaldehyde co-condensation resin crosslinking agent for rubber |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006063320A (en) * | 2004-07-27 | 2006-03-09 | Taoka Chem Co Ltd | Resol-type alkylphenol/formaldehyde copolycondensation resin crosslinker |
| JP2006089704A (en) * | 2004-08-27 | 2006-04-06 | Bridgestone Corp | Rubber composition and cross-linked rubber using the same |
| JP2013057060A (en) * | 2011-08-18 | 2013-03-28 | Sumitomo Chemical Co Ltd | Method for producing thermoplastic elastomer composition |
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2004
- 2004-06-29 JP JP2004190978A patent/JP4408394B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006063320A (en) * | 2004-07-27 | 2006-03-09 | Taoka Chem Co Ltd | Resol-type alkylphenol/formaldehyde copolycondensation resin crosslinker |
| JP2006089704A (en) * | 2004-08-27 | 2006-04-06 | Bridgestone Corp | Rubber composition and cross-linked rubber using the same |
| JP2013057060A (en) * | 2011-08-18 | 2013-03-28 | Sumitomo Chemical Co Ltd | Method for producing thermoplastic elastomer composition |
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| JP4408394B2 (en) | 2010-02-03 |
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