JP4764014B2 - Rubber composition and crosslinked rubber using the same - Google Patents
Rubber composition and crosslinked rubber using the same Download PDFInfo
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- JP4764014B2 JP4764014B2 JP2005007474A JP2005007474A JP4764014B2 JP 4764014 B2 JP4764014 B2 JP 4764014B2 JP 2005007474 A JP2005007474 A JP 2005007474A JP 2005007474 A JP2005007474 A JP 2005007474A JP 4764014 B2 JP4764014 B2 JP 4764014B2
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- 229920001971 elastomer Polymers 0.000 title claims description 101
- 239000000203 mixture Substances 0.000 title claims description 50
- 229920005989 resin Polymers 0.000 claims description 90
- 239000011347 resin Substances 0.000 claims description 90
- 239000003431 cross linking reagent Substances 0.000 claims description 66
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 63
- 239000003921 oil Substances 0.000 claims description 35
- 238000004132 cross linking Methods 0.000 claims description 13
- 229920003987 resole Polymers 0.000 claims description 13
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000010692 aromatic oil Substances 0.000 claims description 3
- 239000010690 paraffinic oil Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 description 12
- 238000003912 environmental pollution Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 7
- 238000009833 condensation Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000010734 process oil Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 4
- 235000005956 Cosmos caudatus Nutrition 0.000 description 4
- 229920005549 butyl rubber Polymers 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920001084 poly(chloroprene) Polymers 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- 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
- 239000006229 carbon black Substances 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
- 229940118056 cresol / formaldehyde Drugs 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000002808 molecular sieve Substances 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
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000000717 retained effect 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
- 238000003860 storage Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- Y02T10/862—
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ゴム組成物及び該ゴム組成物を架橋してなる架橋ゴムに関し、特に環境汚染を引き起こすことがなく、切断時伸び及び引張応力等の力学特性に優れたゴム組成物に関するものである。 The present invention relates to a rubber composition and a crosslinked rubber obtained by crosslinking the rubber composition, and particularly relates to a rubber composition that does not cause environmental pollution and has excellent mechanical properties such as elongation at break and tensile stress. .
従来、タイヤの加硫工程においては、タイヤ加硫用ブラダーに高温高圧ガス、蒸気又は温水の充填と排気とを交互に繰り返すため、ブラダー用ゴム組成物のゴム成分には、主としてブチルゴム（ＩＩＲ）が使用されている。これは、ブチルゴムがポリマーとして化学的に安定性が高く、耐熱性、耐候性、耐オゾン性に優れた性質を有する上、他の種類のゴムとの離型性にも優れているためである。そして、上記ブチルゴムを主成分とするブラダー用ゴム組成物には、一般的に、架橋剤としてレゾール型のアルキルフェノール・ホルムアルデヒド共縮合樹脂が使用されている（特許文献１及び２参照）。 Conventionally, in the tire vulcanization process, filling of tire high temperature high pressure gas, steam or hot water and exhaust is alternately repeated in the tire vulcanization bladder, so that the rubber component of the rubber composition for the bladder is mainly butyl rubber (IIR). Is used. This is because butyl rubber is chemically stable as a polymer, has excellent heat resistance, weather resistance, ozone resistance, and is excellent in releasability from other types of rubber. . In the bladder rubber composition containing butyl rubber as a main component, a resol-type alkylphenol-formaldehyde cocondensation resin is generally used as a crosslinking agent (see Patent Documents 1 and 2).
しかしながら、上記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、ゴム成分ヘの分散性が悪い。ここで、該樹脂の分散性を向上させるには、ゴム組成物の混練温度を上昇させることが好ましいが、混練温度を120℃以上にすると、混練中にゴム成分の架橋反応が進行して、均一なゴム組成物が得られなくなる。そのため、上記架橋剤としては、ゴム成分への分散性と架橋反応開始温度とのバランスから、軟化点が115℃以下のものが一般的に用いられている。 However, the resol type alkylphenol / formaldehyde cocondensation resin has poor dispersibility in the rubber component. Here, in order to improve the dispersibility of the resin, it is preferable to increase the kneading temperature of the rubber composition. However, when the kneading temperature is 120 ° C. or higher, the crosslinking reaction of the rubber component proceeds during the kneading, A uniform rubber composition cannot be obtained. For this reason, as the crosslinking agent, those having a softening point of 115 ° C. or lower are generally used in view of the balance between dispersibility in the rubber component and the crosslinking reaction initiation temperature.
また、近年、環境汚染の防止が社会的課題となっており、上記ブラダーをはじめとするゴム製品中の不純物、残留原材料、残留溶剤の削減が求められている。ここで、ゴム製品中の架橋剤に由来する不純物及び残留原材料を削減するには、架橋剤の原材料であるアルキルフェノールを削減することが有効であるが、この場合、架橋剤の軟化点が上昇してしまう。そして、軟化点の高い架橋剤はゴム成分への分散性が悪いため、最終的に得られるゴム製品のゴム物性が低下するという問題が発生する。 In recent years, prevention of environmental pollution has become a social issue, and reduction of impurities, residual raw materials, and residual solvents in rubber products including the bladder is required. Here, in order to reduce impurities and residual raw materials derived from the crosslinking agent in the rubber product, it is effective to reduce alkylphenol, which is the raw material of the crosslinking agent, but in this case, the softening point of the crosslinking agent increases. End up. And since the crosslinking agent with a high softening point has a bad dispersibility to a rubber component, the problem that the rubber physical property of the rubber product finally obtained falls.
そこで、本発明の目的は、上記従来技術の問題を解決し、環境汚染を引き起こすことがなく、十分なゴム物性を有するゴム組成物を提供することにある。また、本発明の他の目的は、かかるゴム組成物を用いた架橋ゴム、特にタイヤ加硫用ブラダーを提供することにある。 Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art and to provide a rubber composition having sufficient rubber properties without causing environmental pollution. Another object of the present invention is to provide a crosslinked rubber, particularly a tire vulcanization bladder, using such a rubber composition.
本発明者らは、上記目的を達成するために鋭意検討した結果、原料のアルキルフェノール残留量が少なく、オイル及び／又は可塑剤を所定量含有す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架橋剤をゴム組成物に用いることで、原料のアルキルフェノールに起因する環境汚染を防止することができ、更に、該樹脂架橋剤の軟化点が低く、ゴム成分への分散性が良好なため、得られるゴム組成物のゴム物性の低下を防止できることを見出し、本発明を完成させるに至った。 As a result of intensive studies to achieve the above object, the present inventors have found that a resol type alkylphenol / formaldehyde cocondensation resin crosslinking agent containing a predetermined amount of oil and / or plasticizer with a small amount of residual alkylphenol as a raw material is a rubber composition. By using the product, it is possible to prevent environmental pollution caused by the raw material alkylphenol, and since the resin crosslinking agent has a low softening point and good dispersibility in the rubber component, It has been found that deterioration of rubber physical properties can be prevented, and the present invention has been completed.
即ち、本発明のゴム組成物は、ゴム成分100質量部に対して、樹脂架橋剤2〜25質量部を配合してなり、
前記樹脂架橋剤が、オイルを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100質量部に対して1〜30質量部含有し且つ軟化点が85〜115℃であ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架橋剤であり、
前記ゴム成分がイソブチレン・ｐ-メチルスチレン共重合体である
ことを特徴とする。
That is, the rubber composition of the present invention comprises 2 to 25 parts by mass of a resin crosslinking agent with respect to 100 parts by mass of the rubber component.
The resin crosslinking agent, oil in resol type alkylphenol-formaldehyde co-condensed resin crosslinking agent is a and softening point containing from 1 to 30 parts by weight per 100 parts by weight resol type alkylphenol-formaldehyde co-condensed resin 85 to 115 ° C. Yes,
The rubber component is an isobutylene / p-methylstyrene copolymer .
本発明のゴム組成物の好適例においては、前記樹脂架橋剤中のオイルがナフテン系オイルである。この場合、オイルと、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成分との相溶性が良好である。 In a preferred example of the rubber composition of the present invention, the oil in the resin crosslinking agent is a naphthenic oil. In this case, the compatibility of the oil with the resol type alkylphenol / formaldehyde cocondensation resin and the rubber component is good.
本発明のゴム組成物の他の好適例においては、前記樹脂架橋剤中の未反応アルキルフェノールの含有量が1％未満である。この場合、架橋剤に起因する環境汚染を十分に防止することができる。 In another preferred embodiment of the rubber composition of the present invention, the content of unreacted alkylphenol in the resin crosslinking agent is less than 1%. In this case, environmental pollution caused by the crosslinking agent can be sufficiently prevented.
また、本発明の架橋ゴムは、上記ゴム組成物を架橋してなることを特徴とし、ブラダー用として特に好ましい。 The crosslinked rubber of the present invention is characterized by being formed by crosslinking the rubber composition, and is particularly preferable for use in a bladder.
本発明によれば、オイルを所定量含有す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架橋剤を配合してなり、環境汚染を引き起こすことがなく、十分なゴム物性を有するゴム組成物、並びに該ゴム組成物を用いた架橋ゴムを提供することができる。 According to the present invention, a resol-type alkylphenol-formaldehyde cocondensation resin crosslinking agent containing a predetermined amount of oil is blended, and a rubber composition having sufficient rubber properties without causing environmental pollution, and the rubber composition A crosslinked rubber using the product can be provided.
以下に、本発明を詳細に説明する。本発明のゴム組成物は、ゴム成分に対して、オイルを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100質量部に対して1〜30質量部含有し且つ軟化点が85〜115℃であ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架橋剤を配合してなることを特徴とする。本発明のゴム組成物においては、オイルを特定量含有し、特定範囲の軟化点を有する樹脂架橋剤を用いるため、樹脂架橋剤のゴム成分への分散性が良好であり、得られるゴム組成物の物性が良好である。 The present invention is described in detail below. The rubber composition of the present invention comprises a resol-type alkylphenol containing 1 to 30 parts by mass of oil to 100 parts by mass of a resol-type alkylphenol / formaldehyde cocondensation resin and having a softening point of 85 to 115 ° C. -It is characterized by containing a formaldehyde co-condensation resin crosslinking agent. In the rubber composition of the present invention, since a resin cross-linking agent containing a specific amount of oil and having a softening point in a specific range is used, the dispersibility of the resin cross-linking agent in the rubber component is good, and the resulting rubber composition Good physical properties.
上記樹脂架橋剤は、オイルと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を含み、該樹脂架橋剤中のオイルの含有量は、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100質量部に対して１〜30質量部の範囲であることを要し、2〜25質量部の範囲であることが好ましい。樹脂架橋剤中のオイルの含有量が1質量部未満では、樹脂架橋剤の軟化点が低くならず、樹脂架橋剤のゴム成分への分散性が悪化し、一方、30質量部を超えると、架橋ゴムの硬度が低下したり、圧縮永久歪が増大する等の問題が発生する。 The resin crosslinking agent contains oil and a resol type alkylphenol / formaldehyde cocondensation resin, and the content of oil in the resin crosslinking agent is 1 to 30 masses per 100 parts by mass of the resole type alkylphenol / formaldehyde cocondensation resin. It is necessary to be in the range of 2 parts by weight, and is preferably in the range of 2 to 25 parts by weight. If the content of oil in the resin cross-linking agent is less than 1 part by mass, the softening point of the resin cross-linking agent does not become low, and the dispersibility of the resin cross-linking agent in the rubber component deteriorates. Problems such as a decrease in hardness of the crosslinked rubber and an increase in compression set occur.
本発明のゴム組成物に用いる樹脂架橋剤は、軟化点が85〜115℃であることを要し、軟化点が90〜110℃の範囲にあることが好ましい。樹脂架橋剤の軟化点が85℃未満では、樹脂架橋剤の保管中に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同士の互着が生じ易いため、樹脂架橋剤を低温で保管しなければならず、115℃を超えると、ゴム成分への分散性が悪く、また、分散性を改善するために混練温度を上昇させると、混練中に架橋反応が始まってしまい、均一なゴム組成物が得られなくなる。 The resin cross-linking agent used in the rubber composition of the present invention requires a softening point of 85 to 115 ° C, and preferably has a softening point in the range of 90 to 110 ° C. When the softening point of the resin cross-linking agent is less than 85 ° C., resol-type alkylphenol / formaldehyde co-condensation resins tend to adhere to each other during storage of the resin cross-linking agent, so the resin cross-linking agent must be stored at a low temperature, 115 When the temperature exceeds ℃, the dispersibility in the rubber component is poor, and when the kneading temperature is raised to improve the dispersibility, a crosslinking reaction starts during the kneading and a uniform rubber composition cannot be obtained.
上記樹脂架橋剤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することができる。ここで、該共縮合樹脂の原料であるアルキルフェノールにおいて、アルキル基の炭素数は１〜２０の範囲が好ましい。また、該共縮合樹脂は、ポリスチレン換算重量平均分子量が2000〜5000であることが好ましい。 The resol-type alkylphenol / formaldehyde cocondensation resin used for the resin cross-linking agent can be synthesized by a known method described in Plastic Material Course 15 “Phenolic Resin” (published by Nikkan Kogyo Shimbun). Here, in the alkylphenol which is the raw material of the cocondensation resin, the carbon number of the alkyl group is preferably in the range of 1-20. The cocondensation resin preferably has a polystyrene-equivalent weight average molecular weight of 2,000 to 5,000.
上記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して、具体的には、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。これら共縮合樹脂は、一種単独で用いてもよいし、二種以上を混合して用いてもよい。 Specific examples of the resol type alkylphenol / formaldehyde cocondensation resin include cresol / formaldehyde cocondensation resin, ethylphenol / formaldehyde cocondensation resin, butylphenol / formaldehyde cocondensation resin, octylphenol / formaldehyde cocondensation resin, butylphenol / octylphenol / formaldehyde Examples include co-condensation resins. These cocondensation resins may be used alone or in combination of two or more.
上記樹脂架橋剤に用いられるオイルとしては、特に制限はなく、ナフテン系オイル、パラフィン系オイル、芳香族系オイル等を用いることができるが、これらオイルの中でも、上記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成分との相溶性に優れる点で、ナフテン系オイルが好ましい。これらオイルは、一種単独で用いてもよいし、二種以上を混合して用いてもよい。 The oil used for the resin crosslinking agent is not particularly limited, and naphthenic oil, paraffinic oil, aromatic oil, and the like can be used. Among these oils, the resol type alkylphenol / formaldehyde cocondensation resin is used. Naphthenic oils are preferred because they are excellent in compatibility with the rubber component. These oils may be used alone or in a combination of two or more.
上記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）等が挙げられる。 Examples of the naphthenic oil 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.) Co., Ltd. trade name), Esso Process Oil 725,765 (above, Esso Oil Co., Ltd. trade name), SYNTAC N-40, N-60, N-70, N-75, N-85 (above, Kobe Oil) Chemical Industry Co., Ltd. trade name), shelf rex 371JY, 371N, 451, N-40, 22, 22R, 32R, 100R, 100S, 100SA, 220RS, 220S, 260, 320R, 680 (above, manufactured by Shell Japan Co., Ltd.) Trade name), Kyoishi Process R-50, R-200, R-1000 (trade name made by Nikko Kyoishi Co., Ltd.), Sunthen ne) 310,380,410,415,420,430,450,480,3215,4130,4240, Ciro Light R. P. O. (Nippon Sun Oil Co., Ltd. trade name), Komo Rex No. 2, Komo Rex F22 (Nippon Oil Co., Ltd. trade name), Fukkor 1150N, 1400N (Fuji Kosan Co., Ltd. trade name), Mitsubishi 20 ( Mitsubishi Oil Co., Ltd. trade name), Naplex 32, 38 (above, Mobil Sekiyu Co., Ltd. trade name), Petrex PN-3 (Yamabun Yuka Co., Ltd. trade name), and the like.
上記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、三菱石油株式会社製商品名）等が挙げられる。 Examples of the paraffinic oil include Diana process oils PW-32, PW-90, PW-150, PW-380, PS-32, PS-90, PS-430, PX-32, and PX-90. (Trade name made by Co., Ltd.), stanol 40, 43N, 52, 69, 149, LP40, LP69, flexon 845 (above, trade name made by Esso Oil Co., Ltd.), syntax PA-95, PA-100, PA-140 (above , Kobe Oil Chemical Co., Ltd. trade name), Cosmo Process 10, 40, 40C (above, Cosmo Oil Co., Ltd. trade name), Lubflex 26, 100, 400 (above, Shell Japan Corporation trade name), Kyoishi process P-200, P-300, P-500 (above, Nikko Kyoishi Co., Ltd., trade name), Thamper 11 , 115, 120, 130, 150, 180, 2100, 2210, 2280 (above, product names manufactured by Nippon Sun Oil Co., Ltd.), Fukkor P-200, P-400, P-500 (above, products manufactured by Fuji Kosan Co., Ltd.) Name), Mitsubishi 10, Mitsubishi 12 (above, trade name manufactured by Mitsubishi Oil Corporation), and the like.
上記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）等が挙げられる。 Examples of the aromatic oil include Diana Process Oil AC-12, AC-460, AE-24, AE-50, AE-200, AH-16, AH-58 (above, trade name of 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 manufactured by Cosmo Oil Co., Ltd.), Dutrex 729UK, 739 (above, product name manufactured by Shell Japan Co., Ltd.), Kyoishi Process X100-A, X100 (above, product name manufactured by Nippon Mining & Co., Ltd.), JSO Aroma 790 (trade name, manufactured by Nippon San Oil Co., Ltd.), Komolex 300,700 (above, product name manufactured by Nippon Oil Corporation), aroma # 1, # 3, # 5 (trade name, manufactured by Fuji Kosan 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.), and the like.
上記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、特に限定されず、例えば、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、有機溶剤を留去させる方法が最も簡便な方法であるが、上記共縮合樹脂の軟化点以上の温度でオイルと混合する方法を採ってもよい。ここで、混合に有機溶剤を使用した場合、環境汚染を防止する観点から、樹脂架橋剤中に残留する有機溶剤の含有量は、1％未満であることが好ましい。 The method of mixing the resol type alkylphenol / formaldehyde cocondensation resin and oil is not particularly limited. For example, after the oil is uniformly dissolved in the organic solvent solution of the resol type alkylphenol / formaldehyde cocondensation resin, the organic solvent is retained. a method of causing removed by being the most convenient way, may be adopted a method of mixing with oil at a temperature above the softening point of the co-condensation resin. Here, when an organic solvent is used for mixing, the content of the organic solvent remaining in the resin crosslinking agent is preferably less than 1% from the viewpoint of preventing environmental pollution.
本発明のゴム組成物に用いる樹脂架橋剤は、未反応のアルキルフェノールの含有量が1％未満であることが好ましい。樹脂架橋剤中の未反応アルキルフェノールの含有量が1％未満であれば、ゴム組成物及びそれを架橋して得られる架橋ゴム中に残留するアルキルフェノールの量が低く、環境汚染を十分に防止することができる。 The resin crosslinking agent used in the rubber composition of the present invention preferably has an unreacted alkylphenol content of less than 1%. If the content of unreacted alkylphenol in the resin crosslinking agent is less than 1%, the amount of alkylphenol remaining in the rubber composition and the crosslinked rubber obtained by crosslinking it is low, and environmental pollution is sufficiently prevented. Can do.
本発明のゴム組成物に用いるゴム成分は、イソブチレン・ｐ-メチルスチレン共重合体である。ゴム組成物をブラダーに用いる場合、化学的安定性に優れる点で、イソブチレン・ｐ-メチルスチレン共重合体が最も好ましい。ゴム成分がイソブチレン・ｐ-メチルスチレン共重合体であるゴム組成物は、耐熱老化性に特に優れるため、該ゴム組成物をブラダーに適用することで、ブラダーの寿命を大幅に延ばすことができる。 The rubber component used in the rubber composition of the present invention is an isobutylene / p-methylstyrene copolymer . When a rubber composition is used for a bladder, an isobutylene / p-methylstyrene copolymer is most preferable because of excellent chemical stability. Since the rubber composition in which the rubber component is an isobutylene / p-methylstyrene copolymer is particularly excellent in heat aging resistance, the life of the bladder can be greatly extended by applying the rubber composition to the bladder.
本発明のゴム組成物において、上記樹脂架橋剤の配合量は、上記ゴム成分100質量部に対して2〜25質量部の範囲である。樹脂架橋剤の配合量がゴム成分100質量部に対して2質量部未満では、ゴム組成物を十分に架橋することができず、得られる架橋ゴムのゴム物性が低下し、一方、25質量部を超えると、硬度が上がりすぎ、ゴム物性が低下する。 In the rubber composition of the present invention, the amount of the resin crosslinking agent is in the range of 2 to 25 parts by mass with respect to 100 parts by mass of the rubber component. When the blending amount of the resin crosslinking agent is less than 2 parts by mass with respect to 100 parts by mass of the rubber component, the rubber composition cannot be sufficiently crosslinked, and the rubber properties of the resulting crosslinked rubber are lowered, whereas 25 parts by mass If it exceeds, the hardness will increase too much and the physical properties of the rubber will decrease.
本発明のゴム組成物には、上記樹脂架橋剤による架橋反応を促進するために、クロロプレンゴム（ＣＲ）、塩化スズ、ベンゼンスルホン酸、酸化カルシウム、モレキュラーシーブ等の架橋促進剤を配合してもよい。 The rubber composition of the present invention may contain a crosslinking accelerator such as chloroprene rubber (CR), tin chloride, benzenesulfonic acid, calcium oxide, molecular sieve, etc., in order to promote the crosslinking reaction by the resin crosslinking agent. Good.
また、本発明のゴム組成物には、上記樹脂架橋剤、ゴム成分及び架橋促進剤の他に、ゴム工業界で通常使用される配合剤、例えば、カーボンブラック等の充填剤、酸化亜鉛、ステアリン酸、オイル類等を、本発明の目的を害しない範囲内で適宜選択して配合することができ、これら配合剤としては、市販品を好適に使用することができる。なお、上記ゴム組成物は、ゴム成分に、樹脂架橋剤と、必要に応じて適宜選択した各種配合剤とを配合して、混練り、熱入れ、押出等することにより製造することができる。 In addition to the resin crosslinking agent, the rubber component and the crosslinking accelerator, the rubber composition of the present invention includes a compounding agent usually used in the rubber industry, for example, a filler such as carbon black, zinc oxide, stearin. Acids, oils and the like can be appropriately selected and blended within a range that does not impair the object of the present invention, and commercially available products can be suitably used as these blending agents. In addition, the said rubber composition can be manufactured by mix | blending a resin crosslinking agent and the various compounding agents selected suitably as needed to a rubber component, kneading | mixing, heat-inserting, extrusion.
本発明の架橋ゴムは、上述したゴム組成物を架橋してなる。ここで、架橋温度は、特に限定されるものではないが、120〜230℃の範囲が好ましい。また、該架橋ゴムは、各種ゴム製品として使用でき、タイヤ加硫用ブラダーとして特に好適に使用することができる。 The crosslinked rubber of the present invention is obtained by crosslinking the rubber composition described above. Here, the crosslinking temperature is not particularly limited, but is preferably in the range of 120 to 230 ° C. The crosslinked rubber can be used as various rubber products, and can be particularly suitably used as a tire vulcanization bladder.
以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
（樹脂架橋剤Ａの調製）
公知の方法に従って、ホルムアルデヒド及び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残留量が1.0％未満のレゾール型ｐ-オクチルフェノール・ホルムアルデヒド共縮合樹脂を合成した。次に、得られた共縮合樹脂のトルエン溶液に、共縮合樹脂88質量％に対してコウモレックスＦ２２［日本石油株式会社製ナフテン系オイル］12質量％を加えた。その後、減圧下で、トルエンを留去し、樹脂架橋剤Ａを得た。
(Preparation of resin crosslinking agent A)
According to a known method, a resol-type p-octylphenol / formaldehyde co-condensation resin having a residual p-octylphenol content of less than 1.0% was synthesized using formaldehyde and p-octylphenol as raw materials and an alkali catalyst. Next, 12% by mass of Komolex F22 [Naphthenic oil manufactured by Japan Petroleum Corporation] was added to 88% by mass of the cocondensation resin in the toluene solution of the obtained cocondensation resin. Thereafter, toluene was distilled off under reduced pressure to obtain a resin crosslinking agent A.
（樹脂架橋剤Ｂの調製）
コウモレックスＦ２２の配合量を共縮合樹脂92質量％に対して8質量％に変更する以外は上記樹脂架橋剤Ａの調製と同様にして樹脂架橋剤Ｂを調製した。
(Preparation of resin crosslinking agent B)
Resin crosslinking agent B was prepared in the same manner as in the preparation of resin crosslinking agent A, except that the blending amount of Komulex F22 was changed to 8% by mass with respect to 92% by mass of cocondensation resin.
（樹脂架橋剤Ｃの調製）
コウモレックスＦ２２の配合量を共縮合樹脂96質量％に対して4質量％に変更する以外は上記樹脂架橋剤Ａの調製と同様にして樹脂架橋剤Ｃを調製した。
(Preparation of resin crosslinking agent C)
Resin cross-linking agent C was prepared in the same manner as the resin cross-linking agent A, except that the amount of humorex F22 was changed to 4% by mass with respect to 96% by mass of the co-condensation resin.
（樹脂架橋剤Ｄの調製）
コウモレックスＦ２２を配合しない以外は上記樹脂架橋剤Ａの調製と同様にして樹脂架橋剤Ｄを調製した。
(Preparation of resin crosslinking agent D)
Resin cross-linking agent D was prepared in the same manner as the resin cross-linking agent A, except that humorex F22 was not blended.
（樹脂架橋剤Ｅの調製）
コウモレックスＦ２２の配合量を共縮合樹脂80質量％に対して20質量％に変更する以外は上記樹脂架橋剤Ａの調製と同様にして樹脂架橋剤Ｅを調製した。
(Preparation of resin crosslinking agent E)
Resin cross-linking agent E was prepared in the same manner as the resin cross-linking agent A, except that the amount of humorex F22 was changed to 20% by mass with respect to 80% by mass of the co-condensation resin.
上記のようにして得られた樹脂架橋剤Ａ〜Ｅの残留ｐ-オクチルフェノール量及び軟化点を下記の方法で測定し、結果を表１に示した。また、比較のために、田岡化学工業(株)製タッキロール２０１の残留ｐ-オクチルフェノール量及び軟化点を測定し、その結果も表１に示した。 The amount of residual p-octylphenol and the softening point of the resin crosslinking agents A to E obtained as described above were measured by the following methods, and the results are shown in Table 1. For comparison, the amount of p-octylphenol remaining and the softening point of Taccolol 201 manufactured by Taoka Chemical Industry Co., Ltd. were measured, and the results are also shown in Table 1.
（１）残留ｐ-オクチルフェノール量の測定
樹脂架橋剤1gに、内部標準物質としてアニソール0.1gを加え、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。
(1) Measurement of residual p-octylphenol amount 0.1 g of anisole as an internal standard substance was added to 1 g of a resin cross-linking agent, dissolved in 20 mL of acetone, and measured by gas chromatography.
（２）軟化点の測定
ＪＩＳ Ｋ２２０７に準拠して、各樹脂架橋剤の軟化点を測定した。
(2) Measurement of softening point The softening point of each resin crosslinking agent was measured according to JIS K2207.
次に、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、表２に示す配合処方のゴム組成物50gを、設定温度90℃で15分間混練して調製し、得られたゴム組成物をロールで厚さ0.5mmにシート成形し、目視で凝集物の有無を観察した。ここで、シートに凝集物の無いものの分散性を○とし、凝集物があるものの分散性を×とし、評価結果を表２に示した。また、得られたゴム組成物に対して下記の方法で引張試験を行い、結果を表２に示した。 Next, using a Toyo Seiki Lab Plast Mill Roller Mixer (chamber capacity 60 cc), 50 g of a rubber composition having the formulation shown in Table 2 was kneaded for 15 minutes at a set temperature of 90 ° C., and the resulting rubber was obtained. The composition was sheet-formed with a roll to a thickness of 0.5 mm, and the presence or absence of aggregates was visually observed. Here, the dispersibility of the sheet without agglomerates was rated as ◯, the dispersibility of the sheets with agglomerates as x, and the evaluation results are shown in Table 2. Further, the obtained rubber composition was subjected to a tensile test by the following method, and the results are shown in Table 2.
（３）引張試験
ＪＩＳ Ｋ６２５１に準拠して引張試験を行い、190℃で30分間架橋させて得た架橋ゴムの引張強さ（Ｔb）、切断時伸び（Ｅb）、300％伸長時の引張応力（Ｍ300）を測定し、更に初期の引張強さに対する老化後の引張強さの保持率を算出した。なお、架橋ゴムの老化後の引張強さ（Ｔb）は、上記架橋ゴムを、180℃で24時間老化させた後に測定した。
(3) Tensile test Tensile strength (Tb), elongation at break (Eb), and tensile stress at 300% elongation of a crosslinked rubber obtained by performing a tensile test in accordance with JIS K6251 and crosslinking at 190 ° C for 30 minutes. (M 300 ) was measured, and the retention ratio of the tensile strength after aging with respect to the initial tensile strength was calculated. The tensile strength (Tb) after aging of the crosslinked rubber was measured after aging the crosslinked rubber at 180 ° C. for 24 hours.
*1 ＪＳＲ製, Ｂｕｔｙｌ１２６８.
*2 昭和ネオプレン製, ネオプレンＷ.
*3 ＥＸＸＯＮ ＭＯＢＩＬ社製, ＥＸＸＰＲＯ３０３５.
*4 東海カーボン製, シースト６００Ａ.
* 1 Made by JSR, Butyl1268.
* 2 Showa Neoprene, Neoprene W.
* 3 EXXPRO 3035, manufactured by EXXON MOBIL.
* 4 Tokai Carbon, Seast 600A.
表１及び表２から明らかなように、オイルを特定量配合することにより軟化点を85〜115℃にした樹脂架橋剤Ａ〜Ｃを配合した実施例及び参考例のゴム組成物は、タッキロール２０１を配合した比較例３のゴム組成物と同様に凝集物が見られず、樹脂架橋剤のゴム成分への分散性が良好であり、また、引張強さ、切断時伸び、引張応力についても比較例３のゴム組成物と同等であった。なお、樹脂架橋剤Ａ〜Ｃは、タッキロール２０１に比べて、残留するｐ-オクチルフェノールの量が少ないため、実施例及び参考例のゴム組成物をゴム製品に用いることで、環境汚染を防止することができる。 As is clear from Tables 1 and 2, the rubber compositions of Examples and Reference Examples in which resin cross-linking agents A to C having a softening point of 85 to 115 ° C. were blended by blending a specific amount of oil, In the same manner as in the rubber composition of Comparative Example 3 containing No. 1, no agglomerates were observed, the dispersibility of the resin cross-linking agent in the rubber component was good, and the tensile strength, elongation at break, and tensile stress were also compared. It was equivalent to the rubber composition of Example 3. In addition, since resin cross-linking agents A to C have a smaller amount of p-octylphenol remaining than tack roll 201, the rubber compositions of Examples and Reference Examples are used for rubber products to prevent environmental pollution. Can do.
また、参考例１と実施例４との比較から、ゴム成分としてイソブチレン・ｐ-メチルスチレン共重合体を用いることで、老化後の物性の低下を抑制できることが分る。 Moreover, it turns out that the fall of the physical property after aging can be suppressed from the comparison with the reference example 1 and Example 4 by using an isobutylene and p-methylstyrene copolymer as a rubber component.
一方、オイルを含まず、軟化点が高過ぎる樹脂架橋剤Ｄを配合した比較例１のゴム組成物は、樹脂架橋剤のゴム成分への分散性が悪かった。また、オイルを過剰に含み、軟化点が低過ぎる樹脂架橋剤Ｅを配合した比較例２のゴム組成物は、引張応力が低く、ゴムの剛性が低下していた。
On the other hand, the rubber composition of Comparative Example 1 containing no resin and containing a resin crosslinking agent D having a too high softening point had poor dispersibility of the resin crosslinking agent in the rubber component. Further, the rubber composition of Comparative Example 2 containing an excessive amount of oil and a resin cross-linking agent E having a too low softening point had low tensile stress and reduced rubber rigidity.
Claims (6)
前記樹脂架橋剤が、オイルを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100質量部に対して1〜30質量部含有し且つ軟化点が85〜115℃であ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架橋剤であり、
前記ゴム成分がイソブチレン・ｐ-メチルスチレン共重合体である
ことを特徴とするゴム組成物。 It is composed of 2 to 25 parts by mass of a resin cross-linking agent with respect to 100 parts by mass of the rubber component.
The resin crosslinking agent, oil in resol type alkylphenol-formaldehyde co-condensed resin crosslinking agent is a and softening point containing from 1 to 30 parts by weight per 100 parts by weight resol type alkylphenol-formaldehyde co-condensed resin 85 to 115 ° C. Yes,
A rubber composition, wherein the rubber component is an isobutylene / p-methylstyrene copolymer .
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| JP5221623B2 (en) * | 2010-10-27 | 2013-06-26 | 住友ゴム工業株式会社 | Rubber composition for bladder and bladder |
| WO2013146064A1 (en) * | 2012-03-27 | 2013-10-03 | 田岡化学工業株式会社 | Resol type para octyl phenol-formaldehyde cocondensation resin and method for producing same |
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