JP2012167158A - Butyl rubber composition - Google Patents
Butyl rubber composition Download PDFInfo
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- JP2012167158A JP2012167158A JP2011028157A JP2011028157A JP2012167158A JP 2012167158 A JP2012167158 A JP 2012167158A JP 2011028157 A JP2011028157 A JP 2011028157A JP 2011028157 A JP2011028157 A JP 2011028157A JP 2012167158 A JP2012167158 A JP 2012167158A
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- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 22
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 20
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 20
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 18
- 239000000460 chlorine Substances 0.000 claims abstract description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011787 zinc oxide Substances 0.000 claims abstract description 16
- 235000014692 zinc oxide Nutrition 0.000 claims abstract description 16
- 229920005555 halobutyl Polymers 0.000 claims abstract description 12
- 238000004073 vulcanization Methods 0.000 claims description 28
- 229920001973 fluoroelastomer Polymers 0.000 claims 2
- 238000000465 moulding Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 10
- 229920001971 elastomer Polymers 0.000 abstract description 9
- 239000005060 rubber Substances 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 239000003431 cross linking reagent Substances 0.000 description 13
- 229920005556 chlorobutyl Polymers 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 239000004971 Cross linker Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000006229 carbon black 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
- 230000000704 physical effect Effects 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 238000010059 sulfur vulcanization Methods 0.000 description 3
- -1 butyl halide Chemical class 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 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
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920005557 bromobutyl Polymers 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Abstract
Description
本発明は、ブチルゴム組成物に関する。さらに詳しくは、ハロゲンフリーの加硫物を与え得るブチルゴム組成物に関する。 The present invention relates to a butyl rubber composition. More specifically, the present invention relates to a butyl rubber composition capable of providing a halogen-free vulcanizate.
従来から、電子・電気機器には、塩素、臭素等のハロゲン原子を含む多くの電子部品が使用されており、これらを廃棄するときの燃焼条件によってはダイオキシン等が発生し、環境汚染の原因ともなっている。また、製品を製造する過程においては、ハロゲン原子の含有量によっては、製造設備の劣化といった悪影響が指摘されている。 Conventionally, many electronic components containing halogen atoms such as chlorine and bromine have been used in electronic and electrical equipment. Depending on the combustion conditions when these are discarded, dioxins and the like are generated, causing environmental pollution. ing. Moreover, in the process of manufacturing a product, adverse effects such as deterioration of manufacturing equipment have been pointed out depending on the content of halogen atoms.
このような背景から、国際規格であるIEC(国際電気標準会議)61249-2-21や米国IPC(電子回路工業協会)4101Bにおいて、また国内においては社団法人日本電子回路工業会(JPCA)において、ハロゲンフリーが定義されており、定義されたハロゲンフリーは塩素900ppm以下、臭素900ppm以下、これら両者の合計量が1500ppm以下とされている。 From such a background, in the international standard IEC (International Electrotechnical Commission) 61249-2-21 and American IPC (Electronic Circuits Industry Association) 4101B, and in Japan, the Japan Electronic Circuits Association (JPCA), Halogen-free is defined, and the defined halogen-free is chlorine 900 ppm or less, bromine 900 ppm or less, and the total amount of both is 1500 ppm or less.
また、電子・電気機器に使用される防振ゴムにおいても、IEC61249-2-21に基づくハロゲンフリー材への移行が求められているが、衝撃吸収性、エネルギー吸収性にすぐれた防振部材として有用なブチルゴムは、ポリマー分子あるいは加硫剤にハロゲンを含有するケースが多く、ハロゲンフリーブチルゴムについてのニーズがみられる。 In addition, vibration-proof rubbers used in electronic and electrical equipment are also required to shift to halogen-free materials based on IEC61249-2-21, but as vibration-proof members with excellent shock absorption and energy absorption Useful butyl rubber often contains halogen in the polymer molecule or vulcanizing agent, and there is a need for halogen-free butyl rubber.
ブチルゴムは、ポリマー分子中に塩素や臭素を含まないレギュラーブチルゴム(0.5〜3重量％程度のイソプレンを共重合させたイソブチレン共重合体；以下単にブチルゴムと称する)と塩素化ブチルゴム、臭素化ブチルゴムであるハロゲン化ブチルゴムとに大別される。 The butyl rubber is a regular butyl rubber containing no chlorine or bromine in the polymer molecule (an isobutylene copolymer obtained by copolymerizing about 0.5 to 3% by weight of isoprene; hereinafter simply referred to as butyl rubber), chlorinated butyl rubber, or brominated butyl rubber. Broadly divided into halogenated butyl rubber.
ブチルゴムを用いた場合に選択できる架橋系は、イオウ加硫、サルファードナー(イオウ供与性化合物)加硫、キノイド加硫、樹脂加硫等であるが、電子・電気機器内の金属部品の腐食による導通不良を避けるためにはイオウ加硫、サルファードナー加硫は使えず、キノイド加硫も実用配合上はイオウ加硫促進剤の併用が必要なため使用することができない。一方、ブチルゴムを加硫することができる樹脂、例えば臭素化アルキルフェノール・ホルムアルデヒド縮合体には臭素が含まれており、それだけではハロゲンフリーを達成できない。なお、ゴムポリマー中に塩素または臭素を含まず、過酸化物架橋が可能なポリマーが過去には上市されていたが、現在は市販されていない。 Crosslinking systems that can be selected when butyl rubber is used are sulfur vulcanization, sulfur donor (sulfur donating compound) vulcanization, quinoid vulcanization, resin vulcanization, etc., but due to corrosion of metal parts in electronic and electrical equipment. In order to avoid poor conduction, sulfur vulcanization and sulfur donor vulcanization cannot be used, and quinoid vulcanization cannot be used because it requires a sulfur vulcanization accelerator in combination for practical use. On the other hand, a resin capable of vulcanizing butyl rubber, for example, brominated alkylphenol / formaldehyde condensate, contains bromine and cannot achieve halogen-free alone. A polymer that does not contain chlorine or bromine in the rubber polymer and is capable of peroxide crosslinking has been put on the market in the past, but is not commercially available at present.
一方、ハロゲン化ブチルゴムを用いた場合に選択できる架橋系は、亜鉛華加硫、チウラム加硫、チウラム・チアゾール加硫、チオ尿素加硫、樹脂加硫等であるが、これらいずれの加硫系を選択しても、ゴムポリマー中に塩素あるいは臭素を含むため、それだけではハロゲンフリーを達成できない。 On the other hand, the crosslinking systems that can be selected when using halogenated butyl rubber are zinc white vulcanization, thiuram vulcanization, thiuram / thiazole vulcanization, thiourea vulcanization, resin vulcanization, etc. Even if it is selected, since the rubber polymer contains chlorine or bromine, it cannot be halogen-free by itself.
なお、酸化亜鉛(亜鉛華)については、ハロゲン化ブチルゴムの架橋物に良好な耐熱性が要求される場合には、酸化亜鉛を架橋剤として用いる金属酸化物架橋が好適であるとされているが、酸化亜鉛が配合されたハロゲン化ブチルゴム組成物はスコーチし易く、貯蔵安定性に劣るばかりではなく、押出加工時や加硫成形時に受ける熱処理によってスコーチして硬くなり、以後の加工が不可能になるとされている(特許文献１)。 As for zinc oxide (zinc white), metal oxide cross-linking using zinc oxide as a cross-linking agent is preferred when good heat resistance is required for the cross-linked product of halogenated butyl rubber. In addition, the halogenated butyl rubber composition containing zinc oxide is easy to scorch and is not only inferior in storage stability, but also becomes scorched and hardened by heat treatment applied during extrusion and vulcanization, making subsequent processing impossible. (Patent Document 1).
これらのことから、ブチルゴムの架橋に際して加硫剤としてイオウまたはイオウ供与性化合物を使用しない場合には、ゴムポリマー中か、加硫剤のどちらかに塩素または臭素が必要であるが、実際にはハロゲンフリーブチルゴムは実用化されていない。 From these facts, when sulfur or sulfur donating compound is not used as a vulcanizing agent for butyl rubber cross-linking, chlorine or bromine is required in either the rubber polymer or in the vulcanizing agent. Halogen-free butyl rubber has not been put into practical use.
本発明の目的は、ゴムポリマー中および／または加硫剤に塩素または臭素を含み、ハロゲンフリーの加硫物を与え得るブチルゴム組成物を提供することにある。 An object of the present invention is to provide a butyl rubber composition which can contain a chlorine or bromine in a rubber polymer and / or a vulcanizing agent to give a halogen-free vulcanizate.
かかる本発明の目的は、ブチルゴム97〜85重量％およびハロゲン化ブチルゴム3〜15重量％よりなるブチル系ゴム100重量部に対し、アルキルフェノール・ホルムアルデヒド系縮合体2〜8重量部および亜鉛華3〜25重量部を配合してなるブチルゴム組成物によって達成される。 The object of the present invention is to provide 2 to 8 parts by weight of an alkylphenol / formaldehyde-based condensate and 3 to 25 parts of zinc white based on 100 parts by weight of butyl rubber comprising 97 to 85% by weight of butyl rubber and 3 to 15% by weight of halogenated butyl rubber. This is achieved by a butyl rubber composition containing parts by weight.
本発明に係るブチルゴム組成物は、ゴムポリマー中および加硫剤に塩素または臭素を含んでいるものを用いた場合にあっても、IEC61249-2-21で定義されている塩素900ppm以下、臭素900ppm以下、これら両者の合計量が1500ppm以下というハロゲンフリーを達成せしめている。 The butyl rubber composition according to the present invention is not more than 900 ppm chlorine, 900 ppm bromine as defined in IEC 61249-2-21, even when the rubber polymer and the vulcanizing agent contain chlorine or bromine. In the following, the total amount of these two has achieved a halogen-free of 1500 ppm or less.
ブチルゴムおよびハロゲン化ブチルゴムよりなるブチル系ゴムにおいて、ブチルゴム97〜85重量％、好ましくは95〜90重量％に対し、ハロゲン化ブチルゴムは3〜15重量％、好ましくは5〜10重量％の割合で用いられる。 In a butyl rubber composed of butyl rubber and halogenated butyl rubber, halogenated butyl rubber is used in a proportion of 3 to 15% by weight, preferably 5 to 10% by weight, with respect to 97 to 85% by weight, preferably 95 to 90% by weight of butyl rubber. It is done.
ハロゲン化ブチルゴム量がこれよりも少ない割合で用いられると、ハロゲン量は所望範囲内であってハロゲンフリーとなるが、加硫速度が遅く、加硫度が低いため、離型が困難であり、実用性に欠けるようになる。この場合、例えば臭素化アルキルフェノール・ホルムアルデヒド縮合体である架橋剤をより多く用い、加硫度を上げると離型性の問題はなくなるが、用いられた架橋剤量の影響を受け、臭素量の点で所望範囲を満足されなくなる。一方、ハロゲン化ブチル量をこれよりも多い割合で用いると、ハロゲン化ブチル由来のハロゲン量が多くなり、ハロゲンフリーとしての所望範囲を満足させなくなる。 When the amount of halogenated butyl rubber is used in a proportion smaller than this, the amount of halogen is within the desired range and becomes halogen-free, but because the vulcanization speed is slow and the degree of vulcanization is low, release is difficult, It becomes lacking in practicality. In this case, for example, if more crosslinker, which is a brominated alkylphenol / formaldehyde condensate, is used and the degree of vulcanization is increased, the problem of releasability disappears, but the amount of bromine is affected by the amount of crosslinker used. The desired range cannot be satisfied. On the other hand, when the amount of butyl halide is used in a proportion higher than this, the amount of halogen derived from butyl halide increases and the desired range as halogen-free is not satisfied.
ここで用いられるハロゲン化ブチルゴムは、ブチルゴム中のイソプレン構造部分、具体的には二重結合および／または二重結合に隣接する炭素原子に塩素または臭素を付加または置換反応させた塩素化ブチルゴムまたは臭素化ブチルゴムであり、フェノールホルマリン樹脂、亜鉛華等によって加硫可能である。 The halogenated butyl rubber used herein is a chlorinated butyl rubber or bromine obtained by adding or substituting chlorine or bromine to an isoprene structure portion in butyl rubber, specifically, a double bond and / or a carbon atom adjacent to the double bond. Butyl rubber, which can be vulcanized with phenol formalin resin, zinc white or the like.
ブチルゴムおよびハロゲン化ブチルゴムの所定割合のブレンド物であるブチル系ゴムには、それの100重量部当り2〜8重量部、好ましくは4〜6重量部のアルキル・ホルムアルデヒド系縮合体および3〜25重量部、好ましくは5〜20重量部の亜鉛華(ZnO)が架橋剤として配合されて用いられる。 The butyl rubber, which is a blend of a predetermined proportion of butyl rubber and halogenated butyl rubber, has 2 to 8 parts by weight, preferably 4 to 6 parts by weight of alkyl-formaldehyde condensate and 3 to 25 parts by weight per 100 parts by weight thereof. Parts, preferably 5 to 20 parts by weight of zinc white (ZnO) are used as a crosslinking agent.
アルキル・ホルムアルデヒド系縮合体としては、アルキルフェノール・ホルムアルデヒド縮合体、臭素化アルキルフェノール・ホルムアルデヒド縮合体等が用いられ、実際には市販品、例えば前者としては田岡化学工業製品Tackirol 201、201MB35(ブチルゴムマスターバッチ)、202等が、また後者としてはTackirol 250-I、250-III等がそのまま用いられる。上記規定された割合以上でアルキル・ホルムアルデヒド系縮合体、特に臭素化アルキルフェノール・ホルムアルデヒド縮合体を架橋剤として用いた場合には、前記した如くハロゲンフリーとしての所望範囲を満足させなくなる。一方、これよりも少ない割合でこの架橋剤を用いると、加硫度が低くなり、離型が困難となる。 As the alkyl-formaldehyde condensate, alkylphenol-formaldehyde condensate, brominated alkylphenol-formaldehyde condensate, etc. are used. 202, etc., and as the latter, Tackirol 250-I, 250-III, etc. are used as they are. When an alkyl / formaldehyde-based condensate, particularly a brominated alkylphenol / formaldehyde condensate, is used as a cross-linking agent in the above-specified ratio or more, the desired range as halogen-free cannot be satisfied as described above. On the other hand, when this cross-linking agent is used in a proportion smaller than this, the degree of vulcanization becomes low and release becomes difficult.
亜鉛華については、これを架橋剤として併用する場合、これよりも多い割合で亜鉛華を用いると、常態物性の低下がみられ、一方これよりも少ない割合で用いると、加硫速度が遅くなるばかりではなく、受酸剤の役割を果たさなくなり、金型の腐食を招くようになる。 As for zinc white, when it is used as a cross-linking agent, a decrease in normal physical properties is observed when zinc white is used in a larger proportion, while a vulcanization rate is slow when used in a proportion smaller than this. Not only does it play the role of an acid acceptor, but the mold will be corroded.
以上の各成分を必須成分とする本発明のブチルゴム組成物中には、必要に応じて、ブチルゴムの配合剤として配合されるカーボンブラック、シリカ等の補強剤または充填剤、ステアリン酸等の滑剤、老化防止剤などが配合されて用いられる。 In the butyl rubber composition of the present invention containing the above components as essential components, carbon black, a reinforcing agent or filler such as silica, which is blended as a compounding agent for butyl rubber, a lubricant such as stearic acid, if necessary, Anti-aging agent etc. are blended and used.
ブチルゴム組成物の調製は、2種の架橋剤を除く各成分をニーダ等で混練した後、ニーダ等から排出し、オープンロールを用いて架橋剤を配合することにより行われる。それの加硫は、約160〜200℃で約3〜20分間行われるプレス加硫および必要に応じて行われるオーブン加硫(二次加硫)によって行われ、電子・電気機器用電子部品、例えば防振マウント等が加硫成形される。 Preparation of the butyl rubber composition is carried out by kneading each component except for the two kinds of crosslinking agents with a kneader and the like, then discharging from the kneader and blending the crosslinking agent using an open roll. The vulcanization is performed by press vulcanization performed at about 160 to 200 ° C. for about 3 to 20 minutes and oven vulcanization (secondary vulcanization) performed as necessary, and electronic parts for electronic and electrical equipment, For example, a vibration-proof mount or the like is vulcanized.
次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
実施例１
塩素化ブチルゴム(エクソンモービル社製品HT10-66) 5重量部
ブチルゴム(JSR製品365) 95 〃
N990カーボンブラック 100 〃
ステアリン酸 1 〃
ZnO架橋剤 15 〃
臭素化アルキルフェノール・ホルムアルデヒド縮合体架橋剤 5 〃
(田岡化学工業製品Tackirol 250-III)
上記各成分の内、2種の架橋剤を除く各成分を3Lニーダで20分間混練した後、ニーダから排出し、10インチオープンロールを用いて架橋剤を配合してブチルゴム組成物を調製した。
Example 1
Chlorinated butyl rubber (ExxonMobil product HT10-66) 5 parts by weight Butyl rubber (JSR product 365) 95 部
N990 carbon black 100 〃
Stearic acid 1 〃
ZnO crosslinker 15 〃
Brominated alkylphenol / formaldehyde condensate crosslinker 5 〃
(Taoka Chemical Product Tackirol 250-III)
Among the above components, each component except for the two types of crosslinking agents was kneaded with a 3 L kneader for 20 minutes, then discharged from the kneader, and a butyl rubber composition was prepared by blending the crosslinking agent using a 10 inch open roll.
得られたブチルゴム組成物を180℃で8分間プレス加硫し、さらに120℃で20時間オーブン加硫(二次加硫)を行って、厚さ2mmのシートを得た。このシートについて、次の各項目の評価、測定を行った。
離型性：離型のし易さを評価し、シートが破断せず、冷却後に変形しないものを○
、シートが破断し、または冷却後に変形するものを×と評価した
常態物性：JIS K6253、K6251準拠
ハロゲン量：BS EN 1458に準拠して、塩素量および臭素量を測定
(加熱した石英燃焼管中に酸素を導入して加硫テストピースを燃焼さ
せ、生成した燃焼ガスをNaOH水溶液よりなる吸収液中に吸収し、こ
の吸収液をイオンクロマトグラフにて分別定量した)
The resulting butyl rubber composition was press vulcanized at 180 ° C. for 8 minutes, and further oven vulcanized (secondary vulcanization) at 120 ° C. for 20 hours to obtain a sheet having a thickness of 2 mm. About this sheet | seat, the following each item was evaluated and measured.
Releasability: Evaluates ease of release, and the sheet does not break and does not deform after cooling
, The sheet was broken or deformed after cooling was evaluated as x Normal physical properties: JIS K6253, K6251 conformity Halogen content: Chlorine and bromine content were measured according to BS EN 1458
(Oxygen is introduced into the heated quartz combustion tube to burn the vulcanized test piece.
The generated combustion gas is absorbed in an absorbing solution consisting of NaOH aqueous solution.
The absorption solution was fractionated and determined by ion chromatography)
実施例２
実施例１において、塩素化ブチルゴム量を10重量部に、またブチルゴム量を90重量部にそれぞれ変更した。
Example 2
In Example 1, the amount of chlorinated butyl rubber was changed to 10 parts by weight, and the amount of butyl rubber was changed to 90 parts by weight.
比較例１
実施例１において、塩素化ブチルゴム量を20重量部に、またブチルゴム量を80重量部にそれぞれ変更した。
Comparative Example 1
In Example 1, the amount of chlorinated butyl rubber was changed to 20 parts by weight, and the amount of butyl rubber was changed to 80 parts by weight.
比較例２
実施例１において、塩素化ブチルゴムを用いず、ブチルゴム量が100重量部に変更された。
Comparative Example 2
In Example 1, chlorinated butyl rubber was not used, and the amount of butyl rubber was changed to 100 parts by weight.
比較例３
比較例２において、架橋剤量10重量部に変更された。
Comparative Example 3
In Comparative Example 2, the amount of the crosslinking agent was changed to 10 parts by weight.
比較例４
比較例２において、架橋剤が用いられなかった。加硫は、行われなかった。
Comparative Example 4
In Comparative Example 2, no crosslinking agent was used. Vulcanization was not performed.
比較例５
実施例１において、ブチルゴムおよび架橋剤が用いられず、塩素化ブチルゴム量が100重量部に変更された。
Comparative Example 5
In Example 1, butyl rubber and a crosslinking agent were not used, and the amount of chlorinated butyl rubber was changed to 100 parts by weight.
以上の各実施例および比較例で得られた結果は、N990カーボンブラック(100重量部)、ステアリン酸(1重量部)およびZnO(15重量部)を除くブチルゴム組成物の配合量(重量部)と共に、次の表に示される。
表
実施例 比較例
１ ２ １ ２ ３ ５
〔ブチルゴム組成物〕
塩素化ブチルゴム 5 10 20 − − 100
ブチルゴム 95 90 80 100 100 −
架橋剤 5 5 5 5 10 −
〔評価・測定結果〕
離型性 ○ ○ ○ × ○ ○
常態物性
硬さ (Duro A)瞬間 60 60 61 61 62 60
引張強さ (MPa) 8.8 9.7 9.2 7.9 8.5 8.2
破断時伸び (％) 510 470 490 600 500 740
ハロゲン量
塩素 (ppm) 295 570 1100 0 0 3980
臭素 (ppm) 590 600 605 580 1100 0
合計量 (ppm) 885 1170 1705 580 1100 3980
The results obtained in each of the above examples and comparative examples are as follows: N990 carbon black (100 parts by weight), stearic acid (1 part by weight) and butyl rubber composition excluding ZnO (15 parts by weight) (parts by weight) In addition, it is shown in the following table.
table
Example Comparative Example
1 2 1 2 3 5
[Butyl rubber composition]
Chlorinated butyl rubber 5 10 20 − − 100
Butyl rubber 95 90 80 100 100 −
Cross-linking agent 5 5 5 5 10 −
[Evaluation and measurement results]
Releasability ○ ○ ○ × ○ ○
Normal physical properties
Hardness (Duro A) Moment 60 60 61 61 62 60
Tensile strength (MPa) 8.8 9.7 9.2 7.9 8.5 8.2
Elongation at break (%) 510 470 490 600 500 740
Halogen content
Chlorine (ppm) 295 570 1100 0 0 3980
Bromine (ppm) 590 600 605 580 1100 0
Total amount (ppm) 885 1170 1705 580 1100 3980
以上の結果から、次のようなことがいえる。
(1) 各実施例の場合には、離型性からみて加硫速度も速く、ハロゲン量も所望範囲内である。
(2) 比較例１では、塩素量が1100ppmであり、所望範囲(900ppm以下)を満足させない。
(3) 比較例２では、ハロゲン量は所望範囲内であるが、加硫速度が遅く、加硫度が低いため、離型が困難であり、実用的ではない。
(4) 比較例３では、臭素量が1100ppmであり、所望範囲(900ppm以下)を満足させない。
(5) 比較例４では、ブチルゴムの亜鉛華加硫が行われない。
(6) 比較例５では、塩素化ブチルゴムの亜鉛華加硫は行われるが、塩素量が3980ppmとなり、所望範囲を満足させない。
From the above results, the following can be said.
(1) In each example, the vulcanization rate is high from the viewpoint of releasability, and the halogen content is within the desired range.
(2) In Comparative Example 1, the amount of chlorine is 1100 ppm, which does not satisfy the desired range (900 ppm or less).
(3) In Comparative Example 2, the halogen content is in the desired range, but the vulcanization speed is slow and the vulcanization degree is low, so that it is difficult to release the mold, which is not practical.
(4) In Comparative Example 3, the bromine content is 1100 ppm, which does not satisfy the desired range (900 ppm or less).
(5) In Comparative Example 4, zinc vulcanization of butyl rubber is not performed.
(6) In Comparative Example 5, chlorinated butyl rubber is subjected to zinc white vulcanization, but the chlorine content is 3980 ppm, which does not satisfy the desired range.
Claims (4)
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09157466A (en) * | 1995-12-07 | 1997-06-17 | Fujikura Rubber Ltd | Rubber composition |
| JPH1180444A (en) * | 1997-09-08 | 1999-03-26 | Jsr Corp | Thermoplastic elastomer composition and stopper for medical container |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09157466A (en) * | 1995-12-07 | 1997-06-17 | Fujikura Rubber Ltd | Rubber composition |
| JPH1180444A (en) * | 1997-09-08 | 1999-03-26 | Jsr Corp | Thermoplastic elastomer composition and stopper for medical container |
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