JPS6151041A - Rubber composition - Google Patents
Rubber compositionInfo
- Publication number
- JPS6151041A JPS6151041A JP59173487A JP17348784A JPS6151041A JP S6151041 A JPS6151041 A JP S6151041A JP 59173487 A JP59173487 A JP 59173487A JP 17348784 A JP17348784 A JP 17348784A JP S6151041 A JPS6151041 A JP S6151041A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- bismaleimide
- sulfide resin
- group
- halogenated butyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims description 18
- 229920001971 elastomer Polymers 0.000 title abstract description 15
- 239000005060 rubber Substances 0.000 title abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 229920005555 halobutyl Polymers 0.000 claims abstract description 14
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000002015 acyclic group Chemical group 0.000 claims abstract description 3
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 abstract description 36
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 abstract description 32
- 238000004073 vulcanization Methods 0.000 abstract description 15
- 239000004636 vulcanized rubber Substances 0.000 abstract description 6
- 238000013329 compounding Methods 0.000 abstract description 5
- COOCXHSGXWAOHD-UHFFFAOYSA-N 3-(2,4,4-trimethylpentan-2-yl)-7-thiabicyclo[4.1.0]hepta-2,4-dien-6-ol Chemical compound C1=CC(C(C)(C)CC(C)(C)C)=CC2SC21O COOCXHSGXWAOHD-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010058 rubber compounding Methods 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 150000003949 imides Chemical class 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 8
- -1 imide compound Chemical class 0.000 description 6
- 229920005556 chlorobutyl Polymers 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- JIQJZNXTUPSVCA-UHFFFAOYSA-N 3-octyl-7-thiabicyclo[4.1.0]hepta-2,4-dien-6-ol Chemical compound C1=CC(CCCCCCCC)=CC2SC21O JIQJZNXTUPSVCA-UHFFFAOYSA-N 0.000 description 2
- DAHNHFFZIVPQRU-UHFFFAOYSA-N 4-nonyl-7-thiabicyclo[4.1.0]hepta-2,4-dien-1-ol Chemical compound C(CCCCCCCC)C1=CC2C(C=C1)(O)S2 DAHNHFFZIVPQRU-UHFFFAOYSA-N 0.000 description 2
- 125000004939 6-pyridyl group Chemical group N1=CC=CC=C1* 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 229920005557 bromobutyl Polymers 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 2
- OFHMODDLBXETIK-UHFFFAOYSA-N methyl 2,3-dichloropropanoate Chemical compound COC(=O)C(Cl)CCl OFHMODDLBXETIK-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- OEUTXEVXKFXZPB-UHFFFAOYSA-N 1-[12-(2,5-dioxopyrrol-1-yl)dodecyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCCCCCCCCCCCN1C(=O)C=CC1=O OEUTXEVXKFXZPB-UHFFFAOYSA-N 0.000 description 1
- PUKLCKVOVCZYKF-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)ethyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCN1C(=O)C=CC1=O PUKLCKVOVCZYKF-UHFFFAOYSA-N 0.000 description 1
- KSNRDYQOHXQKAB-UHFFFAOYSA-N 2,2,4-trimethyl-3,4-dihydro-1h-quinoline Chemical compound C1=CC=C2C(C)CC(C)(C)NC2=C1 KSNRDYQOHXQKAB-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- REEVYFXNAWGHCO-UHFFFAOYSA-N 3-(2-methylbutan-2-yl)-7-thiabicyclo[4.1.0]hepta-2,4-dien-6-ol Chemical compound C1=CC(C(C)(C)CC)=CC2SC21O REEVYFXNAWGHCO-UHFFFAOYSA-N 0.000 description 1
- KXQAVEKAVCNEPJ-UHFFFAOYSA-N 3-tert-butyl-7-thiabicyclo[4.1.0]hepta-2,4-dien-6-ol Chemical compound C1=CC(C(C)(C)C)=CC2SC21O KXQAVEKAVCNEPJ-UHFFFAOYSA-N 0.000 description 1
- DKRSZEMEBAWENC-UHFFFAOYSA-N 4-butyl-7-thiabicyclo[4.1.0]hepta-2,4-dien-1-ol Chemical compound C(CCC)C1=CC2C(C=C1)(O)S2 DKRSZEMEBAWENC-UHFFFAOYSA-N 0.000 description 1
- CGTLMVREWQIWEC-UHFFFAOYSA-N 4-decylphenol Chemical compound CCCCCCCCCCC1=CC=C(O)C=C1 CGTLMVREWQIWEC-UHFFFAOYSA-N 0.000 description 1
- UXKQNCDDHDBAPD-UHFFFAOYSA-N 4-n,4-n-diphenylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 UXKQNCDDHDBAPD-UHFFFAOYSA-N 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はゴム組成物に関し、さらに詳しくは加硫特性が
優れ、しかも耐熱性に優れた加硫ゴムを与えるハロゲン
化ブチルゴム組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a rubber composition, and more particularly to a halogenated butyl rubber composition that provides a vulcanized rubber with excellent vulcanization properties and excellent heat resistance.
ハロゲン化ブチルゴムはゴム分として、それ単独もしく
はそれとジエン系ゴムなどと混合され、加硫剤その他の
配合剤を配合してタイヤのホワイトサイドウオール部、
チェーブレスタイヤのインナーライナ一部などに用いら
れており、近年におけるドライバーのタイヤに対するカ
ラフル化指向、チェーブレス化指向などに併なってその
需要が増大している。Halogenated butyl rubber is used as a rubber component, either alone or mixed with diene rubber, etc., and mixed with a vulcanizing agent and other compounding agents to form the white sidewall part of a tire.
It is used as part of the inner liner of chevronless tires, and the demand for it has increased in recent years as drivers have become more interested in colorful tires and chevronless tires.
従来誹り、かかるハロゲン化ブチルゴム、の加硫剤とし
て、Ｐ−アルキルフェノールと１塩化イオウの反応物で
あるＰ−アルキルフェノールサルファイド樹脂を使用す
ることか知られている（米国特許第８，９６８，０６２
号、第８．９１９゜１７１号）。Conventionally, it has been known to use P-alkylphenol sulfide resin, which is a reaction product of P-alkylphenol and sulfur monochloride, as a vulcanizing agent for such halogenated butyl rubber (U.S. Pat. No. 8,968,062).
No. 8.919゜171).
しかしながら、これらの加仇刑を用いたゴム九
組成物は、加硫両度が遅いため、生産性の面で問題があ
るのみならず加硫して得られた加硫ゴムの物性、特に耐
熱性の点でも充分満足し得るものではなく、これらの問
題点の改良が強く望まれてい１こ。However, rubber compositions using these vulcanization methods have slow vulcanization, which not only poses problems in terms of productivity, but also has problems with the physical properties of the vulcanized rubber, especially heat resistance. It is not fully satisfactory in terms of performance, and improvements in these problems are strongly desired.
このような状況に鑑み、本発明者らは上記問題点を改良
すべく鋭意検討を重ねた結果、ハロゲン化ブチルゴムに
Ｐ−アルキルフェノールサルファイド樹脂と特定のイミ
ド化合物とを共存せしめれば、加硫速度が向上し、しか
も加硫して得られｆコ加硫ゴムの耐熱性が著しく優れる
ことを見出し本発明を完成した。In view of this situation, the inventors of the present invention have made extensive studies to improve the above problems, and have found that if P-alkylphenol sulfide resin and a specific imide compound coexist in halogenated butyl rubber, the vulcanization rate can be increased. The present invention was completed based on the discovery that the heat resistance of the vulcanized rubber obtained by vulcanization is significantly improved.
すなわち本発明は、Ｐ−アルキルフェノールサルファイ
ド樹脂と下記一般式（Ｉ）
（式中、几は２価の非環状脂肪族基、環状脂肪族基、芳
香族基、アルキル芳香族基であって、これらは鎖中また
は側部置換基に０、Ｎ。That is, the present invention provides a P-alkylphenol sulfide resin and the following general formula (I) (wherein, 几 is a divalent acyclic aliphatic group, a cycloaliphatic group, an aromatic group, an alkyl aromatic group, is 0, N in the chain or on a side substituent.
Ｓのようなヘテロ原子を含むことができる。、）で示さ
れるビスマレイミド類とを含有することを特徴とするハ
ロゲン化ブチルゴム組成物を提供するものである。Heteroatoms such as S can be included. The present invention provides a halogenated butyl rubber composition characterized by containing a bismaleimide represented by , ).
本発明の成分の一つであるビスマレイミド類は米国特許
第２，９２５．４０７号に開示されてｔ）るようにパー
オキサイド架橋系における架橋剤として知られているが
、バロゲン化ブチルゴムにビスマレイミド類を単独使用
し１こ場合は加硫速度が遅く、シかも耐熱性の劣りＴコ
加硫コ°ムしか得られなかった。また本発明のもう一つ
の成分であるサルファイド樹脂も、それ単独使用では前
記したように加硫速度、得られた加硫ゴムの耐熱性等の
点で充分満足し得るものではなかった。Bismaleimides, which are one of the components of the present invention, are known as crosslinking agents in peroxide crosslinking systems as disclosed in U.S. Pat. No. 2,925.407. When a maleimide was used alone, the vulcanization rate was slow and the heat resistance was poor, resulting in only a T-co-vulcanized comb. Furthermore, when the sulfide resin, which is another component of the present invention, is used alone, the vulcanization rate and the heat resistance of the obtained vulcanized rubber are not sufficiently satisfactory as described above.
ところが、驚ろくべきことに、ビスマレイミド類とサル
ファイド樹脂とを共存せしめることによって、はじめて
、加硫速度が向上し、ミしかも耐熱性が格段優れた加硫
ゴムを与える／’％ロゲン化ブチルゴム組成物が得られ
γこのである。However, surprisingly, by coexisting bismaleimides and sulfide resin, the vulcanization rate is improved and a vulcanized rubber with significantly superior heat resistance can be obtained. This is what you get.
本発明に使用されるｐ−アルキルフェノールサルレアイ
ド樹脂はｐ−アルキルフェノールと一塩化硫黄との反応
により容易に製造でき、具体的化合物としては、例えば
ｐ−ｔ−ブチルフェノールサルファイド樹脂ｐ−ｔ−ア
ミルフェノールサルファイド樹脂ｐ−ｎ−へブチルフェ
ノールサルファイド樹脂
Ｐ−オクチルフェノールサルファイド樹脂ｐ−ｔ−オク
チルフェノールサルファイド樹脂
ｐ −ｎ−ノニルフェノールサルファイド樹脂Ｐ−デシ
ルフェノールサルファイド樹脂□などが挙げられ、中で
も炭素数８〜９のアルキル基を有するｐ −Ｌ−オクチ
ルフェノールサルファイド樹脂、ｐ−オクチルフェノー
ルサルファイド樹脂、ｐ−ｎ−ノニルフェノールサルフ
ァイド樹ＩＩｉどが好ましい。The p-alkylphenol salleide resin used in the present invention can be easily produced by the reaction of p-alkylphenol and sulfur monochloride, and specific compounds include, for example, p-t-butylphenol sulfide resin p-t-amylphenol Sulfide resin p-n-butylphenol sulfide resin P-octylphenol sulfide resin p-t-octylphenol sulfide resin p -n-nonylphenol sulfide resin P-decylphenol sulfide resin p-L-octylphenol sulfide resin, p-octylphenol sulfide resin, p-n-nonylphenol sulfide resin IIi, etc. having the following are preferred.
まＴこ本発明の一般式（Ｉ）で示されるビスマレイミド
類としては例えば、
Ｎ 、 Ｎ’−エチレンビスマレイミドＮ、Ｎ−ヘキサ
メチレンビスマレイミドＮ、Ｎ’−ドデカメチレンビス
マレイミドＮ、Ｎ −（２，２，４−トリメチル−ヘキ
サメチレン）ビスマレイミド
ＮＩＮ−（オキシ−ジプロピレン〕ビスマレイ ミ
ド
Ｎ、Ｎ−（アミノ−ジプロピレン）ビスマレイ ミ
ド
Ｎ、Ｎ−（エチレン−ジオキシジプロピレン）ビスイミ
ド
Ｎ、Ｎ−（１，４−シクロヘキシレン〕ビスマ゛レイ
ミド
Ｎ 、 Ｎ’□−〔１，８−シクロヘキシレン〕ビスマ
Ｌ／イｌド
Ｎ、’Ｎ’−（メチレン−１，４−ジシク・ヘキシルシ
〕ビスマレイミド
Ｎ、Ｎ”−”（′イソプロピリデンー１，４−ジシクロ
ヘキシレン〕ビスマレイミド
、 Ｎ７−（オキシ−１，４−ジシクロベキシレン）ビ
スマレイミド
Ｎ 、 Ｎ −（ｍ−フェニレン）ビスマレイミド
Ｎ 、 Ｎ −（ｐ−７ｚ ＝ Ｌ’ ：’ ）ビ、、
、７．イ、ドＮ、Ｎ−（ｏ−フェニレン）ビスマレイミ
ドＮ、Ｎ−（１，８−ナフチレン）ビスマレイミド
Ｎ、Ｎ−（１，４−ナフチレン）ビスマレイミド
Ｎ、Ｎ−（１，５−＋７％、＞）？’、、ＷＬ／イミド
エニレン）ビスマレイミド
エニレン）ビスマレイミド
Ｎ、Ｎ −（２，４−ピリジル）ビスマレイミド
Ｎ、Ｎ’−（２，’６−ピリジル）ビスマレイミド
Ｎ 、 Ｎ’ −（４−メチル−２，６−ピリジル）ビ
スマレイミド
Ｎ、Ｎ−（１，４−アントラキノンジイル）ビスマレイ
ミド
Ｎ 、 Ｎ −（ｍ −トリレン）ビスマレイミドＮ、
Ｎ−（Ｐ−トリレン）ビスマレイミドＮ、Ｎ−（４，６
−シメチルー１，３−）ユニしン〕ビスマレイミド
Ｎ、Ｎ−（２，３’）ｉｆ）Ｌｔ−１，４−７ｚニレン
）ビスマレイミド
Ｎ、Ｎ −（４，６−ジクロロ−１，８−フェニレン〕
ビスマレイミド
Ｎ、Ｎ−４５−クロロ−１，ｉ３−フェニレン）ビスマ
レイミド
Ｎ、Ｎ−（５−ヒドロキシ−１，１−フェニレン〕ビス
マレイミド
Ｎ、Ｎ−（５−メトキシ−１，３−）ユニしン〕ビスマ
レイミド
Ｎ 、 Ｎ −（ｍ−キシリレン〕ビスマレイミドＮ、
Ｎ−（ｐ−キシリレン）ビスマレイミドＮ、Ｎ−（メチ
レン−ジーｐ−）よニレン）ビスマレイミド
Ｎ、Ｎ’−（イソプロピリデン−ジーＰ−）ユニしン〕
ビスマレイミド
Ｎ、Ｎ’−（オキシ−ジーｐ−フェニレン〕ビスマレイ
ミド
Ｎ、Ｎ−（チオ−ジーＰ−）ユニしン〕ビスマレイミド
Ｎ、Ｎ’−（ジチオ−ジーｐ−）二二しン）ビスマレイ
ミド
Ｎ、Ｎ−（スルフオージーｐ−フェ０レン）ビスマレイ
ミド
Ｎ、Ｎ−（カルボニル−ジーｐ−フェニレン〕ビスマレ
イミド
などが挙げられる。The bismaleimides represented by the general formula (I) of the present invention include, for example, N,N'-ethylene bismaleimide N, N-hexamethylene bismaleimide N, N'-dodecamethylene bismaleimide N, N- (2,2,4-trimethyl-hexamethylene)bismaleimideNIN-(oxy-dipropylene)bismaleimide
Do-N,N-(amino-dipropylene)bismaleimi
N,N-(ethylene-dioxydipropylene)bisimideN,N-(1,4-cyclohexylene)bisimide
Mido N, N'□-[1,8-cyclohexylene] bismuth L/yldo N, 'N'-(methylene-1,4-disyc-hexylcy) bismaleimide N, N"-"('isopropylidene N-1,4-dicyclohexylene]bismaleimide, N7-(oxy-1,4-dicyclohexylene)bismaleimide N, N-(m-phenylene)bismaleimide N, N-(p-7z = L': ') Bi,,
,7. A, Do N, N-(o-phenylene) bismaleimide N, N-(1,8-naphthylene) bismaleimide N, N-(1,4-naphthylene) bismaleimide N, N-(1,5-+7 %, >)? ',, WL/imidoenylene)bismaleimideenylene)bismaleimide N, N-(2,4-pyridyl)bismaleimide N, N'-(2,'6-pyridyl)bismaleimide N, N'-(4- Methyl-2,6-pyridyl)bismaleimide N, N-(1,4-anthraquinonediyl)bismaleimide N, N-(m-tolylene)bismaleimide N,
N-(P-tolylene)bismaleimide N,N-(4,6
-Simethyl-1,3-)unisine]bismaleimideN,N-(2,3')if)Lt-1,4-7znylene)bismaleimideN,N-(4,6-dichloro-1,8 −Phenylene]
Bismaleimide N,N-45-chloro-1,i3-phenylene)bismaleimide N,N-(5-hydroxy-1,1-phenylene)bismaleimide N,N-(5-methoxy-1,3-)uni Shin] Bismaleimide N, N-(m-xylylene) Bismaleimide N,
N-(p-xylylene) bismaleimide N, N-(methylene-di-p-)ynylene) bismaleimide N, N'-(isopropylidene-di-p-)unisine]
Bismaleimide N,N'-(oxy-di-p-phenylene)bismaleimide N,N-(thio-di-p-)unicine]bismaleimide N,N'-(dithio-di-p-)22cine ) bismaleimide N, N-(sulfo-p-phenylene) bismaleimide N, N-(carbonyl-p-phenylene) bismaleimide, and the like.
本発明のハロゲン化ブチルゴム組成物は上記のようなＰ
−フルキルフェノールサルファイド樹脂とビスマレイミ
ド類とを共存せしめることを特徴とするものであるが、
これらはゴム１００重量部に対してそれぞれ通常０．８
〜８重量部、好ましくは０．５〜２重量部、従来より公
知の種々のゴム用配合剤とともに配合される。ゴムへの
配合は通常の方法、例えばオーブンロール、バンバリー
ミキサ−などを用いて配合され、この場合はサルファイ
ド樹脂とビスマレイミド類は別々に添加しても良く、あ
るいはあらかじめ混合したものを用いても良い。ここで
ハロゲン化ブチルゴムとはクロルブチルゴム、ブロムブ
チルゴムなどであり、本発明のハロゲン化ブチルコム組
成物においては、ゴム分としてハロゲン化ブチルゴム単
独もしくはそれと天然ゴム、ポリイソプレゴム、スチレ
ン・ブタジェン共重合ゴムなどのジエン系ゴムとの混合
物であってもよい。混合物の場合は、ハロゲン化ブチル
ゴムとジエン系ゴムとの比率（重ｌは通常９５１５〜５
０１５０である。The halogenated butyl rubber composition of the present invention has P as described above.
- It is characterized by coexisting a furkylphenol sulfide resin and a bismaleimide,
Each of these is usually 0.8 parts by weight per 100 parts by weight of rubber.
~8 parts by weight, preferably 0.5 to 2 parts by weight, is blended with various conventionally known rubber compounding agents. The compounding into rubber is carried out in the usual manner, such as using an oven roll or a Banbury mixer. In this case, the sulfide resin and bismaleimides may be added separately, or they may be mixed in advance. good. Here, the halogenated butyl rubber includes chlorobutyl rubber, bromobutyl rubber, etc. In the halogenated butyl rubber composition of the present invention, the rubber component may be halogenated butyl rubber alone or in combination with natural rubber, polyisoprene rubber, styrene-butadiene copolymer rubber, etc. It may also be a mixture with other rubbers. In the case of a mixture, the ratio of halogenated butyl rubber and diene rubber (weight 1 is usually 9515 to 5
It is 0150.
また配合剤としては加硫促進剤、老化防止剤、亜鉛華、
プロセスオイル、カーボン、ステアリン酸、炭酸カルシ
ウム、ワックスなどゴム用配合剤として通常使用されて
いるものが挙げられる。加硫促進剤の具体例としてはジ
ベンゾチアジルスルフィド、テトラメチルチウラムジス
ルフィド、ジペンタメチレンチウラムへキサスルフィド
、テトラエチルチウラムジスルフィド、テトラブチルチ
ウラムジスルフィドなどが例示できるが、とりわけジベ
ンゾチアジルジスルフィド、テトラメチルチウラムジス
ルフィド、ジペンタメチレンチウラムへキサスルフィド
等もしくはこれらの混合物が好ましい。In addition, compounding agents include vulcanization accelerators, anti-aging agents, zinc white,
Examples include those commonly used as compounding agents for rubber, such as process oil, carbon, stearic acid, calcium carbonate, and wax. Specific examples of the vulcanization accelerator include dibenzothiazyl sulfide, tetramethylthiuram disulfide, dipentamethylenethiuram hexasulfide, tetraethylthiuram disulfide, and tetrabutylthiuram disulfide, but especially dibenzothiazyl disulfide and tetramethylthiuram. Disulfide, dipentamethylenethiuram hexasulfide, etc. or mixtures thereof are preferred.
また老化防止剤の具体化合物としては、２゜２−メチレ
ンビス（４−メチル−ｅ−ｔ−ブチルフェノール）、４
．４−ブチリテ゛ンビス（８−メチル−６−ｔ−ブチル
フェノール）、４゜４−チオビス（８−メチル−６−ｔ
−ブチルフェノール）、２，６−ジーｔ−ブチルフェノ
ール、フチレン化フェノール、ｎ−オクタデシル８−Ｃ
８，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プ
ロピオネート、ペンタエリスリトール テトラキス（８
−（８−フルキル−５−ｔ ブチル−４−ヒドロキシ
フェニルプロピオネ−））、１１１−ビス（４−ヒドロ
キシフェニル）シクロヘキサンの如きフェノール系安定
剤、オクチル化ジフェニルアミン、ノニル化ジフェニル
アミン、Ｎ、Ｎ−ジフェニル−Ｐ−フェニレンジアミン
、Ｎ−フェニル−Ｎ−イソプロピル−Ｐ−フェニレンジ
アミン、Ｎ−フェニル−Ｎ−１，８−ジメチルブチル−
ｐ−フェニレンジアミン、２，２．４−トリメチルジヒ
ドロキノリン重合物、ジフェニル７ミンと７セトンとの
縮合物、６−ニトキシー２．２．４−トリメチル−１，
２−ジヒドロキノリンの如きアミン系安定剤などが挙げ
られる。Specific compounds of anti-aging agents include 2゜2-methylenebis(4-methyl-et-butylphenol), 4-methyl-et-butylphenol,
．． 4-Butyrite bis(8-methyl-6-t-butylphenol), 4゜4-thiobis(8-methyl-6-t
-butylphenol), 2,6-di-t-butylphenol, phthyrenated phenol, n-octadecyl 8-C
8,5-di-t-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis(8
-(8-furkyl-5-t-butyl-4-hydroxyphenylpropione-)), phenolic stabilizers such as 111-bis(4-hydroxyphenyl)cyclohexane, octylated diphenylamine, nonylated diphenylamine, N,N-diphenyl -P-phenylenediamine, N-phenyl-N-isopropyl-P-phenylenediamine, N-phenyl-N-1,8-dimethylbutyl-
p-phenylenediamine, 2,2.4-trimethyldihydroquinoline polymer, condensate of diphenyl 7mine and 7cetone, 6-nitoxy2.2.4-trimethyl-1,
Examples include amine stabilizers such as 2-dihydroquinoline.
以下に実施例によって本発明を具体的に説明するが、本
発明はこれらの実施例によって限定されるもので嘴ない
。The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.
実施例１
６インチオーブンロールにより下記の配合例１に示した
クロロブチルゴム配合物に第１表に示したアルキルサル
ファイド樹脂およびビスマレイミド類を添加しハロゲン
化ブチルゴム組成物を作成し１こ。Example 1 A halogenated butyl rubber composition was prepared by adding the alkyl sulfide resin and bismaleimide shown in Table 1 to the chlorobutyl rubber compound shown in Formulation Example 1 below using a 6-inch oven roll.
（配合例）
クロロブチルゴム（エッソ化学品） ６５重量部
天然コム（Ｒ８８参１） ８５ＧＰＦブラ
ツク Ｔ。(Blend example) Chlorobutyl rubber (Esso Chemicals) 65 parts by weight Natural comb (R88 reference 1) 85GPF Black T.
炭酸カルシウム ５゜プロセ
ス油 １゜ステアリン酸
ｌ亜赫
８ツクシノ一ル■ＤＭ’″）（住友化
学品）１（脣）ジベンゾチアジルジスルフィド
次に得られたゴム配合物について加硫速度を調ヘル１コ
メニム８ＴＭ−Ｄ−２０８４Ｒ：準拠しレオメータ−加
硫試験を行った。また加硫温度１５０ ’Ｃ下４ｏ分間
プレス加硫を行いＪＩＳ−４−６１０１に準拠して熱老
化試験を行った。熱老化試験はギヤーオーブン老化機を
用い１００’ＣＸ７２時間老化せしめ、伸び（ｓ）を測
定した。これらの試験結果を第２表に示した。Calcium carbonate 5゜process oil 1゜stearic acid
8 Tsukushinol ■ DM''') (Sumitomo Chemicals) 1 (脣) Dibenzothiazyl disulfide Next, the vulcanization rate was adjusted for the obtained rubber compound. A vulcanization test was conducted. Press vulcanization was performed for 4 o'clock at a vulcanization temperature of 150'C, and a heat aging test was conducted in accordance with JIS-4-6101. The heat aging test was conducted using a gear oven aging machine at 100'CX72. The specimens were aged over time and the elongation (s) was measured.The results of these tests are shown in Table 2.
第１表
第 ２ 表
実施例２
実施例１と全く同様にして下記配合例２のクロロブチル
ゴム配合物を作成し、実施例１と同様の試験を行なった
。Table 1 Table 2 Example 2 A chlorobutyl rubber compound of Formulation Example 2 below was prepared in exactly the same manner as in Example 1, and the same tests as in Example 1 were conducted.
結果を第３表に示す。The results are shown in Table 3.
クロロブチルゴム（エッソ化学品） １００重量部ＯＦ
Ｆブラック ５０プロセス油
１０ステアリン酸
１亜鉛華
８ソクシノ一ノρＤＭ （住友化
学品） １．２５ソクシノーノρ’、Ｔ
Ｔ”（住友化学品） ０．２５畳 テト
ラメチルチウラムジスルフィド第８表
実施例８
、 実施例１と全く同様にして、下記配合例８のブロム
ブチルゴム組成物について、実施例１と全く同様の試験
を行なった。結果を第４表に示す。Chlorobutyl rubber (Esso Chemicals) 100 parts by weight OF
F black 50 process oil
10 stearic acid
1 Zinc white
8 Soccino Ichino ρDM (Sumitomo Chemicals) 1.25 Soccino no ρ', T
T" (Sumitomo Chemicals) 0.25 tatami Tetramethylthiuram disulfide Table 8 Example 8 In exactly the same manner as in Example 1, the bromobutyl rubber composition of Formulation Example 8 below was tested in exactly the same manner as in Example 1. The results are shown in Table 4.
配合例８Formulation example 8
Claims (1)
（ I ） ▲数式、化学式、表等があります▼（ I ） （式中、Ｒは２価の非環状脂肪族基、環状脂肪族基、芳
香族基、アルキル芳香族基であって、これらは鎖中また
は側部置換基にＯ、Ｎ、Ｓのようなヘテロ原子を含むこ
とができる。）で示されるヒスマレイミド類とを含有す
ることを特徴とするハロゲン化ブチルゴム組成物。[Claims] P-alkylphenol sulfide resin and the following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ (I) (In the formula, R is a divalent acyclic aliphatic group, a cycloaliphatic group , aromatic groups, alkyl aromatic groups which may contain heteroatoms such as O, N, S in the chain or in side substituents). A halogenated butyl rubber composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59173487A JPS6151041A (en) | 1984-08-21 | 1984-08-21 | Rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59173487A JPS6151041A (en) | 1984-08-21 | 1984-08-21 | Rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6151041A true JPS6151041A (en) | 1986-03-13 |
| JPH0550538B2 JPH0550538B2 (en) | 1993-07-29 |
Family
ID=15961412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59173487A Granted JPS6151041A (en) | 1984-08-21 | 1984-08-21 | Rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6151041A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4933385A (en) * | 1987-11-02 | 1990-06-12 | Bridgestone Corporation | Rubber composition |
| US5872188A (en) * | 1993-06-14 | 1999-02-16 | Akzo Nobel Nv | Vulcanized rubber compositions comprising anti-reversion coagent and a sulfide resin |
| US6467520B2 (en) | 2000-12-19 | 2002-10-22 | The Goodyear Tire & Rubber Company | Tire with apex rubber containing in-situ resin |
| EP1676876A1 (en) * | 2004-12-30 | 2006-07-05 | The Goodyear Tire & Rubber Company | Amine free vulcanizable rubber |
| JP2007039502A (en) * | 2005-08-01 | 2007-02-15 | Taoka Chem Co Ltd | Alkylphenol-sulfur chloride cocondensation product resin cross-linking agent |
| WO2009044652A1 (en) * | 2007-10-05 | 2009-04-09 | Sumitomo Rubber Industries, Ltd. | Rubber composition for inner liner and tire having inner liner made of the same |
| WO2009075127A1 (en) * | 2007-12-10 | 2009-06-18 | Sumitomo Rubber Industries, Ltd. | Rubber composition for inner liner and tire having inner liner made of the same |
| US8637599B2 (en) | 2007-10-05 | 2014-01-28 | Sumitomo Rubber Industries, Ltd. | Rubber composition for inner liner and tire having inner liner including thereof |
| WO2014208149A1 (en) * | 2013-06-24 | 2014-12-31 | 株式会社ブリヂストン | Pneumatic tyre |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8674014B2 (en) | 2007-10-03 | 2014-03-18 | Sumitomo Rubber Industries, Ltd. | Rubber composition for sidewall and tire having sidewall using thereof, and rubber composition for clinch and tire having clinch using thereof |
| JP5421400B2 (en) | 2011-06-21 | 2014-02-19 | 住友ゴム工業株式会社 | Rubber composition for clinch or chafer and pneumatic tire |
-
1984
- 1984-08-21 JP JP59173487A patent/JPS6151041A/en active Granted
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4933385A (en) * | 1987-11-02 | 1990-06-12 | Bridgestone Corporation | Rubber composition |
| US5872188A (en) * | 1993-06-14 | 1999-02-16 | Akzo Nobel Nv | Vulcanized rubber compositions comprising anti-reversion coagent and a sulfide resin |
| US6467520B2 (en) | 2000-12-19 | 2002-10-22 | The Goodyear Tire & Rubber Company | Tire with apex rubber containing in-situ resin |
| EP1676876A1 (en) * | 2004-12-30 | 2006-07-05 | The Goodyear Tire & Rubber Company | Amine free vulcanizable rubber |
| JP2007039502A (en) * | 2005-08-01 | 2007-02-15 | Taoka Chem Co Ltd | Alkylphenol-sulfur chloride cocondensation product resin cross-linking agent |
| WO2009044652A1 (en) * | 2007-10-05 | 2009-04-09 | Sumitomo Rubber Industries, Ltd. | Rubber composition for inner liner and tire having inner liner made of the same |
| US8637599B2 (en) | 2007-10-05 | 2014-01-28 | Sumitomo Rubber Industries, Ltd. | Rubber composition for inner liner and tire having inner liner including thereof |
| WO2009075127A1 (en) * | 2007-12-10 | 2009-06-18 | Sumitomo Rubber Industries, Ltd. | Rubber composition for inner liner and tire having inner liner made of the same |
| WO2014208149A1 (en) * | 2013-06-24 | 2014-12-31 | 株式会社ブリヂストン | Pneumatic tyre |
| CN105339184A (en) * | 2013-06-24 | 2016-02-17 | 株式会社普利司通 | Pneumatic tyre |
| CN105339184B (en) * | 2013-06-24 | 2017-08-08 | 株式会社普利司通 | Pneumatic tire |
| US10040315B2 (en) | 2013-06-24 | 2018-08-07 | Bridgestone Corporation | Pneumatic tire |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0550538B2 (en) | 1993-07-29 |
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