JPS63286445A - Improved rubber composition - Google Patents
Improved rubber compositionInfo
- Publication number
- JPS63286445A JPS63286445A JP12131287A JP12131287A JPS63286445A JP S63286445 A JPS63286445 A JP S63286445A JP 12131287 A JP12131287 A JP 12131287A JP 12131287 A JP12131287 A JP 12131287A JP S63286445 A JPS63286445 A JP S63286445A
- Authority
- JP
- Japan
- Prior art keywords
- bismaleimide
- rubber
- yield
- rubber composition
- weight
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 229920001971 elastomer Polymers 0.000 title claims description 31
- 239000005060 rubber Substances 0.000 title claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 5
- 229920001194 natural rubber Polymers 0.000 claims abstract description 5
- 229920003051 synthetic elastomer Polymers 0.000 claims abstract description 4
- 239000005061 synthetic rubber Substances 0.000 claims abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 3
- 244000043261 Hevea brasiliensis Species 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 229920003192 poly(bis maleimide) Polymers 0.000 abstract description 28
- -1 bismaleimide compound Chemical class 0.000 abstract description 3
- 239000006229 carbon black Substances 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract description 2
- 239000004902 Softening Agent Substances 0.000 abstract 1
- 125000001033 ether group Chemical group 0.000 abstract 1
- 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 description 17
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- SLJJEYCPTRKHFI-UHFFFAOYSA-N 3-[6-(2,5-dioxopyrrol-3-yl)hexyl]pyrrole-2,5-dione Chemical compound O=C1NC(=O)C(CCCCCCC=2C(NC(=O)C=2)=O)=C1 SLJJEYCPTRKHFI-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はゴム組成物に関し、詳しくは耐熱性や亀裂成長
性などが著しく改良されたコ９ム組成物に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a rubber composition, and more particularly to a rubber composition having significantly improved heat resistance and crack growth properties.
最近、自動車の性能向上や高速道路網の発達に伴ない、
高運動性能を備えた空気入シタイヤの要求が強まシ、特
にグリップ性能は重要な要求特性であシ、加速性能やブ
レーキ性能に代表される。Recently, with the improvement of automobile performance and the development of expressway networks,
There is an increasing demand for pneumatic tires with high maneuverability, and grip performance is an important characteristic required, typified by acceleration performance and braking performance.
したがってこれらの特性が高いタイヤはどより高速でか
つより正確に走行することができる。Therefore, tires with high levels of these properties can run faster and more accurately.
従来、高グリップ性能を得るためには、トレッドゴム組
成物にポリマーとして高スチレン含有率のスチレン−ブ
タジェン共重合ゴム（ガラス転移温度の高いゴム）を選
択するか、またはオイル及びカーボンブラックを高充填
した配合系を選択する必要があり、トレッドゴム組成物
のヒステリシスロスを大きくすることが必要であった。Conventionally, in order to obtain high grip performance, styrene-butadiene copolymer rubber with a high styrene content (rubber with a high glass transition temperature) was selected as the polymer in the tread rubber composition, or highly filled with oil and carbon black. It was necessary to select a compounding system with a high hysteresis loss, and it was necessary to increase the hysteresis loss of the tread rubber composition.
このため、タイヤが高速で走行する場合、ヒステリシス
ロスのためタイヤが発熱し、高速走行時のタイヤ温度上
昇に伴ないトレッドゴムにブロー（ｂｌｏｗ）が発生し
、ゴム弾性が失なわれ、グリップ性能や耐摩耗性能が著
しく低下してしまういわゆるプロ−アラ） （ｂｌｏｗ
−ｏｕｔ）現象を引き起すとｂった欠点があった。For this reason, when the tire runs at high speed, the tire generates heat due to hysteresis loss, and as the tire temperature rises during high-speed travel, the tread rubber blows, causing a loss of rubber elasticity and grip performance. (blow
-out) phenomenon.
上記欠点を解決するために、本発明者らの一人が特開昭
６１−２３８５０１号公報にて、ｍ−フェニレンビスマ
レイミドやヘキサメチレンビスマレイミドなどを、特定
量の硫黄、加硫促進剤と併用するとブローアウトが改良
されることを提案した。In order to solve the above drawbacks, one of the inventors of the present invention disclosed in Japanese Patent Application Laid-Open No. 61-238501 that m-phenylene bismaleimide, hexamethylene bismaleimide, etc. were used in combination with a specific amount of sulfur and a vulcanization accelerator. He then suggested that the blowout be improved.
しかしながらこれらのビスマレイミドは確かにブローア
ウト性は改良されるが、グリップ性がやや低下してしま
うといった欠点があり、グリップ性と耐熱性の両立化は
未だ達成されていない。However, although these bismaleimides do improve blowout properties, they have the drawback of slightly lowering grip properties, and achieving both grip properties and heat resistance has not yet been achieved.
一方、空気入シタイヤは一般にスチールコードなどの補
強材で構成されているベルト層やカーカス層を備えてい
るが、トレッド部の耐熱性を改良していくと、高速走行
時にタイヤの内部、特にベルト層などが発熱によって破
壊されてしまうといった現象がある。このため本発明者
らは、前記ビスマレイミドを例えばベルトコーティング
ゴムに配合し検討したが、確かにブローアウト性は改良
されるが、耐亀裂成長性が悪化し、ベルト端部セパレー
ションといった故障を引き起こす欠点があった。On the other hand, pneumatic tires generally have a belt layer and a carcass layer made of reinforcing materials such as steel cords, but by improving the heat resistance of the tread, the inside of the tire, especially the belt, can be removed during high-speed driving. There is a phenomenon in which the layers are destroyed due to heat generation. For this reason, the present inventors have investigated blending the bismaleimide into, for example, belt coating rubber, which certainly improves blowout properties, but deteriorates crack growth resistance and causes failures such as belt edge separation. There were drawbacks.
このように従来のビスマレイミドを配合したゴム組成物
では、自動車の性能向上に対応することが難かしく、特
にグリップ性能と耐熱性を同時に改良し、あるいは、亀
裂成長性と耐熱性を同時に改良することができなかった
。本発明は、これら問題点全解決すること全目的とする
。In this way, it is difficult for conventional rubber compositions containing bismaleimide to respond to improvements in automobile performance.In particular, it is difficult to improve grip performance and heat resistance at the same time, or to improve crack growth and heat resistance at the same time. I couldn't do that. The present invention aims to solve all of these problems.
本発明者らは、上記欠点を改善することを目的として鋭
意検討した結果、本発明に到達したものである。The present inventors have arrived at the present invention as a result of intensive studies aimed at improving the above-mentioned drawbacks.
すなわち、本発明は天然ゴム及び／又は合成ゴムからな
るゴム１００重量部に対し、加硫剤として硫黄０．３〜
６重量部及び一般式
０式％
（ここで、Ｒは＋ＣＨ２鈷、少なくとも１つのエーテル
結合を有し、側鎖を有していても工い直鎖状炭化水素を
表わし、ｎは７以上の整数〕で表わされるビスマレイミ
ド化合物０．１〜１０重量部を配合することを特徴とす
るゴム組成物に関する。That is, the present invention uses 0.3 to 0.3 to sulfur as a vulcanizing agent to 100 parts by weight of rubber made of natural rubber and/or synthetic rubber.
6 parts by weight and formula 0% (where R is +CH2, has at least one ether bond, represents a straight chain hydrocarbon even if it has a side chain, and n is 7 or more. The present invention relates to a rubber composition characterized in that it contains 0.1 to 10 parts by weight of a bismaleimide compound represented by [integer].
本発明において使用するゴムは天然ゴム、合成ポリイソ
ルンゴム、スチレン−ブタジェン共重合ゴム、ポリプタ
ジ円ンゴム、ノチルゴム、ハロゲン化！チルゴム等であ
り、これらは単独であっても２種以上併用してもかまわ
ない。The rubbers used in the present invention are natural rubber, synthetic polyisolune rubber, styrene-butadiene copolymer rubber, polybutadiene rubber, notyl rubber, and halogenated rubber! Chill rubber, etc., and these may be used alone or in combination of two or more.
本発明において使用するビスマレイミドの具体例として
は、Ｒが一＋ＣＨ２柑の例としてＮ、Ｎ’−１，８−オ
クタメチレンビスマレイミド、 Ｎ、Ｎ’−１，１０−
７’ヵメチレンビスマレイミド、 Ｎ、Ｎ′−１，１２
−ドデカメチレンビスマレイミド、Ｎ、Ｎ’−テトラテ
力−１，１４−メチレンビスマレイミド、及びＮ、Ｎ’
−１，１９−ノナデカメチレンビスマレイミド、またＲ
が少なくとも１つのエーテル結合を有する例としてＮ、
Ｎ’−４，７−ジオキサ−ｒ力ｙ −１ｍ １０−ビス
マレイミド、Ｎ、Ｎ’−４，９−ジオキサドデカン−１
，１２−ビスマレイミド、及びＲが次の一般式
％式％
で表わされるビスマレイミドなどであり、単独であって
も２種以上を併用してもよい。このうち特にＲＫ少くと
も１つのエーテル結合を有する化合物が好ましい。配合
量はゴム１００重量部に対して０．′ｌ〜１０重量部で
ある。０．１重量部未満では添加の効果がなく、１０重
量部を越えるともはや増量効果は期待できず好ましくな
い。Specific examples of bismaleimide used in the present invention include N,N'-1,8-octamethylene bismaleimide, N,N'-1,10- as an example of R1+CH2,
7'camethylene bismaleimide, N,N'-1,12
-dodecamethylene bismaleimide, N,N'-tetratate-1,14-methylene bismaleimide, and N,N'
-1,19-nonadecamethylene bismaleimide, also R
As an example where N has at least one ether bond,
N'-4,7-dioxa-r force y -1m 10-bismaleimide, N,N'-4,9-dioxadodecane-1
, 12-bismaleimide, and bismaleimide in which R is represented by the following general formula %.They may be used alone or in combination of two or more. Among these, RK compounds having at least one ether bond are particularly preferred. The blending amount is 0.00% per 100 parts by weight of rubber. 1 to 10 parts by weight. If it is less than 0.1 part by weight, there is no effect of addition, and if it exceeds 10 parts by weight, no increase in weight can be expected, which is not preferable.
本発明において、上記ビスマレイミドに硫黄ヲ併用して
使用するが、その配合量は０．２〜６重量部である。配
合量が０．２重量部未満では添加の効果がなくしかもビ
スマレイミドの架橋が遅延するため好ましくなく、６重
量部を越えるとグリッグ性能等が低下するため好ましく
ない。In the present invention, sulfur is used in combination with the bismaleimide, and the amount thereof is 0.2 to 6 parts by weight. If the amount is less than 0.2 parts by weight, it is not preferable because the addition has no effect and crosslinking of bismaleimide is delayed, and if it exceeds 6 parts by weight, it is not preferable because the glyph performance etc. deteriorate.
本発明のゴム組成物においては、カーボンブラックやシ
リカ等の充填剤、アロマオイル等の軟化剤や力Ｕ硫剤、
加硫促進剤、那硫促進助剤、老化防止剤等、通常がム工
業で使用される配合剤を、通常の配合量で適宜配合する
ことができる。In the rubber composition of the present invention, fillers such as carbon black and silica, softeners such as aroma oil, and sulfur agents,
Compounding agents commonly used in the mu industry, such as vulcanization accelerators, vulcanization accelerators, and antiaging agents, can be appropriately blended in the usual amounts.
また、本発明のゴム組成物は、タイヤを始めとして、コ
ンベヤベルト、ホース等のゴム製品、特にスチールコー
ドを被覆するゴム組成物として好適に使用される。Furthermore, the rubber composition of the present invention is suitably used as a rubber composition for coating rubber products such as tires, conveyor belts, and hoses, especially steel cords.
以下、本発明を実施例により詳細に説明する。Hereinafter, the present invention will be explained in detail with reference to Examples.
合成例Ｉ Ｎ、Ｎ’−１，６−ヘキサメチレンビスマ
レイミド攪拌機、温度計、還流冷却器および滴下ロート
を設置した５００ｍの四つ口丸底フラスコに予めＮ２ガ
スにてフラスコ内の空気を置換した後、無水マレイン酸
５０９およびＮ、Ｎ−ジメチルアセトアミド１３Ｑｄ’
ｉＨ入れ攪拌機を作動させて無水マレイン酸を溶解した
。次にこの溶液に１．６−ヘキサメチレンジアミン２９
ｇｔＮ、Ｎ−ジメチルアセトアミド１３０ｍに溶解した
溶液を滴下ロートから徐々に滴下した。この間、反応液
の温度を２５℃に保持するためフラスコは氷水に浸した
。滴下終了後、反応温度２５℃で１５時間攪拌を続けた
後、ステアリン酸コバルト５． Ｏｇｆ加えて昇温し、
６０℃に保持して無水酢酸１０２ｇｋ滴下ロートから３
０分かけて徐々に滴下した。その後反応温度６０℃で２
時間攪拌を続けた。次に反応液を室温まで冷却した後充
分に攪拌している５００−の氷水中へ徐々に投入し沈殿
を生成せしめ、沈殿全吸引ろ過し、さらに充分に水洗し
て乾燥した。得られたＮ、Ｎ’−１，６−へキサメチレ
ンビスマレイミｌ’ノ収量は４７．６ ｇ、その収率は
６９チで融点は１３４〜１３７℃であった。Synthesis Example I N,N'-1,6-hexamethylene bismaleimide A 500 m four-neck round bottom flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel was replaced with N2 gas in advance to replace the air inside the flask. After that, maleic anhydride 509 and N,N-dimethylacetamide 13Qd'
The maleic anhydride was dissolved by turning on the iH stirrer. Next, add 1,6-hexamethylene diamine 29 to this solution.
A solution dissolved in 130 m of gtN,N-dimethylacetamide was gradually dropped from the dropping funnel. During this time, the flask was immersed in ice water to maintain the temperature of the reaction solution at 25°C. After the dropwise addition was completed, stirring was continued for 15 hours at a reaction temperature of 25°C, and then 5.5% of cobalt stearate was added. Add Ogf and raise the temperature,
102 gk of acetic anhydride was added from the dropping funnel while maintaining the temperature at 60°C.
It was gradually added dropwise over 0 minutes. Then, at a reaction temperature of 60℃,
Stirring was continued for an hour. Next, the reaction solution was cooled to room temperature, and then gradually poured into 500-degree ice water with sufficient stirring to form a precipitate.All the precipitate was suction-filtered, and further thoroughly washed with water and dried. The yield of N,N'-1,6-hexamethylene bismaleimyl' obtained was 47.6 g, the yield was 69 g, and the melting point was 134-137°C.
合成例２ Ｎ、Ｎ’−１，８−オクタメチレンビスマ
レイミド無水マレイン酸５０９ｔ−１３０−〇Ｎ、Ｎ−
ジメチルアセトアミドに溶解した溶液に、１，６−へキ
サメチレンジアミンの代りに１，８−オクタメチレンジ
アミン３６ｇを、更にＮ、Ｎ−ツメチルアセトアミド１
５０ｓｇｉ加えて溶解した溶液を使用した他は合、成例
１に準じてＮ、Ｎ’−１，８−オクタメチレンビスマレ
イミドを得た。収量は５７．１ ｇ、収率７６％で融点
１０２〜１０７℃であった。Synthesis Example 2 N,N'-1,8-octamethylene bismaleimide maleic anhydride 509t-130-〇N,N-
In a solution dissolved in dimethylacetamide, 36 g of 1,8-octamethylene diamine was added in place of 1,6-hexamethylene diamine, and 1 liter of N,N-tmethylacetamide was added in place of 1,6-hexamethylene diamine.
N,N'-1,8-octamethylene bismaleimide was obtained according to Synthesis Example 1, except that a solution containing 50 sgi and dissolved therein was used. The yield was 57.1 g, a yield of 76%, and a melting point of 102-107°C.
無水マレイン酸５０９を１３０−〇Ｎ、Ｎ−ジメチルア
セトアミドに溶解した溶液に、１，６−へキサメチレン
ジアミンの代９に１，１０−デカメチレンジアミン４３
ｇ’ｉ、更にＮ、Ｎ−ジメチルアセトアミド１８０−を
加えて溶解した溶液を使用した他は合成例１に準じてＮ
、Ｎ’−１，１０−デカメチレンビスマレイミドを得た
。収量は６２．０ｇ、収率７６チで、融点は９７．５〜
１０６℃であった。To a solution of maleic anhydride 509 dissolved in 130-〇N,N-dimethylacetamide, 1,10-decamethylenediamine 43 was added to 1,6-hexamethylenediamine 9 and 1,10-decamethylenediamine 43
N.
, N'-1,10-decamethylene bismaleimide was obtained. Yield: 62.0g, yield: 76cm, melting point: 97.5~
The temperature was 106°C.
合成例４ Ｎ、Ｎ’−１，１２−ドデカメチレンビ
スマレイミド無水マレイン酸５０ｇを１３０−〇Ｎ、Ｎ
−ジメチルアセトアミドに溶解した溶液に、１．６−ヘ
キサメチレンビスマレイミドの代シに１，１２−ドデカ
メチレンジアミン５０９ｆ、更にＮ、Ｎ−ジメチルアセ
トアミド２２０−を加えて溶解した溶液を使用した他は
合成例１に準じてＮ、Ｎ’−１，１２−ドデカメチレン
ビスマレイミドを得た。収量は７３．２ｇ、収率８４％
で、融点１０９〜１１２℃であった。Synthesis Example 4 N,N'-1,12-dodecamethylene bismaleimide 50g of maleic anhydride was mixed with 130-〇N,N
- A solution prepared by adding and dissolving 1,12-dodecamethylenediamine 509f in place of 1,6-hexamethylene bismaleimide, and further adding N,N-dimethylacetamide 220- to a solution dissolved in dimethylacetamide was used. According to Synthesis Example 1, N,N'-1,12-dodecamethylene bismaleimide was obtained. Yield: 73.2g, yield 84%
The melting point was 109-112°C.
合成例５ Ｎ、Ｎ’−４，７−シオキ？’ｙ’カｙ−
１，１０−ビ合成例１と同様にＮ２ガスにて置換した５
００ｍ／の四つ口の丸底フラスコに無水マレイン酸４５
ｇお工びＮ、Ｎ−ジメチルアセトアミド１４０ｄｉ入れ
攪拌して無水マレイン酸を溶解した。次にフラスコを氷
水浴に浸し、反応液を２０℃に保持して、４．７−シオ
キサデカンー１，１０−ジアミン３５．２．９を徐々に
滴下し、滴下終了後、温度２０℃で１．５時間攪拌を続
けた。その後ステアリン酸コバルト３ｇ、および無水酢
酸４９９ｆ加えて昇温し反応温度７０℃で３時間攪拌を
続けた。ついで減圧下に７０℃で反応液ｔｍ縮し３０分
間で１１０−の副生じた酢酸およびＮ、Ｎ−ジメチルア
セトアミドを留去し、室温まで冷却した。その後反応液
全２１Ｏ分液ロートに予め入れている水３００−中に投
入し、トルエン３０（ｌｔＱ−加えて抽出操作を行い、
トルエン相を充分４Ｃ水洗した後、減圧下、５０℃でト
ルエンを完全に留去して目的物を得た。収量は４７．７
ｆｉ、収率は７１チで、融点は６９〜７８℃であった。Synthesis Example 5 N,N'-4,7-shioki? 'y'kay-
5 substituted with N2 gas in the same manner as in 1,10-Bi Synthesis Example 1
Maleic anhydride 45 in a 00m/4-necked round bottom flask
140 di of N,N-dimethylacetamide was added and stirred to dissolve maleic anhydride. Next, the flask was immersed in an ice water bath, the reaction solution was maintained at 20°C, and 4,7-thioxadecane-1,10-diamine 35.2.9 was gradually added dropwise, and after the completion of the dropwise addition, 1. Stirring was continued for 5 hours. Thereafter, 3 g of cobalt stearate and 499 f of acetic anhydride were added, the temperature was raised, and stirring was continued for 3 hours at a reaction temperature of 70°C. The reaction mixture was then condensed at 70° C. under reduced pressure to remove by-produced acetic acid and N,N-dimethylacetamide in 30 minutes, and cooled to room temperature. After that, all of the reaction solution was poured into 300ml of water previously placed in a 210O separatory funnel, and 30ml of toluene (ltQ) was added to carry out an extraction operation.
After thoroughly washing the toluene phase with 4C water, toluene was completely distilled off at 50°C under reduced pressure to obtain the desired product. Yield is 47.7
fi, yield was 71%, and melting point was 69-78°C.
無水マレイン酸４５ｇ’ｔＮ、Ｎ−ジメチルアセトアミ
ド１４０ゴに溶解した溶液に、４．７−シオキサデカン
ー１．１０−ジアミンの代υに４．９−ジオキサドデカ
ン−１，１２−ジアミン４０．８ｇｔ滴下した他は合成
例５に準じてＮ、Ｎ’−４，９−Ｓ）オキサドデカン−
１，１２−ビスマレイミドを得た。収量５３．５夕、収
率７４％で、融点は４７． ！５〜５６℃であった。To a solution of 45 g of maleic anhydride and 140 g of N-dimethylacetamide, 40.8 g of 4.9-dioxadodecane-1,12-diamine was added dropwise to 4.7-thioxadecane-1,10-diamine. N,N'-4,9-S)oxadodecane-
1,12-bismaleimide was obtained. Yield: 53.5 mm, yield 74%, melting point: 47. ! The temperature was 5-56°C.
合成例７ ビスマレイミドＡ
無水マレイン酸４５ｇＱＮ、Ｎ−ツメチルアセトアミド
１６０−に溶解した溶液に、４．７−シオキサデカンー
１．１０−ジアミンの代シにＪｅｆｆｇｒｍｉｎ Ｄ−
２３０（Ｔｅｘａｃｏ Ｃｈｅｍ、 裂）注１４５．０
ｇ’ｉ滴下した他は合成例５に準じて液状のビスマレイ
ミドＡを得た。収量５１．９９、収率６８チであった。Synthesis Example 7 Bismaleimide A In a solution of 45 g of maleic anhydride and 160 g of N-methylacetamide, 4,7-thioxadecane-1,10-diamine was added with Jeffgrmin D-
230 (Texaco Chem, crack) Note 145.0
Liquid bismaleimide A was obtained according to Synthesis Example 5 except that g'i was added dropwise. The yield was 51.99, and the yield was 68.
ここでａは約２，６
無水マレイン酸４５＆’ｋＮ、Ｎ−ジメチルアセトアミ
ド２００ｍ７！に溶解した溶液に、４．７−シオキサデ
カンー１．’ＩＯ−ジアミンの代りにＪｅｆｆｅｒｍｉ
ｎ Ｄ−４，００（Ｔｅｘａｃｏ Ｃｈｅｍ、製）注２
７９．’ｌｆｆ１１１１Ｍ下した他は合成例５に準じ
て液状のビスマレイミドＢを得た。収量’１８．８ｇ、
収率７３％であった。Here a is about 2,6, maleic anhydride 45'kN, N-dimethylacetamide 200m7! 4.7-thioxadecane-1. 'Jeffermi instead of IO-diamine
n D-4,00 (manufactured by Texaco Chem) Note 2
79. Liquid bismaleimide B was obtained according to Synthesis Example 5 except that 'lff1111M was added. Yield '18.8g,
The yield was 73%.
ここでａは約５．６
無水マレイン酸４５．！９ｔＮ、Ｎ−ジメチルアセトア
ミド３００−に溶解した溶液に４．７−シオキサデカ７
−１１１０−ジアミンの代りにＪｅｆｆｅｒｍｉｎ Ｅ
Ｄ−６００（Ｔｅｘａｃｏ Ｃｈｅｍ、製）注３１７４
．５５１−滴下した他は合成例５に準じて液状のビスマ
レイミドＣを得た。収量１４４ｇ、収率７４％であった
。Here a is about 5.6 maleic anhydride 45. ! 4,7-thioxadeca7 in a solution dissolved in 9tN,N-dimethylacetamide 300-
-1110-diamine instead of Jeffermin E
D-600 (manufactured by Texaco Chem) Note 3174
．． Liquid bismaleimide C was obtained according to Synthesis Example 5 except that 551-551 was added dropwise. The yield was 144 g, and the yield was 74%.
（注３）
ここでｂ十ｄは約３．５、Ｃは約１３．５実施例１〜８
、比較例１〜３
第１表に示した配合内容による各種ゴム組成物を作成し
、加硫後、ブローアウト性を評価した。(Note 3) Here, b + d is approximately 3.5, C is approximately 13.5 Examples 1 to 8
, Comparative Examples 1 to 3 Various rubber compositions were prepared according to the formulations shown in Table 1, and after vulcanization, blowout properties were evaluated.
次いでこれらゴム組成物をタイヤサイズ１９５／６０
ＨＲ１４のトレッドに使用して、高速性能を評価した。Next, these rubber compositions were applied to tire size 195/60.
It was used in the tread of HR14 to evaluate high-speed performance.
結果を第１表に示した。The results are shown in Table 1.
尚、評価方法は以下の通りである。The evaluation method is as follows.
ブローアウト性
グツドリッチ式フレクツメーターを用いＡＳＴＭＤ−６
２３−５８の方法Ａに一拠して行ない、サンプルがブロ
ーアウトした時の温度を評価。Blowout properties using a Gutdrich flexmeter ASTM D-6
23-58 and evaluate the temperature at which the sample blows out.
サーキット（１周２．０４ｋｎ＋）を実車走行を行うこ
とＫよシララグタイムの実測、及び高速走行時のフィー
リング並びに試験後の外観観祭によって行った。This was done by driving an actual car around the circuit (2.04kn+ per lap), measuring the car's lag time, and observing the feeling during high-speed driving and the appearance after the test.
なお、サーキット走行時のフィーリングは駆動、制動特
性、ハンドル応答性、操舵時の路面グリップ特性及びス
リップ限界を越えてからのコントロール性を総合評価し
たもので、比較例１’１ｌＯＯとして指数表示した。値
が大なる程良好。The feeling during circuit driving is a comprehensive evaluation of driving, braking characteristics, steering response, road grip characteristics during steering, and controllability after exceeding the slip limit, and is expressed as an index as Comparative Example 1'1lOO. . The higher the value, the better.
第１表より、本発明のゴム組成物は比較例に対してブロ
ーアウト温度が高くしかも高速性能（グリップ性）も同
時に改良されており、特にブリップがメチレン鎖の場合
は炭素数が１０以上で特に好ましく、更にエーテル結合
を含有する直鎖の場合は更に耐熱性と高速性能が改良さ
れていることがわかる。From Table 1, it can be seen that the rubber composition of the present invention has a higher blowout temperature than the comparative example, and also has improved high-speed performance (grip property). Especially when the blip is a methylene chain, the number of carbon atoms is 10 or more. It can be seen that heat resistance and high-speed performance are particularly preferred, and in the case of a linear chain containing an ether bond, the heat resistance and high-speed performance are further improved.
実施例９〜１３、比較例４〜６
第２表に示した配合内容による各種ゴム組成物全作成し
、加硫後、亀裂成長性を評価した。結果を第２表に示し
た。Examples 9 to 13, Comparative Examples 4 to 6 Various rubber compositions were prepared according to the formulations shown in Table 2, and after vulcanization, crack growth properties were evaluated. The results are shown in Table 2.
尚、評価法は以下の通りである。The evaluation method is as follows.
亀裂成長性
厚さ２■の加硫ゴムシートに初期傷０．３籠を入れ、回
転数３０ 、Ｏｒｐｍで〈シ返し３０チの定伸張を与え
た。一定時間後の亀裂成長速度を評価し、比較例４を１
００として指数で示した。値が大なる程、亀裂成長性が
良好なこと金示す。Crack Growth A vulcanized rubber sheet with a thickness of 2 cm was placed with an initial flaw of 0.3 cm, and a constant elongation of 30 cm was applied at a rotational speed of 30 rpm. The crack growth rate after a certain period of time was evaluated, and Comparative Example 4 was compared to 1.
00 and expressed as an index. The larger the value, the better the crack growth properties.
第２表より本発明のゴム組成物は亀裂成長性が著しく改
善されており、特にメチレン鎖の炭素数が１０以上と、
更にエーテル結合を含有する直鎖はよシ好ましいことが
わかる。Table 2 shows that the rubber composition of the present invention has significantly improved crack growth properties, especially when the number of carbon atoms in the methylene chain is 10 or more.
Furthermore, it can be seen that a straight chain containing an ether bond is more preferable.
Claims (1)
に対して、加硫剤として硫黄０．２〜６重量部、及び一
般式 ▲数式、化学式、表等があります▼ （ここで、Ｒは−（ＣＨ＿２）−＿ｎ、少なくとも１つ
のエーテル結合を含有し、側鎖を有してもよい直鎖状炭
化水素を表わし、ｎは７以上の整数） で表わされるビスマレイミド化合物０．１〜１０重量部
を配合することを特徴とする改良されたゴム組成物。[Claims] For 100 parts by weight of rubber made of natural rubber and/or synthetic rubber, 0.2 to 6 parts by weight of sulfur as a vulcanizing agent, and general formula ▲ Numerical formula, chemical formula, table, etc. ▼ ( Here, R represents -(CH_2)-_n, a linear hydrocarbon containing at least one ether bond and optionally having a side chain, and n is an integer of 7 or more. An improved rubber composition characterized by blending 0.1 to 10 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12131287A JPS63286445A (en) | 1987-05-20 | 1987-05-20 | Improved rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12131287A JPS63286445A (en) | 1987-05-20 | 1987-05-20 | Improved rubber composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63286445A true JPS63286445A (en) | 1988-11-24 |
Family
ID=14808125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12131287A Pending JPS63286445A (en) | 1987-05-20 | 1987-05-20 | Improved rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63286445A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5109055A (en) * | 1989-07-24 | 1992-04-28 | Sumitomo Chemical Company, Limited | Rubber composition having excellent dynamic properties |
| US5610240A (en) * | 1990-10-29 | 1997-03-11 | Akzo Nobel Nv | Anti-reversion coagents for rubber vulcanization |
| US7432331B2 (en) | 2002-12-31 | 2008-10-07 | Nektar Therapeutics Al, Corporation | Hydrolytically stable maleimide-terminated polymers |
| WO2015159492A1 (en) * | 2014-04-17 | 2015-10-22 | 株式会社ブリヂストン | Rubber composition for conveyor belts and conveyor belt |
-
1987
- 1987-05-20 JP JP12131287A patent/JPS63286445A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5109055A (en) * | 1989-07-24 | 1992-04-28 | Sumitomo Chemical Company, Limited | Rubber composition having excellent dynamic properties |
| US5610240A (en) * | 1990-10-29 | 1997-03-11 | Akzo Nobel Nv | Anti-reversion coagents for rubber vulcanization |
| US7432331B2 (en) | 2002-12-31 | 2008-10-07 | Nektar Therapeutics Al, Corporation | Hydrolytically stable maleimide-terminated polymers |
| US8106131B2 (en) | 2002-12-31 | 2012-01-31 | Nektar Therapeutics | Hydrolytically stable maleimide-terminated polymers |
| US8227555B2 (en) | 2002-12-31 | 2012-07-24 | Nektar Therapeutics | Hydrolytically stable maleimide-terminated polymers |
| US8835556B2 (en) | 2002-12-31 | 2014-09-16 | Nektar Therapeutics | Hydrolytically stable maleimide-terminated polymers |
| WO2015159492A1 (en) * | 2014-04-17 | 2015-10-22 | 株式会社ブリヂストン | Rubber composition for conveyor belts and conveyor belt |
| JP2015205961A (en) * | 2014-04-17 | 2015-11-19 | 株式会社ブリヂストン | Rubber composition for conveyor belt, and conveyor belt |
| CN106232700A (en) * | 2014-04-17 | 2016-12-14 | 株式会社普利司通 | Rubber composition used for conveyer belt and conveyer belt |
| EP3133118A4 (en) * | 2014-04-17 | 2017-04-12 | Bridgestone Corporation | Rubber composition for conveyor belts and conveyor belt |
| AU2015248419B2 (en) * | 2014-04-17 | 2017-05-11 | Bridgestone Corporation | Rubber composition for conveyor belts and conveyor belt |
| US9884952B2 (en) | 2014-04-17 | 2018-02-06 | Bridgestone Corporation | Conveyor belt rubber composition and conveyor belt |
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