JPS6323943A - Rubber composition - Google Patents
Rubber compositionInfo
- Publication number
- JPS6323943A JPS6323943A JP16751686A JP16751686A JPS6323943A JP S6323943 A JPS6323943 A JP S6323943A JP 16751686 A JP16751686 A JP 16751686A JP 16751686 A JP16751686 A JP 16751686A JP S6323943 A JPS6323943 A JP S6323943A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- resilience
- temperature
- disulfide
- diphenylamine derivative
- 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
- 229920001971 elastomer Polymers 0.000 title claims abstract description 27
- 239000005060 rubber Substances 0.000 title claims abstract description 27
- 239000000203 mixture Substances 0.000 title claims abstract description 12
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 10
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 10
- 229920001194 natural rubber Polymers 0.000 claims abstract description 10
- 229920003051 synthetic elastomer Polymers 0.000 claims abstract description 6
- 239000005061 synthetic rubber Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 abstract description 6
- 235000021355 Stearic acid Nutrition 0.000 abstract description 4
- 239000000945 filler Substances 0.000 abstract description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 abstract description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010734 process oil Substances 0.000 abstract description 4
- 239000008117 stearic acid Substances 0.000 abstract description 4
- HLBZWYXLQJQBKU-UHFFFAOYSA-N 4-(morpholin-4-yldisulfanyl)morpholine Chemical compound C1COCCN1SSN1CCOCC1 HLBZWYXLQJQBKU-UHFFFAOYSA-N 0.000 abstract description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 3
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 238000003878 thermal aging Methods 0.000 abstract 1
- 238000004073 vulcanization Methods 0.000 description 11
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 6
- 238000013329 compounding Methods 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 4
- 150000008117 polysulfides Polymers 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229920001577 copolymer 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
- 238000009472 formulation Methods 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical class C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- ZYQXAWUHKYAPTJ-UHFFFAOYSA-N 2-(propan-2-yltetrasulfanyl)propane Chemical compound CC(C)SSSSC(C)C ZYQXAWUHKYAPTJ-UHFFFAOYSA-N 0.000 description 1
- QRYFCNPYGUORTK-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-yldisulfanyl)morpholine Chemical compound C1COCCN1SSC1=NC2=CC=CC=C2S1 QRYFCNPYGUORTK-UHFFFAOYSA-N 0.000 description 1
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004129 EU approved improving agent Substances 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N cyclobenzothiazole Natural products C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 238000006210 cyclodehydration reaction Methods 0.000 description 1
- YHNUQWOWFPKIPU-UHFFFAOYSA-N cyclohexyloxy-cyclohexylsulfanyl-hydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound C1CCCCC1SP(=S)(O)OC1CCCCC1 YHNUQWOWFPKIPU-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SZXCCXFNQHQRGF-UHFFFAOYSA-N di(propan-2-yloxy)-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CC(C)OP(S)(=S)OC(C)C SZXCCXFNQHQRGF-UHFFFAOYSA-N 0.000 description 1
- IRDLUHRVLVEUHA-UHFFFAOYSA-N diethyl dithiophosphate Chemical compound CCOP(S)(=S)OCC IRDLUHRVLVEUHA-UHFFFAOYSA-N 0.000 description 1
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 1
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 1
- ZUNFAOLVHKUWCL-UHFFFAOYSA-N dipropoxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCCOP(S)(=S)OCCC ZUNFAOLVHKUWCL-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- GSJYSUQLJKYYRS-UHFFFAOYSA-N hydroxy-octoxy-octylsulfanyl-sulfanylidene-lambda5-phosphane Chemical compound CCCCCCCCOP(O)(=S)SCCCCCCCC GSJYSUQLJKYYRS-UHFFFAOYSA-N 0.000 description 1
- BXYFLGJRMCIGLW-UHFFFAOYSA-N hydroxy-propan-2-yloxy-propan-2-ylsulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CC(C)OP(O)(=S)SC(C)C BXYFLGJRMCIGLW-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- -1 maleimide compound Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- XBMQPSNBDWCCBJ-UHFFFAOYSA-N n,n-dicyclohexylthiohydroxylamine Chemical compound C1CCCCC1N(S)C1CCCCC1 XBMQPSNBDWCCBJ-UHFFFAOYSA-N 0.000 description 1
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- 229940032017 n-oxydiethylene-2-benzothiazole sulfenamide Drugs 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 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〉 本発明はレジリエンスの向上したゴム組成物に関する。[Detailed description of the invention] <Industrial application field> The present invention relates to rubber compositions with improved resilience.
〈従来の技術〉
近年、自動車等の省燃費が大きな社会的要求となり、こ
のため、たとえばタイヤの走行時のエネルギーロスを低
下させることが重要な課題となっている。<Prior Art> In recent years, fuel efficiency of automobiles and the like has become a major social demand, and for this reason, it has become an important issue, for example, to reduce energy loss during running of tires.
かかるエネルギーロスを低下させる方法としてゴムのレ
ジリエンスを向上させることが有効であることが従来よ
り知られており、そのための方法として、ゴムのミクロ
構造や分子量分布などの改良あるいは有機ゴム薬品や充
填剤の配合処方の改良、レジリエンス向上剤の添加など
の方法もよく知られている。It has long been known that improving the resilience of rubber is an effective way to reduce such energy loss, and methods for this include improving the microstructure and molecular weight distribution of rubber, or adding organic rubber chemicals or fillers. Methods such as improving the formulation and adding resilience-improving agents are also well known.
これらの方法のうち、レジリエンス向上剤を添加する方
法は、他の方法に比して容易にレジリエンスを向上させ
得ることや天然ゴムにも適用可能であることなどから注
目され、かかるレジリエンス向上剤として、たとえば特
開昭５８−１１８８８７号に示されるような特定構造か
らなる８−オキシキノリン誘導体が知られている。Among these methods, the method of adding a resilience improver has attracted attention because it can improve resilience more easily than other methods and can also be applied to natural rubber. For example, 8-oxyquinoline derivatives having a specific structure as shown in JP-A-58-118887 are known.
〈発明が解決しようとする問題点〉
しかし、上記８−オキシキノリン誘導体はレジリエンス
向上についてはすぐれた効果を示すものの、スコーチ性
を早めるという欠点があり、そのため用途が限定される
という問題があった。<Problems to be Solved by the Invention> However, although the above-mentioned 8-oxyquinoline derivatives exhibit excellent effects in improving resilience, they have the disadvantage of accelerating scorch properties, which limits their use. .
このようなことから、本発明者らはスコーチ、性が少な
く、加硫ゴムのレジリエンスを向上させるゴム組成物に
ついて検討の結果、特定構造のジフェニルアミン誘導体
を含有してなるゴム組成物が上記目的に非常に優れるこ
とを見出し、本発明に至った。For these reasons, the present inventors have investigated rubber compositions that have less scorch and improve the resilience of vulcanized rubber, and have found that a rubber composition containing a diphenylamine derivative with a specific structure can meet the above objectives. We have discovered that this is very excellent, and have led to the present invention.
く問題点を解決するための手段〉
本発明は、天然ゴムまたは合成ゴム中に、式で示される
ジフェニルアミン誘導体を含有してなることを特徴とす
るゴム組成物を提供するものである。Means for Solving the Problems> The present invention provides a rubber composition characterized by containing a diphenylamine derivative represented by the formula in natural rubber or synthetic rubber.
本発明におけるジフェニルアミン誘導体はＮ−フェニル
ーｐ−フェニレンジアミンと無水マレイン酸とを反応さ
せることにより製造することができる。The diphenylamine derivative in the present invention can be produced by reacting N-phenyl-p-phenylenediamine and maleic anhydride.
一般に、天然ゴムや合成ゴムに配合剤を配合する場合、
その配合は基本的に２つの工程で行われる。Generally, when compounding agents are added to natural rubber or synthetic rubber,
The formulation is basically carried out in two steps.
すなわち、カーボンブラックなどの充填剤、プロセスオ
イル、ステアリン酸などの配合剤はゴム温度１２０〜１
７０°Ｃ程度の比較的高温での第１の工程で配合され、
加硫促進剤や加硫剤はゴム温度６０〜１２０°Ｃ程度の
比較的低温の第２の工程で配合される。In other words, fillers such as carbon black, process oil, and compounding agents such as stearic acid have a rubber temperature of 120 to 1
It is blended in the first step at a relatively high temperature of about 70°C,
The vulcanization accelerator and the vulcanizing agent are blended in the second step at a relatively low rubber temperature of about 60 to 120°C.
本発明の方法において、ジフェニルアミン誘導体のゴム
への配合方法は任意の方法でＣわれ、加硫促進剤や加硫
剤とともに第２の工程で配合してもよいが、カーボンブ
ラック等が配合される第１の工程で配合するのが好まし
い。その際の配合温度は１５０°Ｃ以上の高温であるこ
とが望ましいが、あまりに高温になるとゴムの酸化劣化
が著しくなる傾向があるため、通常は２００℃以下であ
る。In the method of the present invention, the diphenylamine derivative may be blended into the rubber by any method, and may be blended with a vulcanization accelerator or vulcanizing agent in the second step, but carbon black or the like may be blended. Preferably, it is blended in the first step. The compounding temperature at this time is preferably a high temperature of 150° C. or higher, but if the temperature is too high, oxidative deterioration of the rubber tends to become significant, so the compounding temperature is usually 200° C. or lower.
尚、第１の工程でジフェニルアミン誘導体を添加する際
、助剤として加硫促進剤やポリスルフィド基を有する加
硫剤を併用することによりレジリエンス向上効果をより
改良することができ、更にはこのような助剤を併用する
ことにより第１の工程での配合温度を１２０〜１７０°
Ｃ程度とすることができる。In addition, when adding the diphenylamine derivative in the first step, the resilience improving effect can be further improved by using a vulcanization accelerator or a vulcanizing agent having a polysulfide group as an auxiliary agent. By using an auxiliary agent, the blending temperature in the first step can be adjusted to 120 to 170°.
It can be about C.
本発明に使用し得る加硫促進剤やポリスルフィド基を有
する加硫剤として、具体的にはメルカプトベンゾチアゾ
ール、ジペンゾチアジルジスルフィドなどのチアゾール
類、テトラメチルチウラムジスルフィド、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、ジペンタメチレンチウラムテトラスルフィドなど
のチウラム類、ジエチルジチオリン酸ジスルフィド、ジ
−イソプロジチオリン酸ジスルフィド、ジ−ｎ−プロピ
ルジチオリン酸ジスルフィド、ジオクチルジチオリン酸
ジスルフィド、ジシクロへキシルジチオリン酸ジスルフ
ィド、ジ−イソプロピルジチオリン酸トリスルフィド、
ジ−イソプロピルテトラスルフィドなどのジチオリン酸
類、Ｎ−シクロへキシル−２−ベンゾチアゾールスルフ
ェンアミド、Ｎ−ｔ−ブチル−２−ベンゾチアゾールス
ルフェンアミド、Ｎ−オキシジエチレン−２−ベンゾチ
アゾールスルフェンアミド、Ｎ、Ｎ−ジシクロへキシル
スルフェンアミド、Ｎ、Ｎ−ジイソプロピル−２−ペン
ゾチアゾールスルフエンアミド、２−（モルフォリノジ
チオ）ベンゾチアゾールなどのスルフェンアミド類に例
示される加硫促進剤、ならびにジモルフオリンジスルフ
ィド、アルキルフェノールポリスルフィドなどに例示さ
れる加硫剤が挙げられる。Examples of the vulcanization accelerator and the vulcanizing agent having a polysulfide group that can be used in the present invention include thiazoles such as mercaptobenzothiazole and dipenzothiazyl disulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, and tetrabutyl Thiurams such as thiuram disulfide and dipentamethylenethiolam tetrasulfide, diethyldithiophosphate disulfide, di-isoprodithiophosphate disulfide, di-n-propyldithiophosphate disulfide, dioctyldithiophosphate disulfide, dicyclohexyldithiophosphate disulfide, di-isopropyl dithiophosphate trisulfide,
Dithiophosphoric acids such as di-isopropyl tetrasulfide, N-cyclohexyl-2-benzothiazolesulfenamide, N-t-butyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolesulfenamide , N,N-dicyclohexylsulfenamide, N,N-diisopropyl-2-penzothiazolesulfenamide, 2-(morpholinodithio)benzothiazole, and other sulfenamides. , as well as dimorpholine disulfide, alkylphenol polysulfide, and the like.
これらの加硫促進剤のうち、スコーチ性やレジリエンス
向上効果などから、ジペンゾチアジルジスルフィド、ス
ルフェンアミド項、ジチオリン酸類が好ましく使用され
る。Among these vulcanization accelerators, dipenzothiazyl disulfide, sulfenamide, and dithiophosphoric acids are preferably used because of their effects on improving scorch property and resilience.
本発明において、ジフェニルアミン誘導体の添加量は特
に限定されるものではないが、あまりに少いとレジリエ
ンスの向上効果の発現が不十分であり、また多すぎても
効果が飽和するため不経済となることから、通常ゴム１
００重量部あたり０．１〜１０重量部である。In the present invention, the amount of the diphenylamine derivative added is not particularly limited, but if it is too small, the effect of improving resilience will not be sufficiently expressed, and if it is too large, the effect will be saturated and it will be uneconomical. , normal rubber 1
It is 0.1 to 10 parts by weight per 00 parts by weight.
また、助剤として添加される加硫促進剤やポリスルフィ
ド基を有する加硫剤の添加量は、ジフェニルアミン誘導
体の添加量によっても異るが、通常ゴム１００Ｍ量部あ
たり８重量部以下である。Further, the amount of the vulcanization accelerator or the vulcanizing agent having a polysulfide group added as an auxiliary agent varies depending on the amount of the diphenylamine derivative added, but is usually 8 parts by weight or less per 100 M parts of rubber.
本発明に適用し得るゴムとしては、天然ゴムのほかポリ
イソプレンゴム（ＩＲ）、スチレン・ブタジェン共重合
ゴム（ＳＢＲ）、ポリブタジェンゴム（ＢＲ）、アクリ
ロニトリル、フタジエン共重合ゴム（ＮＢＲ）、イソプ
レン・イソブチレン共重合ゴム（ＩＩＲ）などの各種の
合成ゴムが例示されるが、高不飽和ゴムが好ましい。Rubbers that can be applied to the present invention include, in addition to natural rubber, polyisoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), acrylonitrile, phtadiene copolymer rubber (NBR), and isoprene rubber. - Various synthetic rubbers such as isobutylene copolymer rubber (IIR) are exemplified, but highly unsaturated rubbers are preferred.
また、本発明において、ジフェニルアミン誘導体の配合
にあたって一般の有機ゴム薬品や充填剤などを併用して
もよいことはいうまでもない。Further, in the present invention, it goes without saying that general organic rubber chemicals, fillers, etc. may be used in combination with the diphenylamine derivative.
〈発明の効果〉
本発明のゴム組成物はレジリエンスが向上するのみなら
ず、加硫ゴムの耐熱老化性が向上し、また加硫ゴムの耐
発熱性および耐屈曲亀裂性なども向上するというすぐれ
た効果を有する。<Effects of the Invention> The rubber composition of the present invention not only improves resilience, but also improves the heat aging resistance of vulcanized rubber, and also improves the heat resistance and flex cracking resistance of vulcanized rubber. It has a good effect.
参考例Ｉ
Ｎ−フェニル−ｐ−フェニレンジアミンと無水マレイン
酸を無水酢酸共存下に１００°Ｃ以下の低温で脱水環化
して得られる反応生成物をトルエン中で再結晶精製して
、融点１５５〜１５７°Ｃの赤色結晶状の下記構造式で
示されるＮ−（Ｎ’−フェニル−ｐ−アミノフェニル）
イソマレイミドを得た。Reference Example I The reaction product obtained by cyclodehydration of N-phenyl-p-phenylenediamine and maleic anhydride at a low temperature of 100°C or lower in the coexistence of acetic anhydride is purified by recrystallization in toluene to obtain a product with a melting point of 155-155°C. N-(N'-phenyl-p-aminophenyl) shown by the following structural formula in the form of red crystals at 157°C
Isomaleimide was obtained.
なおこのイソマレイミド体について以下の確認を行なっ
た。The following confirmation was made regarding this isomaleimide compound.
■ 元素分析
Ｃ（％） Ｈ（％） Ｎ（％）計算値 ７
２．７２ ４．５４ １０．６０測定値
７２．９８ ４．６１ １０．６８■ ＦＤ
−ＭＳ
鴇ビーク２６４を確認。■ Elemental analysis C (%) H (%) N (%) Calculated value 7
2.72 4.54 10.60 Measured value
72.98 4.61 10.68■ FD
- Confirmed MS Tobeak 264.
■ ＩＲ Ｃ＝Ｏ伸縮振動１７６０ａｎ Ｉ Ｃ＝Ｎ伸縮振動１６６０ｃｍ−１ を確認っ ■ ＮＭＲ イソマレイシドのプロトンシグナル２ 本６．８，７．５ｐｐｍ（グブレット）を確認。■ IR C=O stretching vibration 1760an I C=N stretching vibration 1660cm-1 Check ■ NMR Proton signal 2 of isomaleiside Confirmed 6.8 and 7.5 ppm (goblet).
なお、本化合物の構造異性体であるマレイミド体、即ち
Ｎ−（Ｎ’−フェニル−ｐ−アミノフェニル）モノマレ
イミドは、１点１８２〜１３５°Ｃの黄色結晶体である
。The maleimide compound, which is a structural isomer of the present compound, ie, N-(N'-phenyl-p-aminophenyl) monomaleimide, is a yellow crystalline substance with a temperature of 182 to 135°C at one point.
実施例１
天然ゴムをベースに下記配合処方に基づきバンバリーミ
キサ−およびオープンミルを用いて、ゴム配合物を作製
し、加硫プレスにより、１４５°Ｃ１４０分の条件で加
流し、所定の形状にした後、各皿試験に供した。なお配
合物のうちカーボンブラック、亜鉛華、プロセスオイル
、ステアリン酸については、第１段目のバンバリーミキ
サ−で各種温度条件で混線配合し、加硫促進剤、イオウ
は、第２段目のオープンミルで４０〜５０°Ｃの温度に
て混線配合した。ジフェニルアミン誘導体は、第１段目
のバンバリーミキサ−で各面温度で、助剤との併用の有
無の系で配合されるか、もしくは、第２段目のオープン
ミルで、加硫促進剤およびイオウと共に配合された。Example 1 A rubber compound was prepared using a Banbury mixer and an open mill based on the following compounding recipe based on natural rubber, and was heated in a vulcanization press at 145°C for 140 minutes to form a predetermined shape. After that, each dish was subjected to a test. Of the ingredients, carbon black, zinc white, process oil, and stearic acid are mixed in the Banbury mixer in the first stage under various temperature conditions, and the vulcanization accelerator and sulfur are mixed in the open mixer in the second stage. Cross-mixing was carried out in a mill at a temperature of 40 to 50°C. The diphenylamine derivative is blended in the first-stage Banbury mixer at each surface temperature, with or without auxiliary agents, or in the second-stage open mill, where it is blended with a vulcanization accelerator and sulfur. It was blended with.
配合条件および結果を第１表に示す。The blending conditions and results are shown in Table 1.
（配合処方）
天然ゴム（ＲＳＳ＃１） １００重】部
ＨＡＦブラック ４５ステアリ
ン酸 ８芳香族系プロセス
オイル ８亜鉛華 ５
加硫促進剤（＊）１
イ オ ウ
２助 剤
０．５ＤＰＡ 表中記
載（＊）ソクシノーノＪＣ２：Ｎ−シクロへキシル−２
−ベンゾチアゾールスルフェンアミド（住友化学）
なお各項の試験法は下記の通りである。(Composition formula) Natural rubber (RSS#1) 100 parts HAF black 45 Stearic acid 8 Aromatic process oil 8 Zinc white 5 Vulcanization accelerator (*) 1 Sulfur
2 Auxiliary agent
0.5DPA Listed in the table (*) Soccinono JC2: N-cyclohexyl-2
-Benzothiazole sulfenamide (Sumitomo Chemical) The test method for each item is as follows.
（１） ムーニースコーチ性
ＪＩＳ−に−８３００に準拠し、１８０°Ｃで最低値よ
り５ポイント上昇までの時間をスコーチタイムとした。(1) Mooney scorch property Based on JIS-8300, the time required for the scorch to rise by 5 points from the lowest value at 180°C was defined as the scorch time.
ただしＳＢＲ系は１８５°Ｃで行なった。However, the SBR system was conducted at 185°C.
（２）引張物性、レジリエンス
ＪＩＳ−に−６８０１に準拠し測定を行なった。引張応
力（Ｍ８００ ’）は、５号型リングを用いた。レジリ
エンスは、リュプケタイプの試験機を用いた。(2) Tensile properties and resilience Measured according to JIS-6801. For tensile stress (M800'), a No. 5 ring was used. Resilience was measured using a Lübke type tester.
（８）耐発熱性 ＡＳＴＭ−Ｄ−６２８−５８に準拠した。(8) Heat resistance Compliant with ASTM-D-628-58.
グツドリッチ式の発熱試験機を用い、荷重８５Ａｂ、、
ストローク６、８５ ｗｇ、振動数１８００ ｒ＊ｐ＊
ｍ−、槽内温度４０℃の条件で、４０分後の発熱温度（
４０分後のゴム温度−槽内温度）を測定した。Using a Gutdrich type heat generation tester, the load was 85 Ab.
Stroke 6, 85 wg, frequency 1800 r*p*
m-, exothermic temperature after 40 minutes under the condition that the temperature inside the tank is 40℃ (
After 40 minutes, the rubber temperature (rubber temperature - tank internal temperature) was measured.
（４）耐屈曲疲労性
モンサント社のＦａｔｉｇｕｅ−ｔｏ−Ｆａｉｌｕｒｅ
’ｒｅｓｔｅｒ を用い、歪み率１００％の条件で、
破断までの屈曲回数を測定した。(4) Flexural fatigue resistance Monsanto's Fatigue-to-Failure
Using 'rester, under the condition of 100% distortion rate,
The number of bends until breakage was measured.
（＊ｌ）助剤は、第１段目のバンバリーミキサ−にて配
合された。(*l) The auxiliary agent was blended in the first stage Banbury mixer.
（＊２） ＤＰＡニジフェニルアミン誘導体。(*2) DPA nidiphenylamine derivative.
Ｂ ニジフェニルアミン誘導体を第１段目のバンバリー
宅キサ−にて配合。B Nidiphenylamine derivative is blended in the first stage at the Banbury home brewing facility.
Ｏ：゛シフエコげミン誘導体を、第２段目のオープンミ
ルにて、比較的低温
で配合。O: ゛Shiffekogemin derivative is blended at a relatively low temperature in the second stage open mill.
（＊ｊｌ） ］［洋精精機うＩプラストミル■を用い
、カーボンブラック他薬剤全て配合後、５０ｒｐｍで（
＊ｓ） ＯＢＳ ：Ｎ−オキシジエチレン−２−
ベンゾチアゾールスルフェンドア
ミド
（＊６） ＤＩＰＤニジイソプロピルジチオリン酸ジ
スルフィド
（＊７） ＤＭＤＳ：ジモルフォリンジスルフィド実
施例２
天然ゴムのかわりに、５ＢＲ１５００を用い、加硫時間
を、１５０℃、５０分とする以外は実施例１と同様の方
法により試験を行なった。(*jl) ] [Using Yosei I Plastomill ■, after blending all the chemicals including carbon black, at 50 rpm (
*s) OBS: N-oxydiethylene-2-
Benzothiazole sulfendamide (*6) DIPD diisopropyl dithiophosphoric acid disulfide (*7) DMDS: dimorpholine disulfide Example 2 5BR1500 was used instead of natural rubber, and the vulcanization time was 150°C for 50 minutes. The test was conducted in the same manner as in Example 1 except for the following.
配合条件および結果を第２表に示す。The blending conditions and results are shown in Table 2.
尚、表中の（＊１）〜 （＊４）は実施例１と同じであ
る。Note that (*1) to (*4) in the table are the same as in Example 1.
Claims (1)
を特徴とするゴム組成物。[Scope of Claims] A rubber composition characterized by containing a diphenylamine derivative represented by the formula ▲numerical formula, chemical formula, table, etc.▼ in natural rubber or synthetic rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16751686A JPS6323943A (en) | 1986-07-16 | 1986-07-16 | Rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16751686A JPS6323943A (en) | 1986-07-16 | 1986-07-16 | Rubber composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6323943A true JPS6323943A (en) | 1988-02-01 |
Family
ID=15851135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16751686A Pending JPS6323943A (en) | 1986-07-16 | 1986-07-16 | Rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6323943A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0448975U (en) * | 1990-08-24 | 1992-04-24 |
-
1986
- 1986-07-16 JP JP16751686A patent/JPS6323943A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0448975U (en) * | 1990-08-24 | 1992-04-24 | ||
| JP2529127Y2 (en) * | 1990-08-24 | 1997-03-19 | 株式会社シマノ | Fishing reel display case |
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