JPH01234442A - Crosslinking agent for rubber polymer - Google Patents
Crosslinking agent for rubber polymerInfo
- Publication number
- JPH01234442A JPH01234442A JP5824988A JP5824988A JPH01234442A JP H01234442 A JPH01234442 A JP H01234442A JP 5824988 A JP5824988 A JP 5824988A JP 5824988 A JP5824988 A JP 5824988A JP H01234442 A JPH01234442 A JP H01234442A
- Authority
- JP
- Japan
- Prior art keywords
- crosslinking agent
- rubber
- sulfur
- reaction
- weight ratio
- 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
- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 37
- 229920001971 elastomer Polymers 0.000 title claims abstract description 30
- 239000005060 rubber Substances 0.000 title claims abstract description 29
- 229920000642 polymer Polymers 0.000 title claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 33
- 239000011593 sulfur Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 12
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 claims abstract description 6
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 229920003051 synthetic elastomer Polymers 0.000 abstract description 7
- 239000005061 synthetic rubber Substances 0.000 abstract description 6
- 229920003052 natural elastomer Polymers 0.000 abstract description 5
- 229920001194 natural rubber Polymers 0.000 abstract description 5
- 244000043261 Hevea brasiliensis Species 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 4
- 238000003878 thermal aging Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 11
- 230000032683 aging Effects 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000009472 formulation Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000003712 anti-aging effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000013329 compounding Methods 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 241001441571 Hiodontidae Species 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000000034 method Methods 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
- 239000008117 stearic acid Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 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 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000006235 reinforcing carbon black Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012261 resinous substance Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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）
この発明は、ゴム重合体用新規架橋剤、特に天然ゴム及
び合成ゴムの架橋に使用され、架橋後のゴムの耐熱老化
性及び動的疲労性を大幅に改良するゴム重合体用架橋剤
に関し、空気入りタイヤを初めベルトなどの工業用ゴム
製品に適用可能である。Detailed Description of the Invention (Field of Industrial Application) The present invention is a novel crosslinking agent for rubber polymers, which is particularly used for crosslinking natural rubber and synthetic rubber, and is used to improve the heat aging resistance and dynamic fatigue resistance of crosslinked rubber. The present invention relates to a crosslinking agent for rubber polymers that significantly improves properties, and can be applied to industrial rubber products such as pneumatic tires and belts.
（従来の技術）
従来、架橋剤に対して望まれる特性は、架橋剤をゴム配
合物中に練りこんだ時にブルーミング傾向が小さく、ス
コーチ安全性が高く、効率的な架橋をつくり、しかも安
価であるという特性であった。更に、最近、空気入りタ
イヤ及びベルト用製品等においては、ゴム組成物の耐熱
老化性及び動的疲労性の改善が強く要求されるに至った
。(Prior Art) Traditionally, the desired properties of a crosslinking agent are that when the crosslinking agent is incorporated into a rubber compound, it has a low tendency to bloom, has high scorch safety, creates efficient crosslinking, and is inexpensive. It was a characteristic that there is. Furthermore, recently, there has been a strong demand for improvements in the heat aging resistance and dynamic fatigue resistance of rubber compositions in products for pneumatic tires and belts.
従来のごとく、硫黄のみを加硫剤として含むゴム組成物
をベースとした加硫ゴムは、一般に、熱による架橋硫黄
の切断、未反応硫黄の二次的架橋反応等に基づく、熱老
化後の硬度及び引張応力の増大、破断時の引張強度及び
伸びの著しい低下などの加熱前後のゴム物性の変化が大
きい。更に、このような硫黄のみによる加硫ゴムは、動
的疲労を与えることによっても、加熱による挙動と同様
な挙動を示しながらへたってゆき、ゴム本来の弾性を失
ってしまう。Conventionally, vulcanized rubbers based on rubber compositions containing only sulfur as a vulcanizing agent generally undergo heat-aging sulfur cleavage, secondary cross-linking reactions of unreacted sulfur, etc. There are significant changes in rubber physical properties before and after heating, such as an increase in hardness and tensile stress, and a significant decrease in tensile strength and elongation at break. Furthermore, even when subjected to dynamic fatigue, such vulcanized rubber made only of sulfur weakens while exhibiting a behavior similar to that caused by heating, and loses its original elasticity.
上記問題の解決に関して、例えば、特開昭６２−８４１
３３号公報にｄ −ＩＪモネン、５−エチリデン−２−
ノルボルネン、スチレン及びジシクロペンタジェンから
選択された不飽和反応体と硫黄とを反応させた生成物を
天然ゴム及び合成ゴムの加硫剤として使用し、これによ
りブルーミング、スコーチ性及び蒸気老化条件下での接
着性を改良しうろことが示されている。Regarding the solution of the above problem, for example, Japanese Patent Application Laid-Open No. 62-841
33, d-IJ monene, 5-ethylidene-2-
The product of the reaction of sulfur with an unsaturated reactant selected from norbornene, styrene and dicyclopentadiene is used as a vulcanizing agent for natural and synthetic rubber, thereby reducing blooming, scorch and steam aging conditions. It has been shown to improve adhesion.
特開昭６２−８４１３３号公報に示される架橋剤は、上
記効果を有するものの、加硫後の耐熱老化性及び動的疲
労性の点で実用上十分とは言えない。特に、この架橋剤
の高硫黄相当配合系においては、従来の耐熱性老化防止
剤を用いてもその効果は不十分であるばかりでなく、ゴ
ム練り、シーテイング、押出し等の加工工程において、
スコーチを起こし、作業性を著しく阻害する欠点がある
。また、使用する耐熱老化防止剤が極めて高価な為、耐
熱性向上に多量に使用することは、経済的に好ましくな
い。Although the crosslinking agent disclosed in JP-A-62-84133 has the above effects, it cannot be said to be practically sufficient in terms of heat aging resistance and dynamic fatigue resistance after vulcanization. In particular, in the high sulfur equivalent compounding system of this crosslinking agent, not only is the effect insufficient even if conventional heat-resistant anti-aging agents are used, but also in processing steps such as rubber kneading, sheeting, extrusion, etc.
It has the disadvantage of causing scorch, which significantly impedes workability. Furthermore, since the heat-resistant anti-aging agent used is extremely expensive, it is economically undesirable to use a large amount to improve heat resistance.
（発明が解決しようとする課題）
ブルーミング傾向が小さく、スコーチ安全性が高いこと
という従来の要求を満たしながら、最近の耐熱老化性及
び動的疲労性の改善要求をも満たすゴム重合体用架橋剤
を提供することがこの発明の解決しようとする課題であ
る。(Problems to be Solved by the Invention) A crosslinking agent for rubber polymers that satisfies the conventional requirements of low blooming tendency and high scorch safety, while also meeting recent demands for improved heat aging resistance and dynamic fatigue resistance. It is an object of the present invention to provide the following.
（課題を解決するための手段）
本発明者は、不飽和有機化合物と硫黄との反応生成物よ
り成る型の架橋剤により上記課題を解決するために鋭意
研究を重ねた結果、不飽和有機化合物として５−ビニル
ビシクロＣ２，２，１）ヘプト−２−エン又は３ａ、
４．７．７ａテトラヒドロインデンを選択した場合、加
硫ゴムの耐熱老化性及び動的疲労性に意外にも顕著な改
善効果があることを見いだし、この知見に基づいてこの
発明をなすに至った。(Means for Solving the Problems) As a result of extensive research to solve the above problems with a crosslinking agent of the type consisting of a reaction product of an unsaturated organic compound and sulfur, the present inventor has discovered that an unsaturated organic compound as 5-vinylbicycloC2,2,1)hept-2-ene or 3a,
It was discovered that when 4.7.7a tetrahydroindene was selected, there was a surprisingly significant improvement effect on the heat aging resistance and dynamic fatigue resistance of vulcanized rubber, and based on this knowledge, the present invention was made. .
すなわち、この発明は、５−ビニルビシクロ［：２．２
．１）ヘプト−２−エン
及び３ａ、 ４．７．７ａテトラヒドロインデンより成
る群の中から選ばれた不飽和五員環を有する有機化合物
の少なくとも１種と硫黄とを５７９５〜９５１５の重量
比の範囲内で加熱反応させて得られる反応生成物より成
るゴム重合体用架橋剤を提供するものである。That is, this invention provides 5-vinylbicyclo[:2.2
．． 1) At least one organic compound having an unsaturated five-membered ring selected from the group consisting of hept-2-ene and 3a, 4.7.7a tetrahydroindene and sulfur in a weight ratio of 5795 to 9515. The object of the present invention is to provide a crosslinking agent for rubber polymers, which is made of a reaction product obtained by heating the reaction within a certain range.
この発明の架橋剤を製造する場合、具体的には前記不飽
和五員環を有する有機化合物Ｉ又は■又は両者の混合物
と硫黄とを、硫黄の融点より高く、かつ不飽和有機化合
物成分をも十分に液体状態に保ちうる温度で反応させる
。反応は、前記温度に保たれた溶融硫黄中にかきまぜな
がら不飽和有機化合物成分を徐々に添加することにより
行うのが好ましく、最終的に不飽和有機化合物成分対硫
黄の重量比が５７９５〜９５１５となり、かつ未反応の
不飽和有機化合物成分がなくなるまで続けられ、これに
より中間生成物を与える。反応時間は、反応温度によっ
て異なるが、数時間程度、例えば約３時間である。この
反応の終結点は、不飽和有機化合物成分のにおいの消失
などで知ることができる。When producing the crosslinking agent of the present invention, specifically, the organic compound I having an unsaturated five-membered ring, The reaction is carried out at a temperature sufficient to maintain the liquid state. The reaction is preferably carried out by gradually adding the unsaturated organic compound component to molten sulfur kept at the above temperature while stirring, and the final weight ratio of the unsaturated organic compound component to sulfur is 5795 to 9515. , and continues until there is no unreacted unsaturated organic compound component, thereby giving an intermediate product. The reaction time varies depending on the reaction temperature, but is about several hours, for example about 3 hours. The end point of this reaction can be determined by the disappearance of the odor of the unsaturated organic compound component.
次いで、この中間生成物を上記温度でかきまぜながら、
更に反応させると、反応混合物の粘度が徐々に上昇して
ゆく、粘度上昇のためかきまぜが不能になる少し前にこ
の後段の反応を停止し、冷却後、反応生成物をゴム練り
ができる程度の適当な粒度に粉砕して架橋剤を得ること
ができる。Next, while stirring this intermediate product at the above temperature,
As the reaction continues, the viscosity of the reaction mixture gradually increases. Just before stirring becomes impossible due to the increase in viscosity, the subsequent reaction is stopped, and after cooling, the reaction product is mixed to a level that can be kneaded into rubber. The crosslinking agent can be obtained by grinding to an appropriate particle size.
前記中間生成物を得る反応温度としては、通常的１３０
〜１７０℃であり、好ましくは１３０〜１４０℃の範囲
である。後段の反応温度も、上記範囲内で行われる。不
飽和有機化合物成分対硫黄の重量比は、５／９５〜９５
１５の範囲内であり、好ましくは３０／７０〜８０／２
０の範囲内である。５７９５未満では、耐熱老化性及び
動的疲労性の改良を達成し得ない。また、９５１５を超
えると、反応時間が大変長くなり、樹脂化に時間がかか
るため、架橋剤として扱うにも作業性が悪化する。更に
、硫黄含有率が低下するほど、硫黄量換算配合において
、架橋剤そのものの投入量が著しく増大する。樹脂量が
著しく増大した場合、これによる配合ゴムの発熱性が悪
化するので、このような条件は避けるべきである。The reaction temperature for obtaining the intermediate product is usually 130
-170°C, preferably in the range of 130-140°C. The reaction temperature in the latter stage is also within the above range. The weight ratio of unsaturated organic compound component to sulfur is 5/95 to 95.
Within the range of 15, preferably 30/70 to 80/2
It is within the range of 0. If it is less than 5795, improvements in heat aging resistance and dynamic fatigue resistance cannot be achieved. Moreover, when it exceeds 9515, the reaction time becomes very long and it takes time to form a resin, so that the workability becomes worse when used as a crosslinking agent. Furthermore, as the sulfur content decreases, the amount of crosslinking agent itself to be added increases significantly in terms of sulfur content. If the amount of resin increases significantly, the heat generation properties of the compounded rubber will deteriorate, so such conditions should be avoided.
反応時間は、通常全体で２〜８時間である。反応時間を
長くすると、硫黄量が短くなり、より硬い樹脂となって
ゆくため、反応温度及び反応時間を変えることにより、
練り込むゴムの硬さ、練り条件、加硫温度、加硫時間の
諸条件に合わせてこの発明の架橋剤の硬さを任意に調節
することができる。The reaction time is usually 2 to 8 hours in total. As the reaction time increases, the amount of sulfur decreases, resulting in a harder resin, so by changing the reaction temperature and reaction time,
The hardness of the crosslinking agent of the present invention can be adjusted as desired depending on the hardness of the rubber to be kneaded, kneading conditions, vulcanization temperature, and vulcanization time.
この発明の架橋剤は、前記不飽和五員環を有する有機化
合物と硫黄とが前記特定の重量比で反応し高分子化され
た軟化点６０〜１３０℃の樹脂状物質である。軟化点が
６０℃未満である場合、架橋剤が低粘性であるので作業
性が劣り、かつ樹脂化反応が完結していないのでこの発
明の効果が十分達成されない。１３０℃番超えると、ゴ
ム練り中に十分な架橋剤の分散が行われず、ゴム物性低
下の原因となりうるので好ましくない。The crosslinking agent of the present invention is a resinous substance having a softening point of 60 to 130° C., which is made into a polymer by reacting the organic compound having an unsaturated five-membered ring with sulfur at the specified weight ratio. If the softening point is less than 60° C., the crosslinking agent has a low viscosity, resulting in poor workability, and the resin formation reaction is not completed, so the effects of the present invention cannot be fully achieved. If the temperature exceeds 130°C, the crosslinking agent will not be sufficiently dispersed during rubber kneading, which may cause deterioration of the physical properties of the rubber, which is not preferable.
この発明の架橋剤は、ゴム重合体用架橋剤として使用さ
れる。ゴムとして天然ゴム及び合成ゴムが用いられ、合
成ゴムとしては、ジエン系合成ゴム特に合成ポリイソプ
レン、ポリブタジェン及びスチレンブタジェンゴムが挙
げられる。この発明の架橋剤の使用量は、ゴム用硫黄又
は不溶性硫黄とほぼ同じ硫黄量となるように該架橋剤の
硫黄含有量（仕込み割合に等しい。）で測って、ゴム１
００重量部当り０．５〜２０重量部、好ましくは１〜１
０重量部の範囲である。The crosslinking agent of this invention is used as a crosslinking agent for rubber polymers. Natural rubber and synthetic rubber are used as the rubber, and examples of the synthetic rubber include diene-based synthetic rubbers, particularly synthetic polyisoprene, polybutadiene and styrene-butadiene rubbers. The amount of crosslinking agent used in this invention is measured by the sulfur content (equal to the charging ratio) of the crosslinking agent so that the amount of sulfur is approximately the same as that of rubber sulfur or insoluble sulfur.
0.5 to 20 parts by weight per 00 parts by weight, preferably 1 to 1
It is in the range of 0 parts by weight.
この発明の架橋剤は、通常の硫黄加硫の場合と同様に、
補強性カーボンブラック、軟化剤、ＺｎＯ、ステアリン
酸、加硫促進剤、老化防止剤等を必要量とともに配合す
ることができる。The crosslinking agent of this invention, as in the case of normal sulfur vulcanization,
Reinforcing carbon black, a softener, ZnO, stearic acid, a vulcanization accelerator, an anti-aging agent, etc. can be blended together with necessary amounts.
この発明の架橋剤は、空気入りタイヤを初め工業用ベル
）１品に至るまで、耐熱老化性、耐熱性、動的疲労性の
改善が特に要求されるゴム製品に幅広く利用することが
できる。The crosslinking agent of the present invention can be widely used in rubber products that particularly require improvements in heat aging resistance, heat resistance, and dynamic fatigue resistance, from pneumatic tires to industrial bells.
（実施例） 以下この発明を例によって説明する。(Example) The invention will now be explained by way of example.
参考例１ この発明の架橋剤を以下の方法により製造した。Reference example 1 The crosslinking agent of this invention was produced by the following method.
マグネチックスクーラーをそなえる５００ｍ１ビーカー
に硫黄３５０ｇを入れ、オイルバス上で１３０℃に加熱
溶融した。これにかきまぜながら５−ビニルビシクロ（
２，２，１３ヘプト−２−エン（１）粉末１５０ｇを約
３０分間にわたって徐々に添加した。350 g of sulfur was placed in a 500 ml beaker equipped with a magnetic cooler and melted by heating to 130° C. on an oil bath. While stirring, add 5-vinylbicyclo(
150 g of 2,2,13 hept-2-ene (1) powder was added gradually over about 30 minutes.
１／Ｓ重量比３０／７０゜更に、かきまぜながら１３０
℃で３時間反応させると、化合物（Ｉ）のにおいがなく
なって、化合物（Ｉ）がほとんどすべて反応したことが
分かった。1/S weight ratio 30/70゜Furthermore, while stirring, 130
After 3 hours of reaction at °C, the odor of compound (I) disappeared, indicating that almost all of compound (I) had reacted.
上記中間生成物を、更に１３０℃に加熱し続けると、反
応がいっそう進行して粘度が徐々に上昇してゆく。かき
まぜが不能になる程度に粘度が上昇する少し前に加熱を
中止し、ビーカーの内容物を水中に流しこみ急冷した。When the intermediate product is further heated to 130° C., the reaction proceeds further and the viscosity gradually increases. Heating was stopped shortly before the viscosity rose to such an extent that stirring became impossible, and the contents of the beaker were poured into water and rapidly cooled.
次いで、この反応生成物を取り出し、−昼夜室温で放置
後、粉砕してゴム用材料としてゴム練りができる程度の
固形状粒子とした。硫黄含量７０重量％、これを架橋剤
（Ａ） と呼ぶ。Next, this reaction product was taken out, left to stand at room temperature day and night, and then pulverized into solid particles that could be kneaded into rubber as a rubber material. The sulfur content is 70% by weight, and this is called the crosslinking agent (A).
参考例２
を考例１の５−ビニルビシクロ（２，２，１：）ヘプト
−２−エンの代わりに３ａ、 ４．７．７ａテトラヒド
ロインデン（ＩＩ） ３５０ｇを用い、硫黄１５０ｇを
用いた。Ｉｆ／Ｓ重量比７０／３０゜その外は参考例１
と同様に行ってこの発明の架橋剤（Ｂ）を得た。硫黄含
量３０重量％。Reference Example 2 was prepared using 350 g of 3a, 4.7.7a tetrahydroindene (II) instead of 5-vinylbicyclo(2,2,1:)hept-2-ene in Example 1, and 150 g of sulfur. If/S weight ratio 70/30°Other reference example 1
A crosslinking agent (B) of the present invention was obtained in the same manner as above. Sulfur content 30% by weight.
実施例１〜４．比較例１〜４
比較例１及び３は、対照配合であり、比較例１は次に示
す配合系イ、比較例３は次に示す配合系口を用いた。Examples 1-4. Comparative Examples 1 to 4 Comparative Examples 1 and 3 were control formulations; Comparative Example 1 used the following formulation system A, and Comparative Example 3 used the following formulation system.
配合系イ
配合剤 重量部
天然ゴムＲ３Ｓ ＃１ １００１１ＡＦカ
ーボンブラツク ５０アロマオイル
１０
ステアリン酸 °３
Ｚｎ０ ５
ナフテン酸コバルト ４
老化防止剤サンフレツクス１３１
促進剤 Ｎ０ＢＳ ” ０．５硫黄
６．０
本ＩＮ−オキシジエチレン−２−ベンツ′チアジルスル
フエンアミド
配合系口
配合剤 重量部
Ｓ Ｂ ＲＪＳＲ１５０２” １００ＩＳ
ＡＦカーボンブラツク ６０アロマオイル
１０
ステアリン酸 ｌ
ＺｎＯ３
促進剤ＤＰＧ９２０．５
促進剤Ｄ）、１ ０３１．０
老化防止剤サントフレックス１３ １．０硫黄
４．０
料日本合成ゴム社製ＳＢＲ
本２ジフエニルグアニジン
零３ジベンゾチアジルジスルフィド
実施例１． ２及び比較例２は配合系イを、実施例３．
４及び比較例４は配合系口を用いるが、これらの例では
、それぞれ配合系中の硫黄の代わりにこれに相当する硫
黄含量を有する架橋剤の量を配合し、更に、架橋剤（Ｂ
）を用いた実施例２及び４では、配合系中のアロマオイ
ルは配合しなかった。比較例２及び４の架橋剤（Ｃ）は
、特開昭６２−８４１３３号公報記載の例によってジシ
クロペンタジェンと硫黄とから合成した架橋剤であり、
その硫黄含量８０重量％であった。Compounding system A Compounding agent Part by weight Natural rubber R3S #1 10011AF Carbon Black 50 Aroma oil
10 Stearic acid °3 Zn0 5 Cobalt naphthenate 4 Anti-aging agent Sunflex 131 Accelerator N0BS ” 0.5 Sulfur
6.0 IN-oxydiethylene-2-benz'thiadylsulfenamide compounding agent Part by weight S B RJSR1502" 100IS
AF carbon black 60 aroma oil
10 Stearic acid l ZnO3 Accelerator DPG920.5 Accelerator D), 1 031.0 Anti-aging agent Santoflex 13 1.0 Sulfur
4.0 SBR manufactured by Nippon Gosei Rubber Co., Ltd. Diphenylguanidine Zero 3 Dibenzothiazyl disulfide Example 1. Comparative Example 2 and Comparative Example 2 use the blending system A, and Example 3.
4 and Comparative Example 4 use a blending system, but in these examples, instead of sulfur in the blending system, an amount of a crosslinking agent having a corresponding sulfur content is blended, and a crosslinking agent (B
) in Examples 2 and 4, no aroma oil was blended in the blending system. The crosslinking agent (C) in Comparative Examples 2 and 4 was a crosslinking agent synthesized from dicyclopentadiene and sulfur according to the example described in JP-A-62-84133,
Its sulfur content was 80% by weight.
前記及び第１表に示す配合内容の組成物を、１４５℃で
４５分間加硫した。この加硫ゴムの物性評価は、次に示
す方法に従って行った。The compositions having the formulations shown above and shown in Table 1 were vulcanized at 145° C. for 45 minutes. The physical properties of this vulcanized rubber were evaluated according to the following method.
（１）オリジナル物性の破断伸び（Ｅ＋＋） 、破断強
度（Ｔ、）の測定
ＪＩＳ Ｋ ６３０１の引張り試験法によった。(1) Measurement of original physical properties of elongation at break (E++) and strength at break (T, ) The tensile test method of JIS K 6301 was used.
（２）耐熱老化性
オリジナルの物性測定用のテストピースをギヤーオーブ
ン中で１２０℃×７２時間放置後、ＪＩＳ Ｋ６３０１
法によりＥＢ、 ＴＢ及び１００％モジュラス値（１０
０％−１０ｄ）を測定し、オリジナルのもの対比の物性
の保持率（％）で示した。値の大きいほど良好である。(2) Heat aging resistance After leaving the original test piece for physical property measurement in a gear oven at 120°C for 72 hours, it was tested according to JIS K6301.
EB, TB and 100% modulus value (10
0%-10d) was measured and expressed as the retention rate (%) of physical properties compared to the original. The larger the value, the better.
（３）耐熱性
ギヤーオーブン中で１００℃で０．５時間放置後、１０
０℃の雰囲気恒温槽で月Ｓ Ｋ ６３０１に基づく引張
り試験でＥａ 、 Ｔｓを測定した。(3) After being left at 100℃ for 0.5 hours in a heat-resistant gear oven, 10
Ea and Ts were measured by a tensile test based on Moon SK 6301 in a 0°C atmospheric constant temperature bath.
（４） Ｍ、 Ｓ、Ｔ。(4) M, S, T.
東洋精機製のムーニー粘度計を用い、試験温度１３０℃
にてムーニー値の最低値（ＭＬ−＋、、）から５ポイン
ト上昇時点までの時間を測定し、各表示した。値が大き
いほどスコーチ性が良好であることを示す。Using a Mooney viscometer manufactured by Toyo Seiki, the test temperature was 130°C.
The time from the lowest Mooney value (ML-+, . . .) to the time point when the Mooney value increased by 5 points was measured and displayed. The larger the value, the better the scorch property.
（５）ブルーム性
各配合ゴムを室内１０インチロールで温度１１０℃で２
０分間機械的刺激を与えた後、１ｍｍ厚さのシート状に
して室温で放置し、ブルーム度を指数により評価した。(5) Bloom property Each compounded rubber was rolled indoors with a 10-inch roll at a temperature of 110°C.
After applying mechanical stimulation for 0 minutes, it was formed into a 1 mm thick sheet and left at room temperature, and the degree of bloom was evaluated using an index.
ブルーム度指数は、肉眼により評価してブルームが皆無
の状態を０、全面ブルームの状態を１０とし、それらの
間をブルーム発生面積に応じて各段階に区分し、経時変
化を見た。値の小さいほど良好である。The bloom degree index was evaluated with the naked eye, with 0 indicating no blooms and 10 indicating full bloom, and these were divided into stages according to the area where blooms occurred, and changes over time were observed. The smaller the value, the better.
（６）耐疲労性（ｖＪ的疲労性）
デマチャ式試験機を用いて、３００回／分の速さで１２
時間屈曲疲労を与え、疲労後の試験片をスライスし、Ｄ
ＩＮ引張試験によりＥ、、 ＴＢ及び１００％モジニラ
スを測定した。(6) Fatigue resistance (vJ fatigue resistance) Using a Demacha type tester, 12
Apply time bending fatigue, slice the specimen after fatigue, D
E, TB and 100% modinilas were determined by IN tensile test.
（発明の効果）
実施例及び比較例から明らかなように、この発明の架橋
剤（Ａ）（実施例１，３）及び（Ｂ）（実施例２，４）
は、従来の硫黄配合（対照配合：比較例１．３）はもと
より、先行技術に開示される架橋剤Ｃ（比較例２．４）
より、オリジナル物性がすぐれ、スコーチ性及びブルー
ム性も同時に改良されており、しかも特に耐熱老化性の
改良が著しく（２５％程度）、耐熱性及び動的疲労性も
顕著に改良されている。これは、特開昭６２−８４１３
３号公報記載の先行技術からも全く予期し得ない効果で
ある。この発明の架橋剤は、上記効果により、空気入り
タイヤ、工業用ゴムベルト製品等のゴム製品の実用要求
を十分満足させるものである。(Effect of the invention) As is clear from the Examples and Comparative Examples, the crosslinking agent (A) (Examples 1, 3) and (B) (Examples 2, 4) of the present invention
is a conventional sulfur formulation (control formulation: Comparative Example 1.3) as well as crosslinking agent C disclosed in the prior art (Comparative Example 2.4).
Therefore, the original physical properties are excellent, and the scorch property and bloom property are also improved at the same time.In particular, the heat aging resistance is significantly improved (about 25%), and the heat resistance and dynamic fatigue property are also significantly improved. This is Japanese Patent Publication No. 62-8413
This effect is completely unexpected from the prior art described in Publication No. 3. Due to the above effects, the crosslinking agent of the present invention fully satisfies the practical requirements for rubber products such as pneumatic tires and industrial rubber belt products.
Claims (1)
ン及び３ａ，４，７，７ａテトラヒドロインデンより成
る群の中から選ばれた不飽和五員環を有する有機化合物
の少なくとも１種と硫黄とを５／９５〜９５／５の重量
比の範囲内で加熱反応させて得られる反応生成物より成
ることを特徴とするゴム重合体用架橋剤。[Scope of Claims] Having an unsaturated five-membered ring selected from the group consisting of 1,5-vinylbicyclo[2.2.1]hept-2-ene and 3a,4,7,7a tetrahydroindene A crosslinking agent for rubber polymers, comprising a reaction product obtained by subjecting at least one organic compound and sulfur to a heat reaction within a weight ratio of 5/95 to 95/5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5824988A JPH01234442A (en) | 1988-03-14 | 1988-03-14 | Crosslinking agent for rubber polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5824988A JPH01234442A (en) | 1988-03-14 | 1988-03-14 | Crosslinking agent for rubber polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01234442A true JPH01234442A (en) | 1989-09-19 |
Family
ID=13078853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5824988A Pending JPH01234442A (en) | 1988-03-14 | 1988-03-14 | Crosslinking agent for rubber polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01234442A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003080533A1 (en) * | 2002-03-25 | 2003-10-02 | Nippon Oil Corporation | Method for producing material containing modified sulfur |
-
1988
- 1988-03-14 JP JP5824988A patent/JPH01234442A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003080533A1 (en) * | 2002-03-25 | 2003-10-02 | Nippon Oil Corporation | Method for producing material containing modified sulfur |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2655500B1 (en) | Vegetable oil derivatives as extender oils for elastomer compositions. | |
| DE60133364T2 (en) | RUBBER COMPOSITION AND NETWORKED RUBBER | |
| TW201527395A (en) | Functionalized polymer composition | |
| Tamási et al. | Effect of different sulfur content in Natural Rubber mixtures on their thermo-mechanical and surface properties | |
| JP2011046858A (en) | Vulcanized rubber and method of manufacturing the same | |
| KR950001637B1 (en) | Ethylene-propylen-diene rubber, elastomer composition, and canized rubber prepared therefrom | |
| Payungwong et al. | The role of model fatty acid and protein on thermal aging and ozone resistance of peroxide vulcanized natural rubber | |
| JP2002362107A (en) | Radial tire for heavy-duty vehicle | |
| US7678855B2 (en) | Rubber composition | |
| US5998531A (en) | Vulcanizable rubber composition for use as hot-water seals | |
| JP2011012096A (en) | Vulcanized rubber and production method of the same | |
| WO2021039408A1 (en) | Vulcanized rubber composition, production method for vulcanized rubber composition, and tire | |
| US6245861B1 (en) | Use of peroxides to crosslink rubber compositions containing high vinyl styrene-butadiene rubber | |
| JPH01234442A (en) | Crosslinking agent for rubber polymer | |
| US3259598A (en) | Vulcanizing agent prepared from sulfur, linseed oil and styrene | |
| US3231546A (en) | Solid styrene-sulfur compounds and vulcanizates made therewith | |
| JP4748898B2 (en) | Radial tire for large vehicle and rubber composition | |
| JP2001323071A (en) | Method for producing carbon master batch | |
| JPH02284935A (en) | Rubber composition | |
| JP3469376B2 (en) | Rubber composition | |
| US2540651A (en) | Compounding vulcanizable elastomers employing bitumen softeners and resultant vulcanizates | |
| JPH02163139A (en) | Nitrile rubber compound | |
| KR20020003414A (en) | Rubber composition for bead insulation | |
| JPH0826177B2 (en) | Method for producing vulcanizing agent for rubber polymer | |
| JP2001335662A (en) | New vulcanizing agent for diene-based rubber and rubber composition using the same |