JPH04216837A - Rubber composition, hose, and production of hose - Google Patents
Rubber composition, hose, and production of hoseInfo
- Publication number
- JPH04216837A JPH04216837A JP40322490A JP40322490A JPH04216837A JP H04216837 A JPH04216837 A JP H04216837A JP 40322490 A JP40322490 A JP 40322490A JP 40322490 A JP40322490 A JP 40322490A JP H04216837 A JPH04216837 A JP H04216837A
- Authority
- JP
- Japan
- Prior art keywords
- hose
- rubber
- vulcanization
- rubber composition
- vulcanized
- 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.)
- Withdrawn
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 87
- 239000005060 rubber Substances 0.000 title claims abstract description 87
- 239000000203 mixture Substances 0.000 title claims description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 33
- 150000001993 dienes Chemical class 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- 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 claims abstract description 7
- 238000004073 vulcanization Methods 0.000 claims description 59
- 239000004636 vulcanized rubber Substances 0.000 claims description 23
- 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 claims description 7
- 230000000704 physical effect Effects 0.000 abstract description 14
- 229920000459 Nitrile rubber Polymers 0.000 description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 description 7
- 239000002174 Styrene-butadiene Substances 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VXPSQDAMFATNNG-UHFFFAOYSA-N 3-[2-(2,5-dioxopyrrol-3-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C(=CC=CC=2)C=2C(NC(=O)C=2)=O)=C1 VXPSQDAMFATNNG-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、高温加硫を行なっても
優れた物性の加硫ゴムとなるゴム組成物、少なくとも一
層が該ゴム組成物の加硫ゴムで構成されてなるホース、
および、該ゴム組成物を用い、高温で加硫を行なうホー
スの製造方法に関する。[Industrial Application Field] The present invention relates to a rubber composition that becomes a vulcanized rubber with excellent physical properties even when vulcanized at high temperatures, a hose having at least one layer composed of the vulcanized rubber of the rubber composition, and
The present invention also relates to a method for producing a hose using the rubber composition and performing vulcanization at a high temperature.
【０００２】0002
【従来の技術】従来より、ホースの生産性改善を目的と
して、連続加硫化や加硫の短時間化が検討されている。
このような連続加硫化や加硫の短時間化を実現する一手
法として、加硫を通常の加硫温度（１３０℃〜１７０℃
）で行なわずに高温（１８０〜２５０℃）で行なう方法
が知られている。BACKGROUND OF THE INVENTION Conventionally, continuous vulcanization and shortening of vulcanization time have been studied for the purpose of improving productivity of hoses. As a method for achieving continuous vulcanization and shortening the time of vulcanization, vulcanization is carried out at normal vulcanization temperatures (130°C to 170°C).
), but a method is known in which the process is carried out at high temperature (180 to 250°C).
【０００３】ところで、周知のように、ゴム組成物に用
いられるポリマーには多種類あり、ＣＳＭ、ＡＣＭ、Ｆ
ＫＭ等を含むゴム組成物は、高温加硫を行なっても十分
な物性を有する加硫ゴムとなる。しかし、ジエン系ポリ
マーを含むゴム組成物を高温加硫すると、引張り強さ並
びに引張り応力が低く、かつ、圧縮永久歪率が大きい、
物性に劣る加硫ゴムしか得られず、従って、高圧ホース
等の大きいゴム弾性が要求される製品の製造に際しては
、ジエン系ポリマーを含むゴム組成物を用いる場合、高
温加硫を行なうことができなかった。By the way, as is well known, there are many types of polymers used in rubber compositions, including CSM, ACM, F
A rubber composition containing KM or the like becomes a vulcanized rubber having sufficient physical properties even after high-temperature vulcanization. However, when a rubber composition containing a diene polymer is vulcanized at high temperature, the tensile strength and tensile stress are low, and the compression set is high.
Only vulcanized rubber with inferior physical properties can be obtained. Therefore, when manufacturing products that require high rubber elasticity such as high-pressure hoses, high-temperature vulcanization cannot be performed when using a rubber composition containing a diene polymer. There wasn't.
【０００４】0004
【発明が解決しようとする課題】本発明は、ジエン系ポ
リマーを主成分とするゴム組成物であって、高温で加硫
されても、優れた物性を示す加硫ゴムとなるゴム組成物
、少なくとも一層が該ゴム組成物の加硫ゴムで構成され
てなるホース、および、該ゴム組成物を用い、高温加硫
の工程を経るホースの製造方法の提供を目的とする。SUMMARY OF THE INVENTION The present invention relates to a rubber composition containing a diene polymer as a main component, which becomes a vulcanized rubber that exhibits excellent physical properties even when vulcanized at high temperatures. The object of the present invention is to provide a hose at least one layer of which is composed of a vulcanized rubber of the rubber composition, and a method for manufacturing a hose that uses the rubber composition and undergoes a high-temperature vulcanization process.
【０００５】[0005]
【課題を解決するための手段】本発明第一の態様は、ポ
リマー（Ａ）中の主成分がジエン系ポリマー（ａ）であ
り、加硫系（Ｂ）として、硫黄（ｂ）、ジベンゾチアジ
ル・ジスフィド（Ｃ）および／またはテトラメチルチウ
ラム・モノスルフィド（ｄ）、および、Ｎ，Ｎ´−ｍ−
フェニレンジマレイミド（ｅ）を含有し、Ｎ，Ｎ´−ｍ
−フェニレンジマレイミド（ｅ）の含有量は、前記ポリ
マー（Ａ）１００重量部に対して０．１重量部以上であ
ることを特徴とするゴム組成物である。[Means for Solving the Problems] In the first aspect of the present invention, the main component in the polymer (A) is a diene polymer (a), and the vulcanization system (B) includes sulfur (b), dibenzothia dilsulfide (C) and/or tetramethylthiuram monosulfide (d), and N,N'-m-
Contains phenylene dimaleimide (e), N,N'-m
- The rubber composition is characterized in that the content of phenylene dimaleimide (e) is 0.1 parts by weight or more based on 100 parts by weight of the polymer (A).
【０００６】本発明第二の態様は、ホースの内管ゴム層
、中間ゴム層および外管ゴム層のうちのいずれか一層以
上が、本発明第一の態様のゴム組成物の加硫ゴムで構成
されてなることを特徴とするホースである。[0006] In a second aspect of the present invention, at least one of the inner tube rubber layer, intermediate rubber layer, and outer tube rubber layer of the hose is made of the vulcanized rubber of the rubber composition of the first aspect of the present invention. This hose is characterized by being configured as follows.
【０００７】また、本発明第三の態様は、未加硫ホース
の内管ゴム層、中間ゴム層および外管ゴム層のうちのい
ずれか一層以上を本発明第一の態様のゴム組成物で構成
し、それを１８０〜２５０℃で加硫することを特徴とす
るホースの製造方法である。[0007] Furthermore, in a third aspect of the present invention, at least one of the inner tube rubber layer, intermediate rubber layer, and outer tube rubber layer of the unvulcanized hose is made of the rubber composition of the first aspect of the present invention. This is a method for manufacturing a hose, which comprises vulcanizing the same at 180 to 250°C.
【０００８】以下に、本発明を詳細に説明する。はじめ
に、本発明第一の態様について説明する。The present invention will be explained in detail below. First, the first aspect of the present invention will be explained.
【０００９】本発明第一の態様のゴム組成物中に含有さ
れるポリマー（Ａ）は、ジエン系ポリマー（ａ）を主成
分とする構成となっている。The polymer (A) contained in the rubber composition of the first aspect of the present invention has a structure in which the diene polymer (a) is the main component.
【００１０】ここで、「主成分とする」とは、ポリマー
（Ａ）中の約５０重量％以上がジエン系ポリマー（ａ）
であることをいう。Here, "containing as a main component" means that about 50% by weight or more of the polymer (A) is the diene polymer (a).
It means that.
【００１１】本発明で用いるジエン系ポリマー（ａ）は
、通常ゴム組成物に用いられているジエン系ポリマーで
あればいずれでもよいが、一例を挙げると、天然ゴム（
ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（Ｂ
Ｒ）、１，２−ポリブタジエン（１，２−ＢＲ）、スチ
レン−ブタジエンゴム（ＳＢＲ）、クロロプレンゴム（
ＣＲ）、アクリロニトリルブタジエンゴム（ＮＢＲ）、
ブチルゴム（ＩＩＲ）等がある。The diene polymer (a) used in the present invention may be any diene polymer commonly used in rubber compositions, but for example, natural rubber (
NR), isoprene rubber (IR), butadiene rubber (B
R), 1,2-polybutadiene (1,2-BR), styrene-butadiene rubber (SBR), chloroprene rubber (
CR), acrylonitrile butadiene rubber (NBR),
There are butyl rubber (IIR), etc.
【００１２】また、ジエン系ポリマー（ａ）と併用され
るポリマーとしては、硫黄加硫可能なポリマーが挙げら
れ、具体的には、ＣＳＭ、ＥＰＤＭ、ＨＳＮ、ＡＣＭ等
が例示される。[0012] Examples of the polymer used in combination with the diene polymer (a) include sulfur-vulcanizable polymers, and specific examples include CSM, EPDM, HSN, and ACM.
【００１３】本発明第一の態様のゴム組成物は、その加
硫系（Ｂ）に特徴がある。The rubber composition according to the first aspect of the present invention is characterized by its vulcanization system (B).
【００１４】すなわち、加硫系（Ｂ）として、硫黄（ｂ
）、ジベンゾチアジル・ジスルフィド（ｃ）および／ま
たはテトラメチルチウラム・モノスルフィド（ｄ）、お
よび、Ｎ，Ｎ´−ｍ−フェニレンジマレイミド（ｅ）を
含有する。That is, as the vulcanization system (B), sulfur (b
), dibenzothiazyl disulfide (c) and/or tetramethylthiuram monosulfide (d), and N,N'-m-phenylene dimaleimide (e).
【００１５】加硫系（Ｂ）のうち、硫黄（ｂ）は、古く
から知られている加硫剤であり、粉末硫黄、不溶性硫黄
、高分散性硫黄等があるが、いずれを用いてもよい。In the vulcanization system (B), sulfur (b) is a vulcanizing agent that has been known for a long time, and there are powdered sulfur, insoluble sulfur, highly dispersed sulfur, etc., but no matter which one is used, good.
【００１６】また、本発明第一の態様のゴム組成物の硫
黄（ｂ）含有量は、特に限定されないが、通常は、前記
ポリマー（Ａ）１００重量部に対して０．５〜５重量部
程度含有させる。この範囲内であると、伸び、硬さ、応
力、圧縮永久歪等で示される諸物性に優れる加硫ゴムが
得られる。The sulfur (b) content of the rubber composition of the first aspect of the present invention is not particularly limited, but is usually 0.5 to 5 parts by weight per 100 parts by weight of the polymer (A). Contain a certain amount. Within this range, a vulcanized rubber with excellent physical properties such as elongation, hardness, stress, and compression set can be obtained.
【００１７】加硫系（Ｂ）のうち、ジベンゾチアジル・
ジスフィド（ｃ）およびテトラメチルチウラム・モノス
ルフィド（ｄ）は、加硫促進剤として知られる化合物で
ある。Of the vulcanization system (B), dibenzothiazyl
Disulfide (c) and tetramethylthiuram monosulfide (d) are compounds known as vulcanization accelerators.
【００１８】ゴム組成物に用いられる加硫促進剤として
は、多種類の化合物が知られているが、本発明では、ジ
ベンゾチアジル・ジスルフィド（ｃ）および／またはテ
トラメチルチウラム・モノスルフィド（ｄ）を用いる。
これ以外の加硫促進剤を用いると、高温加硫した際に、
前記諸物性に優れる加硫ゴムが得られない。Many types of compounds are known as vulcanization accelerators used in rubber compositions, but in the present invention, dibenzothiazyl disulfide (c) and/or tetramethylthiuram monosulfide (d ) is used. If other vulcanization accelerators are used, during high temperature vulcanization,
Vulcanized rubber excellent in the above-mentioned physical properties cannot be obtained.
【００１９】本発明第一の態様のゴム組成物の、ジベン
ゾチアジル・ジスルフィド（ｃ）および／またはテトラ
メチルチウラム・モノスルフィド（ｄ）含有量は、特に
限定されないが、通常は、前記ポリマー（Ａ）１００重
量部に対して０．１〜５重量部程度含有させる。この範
囲内であると、効果的且つ実用的である。The content of dibenzothiazyl disulfide (c) and/or tetramethylthiuram monosulfide (d) in the rubber composition of the first aspect of the present invention is not particularly limited, but usually the content of the polymer ( A) Contain about 0.1 to 5 parts by weight per 100 parts by weight. Within this range, it is effective and practical.
【００２０】加硫系（Ｂ）のうち、Ｎ，Ｎ´−ｍ−フェ
ニレンジマレイミド（ｅ）は、加硫ゴムの耐熱性を向上
させる化合物として知られている。 そして、本発明
においては、ゴム組成物が高温加硫された場合にも、前
記諸物性に優れる加硫ゴムとなることに対し、加硫系の
他の成分と相乗的に寄与しているものと思われる。Of the vulcanization system (B), N,N'-m-phenylene dimaleimide (e) is known as a compound that improves the heat resistance of vulcanized rubber. Further, in the present invention, even when the rubber composition is vulcanized at high temperature, the components that contribute synergistically with other components of the vulcanization system to become a vulcanized rubber with excellent physical properties as described above. I think that the.
【００２１】本発明第一の態様のゴム組成物のＮ，Ｎ´
−ｍ−フェニレンジマレイミド（ｅ）含有量は、前記ポ
リマー（Ａ）１００重量部に対して０．１重量部以上で
あるが、０．５〜５重量部が好ましく、０．５〜２重量
部がさらに好ましい。０．１重量部未満であると、高温
加硫された加硫ゴムが、前記諸物性に優れるものとなら
ない。また、その含有量に特に上限はないが、約２重量
部で十分な効果が得られ、約５重量部で効果が飽和する
ので、それ以上含有させても、コストの点で不利となる
ばかりである。N, N' of the rubber composition of the first embodiment of the present invention
-m-phenylene dimaleimide (e) content is 0.1 parts by weight or more based on 100 parts by weight of the polymer (A), preferably 0.5 to 5 parts by weight, and preferably 0.5 to 2 parts by weight. Part is more preferable. If it is less than 0.1 part by weight, the vulcanized rubber vulcanized at high temperature will not have excellent physical properties. Although there is no upper limit to its content, a sufficient effect can be obtained with about 2 parts by weight, and the effect is saturated with about 5 parts by weight, so even if it is contained in more than that, it will only be disadvantageous in terms of cost. It is.
【００２２】以上が本発明第一の態様のゴム組成物の必
須成分とそれらの含有割合であるが、このゴム組成物に
は、必要に応じ、通常使用されているマグネシア等の受
酸剤、充填剤、補強剤、可塑剤、老化防止剤、加工助剤
等の配合剤も含有せしめてもよい。The above are the essential components and their content ratios of the rubber composition according to the first aspect of the present invention. This rubber composition may optionally contain commonly used acid acceptors such as magnesia, Compounding agents such as fillers, reinforcing agents, plasticizers, anti-aging agents, and processing aids may also be included.
【００２３】本発明第一の態様のゴム組成物は、タイヤ
、ベルト、型物、ロール、ホースを始めとする、多くの
ゴム製品に応用することができるが、特に、連続加硫、
短時間加硫等を行なうために１８０〜２５０℃程度の高
温で加硫されて製造されるゴム製品に好適である。
より具体的には、一般油圧機器用高低圧ホース、自動車
用高低圧ホース、水、空気用一般高低圧ホース等に用い
るとよい。The rubber composition of the first aspect of the present invention can be applied to many rubber products including tires, belts, molds, rolls, and hoses, but it is particularly applicable to continuous vulcanization,
It is suitable for rubber products manufactured by vulcanization at a high temperature of about 180 to 250° C. for short-time vulcanization. More specifically, it may be used in high and low pressure hoses for general hydraulic equipment, high and low pressure hoses for automobiles, general high and low pressure hoses for water and air, and the like.
【００２４】本発明第一の態様のゴム組成物の加硫方法
は、通常行なわれる方法、すなわち、１３０〜１８０℃
程度の温度で、プレス加硫、温水加硫等の方法で加硫し
てもよいが、１８０〜２５０℃程度の高温で、熱風加硫
（ＨＡＶ）、ロートキュア、ＬＣＭ、流動床加硫、マイ
クロ波加硫（ＶＨＦ）、蒸気加硫等の連続加硫に適した
加硫方法を採用し、連続加硫を行なってもよい。The rubber composition according to the first aspect of the present invention is vulcanized by a conventional method, that is, from 130 to 180°C.
Vulcanization may be carried out by press vulcanization, hot water vulcanization, etc. at a temperature of about 180 to 250 °C, but hot air vulcanization (HAV), roto cure, LCM, fluidized bed vulcanization, Continuous vulcanization may be performed by employing a vulcanization method suitable for continuous vulcanization, such as microwave vulcanization (VHF) or steam vulcanization.
【００２５】次に、本発明第二の態様について説明する
。本発明第二の態様は、ホースの内管ゴム層、中間ゴム
層および外管ゴム層のうちのいずれか一層以上が、本発
明第一の態様のゴム組成物の加硫ゴムで構成されてなる
ことを特徴とするホースである。Next, the second aspect of the present invention will be explained. In a second aspect of the present invention, at least one of the inner tube rubber layer, intermediate rubber layer, and outer tube rubber layer of the hose is composed of the vulcanized rubber of the rubber composition of the first aspect of the present invention. This hose is characterized by:
【００２６】すなわち、ホースとしては、単管のホース
、内管ゴム層と外管ゴム層との二層構造のもの、内管ゴ
ム層と外管ゴム層との間に線維や鋼線製の補強層を有す
るもの、また、その補強層部分にさらに中間ゴム層を有
するもの等の複層構造のホースが知られており、複層構
造のホースの場合は、例えば内管ゴム層と外管ゴム層と
は、用いられているポリマーは同じであるが、他の配合
成分が異なる場合と、ポリマーも異なる場合とがある。
そして、本発明第二の態様のホースは、単管ホースの場
合は全体が、複層構造のホースの場合は、そのいずれか
一層以上が、本発明第一の態様のゴム組成物の加硫ゴム
で構成されてなるものである。That is, the hose has a single tube structure, a two-layer structure consisting of an inner tube rubber layer and an outer tube rubber layer, and a hose made of fiber or steel wire between the inner tube rubber layer and the outer tube rubber layer. Hoses with a multi-layer structure are known, such as those with a reinforcing layer, and those with an intermediate rubber layer in the reinforcing layer. Although the rubber layer and the rubber layer use the same polymer, other compounding components may be different, and the polymer may also be different. In the hose of the second aspect of the present invention, in the case of a single pipe hose, the entire hose is vulcanized with the rubber composition of the first aspect of the present invention, and in the case of a multilayer hose, any one or more of the layers is vulcanized. It is made of rubber.
【００２７】なお、複層構造でその内管ゴム層に本発明
第一の態様のゴム組成物の加硫ゴムを配する場合、内管
ゴム層には、ジエン系ポリマー（ａ）としてＮＢＲ、Ｃ
Ｒ、ＳＢＲ等を用いた本発明第一の態様のゴム組成物の
加硫ゴムが適しており、その場合、中間ゴム層には、ポ
リマーとしてＮＢＲ、ＣＲ、ＳＢＲ、ＣＳＭ等を、また
、外管ゴム層には、ポリマーとして、ＣＲ、ＳＢＲ、Ｎ
ＢＲ、ＣＳＭ、ＥＰＤＭ等を用いるのがよい。When the vulcanized rubber of the rubber composition of the first embodiment of the present invention is disposed in the inner tube rubber layer of a multilayer structure, the inner tube rubber layer contains NBR, NBR, etc. as the diene polymer (a). C
The vulcanized rubber of the rubber composition of the first aspect of the present invention using R, SBR, etc. is suitable, and in that case, the intermediate rubber layer may contain NBR, CR, SBR, CSM, etc. as a polymer, and The tube rubber layer contains CR, SBR, and N as polymers.
It is preferable to use BR, CSM, EPDM, etc.
【００２８】また、その外管ゴム層に本発明第一の態様
のゴム組成物の加硫ゴムを配する場合、外管ゴム層には
、ジエン系ポリマー（ａ）としてＣＲ、ＳＢＲ、ＮＢＲ
等を用いた本発明第一の態様のゴム組成物の加硫ゴムが
適しており、その場合、中間ゴム層には、ポリマーとし
てＮＢＲ、ＣＲ、ＳＢＲ、ＣＳＭ等を、また、内管ゴム
層には、ポリマーとしてＮＢＲ、ＣＲ、ＳＢＲ等を用い
るのがよい。[0028] When the outer tube rubber layer is provided with the vulcanized rubber of the rubber composition of the first aspect of the present invention, the outer tube rubber layer may contain CR, SBR, NBR as the diene polymer (a).
Vulcanized rubber of the rubber composition according to the first aspect of the present invention is suitable, in which case the intermediate rubber layer contains NBR, CR, SBR, CSM, etc. as the polymer, and the inner tube rubber layer It is preferable to use NBR, CR, SBR, etc. as the polymer.
【００２９】本発明第二の態様のホースは、どのような
加硫条件で加硫されたものであってもよい。The hose of the second aspect of the present invention may be vulcanized under any vulcanization conditions.
【００３０】続いて、本発明第三の態様について説明す
る。本発明第三の態様は、未加硫ホースの内管ゴム層、
中間ゴム層および外管ゴム層のうちのいずれか一層以上
を本発明第一の態様のゴム組成物で構成し、それを１８
０〜２５０℃で加硫することを特徴とするホースの製造
方法である。Next, the third aspect of the present invention will be explained. A third aspect of the present invention is an inner tube rubber layer of an unvulcanized hose,
At least one of the intermediate rubber layer and the outer tube rubber layer is composed of the rubber composition of the first aspect of the present invention, and
This is a method for manufacturing a hose characterized by vulcanization at 0 to 250°C.
【００３１】すなわち、単管ホースの場合は全体を、複
層構造のホースの場合はそのいずれか一層以上を本発明
第一の態様のゴム組成物で構成して未加硫ホースを得る
ことと、その加硫を１８０〜２５０℃で行なうことを必
須要件とするホースの製造方法である。That is, an unvulcanized hose can be obtained by constructing the whole of a single tube hose, or one or more layers of a multi-layered hose, of the rubber composition of the first aspect of the present invention. , is a method for manufacturing a hose that requires the vulcanization to be performed at 180 to 250°C.
【００３２】本発明第三の態様においては、上記必須要
件以外の工程は、通常の方法で行なえばよい。In the third embodiment of the present invention, steps other than the above-mentioned essential requirements may be carried out by conventional methods.
【００３３】例えば加硫の具体的方法は、１８０〜２５
０℃の温度範囲内で行なうことが可能な加硫方法であれ
ばいずれでもよく、すなわち、熱風加硫（ＨＡＶ）、ロ
ートキュア、ＬＣＭ、流動床加硫、マイクロ波加硫（Ｕ
ＨＦ）、蒸気加硫等の方法を採用すればよく、かつ、連
続加硫でもバッチ加硫でもよい。For example, the specific method of vulcanization is 180 to 25
Any vulcanization method that can be carried out within the temperature range of 0°C may be used, i.e. hot air vulcanization (HAV), rotocure, LCM, fluidized bed vulcanization, microwave vulcanization (U
HF), steam vulcanization, etc., and continuous vulcanization or batch vulcanization may be used.
【００３４】また、加硫の際、未加硫ホースに鉛被覆ま
たは樹脂被覆を施してもよいし、何も被覆しなくてもよ
い。Further, during vulcanization, the unvulcanized hose may be coated with lead or resin, or may not be coated with anything.
【００３５】さらに、加硫時間についても特に限定はな
いが、通常、１８０℃での加硫の場合は５〜２０分間程
度、２００℃での加硫の場合は３〜１０分間程度、２２
０℃での加硫の場合は１〜６分間程度、２５０℃での加
硫の場合は１〜５分間程度である。Furthermore, there is no particular limitation on the vulcanization time, but usually, in the case of vulcanization at 180°C, it is about 5 to 20 minutes, and in the case of vulcanization at 200°C, it is about 3 to 10 minutes.
In the case of vulcanization at 0°C, the time is about 1 to 6 minutes, and in the case of vulcanization at 250°C, it is about 1 to 5 minutes.
【００３６】[0036]
【実施例】以下に、実施例により、本発明を具体的に説
明する。[Examples] The present invention will be specifically explained below with reference to Examples.
【００３７】（実施例）
表１および表２に組成を示すゴム組成物を用意した。こ
れらの組成物を用い、その加硫ゴム（加硫温度および加
硫時間は表３、表４、表５および表６に示す通り）につ
いて、下記の方法で物性評価を行なった。結果は表３、
表４、表５および表６に示した。(Example) Rubber compositions whose compositions are shown in Tables 1 and 2 were prepared. Using these compositions, the physical properties of the vulcanized rubbers (the vulcanization temperatures and vulcanization times are shown in Tables 3, 4, 5, and 6) were evaluated in the following manner. The results are shown in Table 3.
It is shown in Table 4, Table 5 and Table 6.
【００３８】（物性の評価方法）
（１）引張試験
各ゴム組成物それぞれについて、ミキシングロールにて
、６０℃で１５分間混合し、次いで、ラボ用小型ロール
にて、２．０ｍｍ厚にシート出しを行なった。このシー
ト状ゴムを、ラボ用プレス成型機にて、表３、表４、表
５および表６に示す温度および時間で、面圧３０Ｋｇｆ
／ｃｍ２ で加圧加硫した。これらを、ＪＩＳ Ｋ６
３０１に規定される引張試験機を用い、引張速さ５００
ｍｍ／ｍｉｎで引っ張り、引張強さ（ＴＢ ）、伸び（
ＥＢ ）、５０％モジュラス（Ｍ５０）、１００％モジ
ュラス（Ｍ１００ ）を測定、算出した。尚、測定の方
法および計算は、すべてＪＩＳ Ｋ６３０１ ３．
引張試験に記載の方法に準拠して行なった。(Method for evaluating physical properties) (1) Tensile test Each rubber composition was mixed for 15 minutes at 60°C using a mixing roll, and then rolled out into a sheet with a thickness of 2.0 mm using a small laboratory roll. I did this. This sheet-like rubber was molded using a laboratory press molding machine at the temperature and time shown in Tables 3, 4, 5, and 6 at a surface pressure of 30 Kgf.
/cm2. These are JIS K6
Using a tensile tester specified in 301, the tensile speed was 500.
Tensile strength (TB), elongation (
EB ), 50% modulus (M50), and 100% modulus (M100) were measured and calculated. All measurement methods and calculations are in accordance with JIS K6301 3.
The tensile test was conducted in accordance with the method described in the section.
【００３９】（２）硬さ試験
（１）と同様の方法で、加硫ゴムを得た。それらについ
て、ＪＩＳ Ｋ６３０１に準拠して硬さ試験を行ない
、スプリング硬さ（ＨＳ ）（Ａ形）を測定した。(2) Hardness Test A vulcanized rubber was obtained in the same manner as in (1). A hardness test was conducted on them in accordance with JIS K6301, and spring hardness (HS) (A type) was measured.
【００４０】（３）圧縮永久歪試験
（１）と同様の方法で、加硫ゴムを得た。それらについ
て、ＪＩＳ Ｋ６３０１に準拠して圧縮永久歪試験を
行ない、圧縮永久歪率を算出した。なお、圧縮時の熱処
理温度と時間は、１００℃で７０時間とした。(3) Compression set test A vulcanized rubber was obtained in the same manner as in (1). A compression set test was performed on them in accordance with JIS K6301, and the compression set rate was calculated. The heat treatment temperature and time during compression were 100° C. for 70 hours.
【００４１】表１〜表６に示されるように、本発明のゴ
ム組成物は、高温（１８０℃以上）で加硫されても、通
常の温度（１５０℃）で加硫されたものと同等以上の物
性を示す。しかし、加硫促進剤として、ジベンゾチアジ
ル・ジスルフィド（ｃ）、テトラメチルチウラムモノス
ルフィド（ｄ）以外の化合物を用いたり、Ｎ，Ｎ´−ｍ
−フェニレンジマレイミド（ｅ）を含有しないゴム組成
物（比較例）は、高温で加硫されると、通常の温度で加
硫されたものに比べていずれかの物性が劣る加硫ゴムと
なる。As shown in Tables 1 to 6, even when the rubber compositions of the present invention are vulcanized at high temperatures (180°C or higher), they are equivalent to those vulcanized at normal temperatures (150°C). It shows the above physical properties. However, as a vulcanization accelerator, compounds other than dibenzothiazyl disulfide (c) and tetramethylthiuram monosulfide (d) are used, and N,N'-m
- When a rubber composition that does not contain phenylene dimaleimide (e) (comparative example) is vulcanized at high temperatures, it becomes a vulcanized rubber that has some physical properties inferior to those vulcanized at normal temperatures. .
【００４２】[0042]
【表１】[Table 1]
【００４３】[0043]
【表２】[Table 2]
【００４４】[0044]
【表３】[Table 3]
【００４５】[0045]
【表４】[Table 4]
【００４６】[0046]
【表５】[Table 5]
【００４７】[0047]
【表６】[Table 6]
【００４８】[0048]
【発明の効果】本発明により、ジエン系ポリマーを主成
分とするゴム組成物であって、高温で加硫されても優れ
た物性を有する加硫ゴムとなるゴム組成物、その一部の
層または全部が該ゴム組成物の加硫ゴムで構成されてな
るホース、および、該ゴム組成物を用い、高温加硫の工
程を経るホースの製造方法が提供される。従って、本発
明により、ホース等のゴム製品の製造に際し、短時間加
硫及び連続加硫が可能となり、生産性の向上が図れる。Effects of the Invention The present invention provides a rubber composition containing a diene polymer as a main component, which becomes a vulcanized rubber having excellent physical properties even when vulcanized at high temperatures, and some layers thereof. Alternatively, there is provided a hose entirely composed of vulcanized rubber of the rubber composition, and a method for producing a hose that uses the rubber composition and undergoes a high-temperature vulcanization process. Therefore, according to the present invention, when manufacturing rubber products such as hoses, short-time vulcanization and continuous vulcanization are possible, and productivity can be improved.
Claims (4)
ポリマー（ａ）であり、加硫系（Ｂ）として、硫黄（ｂ
）、ジベンゾチアジル・ジスフィド（Ｃ）および／また
はテトラメチルチウラム・モノスルフィド（ｄ）、およ
び、Ｎ，Ｎ´−ｍ−フェニレンジマレイミド（ｅ）を含
有し、Ｎ，Ｎ´−ｍ−フェニレンジマレイミド（ｅ）の
含有量は、前記ポリマー（Ａ）１００重量部に対して０
．１重量部以上であることを特徴とするゴム組成物。Claim 1: The main component in the polymer (A) is a diene polymer (a), and the vulcanization system (B) contains sulfur (b).
), dibenzothiazyl disulfide (C) and/or tetramethylthiuram monosulfide (d), and N,N'-m-phenylene dimaleimide (e); The content of rangemaleimide (e) is 0 with respect to 100 parts by weight of the polymer (A).
．． A rubber composition characterized in that the amount is 1 part by weight or more.
に記載のゴム組成物。[Claim 2] Claim 1 used for a high temperature vulcanized hose.
The rubber composition described in .
び外管ゴム層のうちのいずれか一層以上が、請求項１に
記載のゴム組成物の加硫ゴムで構成されてなることを特
徴とするホース。3. At least one of the inner tube rubber layer, intermediate rubber layer, and outer tube rubber layer of the hose is composed of vulcanized rubber of the rubber composition according to claim 1. hose.
層および外管ゴム層のうちのいずれか一層以上を請求項
１に記載のゴム組成物で構成し、それを１８０〜２５０
℃で加硫することを特徴とするホースの製造方法。4. At least one of the inner tube rubber layer, intermediate rubber layer, and outer tube rubber layer of the unvulcanized hose is composed of the rubber composition according to claim 1, and
A method for manufacturing a hose characterized by vulcanization at °C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP40322490A JPH04216837A (en) | 1990-12-18 | 1990-12-18 | Rubber composition, hose, and production of hose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP40322490A JPH04216837A (en) | 1990-12-18 | 1990-12-18 | Rubber composition, hose, and production of hose |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04216837A true JPH04216837A (en) | 1992-08-06 |
Family
ID=18512978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP40322490A Withdrawn JPH04216837A (en) | 1990-12-18 | 1990-12-18 | Rubber composition, hose, and production of hose |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04216837A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016051874A1 (en) * | 2014-09-29 | 2016-04-07 | 豊田合成株式会社 | Air hose for automobile |
-
1990
- 1990-12-18 JP JP40322490A patent/JPH04216837A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016051874A1 (en) * | 2014-09-29 | 2016-04-07 | 豊田合成株式会社 | Air hose for automobile |
| JP2016070347A (en) * | 2014-09-29 | 2016-05-09 | 豊田合成株式会社 | Vehicular air hose |
| CN106104128A (en) * | 2014-09-29 | 2016-11-09 | 丰田合成株式会社 | Automobile air flexible pipe |
| US9809700B2 (en) | 2014-09-29 | 2017-11-07 | Toyoda Gosei Co., Ltd. | Air hose for automobile |
| CN106104128B (en) * | 2014-09-29 | 2018-04-24 | 丰田合成株式会社 | Automobile air hose |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH06116439A (en) | Pneumatic tire having multi-layer inner liner | |
| EP3553120B1 (en) | Rubber composition for marine hose and marine hose | |
| JP2008184551A (en) | Rubber composition for covering tire cord | |
| JP2609369B2 (en) | Tire side surface composition | |
| EP3406665A1 (en) | Rubber composition for coolant transport hose, and coolant transport hose | |
| US10590253B2 (en) | Rubber composition for flame-retardant hose, and flame-retardant hose | |
| JP4543685B2 (en) | Rubber composition for hose interlayer rubber and hose | |
| US20070232752A1 (en) | Rubber composition, vulcanizate, and air intake hose | |
| US6812312B1 (en) | Rubber, rubber composition, and crosslinked object | |
| US3704741A (en) | Ozone resistant ethylene/propylene terpolymer laminates to other rubber | |
| US4584350A (en) | Method for improving green strength properties of vulcanizable rubber compositions | |
| JPH04216837A (en) | Rubber composition, hose, and production of hose | |
| JP5230107B2 (en) | Tire vulcanization bladder | |
| JPH0552782B2 (en) | ||
| JP2906910B2 (en) | Vulcanizable rubber composition | |
| JP2008069276A (en) | Rubber composition, fiber/rubber composite and hose | |
| US4839428A (en) | Method for improving green strength properties of vulcanizable rubber compositions | |
| JP2004161897A (en) | Rubber composition for high damping laminate and rubber laminate therewith | |
| KR100380761B1 (en) | Rubber composition for bead insulation | |
| JPS61143458A (en) | High-hardness rubber composition | |
| JPS5811532A (en) | Rubber composition | |
| WO2024176566A1 (en) | Rubber composition for hoses, and hose | |
| JPH09316414A (en) | Rubber adhesive composition and production of rubber composite | |
| JP6230979B2 (en) | Rubber bearing | |
| JPS62104864A (en) | Adhesive rubber composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Application deemed to be withdrawn because no request for examination was validly filed |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19980312 |