阅读说明：本技术 橡胶组合物以及软管 (Rubber composition and hose ) 是由 杉原孝树 于 2018-03-23 设计创作，主要内容包括：本发明的目的在于,提供一种能制成耐起霜性优异的橡胶的橡胶组合物以及软管。本发明为一种橡胶组合物,其含有：乙烯-丙烯-二烯共聚物、对苯二胺系抗老化剂、炭黑以及氧化锌,相对于上述乙烯-丙烯-二烯共聚物100质量份,上述对苯二胺系抗老化剂的含量为0.1质量份以上且5.0质量份以下；以及一种软管,其具有由上述橡胶组合物形成的外层。(The object of the present invention is to provide a kind of rubber compositions and hose that the excellent rubber of frost-resistance can be made.The present invention is a kind of rubber composition, it contains: ethylene-propylene-diene copolymer, p-phenylenediamine system age resister, carbon black and zinc oxide, relative to above-mentioned 100 mass parts of ethylene-propylene-diene copolymer, the content of above-mentioned p-phenylenediamine system age resister be 0.1 mass parts or more and 5.0 below the mass；And a kind of hose, there is the outer layer formed by above-mentioned rubber composition.)

1. a kind of rubber composition, contains: ethylene-propylene-diene copolymer, p-phenylenediamine system age resister, carbon black and Zinc oxide,

Relative to 100 mass parts of ethylene-propylene-diene copolymer, the content of p-phenylenediamine system age resister is 0.1 More than mass parts and 5.0 below the mass.

2. rubber composition according to claim 1, wherein

The diene for constituting the ethylene-propylene-diene copolymer at least contains ethylidene norbornene,

The content of structural unit based on the ethylidene norbornene is 5 mass % of the ethylene-propylene-diene copolymer ~13 mass %.

3. rubber composition according to claim 1 or 2, also contains vulcanization accelerator,

Relative to 100 mass parts of ethylene-propylene-diene copolymer, the content of the vulcanization accelerator be 2.0 mass parts with On.

4. rubber composition according to claim 3, wherein

The vulcanization accelerator at least contains thiuram system vulcanization.

5. rubber composition according to any one of claims 1 to 4, also contains crosslinking agent,

The crosslinking agent at least contains sulphur,

Relative to 100 mass parts of ethylene-propylene-diene copolymer, the content of the crosslinking agent is 0.5 mass parts or more.

6. rubber composition according to any one of claims 1 to 5, wherein

P-phenylenediamine system age resister at least contains N, bis- -2- naphthyl-p-phenylenediamine of N'-.

7. rubber composition described according to claim 1~any one of 6, wherein

Mass ratio of the p-phenylenediamine system age resister relative to the zinc oxide, i.e. p-phenylenediamine system age resister/oxidation Zinc is 0.1~1.0.

8. rubber composition according to any one of claims 1 to 7, contains substantially no peroxide.

9. rubber composition described according to claim 1~any one of 8 is used for the outer layer of hose.

10. a kind of hose has the outer layer formed by rubber composition according to any one of claims 1 to 9.

Technical field

The present invention relates to a kind of rubber composition and hoses.

Background technique

In the past, ozone resistance and the ethylene-propylene-diene copolymer having excellent weather resistance were (hereinafter, also referred to as " EPDM ") such as the outer layer of air conditioner for automobile (AC) hose.

For will the rubber composition containing ethylene-propylene-diene copolymer it is Nian Jie with organic fiber made of rubber/curtain Line complex, such as propose patent document 1.

In recent years, for requiring to simplify in the engine of automobile, on the other hand, turbocharger is directed into engine It is interior.

Summary of the invention

Problems to be solved by the invention

Although EPDM used in hose is that ozone resistance etc. is excellent but the rubber of easy frosting, therefore, the rubber containing EPDM Glue composition is needed using the formula for considering frost-resistance.Therefore, for bloom-inhibiting, to contained by above-mentioned rubber composition Type, a combination thereof or the use level of additive (such as vulcanization accelerator) limit.

In turn, as described above, by the way that turbocharger to be directed into the engine of automobile, may become in engine room It is narrow and be likely to become high temperature.

The air conditioning hose requirement used in engine room under the high temperature conditions as described above has high-fire resistance, as mentioning The scheme of high-fire resistance, it is contemplated that heat-resisting age resister, the heat-resisting group with vulcanizing system are used to the rubber composition of each component The mode of conjunction still, while becoming easy generation frosting, limits to cooperation.In addition, the feelings under certain hot conditions Under condition, become easier to that frosting occurs.

In this case, the present inventor is prepared for the rubber composition containing EPDM and is evaluated it, knot Fruit specifies that the frost-resistance of the rubber made of such rubber composition is low.

Therefore, the object of the present invention is to provide a kind of rubber compositions that the excellent rubber of frost-resistance can be made.

In addition, the present invention also aims to provide a kind of hose.

Technical solution

The present inventor has made intensive studies to solve the above-mentioned problems, as a result, it has been found that following fact, thus hair at The present invention, that is, by using p-phenylenediamine system age resister to EPDM, desired effect can be obtained.

The present invention is the invention made based on above-mentioned opinion etc., specifically, by it is below constitute it is above-mentioned to solve Problem.

1. a kind of rubber composition, contains: ethylene-propylene-diene copolymer, p-phenylenediamine system age resister, carbon black And zinc oxide, relative to above-mentioned 100 mass parts of ethylene-propylene-diene copolymer, above-mentioned p-phenylenediamine system age resister contains Amount is 0.1 mass parts or more and 5.0 below the mass.

2. the rubber composition according to above-mentioned 1, wherein constitute the diene of above-mentioned ethylene-propylene-diene copolymer extremely Contain ethylidene norbornene less, the content of the structural unit based on above-mentioned ethylidene norbornene is above-mentioned ethylene-propylene-two 5 mass of mass %~13 % of alkene copolymer.

3. the rubber composition according to above-mentioned 1 or 2, also contains vulcanization accelerator, relative to above-mentioned ethylene-the third 100 mass parts of alkene-diene copolymers, the content of above-mentioned vulcanization accelerator are 2.0 mass parts or more.

4. the rubber composition according to above-mentioned 3, wherein above-mentioned vulcanization accelerator at least contains the vulcanization of thiuram system and promotees Into agent.

5. the rubber composition according to above-mentioned any one of 1~4 also contains crosslinking agent, above-mentioned crosslinking agent is at least Containing sulphur, relative to above-mentioned 100 mass parts of ethylene-propylene-diene copolymer, the content of above-mentioned crosslinking agent be 0.5 mass parts with On.

6. the rubber composition according to above-mentioned any one of 1~5, wherein above-mentioned p-phenylenediamine system age resister is extremely Contain N, bis- -2- naphthyl-p-phenylenediamine of N'- less.

7. the rubber composition according to above-mentioned any one of 1~6, wherein above-mentioned p-phenylenediamine system age resister phase Mass ratio (p-phenylenediamine system age resister/zinc oxide) for above-mentioned zinc oxide is 0.1~1.0.

8. the rubber composition according to above-mentioned any one of 1~7, contains substantially no peroxide.

9. the rubber composition according to above-mentioned any one of 1~8 is used for the outer layer of hose.

10. a kind of hose, the outer layer formed with the rubber composition as described in above-mentioned any one of 1~9.

Beneficial effect

The excellent rubber of frost-resistance can be obtained in rubber composition according to the present invention.

The frost-resistance of hose of the invention is excellent.

Detailed description of the invention

Fig. 1 is the perspective view that an example of hose of the invention is shown in a manner of cutting each layer.

Specific embodiment

The present invention is described in detail below.

It should be noted that in the present specification, (methyl) acrylate indicates acrylate or methacrylate, (methyl) acryloyl group indicates that perhaps methylacryloyl (methyl) acrylic acid indicates acrylic acid or metering system to acryloyl group Acid.

In addition, the numberical range for using "~" to indicate in the present specification is it is meant that number documented by the front and back comprising "~" Value is as lower limit value and the range of upper limit value.

In the present specification, as long as no prior explanation, each ingredient can will meet the substance of this ingredient individually or Person is used in combination of two or more.In the case where ingredient includes two or more substances, the content of ingredient refers to two or more substances Total content.

In the present specification, as long as no prior explanation, the manufacturing method of each ingredient is not particularly limited.For example, can arrange Enumerate known manufacturing method.

In the present specification, sometimes that the frost-resistance of the rubber formed by rubber composition of the invention is excellent referred to as " frost-resistance is excellent ".

[rubber composition]

Rubber composition (composition of the invention) of the invention is following rubber composition, is contained: ethylene-the third Alkene-diene copolymers, p-phenylenediamine system age resister, carbon black and zinc oxide are copolymerized relative to above-mentioned Ethylene-Propylene-Diene 100 mass parts of object, the content of above-mentioned p-phenylenediamine system age resister be 0.1 mass parts or more and 5.0 below the mass.

Hereinafter, each ingredient contained in composition of the invention is described in detail.

<ethylene-propylene-diene copolymer>

Ethylene-propylene-diene copolymer (EPDM) contained by composition of the invention as long as ethylene and propylene and two The copolymer of alkene, is just not particularly limited.

As the diene of the above-mentioned EPDM of composition, such as unconjugated diene compound can be enumerated, as non-conjugated diene Object is closed, specifically, can for example enumerate: bicyclopentadiene (DCPD)；Asia as 5- ethylidene -2- norbornene (ENB) Ethyl norbornene；1,4- hexadiene (HD).

For the diene for constituting above-mentioned ethylene-propylene-diene copolymer, the more excellent, vulcanizing system from effect of the invention Type can be carried out with wide scope using, mechanical property it is excellent from the viewpoint of, it is preferred that at least ice drops containing ethylidene Piece alkene.

From effect of the invention, more excellent, vulcanizing system type can be carried out excellent using, mechanical property with wide scope From the viewpoint of, the content of the structural unit based on above-mentioned diene (such as ethylidene norbornene) is preferably above-mentioned ethylene-the third The 5 mass % of mass %~13 of alkene-diene copolymers, more preferably 8 mass of mass %~12 %.

It should be noted that in the present invention, the structural unit of above-mentioned diene (such as ethylidene norbornene) will be based on The benchmark of content be set as: there is the structural unit based on above-mentioned diene (such as ethylidene norbornene), ethylene-propylene- Diene copolymers (ethylene-propylene-ethylidene norbornene copolymer) itself.

<p-phenylenediamine system age resister>

P-phenylenediamine system age resister contained by composition of the invention is the anti-aging of the structure with p-phenylenediamine Agent.

Composition of the invention contains p-phenylenediamine system age resister, and frost-resistance is excellent as a result,.

In addition, composition of the invention contains p-phenylenediamine system age resister, also contain in composition of the invention as a result, In the case where vulcanization accelerator, for the type of above-mentioned vulcanization accelerator, a combination thereof or its use level, it is difficult to by the past in this way Limitation therefore can widen the freedom degree of matching design.

As the structure of above-mentioned p-phenylenediamine, such as the structure indicated by following formula (1) can be enumerated.

Formula (1)

Organic group can be bonded each independently in the two sides of the structure indicated by above-mentioned formula (1).

Above-mentioned organic group is not particularly limited.It can have heteroatomic alkyl for example, can enumerate.

As above-mentioned alkyl, such as can enumerate: aliphatic alkyl (can be any in straight-chain, branched or ring-type Kind, can also have unsaturated bond), aromatic hydrocarbyl and their combination.

As aromatic hydrocarbyl, such as phenyl, naphthalene can be enumerated.Wherein, preferably naphthalene.

It as hetero atom, such as can enumerate: oxygen atom, nitrogen-atoms, sulphur atom.Hetero atom can be former with hydrogen atom, oxygen Son or other hetero atoms are bonded and form substituent group.It as above-mentioned substituent group, such as can enumerate: ester bond, hydroxyl, sulfonyl.

As p-phenylenediamine system age resister, such as can enumerate: (above-mentioned diaryl can for N, N'- diaryl-p-phenylenediamine There is alkyl each independently), N- alkyl-N'- aryl-p-phenylenediamine (do not include above-mentioned N, N'- diaryl-p-phenylenediamine), N, N'- dialkyl group-p-phenylenediamine (do not include above-mentioned N, N'- diaryl-p-phenylenediamine).

As N, N'- diaryl-p-phenylenediamine (in the case where above-mentioned diaryl does not have alkyl), such as can enumerate N out, N'- diphenyl-p-phenylenediamine, N, bis- -2- naphthyl-p-phenylenediamine of N'-.

As N, (one or all aryl have N'- diaryl-p-phenylenediamine each independently among above-mentioned diaryl In the case where alkyl), such as N can be enumerated, N'- bis- (alkyl phenyl)-p-phenylenediamine, to (para toluene sulfonamide) diphenyl Amine.

As N- alkyl-N'- aryl-p-phenylenediamine (not including above-mentioned N, N'- diaryl-p-phenylenediamine), such as can arrange It enumerates: N- isopropyl-N'- phenyl-pphenylenediamine, N- dimethylbutyl-N'- phenyl-pphenylenediamine, N- (3- (methyl) propylene Acyloxy -2- hydroxypropyl)-N'- phenyl-pphenylenediamine, N ((methyl) acryloyl group)-N'- phenyl-pphenylenediamine.

Wherein, from the viewpoint of from effect of the invention, more excellent, heat-resistant aging and/or resist bending aging are excellent, Above-mentioned p-phenylenediamine system age resister is preferably N, and (above-mentioned diaryl can have alkane to N'- diaryl-p-phenylenediamine each independently Base), above-mentioned N- alkyl-N'- aryl-p-phenylenediamine, more preferably N, (above-mentioned diaryl does not have N'- diaryl-p-phenylenediamine Have alkyl), bis- -2- naphthyl-p-phenylenediamine of further preferably N, N'-.

<content of p-phenylenediamine system age resister>

In the present invention, relative to above-mentioned 100 mass parts of ethylene-propylene-diene copolymer, above-mentioned p-phenylenediamine system is anti-ageing The content of agent is 0.1 mass parts or more and 5.0 below the mass.

From the viewpoint of, heat-resistant aging more excellent from effect of the invention is excellent, relative to above-mentioned ethylene-propylene-two 100 mass parts of alkene copolymer, the content of above-mentioned p-phenylenediamine system age resister is preferably 0.5 mass parts~2.0 mass parts, more excellent It is selected as 1.5 mass parts~2.0 mass parts.

From the viewpoint of, heat-resistant aging more excellent from effect of the invention is excellent, above-mentioned p-phenylenediamine system age resister Mass ratio (p-phenylenediamine system age resister/zinc oxide) relative to aftermentioned zinc oxide is preferably 0.1~1.0, more preferably 0.3~0.4.

<carbon black>

Carbon black contained by composition of the invention is not particularly limited.For example, known carbon black can be enumerated.

As above-mentioned carbon black, for example, can enumerate: FEF (Fast Extruding Furnace: extruding furnace fastly) carbon black, GPF (General Purpose Furnace: versatible furnace) carbon black, SRF (Furnace: half reinforcement of Semi-Reinforcing Furnace) carbon black.

Wherein, from effect of the invention from the viewpoint of more excellent, excellent heat resistance, preferably SRF carbon black.

It is total relative to above-mentioned Ethylene-Propylene-Diene from effect of the invention from the viewpoint of more excellent, excellent heat resistance 100 mass parts of polymers, the content of above-mentioned carbon black are preferably 50 mass parts~100 mass parts, more preferably 70 mass parts~90 matter Measure part.

<zinc oxide>

Zinc oxide contained by composition of the invention is not particularly limited.For example, known oxidation can be enumerated Zinc.

From the viewpoint of, mechanical property more excellent from effect of the invention is excellent, relative to above-mentioned Ethylene-Propylene-Diene 00 mass parts of copolymer 1, the content of above-mentioned zinc oxide are preferably 2 mass parts~15 mass parts, more preferably 4 mass parts~6 matter Measure part.

(vulcanization accelerator)

Composition of the invention can also contain vulcanization accelerator.

Above-mentioned vulcanization accelerator is not particularly limited.As vulcanization accelerator, such as can enumerate: the vulcanization of thiuram system promotees Into agent, thiazole system vulcanization accelerator, sulfenamide system vulcanization accelerator, guanidine system vulcanization accelerator, alkyl phenyl dithiocarbamates Formates system vulcanization accelerator.

Above-mentioned vulcanization accelerator can at least contain thiuram system vulcanization.

It as thiuram system vulcanization, such as can enumerate: tetramethylthiuram disulfide, tetraethyl base autumn Lan Mu, tetrabutylthiuram disulfide, tetra-benzyl thiram disulfide, curing four (2- ethylhexyl) thiuram, a vulcanization Tetra methylthiuram, DPMTTS dipentamethylene thiuram tetrasulfide etc..

Wherein, from the viewpoint of more excellent from effect of the invention, mechanical property is excellent, it is preferred that curing tetramethyl Base thiuram, tetraethylthiuram disulfide, tetrabutylthiuram disulfide.

From effect of the invention from the viewpoint of more excellent, mechanical property and/or excellent heat resistance, relative to above-mentioned second Propylene diene copolymerized 100 mass parts of object of alkene-, the content of vulcanization accelerator is preferably 2.0 mass parts or more, more preferably 2.0 matter Measure part~4.0 mass parts.

(crosslinking agent)

Composition of the invention can also contain crosslinking agent.

Above-mentioned crosslinking agent preferably at least contains sulphur, more preferably sulphur.

Sulphur is not particularly limited.For example, known sulphur can be enumerated.

It is total relative to above-mentioned Ethylene-Propylene-Diene from effect of the invention from the viewpoint of more excellent, excellent heat resistance 100 mass parts of polymers, the content of crosslinking agent are preferably 0.5 mass parts or more, more preferably 0.6 mass parts~1.0 mass parts.

(additive)

Composition of the invention can also contain additive as needed and within the scope of the effect of the invention.

It as additive, such as can enumerate: the reinforcing agent other than rubber, above-mentioned carbon black, processing other than above-mentioned EPDM Age resister, plasticizer other than auxiliary agent, vulcanization accelerator additive (for example, stearic acid), p-phenylenediamine system age resister, vulcanization are prolonged Slow agent etc..

(manufacturing method of rubber composition)

The manufacturing method of composition of the invention is not particularly limited.For example, can be under conditions of 100 DEG C~180 DEG C By above-mentioned essential component with can carry out as needed using any ingredient mix and manufacture.

Composition of the invention can be the composition for containing substantially no peroxide.

Peroxide means the compound with-O-O-.

In the present invention, " peroxide is contained substantially no " it is meant that, peroxidating whole relative to composition of the invention The content of object is 0 mass of mass %~1.0 %.

(vulcanization (crosslinking) of rubber composition)

The method of composition hardening (crosslinking) of the invention is not particularly limited.Such as it can be at 140 DEG C~190 DEG C Under the conditions of press cure, steam vulcanization (cure), baking oven vulcanization (hot-air cure) or water curing carried out to composition of the invention come Vulcanized (crosslinking).

Composition of the invention can for example be suitable for hose.Preferably, composition of the invention is suitable for hose Outer layer.

As above-mentioned hose, such as can enumerate: air-conditioning (conditioner) is used, electronic-controlled power steering is used, oil pressure is used.

Composition of the invention is suitable for the outer layer of the idle call hose of automobile, one of preferred embodiment can be listed as.

[hose]

Hose of the invention is the hose with the outer layer formed by rubber composition of the invention.

Hose of the invention has above-mentioned outer layer, and therefore, frost-resistance is excellent.

<outer layer>

As long as the rubber composition for forming outer layer rubber composition (composition of the invention) of the invention, just without spy It does not limit.

The thickness of outer layer can use 0.2mm~4mm.

Hose of the invention other than above-mentioned outer layer, can also have selected from by enhancing component (enhancement layer), internal layer with And at least one of the group that intermediate rubber layer is constituted.Enhancing component can be one or more layers.Internal layer and intermediate rubber layer It is same.

(enhancing component)

Enhancing component is not particularly limited.For example, known enhancing component can be enumerated.

As the material of enhancing component, such as metal, fibrous material (polyamide, polyester etc.) can be enumerated.Enhance component It can be surface treated enhancing component.

As the form of enhancing component, such as the enhancing component for being woven into helical structure and/or blade construction can be enumerated.

(internal layer)

The rubber composition for being capable of forming internal layer is not particularly limited.Such as it can be formed by rubber composition of the invention Internal layer.

The thickness of internal layer can for example be set as 0.2mm~4mm.

(intermediate rubber layer)

The rubber composition for being capable of forming intermediate rubber layer is not particularly limited.For example, known rubber can be enumerated Glue composition.Composition of the invention can be used to form intermediate rubber layer.

Intermediate rubber layer can for example be configured at outer layer and enhancing component between, internal layer and enhancing component between, enhancing structure Between part and enhancing component.

The thickness of intermediate rubber layer can for example be set as 0.2mm~0.7mm.

Hose of the invention for example can successively have internal layer, enhancing component and outer layer.

In hose of the invention, above-mentioned outer layer can be set as to the outermost layer of hose.

The outer surface (outermost layer) of hose of the invention does not have enhancing component, can be listed as one of preferred embodiment.

It is illustrated referring to example of the attached drawing to hose of the invention.The present invention is not restricted to attached drawing.

Fig. 1 is the perspective view that an example of hose of the invention is schematically shown in a manner of cutting each layer.

In Fig. 1, hose 1 has internal layer 2, has enhancing component 3 on internal layer 2, has outer layer 4 on enhancing component 3.

Outer layer 4 is at least formed by composition of the invention.

The manufacturing method of hose of the invention is not particularly limited.For example, will successively be used to form internal layer on mandrel Rubber composition is used to form rubber composition (rubber composition of the invention) stacking of enhancing component and outer layer and is formed Laminated body covers above-mentioned laminated body with nylon cloth etc., under conditions of 140 DEG C~190 DEG C, 30 DEG C~180 minutes, to above-mentioned The laminated bodies of the coverings such as nylon cloth carry out press cure, steam vulcanization (cure), baking oven vulcanization (hot-air cure) or water curing come into Row bonding by Vulcanization, thereby, it is possible to produce hose of the invention.

As the purposes of hose of the invention, such as can enumerate: air-conditioning (conditioner) is used, electronic-controlled power steering is used, Oil pressure is used.The idle call hose of automobile can be listed as one of preferred embodiment.

Even if hose of the invention for example carried out under conditions of 40 DEG C using, it is also difficult to frosting occurs, frost-resistance is excellent It is different.