JPS58118248A - Rubber hose - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a rubber hose having an oil-resistant inner tube layer with excellent properties such as resistance to deterioration in gasoline and cold resistance, and is suitable for use as fuel hoses for automobiles and the like.

Modern fuel circuit hoses, especially automotive fuel hoses that are applied to fuel circuit systems equipped with electronic fuel injection devices, are susceptible to deterioration due to the gasoline flowing inside them as the engine heats up or the internal pressure increases. Gasoline is charged.

Furthermore, with the spread of automobiles in extremely cold regions, a high degree of cold resistance is also required.

In view of the above, it is an object of the present invention to provide a rubber hose having an oil-resistant inner tube layer with excellent characteristics such as resistance to deterioration of gasoline and cold resistance.

The rubber hose of the present invention is made of a vulcanizate of a partially hydrogenated unsaturated nitric μ-conjugated diene copolymer rubber in which the conjugated diene unit portion is hydrogenated, or a vinyl chloride μ thread resin is mixed with this copolymer rubber. The above object is achieved by forming the inner tube layer with a vulcanizate of a rubber composition.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The following description will be made based on one example of a rubber hose according to the present invention.

Here, a fuel hose with a three-layer structure consisting of an inner tube layer 1, a braided reinforcing yarn layer 2, and an outer tube layer 3 as shown in the Jg/figure will be described as an example, but the explanation is not limited thereto. The present invention is applicable to m rubber hoses consisting of a single layer or two or more layers.

The inner pipe layer 1 of the fuel hose is made of partially hydrogenated unsaturated nitrile.
It is formed from a vulcanized product of a rubber composition mixed with a conjugated diene copolymer rubber (hereinafter referred to as "■-added NBRJ") or this H-added NBR&:filtrated vinyl lv-based resin (hereinafter referred to as "PVOJ"). There is.

The Hfi-added NBR is a product obtained by hydrogenating at least 50% of the conjugated diene unit portion of an unsaturated nitric μ-conjugated Vene copolymer rubber produced by emulsion polymerization or solution polymerization using a conventional method.

The above-mentioned copolymer rubber to be hydrogenated may contain an unsaturated nitrile such as acrylonitrium or methacrylonitrium and 7.3
-Butadiene, isoprene /.

Copolymerization of at least t/shelf of a conjugated diene such as 3-pentadiene, or a part of the conjugated diene is copolymerized with methyl ester μ, butyl ester such as acrylic acid, methacrylic acid, fluorinated acid, itaconic acid, etc. , -ethylhexy)v
These are copolymerized with unsaturated nitriles such as esters, etc., substituted with boronic acid esters (14), or N-methylo-μ acrylamide (7). Specifically, acrylonitrile-1 tadiene copolymer rubber, acrylonitrile-isoprene copolymer rubber, acrylonitrile-butadiene-isoprene copolymer rubber, acrylonitrile-1 tadiene-methyl acrylate F copolymer rubber, acrylonitrile-butadiene-butyl acrylate-F Examples include copolymer rubber, but acrylonitrium getadiene copolymer rubber is most suitable.

The amount of bound unsaturated nitrile in the above HfA7)gNBR is usually 10 to 70 vt%, and is appropriately determined within the above range depending on the compatibility with the PVO to be mixed and the intended use (application).

Furthermore, if the degree of hydrogenation of the conjugated diene unit reaches 50%, the physical properties targeted by the present invention cannot be obtained.The upper limit of the degree of hydrogenation may be 100%, but in the case of sulfur-based vulcanization, In view of the relationship with the vulcanization rate, the degree of hydrogenation is set to less than 1%.

The PvC used is polycyclized vinyl μ or a copolymer of cyclized vinyl and a monoolefin monomer such as vinyl acetate. ).

Preferably it is around 20vt%. jvt % Soman F
There is no effect of adding IPVC, and the amount of PVC added is PV
As the amount of C increases, the resin-like properties become stronger.9 However, there is a naturally determined limit at which the rubber-like properties are impaired even if vulcanization is possible, so the purpose of use and required performance should be determined appropriately within that range. Ba! Yes, l (fgk Canada NB R to PV
The method of OB mixing is not particularly limited, but methods such as kneading using low or bumper mixing, or dispersion mixing in a liquid, coprecipitation, and drying are used.

Each of the above-mentioned H-added NBII or this H-added NBII mixed with FVC is used for each of the commonly used auxiliary materials,
For example, carbon black, V Rica.

Inorganic fillers such as metal oxides, organic fillers such as Yarigenin, softeners, plasticizers, antioxidants, 11 coloring agents, etc. are appropriately blended, and a sulfur-based or peroxide yarn screening agent is added. Add as appropriate and knead. An inner tube layer 1 is extruded from this rubber material in an extrusion manner, then a braided reinforcing yarn layer 2 is formed, an adhesive is applied, and an outer tube layer 3 is further extruded in an extrusion manner. At this time, the rubber material for the outer tube layer is not particularly limited, but for example, synthetic rubber such as 08M%OR%CHB, which has good weather resistance, is used. Vulcanization conditions are temperature/Da 5~/70''C and 30~riQ
Let it be miB.

As shown in the examples below, the fuel hose manufactured in this way is particularly durable compared to the case where the inner layer is formed from a conventional vulcanized product of acrylonitrile-butadiene copolymer rubber (NBR) or its PVO mixed rubber. It has excellent resistance to degraded gasoline and cold resistance, and also has good regular physical properties.

Hereinafter, *1 example will be described together with a comparative example to confirm the effects of the present invention.

Each test piece of Examples and Comparative Examples was made by extruding each rubber material having the formulation shown in Table 1 using Al, and having an outer diameter of 9. Extrude a tube of j■φ (wall thickness 10mat), /jO″CX 30
Vulcanization was carried out at min., and each test piece was punched out from this vulcanizate, and various physical property tests were conducted using the following methods, and the test results are listed in Table 1.

(Gradient normal state physical property breaking strength Tn), breaking elongation (En)...JI8
K-430/CL') Measurement shift (/Nhey
vm3) Hardness: JI8 hardness was measured according to JI8-430/.

(70°C containing 1 wt of deterioration-resistant gasoline-resistant petroleum rubber oxide) Dampe v-type test piece (JI
The length of B3 is 6710) - time (/
Continue immersion while renewing the liquid every cycle. Take out a test piece for each indicated cycle μ, leave it at room temperature for a long time, and then dry it under reduced pressure at 60°C to determine the breaking strength of the test piece T.
m), elongation at break (IB) and elongation at crack initiation (Ea)l
Each was measured according to JI8-430/.

(C) #Base pillar The impact embrittlement temperature was measured according to JI8-630/.

(D) Heat aging resistance / 20'cX After being left in an atmosphere for 70 hours, the breaking strength, breaking elongation, and hardness (JIB person) of the Dampe IV type J1B3 test piece were determined to JI8 - 130/. The difference in hardness, rate of change in breaking strength, and rate of change in breaking elongation with respect to normal physical properties are determined as ΔH, ΔTn, and ΔEm, respectively.
Please be sure to display it as such.

(E) Crack Growth Resistance Dampe μ type JIBI No. ≦01), and the test piece given this elongation was JI87 Yue/L/
The time taken for the test piece to break after being immersed in D was measured.

(F) Gasoline resistant COOX 20X/mt test piece was llO″CJ
The sample was immersed in I87 Yue μC for 1 Iff time, and the volume before and after immersion was measured, and the rate of change (ΔV) was displayed.

(G) Gasohol resistance 20X20X/lut (D test piece re,)i) -1
It was immersed in tito°CJI8YYxtvCj&:411 hours containing W2Q vol %, the volume before and after immersion was measured, and the rate of change (ΔV) was displayed.

From the results in Table 1, the inner tube layer ('j
l! Examples/~6) have excellent resistance to deteriorated gasoline and cold resistance, and the physical properties in normal state are also better than those formed of ordinary NBB (Comparative Examples/~3), and the physical properties are well-balanced. ing. It was. When the inner layer is formed with a rubber material containing PVCi mixed with H-added NBR (Examples λ to t), the physical properties such as normal physical properties and deteriorated gasoline resistance are better than when the inner layer is formed with only FiH-added NBIL (Example/). It can be seen that the results are further improved.

[Brief explanation of drawings]

FIG. 1 is a perspective view showing an example of a rubber hose to which the present invention is applied. 1... Inner tube layer% 2... Braided reinforcing yarn layer, 3... Outer tube layer. 1st WI Procedural Amendment fi7, 11.4 Showa Year/Month, Director General of the Patent Office (Patent Office Examiner) 1, Indication of the case, Showa S6, Patent Application No. 2/3272, 2
, Name of the invention Rubber hose 3, Relationship to the person making the amendment Patent application Hito Showa
Year, month, day (Shipping date: Showa, month, year)
6. Number of inventions increased by amendment 7. Detailed description of the invention in the specification to be amended. 8. Contents of the amendment (1) In the 13th line of page 6 of the original specification, replace the word "desu" with the following communication.ゐ-Kiyoyu''

Claims (2)

[Claims] (1) A rubber hose characterized in that the inner tube layer is formed of a vulcanizate of a partially hydrogenated unsaturated nitric μ-conjugated diene yarn copolymer rubber in which at least 50% of the conjugated diene units are hydrogenated. . (2) 5vt% or more (inner layer) of agglomerated vinyl resin is mixed with a partially hydrogenated unsaturated nitrium-conjugated diene copolymer rubber with a small amount of conjugated diene units (both 10% hydrogenated). A rubber hose characterized by having an inner tube layer formed of a vulcanized product of a rubber composition.