JPH02160867A - Rubber composition having excellent adhesiveness with fluorinated rubber - Google Patents

Abstract

PURPOSE:To obtain a rubber compsn. with excellent adhesiveness with fluorinated rubbers by compounding an epichlorohydrin rubber with Ca(OH)2, specified undecene deriv., a phenol resin and an epoxy compd. CONSTITUTION:100 pts.wt. epichlorohydrin rubber is compounded with 0.5-30 pts.wt. Ca(OH)2, 0.1-5 pts.wt. 1,8-diazabicyclo-(5,4,0)-undecene-7 or its weak acid salt, 0.1-8 pts.wt. phenol resin and 0.1-10 pts.wt. epoxy compd. The obtd. compsn. exhibits extremely excellent adhesiveness with fluorinated rubbers and the interface of adhesion is durable after immersion in a warm fuel oil or heat-aging for a long time. Therefore, this compsn. is extremely effective for such uses as a fuel hose wherein the inner liq.-contacting part is constituted of a fluorinated rubber with excellent resistance to sour gasoline and the outer face is constituted of an epichlorohydrin rubber with excellent aging resistance, gasoline-absorbing resistance and gasoline resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an epichlorohydrin rubber composition that has excellent adhesion to fluororubber.

(Prior Art) Conventionally, acrylonitrile-butadiene copolymer rubber (NBR) has been used as a hose for fuel oil such as gasoline. In recent years, due to the implementation of exhaust gas control measures and energy saving measures, the temperature of the engine room has increased, and as a result of the introduction of V-cycles for exhaust gas glue, etc., the rubber materials used have improved aging resistance, weather resistance, rancidity gasoline resistance, etc. Uf
It has become necessary to have u, and the above N
It was found that B1< is not sufficient as a material that satisfies these various performance requirements. Fluororubber is an example of a rubber material that meets the above requirements, but it is 10 to 20 times more expensive than regular rubber, and it also has problems with cold resistance. The use of multilayer rubber hoses using the N layer and the outer layer of other types of rubber, such as epichlorohydrin rubber, is gradually increasing.

(Problems to be Solved by the Invention) In the case of multilayer rubber hoses, the most important problem is the adhesion between these different types of rubber. In the case of the above-mentioned fluororubber and epichlorohydrin rubber, it is generally known that adhesive properties are poor, and for this reason, a measure is usually taken to incorporate certain additives into the rubber. The present applicant added calcium hydroxide, epoxy compounds, aldehyde amines, aldehyde ammonias, and compounds derived from 1,8-diazabicyclo(5,4,0) undecene-7 or its weak acid salts to epichlorohydrogen rubber. We have already proposed a composition with excellent adhesion to fluororubber (equity 11[161
-29619). The present invention aims to provide an epichlorohydrin rubber composition which is a further improvement on this composition and has poor adhesion to fluororubber.

(Means for Solving the Problems) The present invention provides Epic [1] per 100 parts by weight of ruhydrin rubber, 1 part of water, 0.5 to 30 parts of calcium chloride, 1.8 parts of
- Adhesiveness to fluororubber characterized by blending 0.1 to 5 parts by weight of a weak acid salt of diazabicycloshukeso, 0.1 to 8 parts by weight of a phenolic resin, and 0.1 to 10 parts by weight of an epoxy compound. It is a rubber composition with excellent properties.

The epichlorohydrin rubber used in the present invention includes epichlorohydrin homopolymer, shrimp chlorohydrin-allyl glycidyl ether binary copolymer, epichlorohydrin-allyl glycidyl ether binary copolymer, shrimp chlorohydrin-ethylene oxide Refers to a rubber selected from allyl glycidyl ether terpolymer, and in the case of copolymer rubber, the component composition ratio (mole) is shrimp chlorohydrin-
In the case of allyl glycidyl ether binary copolymer, 85~
99:15-1, 20-80 in the case of Epic[1-ruhydrin-dylene oxide di-copolymer: 80-20
, in the case of epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer, 20 to 79 nia 9
~20: 1 to 20 is preferred. These rubbers may be used alone or in a mixture.

The calcium hydroxide used in the present invention is
A fine powder with a mesh pass of 95% or more is preferable, and the blending amount is 0.5 to 30 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of Epicureidrin rubber. be. If the amount is less than 0.5 parts by weight, there is no effect of improving adhesion, and if it exceeds 30 parts by weight, IJIII
This is not preferred because the mechanical properties of the sulfur are impaired.

The composition of the present invention contains
, 0) Undecene-7 (hereinafter abbreviated as DBU) or its weak acid salt is blended. DBU may be used as such or, depending on its handling, may be used as a weak W1 salt such as a carbonate, a long chain aliphatic carboxylate, a phenol salt, or a salt with a thiol. A typical example of DBU salt is DBU charcoal.
4, DBU-2-ethylhexylate, DBU-benzoate, DBU-naphthoL salt, DBLJ-phenol salt, []BU-2-mercaptobenzothiazole salt, etc. are too numerous to mention. The amount of DBU or a weak acid salt of DBU is 0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight, per 100 parts by weight of the evichloridine rubber. If the blending amount is less than 0.1 part by weight, it may not have a sufficient effect on adhesion to fluororubber.

If the amount exceeds 5 parts by weight, the vulcanization rate of the epichlorohydrin rubber becomes too fast, resulting in difficulty in curing.

The phenolic resins used in the present invention are usually classified as: phenol, cresol, xylenol, alkylphenol, etc.

Phenol compounds such as phenylphenol and resorcinol, formaldehyde, and acetaldehyde.

Examples include resins obtained by a condensation reaction with paraformaldehyde, furfural, etc., modified resins with terpenes, cashews, etc., and those having a softening point of 130°C or less, preferably 60 to 130°C are used. 130
If the temperature exceeds °C, there is a problem in dispersibility during mixing. When blending, it is particularly preferable to use it by mixing it with the DBU in advance in terms of handling, and the adhesion to the fluororubber is further improved. The blending ratio of the phenolic resin is 0.1 to 8 parts by weight, preferably 0.2 to 5 parts by weight, per 100 parts by weight of EPIC[1]ruhydrin rubber. If the amount is less than 0.1 parts by weight, sufficient swallowing force cannot be obtained, and if it exceeds 8,000 parts by weight, it is not particularly effective in improving the effects of the present invention.

As the epoxy compound of the present invention, those normally used are χ1. For example, bisphenol A epoxy (
Δ1 fat, resorcin type soil poxy resin, Tei Rahid [1
Xyphenyl-[tan type epoxy resin.

Examples include novolac-type epoxy resins, glycidyl ether-type compounds of eblene Δ oxide compounds or propylene oxide compounds, and glycidyl needle-type compounds of polyhydric alcohols.

The amount of the epoxy compound to be blended is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight per 100 parts by weight of the Dopic 1-1 ruhydrin rubber. If the blending amount is less than 0.1 part by weight, sufficient adhesion cannot be obtained, and if it exceeds 10 parts by weight, the 101st speed decreases and the physical properties of the cured ruhydrin-based rubber are - It becomes impossible to perform during the F minute.

The composition of the present invention is vulcanized (the T1 agent may be any agent that is normally used in epichlorhydric rubbers, such as a sulfur-based agent that utilizes the unsaturated bonds of the 7-lylglycidyl-ester component of rubber). There are vulcanizing agents such as peroxide-based vulcanizing agents, diamine-based vulcanizing agents that utilize chlorine in rubber, polythiols, and thioureas, among which Chia 1
'l/! For example, use of 2-mercap 1 to imidacillin is /Jl! iJtml body.

It is particularly preferred in terms of the balance of vulcanized physical properties. These/Jll
The blending amount of the fA agent is suitably in the range of 0.2 to 10 parts by weight per 100 parts by weight of Epic (colhydrin rubber).

The composition of the present invention may contain a vulcanization accelerator and vulcanization accelerator as necessary for the above-mentioned components. ! Spreading agent, acid acceptor, reinforcing agent, filler, plasticizer,
Compounds commonly used in the art, such as lubricants, anti-aging agents, additives, flame retardants, etc., can be added. In particular, the addition of a metal compound as an acid acceptor is particularly effective from the viewpoint of thermal stability of the composition of the present invention. The above-mentioned metal compounds include oxides and hydroxides listed in Group 1 of the Table of Circumstances;
Carbonates, carboxylates, silicates, borates, sacrophosphates, periodic matchmakers Group 1 Va metal oxides, basic carbon Q! 2@
, base t) 1 carboxylate, basic phosphite, base'l
:1, If, fit! acid salt.

There are tribasic sulfates, etc. Examples of these shells include magnesia, magnesium hydroxide, barium hydroxide, magnesium carbonate, barium carbonate, cow ash, calcium carbonate, calci silicate, calcium sudeate, zinc stearate, calcium notalate, Magnesium, sacrocalcium phosphate + jlT'-1) Hua, tin oxide,
One door large-sized fish, for hooks, and for white fishing.

Examples include dichloride phthalate, dichloride carbonic acid 341, tin sudealate, basic phosphite, and basic chloride (t1 acid hook). A suitable range is 0.5 to 20 parts by weight per 100 parts by weight of the rubber.

The composition of the present invention is mixed using a roll or pressure kneader.

This is done using a regular mixer such as a Hanbury mixer.
Further, 1J[1 sulfurization can be carried out by various conventional vulcanization methods such as vulcanization using a metal mold/Jll thermoforming, vulcanization using steam, microwave, hot air oven, or salt bath.

As the fluororubber to which the composition of the present invention is applied, highly fluorinated elastic copolymers are suitable.

For example, a copolymer of vinylidene fluoride and another fluorine-containing olefin that can be co-Φ-formed can be mentioned. Examples of fluorine-containing olefins include hexafluoro 10pene, pentafluoropropene, trifluoroethylene, and trifluoroethylene.

Tetrafluoroethylene, vinyl fluoride.

Perfluor [-1 medyl vinyl ale, pernol A-
[1P[1Pyrvinyl ether, etc.], and one or more of these are used as a copolymerization component.

Preferred copolymers include vinylidene fluoride-to-kylyfluoropropene binary copolymers and vinylidene fluoride-tetrafluoroethylene-to-kylyfluoropropene terpolymers. Depending on the purpose, known compounding agents such as a vulcanizing agent, a vulcanization promoter, a stabilizer, a coloring agent, a plasticizer, a reinforcing agent, etc. are added to the fluororubber.

The method for adhering the composition of the present invention and fluororubber is to laminate them together and simultaneously heat them (I) using a hot vulcanizer, or one of them was gently heated at qt for a plug that does not lose its shape. A method of stacking them and heating them sufficiently can be adopted.

(Examples) Examples 1 to 4 Comparative Examples 1 to 3 The epichlorohydrin rubber compositions shown in Table 1 were kneaded using a finch roll at 70 to 80'C for 15 to 20 minutes to form a 1 to 1.5 mm thick product. I bought 1q of sheet A.

On the other hand, a sheet B having a thickness of 1 to 1.5 ttun was prepared by kneading the fluororubber compositions shown in Table 2 in the same manner.

- Laminate sheet B and sheet B at 160°C.
Press at l2O~25kg/crA for 30 minutes to a thickness of 2
A laminated sheet of ~2.5 mm was obtained. This laminated sheet is 2
, 5 x 10 cm short 11 [1] was cut to prepare a test bar, and the test piece was subjected to a T-peel N1 test at 25°C and a tensile rate of 50 mm/min, and the results are shown in Table 3. .

! t(1) DuPont product name “Pyton E-430J (
2) [Paiton AJ* mark indicates rubber failure, and no mark indicates interfacial peeling on the adhesive surface.

As is clear from the results in Table 3, the laminated sheet using the composition of the present invention did not peel off at the rubber adhesive surface even after being immersed in hot fuel oil or after heat aging. In contrast, a comparative example lacking the phenolic resin in the composition of the present invention],
Comparative Example 2, which lacks DBU or its weak acid salt, and Comparative Example 3, which lacks ]-boxy compound, both exhibited interfacial peeling at the bonded surface with low tensile strength after immersion in a fuel cell or after heat aging. There is.

(Effects of the Invention) The composition of the present invention has excellent adhesion to fluororubber and
3. The adhesive interface is strong even after being immersed in hot fuel oil for a long period of time or after being heated and aged for 1 hour.

Therefore, the inner surface liquid part! Fluororubber with excellent physical properties such as 114M resistance to gasoline, outer surface has aging resistance↑↑No.1, weather resistance↑No.1
”.

Epic [1], which has excellent gasoline resistance, has extremely zero effectiveness in applications such as fuel hoses made of hydrin-based rubber.

Claims (1)

[Claims] (1) For 100 parts by weight of epichlorohydrin rubber,
0.5 to 30 parts by weight of calcium hydroxide, 0.1 to 5 parts by weight of 1,8-diazabicyclo(5,4,0)undecene-7 or its weak acid salt, 0.1 to 8 parts by weight of phenolic resin, and epoxy A rubber composition with excellent adhesion to fluororubber, characterized in that it contains 0.1 to 10 parts by weight of a compound.