JPS61244545A - Rubber laminate - 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] <Industrial Application Field> The present invention relates to a rubber laminate in which an FKM layer and an NBR layer are vulcanized and bonded, and is suitable for use as fuel hoses for automobiles, diaphragms for twerp pumps, etc. be.

In this clear ml, “FKM” refers to fluororubber, rN.
BRJ is an abbreviation for nitrile rubber. Also, r
PHRJ is a fine percentage of external weight relative to the rubber content (polymer).

<Conventional technology> FKM has excellent physical properties such as heat resistance, chemical resistance, aging resistance, and cold resistance, and is resistant to oil and fuel, so it is suitable for use in fuel hoses and diaphragms as described in 2. It is attracting attention as a material for pharmaceutical hoses and packing materials, but the cost is NB.
It is 10 to 20 times more expensive than general-purpose rubber such as R, and its usage is limited. Therefore, when using FKM as a material for fuel hoses, etc., the NBR layer, which is a general-purpose rubber with relatively good oil resistance, is used as the base layer, and the FKM layer is vulcanized and adhered to the side that requires higher physical properties. However, it has generally been difficult to vulcanize and bond the FKM layer and the NBR layer together using a normal method. In particular, F.K.
This tendency was particularly noticeable when the M layer was composed of a peroxide-cured compound. In addition, peroxide-cured FKM has a higher vulcanization rate If and higher crosslinking density than other polyamine/polyol-cured FKMs, so it has good resistance even without secondary vulcanization. Compression set (-settling)
It has advantages such as being able to obtain

<Problems to be solved by the invention> Therefore, Japanese Patent Publication Nos. 1983-49391 and 1983-
33304, etc., a method has been proposed to improve the adhesion of unvulcanized NBR compounds by incorporating metal oxides such as magnesium chloride and silica, but FKM
The interlayer adhesion between the layer and the NBR layer was not necessarily sufficient.

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted extensive research and research, and found that in peroxide vulcanization FKM formulations, peroxide vulcanization formulations In addition to the FKM layer, which contains a vulcanization compounding agent used in the polyol vulcanization system,
In the BR compound, the NBR layer is vulcanized and bonded with a metal fused compound (in addition to a metal oxide (or hydroxide) if it is included as a vulcanization aid). For example, they have discovered that good adhesive strength can be obtained between both layers, and have completed the present invention.

Detailed explanation of the structure><A> The FKM layer is a peroxide vulcanization FKM compound containing a vulcanization compound used for polyol vulcanization in addition to a peroxide vulcanization compound. Consisting of

(1) FKM (polymer) is not particularly limited to binary or ternary systems as long as radically active iodine or bromine is introduced into the polymer to enable peroxide vulcanization. Examples of the binary system include (1) vinylidene fluoride/propylene hexafluoride copolymer, and (3) vinylidene fluoride/propylene hexafluoride/ethylene tetrafluoride terpolymer as the ternary system. More specifically, the above (■) is a product name such as Daiel G301, and the (2) is a product name such as Paiton GF, Paiton GH, Paiton V.
They are coated with trade names such as TR5362, Daiel G901, Daiel G902, etc. Incidentally, ``Hyton'' and ``Daiel'' are trademarks of DuPont and Daikin Industries, respectively.

(2) The peroxide vulcanization compound includes organic peroxide as a vulcanizing agent and triallyl isocyanurate as a co-crosslinking agent.
In addition to 1. and the like, it also includes acid acceptors such as MgO and inorganic accelerators such as Ca(OH)2, which have been used in other vulcanization systems. still,
Naturally, reinforcing agents such as carbon black, processing aids, and optionally colorants, scorch inhibitors, etc. are blended into the FKM blend.

``1. As peroxides, dicumyl peroxide; 2.
5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(1-butylperoxy)hexyne-3, 1,1-bis(t-butylperoxy) - Examples include 3,3,5-)limethylcyclohexane, t-butylperoxybenzoate, etc., and the blending amount thereof is usually 1 to 10 PHR.

(3) What is the vulcanization compounding agent used in the polyol vulcanization system?
An aromatic polyol as a vulcanizing agent and an organic phosphonium salt and/or a quaternary ammonium salt (as a vulcanization accelerator)
(can be used alone or in combination). The amount of the above-mentioned vulcanizing agent and vulcanization accelerator is usually 0.5 to 5.
PHR.

Examples of the aromatic polyol include hexafluoroisopropylidene-bis(4-hydroxyphenyl)hydroquinone and impropylidene-bis(4-hydroxyphenyl), and examples of the organic phosphonium salt include triphenylbenzylphosphonium chloride and tetraphenyl Examples of the quaternary ammonium salt include phosphonium chloride and tetraoctylphosphonium chloride, and examples of the quaternary ammonium salt include triphenylbenzylammonium chloride and tetraphenylammonium chloride.

<B> In the NBR formulation, the NBR layer is
Metal oxide (or hydroxide) selected from Groups I-IV
(hereinafter referred to as "metal oxides") is blended with 5 PHR or more (in addition to metal oxides if they are included as vulcanization aids) with other auxiliary materials.

(+)NBR is an acrylonitrile-butadiene copolymer, and from the viewpoint of oil resistance and cold resistance of the NBR layer, an acrylonitrile bond amount of 15 to 55% is usually used. Specifically, two pole DN1, 01/103/302
・202・206, JSRN220S・N230S-N
2310, hiker 1001-1031. Examples include those marketed under trade names such as -1042. Here, ``Niball'' and ``Hiker'' are trademarks of Nihon Joon, and ``JSR'' is a trademark of Japan Synthetic Rubber.

(2) The vulcanization system for this NBR is not particularly limited, and may be sulfur vulcanization, peroxide vulcanization, or the like. Incidentally, as the peroxide vulcanizing agent, those exemplified above are used.

(3) Examples of metal oxides include magnesium oxide, aluminum oxide, zinc oxide, zinc dioxide, calcium oxide, lead oxide (IT, IV), silicon dioxide, and their hydroxides. Magnesium oxide, calcium hydroxide, aluminum hydroxide, lead oxide (
TI) is preferred. The amount of metal oxides added is usually 5 to 30 PHR.

(4) Auxiliary materials other than those listed below include reinforcing agents such as carbon black, vulcanization accelerators, processing aids, plasticizers, coloring agents,
There are anti-aging agents, etc., and they are added as appropriate.

<C> Fluororubber layer 1 made of the blend of <A> above
The vulcanization adhesion method for the NBR layer (substrate layer) 2 made of the above-mentioned compound <B> is not particularly limited.

For example, in the case of a rubber hose as shown in Fig. 1, each compound is extruded simultaneously or separately from one or two extruders and laminated together under appropriate conditions (145-b). In the case of a diaphragm as shown in Figure 2,
Rolled sheets of each compound were punched out, stacked and press-molded (mold temperature: 150-190°C, 1 hour, 3 hours).
~30mln, pressure 50~150kgf/crn')
L. Perform vulcanization adhesion. Note that 3 in the illustrated example indicates the base fabric layer. The configuration of the rubber laminate is not limited to the illustrated example, and can be applied to, for example, a reinforced hose, a hose or diaphragm with FKM layers on the inside and outside (front and back), or a full rubber diaphragm.

<Effects of the Invention> As shown in the examples below, the rubber laminate of the invention thus obtained has significantly improved interlayer adhesion between the FKM layer and the NBR layer, and is resistant to harsh usage conditions. It becomes something you can drink. Furthermore, the FKM layer has good resistance to settling, making it possible to expand the field of application of the invention.

<Examples> Hereinafter, the present invention will be explained in more detail based on Examples.

The preparation of the test pieces for each example meeting comparative example was as follows: The FKM layer was prepared using the following FKM formulation, the peroxide vulcanization type/polyol vulcanization type formulation was prepared according to the specifications shown in Table 1, and the FKM layer was prepared using the following NBR formulation. N- with Ca(OH)2 at 20PHR
NBR layers of 11 N OI+ formulation with 1" or 0 PHR were rolled into sheets of 4 mm thick and heated at 170°C for 15 minutes in the indicated combinations.
The adhesive was bonded by pressure vulcanization under conditions of 0 kgf/cm'. Adhesive strength was determined in accordance with JISK6301 peel test under normal conditions and after immersion in Tsuyuel D (40°C x 49 hr).The normal physical properties and compression set of FKM were also determined after pressure vulcanization under the same conditions as above. A test piece was obtained from the obtained 2 mmt vulcanized plate and measured according to JIS K6301.

(1) FKM formulation (unit double placement) polymer (Daiel G901) 100MT black
20Mg0
3Ca(OH)26 Organic peroxide Variable co-crosslinking agent
variable organic polyol
Variable vulcanization accelerator Variable (2) NBR compounding prescription (unit double placement part) Polymer (J
SRN230S) 100MAF Black
50 stearic acid
lZnO5 Ca(OH) 2
2 0 (or 0) Organic peroxide 3 Co-crosslinking agent
3 Table 1 shows the test results of Examples and Comparative Examples. Each of the examples shows interlayer adhesion strength so large as to cause rubber failure, and also has good FKM resistance to settling.

On the other hand, when the FKM formulation does not contain a polyol vulcanization compound (Comparative Example 1) and when the NBR formulation does not contain metal oxides (Comparative Examples 4 to 7), very small Only interlayer adhesion was exhibited and interfacial peeling occurred. Furthermore, when the FKM compound contained a polyol vulcanization compound (Comparative Examples 2 to 3), similar to the examples, high interlayer adhesion was exhibited, but the FKM did not have good settling resistance. It turns out that there are some problems.

[Brief explanation of the drawing]

The illustrated examples show a laminate to which the present invention can be applied; FIG. 1 is a side view of a rubber hose, and FIG. 2 is a side view of a diaphragm. ]...FKM layer 2...NBR layer Patent application person-13= Figure 1 Figure 2

Claims (1)

[Claims] An FKM layer consisting of the following formulation (A) and the following formulation (B).
) A rubber laminate in which the NBR layer consisting of Contains compounding agents. (B) In NBR formulations, periodic table II-IV
A rubber compound in which a metal oxide (or hydroxide) selected from the group consisting of metal oxides (or hydroxides) is blended with other auxiliary materials (in addition to metal oxides as vulcanization aids if they are included).