JPS62100536A - Bonding of rubber composition and brass - Google Patents

Abstract

PURPOSE:To enable the bonding of a rubber/metal composite product such as tire, by interposing a rubber composition compounded with silica, resorcin donor, etc., between brass and a specific rubber composition compounded with an organic peroxide vulcanization agent and vulcanizing and integrating the product. CONSTITUTION:(A) A composition proudced by compounding 100pts.(wt.) of a nitrile-containing polymer containing 10-45(wt)% unit segment (formula) derived from an unsaturated nitrile (e.g. butadiene-acrylonitrile copolymer rubber) with 1-15pts. of an organic peroxide vulcanization agent (e.g. dicumyl peroxide) is topped with (B) a rubber composition compounded with silica, a resorcin donor, a methylene donor (e.g. hexamethylenetetramine) and a sulfur- based vulcanization agent (e.g. sulfur). Brass is placed on the laminate and the whole assembly is integrated by vulcanization.

Description

Detailed Description of the Invention Technical Field The present invention relates to a method of adhering a rubber composition to brass in the production of rubber/metal composite products used in fields requiring heat and oil resistance. , tires, belts,
It can be used to bond products such as molds, rolls, and hoses.

II. Prior Art In recent years, many rubber products such as tires, belts, molds, rolls, and hoses have been used for long periods of time with heated oil under high temperature and pressure. Deterioration is always a huge problem.

If rubber products are severely deteriorated, maintenance or replacement requires a great deal of time and effort, and can sometimes lead to serious accidents.

It has excellent oil resistance and can withstand such high temperatures (120℃~150℃
) Polymers that can be used continuously under the emitter condition include acrylonitrile-butadiene conjugate rubber (NBR),
Acrylic rubber (AC:M), ethylene acrylic rubber (
AEM): Ethylene/acrylic-vinyl acetate copolymer rubber (ER), chlorosulfonated polyethylene rubber (
CSM), z-celluated polyethylene rubber (CM), and acrylonitrile-butadiene copolymer rubber (NBR)
Rubbers in which the conjugated diene moiety is hydrogenated (so-called hydrogenated NBR) are known.

On the other hand, in order to increase the heat resistance of rubber products, organic peroxide vulcanized rubber compositions that use organic peroxides are more heat resistant than sulfur vulcanized rubber compositions that use sulfur during vulcanization. It is known to have excellent sex.

However, since organic peroxide vulcanized rubber compositions generally do not contain sulfur, they have poor adhesion to brass products such as plus-plated wire (hereinafter referred to as plus wire), and, for example, they cannot be used under high temperature and high pressure. When a positive wire is used as a reinforcing material for a rubber product, there are drawbacks such as the product being destroyed due to interfacial peeling between the rubber product and the positive wire.

In addition, organic peroxide vulcanized rubber compositions have the disadvantage that, unlike ordinary sulfur vulcanized rubber compositions, sulfur/organic peroxides interfere with each other by inhibiting the reaction, so the vulcanized physical properties do not appear and they do not adhere. .

■ Purpose of the Invention The purpose of the present invention is to provide an organic peroxide vulcanized rubber composition that improves the drawbacks of the prior art described above and makes it possible to manufacture rubber/metal composite products that can withstand long-term use in high-temperature environments. and brass.

■ Specific structure of the invention The present invention provides unit moieties from unsaturated di-lyl in 10 to 4
Silica, a resorcin donor, and methylene are added to a rubber composition (A) containing 1 to 15 parts by weight of an organic peroxide vulcanizing agent to 100 parts by weight of a nitrile group-containing elastomer containing 5% by weight. A rubber composition (B
), furthermore, a brass body is disposed on the ``-'', and the rubber composition and brass are bonded by vulcanization and integration. Here, 1: It is known that 1/sorcin and a condensate of resorcin and formaldehyde are commonly used as the resorcin donor, and that hexamethylenetetramine and the like are commonly used as the methane 1/n donor. It is.

Uninventors have conducted various studies in order to produce a rubber/metal composite product that has excellent oil resistance and can be used continuously for a long time at 120°C to 150°C. In general, organic peroxide vulcanized acrylonitrile◆butadiene copolymer rubber is heat resistant,
It is advantageous that the rubber has excellent oil resistance, and that the copolymer rubber obtained by hydrogenating the conjugated diene part of the acrylonitrile-butadiene copolymer rubber (so-called hydrogenated NBR) has excellent heat resistance and a high hydrogenation rate. It is also known that vulcanization with an organic peroxide is necessary if the hydrogenation rate is high. Furthermore, it is known that these rubber compositions do not adhere to positive wires due to organic peroxide vulcanization.The present invention has found a method for improving the adhesion between these rubber compositions and positive wires. A sulfur vulcanized rubber composition containing the HRH is placed between the rubber composition and a brass body such as a positive wire,
The present invention was based on the discovery that adhesiveness between the rubber composition and the positive wire can be imparted by vulcanizing and integrating the rubber composition.

The present invention will be explained in detail below.

In the present invention, the rubber composition (A) and the brass are bonded together by disposing the rubber composition (B) on the rubber composition (A), further disposing the brass body on top of the rubber composition, and vulcanizing and integrating the composition. The rubber composition (A) has a strong initial adhesive strength and effectively utilizes the heat resistance and oil resistance of the rubber composition (A) in rubber products. (1) Rubber Composition (A) Nitrile Group-Containing Polymer 100 Having a Unit Portion from Unsaturated Nitrile This is a composition in which 1 to 15 parts of an organic peroxide vulcanizing agent are added to the part to be covered.

If the unit portion from unsaturated nitrile is less than 101V, the oil resistance of the rubber composition (A) is poor, and the hardness is 45% by weight.
If it exceeds this, cold resistance will deteriorate.

In particular, when the following copolymer rubber called hydrogenated NBR is used in the rubber composition (A), a rubber composition (A) having excellent heat resistance and oil resistance can be obtained. That is, hydrogenated NBR has 10 units of unsaturated nitrile in the polymer chain.
~45% conjugated diene unit part from O~2ot
*%, and a copolymer rubber having 90 to 35% of a intermediate portion in which a degree portion from an ethylenically unsaturated monomer other than unsaturated nitrile and/or a unit portion from a conjugated diene is made into wood, A saturated methylene chain (C
It is a copolymer rubber composed of a carbon-carbon double bond (C=C), a nitrile group (VCN), and a carbon-carbon double bond (C=C).

(-CH2-CH2-)X-(-CH2-CI-).

CmiN [CC] [VCN]-(-CH2
-CH=CH-Oh -)2 [C=C] where (-CH2
-CH-) is a unit from unsaturated nitrile! The C=N moiety is 10 to 45% by weight.

If it is less than 10% by weight, oil resistance will be poor, and if it exceeds 45% by weight, cold resistance will be poor.

Written as a saturated methylene chain (C-C) (-CH2-C))! -) be.

In particular, the hydrogenation rate is preferably 95% or more.

If the saturated methylene chain (ce) exceeds 90% by weight, the unit portion (VCN) derived from unsaturated nitrile will be relatively reduced, and the oil resistance will be poor and unusable. If C-C) is less than 35% by weight and the unit portion (VCN) from unsaturated nitrile is large, cold resistance is poor; if the saturated methylene chain (C-C) is less than 35% by weight, unsaturated nitrile If the intermediate portion (VCN) from 1 to 3 is small and the C-C portion (described later) is large, the resistance to deteriorated oil will deteriorate.

(-CH
2-C:)I-CI-CH2-) is a unit moiety from a conjugated diene and is 1% by weight and 0 to 20% by weight.

This is because if it is outside this range, the resistance to deteriorated oil will be poor.

Specific examples of such copolymer rubber include butadiene-
Hydrogenated acrylonitrile copolymer rubber, isoprene-7 acrylonitrile copolymer rubber, butadiene-isoprene-acrylonitrile copolymer rubber, etc.: Butadiene-
Methyl acrylate-acrylonitrile copolymer rubber, butadiene-acrylic acid-acrylonitrile copolymer rubber, etc., and their hydrogenated products: butadiene-ethylene-acrylonitrile copolymer rubber, butyl acrylate ethoxyethyl acrylate vinyl gloroacetate acrylonitrile copolymer Examples include rubber, butyl acrylate-to-ethoxyethyl acrylate-vinylnorporene-acrylonitrile copolymer rubber, and hydrogenated products thereof. These copolymer rubbers may be used alone or in some cases in combination with other rubbers to the extent that the gist of the present invention is not impaired.

The rubber composition (A) contains fillers, reinforcing agents, plasticizers, anti-aging agents,
Other compounding agents and the following vulcanizing agent are mixed and kneaded to obtain a rubber compound composition.

The organic peroxide used as a vulcanizing agent may be any organic peroxide in which the crosslinking reaction does not proceed excessively at the processing temperature in the rubber composition (A), and preferably has a half-life of 10.
Dialkyl baroxides having a decomposition temperature of 80° C. or higher in hours are preferred.

For example, dicumyl peroxide, 1,3-bis-(t
- Petit Louver Ogycy isobrovir) benzene, 4.
4-tertiarybutylperoxyvaleric acid n
-butyl.

The organic peroxide vulcanizing agent is the nitrile-containing polymer 1 mentioned above.
It is blended in an amount of 1.1 to 15 parts by weight per 1,000 tonne parts. If it is less than 1 part by weight, there will be less crosslinking and it will be difficult to develop physical properties;
If the amount exceeds 1 part by weight, the organic peroxide residue will affect the thermal properties.

(2) Rubber composition (B) A rubber composition containing silica, a resorcinol donor, and a methylene donor. Any rubber composition may be used as long as it uses sulfur as a vulcanizing agent, but preferably a diene-based rubber composition. Rubber to o Hair: *1 to 1 silica to x part
1oot1<♀ part, preferably 1 to 50 parts by weight, resorcin 0.5 to 20 parts by weight, preferably 1 to 1 Q
tQ part, 0.1 to 10 parts by weight of hexamethylenetetramine, preferably 0.5 to 5 parts by weight, and a sulfur-based vulcanizing agent, and other necessary ingredients are mixed and kneaded into a rubber composition. .

If the amount of silica is less than 1 part by weight, it will not be effective in adhesion;
If it exceeds 100 parts by weight, the viscosity becomes too high to be of practical use.

If the resorcin donor is less than 0.5 parts by weight, it will have no effect on adhesion, and even if it exceeds 20 parts by weight, it will also have no effect on adhesion.If the methylene donor is less than 0.1 part by weight, it will not be effective. It has no effect on adhesion, and if it exceeds 10 parts by weight, it becomes scorch and has poor processing stability, making it unusable for practical use.

Typical sulfur-based vulcanizing agents include sulfur, sulfur chloride, organic sulfur-containing compounds, and the like. The amount of the sulfur-based vulcanizing agent is 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the diene rubber. If the amount is less than 0.1 parts by weight, there will be no adhesive effect, and if it exceeds 30 parts by weight, the vulcanization reaction of the organic peroxide vulcanized rubber composition will be inhibited, which will have the opposite effect.

If the rubber composition (B) is placed next to the rubber composition (A) in the following F, and a brass body is further placed on the L side, com, vll animal A is obtained.
) and the brass body can be 4·t ′j.

Place the rubber composition (B) on )Z of the rubber composition (A)! 7゜The method of placing the brass body on top of it may be in any form depending on the type of rubber product; The rubber composition (A) is placed on the surface exposed to water, and an adhesive layer is placed between the rubber composition (A) and the brass body as a reinforcing material, with the rubber composition (B) interposed therebetween.

Here, the brass body is mainly used as a reinforcing material for rubber products such as hoses and tires, and may be made of wire, pipe, plate, steel, etc., and may be made of high carbon steel or other metals.
It may be plated with Zn alloy.

A brass body is placed on the rubber composition (A) via the rubber composition (B), and then vulcanized and integrated. The vulcanization conditions can be selected depending on the type of rubber product, but the vulcanization temperature is preferably 130°C to 200"C, and the vulcanization method is normal press vulcanization, steam vulcanization, Commonly used methods such as hot water vulcanization are possible.

The method of the present invention can be applied to many rubber products such as tires, belts, molds, rolls, and hoses that require oil resistance after long-term use in high-temperature, high-pressure environments.

(2) Examples The present invention will be specifically explained below using examples and comparative examples.

<Example> The rubber compositions of Formulation Examples 1 to 3 shown in Tables 1 and 2 were mixed for 15 minutes on a 60°C mixing roll, and used as samples for each test shown below.

(1) Rubber/rubber adhesion test method Each sample of Formulation Examples 1 to 3 was heated to 2.0
Sheeting was carried out to a thickness of mm, and samples for rubber/rubber adhesion tests were prepared in the following manner using Formulation Examples 1 and 2 as rubber compositions (A) and Formulation Example 3 as rubber composition (B).

As shown in FIG. 1, rubber composition (A) 1 and rubber composition (B) 2 of 15 cm x 10 mm x 2 mm thick were arranged I7.

During the peel test, place cellophane paper 3 on the part gripped by the chuck.
1- to prevent the two layers from adhering to each other.

Ta.

The wood sample was heated to 90°C at 153°C using a laboratory press molding machine.
They were vulcanized under pressure at a surface pressure of 30 kgf/cnf for 30 minutes, and were integrally molded.

After standing at room temperature for 24 hours, the sample was cut to a width of 2.54 cm and subjected to a peel test.

The peel force was measured using a tensile strength tester specified in JIS K fli301 at a tensile speed of 50 mm/min.

Calculation of peeling force is based on JIS K 6301 8, 3,
This was carried out in accordance with the method described in 3(3).

(2) Rubber/brass adhesion test method Samples of formulation examples 1 to 3 were sheeted out to a predetermined thickness using a small roll for rubber compositions. A), Formulation example 3
Rubber composition (B) and rubber composition (B) by the following method.
A sample for brass adhesion test was prepared.

As shown in Fig. 2, the rubber composition (A) and the rubber composition (B) are 5 cm x 10 cm x a predetermined thickness. and brass plate 4
was constructed.

During the peel test, place cellophane paper 3 on the part gripped by the chuck.
was placed to prevent the upper and lower layers from adhering.

The wood sample was molded using a laboratory press molding machine at 153°C.
Pressure vulcanization was carried out for 0 minutes at a surface pressure of 30 kg/c, and the pieces were molded into one piece.

After leaving it at room temperature for 24 hours, a peel test was conducted between the second rubber layer and the brass plate.

The 111# force was measured using a tensile tester specified in JIS K 6301 at a tensile speed of 501 mm/win.

All other procedures were conducted in accordance with the methods described in JIS K 8301 8, 3.

The above experimental results are shown in Table 3.

Comparative Example> As a comparison, without using the second layer rubber composition,
When adhering directly to brass (Table 4, Comparative Examples 1 and 2) and Formulation Example 4 shown in Table 2, which does not contain silica, resorcinol, or hexamethylenetetramine, the second layer was prepared using the same method as in Example 1ζ. (Comparative Example 3, 4.5)
Similar experiments were conducted using the rubber compositions of 6) and 6) as samples for adhesion testing in the same manner as in the examples.

The results are shown in Table 4.

""Table 5A"1" (゛)0601
Parts by weight) VCN: Bonded acrylonitrile f? f [Description of raw materials used 1) SRF Asahi Carbon
Asahi #502) Vulkanox DDA
Nokuie Jshisha Dipheni J Reamine derivative 3) IJulkanoxZMB-2 Bayer 4.5-Methylmet) Lt captobenzylimidazole zinc salt 4) WAX Hoechjt AG
PE 5205) TAIC Nippon Kasei
1-nor-1-norisocyanate 8) Wita
mol 218 Dynamite Φ Nobel Co., Ltd. 1 pinch l) + 7 tonic acid ester 7) Bar force dox 14/
40 Kayaku Nouri 1.3-bis(t
-buty J Reno arm - oxyisopropyl) benzene (JL 4oz) 8) N1pol l O42 Nippon Zeon
Nido 1 norbutadiene rubber 8) Anti-aging OD
Kawaguchi Chemical Antage 0D1
0) Old defense BHT Seiko Chemical
Swanotx BHTll)TMP
Mitsubishi Rayon To1nometaku1
Trimethylolpropane norate 12) Coumaron resin Kobe Yui Anko Kogyo
Soft Kubron 25B13) Silica
Japan Silicani Industry Nip Seal AQ
14) Resorcinol Sumitomo Chemical 15) DO
P Nisso stone mud Hbit16) Accelerator CM Sankai Kagaku Kogyo Sunceller CM-PO17) Hexamethylene Omukai Shinko Kagaku Tsukuseller H Tetramine Table 3 Experimental results (Results) Rubber/Rubber adhesion test Rubber/Rubber/Shinron adhesion Test Table 4) Rubber/rubber adhesion Oligom/brass adhesion 11 Re-rubber/rubber/brass adhesion ■ Effects of the invention Due to the adhesion between the rubber composition of the present invention and brass, organic peroxide addition, which has been difficult in the past, has been achieved. It is now possible to bond nitrile group-containing elastomers containing sulfuric agents to brass, resulting in heat resistance,
It has become possible to manufacture rubber/metal composite products with excellent oil resistance.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view of a sample used in the rubber/rubber adhesion test. Figure 2 is a cross-sectional view of the sample used in the rubber/rubber/brass adhesion test.4 Explanation of symbols

Claims (1)

[Claims] For 100 parts by weight of a nitrile group-containing elastomer containing 10 to 45% by weight of units derived from unsaturated nitrile,
A rubber composition (B) containing silica, a resorcin donor, a methylene donor, and a sulfur-based vulcanizing agent is added to a rubber composition (A) containing 1 to 15 parts by weight of an organic peroxide vulcanizing agent.
), further disposing a brass body thereon, and bonding the rubber composition and brass by vulcanization and integration.