JPS5973944A - Composite body of rubber and metallic material - 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 applies to rubber and metal surfaces, bamboo to zinc, brass, bronze,
A rubber-metal material composite that has good adhesion to steel and shows little loss of adhesion between rubber and metal materials over a long period of time, so it is suitable for use as a material for the steel cord coating rubber layer of conveyor belts, etc. relating to things.

Conventionally, there are various methods for bonding natural rubber, synthetic rubber, or a mixture of these rubbers to a metal core, especially a steel cord.A typical example is the use of an organic acid such as naphthenic acid as an adhesive reinforcing agent. Methods using rubber compositions containing cobalt salts, methylene donors such as hexamethylenetetramine, methylene acceptors such as resorcinol, or rubber compositions containing silica are known. The rubber composition is known to exhibit excellent vulcanization adhesion by direct adhesion to galvanized steel cords, brass-plated steel cords, and the like. however,
Conventional composites of this kind of rubber and metal materials have extremely high adhesion between the rubber and metal materials immediately after vulcanization, but the adhesive strength decreases significantly in a short period of time due to the environmental effects of heat and moisture. It has the disadvantage of

In fact, when a composite of rubber and metal is used in steel cord conveyor belts, steel radial tires, etc., the above-mentioned phenomenon occurs; This may cause a decrease in adhesive strength with the material, and the product may not be able to withstand long-term use under harsh conditions.

For this reason, it has been desired to suppress the deterioration of the adhesive force between the rubber and the metal material over time and to improve the product life.

In view of the above circumstances, the inventors of the present invention conducted intensive research on rubber-metal composites that exhibit less deterioration in adhesive strength over time, and found that direct adhesion to metal materials through vulcanization. By adding zinc powder, etc. to a rubber composition capable of The present invention was completed based on the discovery that a composite of rubber and a metal material with excellent heat and humidity resistance can be obtained with little decrease in adhesive strength even when the adhesive strength is reduced.

The present invention will be explained in more detail below.

The rubber-metal material composite according to the present invention includes a rubber composition that can be directly bonded to a metal material by vulcanization, zinc powder, aluminum powder, copper powder, nickel powder, magnesium powder,
1 selected from antimony powder, silicon powder and iron powder
A seed or two or more kinds are added, and a metal material is brought into direct contact with the material and vulcanized and bonded.

Here, the rubber composition contains raw material rubber and various compounding agents blended as desired. The raw material rubber used in the present invention is not particularly limited, and includes natural rubber, butadiene rubber, isofluorene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, chlorosolene rubber, ethylene-globylene-diene rubber, and the like. In the present invention, these raw material rubbers may be used alone or in combination of two or more. In addition, compounding agents include vulcanizing agents such as sulfur, crosslinking agents, vulcanization accelerators, reinforcing agents such as carbon black, white carbon, calcium carbonate, basic magnesium carbonate, clay, fillers, plasticizers, aging Examples include inhibitors, and one or more of these may be blended as necessary.

In addition to the above-mentioned components, the rubber composition also contains a co-Glut compound such as an organic acid Co-Glut such as cobalt naphthenate, a methylene donor such as hexamethylenetetramine, a methylene acceptor such as resorcinol, and a phenol resin. (Particularly preferred are those containing hexamethylenetetramine),
Or you can use silica alone or in combination!
preferable.

In this case, for 100 parts by weight of the raw material component, the compound is
5 to 1.5 parts by weight, methylene donor and methylene acceptor each 1 to 5 parts by weight, phenolic resin 1 to 10M
It is preferable to use silica in the range of 5 to 30 parts by weight. , silicon powder and iron powder, and among these, zinc powder is particularly preferred.

The blending amount of these metal powders is preferably 0.1 to 50 parts by weight, particularly 2 to 301 parts by weight, based on 100 parts by weight of the raw material comb, and within this range good sliding effects and moist heat resistance effects can be obtained. . Incidentally, if the amount of the metal powder is too large, the physical properties of the comb may deteriorate, so the upper limit is preferably 50 μm by weight.

The particle size of the metal powder is 500 μm or less, particularly 150 μm.
The particle size is preferably 75 or less, and if it is too thick, large foreign particles may form and the physical properties of the comb may deteriorate, resulting in undesirable situations.

Examples of metal materials that can be vulcanized together with the rubber composition include wires and cords such as steel, zinc, yellow lead-plated steel, brass-plated steel, and bronze-plated steel, which can be selected depending on the purpose. used.

Note that among the above-mentioned metal powder and metal shell, the most preferable combination in terms of effectiveness is zinc powder and zinc or galvanized metal material.

The rubber-metal material composite of the present invention is obtained by vulcanizing a metal material by directly contacting a rubber composition containing the metal powder. A gold-metal composite with strongly bonded materials can be obtained.

In this case, the composite of the present invention has a high initial adhesion strength between the comb (vulcanized comb) and the metal material due to the metal powder force being combined with the metal powder, and moreover, it can be left in a high temperature and humid atmosphere for a long period of time. The adhesive strength between rubber and metal materials does not deteriorate even when the rubber is used, and it has excellent thermal stability and maintains sufficient adhesion over a long period of time. It is suitably used as

EXAMPLES Hereinafter, the present invention will be specifically explained by showing examples and comparative examples, but the present invention is not limited to the following examples.

[Examples 1 to 4, Comparative Example 1] Four galvanized steel wire strands (039φ) arranged in parallel at 10 mm intervals under tension were coated on both sides (11 with an adhesive rubber composition having the following formulation). , 155
It was vulcanized at .degree. C. for 20 minutes to obtain a rubber-metal composite having a length of 240 mm, a width of 50 mm, and a thickness of 3 mm, with the wire adhered to the center.

Adhesive rubber composition formulation Natural rubber 70 parts by weight Impregnated rubber 30 Carbon black (HAF) 50 ZnO10 Anti-aging agent 2 Softener 5 Phenol resin 3 Sulfur 5 Vulcanization accelerator 07 Zinc powder (average particle size approximately 50 μm) See Table 1 At the indicated monthly intervals, the composite was divided into five equal parts and used as pull-out test samples.

The pull-out test was carried out using the length 107 of the central part of the divided sample.
Leaving an 11m long rubber section, remove the rubber from the other sections to expose the wire, and add reinforcing rubber (10mm x 50mm x 4mm) on both sides of the central comb section.
) with cyanoacrylate adhesive and reinforced, AS
50 +nm/m by a method compliant with TM p-2229
The wire was pulled out at a tensile speed of il, and its adhesive strength was evaluated.

At that time, the condition of the rubber attached to the wire is shown below.
1iTIi standard, and rubber adhesion was classified and evaluated as fracture shape.

k'F value standard stickiness fracture shape judgment Note that the adhesion strength and rubber adhesion by pull-out tests were carried out on samples before storage under moist heat (initial sample) and samples after storage under moist heat, respectively. In this case, moist heat storage was carried out by leaving each sample in an atmosphere of 70° C. and relative humidity of 100° C. for 21 days.

The results are shown in Table 1.

Table 1 [Example 5~. 8. Comparative Example 2] In the above example, the galvanized steel wire 9
A rubber-metal composite was produced in the same manner as in the above example except that a brass-plated steel wire (0.38φ) was used, and its adhesive strength and rubber adhesion were evaluated. The results are shown in Table 2.

Tsukasa - Itomari Nyama Seido 1 (Jikou) January 17, 1980 '1: [Author Office 1'4 Official Kazuo Wakasugi, Tono 1, Matters ('l Indication III H5 F - Patent Application No. 184498 No. 2, name of the invention Compound of rubber and metal strip 3, relationship between the old facts and fl that makes the amendment Special V1 Idaka 1 representative Kunio Hattori 4, agent 10/1 5, Supplementary i1E Tsuzuka 2 6. Contents of amendment (1) In the second line of page 2 of the specification, the phrase “donor” has been replaced with “
"With the donor," he corrected.

(2) In the third line of the second sentence, after “or”, “these and”
Insert.

(3) On the 2nd page, line 10, "moisture" is replaced with "moisture".
I am corrected.

(4) In the 11th line of page 2, the phrase "adhesive strength decreases significantly in a short period of time" is corrected to "adhesive strength gradually decreases as time passes."

(5) On page 4, line 18, the phrase ``methylene donor'' has been corrected to ``methylene donor.''

(6) From page 4, line 18 to page 5, line 1, the phrase ``Methylene acceptor is preferred...'' has been replaced with ``It is preferable to use a methylene acceptor alone or in combination.'' Incidentally, a phenol resin, silica, or the like may be added as necessary. Correct it as j.

(7) Page 5, line 5 “Phenol resin is 1 to 10”
``Phenolic resin is 1 to 15J.

. ``(Average particle size approximately 50 μm) J
Please correct me with "F (average particle size approximately 10 μm)".

(10) On page 8, line 16, correct the phrase ``center section'' to 1 medium heat section side J.

(11) On page 8, line 18, the phrase ``the central portion'' is corrected to read ``1 the central portion side''.

that's all

Claims (1)

[Claims] zinc powder, aluminum powder, copper powder, nickel powder,
A composite of rubber and a metal material, which is obtained by directly contacting a metal material with a rubber composition containing one or more selected from magnesium powder, antimony powder, silicon powder, and iron powder and bonding with 6 sulfur sulfur. .