JPS6041084B2 - Bonding method between diene rubber and metal materials - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method of adhering a Gen-based rubber and a metal material.

Composite materials consisting of polymer materials and metal materials include laminates of metal and rubber, reinforced polymer materials reinforced with metal materials, metal materials coated with polymer materials, polymer materials containing metal fillers, etc. Its application fields are extremely wide.
Among them, gene-based rubber is widely used as a synthetic rubber material due to its excellent elasticity, oil resistance, heat resistance, etc., and is often used as a composite material with metal materials. For example, when a metal material is embedded in rubber for the purpose of reinforcing a Jen-based rubber material, a reinforced Jen-based rubber material having various characteristics can be obtained depending on the type and shape of the metal material.

However, since these reinforcing rubber materials are generally used under severe conditions, strong adhesive strength between rubber and metal is required. In order to obtain such strong adhesion, it is desirable to form some kind of chemical bond between the gen-based rubber and the metal, but to date, there are no compounds known that can chemically bond between the gen-based rubber and the metal. Not yet. Furthermore, when a metal comes into contact with a rubber material, there are also drawbacks such as deterioration of the rubber material by the metal or corrosion of the metal by the rubber material. SUMMARY OF THE INVENTION An object of the present invention is to eliminate the above-mentioned drawbacks and to provide an adhesion method that firmly adheres both materials by chemical bonding and does not cause deterioration or corrosion of both materials.

The present invention is a method for bonding a DEN-based rubber and a metal material by bringing the DEN-based rubber and a metal material into contact in the presence of at least one specific dithiol-s-triazine derivative detailed below.

In the present invention, the gen-based rubber is a rubber made of a polymer or copolymer containing a monomer having a gen structure, and representative examples include polybutadiene, SBR, NBR, chloroprene, polyisoprene, isoprene, and isoptylene copolymers. This can be cited as an example.

As the metal material, various shapes such as a plate, a wire, a net, a tube, a granule, or a powder made of a single metal or an alloy thereof are used, and the types thereof are not limited to, for example, copper,
Typical examples include zinc, lead, nickel, aluminum, iron, and alloys thereof.

The thiol-s-triazine derivative used in the present invention has the following formula (where R is -OR' or -SR';R' is day, alkyl group, alkenyl group, phenyl group, phenylalkyl group, alkylphenyl group). group or cycloalkyl group:
M is day, Na, K, Li, NH4, 1/2Mg, 1'2
2-R with Ca, 1/Emo or 1/Shio n
-4,6-dithio-s triazine, and the following formula (where R. and R2 represent day, an alkyl group, an alkenyl group, a phenyl group, a phenylalkyl group, an alkylphenyl group, or a cycloalkyl group; M is the above-mentioned )
At least one dithiol-s-triazine derivative of 2-amino-substituted-4,6-dithiol-s-triazine having the following formula is selected.

Compounds having the above formula (1) include 2,4,6-trithiol-s-triazine, 2-phenyl-4,6-dithiol-s-triazine, 2-methoxy-4,6-
Dithiol-s-triazine, 2-ethoxy-4,6-dithiol-s-triazine, 2-phenoxy 416
Typical examples include -dithiol-s-triazine. Examples of compounds having the formula (0) include 2-dibutylamino-4,6-dithiol-s triazine, 2-dilaurylamino-4,6-dithiol calcium, and 2-ethylphenylamino-4,6-dithiol- s-triazine dilithium, 2-(6-carboxylpropylamino)-4,6-dithiol-s-triazine calcium, 2-octylamino-4-butylamino-6-thiol-s-triazine steel, 2-anili/-4,6-dithiol-s-triazine, 2,4-dianilino 6
Typical examples include -thiol-s-triazine, 2,4-bisdimethylamino-6-thiol-s-triazine, and 2-(p-dimethylamino)-4-methoxy6-thiol-s-triazine.

There are various ways to bring the diene-based rubber into contact with the metal material in the presence of the dithiol-striazine derivatives of formulas (1) and/or (b) above, but typical cases include [1] - Mixing and molding the Gen-based rubber, metal material and TTA, ■ Laminating or coating the Gen-based rubber containing TTA on the metal material, {3'
Examples include treating a metal material with an aqueous solution or an organic solvent solution of TTA, and then laminating or coating it with a Gen-based rubber containing or not containing TTA.

Although the metal material can be used as it is in the above cases, it is preferable to use one that has been oxidized in advance, since this further improves the adhesion to the Jenn rubber.

The oxidation treatment may be carried out, for example, by adding 202 days of water-soluble hydroperoxide, water-soluble peroxide, NaCIO or NaCI02.
．． 1 to 1% by weight and Hbu 04, C horse COO day or HC
An aqueous solution containing 0.1 to 1% by weight of I at room temperature to 100 oo
This is done by soaking for 1 second to 2 hours. For example, in the case of {l- or [3} above, to pre-treat the metal material using TTA, add 0.0001 to 10% by weight of TTA.
0 to 100oo in the aqueous solution or organic agent solution containing,
It may be immersed for 0.01 seconds to 9 minutes.

In the method of [1) or (2} above, TT is added to the gene-based rubber.
When A is contained, TTA is 0.0% based on the rubber weight.
A good adhesion effect with metal materials can be obtained with an addition amount of 1 to 2% by weight, preferably 0.5 to 5% by weight. In addition, if the metal material is pre-treated with TTA, T
In many cases, an amount of TA added of 0.5% or less is sufficiently effective. Gen-based rubber compositions usually contain vulcanization compounding agents and other various compounding agents, but these compounding agents can be used in the present invention without impairing the effects of TTA.

Examples of compounding agents include sulfur, 2-mercaptobenzothiazole, 2-penzothiazole disulfide, 2-mercaptobenzothiazole zinc salt, N-cyclohexy-2-benzothiazole sulfenamide, N-oxyethylene-2-benzo Thiazole sulfenamide, 2-(4-morpholinodithio)penzothiazole, diphenylguanidine, tetrabutylthiuram disulfide, diventamethylene lentiyulam tetrasulfide, ethylenethiourea, dimethylthiocarbamate zinc salt, Vulcanizing agent or accelerator such as penzoquinone dioxime, polydinitrosobenzene; ANTAGE D, ANTAGE 3C, ANTAGE BHT, ANTAGE RD, ANTAGE AW, ANTAGE RC, ANTAGE W-300, ANTAGE MB
, Antiaging agents such as Antige N8C: ZnO, P et al.
4, stearic acid, stearic acid a, stearic acid M
g, zinc stearate, Mza0, CaO, Ba0, etc.

The amount of these compounding agents added is appropriately determined within the range commonly used for the vulcanization of gene-based rubbers, and is not particularly limited.
In the present invention, by bringing the gene-based rubber and the metal material into contact in the presence of TTA according to the various embodiments described above, both materials can be strongly bonded, and the resulting composite material has a bond between the materials. stabilized without deterioration or corrosive effects.

In particular, by coexisting 2-R-4,6-dithiol-s-triazine of formula (1) and 2-amino/substituted-4,6-dithiol-s-triazine of formula (n) as TTA, the adhesive strength is further increased significantly. Effects can be obtained.
The conditions for contacting the gen-based rubber with the metal material in the presence of TTA vary depending on the mode of contact and cannot be unambiguously determined, but if the vulcanization of the gen-based rubber is also performed at the time of contact, the conditions should be 80 to 200 q○. 1-120 minutes, 1-200 [9/
An excellent adhesive effect can be obtained by heating under pressure.

Although the mechanism of action of TTA in the present invention to improve the adhesion between the DEN-based rubber and the metal material has not yet been fully elucidated, it is clear that the unsaturated groups in the DEN-based rubber and the
Cross-linking by reaction with mercapto group of A and metal and TT
It is presumed that strong adhesion by primary bonding is obtained by the simultaneous formation of mercaptide through the reaction with the mercapto group of A.

In particular, as TTA, 2-R, which has a relatively low cross-linking reaction rate and mainly contributes to mercaptide formation, as shown in formula (1).
The substituent and the large cross-linking reaction rate as shown in formula (n).
It is thought that when used in combination with the -amino substituent, cross-linking with the unsaturated group and mercaptide formation with the metal proceed in a well-balanced manner, resulting in a significant improvement in adhesive strength. The present invention will be further explained below with reference to Examples.

Note that "parts" or "%" means "parts by weight" or "% by weight" unless otherwise specified. Example 1
Copper-plated tire cord with steel wire 2-anilino 4.
A 0.1% aqueous solution of 6-dithiol-s triazine monosodium (hereinafter abbreviated as "AF") was heated at 80 to 90°C.
After soaking with sand in step 1, it was dried with 150 oo of hot air to obtain a surface-treated tire cord.

On the other hand, 100 parts of SBR (Nitsupol 1500), 5 parts of carbon (HAF), 2 parts of sulfur, 1.5 parts of Kason accelerator (manufactured by Kawaguchi Kagaku Kogyo Co., Ltd., OM), anti-aging agent (manufactured by JI Kagaku Kogyo Co., Ltd., Antige W-300) 1.5 parts of blended rubber was prepared, the above surface-treated tire cord was embedded, and the AS
Addition was made to 150 qo for 30 minutes according to TM-D2229.

The steel cord embedded in the vulcanized rubber was pulled out using a tensile tester and the pull-out strength was measured. The pull-out strength of the triazine-treated cord was 80 to 90 k9' inch, but the one that was not triazine-treated Items are 10~
40 kg/inch, and the effect of triazine treatment was clearly recognized.

Another important feature is that the triazine treatment makes the strength uniform and shows no decrease in strength over time. Example 2 - The surface of a 925 x 60 x 1 copper plate was
Polished with 240 abrasive paper, day 2024%, mother S0410
% aqueous solution at 5,000 for 2 minutes, then washed with water and dried.

On the other hand, SBRIO foundation, carbon 5 anchor and anti-aging agent (
Antige W-300) TTA listed in Table 1 on Part 2
Add the ingredients and roll blend for 5 minutes at 60 pm.

The blended rubber and the oxidized steel plate were laminated and press-carouselized under pressure of 100K9 for 40 minutes at 160K to obtain a copper-SBR rubber adhesive sample.

A 1-arc cut was made in this adhesive sample, and the peel strength was measured. Table 1 shows the results.

It is clear that the adhesion is improved by incorporating TTA. Table 1 (Note) ■ (□) TTA of formula: R, = R2 = 04th 9, M
= day, Na■ TTA of formula (1): R=SH, M=
100 parts of Na Example 10-17BR (manufactured by Nippon Zeon Co., Ltd.: butadiene rubber), 5 parts of carbon, 2 parts of anti-aging agent (Antage W-300), and TTA of the second notation.
Adhesion samples with oxidized copper plates were prepared in the same manner as in Examples 2 to 10 above, except that the adhesion and compounding agents were blended.

Table 2 shows the results of measuring the adhesive strength of these samples. Table 2 ■ BAMA: 1-(0 nitrophenylazo) 1 p-cresol Example 1825 x 60 x 1 skin yellow steel (Cu
6.5%, Zn34.1%) plate was coated with 2-dibutylamino-4,6-dithiol-s triazine monosodium (
DB) in a 1% aqueous solution with 8,000 ml of inkstone sand, 1
A TTA-treated yellow steel plate is obtained by drying with hot air at 00o0 in a sand bath.

On the other hand, BRIOO club, TT of third notation match in carbon 50 club
A and the ingredients are roll blended, and the blend and TT
Layer A-treated brass plates, 16000, 40 minutes, 100
A bonded sample is obtained by pressing and heating under conditions of 1 kg'.

Table 3 shows the results of measuring the peel strength of these samples.

Table 3 Examples 19 to 22 The surface of a 25×60×1 steel plate was polished with E240 abrasive paper, diluted with acetone, degreased, and then dried.

On the other hand, a rubber compound having the composition shown in Table 4 was heated at 60°C for 5
Roll blend for a minute. The above blended rubber and steel plate were stacked and press-vulcanized at 170oC for 30 minutes under a pressure of 100 kg' to obtain a copper-rubber bonded sample (rubber thickness: 1.5 skin).

The peel strength of these adhesive samples was measured in the same manner as in Examples 2 to 9, and the results are shown in Table 4. Table J4 *OR: W type Example 23 The surfaces of the various metal plates (25 x 60 x 1 side) listed in Table 5 were polished with E240 abrasive paper, and the ratio of
After soaking in a mixed aqueous solution of 0.042% at 75° C. for 4 minutes, washing with water and drying, an oxidized metal plate is obtained.

After polishing the metal plate, it is diluted in acetone and dried to obtain a degreased metal plate. On the other hand, SBRIO Takube, Carbon 5
$ parts, stearic acid 1 part, DM 3.32 parts, DBI part,
3 parts of F and 05 parts of Zn are blended and roll blended at 60°C for 5 minutes.

The blended rubber obtained as described above and a metal plate were placed one on top of the other, and heated at 180°C for 30 minutes if the oxidized metal plate was used, or at 180°C for 6 minutes if the degreased metal plate was used.
Rubber-metal plate bonded samples are obtained by press vulcanization for 0 minutes under a pressure of 100 k9/kg, respectively. The peel strength of these adhesive samples was measured in the same manner as in Examples 2 to 9, and the results are shown in Table 6. Table 5 Table 6 * Adhesive sample using degreased metal plate** Adhesive sample using oxidized metal plate

Claims (1)

[Claims] Primary formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R is -OR' or -SR';R' is H, alkyl group, alkenyl group, phenyl group, phenyl alkyl group , alkylphenyl group or cycloalkyl group; M is H
, Na, K, Li, NH_4, 1/2Mg, 1/2Ca
, 1/2Ba or 1/2Zn)
-4,6-dithiol-s-triazine and the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R_1 and R_2 are H, alkyl group, alkenyl group, phenyl group, phenylalkyl group, alkylphenyl group or cycloalkyl group; M is H, Na, K, L
i, NH_4, 1/2Mg, 1/2Ca, 1/2Ba or 1/2Zn).
1. A method for adhering a diene rubber and a metal material, which comprises bringing the diene rubber and the metal material into contact in the presence of at least one dithiol-s-triazine derivative selected from 6-dithiol-s-triazine.