JPS5827102B2 - Ketsugohou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to bonding rubber to copper and its alloys and more particularly to the use of certain phenolic triazine compounds to provide improved adhesion.

Composites such as rubber combined with copper and its alloys are useful for many purposes.

For example, rubber tires, hoses, and belts are often reinforced with brass-coated steel core wire.

Additives are commonly used in rubbers to improve bond strength; however, such additives, such as formaldehyde formers in the presence of resorcinol, may have adverse effects, such as on the scorching safety of the mixture. In addition to causing reduction, changes in vulcanization rate, and fuming at high temperatures, these additives can irritate the skin.

The present invention relates to additives that can be used alone in rubber and are not disadvantageous components.

According to the present invention, a method is obtained, in which the bonding of rubber to copper or its alloy significantly increases the bonding strength of the vulcanizable rubber composition, where X is not substituted and has 1 to 4 carbon atoms. A group derived by losing one hydrogen atom from the hydroxyl group of dihydroxybenzene, the amino group of aminophenol, or the mercapto group of mercaptophenol, which may contain an alkyl group or other hydroxyl group, and Z is the same or different, and is a group of the type represented by
adding a triazine compound which is an alkyl group (optionally substituted with 12 alkyl groups, an alkenyl group having 3 to 12 carbon atoms) or a mercapto group, and contacting the vulcanizable rubber composition with copper or an alloy thereof; The method is characterized in that the composite is heated to vulcanize the rubber.

Rubbers include natural rubber or vulcanizable synthetic rubbers, such as cispolymers of butadiene and isoprene, polymers including polychlorobutadiene, and compounds polymerizable with dienes, such as butadiene and isoprene, such as styrene, isobutyne, acrylonitrile and Copolymers with methyl methacrylate and terpolymers of, for example, ethylene, propylene and diolefins and mixtures of the rubbers may also be used.

The present invention is particularly important in that it enhances the bond strength of rubber to brass coated steel core wire.

This is because the steel core wires are used to reinforce tires and do not adhere strongly to rubber without a binder.

However, the invention also relates to other copper products and products of copper alloys,
It is also used, for example, to enhance the bond to engine equipment, shock absorbers, plant linings and hoses of metal reinforcement.

The group represented by 2-3- and 4-hydroxyanilino,
Mention may be made of 2- and 4-hydroxyphenoxy, and 2-13- and 4-hydroxyphenylthio groups.

Groups that can substitute one or more hydrogen atoms in the hydroxy group and amino group represented by Y and Z include alkyl groups such as methyl, ethyl, inglovir, secondary butyl, n-hexyl, dodecyl and Mention may be made of tertiary octyl, alkenyl groups such as allyl and but-2-enyl groups.

Examples of suitable triazine compounds are 2-amino-4-chloro-6-(3'-hydroxyphenoxy)triazine,
2-Methylamino-4-chloro-6(3/-hydroxyphenoxy)triazine and 2-amino-4-chloro-
6(3',5'-dihydroxydifenoquine)triazine.

Preferred triazine compounds which generally confer particularly strong binding forces are those in which X is an optionally substituted m-hydroxyphenoxy or m-hydroxyanilino group,
and Y and Z are the same or different and each is a group X or an amino group, a methylamino group or a chloro group, and in particular m-hydroxyphenoxy in which X optionally further contains a hydroxyl group Y is a chlorine atom and Z is an amino group.

These advantageous triazine compounds are novel compounds and represent another feature of the invention.

the triazine compound is at least 0.1% by weight of the rubber;
It should advantageously be used in amounts of 1 to 5%.

The triazine compound does not need to be dispersed throughout the rubber;
It just needs to be present in a suitable amount in the region of the rubber-metal interface.

Therefore, a relatively small amount of the rubber containing the triazine compound is used as a binder at the point of contact between the metal and the rubber that does not contain the triazine compound.

Vulcanization can be carried out by heating the composite to temperatures commonly used to vulcanize the vulcanizable rubber composite in question.

Vulcanizable rubber compositions generally contain vulcanizing agents such as sulfur or sulfur donors such as N-N'-dithio-bis(hexahydro-2H-azepinone-3), 4,4'-dithiomorpholine or bis-(diethyl -thiophosphoryl)trisulfide and vulcanization accelerators, such as benzothiazylsulfenamides, such as benzothiazyl-2-cyclohexylsulfenamide, 2-(morpholinothio)benzothiazole, benzof7di-2-dicyclohexylsulfenamide, etc. It contains phenamide, N-tertiary butyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole, 2-mercaptobenzothiazirou disulfide, diarylguanidines, thiurams, and dithiocarbamates.

Optionally, the vulcanizable rubber composition contains other optional rubber auxiliaries such as anti-aging agents, anti-ozonants, fillers, reinforcing agents, pigments, processing oils and promoting actives such as zinc oxide and stearin. It may also contain acids and other components used in the bonding system, such as formaldehyde formers.

Preferred triazine compounds are prepared by any known method for replacing the chlorine atom in triazinyl chloride with a group X and one or two groups Y and 2.

For example, triazinyl chloride can be mixed with compound XH and optionally compounds YH and ZH in any order in the required molar ratio;
H is optionally substituted m-hydroxyphenol or m-hydroxyaniline, and YH and Z
When H is a group XH, ammonia or methylamine, the reaction can be carried out by gradually raising the temperature in the presence of an acid binder.

Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.

In the examples, unless otherwise specified, "1 part" and "%" are all "% by weight."

Example 1 A vulcanizable rubber composition was prepared on a two roll mill from the following ingredients.

Natural Comb Smoked Sheet 100% Zinc Oxide IO Stearic Acid
High Abrasion Furna
ceCarbon B 1ack) 5 Processing oil N-dicyclohexyl-2-penzthiazylsulfenamide 0.7 Sulfur anti-aging agent (condensation product of acetone and diphenylamine) Binder according to Table 1 7 〃 Approximately 3.1 cIIlX 1.03 CrrL (1-X −)
Samples of size between X 7.3 16 were taken from the above composition and a long length of brass coated steel core wire was sandwiched between the two samples.

The resulting sandwich-shaped product was placed in a mold and heated at 150°C for 3
Press vulcanization was performed for 0 minutes.

Approximately 3. ICrrLl // 7 //
1 // X1.03CrfLX1.25CrIl(1-x -x
-) 4 16 2 flocs were taken out from the mold, cut into two pieces across the steel core wire, and the force required to separate the core wire from the rubber was measured.

Table I Rubber in the composition 167.7 167.7
2-chloro-4-amino-6-m-hydroxyphenoxy-5-) riazine 3.0 1〃 The force required to peel the core wire from a block of length 3.1CIIl(1-) 46 57 (kg) The 2-amino-4-chloro-6m-hydroxyphenoxy-S-)riazine used above was produced as follows: An aqueous suspension of cyanuric chloride was prepared by adding 369 parts of cyanuric chloride to 1100 parts of acetone. was prepared by dissolving, filtering to remove traces of insoluble matter, and adding the solution to a mixture of 500 parts of ice and 500 parts of water.

The suspension was stirred at 0-5°C, while a solution of 160 parts of sodium hydroxide in 500 parts of water and a mixture of 119 parts of aqueous ammonia (specific gravity 0.88) and 38 parts of water were each added to 30 parts of water.
Add over a period of minutes.

After subsequent stirring for 30 minutes at 0-5 DEG C., the temperature was raised to 25 DEG C. and a solution of 220 parts of resorcinol and 80 parts of sodium hydroxide in 500 parts of water was added with stirring over a period of 20 minutes.

The suspension was then stirred for 30 minutes at 25°C and 1 hour at 35°C, cooled to 15°C, and the insoluble product was collected by filtration, washed with water until free of chlorine and concentrated under reduced pressure. Dry at room temperature.

The product is a white powder with a well-defined specific melting point due to decomposition; analysis shows 22.4% nitrogen and 14% chlorine.
7% (C9H7Ct N402 is nitrogen 23.
5% and 14.9% chlorine).

Example 2 A vulcanizable rubber composition is prepared and bonded to a brass coated steel core wire using the binders listed below in the manner described in Example 1 and the force required to peel the core from the rubber is It was measured.

The results obtained and comparative results without the use of binder were as follows: Required amount of binder to release the core wire No binder used 2-Chlor-4 -Alylamino 6-m-hydroxyphenoxy-8-triazine (3 parts) 4 2-chloro-4-amino-6 (3',5'-dihydroxyphenoxy)-5-triazine (3 parts) 0 4 2-chloro- 4-Methylamino-6-m-hydroxyphenoxy-8-triazine (3 parts) 0 6 2-chloro-4=amino-6 p-hydroxy-phenoxy-s-)riazine (3 parts) 0 4 2-chloro-4 -amino-6 (2'-methyl-3'-hydroxyphenoxy)-s-) riazine (2 parts) 5 7 2-chloro-4-amino-6 (m-hydroxy-phenylmercapto)-8-triazine (2 parts) 5 2 2-chloro-4-amino-6 (2', 3'-dihydroxyphenoxy)-3-triazine (2 parts) 5 6 The binder used above was prepared using chemicals in equimolar ratios. Produced by the general method described in Example 1.

The product was a white powder of unspecified melting point.

The analysis result is 2-chloro-4-allylamino-6-m hydroxyphenoxy-8-triazine; actual value nitrogen 2
0.1%, chlorine 12.7%, Cl2H11CIN402
Calculated values Nitrogen 22.7%, Chlorine 12.8%, 2-
Chlor-4-amino-6-(3',5'-dihydroxy-phenoxy)-8-)riazine; actual value nitrogen 24.0
%, chlorine 14.4%, calculated value by C0H7CIN403 Nitrogen 22.0%, chlorine 13.9%, 2-chloro-4
-methylamino-6-m-hydroxyphenoxy-5-
) Reazine; Actual value Nitrogen 26.2%, Chlorine 16.7%
, calculated value by C1oH9C1N402 Nitrogen 22.2
%, chlorine 14%, 2-chloro-4-amino-6-p-hydroxyphenoxy-3-) 1) Azine; Actual value Nitrogen 26.5%, chlorine 13.2%, calculated value based on C9H7C140□ Nitrogen 23. 5%, chlorine 14.9%, 2-chloro-4-amino-6-(2'-methyl-3'-hydroxyphenoxy)-s-) riazine; actual value nitrogen 21
．． 7%, chlorine 13.7%, calculated by C1oH9CIN402 nitrogen 22.1%, chlorine 14.5%, and 2-chloro-4-amino-6-(2',3'-dihydroxyphenoxy)-s-) ! J azine; actual value nitrogen 22.2
%, chlorine 14.1%, calculated value based on C0H7C1N403 nitrogen 22.2%, chlorine 14.5%.

Example 3 A vulcanizable rubber composition was prepared on a two-roll mill from the following ingredients: Natural Rubber Smoked Sea) 100 Zinc Oxide 10 Stearic Acid
3 High Ablation Furnace 65 Black Processing Oil 4N-
Morpholyl-2 Sulfenamidobenzthiazyl 2.5 Sulfur 1.5 Anti-aging agent (condensation product of acetone and diphenylamine) Binder The composition is bonded to brass-coated steel core wire and vulcanized, and e.g. The force required to peel the core wire from the rubber was measured as described in 1.

The results obtained and the comparative results when no binder was used were as follows.

: Binder No binder used Used 2-chloro-4-amino-6- (3', 5'-dihydroxy-phenoxy-8-) riazine 1 3 2-chloro-4-amino-6- m-hydroxy-phenoxy - 8-triazine 1 9 2-chloro-4-amino-6 0-hydroxy-anilino-S -triazine 4 5 2-chloro-4-amino-6- m-hydroxy-anilino-8 triazine 1 2-chloro-4 p-Hydroxytriazineamino-6-anilino-S 5 8 Binder No binder used Used 2-chloro-4-allylamino-6-m-hydroxyphenoxy S-1 Lyazine 4 0 2-Amino-4,6-bis( m monohydroxy~phenoxy)-2932 s-) riazine 2-hydroxy-4,6-bis(m-hydroxy-phenoxy)2937=S~triazine 2-chloro-4-amino-6-0-hydroxy used above Anilino-S-triazine and the corresponding m- and p-hydroxy compounds were prepared by the general method described in Example 1 using equimolar amounts of chemicals.

The compound is a white powder of unspecified melting point and analysis results show 29.2% nitrogen, 14.8% chlorine, and 2% nitrogen, respectively.
9.6% and chlorine 16.2%, and nitrogen 26.5% and chlorine 13.2%.

(C, H, CIN50 calculated values are 29.5% nitrogen and 14.9% chlorine)

Claims (1)

[Scope of Claims] 1. When bonding rubber to copper or its alloys, a sulfurable rubber composition is formed of the formula: A group derived by losing one hydrogen atom from the hydroxyl group of dihydroxybenzene, the amino group of aminophenol, or the mercapto group of mercaptophenol, which may contain , a group of the type represented by (optionally substituted with 3 to 12 alkenyl groups) or mercapto group] is added, the vulcanizable rubber composition is brought into contact with copper or its alloy, and the composition is heated. A bonding method characterized by vulcanization of rubber.