DE2251318A1 - BINDERS FOR ANCHORING RUBBER TO OR. ON METALS - Google Patents

Description

Patent attorney patent attorneys

Dr. phil. Gerhard Henkel Dr. rer. nat. Wolf-Dieter Henkel

D-757 Baden-Baden Balg. Dipl.-I ng. Ralf M. Kern

JUÜSSTS Dr. rer. nat. Lothar Feller

D-8 Munich 90

Eduard-Schmld-Str. 2 Γ -ή Τ · ».: (0811) 643197

T «l * gr. ^ Dr.t ΕΙΙΙρ · οΜ MOndiwi

Anchor Chemical τ * _":

Company Limited
Clayton, Manchester
M11 4SR, England

L j 19. 0Κ1.Ί97Ζ

: Dr.F _e / jO

Binder for anchoring rubbers to metals

The invention relates to binders for anchoring rubbers to metals. With the rubbers to be anchored it can be natural rubber, synthetic polyisoprene, polybutadiene, styrene / butadiene copolymers, acrylonitrile / butadiene copolymers, Butyl rubber, polychloroprene, chlorobutyl rubber and ethylene / propylene terpolymers Act. These rubbers can be used on metals such as iron, carbon steel, stainless steel, Lead, aluminum, magnesium, copper, bronze, brass, zinc, titanium, nickel and / or Monel metal, can be anchored.

Binders according to the invention usually contain a halogenated one dissolved in an organic solvent Elastomer together with a crosslinking agent. If appropriate, such binders can also contain fillers, resins and stabilizers contain, the bonding or anchoring of the rubber to the metal takes place in the course of vulcanization.

-2-

309817 / 088.0

The invention thus provides a binder for anchoring rubbers to or on metals, which characterized in that there is at least one halogenated compound dissolved in an organic solvent Elastomer and at least one crosslinking agent, consisting of

a.) a dithiocarbamate of the general formula

s \ Il

where mean:

1 2
R and R individually each represent an alkyl, cycloalkyl,

Aryl or aralkyl radical and together with the N atom a heterocyclic ring,

M a metal and

χ and y are each an integer from 1 to 5

em
b.) a / thiuram sulfide of the general formula

r \ ssr ³

Il

'N - C - S_ - C - N

where mean:

R ¹ , R ² , R ³ and R ^ individually each represent an alkyl,

Cycloalkyl, aryl or aralkyl

-3-309817 / 0860

rest and together with the respective N atom a heterocyclic ring and

χ an integer from 1 to 4

contains.

Examples of dithiocarbamates which can be used in binders according to the invention are zinc dimethyldithiocarbamate, zinc dibutyldithiocarbamate, Zinc morpholinodithiocarbamate, zinc dibenzyldithiocarbamate, bismuth dimethyldithiocarbamate tellurium dimethyldithiocarbamate, zinc ethylphenyldithiocarbamate, cobalt dibutyldithiocarbamate, nickel dibutyldithiocarbamate, Zinc di (dodecyl) dithiocarbamate, nickel di (octadecyl) dithiocarbamate, Zinc di (octadecyl) dithiocarbamate and / or cobalt di-Cdocosanyiy dithiocarbamate.

Instead of the metals mentioned, the dithiocarbamates which can be used according to the invention can also be selenium, lead, copper, Contains mercury and / or iron.

The dithiocarbamates can optionally be used in binders according to the invention also in the form of complexes with amines be included.

Typical examples of thiuram sulfides which can be used in binders according to the invention are tetramethylthiuram monosulfide, Tetrabutylthiuram disulfide, tetrabenzylthiuram tetrasulfide, Bis (pentamethylene thiuram) tetrasulphide, tetra (dodecyl) thiuram monosulphide, Tetra (octadecyl) thiuram disulfide and / or tetra (undecyl) thiuram tetrasulfide.

In the case of the binders according to the invention, it can also be are those in which the constituents mentioned form in situ under vulcanization conditions.

309817/0860

As halogenated elastomers, binders can be used according to Invention of one or more of the following substances:

1) Halogenated natural rubber;

2) post-halogenated isoprene copolymers or copolymers;

3) post-halogenated butadiene homopolymers or copolymers;

4) optionally post-halogenated 2-chlorobutadiene polymers including copolymers of 2-chlorobutadiene with one or more others Monomers;

5) optionally post-halogenated 1,4- or 2,3-Di ^ - chlorobutadiene polymers including copolymers of 1,4- or 2,3-chlorobutadiehs with one or more other monomers j

6) halogenated butyl elastomers;

7) gem-dihalogenated polymers obtained by adding a dihalogenated carbene on an unsaturated elastomer are obtained; or

8) chlorosulfonated polyethylene!

contain.

Binders according to the invention can optionally contain fillers such as carbon black and / or silicon dioxide. Further suitable additives which improve the adhesion to the respective metal are, for example, phenolic and epoxy resins.

Furthermore, binders according to the invention can also be metal salts included as stabilizers. Finally, in

-5- 309817/0860

Binders according to the invention, the crosslinking agents mentioned in a mixture with each other or with other crosslinking agents, e.g. nitroso compounds.

In binders according to the invention can be used as solvents those solvents are used which are compatible with the elastomer base. Usually be aromatic and / or more polar solvents are preferred. Typical examples of such solvents are Toluene, xylene, mesitylene, n-butyl acetate, isobutyl acetate, 4-methylpentan-2-one, perchlorethylene, carbon tetrachloride and / or chlorobenzene.

The total solids content of binders according to the invention can be between 5 ^and 60% by weight. The ratio of crosslinking agent to elastomer base can be 0.5 to 50 parts by weight of crosslinking agent per 100 parts by weight of halogenated elastomer *

The on the mentioned halogenated elastomers and crosslinking agents based binders according to the invention are general-purpose adhesives, which in a single Layer can be applied. You can (but also are used in areas where a Prime.r or top layer is used.

The actual anchoring process takes place in the way that first the binder in the form of a film on a suitably prepared metal surface is applied and then the solvent is allowed to evaporate. The rubber material to be anchored on the metal surface is then combined with the metal surface, whereupon the whole is heated to vulcanize the rubber material and the binder layer with the formation of the bond or anchoring.

-6-

309817/0860

The following examples are intended to illustrate the invention in more detail. The following rubber materials were used in these examples:

1. Smoked natural rubber heads 100

Zinc oxide 5

Stearic acid 2

Phenyl-ö-naphthylamine 1

Soot 50

Extending Oil 5

N-Cyclohexylbenzthiazolesulfenamide 0.65

Sulfur 2.5 vulcanization time; 20 min at one temperature of 153 ° C (15 min at a temperature of 153 ° C in example 1)

2. ⁺ soft natural rubber heads 100

Zinc oxide 5

Stearic acid ■ - 1

Fhenyl-ß-naphthylamine 1

Soot 15

Extending Oil 15

Dibenzothiazyl disulfide 1

Sulfur 2.5 vulcanization time 15 minutes at one temperature from 153 ° C,

3. Commercially available styrene-butadlene catitechuk 100

Zinc oxide 5

Stearic acid 1

Fhenyl-ß-naphthylamine 1

Soot 50

Extending Oil 2.5

N-Cyclohexylbenzthiazole sulfenamide 0.75

+ Smoked -7-

309817/0860

Sulfur 2

Vulcanization time: 35 min at a temperature of 153 ° C.

4 “Commercially available polychloroprene · 100

Zinc oxide 5

Stearic acid 0,

lightly calcined magnesia 4

Soot 50

StreckÖl 5

Fhenyl-beta-naphthylamine, 2 Vulkanisierdauer: 20 min at a temperature of 153 ⁰ C.

example 1

First of all, three binders were used according to the following recipes manufactured:

ABC

Dichlorobutadiene / 06 -Bromoacrylonitrile-Mis chpoly-

merisat

Chlorinated natural rubber

stabilizer

Zinc dimethyldithiocarbamate

Solvent (xylene + n-butyl acetate)

Then was applied to existing carbon steel cone, which had been pretreated with a sand blasting and then degreased, a film of the nen Various binders was evaporated ver and the solvent. A dry, non-tacky film was obtained. Eventually got in touch with the in

309817/0860

30th 30th 30th 70 70 70 10 10 10 9 9 9 4th 8th 16 4oo 400 400

steel cones prepared in the manner described, the natural rubber material No. 1 for 15 minutes at a temperature Hardened at 153 ° C. The bond strengths obtained with the various binders were, for binders A 130.2 kg, for binder B 167.8 kg and for binder C 182.8 kg.

Further details regarding this cone test procedure were provided by G.W. Painter in "Rubber Age" magazine, November 1959, page 86.

Furthermore, the bond strength of steel strips was determined according to the method described in BS 903, Part A21 (1961) -Procedure B-. It was found that the En
rips.

Example 2

the determination of the 90 ° peel strength the elastomer

Using binders B and C from Example 1 In addition, the No. 2 soft rubber material was anchored on steel cones of the type described. Here could the bond strengths measured for binder B are 24.0 kg and for binder C 51.7 kg.

In the 90 ° peel test, the elastomer, Example 3, tore

First, there were two binders of the following composition manufactured:

-9-

309817/0860

30th 30th 70 70 10 10 9 9 12th 16 400 400

AWAY

Dichlorobutadiene / οό -bromoacrylonitrile mixed poly-

merisat

Chlorinated natural rubber soot

stabilizer

Zinc dibutyl dithiocarbamate

Solvent (xylene)

As part of the steel cone test described, when using binder A and the natural rubber material No. 1 has a binding strength of 149.1 kg and when using the binder A and the soft rubber material No. * 2 measured a bond strength of 34.5 kg. When using binder B and natural rubber material No. 1 became a bond strength of 184.1 kg using Binder B and No. 2 soft rubber material measured a bond strength of 71.2 kg.

When using binder B and the polychloroprene material No. 4 was measured to have a bond strength of 360.6 kg.

In all cases the elastomer tore in the 90 ° peel test.

Example 4

As part of the steel cone test described, at Use of a binder of the following composition:

Dichlorobutadiene / o ^ -bromoacrylonitrile copolymer 30

Chlorinated natural rubber 70

Soot 10

Stabilizer 9

-10- 309817/0860

- ίο -

Zinc dibutyl dithiocarbamate / dibutylamine complex 16 Solvent (xylene) 400

and the No. 1 natural rubber material, a bonding strength of 115.2 kg, when using the same binder and soft natural rubber material No. 2, a bond strength measured at 43.1 kg.

The elastomer tore in the 90 ° peel test. Example 5

As part of the steel cone test described, at Use of a binder of the following composition ϊ

Post-chlorinated polychloroprene 15

Chlorinated natural rubber 85

Zinc dibutyl dithiocarbamate 10 Hydrocarbon wax 2

Pigment 0.5

Solvent (xylene) 450

and No. 4 polychloroprene material, a bonding strength measured from 411 kg. The elastomer tore in the 90 ° peel test.

Example 6

As part of the steel cone test described above, when using binders of the following composition!

AWAY

Diclilorbutadiene / ÖC -bromoacrylonitrile copolymer 55

Chlorinated natural rubber 75

Stabilizer 9

Soot 10

-11- 309817/0860

12th _ - - 12th 450 450

- 11 -

A. B.

Zinc ethylphenyldithio carbamate Zinc morpholinodithiocarbamate Solvent (n-butyl acetate)

when using the binder A and the polyurethane rubber material No. 1 has a binding strength of 183.2 kg and when using binder B and natural rubber ■ materials Mr. 1 measured a bond strength of 89.4 kg. When using the binder A, the elastomer tore at 90 ° peel test. When using the binder B, it was mainly the elastomer that tore in the 90 ° peel test.

Example 7

First, two binders with the following composition were produced:

Dichlorobutadiene / oC -bromoacrylonitrile copolymer 25 25

Chlorinated natural rubber 75 75

Stabilizer 9 9

Soot. 10 10 '

Cobalt dibutyl dithiocarbamate 16 -

Nickel dibutyl dithiocarbamate - 16

Solvent 450 450

κ.

As part of the steel cone test described above, when using of the binder A and the natural rubber material No. 1 measured a binding strength of 128.4 kg. At 90 ° Peel test mainly tore the rubber.

When using binder B and styrene / butadiene rubber In the context of the steel cone test described, a bond strength of 228.3 kg was measured. At 90 ° Peel test the rubber tore.

309817/0860 ~ ^1? "~ _{1 /% lkl} ..

BATH ORIGINAL

Example 8

As part of the steel cone test described above, when a binder with the following composition was used:

Partially chlorinated natural rubber 10

Chlorinated natural rubber 90

Tetramethylthiuram disulfide 10

Soot 9

Antioxidant 2

Solvent (xylene) 450

and the natural rubber material No. 1 measured a bond strength of 142.9 kg. The elastomer tore in the 90 ° peel test.

Example 9

As part of the steel cone test described above, when a binder with the following composition was used:

Chlorinated styrene / butadiene rubber 40

Chlorinated natural rubber 60

Soot 11

Stabilizer 9

Tetramethylthiuram disulfide 10

Solvent (xylene) 500

and No. 4 polychloroprene material measured a bond strength of 412.8 kg. The rubber tore in the 90 ° peel test.

Example 10

In the context of the described Stalilkegestest was at Verv / endung a binder of the following composition:

309817/0860 -13-

Chlorinated natural chewing school 100

Soot 9

Bis (pentamethylene thiuram) tetrasulfide 10

Antioxidants ■ 2

Solvent (xylene) 450

and No. 4 polychloroprene material measured a bond strength of 401.9 kg. The rubber tore in the 90 ° peel test.

Example 11

Initially, three binders with the following composition were produced:

ABC

Dichlorobutadiene / o ^ -Bromoacrylonitrile mixed

polymer. 25 25 25

Chlorinated natural rubber 75 75 75

Stabilizer 9.9 9

Soot 10 10 10

Tetramethylthiuram monosulfide 12 -

Tetramethylthiuram disulfide - 12 -

Bis (pentamethylene thiuram) tetrasulfide - - 12

Solvent (n-butyl acetate + xylene) 450 450 450

In the steel cone test described above, when using binder A and Naiir rubber material No. 1, a binding strength of 141 kg, when using binder B and natural rubber material No. 1, a binding strength of 165.5 kg and when using Binder C and Nainir rubber material No. ₀ 1 measured a bond strength of 181 kg.

In all cases, the rubbers tore in the 90 ° peel test

"14-3 09817/0880

Example 12

As part of the steel cone test described above, when a binder with the following composition was used:

Post-brominated polychloroprene 25

Chlorinated natural rubber 12

Stabilizer 1.5

Carbon black 1.7

Bis (pentamethylene thiuram) tetrasulfide 2.8

Solvent (xylene) 145

and No. 4 commercially available polychloroprene material Bond strength of 313 kg measured. In the 90 ° peel test tore the elastomer.

Example 13

As part of the steel cone test described, the following was carried out at Ver: Application of a binder of the following composition:

Post-chlorinated polychloroprene 15

Chlorinated natural rubber 85 Tetramethylthiuram disulfide 10

Hydrocarbon wax 2

Pigment 0.5

Solvent (xylene) 450

and the commercial polychloroprene material No. 4 measured a binding strength of 338.8 kg. In the 90 ° peel test tore the elastomer.

Example 14

As part of the steel cone test described above,

-15-309817 / 0860

Application of a binder of the following composition:

Near-brominated polychloroprene. - 16.5

Chlorinated natural rubber. 16.5

Tetramethylthiuram disulfide 2

Hydrocarbon wax 0.3

Pigment 0.1

Solvent (xylene) 65

and No. 4 commercially available polychloroprene material Bond strength of 363.3 kg measured. The elastomer tore in the 90 ° peel test.

Example 15

As part of the steel cone test described above, when using a binder of the following composition

Dichlorobutadiene / 4 ^ -bromoacrylonitrile copolymer 35

Chlorinated natural rubber 65 stabilizer 9

Carbon black 10 zinc dimethyldithiocarbamate 2

Pigment 0.5

Dinitrosobenzene 5

Solvent (xylene + n-butyl acetate) 550

and the natural rubber material No. 1 measured a bond strength of 144.7 kg. In the 90 ° pull test, the elastomer tore.

-16-

309817/0860

Claims (14)

P ate η ta η s ρ r ti ch e Binder for anchoring rubbers to or on metals, characterized in that it is at least
a halogenated elastomer dissolved in an organic solvent and at least one crosslinking agent consisting of a.) a dithiocarbamate of the general formula rN - C - S - where mean: 1 2
R and R individually each represent an alkyl, cycloalkyl, Aryl or aralkyl radical and together with the N atom has a heterocyclic ring, M a metal and χ and y are each an integer from 1 to 5 or em b.) a / thiuram sulfide of the general formula R ' Il -N-C - S "- c - n; , R- ¹ row where mean: - 17- 3098 17/0860 R, R-, R ^ and R individually each represent an alkyl, cycloalkyl, Aryl or aralkyl radical and together with the respective N atom a heterocyclic ring and χ an integer from 1 to 4 contains. 2. Binder according to claim 1, characterized in that the crosslinking agent is at least one dithiocarbamate, consisting of zinc dimethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc morpholinodithiocarbamate, zinc dibenzyldithiocarbamate, Bismuth dimethyldithiocarbamate, TeI-lurdimethyldithiocarbamate, Zinc ethylphenyldithiocarbamate, Cobalt dibutyl dithiocarbamate, nickel dibutyl dithiocarbamate, zinc di - '(dodecyl) dithiocarbamate, nickel di (octadecyl) dithiocarbamate, Zinc di (octadecyl) dithiocarbamate or cobalt di (docosanyl) dithiocarbamate. 3. Binder according to one of claims 1 and / or 2, characterized in that the crosslinking agent consists of one Dithiocarbamate exists in the form of a complex with an amine. 4. Binder according to claim 1, characterized in that the crosslinking agent is at least one thiuram sulfide, consisting of Tetramethylthiuramonosulfide Tetrab.utylthiuramdisulfid and tetrabenzylthiuram tetrasulfide bis (pentamethylene thiuram) tetrasulfide, Tetra- (dodecyl) thiuramraonosulfide, Tetra (octadecyl) thiuram disulfide or tetra (undecyl) thiuram tetrasulfide, contains « 5. Binder according to one or more of the preceding claims, characterized in that it is used as a halogen -18-S09817 / 086Ö nated elastomer at least one of the following substances: 1) Halogenated natural rubber; 2) post-halogenated isoprene homopolymers or copolymers; 3) post-halogenated butadiene homopolymers or copolymers; 4) optionally post-halogenated 2-chlorobutadiene polymers including copolymers of 2-chlorobutadiene with one or more other monomers; 5) optionally post-halogenated 1,4- or 2,3-dichlorobutadiene polymers including copolymers of 1,4- or 2,3-dichlorobutadiene with one or more other monomers; 6) halogenated butyl elastomers; 7) gem-dihalogenated polymers obtained by adding a dihalogenated carbene on an unsaturated elastomer are obtained; or 8) Contains chlorosulfonated polyethylene}. 6 “Binder according to one or more of the preceding Claims, characterized in that it contains the halogenated elastomer in one of toluene, xylene, mesity ■ len, n-butyl acetate, isobutyl acetate, 4-methylpentan-2-one, perchlorethylene, carbon tetrachloride and / or chlorobenzene contains dissolved solvents. 7. Binder according to one or more of the preceding Claims, characterized in that it is additionally contains a filler. -19-309817 / 0860 8. binder according to claim 7, characterized in that that it contains carbon black as a filler. 9. Binder according to claim 1, characterized in that it is per 100 parts by weight of the halogenated elastomer Contains 0.5 to 50 parts by weight of crosslinking agent. 10. Binder according to claim 1, characterized in that it has a total solids content of 5 to 60 wt .-% having. 11. Binder according to claim 1, characterized in that there is at least one dithiocarbamate as a crosslinking agent together with at least one thiuram compound. 12. Binder according to one or more of claims 1 to 10, characterized in that it additionally contains an aromatic nitroso compound. 13. method for anchoring rubbers on metals, characterized in that there is a layer of a binder between the rubber and the metal according to brings in one or more of the preceding claims and that. to vulcanize the whole thing Rubber and heated for anchoring the same on the metal. 14. Structure consisting of one on or on a metal anchored rubber, the anchoring of the rubber to or on the metal with the help of a binder according to one or more of claims 1 to 13. BATH ORIGINAL 309817/0860