DE1266959B - Process for firmly binding cords made of polyamides or artificial silk to rubber - Google Patents

Description

GERMAN WwWt PATENT OFFICE

EDITORIAL

German class: 39 \ & £ ftSr

Number: 1266 959

File number: M 54533IV d / 39 b

1266959 filing date: October 17, 1962

Opening day: April 25, 1968

The invention relates to a method for improving the adhesive strength of rubber to rayon and Polyamide cord using customary and known fiber impregnating agents such as resorcinol-formaldehyde resins and vinylpyridine rubber latexes, especially at high temperatures of about 130 ° C, as they occur in vehicle tires.

The problem of adhering rubber mixtures with rayon cord has been largely solved, while difficulties still arise when using polyamide cord. There have already been several Work on the problem of permanently bonding polyamides with rubber has been published. Indeed also the impregnation of polyamide fibers with known adhesives such as resorcinol-formaldehyde resins and vinyl pyridine rubber, did not produce any significant success. Particular difficulties in sticking occur at the cut ends of the fabric webs or thread ends of polyamide cords. Through the so-called Isocyanate method, the adhesion can be improved, but this is not easy from an operational point of view is to be carried out. The standard method currently in use in industry for treating Polyamide cord is therefore still impregnating with resorcinol-formaldehyde resin solutions and vinyl pyridine rubber latex.

The other problem, heat-resistant rubber compounds, especially those made from natural rubber, Developing for treads and carcass has already led to many successes, but in particular together with the good adhesion of these blends to polyamide cord were never completely satisfied. the Aging test of vulcanized rubber for the tread and carcass of tires is normally carried out for 7 days at 70 ° C. This test condition is insufficient for today's requirements placed on truck tires, since the running temperature such tires in the shoulder rises to about 100 to 130 ° C. That is why it is necessary that relevant mixtures to age for 3 days at least at 100 ° C and to test so that the resulting Values compared with the test results found in the practical use of the tires can be. The physical values of vulcanized rubber are considered from this point of view of all conventional compounds pretty bad after aging of all possible tires.

These disadvantages are intended to be eliminated with the aid of the mixtures to be used according to the invention.

The invention relates to a method for firmly tying cords made of polyamides or Rayon on mixtures of natural rubber, Gege process for firmly tying cords Polyamides or rayon on rubber

Applicant:

Metzeler Aktiengesellschaft,

8000 Munich, Westendstr. 131-133

Named as inventor:

Hrishikesh Chandra Roy, 8033 Planegg

if necessary butadiene-styrene rubber, synthetic cis-1,4-polyisoprene, cis-1,4-polybutadiene or their blends, which contain carbon black and customary processing, ao aging and vulcanizing aids, the cords optionally being impregnated with rubber latex and phenolic resins by embedding the treated or untreated cords in the rubber mixtures and heating the resulting layered body to vulcanization temperatures, which is characterized in that rubber mixtures containing p, p'-dibenzoylquinone dioxime are used.
With such mixtures, extremely heat-resistant vulcanizates are obtained whose adhesion to polyamide and rayon cord, both static and dynamic, unaged and aged, is very high.

In the conventional method, the adhesion is between the carcass mixture and the polyamide cord on the bond via the methylol groups of the resorcinol-formaldehyde resin. But the number This active group is after reacting with polyamide cord for a chemical bond with the carcass compound no longer big enough. This deficiency is caused by the addition of p, p'-dibenzoylquinone dioxime according to the invention compensated for the rubber compound.

According to the claimed process, furnace and sewer black can be used without affecting the adhesion shows any differences between the rubber compound and the tire cord.

In the following example 1 are two mixtures I and II of known standard qualities with the associated test results as a basis for comparison with the following to be used according to the invention Mixtures shown. The mi-

809 540/454

schungl on a carcass mixture and mixture II on a mixture for reinforcement belts.

example 1

Mixtures I. Π (Parts by weight) Natural rubber (BorneoII) 100 0 Natural rubber (Para II 14 K) 0 100 Plasticizers (hydrocarbons)
mixture) 5 5.5 Zinc oxide 10 10 Stearic acid 2 3 Phenylbetanaphthylamine 0.75 1 N-phenyl-N'-isopropyl-p-phenylene- 0.75 1 Adhesive resin 1.5 1 0.15 0.14 20th 43 Semi-active soot 20th 0 Oil sulfur 0.2 2.2 1.65 Oil sulfur (20 parts oil) 1.2 1.8 N-Merphohno-2-mercaptobenz- 1.1 1.1

Test results

I I Π heating at 143 ° C (minutes)

35 60 35 60 Modulus at 300% (kg / cm ^s ) 92 80 122 111 Module at 500% (kg / cm ² ) 201 176 Tensile strength (kg / cm ² ) ... 210 191 161 170 Elongation at break (%) 505 520 365 395 Shore hardness ( ⁰ A) 55 55 59 58 Elasticity (%) 49 43 48 43 Notch toughness (kg / cm) ... 10 13th Pull-out strength (kg / cm) 64 73 Aging for 3 days at 100 ° C I. Π Heating at 143 ° C (minutes) 35 60 35 60 Tensile strength (kg / cm ² ) ... 71 87 31 38 Elongation at break (%) 185 235 85 115 Shore hardness ( ⁰ A) 61 58 65 63 Elasticity (%) .......... 45 43 45 45 Notch toughness (kg / cm) ... 6th 8th Pull-out strength (kg / cm) 27 36

ίο

Cord liability (kg / cm thread length) static I.
Carcasses mixture dyna Arts Poly Poly mix silk amide amide impregnated blank .Dei Jxd uintciiipcratur gc- measure, ungeaiicix ^ ge neizi λ öiunoen ίο jyu- 9.37 12.2 2, / 4 1.9-IO ⁴ At room temperature mpQQMi Op ^ ni ^x XTf 0 Stnn
JUlvooCJU, tit / lXt / l / -. L OLliJUL ueu Ij jyimuicn, geal tert (5 hours at 130 ° Q 7.11 10.8 2.89 0.2-10 * Ge at room temperature measure, aged (24 hours at IOO ⁰ Q 9.91 12.0 3.5 Measured at 100 ⁰ C, un- 6.97 9.8 2.03

Measured at room temperature, unaged (heated 2 hours 15 minutes)

Measured at room temperature, aged (5 hours at 130 ° C)

Measured at room temperature, aged (24 hours at 100 ° C)

In IOO ⁰ C measured unaged

Cord adhesion (kg / cm thread length) static Π

Reinforcement belt art

silk

polyamide

impregnated

11.83 10.54 9.54 9.46 11.03 10.69 10.71 8.09

In the following example II, mixtures IH and IV are shown which are constructed according to the invention are.

Example 2

Mixtures m IV (Parts by weight) 25th 25th 25th 25th Butadiene-styrene rubber 50 50 Plasticizer (hydrocarbon 5 5 3 3 2 2 N-phenyl-N'-cyclohexyl-p-phenylene- 1 1 0.6 0.6

Example 2 (continued)

Mixtures III IV (Parts by weight) Ph f »tivt a 1 nil π π a nh f hvl a m i π 0.35 0.35 0.06 0.06 1 1 Adhesive resin 1.5 1 Semi-active soot 20th 0 Furnace soot 20th 42.5 A / fprfiantoben7iTnifla7ol. . * 1 1 ftk-sulfur 0 2 0.55 0.55 Stabilized phenol formaldehyde resin with active methylol 1 1 2 2 0.5 0.5 0.1 0.1 p, pV-dibenzoylcbinonedioxime 1.5 1.5

ίο

Test results

in IV Heating at 143 ° C (minutes) 30th 60 30th 60 Module at 300% (kg / cm ² ) 63 65 83 84 Module at 500% (kg / cm ^a ) 124 127 178 178 Tensile strength (kg / cm ² ) ... 174 160 202 200 625 590 555 555 Shore hardness ( ⁰ A) 53 55 59 60 Elasticity (%) 53 51 45 46 Notch toughness (kg / cm) ... 12th 9 24 15th Pull-out strength (kg / cm) 50 88 65 83

Aging for 3 days at 100 ° C Heating at 143 ° C (minutes)

30th 60 30th 60 Module at 300% (kg / cm ² ) 80 78 115 107 Module at 500% (kg / cm ² ) Tensile strength (kg / cm ² ) ... 145 140 188 189 Elongation at break (%) 480 495 440 460 Shore hardness ( ⁰ A) 55 55 61 60 Elasticity (%) 54 53 48 48 Notch toughness (kg / cm) ... 6th 6th 20th 35 Pull-out strength (kg / cm) 32 35 42 42

in

IV Measured at room temperature, unaged (heated 2 hours 15 minutes)

Measured at room temperature, aged (5 hours at 130 ° C)

Measured at room temperature, aged (24 hours at IOO ⁰ C)

In IOO ⁰ C measured unaged

Cord adhesion (kg / cm thread length) static

III

IV Reinforcement belt impregnated with artificial silk

Carcass polyamide

11.91

11.03

11.77 8.37

11.26

10.11

10.71 9.77

polyamide

blank

3.9

3.2

2.45 3.2

The test results for the mixtures III and IV vulcanized according to the claimed process show a significant improvement over the vulcanizates from mixtures I and II.

This poses the problem of producing bit-resistant carcass compounds that are also good Have polyamide cord adhesion has been solved so that this solution should meet current and future needs. The claimed driving can also be used to develop compounds for aircraft tires.

Example 3 Aging for 3 days at 130 ° C

EGG I ^w Heating at 143 ° C (minutes) 30th 60 30th 60 Module at 300% (kg / cm ² ) 82 86 124 Module at 500% (kg / cm ² ) Tensile strength (kg / cm ² ) ... 98 97 124 128 Elongation at break (%) 320 345 285 305 Shore hardness ( ⁰ A) 57 56 62 62 48 47 43 43 Notch toughness (kg / cm) ... 5 7th 26th 8th Pull-out strength (kg / cm) 29 29 32 37

Natural rubber

cis-1,4-polybutadiene

Plasticizer (hydrocarbon mixture)

Zinc oxide

Stearic acid

Adhesive resin

Phenylbetanaphthylamine Phenylalphanaphthylamine

N-phenyl-N'-isopropyl-p-phenylenediamine

Dismantling agents

Furnace soot

Furnace soot

Oil sulfur 0.2 Dibenzothiazyl disulfide

2-mercaptobenzothiazole

Tetramethylthiuram disulfide

ρ, ρ'-dibenzoylquinone dioxime

Stabilized phenol-formaldehyde resin with active methylol groups

2-mercaptobenzimidazole

Mixtures

ν Va (Parts by weight) 70 70 30th 30th 5.5 6th 5 3 3 2 1 1 1 0.6 0.35 1 1 0.14 0.15 43 40 0.55 0.77 2 2.6 0.5 0.5 0.1 0.1 1.5 1.5 1 1 1

Test results

V
Heating at 143 ° C (minutes) 10 15th 35 60 Module at iw "/ ₀ (lcg / cm ^ 75 60 102 116 Module at 500% (kg / cm ⁸ ) 168 81 Tensile strength (kg / cm ² ) ... 195 174 195 182 Elongation at break (%) 585 515 525 485 Shore hardness ( ⁰ A) 59 55 64 60 Elasticity (%) 52 52 57 57 Notchiness (kg / cm) ... , 16 35 16 16 Pull-out strength (kg / cm) 79 73 81 62

Cord liability (kg / cm thread length) static V Va Va to poly dyna amide mix At room temperature ■ mfkooATi in σ & ΐΐΐί & τϊ ( (κ * -
IllCooCilj ULLgWCtllCl L heats 2 hours 15 minutes ten) 12.03 11.9 5.02-10 * Ge at room temperature measure, aged (5 hrs
at 130 ° C) 10.66 12.5 3.88-10 *

Aging for 3 days at 100 ° C

V Heating at 143 ° C (minutes) 10 15th 35 60 Module at 300% (kg / cm ² ) 126 110 144 130 Module at 500% (kg / cm ² ) Tensile strength (kg / cm ² ) ... 168 168 168 138 Elongation at break (%) 360 410 330 330 Shore hardness ( ⁰ A) 64 66 65 65 Elasticity (%) 58 59 60 58 Notchiness (kg / cm). 11 12th 10 10 Pull-out strength (kg / cm) 31 22nd 43 41

Test results

Va unaged Heating at 143 ° C (minutes) 10. 15th 35 60 Module at 300% (kg / cm ² ) 53 75 82 82 Module at 500% (kg / cm ² ) 131 Tensile strength (kg / cm ² ) ... 150 168 146 155 Elongation at break (%) 540 490 425 445 Shore hardness ( ⁰ A) 52 55 58 57 Elasticity (%) 53 65 65 66

Aging for 3 days at 100 ° C

Va aged Heating at 143 ° C (minutes) 10 15th 35 60 Module at 300% (kg / cm ² ) 111 113 106 104 Module at 500% (kg / cm ² ) Tensile strength (kg / cm ² ) ... 126 146 128 129 330 365 345 345 Shore hardness ( ⁰ A) 60 62 61 60 Elasticity (%) 67 61 60 62

The cord adhesion of the mixture to artificial silk is not a problem, as there is always adhesion is better than polyamide fibers. The adhesive behavior of the mixture on artificial silk was therefore not improved shown. Since natural rubber and cis-1,4-polyisoprene are chemically identical and the mixtures III and TV already contain natural rubber, need blending qualities between natural rubber and cis-1,4-polyisoprene not to be shown. These blends have the same properties and characteristics like pure natural rubber compounds. Used in place of butadiene-styrene rubber in the blends III and oil-extended butadiene-styrofoam rubber are used, the adhesion of the so modified Mixture compared to polyamides is the same. Otherwise, the other properties are also correct of the modified mixtures correspond to those of mixtures III and IV. In the following example 4 an oil-extended butadiene-styrene rubber-containing mixture VI is shown.

Example 4

Mixture VI (parts by weight)

Natural rubber - 50

Oil stretched. Butadiene styrene rubber

chuk 68.8

Zinc oxide., 3

Stearic acid 2

N-phenyl-N'-cyclohexyl-p-phenylene-

diamine 1

Dismantling agent 0.06

Phenylbetanaphthylamine 0.6

Phenylalphanaphthylamine 0.35

Wax 1

Furnace black 42.5

Adhesive resin 1

2-mercaptobenzimidazole 1

Oil sulfur 0.2 0.55

Dibenzothiazyl disulfide 2

2-mercaptobenzothiazole 0.5

Tetramethylthiuram disulfide 0.1

ρ, ρ'-dibenzoylquinone dioxime 1.5

Claims (1)

Test results VI Heating at 143 ° C (minutes) 10 15th 35 60 Module at 300% (kg / cm ² ) 27 64 68 68 Module at 500% (kg / cm ² ) 62 139 146 145 Tensile strength (kg / cm ² ) ... 120 172 180 178 Elongation at break (%) 770 575 585 620 Shore hardness ( ⁰ A) 45 54 53 54 Elasticity (%) 43 48 47 45 Notch toughness (kg / cm) ... 29 27 24 25th Pull-out strength (kg / cm) 71 81 75 55 Aging for 3 days at 100 ° C Module at 300% (kg / cm ² )
Module at 500% (kg / cm ² )
Tensile strength (kg / cm ² ) ... Elongation at break (%) Shore hardness ( ⁰ A) Elasticity (%) Notch toughness (kg / cm) ...
Pull-out strength (kg / cm) VI Heating at 143 ⁰ C (minutes) 10 15th 35 60 93 104 88 92 156 166 162 152 445 435 435 400 58 59 56 57 48 48 45 42 7th 7th 6th 11 30th 31 38 40 10 Cord liability (kg / cm thread length) of polyamide static dynamic Tipi R iuiTntPTTTnpriitnr OTmpQifMi unaged (heated 2 hours 9.8 5.7 10 * Measured at room temperature, aged (5 hours at 130 ° C) 8.7 8.1-10 * IO from the above mixtures and their test results can be seen that the static and dynamic adhesion of MischungVI to polyamide cord is good. Even the adhesion to bare polyamide cord has been improved.
Ao The static adhesion values of vulcanizates according MischungVI are compared with those of standard mixtures (mix I) probably lower, but show a small decrease from the unaged in the aged condition. In addition to this advantage, the dynamic adhesion values represent a significant advance, which, unaged and aged, are more than twice as high as what is known and do not show any decrease with aging, but even increase. Claim: Process for firmly binding cords made of polyamides or rayon to mixtures made of natural rubber, possibly oil-extended, butadiene-styrene rubber, synthetic cis-1,4-polyisoprene, cis-1,4-polybutadiene or their blends, the carbon black and the usual processing, Contain aging and vulcanizing aids, the cords optionally with rubber latex and phenolic resins have been impregnated by embedding the treated or untreated Cords into the rubber mixtures and heating of the laminated body obtained from vulcanization temperatures, characterized in that that one uses rubber compounds that. contain ρ, ρ'-dibenzoylquinone dioxime. Considered publications:
German interpretative document No. 1 135 659. 809 540/454 4.68 © Bundesdruckerei Berlin