ADHESIVE COMPOUND FOR REINFORCING PLIES FOR TYRES

Abstract

An adhesive composition that can be applied to reinforcing plies of textile material for tyres and comprising (a) an elastomeric rubber latex, (b) a precondensed resin composed of resorcinol and formaldehyde and comprising protected isocyanate groups, (c) lignin and (d) a compound chosen from urea and thiourea.

Claims

1. An adhesive composition suited to be applied to reinforcing plies of textile material for tyres; said adhesive composition being a single basic aqueous solution comprising (a) a latex of an elastomeric rubber and (b) a precondensed resin composed of resorcinol and formaldehyde and comprising protected isocyanate groups; said adhesive composition being characterized in that said single aqueous solution further comprises (c) lignin and (d) a compound chosen from urea and thiourea.

2. Adhesive composition according to claim 1, characterized in that said elastomeric rubber latex comprises a styrene-butadiene-vinylpyridine latex or a latex from a mixture of styrene-butadiene-vinylpyridine and styrene-butadiene.

3. Adhesive composition according to claim 1, characterized in that the lignin is sulfonated lignin.

4. Adhesive composition according to claim 1, characterized in that it comprises from 5 to 25 phr of said precondensed resin, from 1 to 10 phr of lignin and from 1 to 10 phr of the compound chosen from urea and thiourea.

5. Reinforcing ply of textile material for tyres soaked in the adhesive composition according to claim 1.

6. Tyre comprising a reinforcing ply of textile material according to claim 5.

Description

EXAMPLES

[0018] Two adhesive compositions for reinforcing plies were made. The first is a comparison adhesive composition (Comp.), wherein free formaldehyde was utilized, and the second is an adhesive composition according to the invention (Inv.), wherein free formaldehyde was not utilized, but rather a combination of urea and lignin.

[0019] In Table I the compositions by weight % of the two adhesive compositions are reported.

TABLE-US-00001 TABLE I Comp. Inv. Latex 100 100 Resorcinol 5.5 Free formaldehyde 12 Ammonia 20 20 Condensed resin 19 Urea 2 Lignin 3

[0020] The latex utilized in adhesive compositions is a styrene-butadiene-vinylpyridine latex.

[0021] The condensed resin utilized is indicated with the abbreviation I-168-L and marketed by the company INDSPEC CHEMICAL.

[0022] Hereinafter, by way of example, a procedure is reported for the preparation of the two compositions

[0023] Comparison (Comp.) Adhesive Composition Preparation Procedure

[0024] The resorcinol is dissolved in water at the desired concentration. The formaldehyde is then added in the ratios reported in Table I, and the resulting solution is left to react for a period of time from 5 minutes to 30 minutes. At this point the ammonia is slowly added and left to react for period of time ranging from 5 minutes to 1 h. Finally, the latex is added and left to mature for a period of time from 1 h to 72 h.

[0025] Adhesive Composition of the Invention (Inv.) Preparation Procedure

[0026] The condensed resin is dissolved in water, the pH thereof being previously brought up to a value 9 by adding an appropriate amount of ammonia.

[0027] The urea is then added and the pH of the solution is brought up to a value 10 by further addition of ammonia.

[0028] At this point the lignin and the latex are added.

[0029] The two adhesive compositions described above were applied using the same procedure to polyester cords (1670/2 390390) for the preparation, respectively, of a composite made utilizing the comparison adhesive composition and of a composite made utilizing the adhesive composition of the invention.

[0030] By means of a calendering operation, the cords treated with the adhesive compositions were embedded between two layers of ply skim.

[0031] In Table II the composition of the ply skim compound utilized to embed in the same manner both the cords treated with the comparison adhesive composition Comp. and the cords treated with the adhesive composition of the invention Inv. is reported.

TABLE-US-00002 TABLE II Natural rubber 100 Carbon black 40 Sulfur 7 Accelerant 1.5

[0032] The natural rubber is made up of a polymer base composed of natural origin cis-1,4-polyisoprene.

[0033] The accelerant utilized is N-tert-butyl-2-benzothiazyl-sulfenamide (TBBS).

[0034] Below, a procedure for the preparation of ply skim compounds is reported.

(1.SUP.nd .Mixing Step)

[0035] Before the start of the mixing, a mixer with tangential rotors (commonly called Banbury) and an internal volume of between 230 and 270 liters was loaded with the polymer base and the reinforcing filler, reaching a fill factor of 66-72%.

[0036] The mixer was operated at a speed of 40-60 rpm, and the mixture thus formed was discharged once a temperature of 140-160 C. had been reached.

(2.SUP.nd .Mixing Step)

[0037] The vulcanization system was added to the mixture obtained from the previous step, reaching a fill factor of 63-67%. The mixer was operated at a speed of 20-40 rpm, and the mixture thus formed was discharged once a temperature of 100-110 C. had been reached.

[0038] The composites obtained as a result of the calendering operation, once vulcanized, were subjected to adhesion tests.

[0039] The adhesion tests were performed by separating the two parts of the cord-rubber composite by means of the application of a load in order to then estimate the percentage of ply coated by the rubber.

[0040] In particular, the adhesion tests were conducted both on composites obtained after varying periods of vulcanization and on composites subjected to varying periods of aging.

[0041] In this way it was possible to verify whether the adhesive composition of the invention would be able to ensure the same adhesive strength as the comparison composition even in view of varying periods of vulcanization and varying periods of aging.

[0042] Specifically, the vulcanization periods considered were respectively 10 minutes, 50 minutes, 110 minutes, 170 minutes; whilst the aging periods considered were respectively 8 hours, 16 hours and 24 hours.

[0043] The aging procedure requires that the composites be kept in an oven at 125 C. in accordance with the ISO 188 standard for a variable period of time as indicated in Table III.

[0044] In Table III the forces (Newton/cord) required in order to extract the cords from the rubber as a function of the periods of vulcanization are reported; in Table IV the forces (Newton/cord) required in order to extract the cords from the rubber as a function of the periods of aging to which the composites were subjected are reported.

TABLE-US-00003 TABLE III Comp. Inv. 10 min. 20.0 19.8 50 min. 16.8 15.1 110 min. 13.3 12.1 170 min. 9.0 8.8

TABLE-US-00004 TABLE IV Comp. Inv. 0 hours (no aging) 20.0 19.8 8 hours 16.4 17.3 16 hours 14.5 14.4 24 hours 13.7 12.9

[0045] From the data reported in Tables III and IV it is clear that the presence of lignin, combined with the structure formed by the reaction between the resorcinol and formaldehyde combined resin with the urea or thiourea, manages to overcome the need to utilize free formaldehyde. In fact, the only formaldehyde present within the composition of this invention is not in the free state but rather embedded within the precondensed resin.

[0046] In summary, the adhesive compound, object of the present invention, is capable of ensuring the adhesion levels of the comparison compound without, however, having to utilize free formaldehyde.

[0047] In this way the adhesive compound of the present invention has the great advantage of being able to avoid the use of free formaldehyde, with all of the benefits that this entails in terms of safety, without compromising performance in terms of adhesion.