WATER-BASED CEMENT FOR PRODUCING TYRES

Information

  • Patent Application
  • 20110028597
  • Publication Number
    20110028597
  • Date Filed
    December 02, 2008
    16 years ago
  • Date Published
    February 03, 2011
    13 years ago
Abstract
A water-based cement for producing tyres, having water as solvent, a cross-linkable unsaturated-chain polymer base, sulphur, a reinforcing filler, zinc oxide, accelerators, and an emulsifier of the general formula (I)
Description
TECHNICAL FIELD

The present invention relates to a water-based cement for producing tyres.


BACKGROUND ART

In tyre manufacturing, cements are normally organic-solvent-based. Cements of this sort are highly adhesive and easy to use, mainly on account of rubber dissolving readily in organic solvents and so blending with other rubber to form practically one piece once the organic solvent evaporates.


For environmental reasons, recent European directives have imposed a drastic reduction in the use of organic solvents in the tyre industry, thus forcing manufacturers to devise alternative solutions to ensure correct adhesion of rubber layers.


One alternative to traditional cements is water-based cements, in which organic solvent is replaced by water as solvent, and which poses the problem of ensuring dispersion in water of intrinsically hydrophobic ingredients. This is done using emulsifiers which, as is known, comprise a hydrophobic group capable of bonding the ingredient in question, and a hydrophilic group capable of ensuring its dispersion in water. Since emulsifiers are normally selectively effective as regards a particular compound, the making of water-based cement calls for using different types of emulsifiers.


Tests show that the presence of large quantities and different types of emulsifiers may impair the adhesive strength of the cement, hence the strong demand for water-based cement emulsifiers that are effective over a wide range of ingredients, to reduce both the quantity and the number of types of emulsifiers used.


The Applicant has surprisingly discovered a particular class of emulsifiers that is universally effective over the various ingredients of water-based cement.







BEST MODE FOR CARRYING OUT THE INVENTION

According to the present invention, there is provided a water-based cement for producing tyres, comprising water as solvent, cross-linkable unsaturated-sulphur, reinforcing filler, zinc oxide, and accelerators; said cement being characterized by comprising an emulsifier of the general formula (I)





R1CONR2CHR3COOX  (I)


where:


R1 is an aliphatic group C6-C23


R2 is H or an aliphatic group C1-C8


R3 is H or an aliphatic or aromatic group C1-C8, and


X is a metal cation.


Preferably, the water-based cement comprises by weight 5 to 80% of water, 10 to 60% of a cross-linkable unsaturated-chain polymer base, 0.2 to 1% of sulphur, 1 to 25% of reinforcing filler, 0.1 to 3% of zinc oxide, and 0.1 to 1% of accelerators; said cement being characterized by comprising 0.1 to 10% of an emulsifier of the general formula (I).


Preferably, aliphatic group R1 comprises a double bond.


Preferably, the quantity of emulsifier in the cement ranges between 0.5 and 5% by weight.


The examples below are purely indicative and non-limiting, for a clearer understanding of the invention.


EXAMPLES

Six cements A, B, C, D, E, F were prepared. Cement A is a solvent-based cement; cement B is a known water-based cement; and cements C-F are water-based cements in accordance with the invention and employing emulsifiers of formula (I).


Table I shows the compositions, in percentage by weight, of the six cements.
















TABLE I







A
B
C
D
E
F






















WATER

50.0
50.0
52.0
52.0
52.0


HEPTANE
70.0







NATURAL RUBBER
18.0
25.0
25.6
26.6
26.6
26.6


CARBON BLACK
9.0
13.0
13.0
13.0
13.0
13.0


STEARIC ACID
0.6







ZINC OXIDE
0.3
1.0
1.0
1.0
1.0
1.0


ADHESIVE RESIN
2.0
5.0
3.6
3.6
3.6
3.6


SULPHUR
0.3
0.5
0.5
0.5
0.5
0.5


SULPHONAMIDE
0.3
0.5
0.5
0.5
0.5
0.5


STANDARD EMULSIFIERS

5.0
2.5





EMULSIFIER (a)


2.5
2.0




EMULSIFIER (b)




2.0



EMULSIFIER (c)





2.0









The standard emulsifiers used in cements B and C are: naphthylsulphonic acid for dispersing zinc oxide, sulphur, and accelerators; ethoxylated aliphatic amines and ethoxylated fatty acids for dispersing carbon black.


The emulsifier (a) according to the present invention used in cements C and D is sodium oleyl sarcosine of the formula (CH3)(CH2)18CON(CH3)CH2COONa.


The emulsifier (b) according to the present invention used in cement E is of the formula CH3 (CH2)7CHCH(CH2)7CONHCH2COONa.


The emulsifier (c) according to the present invention used in cement F is of the formula CH2CH(CH2)8CONHCH2COONa.


The emulsifiers used in the cements according to the present invention may differ from those in the above examples. In particular, the group R3 may also comprise heteroatoms such as S, N or O.


As will be clear to an expert, in addition to natural rubber, the cements according to the present invention may comprise any cross-linkable chain polymer base obtained by polymerization of conjugate dienes and/or aliphatic or aromatic vinyl monomers. For example, usable polymer bases are selected from the group comprising natural rubber, 1,4-cis polyisoprene, polybutadiene, isoprene-isobutene copolymers, possibly halogenated, butadiene-acrylonitrile copolymers, styrene-butadiene copolymers and styrene-butadiene-isoprene terpolymers, both in solution and emulsion, and ethylene-propylene-diene terpolymers. The above polymer bases may be used singly or mixed.


Laboratory Tests


Each cement was adhesion-tested on both green and cured rubber, as per ASTM Standard D624, was tested for rheometric properties as per ASTM Standard D5289, and was viscosity-tested as per ASTM Standard D6080. Table II shows the test results.
















TABLE II







A
B
C
D
E
F






















Viscosity (cps)
100
100
100
100
100
100


ML (dNm)
2.1
2.0
2.0
2.1
2.2
2.1


MH (dNm)
18.0
16.8
17.5
16.9
18.0
19.0


T10 (min)
0.7
0.5
0.6
0.5
0.8
0.6


T50 (min)
1.1
1.1
1.2
1.2
1.2
1.1


T90 (min)
2.9
3.0
3.2
3.2
3.1
3.2


Green-rubber
2.00
1.20
1.70
1.70
1.7
1.7


adhesion (N/mm)


Cured-rubber
20.00
10.00
17.00
19.70
21.7
23.2


adhesion* (N/mm)





*The cured rubber was obtained as per ASTM Standard 1382, by curing for 10 minutes at a constant temperature of 160° C.






As shown in Table II, reducing the number of different types of emulsifiers in the cement improves its adhesive strength, so much so that the adhesive strength of cements comprising only one type of emulsifier (cements D-F) is even greater than that of the organic-solvent-based cement (A).


As shown in Table II, using only one type of emulsifier means a smaller amount can be used, thus improving the stability and adhesive strength of the cement.


Moreover, the double bond in the aliphatic chain R1 further improves adhesion of the cement by participating in cross-linking reactions.


In short, using a universal emulsifier, different types of emulsifier need no longer be used, and the amount of emulsifier used can be greatly reduced.


As shown by the results in Table II, using an emulsifier as claimed in no way impairs the other characteristics of the cement, such as viscosity and rheometric properties.

Claims
  • 1) A water-based cement for producing tyres, comprising water as solvent, a cross-linkable unsaturated-chain polymer base, sulphur, a reinforcing filler, zinc oxide, and accelerators; said cement being characterized by comprising an emulsifier of the general formula (I) R1CONR2CHR3COOX  (I)where:R1 is an aliphatic group C6-C23 R2 is H or an aliphatic group C1-C8 R3 is H or an aliphatic or aromatic group C1-C8, andX is a metal cation.
  • 2) A water-based cement for producing tyres as claimed in claim 1, characterized by comprising by weight 5 to 80% of water, 10 to 60% of a cross-linkable unsaturated-chain polymer base, 0.2 to 1% of sulphur, 1 to 25% of reinforcing filler, 0.1 to 3% of zinc oxide, and 0.1 to 1% of accelerators; said cement being characterized by comprising 0.1 to 10% of an emulsifier of the general formula (I).
  • 3) A water-based cement for producing tyres, as claimed in claim 1, characterized in that X is an alkaline metal cation.
  • 4) A water-based cement for producing tyres, as claimed in claim 1, characterized in that said emulsifier is CH3(CH2)18CON(CH3)CH2COONa.
  • 5) A water-based cement for producing tyres, as claimed in claim 1, characterized in that the aliphatic group R1 comprises a double bond.
  • 6) A water-based cement for producing tyres, as claimed in claim 5, characterized in that said emulsifier is CH3(CH2)7CHCH(CH2)7CONHCH2COONa or CH2CH(CH2)8CONHCH2COONa.
  • 7) A water-based cement for producing tyres, as claimed in claim 1, characterized by comprising 0.5 to 5% by weight of said emulsifier.
  • 8) A tyre produced using a water-based cement as claimed in claim 1.
Priority Claims (1)
Number Date Country Kind
TO2007A000874 Dec 2007 IT national
PCT Information
Filing Document Filing Date Country Kind 371c Date
PCT/EP2008/066664 12/2/2008 WO 00 9/21/2010