Bleaching and dyeing; fluid treatment and chemical modification – Chemical modification of textiles or fibers or products thereof – Cellulose fibers
Reexamination Certificate
1999-07-28
2001-08-21
Einsmann, Margaret (Department: 1751)
Bleaching and dyeing; fluid treatment and chemical modification
Chemical modification of textiles or fibers or products thereof
Cellulose fibers
C008S116100, C252S008860, C252S008910
Reexamination Certificate
active
06277152
ABSTRACT:
The present invention relates to a process for finishing a cellulose-based textile, a finishing bath comprising a cross-linking textile finish as well as a cellulose-based textile finished according to this process.
Cross-linking textile finishes are currently used for conferring on cellulose fabrics properties of resistance to creasing or crease recovery, a dimensional stability to domestic washes as well as easy care (easy ironing or no ironing), among other properties.
However, most of these cross-linking textile finishes contain free or combined formaldehyde which is released either in the finishing shop or when using fabrics finished in this way. However, formaldehyde is now considered to be a noxious product, exposure doses of which are limited to very low values by certain national regulations. Textile finishes free of any trace of formaldehyde were therefore actively sought.
Thus, the use of alkane polycarboxylic derivatives such as phosphono succinic acid as cross-linking agents for cellulose was proposed in the Patent Application EP-A-0484.196.
The International Application WO 96/26314 describes the use of maleic acid oligomers for treating cellulose fabrics in the presence of sodium hypophosphite as a cross-linking catalyst.
The Patents U.S. Pat. No. 5,496,476, U.S. Pat. No. 5,496,477, U.S. Pat. No. 5,705,475, U.S. Pat. No. 5,728,771, describe the combination of a phosphonoalkyl polycarboxylic acid with a second polycarboxylic acid which can be butanetetracarboxylic acid or, preferably, a polyacrylic acid of low mass, for cross-linking cellulose textiles in the presence of catalysts containing phosphorous such as sodium hypophosphite or sodium monophosphate.
The Patents U.S. Pat. No. 4,820,307, and U.S. Pat. No. 4,975,209, describe the treatment of cellulose materials by polycarboxylic acids, in particular butane tetracarboxylic acid or citric acid in the presence of catalysts of hypophosphite or phosphate type.
The cross-linking textile finishes mentioned above allow the use of or salting-out of formaldehyde to be avoided. However, their use requires the obligatory presence of a catalyst.
The Patent Application EP-A-0564.346 describes the use as a cross-linking textile finish of phosphinicosuccinic acid, phosphinicobisuccinic acid and their mixtures for finishing cellulose textiles. This type of finish can be used without a catalyst.
The Applicant carried out research with the aim of perfecting a process for finishing a cellulose-based textile which allows the use or salting-out of formaldehyde to be completely avoided and does not require the use of a catalyst, whilst conferring on the textiles properties of resistance to creasing or crease recovery, dimensional stability for domestic washes and very satisfactory easy care.
The Applicant then discovered with astonishment that a new cross-linking composition for cellulose had very useful cellulose cross-linking properties justifying its use as a textile finish, not containing and not salting-out formaldyde either in finishing shops or when using fabrics finished in this way.
The present invention thus consists of a process for finishing a cellulose-based textile, characterized in that the textile is treated using an aqueous finishing bath containing the following cross-linking composition as a cross-linking agent for cellulose:
a) 15-95 molar % of at least one maleic acid telomer and hypophosphorous acid of formula (I)
with
and (m+n)≧3
or A=H or OH and n≧2
b) 0-50 molar % phosphinicosuccinic acid
c) 0-40 molar % phosphinicobisuccinic acid
d) 0-50 molar % phosphonosuccinic acid
e) 0-15 molar % hypophosphorous acid
f) 0-10 molar % phosphorous acid
g) 0-15 molar % phosphoric acid
each of the acids a) to g) of the composition being able to be present either in free form or be partially or totally neutralized in the form of an alkali metal or alkaline-earth metal ammonium or amine salt.
The cross-linking composition used within the scope of the process according to the present invention is designated in what follows under the name of “cross-linking composition A”.
A
31
P NMR analysis revealed that one part of the telomeric fraction of formula (I) could contain several phosphorus atoms randomly distributed per chain.
The cross-linking composition A according to the invention can be prepared by radicular polymerization or telomerization.
This polymerization or telomerization is carried out using maleic acid and a telogenic monomer, preferably sodium hypophosphite. The molar ratio between the maleic acid and the telogenic monomer is generally comprised between 1.5 and 5, preferably between 2 and 4 and very particularly between 2.1 and 3.
The polymerization is initiated by a radicular catalyst, preferably sodium persulphate at doses which can be comprised between 5 and 12% by weight in relation to the weight of monomers.
Firstly, the polymerization can be carried out at temperatures comprised between 50 and 110° C., preferably between 70 and 85° C. The duration of the polymerization is generally comprised between 2 and 12 hours, preferably between 6 and 8 hours. Secondly, the polymerization is prolonged by a thermal treatment at a higher temperature, preferably between 80 and 90° C., for one period which can be comprised between 1 and 3 hours so as to complete the polymerization and destroy all residual trace of the initiator.
Different processes can be used for the polymerization, such as for example, addition of the initiator into the mixture of monomers.
The polymerization can be carried out under an inert atmosphere, for example under a nitrogen atmosphere.
After the polymerization is finished, oxidation of the P-H functions still available into P-OH functions can be carried out by an oxidizing agent, preferably hydrogen peroxide.
With regard to the prior art, the Applicant discovered with astonishment that the combination of 15 to 95 molar % of a telomer of maleic acid and hypophosphorus acid of formula (I) with a cross-linking composition containing phosphinicosuccinic acid phosphinobissuccinic acid and phosphonosuccinic acid as the major quantity and hypophosphorus acid, phosphorus acid and phosphoric acid as the minor quantity, allowed good quality finishing of cellulose-base textiles not containing and not salting-out formaldehyde either in finishing shops or when using fabrics finished in this way, to be obtained without the addition of a catalyst.
However, the use of an esterification catalyst or a mixture of several esterification catalysts allows the performances obtained on the treated fabric to be increased at a given temperature, or a given qualified level to be preserved by lowering the thermal conditions required for cross-linking.
The catalysts can be chosen from known esterification catalysts such as, by way of example, cyanamide, guanidine or one of its salts, dicyandiamide, urea, dimethylurea or thiourea, alkali metal salts of hypophosphorus, phosphorus or phosphoric acids, mineral acids, organic acids or their salts.
Preferred catalysts consist of cyanamide, dicyandiamide, urea, dimethylurea, sodium hypophosphite or their mixtures.
Under preferential conditions for implementing the invention, the cross-linking composition A of the invention comprises 15 to 95 molar % of a telomer of maleic acid and hypophosphorus acid, preferably 30 to 70 molar % and more particularly between 40 to 60 molar %.
The finishing bath used within the scope of the present invention comprises in general 3 to 30% by weight of the cross-linking composition A in solution in water.
The finishing bath containing the cross-linking composition A is preferably partially neutralized with an alkali metal hydroxide in order to obtain an aqueous finishing bath with a pH of 0.5 to 7, especially 1 to 7, preferably 1.5 to 5 and more particularly 2 to 3.5.
Under other preferred conditions for implementing the invention, no catalyst is added to the finishing bath. In fact, we noted that the cross-linking composition A self cross-links the cellulose, which is proven by Examples 12 to 18 which follow the descri
Gelabert Antonio
Kyriazis Jean
Wilhelm Didier
Browdy and Neimark
Clariant (France) S.A.
Einsmann Margaret
LandOfFree
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