EP1432765B1 - Compositions de polysiloxanes et amides d'acides gras quaternises - Google Patents

Compositions de polysiloxanes et amides d'acides gras quaternises Download PDF

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EP1432765B1
EP1432765B1 EP02779364A EP02779364A EP1432765B1 EP 1432765 B1 EP1432765 B1 EP 1432765B1 EP 02779364 A EP02779364 A EP 02779364A EP 02779364 A EP02779364 A EP 02779364A EP 1432765 B1 EP1432765 B1 EP 1432765B1
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Prior art keywords
formula
radical
radicals
component
quaternized
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EP1432765A1 (fr
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Harald Chrobaczek
Gabriele Lindmair
Günther Tschida
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Huntsman Textile Effects Germany GmbH
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Huntsman Textile Effects Germany GmbH
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D06M13/461—Quaternised amin-amides from polyamines or heterocyclic compounds or polyamino-acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/50—Modified hand or grip properties; Softening compositions

Definitions

  • the invention relates to aqueous solutions or dispersions which comprise polydiorganosiloxanes and quaternized fatty acid amides. It further relates to the use of such solutions or dispersions for the treatment of fiber materials, in particular of fabrics.
  • Aqueous dispersions which comprise polysiloxanes and nonquaternized fatty acid amides also have disadvantages.
  • their storage and/or thermal stability is not always optimal. This is true particularly when the polysiloxanes contain quaternized positively charged nitrogen atoms. Said disadvantage thus becomes more evident as the nitrogen content in the polysiloxane increases or as the weight fraction of nitrogen-containing polysiloxane in the dispersion increases.
  • nitrogen-containing polysiloxanes are in many cases desired due to their positive properties. These positive properties consist, firstly, primarily in imparting a pleasantly soft hand to finished textiles.
  • polysiloxanes which contain quaternized nitrogen atoms are preferred if the finished fabrics are to have marked hydrophilicity.
  • a further disadvantage of aqueous dispersions which comprise polysiloxanes and nonquaternized fatty acid amides is that the hydrophilicity of textiles finished with these dispersions is inadequate for many fields of use.
  • the object of the present invention was to provide compositions which are highly suitable for treating fabrics, which have the advantages of known aqueous polysiloxane/fatty acid amide compositions, but which are free from the abovementioned disadvantages.
  • composition in the form of an aqueous solution or an aqueous dispersion which comprises the following components:
  • the invention accordingly provides aqueous solutions or dispersions which, in addition to water, comprise at least one each of the abovementioned components A) and B), and also the use of these solutions or dispersions for the treatment of fiber materials.
  • composition according to the invention which comprises component A, component B and optionally further components may be in the form of an aqueous solution, namely when this mixture is water-soluble (this is possible, for example, when component A) contains polar groups such as polyoxyalkylene groups or groups with quaternized nitrogen atoms).
  • component A contains polar groups such as polyoxyalkylene groups or groups with quaternized nitrogen atoms
  • component C a dispersant or a mixture of dispersants.
  • compositions according to the invention are highly suitable for the treatment of fiber materials, in particular of fabrics, such as wovens or knits, and have the following advantages:
  • compositions according to the invention are aqueous solutions or dispersions. These must comprise a quaternized fatty acid amide (component B).
  • component B) is a product derived from a fatty acid alkanolamide of the formula (Ia) or from a fatty acid amide of the formula (lb) or of the formula (Ic) by quaternization of one or more nitrogen atoms, such that this nitrogen atom (or these nitrogen atoms) has four chemical bonds and has a positive electric charge.
  • a method of preparing a component B) consists in reacting a fatty acid amide of the formula (la), (lb) or (lc) or a mixture of such amides of the formulae (Ia), (Ib) or (Ic) with a quaternizing agent, e.g. with an alkylating agent.
  • Component B) may be a uniform chemical compound. However, it is normally a mixture of compounds whose individual representatives differ, for example, by virtue of the chain length of the radical R.
  • a mixture of quaternized compounds may be present which comprises both quaternized compounds derived from formula (1a), and also quaternized compounds derived from formula (Ib) and/or (1c).
  • reaction (quaternization) can be carried out by generally known methods of organic chemistry.
  • Fatty acid amides of the formulae (Ia), (Ib) and (Ic) are available commercially, in some cases in the form of their salts.
  • One example is the product BELFASIN 2597 from Cognis, DE.
  • Particularly suitable as component B) of compositions according to the invention are products or product mixtures which can be obtained by quaternization of fatty acid alkanolamides of the formula (Ia), in particular of compounds of the formula (IX) R-CO-NH-CH 2 CH 2 -NH-CH 2 CH 2 OH (IX).
  • R here has the meaning given in claim 1.
  • b is a number from 1 to 24, b preferably has the value 1 in formulae (Ia).
  • all of the radicals R k present are, independently of one another, H or are -CO-R. In formula (1c), however, at least one of the radicals R k must be -CO-R.
  • the radicals R are in each case a linear or branched alkyl radical) having 6 to 24 carbon atoms.
  • a is a number from 2 to 6. a preferably has the value 2.
  • the radical R in the formulae (Ia) and (Ib) is a linear or branched alkyl radical having 6 to 24 carbon atoms, preferably a saturated, unbranched alkyl radical having 8 to 18 carbon atoms. The sarre statement is valid for the radicals R in all of those radicals R k in the formulae (Ib) and (Ic) which stand for -CO-R.
  • compositions according to the invention are to comprise a component B) derived from only one of the formulae (Ia), (Ib) or (Ic), for the quaternization reaction, preference is given, for cost reasons, not to using a chemical uniform compound of the formula (Ia), (Ib) or (Ic), but a mixture of compounds which conform to one of these formulae and whose individual representatives differ in the chain length of the radical R.
  • the compounds of the formulae (Ia) to (Ic) can either be used as such or in the form of salts, e.g. those which are formed by reacting a compound of the formula (la), (lb) or (Ic) with acetic acid. Where appropriate, when such salts are used, the pH of the reaction mixture must be optimized.
  • compounds of the formula (Ia), (Ib) and (Ic) are available commercially.
  • compounds of these formulae can be prepared by known methods by reacting the corresponding fatty acid RCOOH or a mixture of such fatty acids with the corresponding amines.
  • One example of the preparation of compounds of the formulae (Ib) and (Ic) is the reaction of technical-grade stearic acid (i.e. a mixture of fatty acids whose individual compounds differ in the chain length of the alkyl radical) with diethylenetriamine ((N-2-aminoethyl)ethylenediamine).
  • esters may also arise as byproducts (e.g. from fatty acid and H 2 N-CH 2 CH 2 -NH-CH 2 CH 2 -NHCH 2 CH 2 OH by reaction of the carboxyl group with the hydroxyl group).
  • cyclic compounds may form, e.g. imidazoline derivatives by intramolecular reaction, in which the carbonyl group of the amide of the formula (1a) reacts with a nitrogen atom of this amide, and water is subsequently cleaved off.
  • the corresponding imidazoline is also partially or completely quaternized.
  • compositions according to the invention can also be used for the treatment of textiles if they comprise these byproducts. In some cases, it has even proved to be advantageous if said quaternized imidazoline derivatives were additionally present in compositions according to the invention. The stability of aqueous dispersions of compositions according to the invention was further improved thereby.
  • the quaternization of the compounds of the formula (Ia), (Ib) or (Ic), which leads to component B) of compositions according to the invention, is carried out such that, in component B), the anions assigned to the quaternized nitrogen atoms are chosen from chloride anions, methylsulfate anions, benzenesulfonate anions and toluenesulfonate anions. Methylsulfate anions, benzenesulfonate anions and toluenesulfonate anions are preferred; the toluenesulfonate anions may be chemically uniform anions or isomeric mixtures.
  • the corresponding anions are preferably likewise chosen from said classes of anions, in which case the anions here are also preferably methylsulfate anions, benzenesulfonate anions or toluenesulfonate anions.
  • suitable compounds for the quaternization reaction are, inter alia, the following:
  • component (B) is prepared by quaternization of compounds of the formula (Ia), (Ib) and/or (Ic) in which one or two hydrogen atoms are also bonded to the nitrogen atom which is to be quaternized, then it must be ensured that sufficient quaternizing agent is used so that no hydrogen atom is any longer bonded to this nitrogen atom after the quaternization, but all hydrogen atoms bonded to N have been substituted by the corresponding organic radical so that 4 carbon atoms are directly bonded to at least one nitrogen atom.
  • compositions according to the invention can also additionally comprise further quaternized fatty acid amides.
  • R here has the meaning given above and in claim 1.
  • compositions according to the invention must also comprise at least one component A).
  • Component A) is a polydiorganosiloxane.
  • Polydiorganosiloxanes are known polymers, e.g. those of the general formula R' 3 Si-O-(SiR' 2 O-) t SiR' 3 .
  • t is normally a number in the range from 10 to 2000.
  • All of the radicals R' are organic radicals, and in some cases one or more of the radicals R' may also be -OH or -OR 4 , where R 4 is an alkyl radical having 1 to 4 carbon atoms or is the phenyl radical. However, more than one radical -OH or -OR 4 is not bonded to any silicon atom.
  • OH or OR 4 groups if present at all, are located exclusively on one of the two chain ends of the polysiloxanes.
  • component A) is not a chemically uniform compound, but a mixture of compounds as is customary for polymers.
  • the individual representatives of this mixture differ, for example, by the chain length, i.e. by the value of t.
  • component B it is also possible to use, as component A), a mixture of polysiloxanes whose individual representatives differ not only in the chain length, but, for example, in the nature of the individual radicals R'.
  • component A it is possible, for example, to use a mixture of 2 polysiloxanes, one of which contains units of the formula (III) described in more detail below, in which X is a radical of the formula (IV), and the other of which contains units of the formula (III) in which X is a radical of the formula (V).
  • polysiloxanes of the abovementioned general formula R' 3 Si-O-(SiR' 2 O-) t SiR' 3 in which, within the polydiorganosiloxane chain, units are also additionally present which do not have the structure -SiR' 2 O- but are units of the formula (M)
  • e is a number from 2 to 6
  • f is the number 1 or 2
  • R 8 is an alkyl radical having 1 to 18 carbon atoms, preferably CH 3 .
  • component A) is a polydiorganosiloxane whose two end-groups are formed by units of the formula R 5 R 4 2 Si-O- and which contains, in the polysiloxane chain, units of the formula (II) -Si(R 4 ) 2 -O- (II) and units of the formula (III) -Si(R 4 )(X)-O- (III) where R 4 is an alkyl radical having 1 to 4 carbon atoms or the phenyl radical and R 5 is R 4 or is X or is OR 4 or is OH or is a radical of the formula (W), in which R 9 is hydrogen or a linear or branched alkyl radical having 1 to 12 carbon atoms, R 10 is an alkyl radical having 1 to 18 carbon atoms, preferably CH 3 , g is a number from 2 to 6, t has the value 0 or 1, all of the radicals X, independently
  • polysiloxanes which are used as component A) contain, within the polymer chain, no units other than those of the formulae (II) and (III), and no end-groups other than R 5 R 2 4 Si-O-.
  • end-groups of these preferred polysiloxanes are formed by units of the formula R 5 R 2 4 Si-O-, where R 5 and R 4 have the meanings given above.
  • Preferred end-groups are HO(CH 3 ) 2 Si-O- and (CH 3,3 Si-O-
  • Further suitable end-groups are (CH 3 O)(CH 3 ) 2 Si-O- and (C 2 H 5 O)(CH 3 ) 2 Si-O-.
  • radicals R 4 are an alkyl radical having 1 to 4 carbon atoms or the phenyl radical, and preferably 80 to 100% of the radicals R 4 present are methyl groups.
  • all of the radicals X present are, independently of one another, a radical of the formula (IV) or of the formula (V)
  • radicals X can also in each case be a radical derived from a radical of the formula (V) such that one or more of the nitrogen atoms present are in quaternized form. If radicals X are present which contain one or more quaternized nitrogen atoms, then the corresponding anions are preferably chosen from the same anions as described above and in claim 1.
  • the distribution of the individual units of the formulae (II) and (III) over the polysiloxane chain may be arbitrary.
  • radicals of the formula (IV) at least one the radicals R 2 and R 3 is hydrogen.
  • the other can be a methyl group, but preferably in 50 to 100% of all units of the formula (IV), both R 2 and also R 3 are hydrogen.
  • the polyorganosiloxanes used as component A) are polyoxyethylene units, through the number of which it is possible to control the hydrophilicity of compositions according to the invention and of textiles treated therewith in a targeted manner.
  • b has a value from 1 to 24, preferably from 6 to 24, R 6 is a branched or unbranched divalent alkylene radical having 2 to 6 carbon atoms, and R 7 is H or CH 3 .
  • R 6 and R 1 have the meanings already given above, c has the value 0, 1 or 2.
  • polysiloxanes suitable as component A) have one or more side chains in which, in each case, 1, 2 or 3 nitrogen atoms are present. It is particularly preferred if, in formula (V), R 6 contains 2 or 3 carbon atoms and all of the radicals R 1 are an alkyl group having 1 to 4 carbon atoms, in particular a methyl group.
  • radicals X are present which contain quaternized nitrogen atoms, i.e. are derived from a radical (V) by quaternization thereof. Thus, no N-H bonds are preferably present in radicals (V) or quaternized derivatives thereof.
  • a particularly suitable component A) of compositions according to the invention is a polysiloxane whose end-groups are formed by units of the formula (CH 3 ) 3 Si-O- and which has units of the formula -Si(CH 3 ) 2 -O- and of the formula (VI) -Si(CH 3 )(X 1 )-O- (VI), in the polysiloxane chain, where all of the radicals X 1 , independently of one another, are a radical of the formula (VII) where d is a number from 6 to 24 and R 2 and R 3 have the meanings given in claim 1, or is a radical of the formula (VIII) where a is a number from 2 to 6 and c has the value 0, 1 or 2, or is a radical derived from a radical of the formula (VIII) such that one or more nitrogen atoms are present in quaternized form.
  • the polydiorganosiloxane comprises both side chains with polyoxyethylene units on the one hand and side chains with amino groups or quaternized nitrogen atoms on the other hand.
  • component A) contains both radicals of the formula (VI) in which X 1 is a radical of the formula (VII), and also radicals of the formula (VI) in which X 1 is a radical of the formula (VIII), or is a radical of the formula (VIII) in with one or more nitrogen atoms are present in quaternized form.
  • Such polydiorganosiloxanes and their preparation are described in US 5 612 409.
  • the preparation can be carried out by reacting linear or cyclic poly- or oligodialkylsiloxanes with bisalkoxyalkylsilanes which additionally comprise a radical with an amino group, and with trisiloxanes of the formula (CH 3 ) 3 Si-O-Si(CH 3 )(X 1 )-O-Si(CH 3 ) 3 , where X 1 is a radical of the formula (VII); such trisiloxanes are available from Goldschmidt, DE.
  • Said bisalkoxyalkylsilanes are monomeric compounds of the general formula (RO) 2 Si(R)(R"), where R is an alkyl radical and R" is a radical which comprises one or more amino groups.
  • polysiloxanes which contain only radicals with amino groups, but no polyoxyethylene units, or polyoxyethylene-group-containing polysiloxanes which do not contain amino groups are also possible.
  • the polysiloxanes obtained in this way are also suitable as component A) of compositions according to the invention.
  • Polysiloxanes which have amino groups in side chains can also be prepared by known methods, e.g. by adding corresponding allylamines onto a polysiloxane which contains Si-H bonds.
  • amino functional polysiloxanes which are suitable as component A) are customary commercially available products, e.g. from Dow Corning and Wacker. Polydiorganosiloxanes which contain both polyoxyethylene groups and also amino groups are therefore particularly preferred because they impart a pleasantly soft hand and a hydrophilicity which can be controlled in a targeted manner to the textiles finished therewith. In polysiloxanes which are suitable as component A), amino-group-containing radicals other than those mentioned above may also be present.
  • Examples thereof are the amino-group-containing radicals bonded to a silicon atom mentioned in US 5 310 783, in particular radicals of the formulae (II), (III), (IV) (column 4, lines 50 to 60 of this US specification), and also the nitrogen-containing radicals mentioned in claim 4 of EP-A 1 076 078.
  • polysiloxanes which contain amino groups and are to be used as component A) of compositions according to the invention contain only tertiary, i.e. no primary or secondary, amino groups. This is true particularly if the amino-functional polysiloxanes as such are not to form the component A), but polysiloxanes are derived from the amino-functional ones such that one or more nitrogen atoms are in quaternized form. This can be carried out by reacting the parent amino-functional polysiloxanes with a quaternizing agent.
  • the quaternizing agent here may be an alkyl chloride, dimethyl sulfate or an alkyl ester of benzenesulfonic acid or toluenesulfonic acid. It is particularly advantageous if the quaternization of the amino-functional polysiloxane is carried out simultaneously in a single operation to the quaternization of the fatty acid amide, i.e. to the preparation of component B). This quaternization can be carried out by known methods in an aqueous dispersion or solution which comprises amino-functional polysiloxane and the nonquaternized fatty acid amide.
  • all of the anions which are assigned to the quaternized nitrogen atoms of component B) in compositions according to the invention are chosen from chloride anions, methylsulfate anions, benzenesulfonate anions and toluenesulfonate anions.
  • the anions which are assigned to quaternized nitrogen atoms in component A) are likewise chosen from the anions mentioned here.
  • Component A) may also be a mixture of different polysiloxanes, although this mixture preferably consists of only polysiloxanes which contain no units other than those of the formulae (II) and/or (III) -Si(R 4 ) 2 -O- (II) -Si(R 4 )(X)-O- (III) in the chain. These formulae have been explained above.
  • all of the polysiloxanes which are used as component A) contain units of the formula (II).
  • the distribution of the individual units of the formulae (II) and (III) over the polysiloxane chain may be arbitrary. It is favorable if the ratio of the number of units of the formula (II) to the number of units of the formula (III) is greater than 1; this ratio is preferably 10:1 to 200:1.
  • compositions according to the invention are in the form of aqueous dispersions and, in addition to components A) and B), also additionally comprise a component C).
  • Component C) is a dispersant or a mixture of dispersants. Suitable dispersants are the known surface-active products, as are known to the person skilled in the art, for example for the preparation of silicone emulsions.
  • Compositions according to the invention which are in the form of aqueous dispersions preferably comprise, as dispersants, only nonionic and/or cationic surface-active products, but no anionic ones.
  • nonionic surfactants particular preference is given to ethoxylated fatty alcohols or ethoxylated fatty acids.
  • suitable dispersants are known surfactants, such as alkyl polyglycosides and ethoxylated branched diols having 4 to 8 carbon atoms in the diol component.
  • cationic surfactants preference is given to quaternary ammonium salts with at least one long-chain organic radical bonded to nitrogen, e.g. an alkyl or alkenyl radical having 8 to 20 carbon atoms.
  • Compositions according to the invention preferably comprise 20 to 95% by weight of water and 3 to 70% by weight of component A), preferably 5 to 50% by weight 2 to 30% by weight of component B), preferably 5 to 25% by weight and 0 to 30% by weight of component C).
  • compositions can comprise further products, as are customary and known for textile finishing. These include, for example, cellulose crosslinkers, flame retardants and polymers which contain fluorine.
  • compositions according to the invention can normally be prepared by generally known methods, such as, for example, simple mixing of component A), component B), water and optionally further components, and mechanical homogenization at room temperature. In individual cases it is possible that it is necessary to work at elevated temperature or that it is necessary to observe a certain order of mixing or dispersing.
  • a preprepared aqueous dispersion of a polydioganosiloxane can be combined with an aqueous solution or dispersion of a fatty acid amide.
  • the fatty acid amide in the second dispersion is already in quaternized form, i.e. as component B).
  • component A) polysiloxane
  • component A polysiloxane
  • the quaternization of the polysiloxane and of the fatty acid amide can be comfortably achieved in a single operation.
  • a nitrogen-free polysiloxane is also possible if a nitrogen-free polysiloxane is to be used as component A), e.g.
  • component A) an ⁇ , ⁇ -dihydroxypolydimethylsiloxane.
  • component B a fatty acid amide
  • emulsion polymerization carried out in aqueous systems, of a polysiloxane precursor for the purposes of preparing an ⁇ , ⁇ -dihydroxypolydimethylsiloxane.
  • compositions according to the invention are highly suitable for the treatment of fiber materials, to which a pleasantly soft hand can be thereby imparted.
  • the fiber materials are preferably fabrics in the form of wovens or knits. They can consist of a very wide variety of materials, such as, for example, cellulose fibers, regenerated cellulose fibers, synthetic fibers or mixtures of these types of fiber.
  • the compositions according to the invention are applied to fabrics preferably in the course of textile finishing, i.e. before manufacturing and after dyeing. Application can be carried out by means of a known padding process, where the concentration of the padding liquor may be within the customary limits known to the person skilled in the art. For this, approximately 20 to 150 g of composition according to the invention are normally used per liter of padding liquor. Further processing of the finished textiles can likewise be carried out by known methods. In this way, it is possible to prepare, inter alia, articles of clothing.
  • an aqueous dispersion was prepared which comprised a polydiorganosiloxane and a fatty acid alkanolamide.
  • the difference between this dispersion and a composition according to the invention consisted in the fact that the fatty acid alkanolamide was not in quaternized form, i.e. no component B) was present.
  • the mixture was then cooled to 45°C and 197 g of water were firstly added, followed by 230 g of the silicone microemulsion obtained as above under a). Mechanical homogenization for 30 minutes gave a low-viscosity, pale-yellow colored emulsion with a pH of about 3.8 at 20°C.
  • This aqueous emulsion which contained a nonquaternized amino-functional polysiloxane and a nonquaternized fatty acid alkanolamide, is referred to below as "comparison dispersion 1".
  • the comparison dispersion 1 was a liquid, opal dispersion which was still stable even after storage for 10 days.
  • comparison dispersion 1 prepared as in example 1 imparted a certain level of hydrophilic properties to the textiles finished therewith, this level was not regarded as adequate for all intended uses.
  • an amino-functional polysiloxane was firstly prepared by means of a known equilibrium reaction from 90 g of octamethylcyclotetrasiloxane 5.2 g of (CH 3 O) 2 Si(CH 3 )CH 2 CH 2 CH 2 NHCH 2 CH 2 NH 2 2 2 g of the trisiloxane given in example 1 from Goldschmidt 1.5 g of water and 0.22 g of 45% strength aqueous KOH solution. 15 g of this amino-functional polysiloxane was dispersed in 70 g of water using 10 g of a mixture of ethoxylated isotridecyl alcohols.
  • the mixture was then quaternized using 3.6 g of methyl p-toluenesulfonate.
  • the comparison dispersion 2 comprised no quaternized fatty acid amide and, after storage for 10 days at room temperature, exhibited crumbly, sandy deposits, i.e. was insufficiently stable for suitability for textile treatment.
  • textiles which had been treated with comparison dispersion 2 had improved hydrophilicity compared with textiles which were treated with comparison dispersion 1.
  • Dispersion 3 was prepared by combining 70 parts by weight of the aqueous dispersion of a polysiloxane with quaternized nitrogen atoms (as described in example 2), with 30 parts by weight of an aqueous polysiloxane dispersion which comprised a quaternized fatty acid alkanolamide.
  • This dispersion which comprised the quaternized fatty acid alkanolamide consisted of 35% by weight of the polysiloxane dispersion which was obtained as in step a) of example 1 and 65% by weight of a mixture which comprised quaternized fatty acid alkanolamide.
  • This mixture can be prepared by reacting 40 g of fatty acid alkanolamide (BELFASIN as described in example 1) with 3.5 g of methyl p-toluenesulfonate in the presence of 450 g of water and 8 g of propylene glycol at room temperature and subsequent heating to 60°C.
  • dispersion 3 according to the invention a pleasantly soft hand and excellent hydrophilicity can be imparted to textiles. This hydrophilicity is higher than in the case of the treatment of the textiles with comparison dispersion 1.
  • the stability of dispersion 3 is significantly better than that of comparison dispersion 2. Even after storage for 10 day at room temperature, dispersion 3 was still homogeneous
  • a dispersion of a polysiloxane with quaternized nitrogen atoms was combined with a polysiloxane dispersion, prepared separately therefrom, which comprised a quaternized fatty acid alkanolamide in order to obtain dispersion 3 according to the invention.
  • the aqueous dispersion of an amino-functional (nonquaternized) polysiloxane was combined with an aqueous dispersion which comprised a (nonquaternized) fatty acid alkanolamide.
  • the quaternization was thus carried out directly on a mixture which comprised nonquaternized polysiloxane and nonquaternized fatty acid alkanolamide.
  • an aqueous dispersion of an amino-functional polysiloxane was also added.
  • the amounts of products used in this example 4 were such that, following simultaneous quaternization of fatty acid alkanolamide and amino-functional polysiloxane and the subsequent addition of further amino-functional polysiloxane, an aqueous dispersion was obtained which had the same chemical composition as dispersion 3 according to the invention.
  • the difference between the dispersions obtained as in examples 3 and 4 was only that in example 3, the polysiloxane and the fatty acid alkanolamide were quaternized separately from one another, whereas in example 4 they were quaternized together.
  • the dispersion according to the invention obtained in this way likewise had good stability upon storage and had the same properties with regard to hydrophilicity and hand of the finished textiles as dispersion 3.
  • the hydrophilicity was determined via the wetting of fabric samples by the 3 dispersions.
  • fabric samples of cotton/polyester (50:50) were treated by means of padding with the dispersions and then dried at 110°C for 10 minutes.
  • 1 drop of water was then applied to various places on the surface of the fabric using a dropping device.
  • the time in seconds between application of the drop and the time until the drop was completely absorbed by the fabric was measured; the latter time point is recognizable from the disappearance of the dome initially formed on the fabric by the drop.
  • This time in seconds is given in table 1 as "hydrophilicity" (average value of the individual results at various places on the surface of the fabric). A lower value accordingly means more rapid wetting and greater hydrophilicity.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)

Claims (10)

  1. Composition sous la forme d'une solution aqueuse ou d'une dispersion aqueuse qui comprend les composants suivants :
    A) un polydiorganosiloxane
    B) un amide d'acide gras quaternisé dérivé d'un amide d'acide gras de formule (Ia) ou de formule (Ib) ou de formule (Ic) par quaternisation d'un ou plusieurs atomes d'azote,

            R-CO-NR1- (CH2)a-NR1- (CHR2-CHR3-O)b-H     (Ia)

            R-CO-NH- (CH2) a-NH- (CH2) a-NH-Rk     (Ib)

            Rk-NH- (CH2)a-N (Rk) - (CH2) a-NH2     (Ic)

    ou un mélange de tels amides d'acides gras quaternisés,
    dans laquelle les anions attribués aux atomes d'azote quaternisés sont choisis parmi les anions chlorure, les anions méthylsulfate, les anions benzènesulfonate
    ou les anions toluènesulfonate, de préférence les anions toluènesulfonate ou les anions benzènesulfonate,
    dans laquelle
    R est un radical alkyle linéaire ou ramifié ayant 6 à 24 atomes de carbone,
    tous les radicaux Rk, indépendamment les uns des autres, sont H ou -CO-R, mais où dans la formule (Ic) au moins un des radicaux Rk est -CO-R,
    tous les radicaux R1, indépendamment les uns des autres, sont un hydrogène, un radical alkyle linéaire ou ramifié ayant 1 à 8 atomes de carbone ou sont un radical -(CHR2-CHR3-O)b-H,
    dans chaque motif - (CHR2-CHR3-O) un des radicaux R2 et R3 est un hydrogène et l'autre est un hydrogène ou CH3, a est un nombre de 2 à 6 et b est un nombre de 1 à 24.
  2. Composition selon la revendication 1, caractérisée en ce qu'elle est une dispersion aqueuse qui comprend additionnellement, comme composant C), un dispersant ou un mélange de dispersants.
  3. Composition selon la revendication 1 ou 2, caractérisée en ce que le composant A) est un polydiorganosiloxane, dont les deux groupes terminaux sont formés par des motifs de formule R5R4 2Si-O- et qui contient, dans la chaîne polysiloxane, des motifs de formule (II)

            -Si (R4)2-O-     (II)

    et des motifs de formule (III)

            -Si (R4) (X) -O-     (III)

    dans laquelle
    R4 est un radical alkyle ayant 1 à 4 atomes de carbone ou le radical phényle et R5 est R4 ou est OR4 ou est OH,
    tous les radicaux X, indépendamment les uns des autres, sont un radical de formule (IV)

            -R6- (CHR2- CHR3 - O) b - R7     (IV)

    ou de formule (V)

            -R6- [NR1-R6] c-NR1 2     (V)

    dans laquelle R1, R2, R3 et b ont les significations données à la revendication 1 et c a la valeur 0, 1 ou 2,
    tous les radicaux R6, indépendamment les uns des autres, sont dans chaque cas un radical alkylène divalent ramifié ou non ramifié ayant 2 à 6 atomes de carbone et
    R7 est H ou CH3,
    ou dans laquelle un ou plusieurs des radicaux X est un radical dérivé d'un radical de formule (V) tel qu'un ou plusieurs des atomes d'azote présents soit sous forme quaternisée.
  4. Composition selon la revendication 3, caractérisée en ce que 80 à 100 % de tous les radicaux R4 présents sont des radicaux méthyle.
  5. Composition selon la revendication 3 ou 4, caractérisée en ce que le composant A) est un polydiorganosiloxane, dont les groupes terminaux sont formés par des motifs de formule

            (CH3) 3Si-O-

    et qui a, dans la chaîne polysiloxane, des motifs de formule

            - Si (CH3)2 -O-

    et de formule (VI)

            -Si(CH3) (X1)-O-     (VI)

    dans laquelle tous les radicaux X1, indépendamment les uns des autres, sont un radical de formule (VII)

            -(CH2)a-(CHR2-CHR3-O)d-H     (VII)

    dans laquelle d est un nombre de 6 à 24 et R2 et R3 mit les significations données à la revendication 1,
    ou sont un radical de formule (VIII)

            - (CH2) a- [NR1- (CH2) a] c-NR12     (VIII)

    dans laquelle a est un nombre de 2 à 6 et c a la valeur 0, 1 ou 2,
    ou sont un radical dérivé d'un radical de formule (VIII) tel qu'un ou plusieurs atomes d'azote sont sous forme quaternisée.
  6. Composition selon la revendication 5, caractérisée en ce que le composant A) contient aussi bien des radicaux de formule (VI) dans laquelle X1 est un radical de formule (VII), que des radicaux de formule (VI) dans laquelle X1 est un radical de formule (VIII), ou est un radical de formule (VIII) dans laquelle un ou plusieurs atomes d'azote sont sous forme quaternisée.
  7. Composition selon une ou plusieurs des revendications 1 à 6, caractérisée en ce que le composant B) est un alcanolamide d'acide gras quaternisé dérivé d'un alcanolamide d'acide gras de formule (IX)

            R-CO-NH-CH2CH2-NH-CH2CH2OH     (IX)

    dans laquelle R a la signification donnée à la revendication 1, dérivé de sorte qu'un atome d'azote soit sous forme quaternisée.
  8. Composition selon une ou plusieurs des revendications 1 à 7, caractérisée en ce qu'elle comprend 3 à 70 % en poids de composant A)
    2 à 30 % en poids de composant B)
    0 à 30 % en poids de composant C)
    et
    20 à 95 % en poids d'eau.
  9. Utilisation d'une composition selon une ou plusieurs des revendications 1 à 8 pour le traitement de matériaux fibreux.
  10. Utilisation selon la revendication 9, caractérisée en ce que les matériaux fibreux sont des tissus sous la forme de tissus ou de tricots et que le traitement avec la composition s'effectue dans le cadre de la finition textile à l'état non terminé.
EP02779364A 2001-09-25 2002-09-17 Compositions de polysiloxanes et amides d'acides gras quaternises Expired - Lifetime EP1432765B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10147210 2001-09-25
DE10147210 2001-09-25
PCT/EP2002/010416 WO2003029351A1 (fr) 2001-09-25 2002-09-17 Compositions de polysiloxanes et amides d'acides gras quaternises

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EP1432765A1 EP1432765A1 (fr) 2004-06-30
EP1432765B1 true EP1432765B1 (fr) 2006-10-11

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AT (1) ATE342310T1 (fr)
DE (1) DE60215370T2 (fr)
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI0415126A (pt) * 2003-10-07 2006-11-28 Clariant Finance Bvi Ltd polissiloxanos quaternários múltiplos
US7511165B2 (en) 2004-10-04 2009-03-31 Clariant Finance (Bvi) Limited Amino-functional silicone waxes

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5183845A (en) * 1990-01-16 1993-02-02 Siltech Inc. Polymer treatment compositions
DE4222483A1 (de) * 1992-07-09 1994-01-13 Pfersee Chem Fab Organosiloxane mit Stickstoff enthaltenden und mit Äthergruppierungen enthaltenden Resten
DE19652524C2 (de) * 1996-12-17 2003-08-14 Rudolf Gmbh & Co Kg Chem Fab Organopolysiloxane enthaltende Emulsionen, deren Herstellung und Verwendung in wäßrigen Systemen

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DE60215370T2 (de) 2007-08-16
EP1432765A1 (fr) 2004-06-30
ATE342310T1 (de) 2006-11-15
ES2274105T3 (es) 2007-05-16
DE60215370D1 (de) 2006-11-23
WO2003029351A1 (fr) 2003-04-10

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