DE10036533B4 - Use of polyquaternary polysiloxanes as washable hydrophilic plasticizers - Google Patents

Abstract

worin Z der Rest

ist, worin R⁶, R⁷, R⁸ C₁-C₂₂-Alkylreste sind und mindestens einer der Reste R⁶, R⁷, R⁸ mindestens 10 Kohlenstoffatome aufweist, R⁹, R¹⁰, R¹², R¹⁴, R¹⁵ C₁-C₂₂-Alkylreste sind, R¹¹ ein -O- oder -NR¹³- Rest ist, worin R¹³ C₁-C₄-Alkyl oder Wasserstoff ist, s = 2 bis 4, und
M ein zweiwertiger Rest, ausgewählt aus der Gruppe

ist, worin das N-Atom des Restes Z mit dem Rest M über das zur C-OH Gruppe im Rest M benachbarte Kohlenstoffatom verbunden ist, r eine Zahl von 0 bis 200 und B ein anorganisches oder organisches Anion ist, als Weichmacher in auf anionischen/nichtionischen Tensiden beruhenden Formulierungen zur Textilwäsche.Use of polysiloxanes of the general formula (III),

wherein Z is the radical

wherein R ⁶ , R ⁷ , R ^{8 are} C ₁ -C ₂₂ -alkyl radicals and at least one of R ⁶ , R ⁷ , R ^{8 has} at least 10 carbon atoms, R ⁹ , R ¹⁰ , R ¹² , R ¹⁴ , R ^{15 are} C ₁ -C ₂₂ -alkyl radicals, R ^{11 is} an -O- or -NR ¹³ - radical, wherein R ^{13 is} C ₁ -C ₄ -alkyl or hydrogen, s = 2 to 4, and
M is a divalent radical selected from the group

in which the N atom of the radical Z is connected to the radical M via the carbon atom adjacent to the C-OH group in the radical M, r is a number from 0 to 200 and B is an inorganic or organic anion, as a plasticizer in on anionic / nonionic surfactant based textile laundering formulations.

Description

The This invention relates to the use of polyquaternary polysiloxanes.

Polysiloxanes which contain amino groups and are used as textile softening agents are already known from US Pat EP 441 530 A2 known. The US 5 591 880 A and US 5 650 529 A disclose the introduction of ethylene oxide / propylene oxide moieties modified amino structures as side chains, which produce an improvement in the effect as a textile plasticizer. The alkylene oxide units allow the targeted adjustment of the hydrophilic-hydrophobic balance. Disadvantageous in the preparation of the compounds in the synthesis is the difficult entrapped esterification of amino alcohols with siloxane-bound carboxylic acid groups. Additional difficulties arise in terms of plasticizing properties due to the general comb structure of the products. The US 5 807 956 A and the US 5,981,681 A describe to eliminate these disadvantages that α, ω-epoxy-modified siloxanes are reacted with α, ω-amino-functionalized alkylene oxides, and to use these products as hydrophilic plasticizers.

To improve substantivity, attempts have been made to introduce quaternary ammonium groups into alkylene oxide-modified siloxanes. Branched alkylene oxide-modified quaternary polysiloxanes can be synthesized by condensation of α, ω-OH-terminated polysiloxanes and trialkoxysilanes. The quaternary ammonium structure is introduced via the silane, the quaternary nitrogen atom being substituted by alkylene oxide units, as in US Pat US Pat. No. 5,625,024 disclosed. Strictly comb-like alkylene oxide-modified quaternary polysiloxanes are already in the US 5 098 979 A described. The hydroxyl groups of comb-like substituted polyethersiloxanes are converted with epichlorohydrin into the corresponding chlorohydrin derivatives. This is followed by quaternization with tertiary amines. A disadvantage of this synthesis is the use of epichlorohydrin and the relatively low reactivity of the chlorohydrin moiety during quaternization.

For this reason, the hydroxyl groups of comb-substituted polyether siloxanes are alternatively esterified with chloroacetic acid. By Carbonylaktivierung the final quaternization can be accomplished, as in the US 5 153 294 A of the US 5,166,297 A. disclosed.

A fundamentally different approach reveals the DE 32 36 466 A1 , The reaction of OH-terminated siloxanes with quaternary ammonium-containing alkoxysilanes provides reactive intermediates which are to crosslink with suitable crosslinking agents such as trialkoxysilanes on the fiber surface to wash-resistant layers. A major disadvantage of this approach is that the stability required for hours of an aqueous finishing bath can not be guaranteed and unforeseen crosslinking reactions in the bathroom can occur even before the textile finish.

The EP 0 282 720 A2 describes polyquaternary polysiloxane polymers, their preparation by reaction of α, ω-diepoxides with tertiary amines in the presence of acids and use in cosmetic preparations as hair treatment agents.

The WO 96/26260 A1 discloses the use of the diquaternary polysiloxanes in cleaning compositions for hard surfaces. In these formulations may a maximum of 1% of the total surfactants anionic surfactants, as the Presence of anionic surfactants to form complexes with the cationic polysiloxane compounds, so its effectiveness be robbed. There was therefore a prejudice that used according to the invention Polysiloxane compounds to be used in applications involving the use of larger amounts of anionic surfactants require.

The DE 19944416 A1 discloses a rinse aid containing the siloxanes used in the invention. The rinse aid serves for use in dishwashing detergents and in particular leads to a shortening of the drying time of the substrates to be treated with their hard surface. There is no reference to laundry detergent formulations for textile laundry. The surfaces of textile fibers and dishwashing substrates, such as ceramic substrates, are by nature not comparable in their properties. The expert could thus the DE 19944416 A1 do not refer to the use of the cationic siloxane compounds in detergent formulations. This applies analogously to the DE 19853720 A1 , which discloses general purpose hard surface cleaners containing the siloxanes used in the invention.

Furthermore, structurally different cationic polysiloxanes are known from WO 99/32539 A1. The authors of WO 99/32539 A1 express their expectation that these polysiloxanes can be used in conventional applications of cationic polymers and siloxane polymers. As expected, these applications also include such applications as cosmetic applications and fiber treatment applications. However, there is no indication of the use of the cationic polysiloxanes disclosed therein in laundry detergent formulations containing textile surfactants containing anionic surfactants. The person skilled in the art could thus find no indication of the use of the siloxanes according to the invention in detergent formulations containing anionic surfactants in WO 99/32539 A1.

Out The prior art is not a satisfactory solution to the problem been found for advanced silicone typical soft feel and pronounced hydrophilicity after original equipment one To ensure that textile material is if this is the attack of aggressive detergent formulations in Course of repeated washing processes if necessary. elevated temperature is suspended.

In the EP 0 282 720 A2 describes a process for preparing compounds, in which the reaction of α, ω-diepoxides with di-tertiary amine in the presence of acids to polymeric structures. A preparation on quaternary Z ¹ and Z ² groups has not been disclosed.

task Therefore, it has been the plasticizer of the present invention find a silicate-typical soft feel and a pronounced hydrophilicity lend this property image even after exposure to Detergent formulations, after repeated washing processes possibly elevated Temperature is not lost.

worin Z der Rest

ist, worin R⁶, R⁷, R⁸ C₁-C₂₂-Alkylreste sind und mindestens einer der Reste R⁶, R⁷, R⁸ mindestens 10 Kohlenstoffatome aufweist, R⁹, R¹⁰, R¹², R¹⁴, R¹⁵ C₁-C₂₂-Alkylreste sind, R¹¹ ein -O- oder -NR¹³- Rest ist, worin R¹³ C₁-C₄-Alkyl oder Wasserstoff ist, s = 2 bis 4, und
M ein zweiwertiger Rest, ausgewählt aus der Gruppe

ist, worin das N-Atom des Restes Z mit dem Rest M über das zur C-OH Gruppe im Rest M benachbarte Kohlenstoffatom verbunden ist, r eine Zahl von 0 bis 200 und B ein anorganisches oder organisches Anion ist, als Weichmacher in auf anionischen/nichtionischen Tensiden beruhenden Formulierungen zur Textilwäsche, insbesondere die Verwendung in Waschmitteln für Textilien sowie die Bereitstellung von Waschmittelformulierungen für Textilien, enthaltend anionische und nichtionische Tenside sowie mindestens ein Polysiloxan der allgemeinen Formel (III).The present invention therefore provides the use of polysiloxanes of the general formula (III)

wherein Z is the radical

wherein R ⁶ , R ⁷ , R ^{8 are} C ₁ -C ₂₂ -alkyl radicals and at least one of R ⁶ , R ⁷ , R ^{8 has} at least 10 carbon atoms, R ⁹ , R ¹⁰ , R ¹² , R ¹⁴ , R ^{15 are} C ₁ -C ₂₂ -alkyl radicals, R ^{11 is} an -O- or -NR ¹³ - radical, wherein R ^{13 is} C ₁ -C ₄ -alkyl or hydrogen, s = 2 to 4, and
M is a divalent radical selected from the group

in which the N atom of the radical Z is connected to the radical M via the carbon atom adjacent to the C-OH group in the radical M, r is a number from 0 to 200 and B is an inorganic or organic anion, as a plasticizer in on anionic / nonionic surfactant-based formulations for textile washing, in particular the use in laundry detergents for textiles and the provision of laundry detergent formulations for textiles containing anionic and nonionic surfactants and at least one polysiloxane of the general formula (III).

The radicals R ⁶ , R ⁷ , R ⁸ , and the radicals R ⁹ , R ¹⁰ , R ¹² , R ¹⁴ and R ¹⁵ may be the same or different in the molecule. Preference is given to those compounds in which two of the radicals R ⁶ , R ⁷ , R ^{8 are} lower alkyl radicals having 1 to 4 carbon atoms and the remaining third radical is a long-chain hydrocarbon radical having at least 10 carbon atoms. Among the long-chain hydrocarbon radicals, preference is given in particular to saturated and unsaturated branched or unbranched hydrocarbon radicals which are derived from the naturally occurring fatty acids.

If the radicals R ⁹ , R ¹⁰ and R ¹² are present next to one another, those compounds are preferred in which R ⁹ and R ^{10 are} a lower hydrocarbon radical having 1 to 4 carbon atoms and the radical R ^{12 is derived} from a fatty acid R ¹² COOH, which has at least 8 carbon atoms.

In EP 0 282 720 A2 and DE 37 19 086 C1 describes the use of the respectively disclosed compounds in cosmetic formulations, especially in hair care. As advantages are generally improved combability, a good gloss, high antistatic effectiveness and preferably in EP 0 282 720 A2 called an improved washout resistance.

The latter property is not to be equated with a washing resistance in the sense of the invention. While hair washout refers to the brief attack of primarily water and very mild non-irritating surfactants, wash resistant, hydrophilic fabric softeners are designed to withstand the attack of concentrated surfactant solutions having high fat and soil release properties. To these surfactant systems, highly alkaline complexing agents, oxidative bleaching agents and complex enzyme systems are added in modern detergents. The action is often over hours at elevated temperatures. For these reasons, a transfer of experience in the field of cosmetics in the field of wash-resistant fabric softeners is not possible. The DE 32 36 466 A1 discloses that in order to achieve a wash resistant textile finish, crosslinkable systems would have to be resorted to.

It was also not deducible that the compounds according to EP 0 282 720 A2 and DE 37 19 086 C1 can be advantageously used as internal plasticizers in formulations based on anionic / nonionic surfactants for washing textiles and fibers. For this case, the considerations made on the aggressive detergent systems, the elevated temperatures and long exposure times also apply.

Claims (2)

Use of polysiloxanes of the general formula (III),

wherein Z is the radical

wherein R ⁶ , R ⁷ , R ^{8 are} C ₁ -C ₂₂ -alkyl radicals and at least one of R ⁶ , R ⁷ , R ^{8 has} at least 10 carbon atoms, R ⁹ , R ¹⁰ , R ¹² , R ¹⁴ , R ^{15 are} C ₁ -C ₂₂ -alkyl radicals, R ^{11 is} an -O- or -NR ¹³ radical in which R ^{13 is} C ₁ -C ₄ -alkyl or hydrogen, s = 2 to 4, and M is a bivalent radical, selected from the group

in which the N atom of the radical Z is connected to the radical M via the carbon atom adjacent to the C-OH group in the radical M, r is a number from 0 to 200 and B is an inorganic or organic anion, as a plasticizer in on anionic / nonionic surfactant based textile laundering formulations. Detergent formulation for textiles containing anionic and nonionic surfactants and at least one polysiloxane of the general Formula (III) as defined in claim 1.