DE10036533A1 - Production of polyquaternary polysiloxanes, useful as wash-resistant fabric conditioners, comprises reacting hydrogen-terminal dimethylpolysiloxane with olefin-terminal epoxide, and reacting with mixture of tertiary and ditertiary amines - Google Patents

Production of polyquaternary polysiloxanes, useful as wash-resistant fabric conditioners, comprises reacting hydrogen-terminal dimethylpolysiloxane with olefin-terminal epoxide, and reacting with mixture of tertiary and ditertiary amines

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Publication number
DE10036533A1
DE10036533A1 DE2000136533 DE10036533A DE10036533A1 DE 10036533 A1 DE10036533 A1 DE 10036533A1 DE 2000136533 DE2000136533 DE 2000136533 DE 10036533 A DE10036533 A DE 10036533A DE 10036533 A1 DE10036533 A1 DE 10036533A1
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Prior art keywords
alkyl
radical
group
radicals
formula
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DE2000136533
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German (de)
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DE10036533B4 (en
Inventor
Horst Lange
Roland Wagner
Anita Witossek
Karl-Heinz Stachulla
Siegfried Teuber
Albert Schnering
Annette Moeller
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Momentive Performance Materials GmbH
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GE Bayer Silicones GmbH and Co KG
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Priority to DE10066215A priority Critical patent/DE10066215B4/en
Priority to DE2000136533 priority patent/DE10036533B4/en
Priority claimed from DE10066215A external-priority patent/DE10066215B4/en
Publication of DE10036533A1 publication Critical patent/DE10036533A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742—Nitrogen containing silicones
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences

Abstract

Production of polyquaternary polysiloxanes (I) comprises reacting a hydrogen-terminal dimethylpolysiloxane with an olefin-terminal epoxide and reacting the product with a mixture of a tertiary amine and a ditertiary amine in the presence of an acid. Production of polyquaternary polysiloxanes of formula (I) comprises: (a) reacting a hydrogen-terminal dimethylpolysiloxane of formula (II) with 1.0-1.5 moles (per SiH group) of an epoxide having a terminal olefinic bonds and comprising at least 4C atoms and optionally a noncyclic ether group, in the presence of a hydrosilylation catalyst at 50-150 deg C; (b) removing excess epoxide; and (c) reacting the product with a mixture of a tertiary amine (NR<1>R<2>R<5>) and a ditertiary amine (R<1>R<2>N-Y-NR<3>R<4>) in the presence of an acid (HA) at 40-120 deg C, the molar ratio of epoxide groups to tertiary amino groups to HA being 1:1:1. X = a divalent hydrocarbon group with at least 4 C atoms, optionally substituted by OH and/or interrupted by O; Y = a divalent hydrocarbon group with at least 2C atoms, optionally substituted by OH and/or interrupted by O or N; Z<1>, Z<2> = bonds forming a cyclic structure, or Z<1> is H, OH, alkyl, alkoxy, OH-substituted \-4C hydrocarbyl (optionally interrupted by one or more O atoms) or a group of formula (i) or (ii) and Z<2> is a group of formula (iii); R<5> = 1-20C alkyl; R<1>-R<4> = 1-4C alkyl or benzyl, or R<1>+R<3> and/or R<2>+R<4> are alkylene; A<-> = an anion; n = 5-20; and m = 1 or more. An Independent claim is also included for wash-resistant diquaternary polysiloxanes of formula (III): Z = a group of formula (iv)-(vi); R<6>-R<8> = optionally OH-substituted 1-22C alkyl or 2-22C alkenyl, at least one having \-10C atoms; R<9>, R<10>, R<12>, R<14>, R<15> = optionally OH-substituted 1-22C alkyl or 2-22C alkenyl; R<11> = O or NR<13>; R<13> = H, 1-4C alkyl or 1-4C hydroxyalkyl; s = 2-4; M = a group of formula (vii)-(xviii) in which the asterisked bond is attached to the N atoms of Z; r = 0-200; and B = anion.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von polyquarternären Polysiloxanen und deren Verwendung als waschbeständige hydrophile Weichmacher.The invention relates to a method for producing polyquaternary Polysiloxanes and their use as washable hydrophilic plasticizers.

Polysiloxane, die Aminogruppen enthalten und als textile Weichmacher verwendet werden, sind bereits aus der EP-A-441 530 bekannt. Die US 5 591 880 und US 5 650 529 offenbaren die Einführung von durch Ethylenoxid-/Propylenoxideinheiten modi­ fizierten Aminostrukturen als Seitenketten, die eine Verbesserung des Effekts als textiler Weichmacher hervorrufen. Die Alkylenoxideinheiten erlauben hierbei die gezielte Einstellung der hydrophilen-hydrophoben Balance. Nachteilig bei der Herstellung der Verbindungen in der Synthese ist die schwierige eingeschlossene Veresterung von Aminoalkoholen mit siloxangebundenen Carbonsäuregruppen. Zusätzliche Schwierigkeiten ergeben sich bezüglich der weichmachenden Eigenschaften durch die generelle Kammstruktur der Produkte. Die US 5 807 956 und die US 5 981 681 beschreiben zur Beseitigung dieser Nachteile, daß α,ω- epoxydmodifizierte Siloxane mit α,ω-aminofunktionalisierten Alkylenoxiden umgesetzt werden sollen, und diese Produkte als hydrophile Weichmacher einzusetzen.Polysiloxanes containing amino groups and used as textile softeners are already known from EP-A-441 530. U.S. 5,591,880 and U.S. 5,650,529 disclose the introduction of modes by ethylene oxide / propylene oxide units fected amino structures as side chains, which improve the effect as cause textile softener. The alkylene oxide units allow this targeted adjustment of the hydrophilic-hydrophobic balance. A disadvantage of the Making the compounds in the synthesis is the difficult one included Esterification of amino alcohols with siloxane-linked carboxylic acid groups. Additional difficulties arise with the softening Properties due to the general comb structure of the products. US 5,807,956 and US Pat. No. 5,981,681 describe to eliminate these disadvantages that α, ω- epoxy-modified siloxanes with α, ω-amino-functionalized alkylene oxides  to be implemented, and these products as hydrophilic plasticizers use.

Zur Verbesserung der Substantivität sind Versuche unternommen worden, quarternäre Ammoniumgruppen in alkylenoxidmodifizierte Siloxane einzuführen. Verzweigte alkylenoxidmodifizierte quarternäre Polysiloxane können durch Kondensation von α,ω-OH-terminierten Polysiloxanen und Trialkoxysilanen synthetisiert werden. Die quarternäre Ammoniumstruktur wird über das Silan eingebracht, wobei das quarternäre Stickstoffatom durch Alkylenoxideinheiten substituiert ist, wie in der US 5 625 024 offenbart. Streng kammartige alkylenoxidmodifizierte quarternäre Poly­ siloxane sind bereits in der US 5 098 979 beschrieben. Die Hydroxylgruppen von kammartig substituierten Polyethersiloxanen werden mit Epichlorhydrin in die entsprechenden Chlorhydrinderivate überführt. Daran schließt sich eine Quaternierung mit tertiären Aminen an. Nachteilig an dieser Synthese ist die Verwendung von Epichlorhydrin und die relativ geringe Reaktivität der Chlorhydrin- Gruppierung während der Quaternierung.Attempts have been made to improve the substantivity, quaternary Introduce ammonium groups in alkylene oxide-modified siloxanes. branched alkylene oxide-modified quaternary polysiloxanes can by condensation of α, ω-OH-terminated polysiloxanes and trialkoxysilanes can be synthesized. The quaternary ammonium structure is introduced over the silane, the quaternary nitrogen atom is substituted by alkylene oxide units, as in US Pat. No. 5,625,024 disclosed. Strictly comb-like alkylene oxide-modified quaternary poly siloxanes have already been described in US Pat. No. 5,098,979. The hydroxyl groups of Comb polyethersiloxanes substituted with epichlorohydrin in the corresponding chlorohydrin derivatives transferred. This is followed by one Quaternization with tertiary amines. The disadvantage of this synthesis is that Use of epichlorohydrin and the relatively low reactivity of chlorohydrin Grouping during quaternization.

Aus diesem Grund werden die Hydroxylgruppen kammartig substituierter Polyethersiloxane alternativ mit Chloressigsäure verestert. Durch die Carbonylaktivierung kann die abschließende Quaternierung erleichtert vollzogen werden, wie in der US 5 153 294 und der US 5 166 297 offenbart.For this reason, the hydroxyl groups are substituted like a comb Alternatively, polyether siloxanes are esterified with chloroacetic acid. Through the The final quaternization can be carried out more easily by carbonony activation as disclosed in US 5,153,294 and US 5,166,297.

Einen grundsätzlich anderen Ansatz offenbart die DE-OS 32 36 466. Die Umsetzung von OH-terminierten Siloxanen mit quarternäre Ammoniumstrukturen enthaltenden Alkoxysilanen liefert reaktive Zwischenprodukte, die mit geeigneten Vernetzungs­ agenzien, wie Trialkoxysilanen, auf der Faseroberfläche zu waschbeständigen Schichten vernetzen sollen. Ein wesentlicher Nachteil dieses Ansatzes ist es, daß die über Stunden notwendige Stabilität eines wässrigen Ausrüstungsbades nicht garantiert werden kann und unvorhergesehene Vernetzungsreaktionen im Bad bereits vor der Textilausrüstung auftreten können.DE-OS 32 36 466 discloses a fundamentally different approach. The implementation of OH-terminated siloxanes containing quaternary ammonium structures Alkoxysilanes provides reactive intermediates with suitable crosslinking agents, such as trialkoxysilanes, on the fiber surface to be wash-resistant Network layers. A major disadvantage of this approach is that the The stability of an aqueous equipment bath that is necessary for hours is not guaranteed can be and unforeseen cross-linking reactions in the bathroom before the Textile equipment can occur.

Die EP-A-0 282 720 beschreibt polyquarternäre Polysilxan-Polymere, deren Herstel­ lung durch Reaktion von α,ω-Diepoxiden mit tertiären Aminen in Gegenwart von Säuren und Verwendung in kosmetischen Zubereitungen als Haarbehandlungsmittel.EP-A-0 282 720 describes polyquaternary polysilxane polymers, the manufacturers of which by reaction of α, ω-diepoxides with tertiary amines in the presence of Acids and use in cosmetic preparations as hair treatment agents.

Aus dem Stand der Technik sind keine befriedigenden Lösungen für das Problem gefunden worden, den für fortschrittliche Silicone typischen weichen Griff und die ausgeprägte Hydrophilie nach Erstausrüstung eines Textilmaterials auch dann zu gewährleisten, wenn dieses dem Angriff aggressiver Detergenzienformulierungen im Verlauf wiederholter Waschprozesse bei gegebenenfalls erhöhter Temperatur ausgesetzt wird.There are no satisfactory solutions to the problem from the prior art have found the soft grip typical of advanced silicones and the  pronounced hydrophilicity even after initial equipping of a textile material ensure if this is attacked by aggressive detergent formulations in the Course of repeated washing processes at an optionally elevated temperature is exposed.

In der EP-A-0 282 720 wird ein Verfahren zur Herstellung von Verbindungen, beschrieben, in der die Reaktion von α,ω-Diepoxiden mit di-tertiärem Aminen in Gegenwart von Säuren zu polymeren Strukturen erfolgt. Eine Herstellung über quarternäre Z1 und Z2-Gruppen ist nichts offenbart worden.EP-A-0 282 720 describes a process for the preparation of compounds in which the reaction of α, ω-diepoxides with di-tertiary amines takes place in the presence of acids to give polymeric structures. Production via quaternary Z 1 and Z 2 groups has not been disclosed.

Aufgabe der vorliegenden Erfindung ist es deshalb gewesen, ein verbessertes Verfahren zur Herstellung von polyquarternären Polysiloxan-Polymere und weitere Applikationen für diese Verbindungen zur Verfügung zu stellen. Hierbei handelt es sich um die Applikationen auf Textilien, da Silicone einen silicontypischen weichen Griff und eine ausgeprägte Hydrophilie verleihen, wobei dieses Eigenschaftsbild auch nach Einwirkung von Detergenzienformulierungen, nach wiederholten Waschprozessen bei gegebenenfalls erhöhter Temperatur nicht verloren geht.The object of the present invention has therefore been to provide an improved one Process for the preparation of polyquaternary polysiloxane polymers and others To provide applications for these connections. This is what it is about the applications on textiles, since silicones give way to a typical silicone Give grip and a pronounced hydrophilicity, whereby this property profile also after exposure to detergent formulations, after repeated Washing processes at a possibly elevated temperature are not lost.

Ein Gegenstand der vorliegenden Erfindung ist es dementsprechend gewesen, ein verbessertes Verfahren zur Herstellung der di- oder polyquarternären Polysiloxan- Polymere der allgemeinen Formel (I)
Accordingly, it was an object of the present invention to provide an improved process for the preparation of the di- or polyquaternary polysiloxane polymers of the general formula (I)

und/oder lineare Verbindungen der allgemeinen Formel (II)
and / or linear compounds of the general formula (II)

worin X ein zweiwertiger Kohlenwasserstoffrest mit mindestens 4 Kohlenstoffatomen ist, der eine Hydroxylgruppe aufweist und der durch ein Sauerstoffatom unterbrochen sein kann, Y ein zweiwertiger Kohlenwasserstsoffrest mit mindestens 2 Kohlenstoffatomen ist, der eine Hydroxylgruppe aufweisen und der durch ein Sauerstoff- oder Stickstoffatom unterbrochen sein kann, Z1 ein H, OH, ein Alkyl- oder ein Alkoxyrest ist, oder die Bedeutung eines Kohlenwasserstoffrestes mit mindestens 4 Kohlenstoffatomen hat, der eine oder mehrere Hydroxylgruppe(n) aufweist und durch eine oder mehrere Sauerstoffatome unterbrochen sein kann oder die Bedeutung des Restes
wherein X is a divalent hydrocarbon radical with at least 4 carbon atoms, which has a hydroxyl group and which can be interrupted by an oxygen atom, Y is a divalent hydrocarbon radical with at least 2 carbon atoms, which have a hydroxyl group and which can be interrupted by an oxygen or nitrogen atom, Z 1 is an H, OH, an alkyl or an alkoxy radical, or has the meaning of a hydrocarbon radical with at least 4 carbon atoms, which has one or more hydroxyl group (s) and can be interrupted by one or more oxygen atoms, or the meaning of the rest

hat, wobei R5 ein C1-C20-Alkylrest, Z2 die Gruppe
has, where R 5 is a C 1 -C 20 alkyl radical, Z 2 the group

R1, R2, R3 und R4 gleich oder verschieden sind und C1-C4-Alkylreste oder Benzylreste bedeuten oder jeweils die Reste R1 und R3 oder R2 und R4 Bestandteile eines verbrückenden Alkylenrestes sein können, A- ein anorganisches oder organisches Anion ist, n 5 bis 20 und, m ganze Zahl ≧ 1,
und durch die Umsetzung von α,ω-Wasserstoffpolysiloxane der allgemeinen Formel
R 1 , R 2 , R 3 and R 4 are identical or different and mean C1-C4-alkyl radicals or benzyl radicals or the radicals R 1 and R 3 or R 2 and R 4 can each be components of a bridging alkylene radical, A - an inorganic one or organic anion, n is 5 to 20 and, m is an integer ≧ 1,
and by the reaction of α, ω-hydrogen polysiloxanes of the general formula

mit, bezogen auf SiH-Gruppen 1,0 bis 1,5 mol eines Epoxides, mit endständigen olefinischen Bindungen, worin das Epoxid mindestens 4 Kohlenstoffatome besitzt und zusätzlich eine nichtcyclische Ethergruppe enthalten kann, in Gegenwart eines Hydrosilylierungskatalysators bei Temperaturen von 50 bis 150°C umgesetzt wird, der Überschuß an olefinischem Epoxid entfernt, und das Reaktionsprodukt mit einer Mischung aus einem tertiären Amin der Formel
with, based on SiH groups, 1.0 to 1.5 mol of an epoxide, with terminal olefinic bonds, in which the epoxide has at least 4 carbon atoms and may additionally contain a noncyclic ether group, in the presence of a hydrosilylation catalyst at temperatures from 50 to 150 ° C. is implemented, the excess of olefinic epoxide is removed, and the reaction product with a mixture of a tertiary amine of the formula

und einem di-tertiärem Amin der Formel
and a di-tertiary amine of the formula

in Gegenwart von Säuren HA bei 40 bis 120°C umsetzt wird, wobei das molare Verhältnis von Epoxidgruppen zu tertiären Aminogruppen und zu den Säuren HA 1 : 1 : 1 beträgt.is reacted in the presence of acids HA at 40 to 120 ° C, the molar Ratio of epoxy groups to tertiary amino groups and to the acids HA 1: 1: 1 is.

In einer weiteren Ausführungsform der vorliegenden Erfindung werden die tertiären und di-tertiären Amine in einem molaren Verhältnis, bezogen auf Aminogruppen, von 0,001 zu 0,999 bis 0,9 zu 0,1 eingesetzt.In a further embodiment of the present invention, the tertiary and di-tertiary amines in a molar ratio, based on amino groups, of 0.001 to 0.999 to 0.9 to 0.1.

In einer weiteren Ausführungsform der vorliegenden Erfindung werden bevorzugt molare Verhältnisse der Aminogruppen der tertiären Aminen zu den di-tertiären Aminen verwendet von 0,001 zu 0,999 bis 0,5 zu 0,5.In a further embodiment of the present invention are preferred molar ratios of the amino groups of the tertiary amines to the di-tertiary Amines used from 0.001 to 0.999 to 0.5 to 0.5.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung wird ein molares Verhältnis von 0,01 zu 0,99 bis 0,2 zu 0,8 eingesetzt.In a preferred embodiment of the present invention, a molar ratio of 0.01 to 0.99 to 0.2 to 0.8 used.

Die Struktur der tertiären Amine ergibt sich aus den Definitionen für R1, R2 und R5. In einer bevorzugten Ausführungsform werden Trimethylamin, Dimethylethylamin, Dimethylpropylamin, Dimethylbutylamin, Dimethylhexylamin, Dimethyloctylamin, Dimethyldecylamin, Dimethyldodecylamin, Dimethyltetradecylamin, Dimethyl­ hexadecylamin, Dimethyl-octadecylamin verwendet.The structure of the tertiary amines results from the definitions for R 1 , R 2 and R 5 . In a preferred embodiment, trimethylamine, dimethylethylamine, dimethylpropylamine, dimethylbutylamine, dimethylhexylamine, dimethyloctylamine, dimethyldecylamine, dimethyldodecylamine, dimethyltetradecylamine, dimethylhexadecylamine, dimethyloctadecylamine are used.

Vorzugsweise werde als Anion B- physiologisch vertretbare anorganische Reste aus der Gruppe bestehend aus Chlorid, Bromid, Hydrogensulfat oder Sulfat, oder organische Reste aus der Gruppe bestehend aus Acetat, Propionat, Octanoat, Decanoat, Dodecanoat, Tetradecanoat, Hexadecanoat, Octadecanoat oder Oleat verwendet.Preferably used as anion B - physiologically acceptable inorganic residues from the group consisting of chloride, bromide, hydrogen sulfate or sulfate, or organic residues from the group consisting of acetate, propionate, octanoate, decanoate, dodecanoate, tetradecanoate, hexadecanoate, octadecanoate or oleate.

In einer weiteren Variante des vorliegenden Herstellungsverfahrens werden bevorzugt für die Verbindungen der Formel (I) und (II) für den Rest X
In a further variant of the present production process, preference is given to the compounds of the formula (I) and (II) for the radical X

verwendet, die in der EP-A-0 282 720 bereits beschrieben worden sind. In einer weiteren Ausführungsform wird für Y -(CH2)o-, mit einem Wert o bevorzugt von 2 bis 6 verwendet. Besonders bevozugt wird für die Reste R1, R2, R3, R4 Methyl verwendet.used, which have already been described in EP-A-0 282 720. In a further embodiment, Y is used for Y - (CH 2 ) o -, with a value o preferably from 2 to 6. Methyl is particularly preferably used for the radicals R 1 , R 2 , R 3 , R 4 .

Ein weiteren Gegenstand der vorliegenden Erfindung sind diquarternären Polysiloxanen der allgemeinen Formel (III),
The present invention further provides diquarternary polysiloxanes of the general formula (III)

worin Z
where Z

R6, R7, R8 C1-C22-Alkylreste oder C2-C22-Alkylenreste, und die Alkyl- oder Alkylenreste Hydroxylgruppen aufweisen können und mindestens einer der Reste R6, R7, R8 mindestens 10 Kohlenstoffatome aufweist, R9 , R10, R12, R14, R15 C1-C22- Alkylreste oder C2-C22Alkylenreste, und die Alkyl- oder Alkylenreste Hydroxylgruppen aufweisen können, R11 -O- oder -NR13- Rest, R13 C1-C4-Alkyl- oder Hydroxyalkylrest oder Wasserstoffrest, S 2 bis 4, M ein zweiwertiger Rest, ausgewählt aus der Gruppe
R 6 , R 7 , R 8 are C 1 -C 22 alkyl radicals or C 2 -C 22 alkylene radicals, and the alkyl or alkylene radicals can have hydroxyl groups and at least one of the radicals R 6 , R 7 , R 8 has at least 10 carbon atoms , R 9 , R 10 , R 12 , R 14 , R 15 C 1 -C 22 alkyl radicals or C 2 -C 22 alkylene radicals, and the alkyl or alkylene radicals can have hydroxyl groups, R 11 -O- or -NR 13 - Radical, R 13 C 1 -C 4 alkyl or hydroxyalkyl radical or hydrogen radical, S 2 to 4, M is a divalent radical selected from the group

Die Reste R6, R7, R8, sowie die Reste R9, R10, R12, R14 und R15 können im Molekül gleich oder verschieden sein. Bevorzugt sind solche Verbindungen, bei denen zwei der Reste R6, R7, R8 niedere Alkylreste mit 1 bis 4 Kohlenstoffatomen sind und der verbleibende dritte Rest ein langkettiger Kohlenwasserstoffrest mit mindestens 10 Kohlenstoffatomen ist. Unter den langkettigen Kohlenwasserstoffresten sind insbesondere gesättigte und ungesättigte verzweigte oder unverzweigte Kohlenwasserstoffreste bevorzugt, die sich von den natürlich vorkommenden Fettsäuren ableiten.The radicals R 6 , R 7 , R 8 and the radicals R 9 , R 10 , R 12 , R 14 and R 15 can be the same or different in the molecule. Preferred compounds are those 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 with at least 10 carbon atoms. Among the long-chain hydrocarbon radicals, particularly preferred are saturated and unsaturated branched or unbranched hydrocarbon radicals which are derived from the naturally occurring fatty acids.

Liegen die Reste R9, R10 und R12 nebeneinander vor, sind diejenigen Verbindungen bevorzugt, bei denen R9 und R10 einen niederen Kohlenwasserstofrest mit 1 bis 4 Kohlenstoffatomen bedeutet und der Rest R12 von einer Fettsäure R12COOH abgeleitet ist, die mindestens 8 Kohlenstoffatome aufweist. If the radicals R 9 , R 10 and R 12 are adjacent to one another, preference is given to those compounds 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-A-0 282 720 und DE-PS 37 19 086 wird die Verwendung der jeweils offenbarten Verbindungen in kosmetischen Formulierungen, speziell in der Haarpflege beschrieben. Als Vorteile werden generell eine verbesserte Kämmbarkeit, ein guter Glanz, eine hohe antistatische Effektivität und bevorzugt in EP-A-0 282 720 eine verbesserte Auswaschbeständigkeit genannt.EP-A-0 282 720 and DE-PS 37 19 086 describe the use of each disclosed compounds in cosmetic formulations, especially in the Hair care described. The advantages are generally improved combability, good gloss, high antistatic effectiveness and preferred in EP-A-0 282 720 called improved washout resistance.

Die letztgenannte Eigenschaft ist nicht mit einer Waschbeständigkeit in erfindungsgemäßem Sinne gleichzusetzen. Während sich die Auswaschbeständigkeit aus Haaren auf den kurzzeitigen Angriff von vornehmlich Wasser und sehr milden, die Haut nicht irritierenden Tensiden bezieht, haben waschbeständige, hydrophile Weichmacher für Textilien dem Angriff konzentrierter Tensidlösungen mit hohem Fett- und Schmutzlösevermögen zu widerstehen. Diesen Tensidsystemen werden in modernen Waschmitteln stark alkalische Komplexbildner, oxydativ wirkende Bleichmittel und komplexe Enzymsysteme hinzugefügt. Die Einwirkung erfolgt häufig über Stunden bei erhöhten Temperaturen. Aus diesen Gründen heraus ist eine Übertragung von Erfahrungen aus dem Kosmetikbereich auf das Gebiet der waschbeständigen Textilweichmacher nicht möglich. Die DE-OS 32 36 466 offenbart, daß zur Erzielung einer waschbeständigen Textilausrüstung auf vernetzungsfähige Systeme zurückzugreifen gewesen wäre.The latter property is not in with a wash resistance equate the inventive sense. While the washout resistance from hair on the short-term attack of primarily water and very mild, non-irritating surfactants, have wash-resistant, hydrophilic Softener for textiles to attack concentrated surfactant solutions with high Resist fat and dirt dissolving ability. These surfactant systems are in modern detergents strongly alkaline complexing agents, oxidizing Bleach and complex enzyme systems added. The action takes place often for hours at elevated temperatures. For these reasons, one is Transfer of experience from the cosmetics sector to the field of wash-resistant fabric softener not possible. DE-OS 32 36 466 discloses that to achieve washable textile equipment on cross-linkable Systems would have been resorted to.

Es war weiterhin nicht ableitbar, daß die Verbindungen gemäß EP-A-0 282 720 und DE-PS 37 19 086 in vorteilhafter Weise als interne Weichmacher in auf anionischen/nichtionogenen Tensiden beruhenden Formulierungen zur Wäsche von Textilien und Fasern benutzt werden können. Für diesen Fall gelten ebenfalls die zu den aggressiven Waschmittelsystemen, den erhöhten Temperaturen und langen Einwirkzeiten gemachten Überlegungen.Furthermore, it could not be derived that the compounds according to EP-A-0 282 720 and DE-PS 37 19 086 in an advantageous manner as an internal plasticizer Formulations based on anionic / nonionic surfactants for washing Textiles and fibers can be used. In this case, too apply the aggressive detergent systems, the elevated temperatures and long Considerations made.

Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung der polyquarternären Polysiloxan-Polymeren gemäß der allgemeinen Formeln (I) bis (III) als Weichmacher nach dem Waschen von Textilien mit nichtionogenen oder anionischen/nichtionogenen Detergenzienformulierungen, als Weichmacher in aus nichtionischen oder anionischen/nichtionischen Tensiden beruhenden Formulierungen zur Textilwäsche gewesen.Another object of the present invention is the use of polyquaternary polysiloxane polymers according to the general formulas (I) to (III) as a softener after washing textiles with nonionic or anionic / nonionic detergent formulations, as plasticizers in from formulations based on nonionic or anionic / nonionic surfactants been to textile washing.

Des weiteren können die Verbindungen gemäß der allgemeinen Formeln (I) bis (III) für die Erstausstattung von Fasern und Textilien, in Polituren für die Behandlung und Ausrüstung harter Oberflächen, in Formulierungen zum Trocknen von Automobilen und anderen harten Oberflächen nach maschinellen Wäschen, verwendet werden. Furthermore, the compounds of the general formulas (I) to (III) for the initial equipment of fibers and textiles, in polishes for treatment and  Hard surface finishing, in formulations for drying automobiles and other hard surfaces after machine washing.  

BeispieleExamples

Die nachfolgende Beispiele sollen die Erfindung näher erläutern, ohne sie jedoch einzuschränken.The following examples are intended to explain the invention in greater detail, but without it limit.

Beispiel 1example 1

1a) In einem 1-Liter-Dreihalskolben wurden 28 g Wasser und 12,2 g (0,14 mol Aminogruppen) N,N,N',N'-Tetramethyl-1,6-hexandiamin bei Raumtemperatur vorgelegt. Innerhalb von 5 Minuten wurden 56,1 g (0,14 mol) Dodecansäure in Form einer 50%igen Lösung in 2-Propanol zugesetzt. Nach Erwärmung des Ansatzes auf 50°C tropfte man innerhalb von 25 Minuten 313,5 g (0,14 mol Epoxygruppen) eines Epoxysiloxans der durchschnittlichen Zusammensetzung
1a) 28 g of water and 12.2 g (0.14 mol of amino groups) of N, N, N ', N'-tetramethyl-1,6-hexanediamine were placed in a 1 liter three-necked flask at room temperature. 56.1 g (0.14 mol) of dodecanoic acid were added in the form of a 50% solution in 2-propanol within 5 minutes. After the batch had been heated to 50 ° C., 313.5 g (0.14 mol epoxy groups) of an epoxysiloxane of the average composition were added dropwise within 25 minutes

und 35 ml 2-Propanol zu. Die trübe Mischung wurde 6 Stunden unter Rückflußtemperatur erhitzt. Nach Entfernung aller bis 100°C und bei 2 mm Hg in Vakuum flüchtigen Bestandteile erhielt man 346,7 g eines hellbraunen, klaren und fließfähigen Materials der Struktur
and 35 ml of 2-propanol. The cloudy mixture was heated under reflux for 6 hours. After removal of all components volatile up to 100 ° C. and at 2 mm Hg in vacuum, 346.7 g of a light brown, clear and flowable material of the structure were obtained

Beispiel 2Example 2

Es wurde wie in Beispiel 1 verfahren, nur mit dem Unterschied, daß eine Mischung aus 10,96 g (0,126 mol Aminogruppen) N,N,N',N'-Tetramethyl-1,6-hexandiamin und 2,06 g (0,014 mol Aminogruppen) einer 40gew.-%igen Lösung von Trimethylamin in Wasser verwendet wurden. Nach Entfernung der flüchtigen Bestandteile wurde 351,4 g einer gelb-hellbraunen, viskosen und leicht leicht trüben Substanz der durchschnittlichen Zusammensetzung
The procedure was as in Example 1, with the difference that a mixture of 10.96 g (0.126 mol amino groups) N, N, N ', N'-tetramethyl-1,6-hexanediamine and 2.06 g (0.014 mol of amino groups) of a 40% by weight solution of trimethylamine in water. After removal of the volatile constituents, 351.4 g of a yellow-light brown, viscous and slightly slightly cloudy substance of the average composition

erhalten.receive.

Beispiel 3Example 3

Zum Nachweis der Eignung als waschbeständige, hydrophile Weichmacher wurde weißer Baumwolljersey der nachfolgend beschriebenen Behandlung mit auf den quarternären Ammoniumsalzen gemäß Beispielen 1 und 2 beruhenden Formulierungen unterworfen. Zum Vergleich wurde ein auf den Patenten US 5 807 956 und US 5 981 681 beruhender und kommerziell erhältlicher hydrophiler Weichmacher benutzt. Es wurden zunächst folgende klare Stammformulierungen hergestellt:
To demonstrate suitability as a wash-resistant, hydrophilic plasticizer, white cotton jersey was subjected to the treatment described below with formulations based on the quaternary ammonium salts according to Examples 1 and 2. For comparison, a commercially available hydrophilic plasticizer based on patents US 5,807,956 and US 5,981,681 was used. The following clear base formulations were first produced:

20 g dieser Stammformulierungen wurden in 980 g destilliertem Wasser gelöst. Anschließend erfolgt mit diesen effektiv 0,4% Siloxanwirkstoff enthaltenden Formulierungen eine Ausrüstung von 60 cm × 90 cm großen und 87 g schweren Baumwolljerseystücken im Foulardverfahren. Hierzu wurde das Baumwollmaterial 5 bis 10 Sekunden vollständig in die jeweilige Formulierung eingetaucht, nach Zwangsapplikation geschleudert und bei 120°C, 3 Minuten getrocknet.20 g of these base formulations were dissolved in 980 g of distilled water. This is followed by effectively containing 0.4% active siloxane Formulations an equipment of 60 cm × 90 cm and 87 g heavy Cotton jersey pieces in the foulard process. For this, the cotton material 5 completely immersed in the respective formulation for up to 10 seconds, after Forced application spun and dried at 120 ° C, 3 minutes.

Nachfolgend wurden die Lappen geteilt und jeweils eine Hälfte fünf maschinellen Waschzyklen in Gegenwart eines Feinwaschmittels (1,7 g Waschmittel/Liter Waschflotte) unterzogen. Jeder Waschzyklus dauerte 25 Minuten, die Waschtemperatur betrug 40°C.The flaps were then divided and one half five by machine Washing cycles in the presence of a mild detergent (1.7 g detergent / liter Wash liquor). Each wash cycle lasted 25 minutes Washing temperature was 40 ° C.

An den ungewaschenen und gewaschenen Textilstücken wurde die Hydrophilie (hierunter ist die Einziehzeit eines Wassertropfens in Sekunden zu verstehen) bestimmt und zusätzlich von 10 Testpersonen der Griff bewertet.The hydrophilicity became apparent on the unwashed and washed textile pieces (this is the pull-in time of a drop of water in seconds) determined and additionally rated the grip by 10 test persons.

Die Ergebnisse zeigten, daß die erfindungsgemäß ausgerüsteten Textilmaterialen auch nach 5 Waschzyklen noch über die gewünschte Eigenschaftskombination aus Hydrophilie, ausgedrückt durch eine sehr kurze Tropfeneinziehzeit, und dem silicontypischem Griff verfügten.The results showed that the textile materials finished according to the invention also after 5 washing cycles, you still have the desired combination of properties Hydrophilicity, expressed by a very short drop-in time, and that typical silicone grip.

Beispiel 4Example 4

Zum Nachweis der weichmachenden Eigenschaften als interner Weichmacher während des Waschprozesses wurden gebleichte und an der Oberfläche nicht weiter ausgerüstete Baumwollstreifen einem Waschprozeß in Gegenwart von Ariel Futur®, bentonithaltigem Dash 2 in 1® sowie des in Beispiel 2 beschriebenen Siliconquats unterworfen.To prove the softening properties as an internal softener during the washing process, bleached and on the surface were no further equipped cotton strips a washing process in the presence of Ariel Futur®, Dash 2 in 1® containing bentonite and the silicone quat described in Example 2 subjected.

Folgende Randbedingungen wurden eingehalten.The following boundary conditions were observed.

Das Wasser wurde auf 60°C erhitzt, die Detergenzien und im Falle des Baumwollstreifens 1 zusätzlich die Verbindung gemäß Beispiel 2 gelöst. Anschließend wurden die Baumwollstreifen in diesen Lösungen 30 Minuten gewa­ schen. Nachfolgend wurden die Streifen 5mal mit jeweils 600 ml Wasser gespült und abschließend 30 Minuten bei 120°C getrocknet.The water was heated to 60 ° C, the detergents and in the case of Cotton stripe 1 additionally dissolved the compound according to Example 2. The cotton strips were then washed in these solutions for 30 minutes rule. The strips were then rinsed 5 times with 600 ml of water and finally dried at 120 ° C for 30 minutes.

13 Testpersonen bewerteten die drei Baumwollstreifen auf Weichheit des Griffs hin, wobei die Note 1 dem weichesten Streifen und die Note 3 dem am härtesten Streifen zugeteilt wurde. 13 test persons evaluated the three cotton strips for softness of the handle, where grade 1 is the softest stripe and grade 3 is the hardest stripe was allocated.  

Im Ergebnis der Bewertung erhielt der Baumwollstreifen 1 die Durchschnittsnote 1,6. Der Baumwollstreifen 2 wurde durchschnittlich mit 2,4 und der bentonitbehandelte Streifen 3 mit 2,0 bewertet.As a result of the evaluation, cotton stripe 1 received an average grade of 1.6. The cotton strip 2 was treated with an average of 2.4 and the bentonite Strip 3 rated 2.0.

Claims (8)

1. Verfahren zur Herstellung polyquarternären Polysiloxan-Polymeren gemäß der allgemeinen Formel (I) oder (II)
und/oder linearen Verbindungen der allgemeinen Formel (II)
worin X ein zweiwertiger Kohlenwasserstoffrest mit mindestens 4 Kohlenstoffatomen ist, der eine Hydroxylgruppe aufweist und der durch ein Sauerstoffatom unterbrochen sein kann, Y ein zweiwertiger Kohlenwasserstsoffrest mit mindestens 2 Kohlenstoffatomen ist, der eine Hydroxylgruppe aufweisen und der durch ein Sauerstoff- oder Stickstoffatom unterbrochen sein kann, Z1 ein H, OH, ein Alkyl- oder ein Alkoxyrest ist, oder die Bedeutung eines Kohlenwasserstoffrestes mit mindestens 4 Kohlenstoffatomen hat, der eine oder mehrere Hydroxylgruppe(n) aufweist und durch eine oder mehrere Sauerstoffatome unterbrochen sein kann oder die Bedeutung des Restes
hat, wobei R5 ein Alkylrest mit 1 bis 20 Kohlenstoffatomen ist, Z2 die Gruppe
R1, R2, R3 und R4 gleich oder verschieden sind und C1-C4-Alkylreste oder Benzylreste bedeuten oder jeweils die Reste R1 und R3 oder R2 und R4 Bestandteile eines verbrückenden Alkylenrestes sein können, A- ein anorganisches oder organisches Anion ist, n 5 bis 20 und, m ganze Zahl ≧ 1, dadurch gekennzeichnet, daß zur Synthese α,ω-Wasserstoffpolysiloxane der allgemeinen Formel
mit, bezogen auf SiH-Gruppen 1,0 bis 1,5 mol eines Epoxides, mit endständiger olefinischer Bindung, worin das Epoxid mindestens 4 Kohlenstoffatome besitzt und zusätzlich eine nichtcyclische Ethergruppe enthalten kann, in Gegenwart eines Hydrosilylierungskatalysators bei Temperaturen von 50 bis 150°C umgesetzt wird, der Überschuß an olefinischem Epoxid entfernt, und das Reaktionsprodukt mit einer Mischung aus einem tertiären Amin der Formel
und einem di-tertiärem Amin der Formel
in Gegenwart von Säuren HA bei 40 bis 120°C umgesetzt wird, und das molare Verhältnis von Epoxidgruppen zu tertiären Aminogruppen und zu den Säuren HA 1 : 1 : 1 beträgt. 1. Process for the preparation of polyquaternary polysiloxane polymers according to the general formula (I) or (II)
and / or linear compounds of the general formula (II)
wherein X is a divalent hydrocarbon radical with at least 4 carbon atoms, which has a hydroxyl group and which can be interrupted by an oxygen atom, Y is a divalent hydrocarbon radical with at least 2 carbon atoms, which have a hydroxyl group and which can be interrupted by an oxygen or nitrogen atom, Z 1 is an H, OH, an alkyl or an alkoxy radical, or has the meaning of a hydrocarbon radical with at least 4 carbon atoms, which has one or more hydroxyl group (s) and can be interrupted by one or more oxygen atoms, or the meaning of the rest
where R 5 is an alkyl radical having 1 to 20 carbon atoms, Z 2 is the group
R 1 , R 2 , R 3 and R 4 are identical or different and mean C1-C4-alkyl radicals or benzyl radicals or the radicals R 1 and R 3 or R 2 and R 4 can each be components of a bridging alkylene radical, A - an inorganic one or is organic anion, n is 5 to 20 and, m is an integer ≧ 1, characterized in that for synthesis α, ω-hydrogen polysiloxanes of the general formula
with, based on SiH groups, 1.0 to 1.5 mol of an epoxide, with terminal olefinic bond, in which the epoxide has at least 4 carbon atoms and may additionally contain a noncyclic ether group, in the presence of a hydrosilylation catalyst at temperatures from 50 to 150 ° C. is implemented, the excess of olefinic epoxide is removed, and the reaction product with a mixture of a tertiary amine of the formula
and a di-tertiary amine of the formula
in the presence of acids HA at 40 to 120 ° C, and the molar ratio of epoxy groups to tertiary amino groups and to the acids HA is 1: 1: 1. 2. Verfahren zur Herstellung polyquarternären Polysiloxan-Polymeren gemäß Anspruch 1, dadurch gekennzeichnet, daß die Mischung von tertiären und di- tertiären Amin bezogen auf die Aminogruppen, in einem molaren Verhältnis von 0,001 : 0,999 bis 0,9 : 0,1 zueinander eingesetzt werden.2. Process for the preparation of polyquaternary polysiloxane polymers according to Claim 1, characterized in that the mixture of tertiary and di- tertiary amine based on the amino groups, in a molar ratio from 0.001: 0.999 to 0.9: 0.1 can be used with each other. 3. Verfahren zur Herstellung polyquarternären Polysiloxan-Polymeren gemäß Ansprüchen 1 bis 2, dadurch gekennzeichnet, daß das molare Verhältnis der Aminogruppen von tertiären Aminen zu di-tertiären Aminen 0,001 : 0,999 bis 0,5 : 0,5 und bevorzugt 0,01 : 0,99 bis 0,2 : 0,8 beträgt.3. Process for the preparation of polyquaternary polysiloxane polymers according to Claims 1 to 2, characterized in that the molar ratio of Amino groups from tertiary amines to di-tertiary amines 0.001: 0.999 bis 0.5: 0.5 and preferably 0.01: 0.99 to 0.2: 0.8. 4. Verfahren zur Herstellung von polyquarternären Polysiloxan-Polymeren gemäß Anspruch 1, dadurch gekennzeichnet, daß als tertiäre Amin bevorzugt solche aus der Gruppe bestehend aus Trimethylamin, Dimethylethylamin, Dimethylpropylamin, Dimethylbutylamin, Dimethylhexylamin, Dimethyloctylamin, Dimethyldecylamin, Dimethyldodecylamin, Dimethyltetradecylamin, Dimethylhexadecylamin, Dimethyl-octadecylamin verwendet werden.4. Process for the preparation of polyquaternary polysiloxane polymers according to claim 1, characterized in that preferred as the tertiary amine those from the group consisting of trimethylamine, dimethylethylamine, Dimethylpropylamine, dimethylbutylamine, dimethylhexylamine, Dimethyloctylamine, dimethyldecylamine, dimethyldodecylamine, Dimethyltetradecylamine, dimethylhexadecylamine, dimethyloctadecylamine be used. 5. Waschbeständige diquarternären Polysiloxanen der allgemeinen Formel (III),
worin Z der Rest
R6, R7, R8 C1-C22-Alkylreste oder C2-C22-Alkylenreste, worin die Alkyl- oder Alkylenreste Hydroxylgruppen aufweisen können und mindestens einer der Reste R6, R7, R8 mindestens 10 Kohlenstoffatome aufweist, R9, R10, R12, R14 , R15 C1-C22-Alkylreste oder C2-C22Alkylenreste, worin die Alkyl- oder Alkylenreste Hydroxylgruppen aufweisen können, R1 -O- oder -NR13- Rest, R13 C1-C4-Alkyl- oder Hydroxyalkylrest oder Wasserstoffrest, S 2 bis 4, M ein zweiwertiger Rest, ausgewählt aus der Gruppe
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.5. wash-resistant diquarternary polysiloxanes of the general formula (III),
where Z is the rest
R 6 , R 7 , R 8 are C 1 -C 22 alkyl radicals or C 2 -C 22 alkylene radicals, in which the alkyl or alkylene radicals can have hydroxyl groups and at least one of the radicals R 6 , R 7 , R 8 has at least 10 carbon atoms , R 9 , R 10 , R 12 , R 14 , R 15 C 1 -C 22 alkyl radicals or C 2 -C 22 alkylene radicals, in which the alkyl or alkylene radicals can have hydroxyl groups, R 1 -O- or -NR 13 - Radical, R 13 C 1 -C 4 alkyl or hydroxyalkyl radical or hydrogen radical, S 2 to 4, M is a divalent radical selected from the group
wherein 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. 6. Verwendung der waschbeständigen hydrophilen Weichmacher auf Basis polyquarternären Polysiloxan-Polymeren gemäß Anspruch 1 oder 3 als Weichmacher nach dem Waschen von Textilien mit nichtionogenen oder anionischen/nichtionogenen Detergenzienformulierungen, als Weichmacher in aus nichtionischen oder anionischen/nichtionischen Tensiden beruhenden Formulierungen zur Textilwäsche.6. Use of the wash-resistant hydrophilic plasticizers based polyquaternary polysiloxane polymers according to claim 1 or 3 as Softener after washing textiles with non-ionic or anionic / nonionic detergent formulations, as plasticizers in based on nonionic or anionic / nonionic surfactants Textile laundry formulations. 7. Verwendung der waschbeständigen hydrophilen Weichmacher auf Basis polyquarternärer Polysiloxan-Polymeren gemäß Anspruch 1 oder 3 zur Erstausstattung von Fasern und Textilien. 7. Use of the wash-resistant hydrophilic plasticizers based polyquaternary polysiloxane polymers according to claim 1 or 3 for Initial equipment of fibers and textiles.   8. Verwendung der waschbeständigen hydrophilen Weichmacher auf Basis polyquarternären Polysiloxan-Polymeren gemäß einem der vorgegehenden Ansprüche, in Polituren für die Behandlung und Ausrüstung harter Oberflächen, in Formulierungen zum Trocknen von Automobilen und anderen harten Oberflächen nach maschinellen Wäschen, als separate Weichmacher nach dem Waschen von Textilien mit nichtionogenen oder anionischen/nichtionogen Detergenzienformulierungen.8. Use of the washable hydrophilic plasticizers based polyquaternary polysiloxane polymers according to one of the foregoing Claims hard in polishes for treatment and finishing Surfaces, in formulations for drying automobiles and others hard surfaces after machine washing, as separate plasticizers after washing textiles with nonionic or anionic / nonionic detergent formulations.
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