EP1497402B1 - Washing-softening rinsing formulations containing betaine ester derivatives and method for improving the washing performance of washing agents - Google Patents

Abstract

The invention relates to washing-softening rinsing formulations containing betaine ester derivatives which can be hydrolysed and liquidic esterquat-softening rinsing formulations for the controlled release of surfactants and a method for improving the washing performance of washing agents by using the washing-softening rinsing formulations.

Description

The invention relates to fabric softener formulations comprising hydrolyzable betaine ester derivatives in addition to liquid esterquat fabric softener formulations for the controlled release of surfactants and to a commercial process for improving the washing performance of detergents using the fabric softener formulations.

The chemical and physical processes occurring during the washing process continue to be the subject of intensive research due to their complexity.

In any case, the wetting of the material to be cleaned with the wash liquor and the wetting of the solid or oily particle dirt are required for a cleaning. Wetting and wetting are effected by surfactants, surfactants. The electrochemical double layer formed between fiber, debris and surfactant is substantially increased by anionic surfactants and builders, thereby enhancing the repellency between soil and fiber.

The detached liquid oil and grease dirt is solubilized by the micelles formed by the surfactants and thus kept in the wash liquor. Particle dirt is electrically charged by adsorption of surfactants and dispersed as a result of the repulsion of the individual particles in the wash liquor, so that a redeposition on the fabric is omitted.

Nonionic surfactants are generally used in detergent formulations because of their ability to remove greasy and oily soils. Likewise, according to the Prior art cationic surfactants used in detergent formulations, especially because of their attributed additional textilpflegenden effects and not exclusively as a cleaning agent. Such additional effects to be observed depending on the structure of the cationic surfactants are, for example, the softening (U.S. 3,607,763), the antistatic (U.S. 3,951,879, U.S. 3,959,157), the bacteriocides (U.S. 2,742,434 US 3 539 520, US 3 965 026) and the color-protecting effect or also the improvement of the water-absorption capacity of the fabrics treated with them. Further, basic detergent formulations are known in which selected nonionic and cationic surfactants are combined to achieve improved soil removal, as described in US Pat. Nos. 4,239,660 and 4,260,529.

For example, US Pat. No. 4,260,529 describes laundry detergent formulations containing betaine ester derivatives in the form of cationic ammonium salts in addition to a biodegradable nonionic surfactant. These laundry detergent formulations for the main wash cycle are said to have a high washing effect if they are used in the alkaline wash temperature range of specifically below 11 in the main wash cycle, so that hydrolysis of the surfactants used is prevented.

Cationic surfactants of different structure are used as raw materials for laundry softeners. Particularly widespread are Esterverbindungen based on triethanolamine such as N-methyl, N, N-bis (beta-C _14-18 -acyloxyethyl) -, N-beta-hydroxyethylammoniummethosulfat that (under trade names such Tetranyl ^® AT 75 trademarks of KAO Corp. .), Stepanex ^® VRH 90 (trademark of Stepan Corp.) or Rewoquat ^® WE 18 (trademark of Goldschmidt Rewo GmbH & Co. KG) are distributed.

U.S. 4,370,272 discloses alkoxylated quaternary ammonium betaine ester surfactants and their use as hair conditioners or fabric softeners. As advantages, their self-emulsifying action in water and the possibility to dispense with additional nonionic surfactants to obtain a stable emulsion are called. However, the softness of laundry treated with such fabric softeners does not meet the standards achieved by modern esterquat fabric softeners.

A disadvantage of the prior art is further that the previously available surfactant molecules have no or no sufficient substantivity to raise from the aqueous liquor onto the fibers, which applies in particular to nonionic surfactant molecules.

The object of the present invention was therefore to provide fabric softener formulations which show a significant detergency enhancing effect in the next wash and at the same time meet the standards of modern esterquat softener formulations, in particular with respect to the softening effect, the antistatic effect or the water absorbency of the fabrics treated therewith. To achieve this effect, the components of the laundry softener formulations must be applied to the textiles (substantivity).

According to the invention, it has surprisingly been found that certain compounds which have been applied together with commercial fabric softener formulations can significantly improve the washing action of conventional laundry detergents in the subsequent wash cycle.

About an activating effect, which could have the treatment with a fabric softener on the effectiveness of the next wash cycle after soiling and rinsing, is so far not known in the literature.

wobei
Y gemäß der Formel (II)

ein substituiertes Phosphor- oder Stickstoffatom oder ein Schwefelatom repräsentiert,

R^a

ein langkettiger Alkylrest mit 7 bis 21 C-Atomen ist,

X

ein Rest aus der Gruppe -O-C(O)-, -(O)C-O-, -NH-C(O)-, -(O)C-NH, -(CH₃)N-C(O)-, -(O)C-N(CH₃)-, -S(O₂)-O-, -O-S(O₂)-, -S(O₂)-NH-, -NH-S(O₂)-, -S(O₂)-N(CH₃)-, -N(CH₃)-S(O₂)- ist,

R^b, R^c

unabhängig voneinander und gegebenenfalls verzweigte Alkylreste mit 1 bis 4 C-Atomen sind, wobei diese gegebenenfalls Heteroatomsubstituenten enthalten können,

die Reste

R^d, R^e

unabhängig voneinander ausgewählt werden aus Wasserstoff (H), gegebenenfalls verzweigten Alkylresten mit 1 bis 4 C-Atomen, gegebenenfalls substituierten Aryl- oder Benzyl-resten sowie CH₂COOH, CH₂COOR, CH₂CH₂COOH, CH₂CH₂COOR,

R^f

ein gegebenenfalls Mehrfachbindungen enthaltender verzweigter und/oder substituierter und/oder zyklischer Kohlenwasserstoffrest mit 1 bis 10, vorzugsweise 2 oder 3 Kohlenwasserstoffatomen oder ein Styrolrest ist oder ausschließlich aus Ethylen-, Propylen-, Butylen- oder Styrolresten aufgebaut ist oder ein die genannten Reste enthaltendes Block-Copolymer oder statistisch aufgebautes Polymer ist,

R^g

ein gegebenenfalls verzweigter, gegebenenfalls Doppelbindungen enthaltender, gegebenenfalls zyklischer Kohlenwasserstoffrest mit 1 bis 30 C-Atomen ist,

Z

ein Rest ist aus der Gruppe Stickstoffatom, Sauerstoffatom, -OC-(O)-, -NH-C(O)-, -(CH₃)N-C(O)-,
n = 1 ist, wenn Z kein Stickstoffatom und o = 1 ist;
n = 2 ist, wenn Z ein Stickstoffatom und o = 1 ist;
n = 1 ist, wenn Z ein Stickstoffatom und o = 2 ist,
k und l unabhängig voneinander 1 bis 4 sind, wobei
k vorzugsweise 2 oder 3, und
l vorzugsweise 1 ist,
m einen Wert von 0 bis 30, vorzugsweise 1 bis 10, insbesondere 3 bis 7 hat und
A^- ein Anion ist und

handelsübliche flüssige Esterquat-Weichspülmittel.The aforementioned object is achieved according to the invention by fabric softener formulations comprising betaine ester derivatives of the following general formula (I):

in which
Y according to the formula (II)

represents a substituted phosphorus or nitrogen atom or a sulfur atom,

R ^a

is a long-chain alkyl radical having 7 to 21 C atoms,

X

a radical from the group -OC (O) -, - (O) CO-, -NH-C (O) -, - (O) C-NH, - (CH ₃ ) NC (O) -, - (O ) CN (CH ₃ ) -, -S (O ₂ ) -O-, -OS (O ₂ ) -, -S (O ₂ ) -NH-, -NH-S (O ₂ ) -, -S (O ₂ ) -N (CH ₃ ) -, -N (CH ₃ ) -S (O ₂ ) -,

^Rb , ^Rc

are independently of each other and optionally branched alkyl radicals having 1 to 4 C atoms, which may optionally contain heteroatom substituents,

the rest

R ^d , R ^e

independently of one another are selected from hydrogen (H), optionally branched alkyl radicals having 1 to 4 C atoms, optionally substituted aryl or benzyl radicals and also CH ₂ COOH, CH ₂ COOR, CH ₂ CH ₂ COOH, CH ₂ CH ₂ COOR,

R ^f

a branched and / or substituted and / or cyclic hydrocarbon radical having 1 to 10, preferably 2 or 3, hydrocarbon atoms or a styrene radical which is optionally containing multiple bonds or is composed exclusively of ethylene, propylene, butylene or styrene radicals or a block containing the radicals mentioned Copolymer or random polymer,

R ^g

is an optionally branched, optionally double bonds containing, optionally cyclic hydrocarbon radical having 1 to 30 carbon atoms,

Z

a radical is selected from the group nitrogen atom, oxygen atom, -OC- (O) -, -NH-C (O) -, - (CH ₃ ) NC (O) -,
n = 1, when Z is not a nitrogen atom and o = 1;
n = 2 when Z is a nitrogen atom and o = 1;
n = 1, when Z is a nitrogen atom and o = 2,
k and l are independently 1 to 4, where
k is preferably 2 or 3, and
l is preferably 1,
m has a value of 0 to 30, preferably 1 to 10, in particular 3 to 7 and
A ^{- is} an anion and

commercially available liquid esterquat fabric softeners.

The radical R ^{a of} the betaine ester derivatives preferably comprises a long-chain alkyl radical having 9 to 17 C atoms.

For the purposes of the present invention, Y according to the formula (II) is a substituted nitrogen atom or phosphorus atom, and the radicals R ^b and R ^c are simultaneously -CH ₃ .

In particular, the radicals R ^d and R ^{e may} be H at the same time.

In a preferred embodiment, X is -C (O) -NH- or C (O) -N (CH ₃ ) -.

Particular preference is given to betaine ester derivatives in which n = 1 and o = 1 and Z is an oxygen atom and / or k = 2 or 3 and 1 = 1.

R ^f is preferably an ethylene radical or a propylene radical.

Furthermore, fabric softener formulations containing betaine ester derivatives which are characterized in that m = 1 to 10 and R ^{g is} an alkyl residue having 1 to 30 C atoms are preferred.

A particularly good effect is characterized by erfindungemäßen Betainesterderivaten in that Y according to formula (II) is a substituted nitrogen or phosphorus atom, R ^{a is} an alkyl radical having 7 to 21 carbon atoms, preferably a long-chain alkyl radical having 9 to 17 carbon atoms, X is equal to -C (O) -NH-, R ^b and R ^c are -CH ₃ , R ^d and R ^{e are} simultaneously H, R ^{f is} an ethylene radical or propylene radical, preferably an ethylene radical, n = 1, o = 1 and Z Is oxygen and k = 3, l = 1, m = 2 and R ^{g is} an alkyl radical having 6 to 22, in particular 8 to 18 carbon atoms.

Y should preferably be a substituted nitrogen atom according to formula (II).

Preferably, R ^{g is} the residue of a fatty alcohol based on natural fatty acids which can be prepared by known processes.

As fatty acids for the preparation of fatty alcohols are - individually or in mixtures - fatty acids such as caproic, caprylic, capric, 2-ethylhexanoic, lauric, myristic, palmitic, palmitoleic, isostearic, stearic, hydroxystearic (ricinoleic), dihydroxystearic, oleic, linoleic, petroleum , Elaidic acid, arachidic acid, behenic acid and erucic acid, gadoleic acid and the technical mixtures obtained in the pressure splitting of natural fats and oils such as oleic acid, linoleic acid, linolenic acid, and especially coconut oil fatty acid, rapeseed oil fatty acid, soybean oil fatty acid, sunflower oil fatty acid, tall oil fatty acid. In principle, all fatty acids with a similar chain distribution are suitable.

The content of these fatty acids or fatty acid esters of unsaturated constituents, if necessary, adjusted by the known catalytic hydrogenation to a desired iodine value or achieved by mixing fully hydrogenated with non-hydrogenated fat components.

The iodine number, as a measure of the average degree of saturation of a fatty acid, is the amount of iodine absorbed by 100 g of the compound to saturate the double bonds.

Partially cured C _8/18 coconut or palm oil fatty acids, rapeseed oil fatty acids, sunflower oil fatty acids, soybean oil fatty acids and tall oil fatty acids with iodine numbers in the range from about 80 to 150 ° C. and in particular technical C _8/18 coconut fatty acids are preferably used, optionally a selection of cis / trans isomers such as elaidic acid C _16/18 fatty acid cuts may be of advantage. They are commercial products and are offered by various companies under their respective trade names.

The laundry softener formulations mentioned are particularly suitable for achieving the effect according to the invention if they are further characterized in that the betaine ester derivative is stable to hydrolysis at pH values below 3.5 (at temperatures up to 70 ° C.) and in the aqueous alkaline range from pH 8 to 14, in particular 9 to 11 spontaneously to form cationic, anionic, zwitterionic and / or nonionic surfactants to form at least one good fat-soluble surfactant having an HLB value of <10, and at least one readily water-soluble surfactant having an HLB value of> 10 is hydrolyzed.

The fabric softener formulations have a content of at least 1% by weight, especially 1 to 10, especially 2 to 5, of at least one of the said betaine ester derivatives, together 5 to 20% by weight, especially 13 to 20, of one or more esterquaternary ester derivatives. Softeners, and the rest up to 100 wt .-% of conventional auxiliaries or additives and optionally water.

The auxiliaries and additives are preferably selected from nonionic and ionic dispersants, (C ₁ to C ₅ ) -alkanols, ethylene glycol, propylene glycol, polyglycol, and derivatives thereof, ethoxylated or propoxylated phenol, benzyl alcohol, isopropanol, isobutanol having a mean degree of alkoxylation of> 2.5 to 3.5 and dyes and perfume oils and in particular in a proportion of together up to 5 wt .-%, especially 1 to 3 included.

The fabric softener formulations of the present invention contain betaine ester derivatives having excellent substantivity, and thus, once grown on the fiber, can be considered to carry an ionic and nonionic surfactant which controls them, that is, releases them at the next wash cycle. In this way, for the first time nonionic surfactants for the subsequent wash cycle by the temporary incorporation into a cationic compound can be fixed on textile fibers.

In addition, one or more further quaternary ammonium compounds may be present in the laundry softeners according to the invention.

mit

R =

-CH₃, -CH₂CH₃, -CH₂-CH (R⁴) -OR¹, -CH2-CH (R⁵) - OR², worin R⁴, R⁵ gleich oder verschieden H, -CH₃ sind,

R¹, R² =

H, -C(O) -R³, worin
R³ ein gegebenenfalls substituierter, mindestens eine Doppelbindung enthaltender Kohlenwsserstoffrest mit 13 bis 19 C-Atomen, mit der Maßgabe, dass wenn R ungleich CH₃ ist, R¹, R² im Mittel mindestens 1 bis 1,4 mal = H ist und wenn R = CH₃ ist, R¹, R² im Mittel maximal 0,4 mal = H ist und

B^-

ein Anion eines Quaternierungsmittels, insbesondere des Dimethylsulfats, Diethylsulfats, Methylchlorids ist.

Quaternary ammonium compounds in this sense can be described, for example, by the general formula (III):

With

R =

-CH ₃ , -CH ₂ CH ₃ , -CH ₂ -CH (R ⁴ ) -OR ¹ , -CH ₂ -CH (R ⁵ ) -OR ² , wherein R ⁴ , R ^{5 are the} same or different and are H, -CH ₃ .

R ¹ , R ² =

H, -C (O) -R ³ , wherein
R ^{3 is} an optionally substituted, containing at least one double bond Kohlenwsserstoffrest having 13 to 19 carbon atoms, with the proviso that when R is not equal to CH ₃ is, R ¹ , R ^{2 is} on average at least 1 to 1.4 times = H and when R = CH ₃ , R ¹ , R ^{2 is} on the average at most 0.4 times = H and

B ^-

is an anion of a quaternizing agent, especially the dimethyl sulfate, diethyl sulfate, methyl chloride.

In this case, those quaternary ammonium compounds are particularly preferred, which are characterized in that
R ⁴ = H and R ⁵ = -CH ₃ or R ⁴ , R ⁵ = -CH ₃ or
R = -CH ₂ -CH (CH ₃ ) -OR ^{1 bz 2} and R ⁴ , R ⁵ = -CH ₃ or
R = -CH ² -CH ² -OR ^1bzw.2 and R ⁴ , R ⁵ = H.

1. (A) Beseitigung der aus dem Waschgang resultierenden Restalkalität;
2. (B) Nachbehandeln der sauberen Wäsche mit einer Wäscheweichspülformulierung wie oben definiert bei pH-Werten unter 3,5 und
3. (C) Waschen der durch Gebrauch oder auf sonstige Weise verschmutzten Wäsche mit einem Waschmittel im wässrigen alkalischen Bereich.

The process according to the invention for improving the washing performance of detergents comprises the following steps:

1. (A) elimination of residual alkalinity resulting from the wash cycle;
2. (B) Post-treating the clean laundry with a fabric softening formulation as defined above at pH values below 3.5 and
3. (C) Washing the laundry soiled by use or otherwise with a detergent in the aqueous alkaline range.

Alternatively, to improve the washing performance, a post-treatment of the clean laundry according to step (B), a post-treatment can be carried out exclusively with Betainesterformulierungen alone. The subsequent washing process is carried out analogously (C).

The adjustment of the required pH values is carried out by a neutralization step with sufficient amounts of inorganic, but preferably conventional organic mono- or polybasic acids. It is also advantageous Applications of fabric softener formulations the use of corresponding buffer substances instead of acids.

A wash usually involves placing the dry or wet soiled laundry in the washing machine and cleaning it with the added detergent and washing mechanics. The usual state-of-the-art detergents wet the dirt located on the textile fibers exclusively from the outside. There are initially no surfactant molecules between the textile fibers and the dirt particles.

In order to increase the cleaning performance of a wash cycle, it is desirable to have available surfactant molecules which are able to cause the wetting of the dirt particles also from the backside, ie from the fiber side. This will accelerate or improve the loading or wetting of the dirt particles. In order to realize this possibility, it is necessary to fix surfactant molecules after the actual washing process on the clean textile fiber. When wearing the now clean textile fiber dirt particles do not deposit directly on the fiber, but above the fixed on the fiber, according to the invention Wäscheweichspülformulierungen. In the next wash, the fabric softener formulations according to the invention are hydrolyzed and release both an ionic and a nonionic surfactant, which can cause the separation of the dirt particles from below.

In the hydrolysis of the betaine esters in the betaine ester derivatives to be used according to the invention, a fat-soluble fatty alcohol ethoxylate and a readily water-soluble betaine surfactant are liberated. This combination is ideal for effective soil removal. Conventional fabric softener formulations, such as those described in DE-A-35 05 269, which contain cationic ester derivatives also cationic, do not have these properties due to other molecular structure.

EXAMPLES

In an application comparison, the influence of the fabric softener formulations according to the invention with regard to their influence on the laundry softness and the detergency of commercially available laundry detergents was investigated.

The soft touch was checked on commercial cotton terry fabric.

As a softener have been made of commercially available esterquats (eg Rewoquat ^® WE 18) and in the inventive formulations 2 to 11 using additives in each case 18 wt .-% aqueous fabric softener strength prepared with the additives according to the formulas 2 to 11 is generally in the amount of 2 wt .-% based on the finished fabric softener, in the case of the formulations 3 and 6 in the amount of 5%, were included in the case of the formulations 4 and 7 in the amount of 9 wt .-%.

The formulations according to the invention with the additions of the betaine ester derivatives Ia-f should ideally have a neutral behavior with respect to the softness of the treated tissue. A negative effect on the softness led to a devaluation in the overall assessment.

The use concentration of all fabric softening formulations was 0.025% by weight for softness evaluation.

After application, the toweling was evaluated by a panel of 10 trained persons for their softness. All betaine ester-containing formulations were used directly against the Fabric softener without beta ester (WE 18) compared. In this case, (5) = very soft and (1) = hard.

All data in Table 1 represent mean values of the test group. Table 1: formulation softness Recipe 1 4 Recipe 2 3.9 Recipe 3 3.2 Recipe 4 2.7 Recipe 5 3.9 Recipe 6 3.3 Recipe 7 2.6 Recipe 8 3.8 Recipe 9 3.7 Recipe 10 3.8 Recipe 11 3.7 3% recipe 4 1.4 5% recipe 4 1.6

recipes:

Betaine esters of the general formula (I) were used, where Y = N-CH, R ^b = -CH ₃ , R ^d , R ^e = H, k = 3, 1 = 2, n = 1.

The radicals R = R ^a -X- and R 'specified = (R ^f = were (Rf-O) _m -R ^f -Z- (R ^g) at the respective formulation examples.

• Rezeptur 1 (Vergleich):
  • 18 Gew.-% Rewoquat^® WE 18
• Rezeptur 2 (erfindungsgemäß):
  • 16 Gew.-% Rewoquat^® WE 18
  • 2 Gew.-% Betainester Ia R = Cocosamido-, R' = C₁₈H₃₇O(C₂H₄O)₄-
• Rezeptur 3 (erfindungsgemäß) :
  • 13 Gew.-% Rewoquat^® WE 18
  • 5 Gew.-% Betainester Ia R = Cocosamido-, R' = C₁₈H₃₇O(C₂H₄O)₄-
• Rezeptur 4 (erfindungsgemäß):
  • 9 Gew.-% Rewoquat^® WE 18
  • 9 Gew.-% Ia R = Cocosamido-, R' = C₁₈H₃₇O (C₂H₄O)₄-
• Rezeptur 5 (erfindungsgemäß):
  • 16 Gew.-% Rewoquat^® WE 18
  • 2 Gew. - % Betainester Ib R = C₁₇H₃₅C (O)NH-, R' = C₁₂H₂₅O (C₂H₄O) ₄-
• Rezeptur 6 (erfindungsgemäß):
  • 13 Gew.-% Rewoquat^® WE 18
  • 5 Gew. - % Betainester Ib R = C₁₇H₃₅C(O)NH-, R' = C₁₂H₂₅O(C₂H₄O)₄-
• Rezeptur 7 (erfindungsgemäß):
  • 9 Gew. -% Rewoquat^® WE 18
  • 9 Gew. - % Betainester Ib R = C₁₇H₃₅C(O)NH-, R' = C₁₂H₂₅O (C₂H₄O) ₄-
• Rezeptur 8 (erfindungsgemäß):
  • 16 Gew.-% Rewoquat^® WE 18
  • 2 Gew. -% Betainester Ic R = C₁₁H₂₃C(O)NH-, R' = C₁₂H₂₅O (C₂H₄O) ₄-
• Rezeptur 9 (erfindungsgemäß):
  • 16 Gew.-% Rewoquat^® WE 18
  • 2 Gew.-% Betainester Id R = CH₃C(O)NH-, R' = C₁₂H₂₅O(C₂H₄O)₄-
• Rezeptur 10 (erfindungsgemäß) :
  • 16 Gew.-% Rewoquat^® WE 18
  • 2 Gew.-% Betainester Ie R = C₁₁H₂₃C(O)NH-, R' = C₁₂H₂₅O(C₂H₄O)₄-
• Rezeptur 11 (erfindungsgemäß):
  • 16 Gew.-% Rewoquat^® WE 18
  • 2 Gew.-% Betainester If R = CH₃C(O)NH-, R' = C₁₂H₂₅O(C₂H₄O)₄-

The following formulations were used as fabric softeners:

• Recipe 1 (comparison):
  • 18 wt .-% Rewoquat ^® WE 18
• Formulation 2 (according to the invention):
  • 16 wt .-% Rewoquat ^® WE 18
  • 2% by weight of betaine ester Ia R = cocoamido, R '= C ₁₈ H ₃₇ O (C ₂ H ₄ O) ₄ -
• Recipe 3 (according to the invention):
  • 13 wt .-% Rewoquat ^® WE 18
  • 5% by weight of betaine ester Ia R = cocoamido, R '= C ₁₈ H ₃₇ O (C ₂ H ₄ O) ₄ -
• Formulation 4 (according to the invention):
  • 9 wt .-% Rewoquat ^® WE 18
  • 9% by weight of Ia R = cocoamido, R '= C ₁₈ H ₃₇ O (C ₂ H ₄ O) ₄ -
• Recipe 5 (according to the invention):
  • 16 wt .-% Rewoquat ^® WE 18
  • 2% by weight of betaine ester Ib R = C ₁₇ H ₃₅ C (O) NH-, R '= C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₄ -
• Formulation 6 (according to the invention):
  • 13 wt .-% Rewoquat ^® WE 18
  • 5% by weight of betaine ester Ib R = C ₁₇ H ₃₅ C (O) NH-, R '= C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₄ -
• Recipe 7 (according to the invention):
  • 9 wt -.% Rewoquat ^® WE 18
  • 9% by weight of betaine ester Ib R = C ₁₇ H ₃₅ C (O) NH-, R '= C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₄ -
• Formulation 8 (according to the invention):
  • 16 wt .-% Rewoquat ^® WE 18
  • 2% by weight of betaine ester Ic R = C ₁₁ H ₂₃ C (O) NH-, R '= C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₄ -
• Recipe 9 (according to the invention):
  • 16 wt .-% Rewoquat ^® WE 18
  • 2 wt.% Betaine ester Id R = CH ₃ C (O) NH-, R '= C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₄ -
• Recipe 10 (according to the invention):
  • 16 wt .-% Rewoquat ^® WE 18
  • 2 wt.% Betaine ester Ie R = C ₁₁ H ₂₃ C (O) NH-, R '= C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₄ -
• Recipe 11 (according to the invention):
  • 16 wt .-% Rewoquat ^® WE 18
  • 2 wt.% Betaine ester If R = CH ₃ C (O) NH-, R '= C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₄ -

The results show that a low content of betaine ester practically does not affect the softness compared to the pure Esterquat formulation Formulation 1.

On the basis of this evaluation, the laundry softening formulations with a maximum of 2% by weight of betaine ester were used for the detergency tests.

In order to simulate possible higher use concentrations of the betaine esters, the fabric softeners were dosed both with the usual concentration of 0.025 wt .-% active content as well as with an excessive concentration of 0.075 wt .-%.

To evaluate the detergency artificially soiled "stain monitors" from the company EMPA were used. These "Stainmonitors" contain on a piece of fabric 16 different types of dirt, so that a fairly comprehensive evaluation of the washing performance, or stain removal is possible.

It was both the commercial "monitors" (standardized spotted test textiles) used, as well as specially pretreated. The specially pretreated were first at the Fa. EMPA customary prewashing process subjected and in addition was in a neutralization step, the residual alkalinity resulting from the wash cycle eliminated. This step is in an industrial car wash but easily programmable, with the usual washing programs in a commercial household washing machine, it is manually interposed. It is necessary to avoid premature hydrolysis of the betaine ester derivatives according to the invention. After neutralization, the "monitors" were treated with a fabric softener.

For testing, the washing tests were carried out in Miele W 715 and W 918 washing machines.

For each wash load, 20 "Stainmonitors" and 2 kg ballast fabrics were washed. The washing temperature was 40 ° C with the washing program coloreds short. As a test detergent "Persil Color Gel ^®," a liquid were, respectively Gelwaschmittel Henkel and "Ariel ^® Essentiel", a powder detergent from Procter & Gamble used. To quantify stain removal, the stains were measured on the monitor using a Dr. Lange Colorimeter " ^Luci® 100" before and after the wash. With the aid of the reference value of the non-soiled test fabric and the two measured values, the percentage of soil removal can be calculated.

Washing results:

The soil removal averages are listed in the following tables.

In order to facilitate the evaluation and to better emphasize the improvement of the washing effect in different fields of application, a standardization was carried out. For standardization, the values of formula 1 (pure softener) = 100 were set and the deviation of the betaine ester-containing formulations 2, 5, 8, 9, 10 and 11 respectively for the two concentrations 0.025 wt .-% and 0.075 wt .-% indicated. Finally, the mean value was calculated using the values within a column.

The evaluation shows that for all formulations according to the invention a good detergency increase is observed, either in one of the two concentrations or in connection with powder and / or liquid detergents. It also follows that the betaine esters used according to the invention can be optimized for the particular specific purpose. Table 2: Powder detergent (batch 1) pollution no fabric softener * Formulation 1 * 0.025% by weight Formulation 2 ++ 0.025% by weight Formulation 2 ++ 0.075 wt .-% Make up 59.3 58.0 62.5 57.2 curry 81.7 84.3 89.8 92.0 red wine 63.9 61.4 66.9 61.8 Spaghetti sauce 87.9 84.8 91.9 96.5 dessert 74.7 75.6 75.8 80.0 peat 61.0 58.4 65.4 61.2 tea 56.8 54.8 62.2 66.9 Beta-carotene 72.1 77.6 75.0 90.0 grass 89.0 60.1 91.7 95.1 animal. fat 27.9 43.5 49.1 44.2 baby food 76.3 73.4 81.3 82.7 aluminum oxide 46.4 49.2 48.9 51.2 butter 78.1 82.9 82.8 89.8 machine oil 55.1 62.2 54.0 60.4 Mean (normalized) 100.0 108.3 110.9 * Comparison
++ according to the invention pollution no fabric softener * Formulation 1 * 0.025% by weight Formulation 2 ++ 0.025% by weight Formulation 2 ++ 0.075 wt .-% Make up 63.8 64.5 65.7 61.7 curry 77.0 75.6 77.0 74.7 red wine 53.6 55.2 53.6 52.9 Spaghetti sauce 84.9 86.7 87.6 78.8 dessert 59.6 60.3 61.6 62.5 peat 53.4 46.7 53.8 46.6 tea 8.8 8.5 9.8 8.5 Beta-carotene 63.0 82.1 88.6 76.2 grass 88.4 84.3 88.9 86.7 animal. fat 29.8 36.4 39.4 37.7 baby food 77.7 76.0 87.7 75.0 aluminum oxide 41.1 43.4 42.3 43.7 butter 78.5 78.1 82.3 78.0 machine oil 67.6 62.5 73.6 57.4 Mean (normalized) 100.00 106.6 98.2 * Comparison
++ according to the invention pollution no fabric softener * Formulation 1 * 0.025% by weight Recipe 5 ++ 0.025% by weight Recipe 5 ++ 0.075 wt .-% Make up 59.3 58.0 69.6 55.5 curry 81.7 84.3 93.5 89.8 red wine 63.9 61.4 72.1 67.6 Spaghetti sauce 87.9 84.8 97.6 94.2 dessert 74.7 75.6 81.1 83.8 peat 61.0 58.4 66.0 61.5 tea 56.8 54.8 69.8 64.9 Beta-carotene 72.1 77.6 94.2 86.9 grass 89.0 60.1 100 90.7 animal. fat 27.9 43.5 43.9 47.2 baby food 76.3 73.4 97.5 78.1 aluminum oxide 46.4 49.2 58.5 54.6 butter 78.1 82.9 95.8 88.2 machine oil 55.1 62.2 63.8 67.9 Mean (normalized) 100 119.3 111.6 * Comparison
++ according to the invention pollution no fabric softener * Formulation 1 * 0.025% by weight Recipe 5 ++ 0.025% by weight Recipe 5 ++ 0.075 wt .-% Make up 63.8 64.5 65.6 59.2 curry 77.0 75.6 72.8 80.5 red wine 53.6 55.2 49.3 57.5 Spaghetti sauce 84.9 86.7 82.7 95.2 dessert 59.6 60.3 62.0 70.5 peat 53.4 46.7 47.2 50.4 tea 8.8 8.5 1.6 13.8 Beta-carotene 63.0 82.1 75.6 98.6 grass 88.4 84.3 84.3 93.2 animal. fat 29.8 36.4 41.1 39.6 baby food 77.7 76.0 75.2 91.0 aluminum oxide 41.1 43.4 43.0 55.7 butter 78.5 78.1 79.9 87.2 machine oil 67.2 62.5 68.8 39.0 Mean (normalized) 100 94.3 111.5 * Comparison
++ according to the invention pollution no fabric softener * Formulation 1 * 0.025% by weight Recipe 8 ++ 0.025% by weight Formulation 8 ++ 0.075 wt .-% Make up 65.9 87.0 88.3 85.7 curry 86.3 89.0 91.1 87.4 red wine 65.7 62.5 69.9 61.7 Spaghetti sauce 92.9 86.8 94.1 81.0 dessert 72.5 81.1 82.2 85.8 peat 65.3 68.4 67.4 70.5 tea 68.3 75.9 70.5 71.9 Beta-carotene 73.7 72.8 78.2 76.2 grass 95.5 96.7 97.2 94.6 animal. fat 57.5 54.4 49.1 62.2 baby food 77.8 79.5 78.6 76.0 aluminum oxide 52.0 68.7 62.8 73.8 butter 77.3 79.3 83.8 83.1 machine oil 54.3 57.1 56.3 61.9 Mean (normalized) 100 100.7 101.8 * Comparison
++ according to the invention pollution no fabric softener * Formulation 1 * 0.025% by weight Recipe 8 ++ 0.025% by weight Formulation 8 ++ 0.075 wt .-% Make up 76.2 73.8 86.4 85.5 curry 74.9 74.2 80.0 77.6 red wine 48.0 51.4 54.1 49.9 Spaghetti sauce 86.8 78.1 88.8 78.4 dessert 63.8 63.1 68.0 71.5 peat 58.2 54.6 54.2 57.7 tea 5.5 4.6 7.7 0.1 Beta-carotene 71.4 71.6 76.1 75.4 grass 93.3 90.5 93.9 88.5 animal. fat 31.6 11.3 35.5 27.1 baby food 69.3 68.6 74.0 67.2 aluminum oxide 46.2 53.5 54.6 63.3 butter 73.7 74.8 80.0 79.4 machine oil 72.9 43.8 77.9 53.2 Mean (normalized) 100 131.2 109.0 * Comparison
++ according to the invention pollution no fabric softener * Formulation 1 * 0.025% by weight Recipe 9 ++ 0.025% by weight Recipe 9 ++ 0.075 wt .-% Make up 65.9 87.0 82.9 85.6 curry 86.3 89.0 89.6 91.5 red wine 65.7 62.5 59.5 61.8 Spaghetti sauce 92.9 86.8 94.4 92.2 dessert 72.5 81.1 81.5 87.5 peat 65.3 68.4 66.6 70.2 tea 68.3 75.9 67.1 70.7 Beta-carotene 73.7 72.8 79.0 84.1 grass 95.5 96.7 97.6 96.5 animal. fat 57.5 54.4 55.2 65.3 baby food 77.8 79.5 80.8 77.3 aluminum oxide 52.0 68.7 59.2 69.9 butter 77.3 79.3 82.4 86.2 machine oil 54.3 57.1 56.4 63.9 Mean (normalized) 100 99.1 104.6 * Comparison
++ according to the invention pollution no fabric softener * Formulation 1 * 0.025% by weight Recipe 9 ++ 0.025% by weight Recipe 9 ++ 0.075 wt .-% Make up 76.2 73.8 83.6 83.8 curry 74.9 74.2 76.2 80.4 red wine 48.0 51.4 52.2 53.3 Spaghetti sauce 86.8 78.1 74.2 87.9 dessert 63.8 63.1 67.9 73.2 peat 58.2 54.6 59.3 54.3 tea 5.5 4.6 6.9 4.7 Beta-carotene 71.4 71.6 71.5 81.4 grass 93.3 90.5 95.6 91.5 animal. fat 31.6 11.3 34.0 21.8 baby food 69.3 68.6 77.3 73.8 aluminum oxide 46.2 53.5 54.2 61.2 butter 73.7 74.8 80.9 80.9 machine oil 72.9 43.8 82.6 54.5 Mean (normalized) 100 128.3 115.6 * Comparison
++ according to the invention pollution no fabric softener * Formulation 1 * 0.025% by weight Recipe 10 ++ 0.025% by weight Recipe 10 ++ 0.075 wt .-% Make up 65.9 87.0 83.0 88.8 curry 86.3 89.0 87.0 92.2 red wine 65.7 62.5 56.6 57.7 Spaghetti sauce 92.9 86.8 84.7 92.8 dessert 72.5 81.1 82.1 86.2 peat 65.3 68.4 65.0 71.2 tea 68.3 75.9 64.4 68.7 Beta-carotene 73.7 72.8 71.6 82.1 grass 95.5 96.7 98.2 95.8 animal. fat 57.5 54.4 55.7 60.8 baby food 77.8 79.5 82.2 71.5 aluminum oxide 52.0 68.7 63.8 72.1 butter 77.3 79.3 80.8 86.5 machine oil 54.3 57.1 57.5 62.5 Mean (normalized) 100 97.4 103.1 * Comparison
++ according to the invention pollution no fabric softener * Formulation 1 * 0.025% by weight Recipe 10 ++ 0.025% by weight Recipe 10 ++ 0.075 wt .-% Make up 76.2 73.8 80.3 83.6 curry 74.9 74.2 72.3 80.1 red wine 48.0 51.4 48.5 48.5 Spaghetti sauce 86.8 78.1 81.5 88.8 dessert 63.8 63.1 68.7 64.8 peat 58.2 54.6 53.8 57.4 tea 5.5 4.6 1.3 6.1 Beta-carotene 71.4 71.6 75.5 81.6 grass 93.3 90.5 96.9 91.3 animal. fat 31.6 11.3 39.6 22.3 baby food 69.3 68.6 71.7 66.7 aluminum oxide 46.2 53.5 54.7 64.2 butter 73.7 74.8 82.7 81.8 machine oil 72.9 43.8 78.7 34.6 Mean (normalized) 100 121.5 113.4 * Comparison
++ according to the invention pollution no fabric softener * Formulation 1 * 0.025% by weight Recipe 11 ++ 0.025% by weight Recipe 11 ++ 0.075 wt .-% Make up 65.9 87.0 72.4 80.8 curry 86.3 89.0 83.7 85.7 red wine 65.7 62.5 68.0 62.9 Spaghetti sauce 92.9 86.8 85.8 82.0 dessert 72.5 81.1 79.7 78.9 peat 65.3 68.4 63.0 64.1 tea 68.3 75.9 76.2 72.7 Beta-carotene 73.7 72.8 73.0 74.8 grass 95.5 96.7 95.2 93.7 animal. fat 57.5 54.4 64.3 66.5 baby food 77.8 79.5 80.4 71.1 aluminum oxide 52.0 68.7 56.8 65.7 butter 77.3 79.3 82.2 87.0 machine oil 54.3 57.1 58.1 63.1 Mean (normalized) 100 98.7 111.6 * Comparison
++ according to the invention pollution no fabric softener * Formulation 1 * 0.025% by weight Recipe 11 ++ 0.025% by weight Recipe 11 ++ 0.075 wt .-% Make up 76.2 73.8 83.9 85.8 curry 74.9 74.2 75.0 76.8 red wine 48.0 51.4 46.5 52.4 Spaghetti sauce 86.8 78.1 80.4 85.8 dessert 63.8 63.1 66.9 74.6 peat 58.2 54.6 53.2 51.1 tea 5.5 4.6 2.8 4.6 Beta-carotene 71.4 71.6 72.6 75.0 grass 93.3 90.5 93.2 90.9 animal. fat 31.6 11.3 30.6 37.9 baby food 69.3 68.6 71.4 64.3 aluminum oxide 46.2 53.5 54.6 59.8 butter 73.7 74.8 78.9 84.3 machine oil 72.9 43.8 73.6 76.1 Mean (normalized) 100 116.2 126.9 * Comparison
++ according to the invention

Claims (11)

1. Rinse cycle fabric softener formulations comprising betaine ester derivatives of the following general formula (I):

   

   wherein Y according to the formula (II)
   Y=

   

   represents a substituted phosphorus or nitrogen atom or a sulfur atom,
   R^a is a long-chain alkyl radical having 7 to 21 C atoms,
   X is a radical from the group consisting of -O-C(O)-, -(O)C-O-, -NH-C(O)-, -(O)C-NH, -(CH₃)N-C(O)-, -(O)C-N(CH₃)-, -S(O₂)-O-, -O-S(O₂)-, -S(O₂)-NH-, -NH-S(O₂)-, -S(O₂)-N(CH₃)- and -N(CH₃)-S(O₂)-,
   R^b, R^c are independent of one another and are optionally branched alkyl radicals having 1 to 4 C atoms, where these can optionally contain heteroatom substituents, the radicals
   R^d, R^e independently of one another are chosen from hydrogen (H), optionally branched alkyl radicals having 1 to 4 C atoms, optionally substituted aryl or benzyl radicals and CH₂COOH, CH₂COOR, CH₂CH₂COOH and CH₂CH₂COOR,
   R^f is a branched and/or substituted and/or cyclic hydrocarbon radical having 1 to 10, preferably 2 or 3 carbon atoms which optionally contains multiple bonds or a styrene radical or is composed exclusively of ethylene, propylene, butylene or styrene radicals or is a block copolymer or randomly composed polymer containing the radicals mentioned,
   R^g is an optionally branched, optionally cyclic hydrocarbon radical having 1 to 30 C atoms which optionally contains double bonds,
   Z is a radical from the group consisting of a nitrogen atom, an oxygen atom, -O-C(O)-, -NH-C(O)- and -(CH₃)N-C(O)-,
   n = 1 if Z is not a nitrogen atom and o = 1;
   n = 2 if Z is a nitrogen atom and o = 1;
   n = 1 if Z is a nitrogen atom and o = 2;
   k and l independently of one another are 1 to 4,
   k preferably being 2 or 3, and
   l preferably being 1,
   m has a value from 0 to 30, preferably 1 to 10, in particular 3 to 7, and
   A^- is an anion and
   commercially available liquid esterquat rinse cycle softeners.
2. Rinse cycle fabric softener formulations according to Claim 1, characterized in that the radical R^a of the betaine ester derivatives comprises a long-chain alkyl radical having 9 to 17 C atoms.
3. Rinse cycle fabric softener formulations according to Claim 1 or 2, characterized in that Y according to the formula (II) is a substituted nitrogen atom or phosphorus atom and the radicals R^b and R^c are simultaneously -CH₃.
4. Rinse cycle fabric softener formulations according to any one of Claims 1 to 3, characterized in that the radicals R^d and R^e are simultaneously H.
5. Rinse cycle fabric softener formulations according to any one of Claims 1 to 4, characterized in that X = -C(O)-NH- or C(O)-N(CH₃)-.
6. Rinse cycle fabric softener formulations according to any one of Claims 1 to 5, characterized in that n = 1 and o = 1 and Z is an oxygen atom.
7. Rinse cycle fabric softener formulations according to any one of Claims 1 to 6, characterized in that k = 2 or 3 and 1 = 1.
8. Rinse cycle fabric softener formulations according to any one of Claims 1 to 7, characterized in that R^f is an ethylene radical or a propylene radical.
9. Rinse cycle fabric softener formulations according to any one of Claims 1 to 8, characterized in that m = 1 to 10 and R^g is an alkyl radical having 1 to 30 C atoms.
10. Rinse cycle fabric softener formulations according to any one of Claims 3 to 9, characterized in that Y according to formula (II) is a substituted nitrogen or phosphorus atom, R^a is an alkyl radical having 7 to 21 C atoms, preferably a long-chain alkyl radical having 9 to 17 carbon atoms, X = -C(O)-NH-, R^b and R^c = -CH₃, R^d and R^e are simultaneously H, R^f is an ethylene radical or propylene radical, preferably an ethylene radical, n = 1, o = 1 and Z is an oxygen atom and k = 3, 1 = 1, m = 2 and R^g is an alkyl radical having 6 to 22, in particular 8 to 18 C atoms.
11. Method of improving the washing performance of detergents, comprising the steps

    (A) elimination of the residual alkalinity resulting from the washing operation;

    (B) after-treatment of the clean laundry with a rinse cycle fabric softener formulation according to any one of Claims 1 to 11 at pH values below 3.5 and

    (C) washing of the laundry soiled by use or in another manner with a detergent in the aqueous alkaline range.