EP0503155B1 - Fabric softener based on quaternary poly(oxyalkylene)-alkanolamine esters - Google Patents

Description

The present invention relates to fabric softeners in the form of aqueous solutions, emulsions or dispersions.

When washing textiles, so-called fabric softeners are known to be used in the last wash cycle in order to reduce the hardening of the fabrics by drying and to pleasantly influence the handle of the treated textiles.

Cationic compounds are usually used as fabric softeners, for example quaternary ammonium compounds which, in addition to long-chain alkyl radicals, can also contain ester or amide groups. Mixtures of various plasticizing components which are added to the rinsing bath in the form of aqueous dispersions are also advantageously used.

Although these cationic compounds are effective plasticizers when used in the final rinse bath, they still have certain disadvantages when used.

One of the disadvantages of such agents is that the softening components cannot be dispersed in cold water; furthermore, the rewetting capacity of the textiles treated with them is still not satisfactory.

Backwetting capacity is generally understood to mean the absorption of moisture by the fiber. Poor network assets have a negative impact where larger amounts of moisture are to be absorbed from the skin surface by textile fabrics, e.g. B. with hand or bath towels as well as underwear or bed linen.

It was an object of the present invention to overcome the above-mentioned disadvantages of conventional fabric softener formulations and to provide laundry fabric softening agents which, in addition to good biodegradability and soft feel, have improved rewetting capacity, are clearly soluble in water or show significantly improved emulsifiability or dispersibility.

Surprisingly, it was found that fabric softening agents consisting of ammonium compounds containing ester groups and a liquid carrier material meet these requirements.

• A) 5 bis 35 Gewichts-% mindestens einer der Verbindungen der allgemeinen Formel (1)
  
  worin
  • R gleich oder verschieden H oder -CH₃
  • R¹, R, R³, R⁴ = gleich oder verschieden die Reste
    
    bedeuten mit
  • R⁵ = gegebenenfalls substituierter, gegebenenfalls Mehrfachbindungen enthaltender Acylrest mit 6 - 22, vorzugsweise mit 8 - 18 Kohlenstoffatomen oder H sein kann und worin
  • R⁵ mindestens einmal, vorzugsweise mindestens zweimal ein Acylrest und mindestens einmal H sein muß und
  • R⁶, R⁷ = gleich oder verschieden H, -CH₃, -C₂H₅, -C₂H₄OH sein können,
  • A⁻ = mindestens ein organisches und/oder anorganisches Anion ist,
  • n = 1 - 30, vorzugsweise 1 - 15, insbesondere 2 - 8 ist
  • m = 1 - 5 und die Summe aller m mindestens 4 ist und gegebenenfalls
• B) 10 - 90 Gew. %, bezogen auf A, übliche Ammoniumverbindungen und gegebenenfalls
• C) 1 - 5 Gew. % übliche Farbstoffe, Duftstoffe und weitere in Weichspülmitteln übliche Hilfs- und Zusatzstoffe und
• D) ergänzend auf 100 Gew. % Wasser.

The invention therefore relates to aqueous fabric softeners containing

• A) 5 to 35% by weight of at least one of the compounds of the general formula (1)
  
  wherein
  • R the same or different H or -CH₃
  • R¹, R, R³, R⁴ = the same or different the radicals
    
    mean with
  • R⁵ = optionally substituted, optionally containing multiple bonds acyl radical having 6-22, preferably having 8-18 carbon atoms or H and where
  • R⁵ must be at least once, preferably at least twice an acyl radical and at least once H and
  • R⁶, R⁷ = identical or different H, -CH₃, -C₂H₅, -C₂H₄OH can be,
  • A⁻ = at least one organic and / or inorganic anion,
  • n = 1-30, preferably 1-15, in particular 2-8
  • m = 1 - 5 and the sum of all m is at least 4 and, if appropriate
• B) 10-90% by weight, based on A, of conventional ammonium compounds and, if appropriate
• C) 1-5% by weight of customary dyes, fragrances and other auxiliaries and additives customary in fabric softeners and
• D) in addition to 100% by weight of water.

Another object of the invention is characterized in that the aqueous fabric softener contains 15-30% by weight of a compound of the general formula (1) in the R = -CH₃ means two or three of the radicals R¹, R, R³, R⁴ = R⁵-O-CH₂-CH₂- with R⁵ = acyl radical with 8 - 18 carbon atoms and once or twice HO-CH₂-CH₂-, n = 1-15, R⁶, R⁷ = identical or different H or -CH₃ and A⁻ the rest of an optionally substituted carboxylic acid with 1 - 8 carbon atoms in the main chain or the methosulfate or. Are ethosulfate residue.

Another object of the invention is characterized in that the aqueous fabric softeners contain 15-30% by weight of a compound of the general formula (1) in which R = -CH₃ means three of the radicals R¹, R, R³, R⁴ = R⁵- O-CH₂-CH₂- with R⁵ = acyl radical with 8 - 18 carbon atoms, one of the radicals with R⁵ = H, n = 2-8, R⁶, R⁷ = H and A⁻ is the lactate radical.

Further objects of the invention are characterized by the claims.

worin

und EO -(O-CH₂-CH₂)- bedeuten und worin a, b, c = 0 - 20 mit a + b + c = n = 1 - 30, vorzugsweise 1 - 15 und insbesondere 2 - 8 sind. Erfindungsgemäß bevorzugt werden Verbindungen mit a + c = 1 - 15 und insbesondere 2 - 8.The following amine compounds of the formula (2) can be used as starting compounds for the preparation of the ammonium compounds used according to the invention:

wherein

and EO - (O-CH₂-CH₂) - and in which a, b, c = 0-20 with a + b + c = n = 1-30, preferably 1-15 and in particular 2-8. According to the invention Compounds with a + c = 1-15 and in particular 2-8 are preferred.

These compounds are commercially available and are obtained by known processes by reacting polyoxyalkylene alcohols with ammonia under pressure.

The polyoxyalkylene alcohols are prepared by adding an alkylene oxide, essentially propylene oxide, ethylene oxide or a mixture of both, using a conventional method to a compound containing one or more active hydrogen atoms or by polymerizing alkylene oxides.

Monoalcohols such as ethanol, isopropanol, butanol, lauryl alcohol, stearyl alcohol, but especially methanol or glycols such as ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, polyglycerol, polyvinyl alcohols can be used as compounds which contain one or more active hydrogen atoms.

The polyoxyalkylene alcohols have molecular weights in the range from approximately 100 to 10,000, preferably approximately 130 to 5000 and particularly preferably approximately 150 to 2000.

The further conversion to the amines is carried out according to methods known per se by aminolysis of the free hydroxyl groups or their esters, in particular the sulfuric acid esters. In the case of higher alcohols, the OH group is replaced by the amino group by means of homogeneous, but in particular heterogeneous, catalysis on fixed contacts. In particular, two methods are available here. The one works with dehydrating, the other with hydrodehydrogenating catalysts.

There is extensive literature on the influence of temperature and pressure and excess ammonia as well as the required dwell times (see Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart 1957, Volume 11/1 p. 108ff and GB-PS 384 714, U.S. Patent 2,017,051, U.S. Patent 2,078,922).

oder $$\begin{gathered} \text{a + c = n = 2 - 3} \\ \text{b = 6 - 9} \end{gathered}$$

According to the invention, the following compounds of formula (2) were preferred: $$\begin{gathered} \text{a - c = n = 2 - 8} \\ \text{b = 0} \end{gathered}$$

or $$\begin{gathered} \text{a + c = n = 2 - 3} \\ \text{b = 6-9} \end{gathered}$$

The compounds of formula (2) are then alkoxylated by methods known per se, i.e. H. preferably ethoxylated or propoxylated. In general, the procedure is such that the amines in a pressure reactor at 120-160.degree. C., optionally in the presence of basic, in particular alkaline, catalysts at 1-4 bar with an amount of alkylene oxide corresponding to the desired degree of alkoxylation; ethylene oxide and propylene oxide are preferred according to the invention or their mixtures, reacted.

worin A -(PO)_a-(EO)_b-(PO)_c bedeutet, und worin a, b, c, EO und PO die gleiche Bedeutung wie oben aufgeführt haben und $$\text{d + e + f + g = m = 4 - 20}$$

und $${\text{R}}^{\text{7}}{\text{, R}}^{\text{8}}{\text{, R}}^{\text{9}}{\text{, R}}^{\text{10}}$$

unabhängig voneinander -H oder -CH₃ sein können.Compounds of the general formula (3) are obtained

wherein A - (PO) _a - (EO) _b - (PO) _c , and wherein a, b, c, EO and PO have the same meaning as listed above and $$\text{d + e + f + g = m = 4 - 20}$$

and $${\text{R}}^{\text{7}}{\text{, R}}^{\text{8th}}{\text{, R}}^{\text{9}}{\text{, R}}^{\text{10th}}$$

can independently be -H or -CH₃.

Preferred compounds according to formula (3) are compounds with $$\begin{gathered} \text{d + e + f + g = m = 4 - 6} \\ {\text{R}}^{\text{7}}{\text{, R}}^{\text{8th}}{\text{, R}}^{\text{9}}{\text{, R}}^{\text{10th}}\text{= H} \end{gathered}$$

wobei A, d, e, f, g, R¹, R, R³, R⁴, R⁷, R⁸, R⁹, R¹⁰ die gleiche Bedeutung wie oben aufgeführt haben.The subsequent esterification of the compounds (4) with carboxylic acids or their derivatives leads to compounds of the general formulas (4)

where A, d, e, f, g, R¹, R, R³, R⁴, R⁷, R⁸, R⁹, R¹⁰ have the same meaning as listed above.

The fatty acids for the esterification or the transesterification are the monobasic synthetic fatty acids known and customary in this field, but in particular the fatty acids based on natural vegetable and animal oils with 6-22 C atoms, in particular with 8-18 C atoms, such as coconut fatty acids, palm, tallow, castor fatty acids. These can be used both as glycerides, as esters with short-chain alcohols or as free acids.

Their esterification or transesterification is carried out according to the known method.

Here, the alkanolamines of the formula (4) are reacted with an amount of fatty acid or fatty acid ester corresponding to the desired degree of esterification, optionally in the presence of a catalyst, at 160-240 ° C. and the water of reaction or the alcohol formed is distilled off continuously, to complete the If necessary, a negative pressure is applied.

wobei R¹¹ = -C₁₇H₃₅ bedeutet oder sich von der natürlichen Mischung der Kokosfettsäuren ableitet.Preferred compounds according to formula (4) are substances with

where R¹¹ = -C₁₇H₃₅ means or is derived from the natural mixture of coconut fatty acids.

The quaternization or the preparation of the salts of the compounds (4) is carried out by the processes known in this field and leads to the esteramine quats or esteramine salts of the general formula (1) according to the invention, in which R⁶ and R⁷ have the meaning given.

The salts are generally prepared by adding the acids, if appropriate as aqueous or alcoholic solutions in an amount corresponding to the desired degree of salt formation, to the poly (oxyalkylene) alkanolamine esters at 20 ° -80 ° C. and, if necessary with stirring, in portions with cooling. The quaternization is carried out in accordance with the generally known processes, the poly (oxyalkylene) alkanolamine esters, optionally with the use of a solvent, being heated to 40-80 ° C. and the quaternizing agent being added in portions in an amount corresponding to the desired degree of quaternization.

-OCC-(CH₂)_n -COO-, Cl⁻, Br⁻, J⁻, SO₄ ^2-, PO₄ ^3-, NO₃ ^-. n = 0 - 10The following are therefore preferably considered as anions:

-OCC- (CH₂) _n -COO-, Cl⁻, Br⁻, J⁻, SO ₄ ^2- , PO ₄ ^3- , NO ₃ ^- . n = 0-10

und/oder

wobei auch mehrere Anionen nebeneinander vorliegen können und in einer Menge zugegeben werden, daß der resultierende pH-Wert der Gesamtmischiing einer 30 %igen Mischung zwischen 2 - 6, vorzugsweise 3 - 5, liegt.According to the invention, the anions Cl⁻, SO₄2⁻,

and or

where several anions can also be present side by side and are added in an amount such that the resulting pH of the total mixture of a 30% mixture is between 2-6, preferably 3-5.

The compounds of the general formula (1) which are also used according to the invention can be used alone or as mixtures, the triester of the general formula (1) being predominantly in dispersions, the diesters of the - depending on the structure of the compounds of the general formula (3) general formula (1) can be converted into solutions.

According to the invention, compounds of the general formula (1) with A⁻ = methosulfate - and in particular lactate radical - are preferably used to prepare the solutions. Surprisingly, it was found that these solutions are quaternized even without the use of conventional ammonium salts Ammonium compounds and other auxiliaries and additives customary in this field give the textiles treated with them, in addition to a soft feel, an excellent rewetting capacity.

Despite the absence of the usual auxiliary agents, highly concentrated solutions can be prepared which contain up to 35% by weight of pure active substance. The solutions can be produced without problems using normal stirrers and, moreover, do not have the known problems which occur when storing dispersions.

While the diester compounds are prepared by simply dissolving in cold or accelerated in heated water, as described, the triester compounds are emulsified or dispersed by the known processes, with the customary equipment and the known auxiliaries and additives also being used.

In a modification or supplement to the known processes, in which the procedure is usually such that the water preheated to about 10 ° C. below the clear melting range of the plasticizers is introduced, the compounds according to the invention can also be used at room temperature (20-25 ° C.) be incorporated. With thorough stirring, the dye solution, then the antifoam emulsion that may be required and finally the individual plasticizers are dispersed in succession or in a mixture. After adding a portion of an electrolyte solution (if necessary), perfume oil is added, followed by the remaining amount of the electrolyte solution. According to the invention, work is preferably carried out without the addition of electrolyte solutions.

• (5), welche hergestellt werden aus Hydroxyalkylendiaminen und C₁₆-C₂₂ Fettsäure in molaren Verhältnissen von 1 : 2 bzw. 1 : 1: $${\text{R}}^{\text{11}}{\text{-CO-NH-R}}^{\text{13}}{\text{-N(-R}}^{\text{12}}{\text{OH)-COR}}^{\text{11}}$$
  
  worin R¹¹ ein gegebenenfalls substituierter Alkyl- oder Alkylenrest mit 15 - 21 C-Atomen, R¹ und R¹³ divalente C₁-C₃-Alkylenreste sind, und/oder
• (6) substituierte Imidazoline der allgemeinen Formel
  
  worin R¹¹, R¹ die oben angegebene Bedeutung haben, R¹⁴ H oder ein C₁-C₄ Alkyl- oder Hydroxyalkylrest und/oder
• (7) Verbindungen der Formel
  
  worin R¹¹, R¹, R¹⁴ die oben angegebene Bedeutung haben und/oder
• (8) Reaktionsprodukte aus C₁₆-C₂₂ Fettsäuren mit Dialkylentriaminen in einem molekularen Verhältnis von 2 : 1 $${\text{R}}^{\text{11}}{\text{-CO-NH-R}}^{\text{12}}{\text{-N(R}}^{\text{14}}{\text{)}}_{\text{2}}{\text{-R}}^{\text{13}}{\text{-NHCOR}}^{\text{11}}$$
  
  worin R¹¹, R¹, R¹³, R¹⁴ die oben angeführte Bedeutung haben und/oder
• (9) substituierte Imidazoline der allgemeinen Formel
  
  worin R¹¹, R¹ und R¹⁴ die oben angeführte Bedeutung haben und worin die Verbindungen der Formeln (5) bis (9) unabhängig voneinander ganz oder teilweise in Form ihrer Salze mit organischen und/oder anorganischen Säuren bzw. ihrer quaternären Verbindungen vorliegen können und/oder
• (10) quaternäre Ammoniumverbindungen der allgemeinen Formel
  
  worin R¹⁵ ein gegebenenfalls substituierter Alkyl- oder Alkylenrest mit 16 - 22 C-Atomen, R¹⁶ und R¹⁷ unabhängig voneinander C₁-C₄ Alkyl- oder Hydroxyalkylreste und R¹⁹ gleich R¹⁵ oder R¹⁶ ist und A⁻ ein Anion darstellt.

The fabric softeners according to the invention can each contain one or more of the components of the general formula (1) and, if appropriate, additionally from 10-50% by weight, preferably 10-30% by weight, based on the amount of the compounds of the general formula (1), one or more of the commercially available compounds

• (5), which are prepared from hydroxyalkylenediamines and C₁₆-C₂₂ fatty acid in molar ratios of 1: 2 and 1: 1: $${\text{R}}^{\text{11}}{\text{-CO-NH-R}}^{\text{13}}{\text{-NO}}^{\text{12th}}{\text{OH) -COR}}^{\text{11}}$$
  
  wherein R¹¹ is an optionally substituted alkyl or alkylene radical having 15-21 carbon atoms, R¹ and R¹³ are divalent C₁-C₃ alkylene radicals, and / or
• (6) substituted imidazolines of the general formula
  
  wherein R¹¹, R¹ have the meaning given above, R¹⁴ H or a C₁-C₄ alkyl or hydroxyalkyl radical and / or
• (7) Compounds of the formula
  
  wherein R¹¹, R¹, R¹⁴ have the meaning given above and / or
• (8) reaction products of C₁₆-C₂₂ fatty acids with dialkylenetriamines in a molecular ratio of 2: 1 $${\text{R}}^{\text{11}}{\text{-CO-NH-R}}^{\text{12th}}{\text{-NO}}^{\text{14}}{\text{)}}_{\text{2nd}}{\text{-R}}^{\text{13}}{\text{-NHCOR}}^{\text{11}}$$
  
  wherein R¹¹, R¹, R¹³, R¹⁴ have the meaning given above and / or
• (9) substituted imidazolines of the general formula
  
  in which R¹¹, R¹ and R¹⁴ have the meaning given above and in which the compounds of the formulas (5) to (9) independently of one another in whole or in part in the form of their salts with organic and / or inorganic acids or their quaternary compounds and / or
• (10) quaternary ammonium compounds of the general formula
  
  wherein R¹⁵ is an optionally substituted alkyl or alkylene radical with 16 - 22 C atoms, R¹⁶ and R¹⁷ independently of one another C₁-C₄ alkyl or hydroxyalkyl radicals and R¹⁹ is R¹⁵ or R¹⁶ and A⁻ is an anion.

These products are commercially available and are available, for example, under the registered trademark REWOQUAT from REWO chemische Werke GmbH, Steinau an der Strasse or the registered trademark VARISOFT from Sherex Chemicals Group, Inc., Ohio, USA.

The proportions in which these compounds are added can be optimized by the person skilled in the art in the present field by means of some well-known tests by means of a few orientation tests.

In addition to the fabric softener components of the general formula (1), the customary auxiliaries and additives can also be used to produce the fabric softener according to the invention. These are, in particular, dyes and fragrances, electrolytes and higher molecular weight ether compounds for viscosity regulation, small amounts of organic solvents and - provided they do not adversely affect the rewetting capacity - customary cationic and / or nonionic surfactants.

By combining the components according to general formula (1) and optionally the commercially available quaternary ammonium compounds and optionally auxiliaries, fabric softeners can be produced which are clearly soluble in water or have good emulsifying or dispersing properties and give textile materials, in particular those made from natural and regenerated cellulose, as well as wool and terry cloth, an improved softness and an improved rewetting capacity.

In addition to the usual textile materials, the fabric softeners according to the invention are therefore used in particular where larger amounts of moisture and moisture are to be removed from the body surface within a short time, such as in the case of hand towels or bath towels. However, the fabric softeners according to the invention can also be used successfully where moisture has to be absorbed directly by the skin within a relatively long period of time, such as for bedclothes or bed linen.

Like the fabric softeners belonging to the known prior art, the fabric softeners according to the invention are added after the actual washing process in the last rinse cycle. After dilution with water, the application concentration is in the range of 0.1 - 10 g of fabric softener per liter of treatment liquor, depending on the area of application.

The analytical methods used in the following examples are the most common in this field and are:

1. Total amine number (GAZ), tertiary amine number (TAZ)

The total amine number indicates the number of milligrams of potassium hydroxide equivalent to the total amine basicity of 1 g of the amine compound (mg KOH / g). The tertiary amine number indicates the number of milligrams of potassium hydroxide equivalent to the tertiary amine basicity of 1 g of the amine compound.

The values are determined according to A.O.C.S. Official Method Tf 2a - 64.

2. Saponification number (VZ)

The saponification number is a measure of the free and bound acids contained in fats and technical fatty acids. It indicates the number of milligrams of potassium hydroxide required to saponify 1 gram of fat or technical fatty acids (mg KOH / g).

The values are determined according to the standard methods of the German Society for Fat Chemistry (DGF): DGF C-V3.

3. hydroxyl number (OHZ)

The hydroxyl number is used to determine the hydroxyl group content and indicates the number of milligrams of potassium hydroxide required to neutralize the acetic acid consumed by 1 gram of fat in acetylation (mg KOH / g).

The values are determined according to the DGF standard method C-V17a.

4. Acid number (SZ)

The acid number is a measure of the fat or technical fatty acid content of free acids and indicates the milligrams of potassium hydroxide that are necessary to neutralize 1 gram of substance.

The values are determined according to the DGF standard method C-V4.

5. content of cation-active substance (Cat SO ₃ )

This method is used to determine the content of cation-active substances. Here, cation-active substances are long-chain compounds which contain quaternary ammonium groups. The content is given in% quaternary compound, calculated as an SO₃ equivalent with a molecular weight of 80 g / mol.

The content is determined by a two-phase titration according to ISO standards 2871-1 and 2871-2 (1988 E).

Preparation of the poly (oxyalkylene) ammonium alkanol esters Examples I. Preparation of the hydroxylamines of the general formula (3) Example 1

wurde in einem Autoklaven bei 145 - 160 °C portionsweise mit 352 g (8 mol) Ethylenoxid versetzt, so daß der Druck zwischen 1 - 3 bar gehalten wurde. Nachdem die zugegebene Menge Ethylenoxid abreagiert war, erhielt man 1.264 g einer hellen Flüssigkeit der allgemeinen Formel (3) mit $$\begin{gathered} \text{a + c = 6,6} \\ \text{b = 0} \end{gathered}$$

$$\text{d + e + f + g = m = 4}$$

und $${\text{R}}^{\text{7}}{\text{, R}}^{\text{8}}{\text{, R}}^{\text{9}}{\text{, R}}^{\text{10}}\text{= H}$$

912 g (2 mol) of an amine of the general formula (2) with $$\begin{gathered} \text{a + c = 6.6} \\ \text{b = 0} \end{gathered}$$

Was added in portions in an autoclave at 145-160 ° C with 352 g (8 mol) of ethylene oxide, so that the pressure was kept between 1-3 bar. After the added amount of ethylene oxide had reacted, 1,264 g of a light liquid of the general formula (3) were obtained $$\begin{gathered} \text{a + c = 6.6} \\ \text{b = 0} \end{gathered}$$

$$\text{d + e + f + g = m = 4}$$

and $${\text{R}}^{\text{7}}{\text{, R}}^{\text{8th}}{\text{, R}}^{\text{9}}{\text{, R}}^{\text{10th}}\text{= H}$$

This compound had a total amine number (GAZ) of 179 mg KOH / g, a tertiary amine number (TAZ) of 175 mg KOH / g and a hydroxyl number (OHZ) of 348 mg KOH / g.

The examples listed in Table I were prepared analogously to Example 1.

II Preparation of the ester amines of the general formulas (4) Example 7

625 g (1 mol) of the amine ethoxylate from Example 1 were mixed with 570 g (2 mol) of tallow methyl ester (C₁₇H₃₅COOCH₃), 1.5 g of solid, powdery NaOH and 3 g of sodium hypophosphite and stirred under a nitrogen atmosphere and heated to 180 ° C. The methanol formed during the reaction was distilled off. After approx. 90% of the theoretical amount of methanol had been removed, a vacuum of approx. 20 mbar was applied and the transesterification was completed. After about 7 hours, 1,135 g of a yellow liquid of the general formulas (4) also formed $$\begin{gathered} \text{a + c = 6.6} \\ \text{b = 0} \\ \text{d + e + f + q = m = 4} \\ {\text{R}}^{\text{7}}{\text{, R}}^{\text{8th}}{\text{, R}}^{\text{9}}{\text{, R}}^{\text{10th}}\text{= H} \end{gathered}$$

• GAZ = 98 mg KOH/g
• TAZ = 97 mg KOH/g
• OHZ = 93 mg KOH/g
• VZ = 106 mg KOH/g

The connection had the following analysis numbers:

• GAZ = 98 mg KOH / g
• TAZ = 97 mg KOH / g
• OHZ = 93 mg KOH / g
• VZ = 106 mg KOH / g

The examples listed in Table II were prepared analogously to Example 7.

III Preparation of the quaternary ammonium compounds or the amine salts Example 14

$${\text{R}}^{\text{6}}{\text{und R}}^{\text{7}}{\text{= -CH}}_{\text{3}}$$

1,149 g (1 mol) of the ester from Example 7 were mixed in portions at 60 ° C. with stirring with 252 g (2 mol) of dimethyl sulfate, so that the temperature of the reaction mixture could be kept between 60-70 ° C. 1,397 g of a yellow liquid of the general formula (1) were formed $$\begin{gathered} \text{a + c + b = n} \\ \text{a + c = 6.6} \\ \text{b = 0} \\ \text{d + e + f + g = m = 4} \\ {\text{R}}^{\text{7}}{\text{, R}}^{\text{8th}}{\text{, R}}^{\text{9}}{\text{, R}}^{\text{10th}}\text{= H} \end{gathered}$$

$${\text{R}}^{\text{6}}{\text{and R}}^{\text{7}}{\text{= -CH}}_{\text{3rd}}$$

Cat SO₃ sauer :

9,6 g SO₃ / 100 g

GAZ :

2,3 mg KOH/g

The analysis numbers of this connection are:

Cat SO₃ sour:

9.6 g SO₃ / 100 g

GAZ:

2.3 mg KOH / g

The examples listed in Table III below were carried out analogously to Example 14.

IV Technical application review A) Preparation of the fabric softener solutions or fabric softener dispersions Procedure 1

Put water, dye solution and, if necessary, a portion of the electrolyte at a temperature of 15 ° C. Slowly emulsify the component at a temperature of 23 ° C while stirring (propeller stirrer), or emulsify the components one after the other or as a mixture under the same conditions. If necessary, add further aliquots of electrolyte during emulsification. Then add the perfume oil while stirring and, if necessary, add the remaining amount of electrolyte after the emulsification process to adjust the viscosity.

The mixture results in a homogeneous emulsion or solution.

Procedure 2

Submit water, dye solution and, if necessary, a portion of the electrolyte at a temperature of 45 ° C. Slowly emulsify in the component at a temperature of approx. 55 ° C while stirring (propeller stirrer), or emulsify the components in succession or as a mixture under the same conditions. If necessary, add further aliquots of electrolyte during emulsification.

Stir the mixture cold to approx. 25 ° C. Then add the perfume oil while stirring and, if necessary, adjust the viscosity with the remaining amount of electrolyte.

The mixture results in a homogeneous emulsion or solution.

B) Check for soft grip

To assess the handle, the textile material made of wool, cotton, polyester / cotton 50: 3 and polyester is soaked for about 10 minutes with a liquor of tap water (about 9 ° dH and a temperature of 15-20 ° C) and an emulsion according to the invention, Dispersion or solution treated. The concentration of the compounds according to the invention in the liquor is 0.025% by weight, based on the total active substance. The dried textiles were checked for their soft feel by nine people with appropriate experience in evaluating the softness of textiles and compared to textiles not treated with fabric softeners. The assessment is based on a graded point system, with the final assessment being represented by the arithmetic mean. After drying, the textile goods treated in this way have an excellent soft, fluffy feel and a greatly improved rewetting capacity compared to commercially available agents.

C) Examples example 1

• 15.0 g of the component according to claim 1

  R⁵

  = 3 x C₈₋₁₈
  = 1 x H

  R⁶ʼ⁷

  = H

  n

  = 5.6

  A⁻

  = Lactate residue

• 0.7 g of dye (1% solution SANDOLAN ^R Walkblau NBL 150; Sandoz)
• ad 100.0 g water 13 ° dH

Introduce water and dye solution at 45 ° C, emulsify the component at 55 ° C while stirring (propeller stirrer) and then stir cold. The approach results in a homogeneous emulsion.

Viscosity (20 ° C measured with Brookfield LVT, spindle 1 at 30 rpm): <100 mPa · s

The following examples were prepared analogously to example 1.

Example 2

• 30.0 g of the component according to claim 1 with

  R⁵

  = 3 x C₈₋₁₈
  = 1 x H

  R⁶ʼ⁷

  = H

  n

  = 5.6

  A⁻

  = Lactate residue

• 1.3 g of dye
• ad 100.0 g water 13 ° dH

The approach results in a homogeneous emulsion.

Viscosity approx. 100 mPas Example 3

• 15.0 g of the substance according to claim 1 with

  R⁵

  = 2 x C₈₋₁₈
  = 2 x H

  R⁶ʼ⁷

  = CH₃

  n

  = 5.6

  A⁻

  = CH₃SO ₄ ^-

• 0.7 g of dye
• ad 100.0 g water 13 ° dH

The approach gives a clear solution.

• Viscosity <100 mPas
• Network assets = 94%

Example 4

• 15.0 g of the component according to claim 1

  R⁵

  = 3 x C₈₋₁₈
  = 1 x H

  R⁶ʼ⁷

  = CH₃

  n

  = 5.6

  A⁻

  = CH₃SO ₄ ^-

• 0.7 g of dye
• ad 100.0 g water 13 ° dH

The approach results in a homogeneous emulsion.
Viscosity <100 mPas

Example 5

• 15.0 g of the component according to claim 1

  R⁵

  = 2 x C₈₋₁₈
  = 2 x H

  R⁶ʼ⁷

  = CH₃; H

  n

  = 5.6

  A⁻

  = CH₃SO ₄ ^- ; Cl⁻

• 0.7 g of dye
• ad 100.0 g water 13 ° dH

• Viskosität < 100 mPa·s
• Rücknetzvermögen > 90 %

The approach gives a clear solution.

• Viscosity <100 mPas
• Network assets> 90%

Example 6

• 3.0 g of the component according to claim 1 with

  R⁵

  = 2 x C₈₋₁₈
  = 2 x H

  R⁶ʼ⁷

  = CH₃

  n

  = 5.6

  A⁻

  = CH₃SO ₄ ^-

• 12.0 g of the component according to claim 1

  R⁵

  = 2 x C₈₋₁₈
  = 2 x H

  R⁶ʼ⁷

  = H

  n

  = 5.6

  A⁻

  = Lactate residue

• 0.7 g of dye
• ad 100.0 g water 13 ° dH

• Viskosität < 100 mPa·s
• Rücknetzvermögen = 95 %

The approach gives a clear solution.

• Viscosity <100 mPas
• Network assets = 95%

Example 7

• 15.0 g of the component according to claim 1

  R⁵

  = 3 x C₈₋₁₈
  = 1 x H

  R⁶ʼ⁷

  = CH₃

  n

  = 5.6

  A⁻

  = CH₃SO ₄ ^-

• 15.0 g of the component according to claim 1

  R⁵

  = 3 x C₈₋₁₈
  = 1 x H

  R⁶ʼ⁷

  = H

  n

  = 5.6

  A⁻

  = Lactate residue

• 0.7 g of dye
• ad 100.0 g water 13 ° dH

• Viskosität ca. 200 mPa·s
• Rücknetzvermögen ca. 85 %

The approach results in a homogeneous emulsion.

• Viscosity approx. 200 mPas
• Network assets approx. 85%

Claims (4)

1. Aqueous softener comprising

   A) from 5 to 35 % by weight of at least one of the compounds of the general formula (1)

   

   wherein

   the groups R, which may be identical or different, represent H or -CH₃,

   R¹, R, R³ and R⁴, which may be identical or different, each represent the radicals R⁵-(O-CH(R)-CH₂)_m-, wherein R⁵ may be an optionally substituted acyl radical having from 6 to 22 carbon atoms that optionally contains multiple bonds, or may be H, and wherein

   at least one R⁵ must be an acyl radical and at least one R⁵ must be H,

   R⁶ and R⁷, which may be identical or different, are each independently of the other H, -CH₃, -C₂H₅ or -C₂H₄OH,

   A⁻ is at least one organic and/or inorganic anion, n has a value of from 1 to 30, and

   m is from to 5 and the sum of all m values is at least 4, and optionally

   B) from 10 to 90 % by weight, based on A), of ammonium compounds customary in softeners, and optionally

   C) from 1 to 5 % by weight of customary dyestuffs, perfumes and other excipients and additives customary in softeners, and

   D) water to make up to 100 % by weight.
2. Aqueous softener according to claim 1, characterised in that it comprises, as component A), from 15 to 30 % by weight of at least one of the compounds of the general formula (1) wherein R is -CH₃, two or three of the radicals R¹, R, R³ and R⁴ are R⁵-O-CH₂-CH₂- wherein R⁵ is an acyl radical having from 8 to 18 carbon atoms, and one or two of the radicals R¹, R, R³ and R⁴ represent HO-CH₂-CH₂-,

   n is from to 15,

   R⁶ and R⁷, which may be identical or different, are each independently of the other H or -CH₃, and

   A⁻ is the radical of an optionally substituted carboxylic acid having from 1 to 8 carbon atoms in the main chain or is the methosulphate or ethosulphate radical.
3. Aqueous softener according to claim 1, characterised in that it comprises, as component A), from 15 to 30 % by weight of at least one of the compounds of the general formula (1) wherein R is -CH₃, three of the radicals R¹, R, R³ and R⁴ are R⁵-O-CH₂-CH₂- wherein R⁵ is an acyl radical having from 8 to 18 carbon atoms and one of the radicals R¹, R, R³ and R⁴ is the radical wherein R⁵ is H,

   n is from 2 to 8,

   R⁶ and R⁷ are each H, and

   A⁻ is the lactate radical.
4. Aqueous softener according to claim 1, characterised in that it comprises as, component B), from 10 to 50 % by weight, based on A), of at least one of the compounds from the group of the general formula (5)
   
           R¹¹-CO-NH-R¹³-N(-R¹OH)-COR¹¹     (5)
   
   
      wherein R¹¹ is an optionally substituted alkyl or alkenyl radical having from 15 to 21 carbon atoms and R¹ and R¹³ are divalent C₁-C₃alkylene radicals, and/or
   substituted imidazolines of the general formula (6)

   

   
      wherein R¹¹ and R¹ are as defined above and R¹⁴ is H or a C₁-C₄alkyl or hydroxyalkyl radical, and/or
   compounds of the formula (7)

   

   
      wherein R¹¹, R¹ and R¹⁴ are as defined above, and/or
   products of the reaction of C₁₆-C₂₂ fatty acids with dialkylenetriamines in a molecular ratio of 2:1
   
           R¹¹-CO-NH-R¹-N(R¹⁴)₂-R¹³-NHCOR¹¹     (8)
   
   
      wherein R¹¹, R¹, R¹³ and R¹⁴ are as defined above, and/or
   substituted imidazolines of the general formula (9)

   

   
      wherein R¹¹, R¹ and R¹⁴ are as defined above and wherein the compounds of formulae (5) to (9), each independently of the other, may be wholly or partially in the form of their salts with organic and/or inorganic acids or of their quaternary compounds, and/or
   quaternary ammonium compounds of the general formula (10)

   

   
      wherein R¹⁵ is an optionally substituted alkyl or alkenyl radical having from 16 to 22 carbon atoms, R¹⁶ and R¹⁷, each independently of the other, are C₁-C₄alkyl or hydroxyalkyl radicals, R¹⁸ is identical to R¹⁵ or R¹⁶ and A⁻ is an anion.