EP0413249A1 - Fabric softener - Google Patents

Abstract

The invention relates to fabric softeners which contain as softening components a mixture of   Aa) compounds of the general formula <IMAGE> in which R<2> can be a radical of the general formula <IMAGE> and at least   Ab) one of the compounds of the general formulae <IMAGE> <IMAGE> <IMAGE> <IMAGE> in the Aa) : Ab) ratio 90-10 : 10-90% by weight.

Description

The present invention relates to fabric softeners in the form of aqueous 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 softening 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. Inadequate rewetting capacity has an adverse effect where larger amounts of moisture are to be absorbed by the skin surface. e.g. B. with hand or bath towels as well as with body or bed linen.

The object of the present invention was to overcome the above-mentioned disadvantages of conventional fabric softener formulations and to provide fabric softening detergents which, in addition to good biodegradability and soft feel, have significantly improved dispersibility and improved rewetting capacity.

It has surprisingly been found that the fabric softener, consisting of mixtures of water-insoluble ammonium compounds containing quaternary ester groups with salts of mono- or polyamine compounds, which can be prepared by protonation with inorganic or organic acids, meets these requirements.

• A) 5 bis 25 Gewichts-% einer Mischung zweier Weichspülkom­ponenten, bestehend aus
  • a) 10 bis 90, vorzugsweise 20 - 80 Gew.-% mindestens einer Verbindung der Formel (I)
    
    in der R für H oder Methyl steht, R¹ ein linearer ge­sättigter oder ungesättigter Acylrest mit 14 - 22, vorzugsweise 16 - 18 Kohlenstoffatome oder H ist, wo­bei R¹ mindestens einmal der Acylrest ist, R² und R³ unabhängig voneinander für einen linearen ge­sättigten, gegebenenfalls OH-Gruppen enthaltenden Alkylrest mit 1 - 4 Kohlenstoffatomen stehen und R² zusätzlich noch für eine Struktur der Formel (II) steht, in der die Reste R¹, R³ die gleiche Bedeutung wie oben aufgeführt haben und R⁴ für einen gesättig­ten oder ungesättigten, linearen aliphatischen Alkyl­rest mit 8 - 22, vorzugsweise 12 - 18 Kohlenstoff­atomen steht
    
    A⁻ für das Anion eines Quaternierungsmittels steht, insbesondere Dimethylsulfat, Diethylsulfat, Methyl­chlorid, n, x und y für 0 oder 1 steht, wobei die Summe von x + y + (3-n) = 4 sein muß, und m gleich der Wertigkeit des Säureanions ist; und
  • b) 90 bis 10 Gew.-%, vorzugsweise 80 - 20, mindestens einer Verbindung der Formel (III) bis (V)
    
    worin R¹, R³, R⁴ die gleiche Bedeutung wie oben ange­geben haben, R⁵ = H oder R⁶ ist, R⁶ die Gruppe -CHX-CHY-­O- bedeutet, worin X und Y Wasserstoff oder Methyl, nicht jedoch gleichzeitig Methyl sein können, und m einen Wert zwischen 0 bis 6 annehmen, p = 1 - 3, R⁹ ein gesättigter oder ungesättigter linearer aliphatischer Alkylrest mit 13 bis 21, insbesondere 17 C-Atomen ist, und q = 0 oder 1 mit p + q ≧ 2 sein kann, n = 1, 2, 3 sein kann, Z⁻ für das Anion einer wasserloslichen ein- oder mehrwertigen anorganischen oder organischen Säure wie Methylschwefelsäure, Ethylschwefelsäure, einer Halogenwasserstoffsäure, Phosphorsäure, Ameisensäure, Essigsäure, Oxalsäure, Glykolsäure, Zitronensäure, Wein­säure, Äpfelsäure und insbesondere Salzsäure und Milch­säure steht, und ergänzend auf 100 Gew.-%.
• B) Wasser, Farbstoffe, Parfüm und weitere in Weichspülmit­teln übliche Hilfsstoffe wie kurzkettige Alkohole, Salze.

The invention therefore relates to aqueous fabric softeners containing

• A) 5 to 25% by weight of a mixture of two fabric softener components, consisting of
  • a) 10 to 90, preferably 20 to 80% by weight of at least one compound of the formula (I)
    
    in which R is H or methyl, R¹ is a linear saturated or unsaturated acyl radical having 14-22, preferably 16-18 carbon atoms or H, where R¹ is at least once the acyl radical, R² and R³ independently of one another represent a linear saturated alkyl radical which may contain OH groups and have 1-4 carbon atoms and R² additionally represents a structure of the formula (II) in which the radicals R¹, R³ have the same meaning as listed above and R⁴ is is a saturated or unsaturated, linear aliphatic alkyl radical having 8-22, preferably 12-18, carbon atoms
    
    A⁻ stands for the anion of a quaternizing agent, in particular dimethyl sulfate, diethyl sulfate, methyl chloride, n, x and y stands for 0 or 1, where the sum of x + y + (3-n) = 4 and m equals the valency of the acid anion; and
  • b) 90 to 10% by weight, preferably 80-20, of at least one compound of the formula (III) to (V)
    
    wherein R¹, R³, R⁴ have the same meaning as given above, R⁵ = H or R⁶, R⁶ represents the group -CHX-CHY-O-, wherein X and Y can be hydrogen or methyl, but not simultaneously methyl, and m assume a value between 0 to 6, p = 1 - 3, R⁹ is a saturated or unsaturated linear aliphatic alkyl radical with 13 to 21, in particular 17 C atoms, and q = 0 or 1 with p + q ≧ 2, n = 1, 2, 3, Z⁻ for the anion of a water-soluble mono- or polyvalent inorganic or organic acid such as methylsulfuric acid, ethylsulfuric acid, a hydrohalic acid, phosphoric acid, formic acid, acetic acid, oxalic acid, glycolic acid, citric acid, tartaric acid, malic acid and especially hydrochloric acid and lactic acid, and in addition to 100 wt .-%.
• B) water, dyes, perfume and other auxiliaries customary in fabric softeners, such as short-chain alcohols, salts.

in der R⁷ für einen linearen, gesättigten oder ungesättig­ten aliphatischen Alkylrest mit 16 - 18 Kohlenstoffatomen steht, R⁸ einen linearen, gesättigten oder ungesättigten aliphatischen Alkylrest mit 11 - 17 Kohlenstoffatomen be­deuten kann und der Komponente b), deren Amingrundkörper folgende Strukturen aufweisen kann

in der R⁷ und R⁸ und m die gleiche Bedeutung wie oben auf­geführt haben und m insbesondere 1 ist, wobei diese Amine mit organischen oder anorganischen Säuren, insbesondere Milchsäure oder Salzsäure, neutralisiert werden.According to the invention, preference is given to using 10-25% by weight of a mixture of the fabric softener components A a) and A b), the compounds of the formula I having the following structures in the preferred embodiment

in which R⁷ is a linear, saturated or unsaturated aliphatic alkyl radical having 16-18 carbon atoms, R⁸ can be a linear, saturated or unsaturated aliphatic alkyl radical having 11-17 carbon atoms and component b), the amine base of which may have the following structures

in which R⁷ and R⁸ and m have the same meaning as listed above and m is in particular 1, these amines being neutralized with organic or inorganic acids, in particular lactic acid or hydrochloric acid.

The compounds according to A a) used according to the invention are prepared by processes known per se, wherein generally an alkanolamine with a long-chain fatty acid methyl ester in the presence of basic catalysts such as sodium methylate, sodium carbonate, transesterified at temperatures of 140-180 ° C. and the resulting methanol is continuously distilled off. Instead of the fatty acid methyl esters, fatty acid glycerides can also be used.

The compounds according to A b) used according to the invention are commercially available products which are protonated in a manner known per se with organic or inorganic acids. The procedure is preferably such that the amine is melted and the protic acid is added to this melt with vigorous stirring.

Examples of the organic acids used are formic acid, acetic acid, methylsulfuric acid, ethylsulfuric acid, in particular lactic acid, malic acid, tartaric acid, citric acid, oxalic acid, glycolic acid; inorganic acids such as hydrohalic acids, especially hydrochloric acid, sulfuric acid, phosphoric acid. Lactic acid and hydrochloric acid are preferred according to the invention.

Examples of the quaternizing agents used are short-chain dialkyl phosphates and sulfates such as, in particular, dimethyl sulfate, diethyl sulfate, dimethyl phosphate, diethyl phosphate, short-chain halogenated hydrocarbons, in particular methyl chloride.

By combining the components according to claim 1 a) and b), fabric softeners can be produced which have good dispersibility and textile materials, especially those made from natural and regenerated cellulose loose, as well as wool and terrycloth, in addition to a pleasantly soft handle, give an improved reed-wetting ability.

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 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.

The fabric softener is produced by emulsifying or dispersing the individual components in water. The usual procedures in this field can be applied.

The usual procedure is to put the water preheated to approx. 10 ° C below the clear melting point of the plasticizer, with good stirring, first the dye solution, then the required antifoam emulsion and finally the clear melt of the individual plasticizers one after the other or the melt the mixture is dispersed. After adding a portion of an electrolyte solution, perfume oil is added, followed by the remaining amount of electrolyte solution and then allowed to cool to room temperature with stirring.

The fabric softeners according to the invention can each contain one or more components a) and b) within the specified limits.

The quantitative ratios are largely uncritical and can be optimized by the person skilled in the present field by means of some well-known tests using the generally known criteria.

In addition to the fabric softener components, the usual auxiliaries and additives can also be used to produce the fabric softener according to the invention. These are, in particular, complexing agents, optical brighteners, 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 raking wettability - conventional surfactants.

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

To assess the handle, the textile material made of wool, cotton, polyester / cotton 50: 3 and polyester is treated for about 3 minutes with a liquor of tap water (about 13 ° dH) and 1 g of the dispersion according to the invention. The dried textiles were checked by five people with appropriate experience in evaluating the softness of textiles for their soft feel and compared to untreated textiles. After drying, the textile goods treated in this way have an excellent, soft, fluffy feel and a greatly improved smoke-wetting ability compared to commercially available agents.

The x-ray power is measured in accordance with DIN 53 924 with the modification that the strips of the fabric (test pieces) are 1.5 cm wide.

Production of the fabric softener dispersions

The fabric softener dispersions according to the invention are prepared from the components given in the examples below in accordance with the following instructions or in analogy thereto:

The dye solution and then the plasticizer components Aa) and Ab) preheated to 45 ° C are first successively dispersed in the water preheated to 35 ° C. with good stirring (propeller stirrer). A portion of the 25% calcium chloride solution is then added, in an amount such that the entire batch remains readily stirrable. After a 10 minute dispersion phase, the perfume oil is added at approx. 35 ° C, then the viscosity is adjusted to the desired value at approx. 30 ° C with the remaining amount of the calcium chloride solution. Allow to cool to room temperature while continuing to stir well and if possible avoid air pockets.

If high-speed agitators (Ultra Turrax, Example 5) are used, water at 20 ° C. is introduced in a modification of the process specified and components Aa) and Ab) are preheated to 30 ° C. as a mixture and dispersed at this temperature. The starting viscosities of the mixtures according to the invention were measured using a Brookfield viscometer, type LVT, spindle 1 at 30 revolutions / min according to the manufacturer's instructions and are between about 40-100 mPas at 25 ° C.

Examples

p, q = 1
R⁴ = C₁₇H₃₅
R⁶ = CH₂-CH₂-O- mit m = 3
Z⁻ = Lactatrest
0,4 g Parfomöl VERTALIA^R100457D der Firma Orissa Dribing
0,45 g Farbstoff (1 %ige Lösung SANDOLAN^R Walkblau NBL 150 der Firma Sandoz)
0,13 g CaCl₂
ad 100 Wasser 13 ° dH example 1
3.00 g of component Aa) with
R = H R¹ = C₁₈ acyl, 2 times; H 1 time
R³ = CH₃
Y = O
A⁻ = CH₃SO₂⁻
12.00 g component Ab) Formula IV with

p, q = 1
R⁴ = C₁₇H₃₅
R⁶ = CH₂-CH₂-O- with m = 3
Z⁻ = lactate residue
0.4 g perfume oil VERTALIA ^R 100457D from Orissa Dribing
0.45 g of dye (1% solution SANDOLAN ^R Walkblau NBL 150 from Sandoz)
0.13 g CaCl₂
ad 100 water 13 ° dH

The washed textiles are treated in a washing-up liquor which treats the agent according to the invention in a conventional manner in concentrations of 0.1 to 10 g / l, preferably 0.5-3 g / l.

In addition to the improved dispersibility of components Aa) and Ab), the treated textiles had an excellent soft feel and an x-ray power of 70% (average of 10 measurements).

A comparative example made from
6 g distearyldimethylammonium chloride (commercial product)
0.2 g perfume oil (as in example 1)
0.2 g of dye (as in Example 1)
0.1 g of silicone antifoam emulsion Antifoam DB 110 A from DOW
ad 100 water 13 ° dH
showed a significantly reduced retorting power of 50%.

Example 2
was carried out analogously to Example 1 with the modification that
12 g of component Aa) as in Example 1
3 g of component Ab) as in Example 1
0.11 g CaCl₂
were used.

In addition to an excellent soft feel, a rewetting capacity of 90% was determined.

Example 3
was carried out analogously to Example 1 with the modification that
18 g of component Aa) as in Example 1
2 g of component Ab) as in Example 1
0.34 g CaCl₂
were used.

In addition to an excellent soft feel, a rewetting capacity of 74% was determined.

Example 4
was carried out analogously to Example 1 with the modification that
9 g of component Aa) as in Example 1
9 g of component Ab) as in Example 1
0.19 g CaCl₂
were used.

In addition to an excellent soft feel, a rewetting capacity of 80% was measured.

Example 5
was dispersed as stated above, with the modification to Example 1
12 g of component Aa) as in Example 1
3 g of component Ab) as in Example 1
0.3 g CaCl₂
were used.

In addition to excellent dispersibility in cold water and an excellent soft feel, a moisture-wicking capacity of 92% was measured.

Example 6
was carried out analogously to Example 1 with the modification that
13.5 g of component Aa) formula I with
R = H
R¹ = C₁₈ acyl radical twice; H once
R³ = -CH₃
y = O
A⁻ = CH₃SO₃-
1.5 g of component Ab) formula V with
R³ = -CH₃
R⁴ = C₁₈H₃₇⁻
Z⁻ = lactate residue
0.02 g of silicone antifoam emulsion Antifoam DB 110 A from DOW
were used.

In addition to excellent dispersibility in cold water and an excellent soft feel, a backwetting capacity of 70% was measured.

Example 7
was carried out analogously to Example 6 with the modification that
1.5 g of component Ab) formula III i) with
R⁷R⁸ = C₁₇H₃₅
A⁻ = lactate residue

In addition to excellent dispersibility in cold water and an excellent soft feel, a backwetting capacity of 75% was measured.

Example 8
was carried out analogously to Example 6 with the modification that
13.5 g of component Aa) formula I with
R = H
R¹ = 2 times C₁₈H₃₇
R³ = CH₃-
R² = Formula II with R, R¹ = H
R³ = CH³-
R⁴ = C₁₈H₃₇
1.5 g of component Ab) formula V with
R³ = -CH₃
R⁴ = C₁₈H₃₇-
Z⁻ = lactate residue
0.02 g of silicone antifoam emulsion Antifoam DB 110 A from DOW
were used.

In addition to excellent dispersibility in cold water and an excellent soft feel, a backwetting capacity of 70% was measured.

Example 9
was carried out analogously to Example 8 with the modification that
1.5 g of component Ab) formula III i) with
R⁷, R⁸ = C₁₇H₃₅-
A⁻ = lactate residue

In addition to excellent dispersibility in cold water and an excellent soft feel, a backwetting capacity of 68% was measured.

-

p, q = 1
R⁶ = -CH₂-CH₂-O- mit m = 3
Z⁻ = Lactatrest
R⁴ = C₁₇H₃₅
0,17 g CaCl₂
eingesetzt werden. Example 10
was carried out analogously to Example 8 with the modification that
1.5 g of component Ab) formula IV with
R¹ = C₁₇H₃₅-

-

p, q = 1
R⁶ = -CH₂-CH₂-O- with m = 3
Z⁻ = lactate residue
R⁴ = C₁₇H₃₅
0.17 g CaCl₂
be used.

In addition to excellent dispersibility in cold water and an excellent soft feel, a rewetting capacity of 74% was measured.

Claims (10)

1. Process for the preparation of aqueous fabric softeners by mixing A) 5 to 25% by weight of a mixture of two fabric softener components, consisting of a) 10 to 90, preferably 20 to 80% by weight of at least one compound of the formula (I)

in which R is H or methyl, R¹ is a linear saturated or unsaturated acyl radical having 14-22, preferably 16-18 carbon atoms or H, where R¹ is at least once the acyl radical, R² and R³ independently of one another for a linear saturated, optionally OH -Groups containing alkyl radicals with 1-4 carbon atoms and R² additionally represents a structure of the formula (II) in which the radicals R¹, R³ have the same meaning as listed above and R⁴ for a saturated or unsaturated, linear aliphatic alkyl radical 8 - 22, preferably 12 - 18 carbon atoms,

A⁻ stands for the anion of a quaternizing agent, in particular dimethyl sulfate, diethyl sulfate, methyl chloride, n, x and y stands for 0 or 1, where the sum of x + y + (3-n) = 4 and m equals the valency of the acid anion; and b) 90 to 10% by weight, preferably 80-20, of at least one compound of the formula (III) to (V)

wherein R1, R³, R⁴ have the same meaning as given above, R⁵ = H or R⁶, R⁶ represents the group -CHX-CHY-O-, wherein X and Y can be hydrogen or methyl, but not simultaneously methyl, and m assume a value between 0 to 6, p = 1 - 3, R⁹ is a saturated or unsaturated linear aliphatic alkyl radical with 13 to 21, in particular 17 C atoms and q = 0 or 1 with p + q ≧ 2, Z⁻ stands for the anion of a water-soluble mono- or polyvalent inorganic or organic acid such as methylsulfuric acid, ethylsulfuric acid, a hydrohalic acid, phosphoric acid, formic acid, acetic acid, oxalic acid, glycolic acid, citric acid, tartaric acid, malic acid and in particular hydrochloric acid and lactic acid, and in addition to 100% by weight %. B) water, dyes, perfume and other auxiliaries customary in fabric softeners, such as short-chain alcohols, salts. 2. A process for the preparation of aqueous fabric softeners according to claim 1, characterized in that the compound as component Aa)

is used. 3. A process for the preparation of aqueous fabric softeners according to claim 1, characterized in that the compound as component Aa)

4. A process for the preparation of aqueous fabric softeners according to claim 1, characterized in that the compound as component Aa)

is used. 5. A process for the preparation of aqueous fabric softeners according to claim 1, characterized in that the compound as component Ab)

is used. 6. A process for the preparation of aqueous fabric softeners according to claim 1, characterized in that the compound as component Ab)

is used. 7. A process for the preparation of aqueous fabric softeners according to claim 1, characterized in that the compound as component Ab)

is used. 8. A process for the preparation of aqueous fabric softeners according to claim 1, characterized in that the compound as component Ab)

is used. 9. A process for the preparation of aqueous fabric softeners as claimed in claims 1 to 7, characterized in that component Aa) in amounts of 20-80% by weight and component Ab) in amounts of 80-20% by weight on total amount of components Aa) and Ab) is used. 10.Use of a mixture according to one of claims 1 to 9 for the treatment of washed laundry when rinsing in an aqueous liquor.