EP1018541A1 - Clear fabric softener compositions - Google Patents

Abstract

Fabric softener rinsing compositions based on a quaternary ammonium compound of formula (I) and a polyalkylene oxide adduct of formula (II) give clear water-white aqueous solutions. Clear softening rinse formulation comprising: (A) 15-35 wt. % of at least one quaternary ammonium compound of formula (I) (B) 5-30 wt. % of at least one compound of formula (II): R<6>-(CH2)a-O(CH2CH(R<4>)-O-)nH (II) R = -CH3, -CH2-CH(R<4>)-OR<1> or -CH2-CH(R<5>)-OR<2> in which R<4> and R<5> (same or different) = H or CH3 R<1> and R<2> = H, -C(O)-R<3> in which R<3> = an optionally substituted 13-19 C hydrocarbon group containing at least one double bond, provided that if R is not CH3 then R<1> and R<2> = H at least 1 to 1.4 times and if R = CH3 then R<1> and R<2> = H at most 0.4 times R<6> = a phenyl group which optionally contains a 1-4 C alkyl group, or a branched 3-6 C alkyl group a = 0 or 1 n = 0-8 A<-> = the anion of a quaternizing agent such as di(m)ethylsulfate or methyl chloride (C) 0.5-18 wt. % conventional assistants and adjuvants and (D) to 100 wt. % with water.

Description

The invention relates to fabric softener formulations based on or more cationic surfactants and at least one other Component that gives the overall formulation a water-bright and clear Give appearance.

The detergent industry has developed fabric softener formulations over time with improved rewetting ability, high stability and good soft grip developed. By far most of these formulations come as aqueous dispersions in the market. Examples of the formulation of Dispersions are inter alia in DE 37 20 331, DE 42 03 489 and EP 0 413 249.

However, the formulations produced according to the regulations given there can only be produced with high energy expenditure and tend to fluctuate strongly in viscosity, especially at high storage temperatures. Furthermore, it is known that agglomerates in fabric softener dispersions lead to the formation of stains on the treated textiles.
Under the increased aesthetic awareness, a prejudice against disperse fabric softener formulations has been established. On the part of consumers, there is an increasing need for naturally clear-looking formulations.

They are already flowable, highly concentrated or clear fabric softener formulations have been described, for example in DE 33 14 677, DE 36 08 093.

The high concentrates described there, which are usually> 35% quaternary Contain fabric softener raw materials, however, have the disadvantage that these Difficult to dilute formulations with water or that during of washing in this highly concentrated formulation in the induction chamber gels that are difficult to dissolve in water are produced and a uniform textile treatment is not guaranteed. It also comes with these highly concentrated fabric softeners often lead to overdoses, too Stains on the tissues treated in this way.

The object of the present invention was therefore to overcome these disadvantages of the prior art to avoid technology and fabric softener formulations ask which one in comparison to the comparable products of the State of the art an at least equally good spectrum of activity have, but also have a clear and water-bright appearance, whose production can be carried out with reduced energy expenditure and their handling is easy for end users Application guaranteed.

It has now been found that fabric softener formulations exist predominantly from cationic surfactants and 5-30% by weight, based on Overall formulation, another connection, meets these requirements.

A) 15-35 Gew% mindestens einer quaternären Ammoniumverbindunge der allgemeinen Formel (I)

und

B) 5-30 Gew% mindestens einer der Verbindungen der allgemeinen Formel (II) R⁶-(CH₂)_a-O(CH₂-CH₂(R⁴)-O-)_nH mit der Bedeutung

R =

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

R¹, R² =

H, -C(O)-R³ worin R³ ein gegebenenfalls substituierter, mindestens eine Doppelbindung enthaltender Kohlenwasserstoffrest mit 13-19 C-Atomen, mit der Maßgabe, daß wenn R ≠ CH₃ ist R¹, R² min 1 bis 1,4 mal = H ist, und wenn R = CH₃ ist R¹, R² max 0,4 mal = H ist

R⁶ =

ein gegebenenfalls C_1-4-Alkylgruppen enthaltender Phenylrest oder verzweigter Alkylrest mit 3 bis 6 C-Atomen

n =

0 bis 8,

a =

0 oder 1

A^- =

Anion eines Quaternierungsmittels, insbesondere des Dimethylsulfats, Diethylsulfats, Methylchlorids sein kann und

C) 0,5- 18 Gew% üblicher Hilfs- und Zusatzstoffe und

D) ad 100 Gew% Wasser.

The invention therefore relates to clear and light-colored fabric softener formulations comprising

A) 15-35% by weight of at least one quaternary ammonium compound of the general formula (I)

and

B) 5-30% by weight of at least one of the compounds of the general formula (II) R ⁶ - (CH ₂ ) _a -O (CH ₂ -CH ₂ (R ⁴ ) -O-) _n H with the meaning

R =

-CH ₃ , -CH ₂ -CH (R ⁴ ) -OR ¹ , -CH ₂ -CH (R ⁵ ) -OR ² , where R ⁴ , R ^{5 may be the} same or different H, -CH ₃ ,

R ¹ , R ² =

H, -C (O) -R ³ in which R ^{3 is} an optionally substituted hydrocarbon radical having 13-19 C atoms and contains at least one double bond, with the proviso that when R ≠ CH ₃ is R ¹ , R ² min 1 to 1 , 4 times = H, and if R = CH ₃ R ¹ , R ² max 0.4 times = H

R ⁶ =

a phenyl radical optionally containing C _1-4 alkyl groups or branched alkyl radical having 3 to 6 C atoms

n =

0 to 8,

a =

0 or 1

A ^- =

Anion of a quaternizing agent, in particular dimethyl sulfate, diethyl sulfate, methyl chloride and can be

C) 0.5-18% by weight of conventional auxiliaries and additives and

D) ad 100% water.

Another subject are aqueous fabric softeners in which as Alkanolamines methyldiethanolamine, methylethanolisopropanolamine, methyldiisopropanolamine, Triisopropanolamine or triethanolamine can be used.

Another subject are aqueous fabric softeners based on esters from fatty acids and alkanolamines in a molar ratio of 1: 1.6 to 1: 2 be implemented.

Further objects of the invention are defined by the claims.

The quaternary compounds of general use which are also used according to the invention Formula (I) are according to those well known in the art Processes by esterification of alkanolamines such as triethanolamine (TEA), Methyl-diethanolamine (MDEA), methyl-diisopropanolamine (MDIA), methylethanol-isopropanolamine (MEIPA), triisopropanolamine (TIPA) with fatty acid and subsequent quaternization.

Ester compounds based on triethanolamine, such as N-methyl, N, N-bis (beta-C _14-18 -acyloxyethyl), N-beta-hydroxyethyl ammonium methosulfate, are particularly widespread and are available under trade names such as TETRANYL® AT 75 (trademark of KAO Corp.), STEPANTEX® VRH 90 (trademark of Stepan Corp.) or REWOQUAT® WE 18 (trademark of Witco Surfactants GmbH).

The fatty acids for the esterification or transesterification are those on this Field known and usual monobasic fatty acids based on natural vegetable or animal oils with 6-22 carbon atoms, especially with 14-18 carbon atoms, such as oleic acid, linoleic acid, linolenic acid, and in particular rapeseed oil fatty acid, soybean oil fatty acid, sunflower oil fatty acid, Tall oil fatty acid which alone or in a mixture in the form of its glycerides, methyl or Ethyl esters or as free acids can be used. Are suitable in principle all fatty acids with a similar chain distribution.

The content of these fatty acids or fatty acid esters in unsaturated portions, - as far as this is necessary - by the known catalytic hydrogenation processes adjusted to a desired iodine number or by mixing fully hydrated with unhydrogenated fat components.

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

According to the invention, fatty acids with iodine numbers in the range from approximately 40 to 160 are preferred, but in particular rapeseed oil fatty acids, sunflower oil fatty acids, soybean oil fatty acids and tall oil fatty acids, with iodine numbers in the range from approximately 80 to 150. They are commercially available products and are offered by various companies under their respective trade names.
The esterification or transesterification is carried out according to known methods. Here, the alkanolamine with the desired degree of esterification corresponding amount of fatty acid or fatty acid ester, optionally in the presence of a catalyst, for. As methanesulfonic acid, reacted under nitrogen at 160-240 ° C and the water of reaction or alcohol formed is distilled off continuously, the pressure being able to be reduced to complete the reaction.

To produce the esters, the fatty acids and Alkanolamine in the ratio implemented so that in view of the desired application properties of the end products a degree of esterification from 1.6 to 2.0 results, a is particularly preferred according to the invention Degree of esterification from 1.8 to 2.0. The connections thus made are technical reaction mixtures, which are predominantly in the form of diesters.

The subsequent quaternization is also carried out using known methods. The procedure according to the invention is such that the ester, optionally under Use of a solvent, preferably isopropanol, ethanol, 1,2-propylene glycol and / or dipropylene glycol, at 60-90 ° C with equimolar Amounts of the quaternizing agent with stirring, if appropriate under pressure, and the completion of the reaction by controlling the Total number of amines is monitored.

Examples of the quaternizing agents used are organic or inorganic acids, but preferably 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.

For the preparation of the quaternary ammonium compounds according to General formula (I) the following fatty acids were also used.

Fatty acid I (FS I)

<C 16

ca. 4 %

C 16

ca. 5 %

C 16'

ca. 5 % (

einfach ungesättigt)

C 17

ca. 1 %

C 18

ca. 2 %

C 18'

ca. 70 %

C 18''

ca. 12 % (

zweifach ungesättigt)

> C 18

ca. 2%

Oleic acid with an acid number of 198-204, an iodine number of approx. 95 and a C chain distribution of

<C 16

approx. 4%

C 16

approx. 5%

C 16 '

approx. 5% (

simply unsaturated)

C 17

approx. 1%

C 18

approx. 2%

C 18 '

approx. 70%

C 18 ''

approx. 12% (

doubly unsaturated)

> C 18

approx. 2%

Fatty acid II (FS II)

<C 16

ca. 2 %

C 16

ca. 5 %

C 16'

ca. 1 %

C 17

C 18

ca. 3 %

C 18'

ca. 73 %

C 18''

ca. 14 %

> C 18

ca. 2 %

Rapeseed oil fatty acid with an acid number of 196-204, an iodine number of approx. 98 and a C chain distribution of

<C 16

approx. 2%

C 16

approx. 5%

C 16 '

approx. 1%

C 17

C 18

approx. 3%

C 18 '

approx. 73%

C 18 ''

approx. 14%

> C 18

approx. 2%

Fatty acid III (FS III)

C 16

ca. 1 %

C 16'

-

C 17

-

C 18

ca. 2 %

C 18'

ca. 37 %

C 18''

ca. 60 %

> C 18

ca. 1 %

Tall oil fatty acid with an acid number of 190-198, an iodine number of approx. 150 and a carbon chain distribution of

C 16

approx. 1%

C 16 '

-

C 17

-

C 18

approx. 2%

C 18 '

approx. 37%

C 18 ''

approx. 60%

> C 18

approx. 1%

Komponente A1:

TEA: FS I = 1 : 1,75

Komponente A2:

TEA: FS II = 1 : 2,0

Komponente A3:

MDEA: FS I = 1 : 1,85

Komponente A4:

MEIPA: FS II = 1 : 1,9

Komponente A5:

MDIA: FSIII = 1 : 1,8

The following compounds were used as examples of the quaternary ammonium compounds of the formula (I):

Component A1:

TEA: FS I = 1: 1.75

Component A2:

TEA: FS II = 1: 2.0

Component A3:

MDEA: FS I = 1: 1.85

Component A4:

MEIPA: FS II = 1: 1.9

Component A5:

MDIA: FSIII = 1: 1.8

Komponente B1:

R⁶ = Phenyl; R⁴ = H; n = 4

Komponente B2:

R⁶ = i-C₄H₉ (ca 60 %)*; n = 0
*Wird unter dem Handelsnamen Isanol (Firma Biesterfeld, Hamburg) vertrieben

Komponente B3:

R⁶ = i-C₄H₉ (ca 60 %)*; R⁴ = H; n = 2,7

Komponente B4:

R⁶ = i-C₄H₉ (ca 60 %)*; R⁴ = CH₃; n = 2,7

The components A1 - A5 were quaternized with dimethyl sulfate and contain 10 mass% isopropanol as a solvent. The following references to components A ¹ to A ⁵ mean these quaternized compounds.

Component B1:

R ⁶ = phenyl; R ⁴ = H; n = 4

Component B2:

R ⁶ = iC ₄ H ₉ (approx. 60%) *; n = 0
* Is sold under the trade name Isanol (company Biesterfeld, Hamburg)

Component B3:

R ⁶ = iC ₄ H ₉ (approx. 60%) *; R ⁴ = H; n = 2.7

Component B4:

R ⁶ = iC ₄ H ₉ (approx. 60%) *; R ⁴ = CH ₃ ; n = 2.7

As component B are alkoxylated phenols which have one or more May contain alkyl substituents, such as ethoxylated and / or propoxylated phenol, o / m / p-cresol, thymol, p-tert. Butyl phenol, benzyl alcohol. According to the invention can also optionally alkoxylated branched short-chain alcohols with 3 to 6 carbon atoms, such as Isopropanol, butanol-2,2-methyl-propanol-1,3-methyl-butanol-1,2-methyl-butanol-1, and their alkoxylation products. The degree of alkoxylation is 0 to about 8, with technical ones according to the invention Mixtures with an average degree of alkoxylation of 0 or> 2.5 to about 3.5 are preferred. The compounds of component B can be used as a mixture with one another and / or with one another in amounts of about 5 to 30% by weight, based on the total mixture, preferably in amounts of 10 to 25 % Are used.

The fabric softeners are prepared by emulsifying or dissolving the quaternized compounds A ¹ - A ⁵ with the use of compounds of the general formula B, by adding the respective individual components to water with stirring. In principle, the usual procedures in this field can be applied.

The procedure according to the invention is such that water is initially introduced at room temperature, with good stirring first the dye solution, then the antifoam emulsion which may be required and finally the plasticizer and component B) are stirred in as a mixture or in any order. Perfume oil is then metered in and, if necessary, a certain amount of an electrolyte solution in order to reduce the viscosity of the finished formulation. The fabric softeners according to the invention can contain the stated components within the limits customary in this field, such as, for example, 15 to 35% by weight of the compounds of the general formula A; 5 to 30% by weight of at least one of the compounds of the general formula B; 0.5 to 18% by weight of one or more of the customary auxiliaries and additives, for example
0.05 to 1% by weight of dyes, 0.05 to 1% by weight of preservatives, 0.1 to 12% by weight of short-chain alcohols / diols with 2 to 6 C atoms, 0.1 to 1% by weight of defoaming agents and in particular 0.1 to 1.5% by weight of an alkali and / or alkaline earth salt; 0.1 to 1.5% by weight perfume oil and the rest 100% (ad 100) water.

How the fabric softeners belonging to the known prior art are the fabric softener according to the invention following the actual one Washing process added in the last rinse. The application concentration after dilution with water lies in the range depending on the application from 0.1 to 10 g of fabric softener per liter of treatment liquor.

Examples: General instructions for the production of clear fabric softener formulations :

Demineralized water is initially introduced at room temperature, the dye solution is added and the quaternary ammonium compound (Quat; component A) is slowly mixed into the water phase with constant stirring. Subsequently, component B is added to the mixture of water and quat with stirring until it is clearly dissolved at 20 ° C. This formulation is then cooled to 4 ° C and must be clearly transparent at this temperature. If necessary, an additional amount of solubilizer B is stirred in until the mixture is clear at 4 ° C. At the same time as, before or after the addition of component B, alcohols, preferably glycols with boiling points> 120 ° C., can be stirred into the reaction mixture to increase the flash point of the finished formulation.
The perfume oil is then added at room temperature with stirring and, if necessary, mineral salts are added to adjust the viscosity in the case of highly viscous solutions in order to improve the stirrability and flowability of the mixture.
In particular, the chlorides of the alkali or alkaline earth metals can be used as mineral salts in amounts of about 0.1 to 1.5% by weight, preferably in the form of their 10 to 30% aqueous solutions, in particular an aqueous calcium chloride solution. Example 1: water 47.4 parts by mass dye 0.8 parts by mass Component A1 30.6 parts by mass Component B1 18.0 parts by mass Product is clear at 20 ° C Propylene glycol 2.0 parts by mass Product is clear at 4 ° C Perfume oil 0.8 parts by mass Example 2: water 47.4 parts by mass dye 0.8 parts by mass Component A4 30.6 parts by mass Component B1 22.0 parts by mass Product is clear at 20 ° C Component B2 2.0 parts by mass Product is clear at 4 ° C Perfume oil 0.8 parts by mass Example 3: water 59.4 parts by mass dye 0.8 parts by mass Component A3 30.6 parts by mass Component B2 10.0 parts by mass Perfume oil 0.8 parts by mass CaCl ₂ solution 1.0 parts by mass Product is clear at 20 ° C and at 4 ° C Example 4: water 51.4 parts by mass dye 0.8 parts by mass Component A4 30.6 parts by mass Component B2 6.0 parts by mass Hexylene glycol 12.0 parts by mass Perfume oil 0.8 parts by mass Product is clear at 20 ° C and at 4 ° C Example 5: water 44.9 parts by mass dye 0.8 parts by mass Component A2 30.6 parts by mass Component B3 12.5 parts by mass Hexylene glycol 12.0 parts by mass Perfume oil 0.8 parts by mass Product is clear at 20 ° C and at 4 ° C Example 6: water 55.4 parts by mass dye 0.8 parts by mass Component A1 30.6 parts by mass Component B4 10.0 parts by mass Component B2 6.0 parts by mass Perfume oil 0.8 parts by mass Product is clear at 20 ° C and at 4 ° C Example 7: water 46.4 parts by mass dye 0.8 parts by mass Component A5 30.6 parts by mass Component B4 13.0 parts by mass Dipropylene glycol 5.0 parts by mass Perfume oil 0.8 parts by mass Product is clear at 20 ° C and at 4 ° C

Claims (7)

Clear fabric softener formulations containing A) 15-35% by weight of at least one quaternary ammonium compound of the general formula (I)

and B) 5-30% by weight of at least one of the compounds of the general formula (II) R ⁶ - (CH ₂ ) _a -O (CH ₂ -CH ₂ (R ⁴ ) -O-) _n H with the meaning

R =

-CH ₃ , CH ₂ -CH (R ⁴ ) -OR ¹ , -CH ₂ -CH (R ⁵ ) -OR ² , where R ⁴ , R ^{5 may be the} same or different H, -CH ₃ ,

R ¹ , R ² =

H, -C (O) -R ³ in which R ^{3 is} an optionally substituted hydrocarbon radical having 13-19 C atoms and contains at least one double bond, with the proviso that when R ≠ CH ₃ is R ¹ , R ² min 1 to 1 , 4 times = H, and if R = CH ₃ R ¹ , R ² max 0.4 times = H

R ⁶ =

a phenyl radical optionally containing C _1-4 alkyl groups or branched alkyl radical having 3 to 6 C atoms

a =

0 or 1

n =

0 to 8,

A ^- =

Anion of a quaternizing agent, in particular dimethyl sulfate, diethyl sulfate, methyl chloride and can be

C) 0.5-18% by weight of conventional hooves and additives and D) ad 100% water. Fabric softener according to claim 1, characterized in that as Alkanolamine at least one of the compounds from the group methyldiethanolamine, Methylethanolisopropanolamine, methyldiisopropanolamine, Triisopropanolamine, triethanolamine is used. Fabric softener according to claims 1 and 2, characterized in that Fatty acids and alkanolamines in a molar ratio of 1: 1.6 to 1: 2 implemented become. Fabric softener according to claim 1, characterized in that as Fatty acid at least one of the compounds from the group of rapeseed oil fatty acids, Sunflower oil fatty acids Soybean oil fatty acids, tall oil fatty acids is used. Fabric softener according to claims 1 to 4, characterized in that Fatty acids with iodine numbers in the range of about 40 to 160 can be used. Fabric softener according to claims 1 to 4, characterized in that Fatty acids with iodine numbers in the range of approximately 80 to 150 can be used. Fabric softener according to claim 1, characterized in that as Component B) ethoxylated or propoxylated phenol, benzyl alcohol, Isopropanol and / or isobutanol with an average degree of alkoxylation from> 2.5 to 3.5 is also used.