EP0663003A1

EP0663003A1 - Process for producing powdered or granular detergent mixtures

Info

Publication number: EP0663003A1
Application number: EP93920769A
Authority: EP
Inventors: Oriol Ponsati Obiols; Nuria Bonastre
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1992-09-28
Filing date: 1993-09-20
Publication date: 1995-07-19
Also published as: WO1994007978A1; DE4232448A1

Abstract

Powdered or granular detergent mixtures with good cold-water dispersibility are obtained by drying and solidifying, in the prior art manner, mixtures containing: a) quaternary di-fatty acid trialkanol amine ester salts of formula (I) in which R1CO is an aliphatic acyl residue with 12 to 22 carbon atoms and 0, 1, 2, or 3 double bonds, n is 2 or 3 and X is halogenated hydrocarbon, methosulphate or methophosphate; and b) hydroxy compounds selected from the group consisting of fatty alcohol polyglycol ethers, polyol fatty acid partial esters and carbohydrates. The products are suitable for the production of laundry revivers and softeners and hair care products.

Description

Process for the preparation of powdery or granular detergent mixtures

Field of the Invention

The invention relates to a process for the production of powdery or granular detergent mixtures, in which mixtures of quaternized difatty acid trialkanolamine ester salts and hydroxy compounds are dried in a manner known per se and brought into solid form.

State of the art

For the treatment of textile fibers, yarns or fabrics, a large number of compounds or mixtures of materials are proposed which impart desired properties to the textiles treated therewith or which are components of agents for textile care. Depending on the type of active ingredients used, the processing properties, the wearing properties of the textiles and their care can be improved. Cationic surfactants are usually used for this purpose, which can attach particularly easily to fibers, fabrics, but also hair. A major technical disadvantage of these products, however, is their inadequate dissolving or dispersing capacity in cold water, which not only makes application, but also the production of low-water concentrates considerably more difficult,

In the past there has been no lack of attempts to deal with this problem. For example, the American patent US 34 54 494 describes fatty acid condensation products with an addition of dispersing polyglycol ethers.

The German patent DE 19 22 046 relates to detergents containing fatty acid condensation products which contain fatty acid glycerides with a dispersing action; In the German patent DE 19 22 047 these substances are also described as textile softeners for liquid laundry aftertreatment agents in particular. These and similar agents can be dispersed in water by placing them in hot water and usually applying high shear forces, or by dispersing the condensation product, which has still been melted, in water. Because of the effort required, the manufacturer therefore usually carries out the dispersion and supplies the user with the dispersions, which is associated with the storage and transport of considerable amounts of water and is therefore not economically viable.

By using the dispersants mentioned, the cold water dispersibility of the cationic surfactants mentioned can also be improved, but this advantage will however, often overcompensated by the fact that the mixtures of cationic surfactant and dispersant have comparatively poorer application properties. Notwithstanding this decisive disadvantage, the mixtures of the prior art can also be processed to low-water concentrates, but in the production of powders or granules the advantage of improved cold water dispersibility that has just been obtained is often lost again.

The object of the invention was therefore to develop a new process for the production of powdery or granular detergent mixtures, by means of which products with good conditioning properties and satisfactory cold water dispersibility can be made available.

Description of the invention

The invention relates to a process for the preparation of powdery or granular detergent mixtures, in which mixtures containing

a) quaternized difatty acid trialkanolamine ester salts of the formula (I),

CH ₃ 1+ ^[ R ¹ CO-0- (CH2) n- ^N - ( ^H 2) n- ° - ^ORl ] ^{x "} ( ^τ )

I (CH ₂ ) _n -OH in which R ^ -CO represents an aliphatic acyl radical having 12 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, n represents 2 or 3 and X represents halide, methosulphate or methophosphate and

b) hydroxy compounds selected from the group formed by fatty alcohols, fatty alcohol polyglycol ethers, partial polyol fatty acid esters and carbohydrates,

dries in a known manner and brings in solid form.

Surprisingly, it has been found that the cold water dispersibility of quaternized difatty acid trialkanolamine ester salts can be significantly improved by addition of the hydroxy compounds mentioned, without the application properties of the products being adversely affected by this measure. The invention includes the knowledge that low-water concentrates of these mixtures can be processed into powders or granules without any problems and that the resulting solids in turn also have satisfactory dispersibility in cold water.

Quaternized difatty acid trialkanolamine ester salts, so-called "esterquats", are known cationic surfactants which can be obtained by the relevant methods of preparative organic chemistry. A process for their preparation consists, for example, in reacting fatty acids with triethanolamine in the presence of reducing agents and with passage of air and then quaternizing the diester with dimethyl sulfate or methyl chloride [WO 91/01295, Henkel]. Since these are technical products, quaternized mono- and triesters are always contained as by-products in the ester quats.

Typical examples of the fatty acid components of these compounds are caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid, and technical acid and mixtures, erucic acid as they occur, for example, in the splitting of vegetable oils or animal fats. Quaternized difatty acid trialkanolamine ester salts of the formula (I) are preferably used in which R ¹ CO is an aliphatic acyl radical having 16 to 18 carbon atoms, n is 2 and X is methosulfate or chloride. Esterquats based on stearic acid, tallow fatty acid or technical grade elaidic acid are particularly preferred.

Hydroxy compounds of the following type are suitable as dispersants:

a) fatty alcohols of the formula (II),

R ² -OH (II)

in which R2 represents an optionally hydroxy-substituted alkyl and / or alkenyl radical having 12 to 22 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, ricinolyl alcohol, 12-hydroxystearyl alcohol, arachyl alcohol, Gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, such as those obtained in the hydrogenation of technical fatty acid methyl ester fractions or aldehydes from Roelen's oxosynthesis. Technical C12 / I8 coconut fatty alcohol or Ci2 / 18 ~ ^Ta l9f ^etta lk ° ° l are ^preferably used.

b) fatty alcohol polyglycol ethers of the formula (III),

R4

IR ³ 0- (CH ₂ CHO) _in H (III)

in which R3 represents an optionally hydroxy-substituted alkyl and / or alkenyl radical having 12 to 22 carbon atoms, R ^ represents hydrogen or a methyl group and m represents numbers from 1 to 40. Typical examples are addition products of 1 to 40, preferably 10 to 25, moles of ethylene and / or propylene oxide onto the alcohols mentioned under a). Addition products of an average of 10 to 25 moles of ethylene oxide with fatty alcohols having 16 to 18 carbon atoms, which may have a conventional or narrow homolog distribution, are preferably used.

c) partial polyol fatty acid esters; this includes mono- and / or diesters of polyols with fatty acids of the formula (IV),

R ⁵ CO-OH (IV) in which R ^ CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds. Typical examples are mono- and / or diesters of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and erucic acid and erucic acid and erucic acid and erucic acid and erucic acid technical mixtures with polyols selected from the group formed by glycerol, diglycerol, triglycerol, trimethylolpropane, pentaerythritol, glucose or sorbitol. Fatty acid monoglycerides based on fatty acids having 12 to 18 carbon atoms are particularly preferred.

d) carbohydrates; typical examples are glucose and in particular sorbitol.

The quaternized difatty acid trialkanola inester salts and the hydroxy compounds can be used in a weight ratio of 1.5: 1 to 2.0: 1. Products with particularly good water dispersibility and excellent leveling properties are obtained if a weight ratio of 1.6: 1 to 1.9: 1 is set between the components.

In a preferred embodiment of the invention, to improve the cold water dispersibility of the ester quats, mixtures of hydroxy compounds are used which have a sorbitol content of 1 to 10, preferably 2 to 5% by weight, based on the mixture of the hydroxy compounds. The mixing of the components is a purely mechanical process; a chemical reaction does not take place. For this purpose it is possible to start from dilute or concentrated aqueous starting materials. The water content of the mixtures is largely uncritical for the production of the powders or granules. For economic reasons, it is of course sensible to convert predominantly those mixtures into solid forms which have a water content which is as low as possible anyway and are present, for example, as concentrates with a solids content of 60 to 70% by weight.

The more or less water-containing detergent mixtures can be converted into solid forms by methods known per se. One possibility is to subject the mixtures to spray drying, as is known for the production of powder detergents. For details of this industrial process, reference is made to RÖMPP Chemistry Lexicon, Thie e Verlag, Stuttgart, 1992, Vol. 6 _# S.4259 / 60.

A variant of this process for the particularly gentle production of powdered detergent compositions is water vapor drying. Here, the detergent mixtures can be spray dried at normal pressure using superheated steam as a hot gas stream. In this way, powders are obtained, the grain of which is distinguished by a particularly high surface area and therefore slight water solubility. For details of this process, reference is made to German patent application DE-Al 40 30 688 (Henkel). In addition to powders, the detergent mixtures can also be provided in the form of granules, for example flakes. The granulation can - if appropriate in the presence of solid carriers such as zeolites or inorganic salts - z. B. in an extruder, a high-speed mixer or a roller granulator.

If desired, the detergent mixtures can also contain further ingredients typical of detergents and cleaning agents, such as. B. contain builders or actuators. The residual water content in the spray-dried or steam-dried products is practically zero; in products which have been produced by granulation, it can be up to 20, preferably up to 15% by weight, based on the mixtures.

Industrial applicability

The powdery or granular detergent mixtures obtainable by the process according to the invention are notable for good cold water dispersibility and excellent softening properties in relation to the feel of fibers and textiles and the wet and dry combability of hair.

Another object of the invention therefore relates to the use of the detergent mixtures for the production of conditioners and fabric softeners and hair care products, such as, for example, hair shampoos or hair rinses, in which they are used in amounts of 1 to 50, preferably 10 to 30,% by weight moved to the means - may be included. The following examples are intended to explain the subject matter of the invention in more detail without restricting it.

Examples

I. Substances used

A) Quaternized difatty acid trialkanolamine salt

AI) Distearic acid triethanolamine ester, quaternized with dimethyl sulfate (Dehyquart ( ^R ) AU-36, Pulcra SA, Barcelona / ES)

B) Hydroxy compounds

B1) dodecyl alcohol

B2) dodecyl alcohol / sorbitol (95: 5 parts by weight)

B3) dodecyl alcohol / sorbitol (96: 4 parts by weight)

B4) Cetyl alcohol

B5) cetyl / stearyl alcohol / sorbitol (96: 4 parts by weight)

B6) cetyl / stearyl alcohol / sorbitol (95: 5 parts by weight)

B7) 12-hydroxystearyl alcohol

B8) Cetyl / stearyl alcohol-20 EO

(Eumulgin ( ^R ) B2, Henkel KGaA, Düsseldorf / FRG) B9) Ci2 i4 coconut fatty acid monoglyceride

(Monomuls ( ^R) 90L12, Co. Grünau, Illertissen / FRG) BIO) stearic acid monoglyceride

(Cutina ( ^R ) MD, Henkel KGaA, Düsseldorf / FRG) Bll) Stearic acid monoglyceride / sorbitol (96: 4 parts by weight)

II. Application studies

In a first step, starting from concentrated quaternized difatty acid trialkanolamine ester salts and the hydroxy compounds, detergent mixtures were produced, which were processed in a high-speed mixer into granules with a residual water content of 15% by weight.

Then 5% by weight dispersions of the granules in water (16 ° C., 20 ° C.) were prepared and stirred at a speed of 500 rpm until a homogeneous distribution was achieved. The dispersions were stored at 20 ° C. and their stability was assessed over a period of 14 days.

The composition of the granules, the time until a homogeneous dispersion is reached and details of their stability can be found in Table 1.

Tab. 1; Examination of the dispersions

Legend; t (Disp.) = dispersion time

++ = homogeneous, light sedimentation +++ = homogeneous, no sedimentation

Claims

1. A process for the preparation of powdery or granular detergent mixtures, in which mixtures containing

a) quaternized difatty acid trialkanolamine ester salts of the formula (I),

CH ₃

1 ⁺ [R ¹ CO-0- (CH2) _n -N- (CH2) n-0-COR ¹ ] X ~ (I)

I (CH ₂ ) _n -OH

in which R ^ CO represents an aliphatic acyl radical having 12 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, n represents 2 or 3 and X represents halide, methosulfate or methophosphate and

b) hydroxy compounds selected from the group consisting of fatty alcohols, fatty alcohol polyglycol ethers, polyol fatty acid partial esters and carbohydrates,

dries in a known manner and brings in solid form.

2. The method according to claim 1, characterized in that quaternized difatty acid trialkanolamine ester salts of the formula (I) are used in which R ^ CO for one aliphatic acyl radical with 16 to 18 carbon atoms, n for 2 and X for methosulfate or chloride.

3. The method according to claim 1, characterized in that fatty alcohols of the formula (II) are used,

R ² -OH (II)

in which R ^{2 represents} an optionally hydroxy-substituted alkyl and / or alkenyl radical having 12 to 22 carbon atoms.

4. The method according to claim 1, characterized in that one uses fatty alcohol polyglycol ethers of the formula (III),

R4

I.

R ³ 0- (CH ₂ CHO) _m H (III)

in which R ^{3 represents} an optionally hydroxy-substituted alkyl and / or alkenyl radical having 12 to 22 carbon atoms, R ^ represents hydrogen or a methyl group and m represents numbers from 1 to 40.

5. The method according to claim 1, characterized in that one uses as polyol fatty acid partial esters mono- and / or diesters of polyols with fatty acids of formula (IV),

R ⁵ CO-OH (IV) in which R ^ CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds.

6. The method according to claim 5, characterized in that polyols are used which are selected from the group formed by glycerol, diglycerol, triglycerol, triethylolpropane, pentaerythritol, glucose or sorbitol.

7. The method according to claim 1, characterized in that one uses glucose or sorbitol as carbohydrates.

8. The method according to claim 1, characterized in that one uses the quaternized difatty acid trialkanolamine ester salts and the hydroxy compounds in a weight ratio of 1.5: 1 to 2.0: 1.

9. The method according to claim 1, characterized in that the detergent mixtures are brought into solid form by subjecting them to spray drying, steam drying or granulation in a manner known per se.

10. Use of powdered or granular detergent mixtures according to claim 1 for the production of softeners and fabric softeners and hair care products.