EP0876454A1

EP0876454A1 - Liquid initial products for washing, rinsing and cleaning agents

Info

Publication number: EP0876454A1
Application number: EP96939101A
Authority: EP
Inventors: Karl Heinz Schmid; Michael Neuss
Original assignee: Henkel AG and Co KGaA
Current assignee: BASF Personal Care and Nutrition GmbH
Priority date: 1995-11-25
Filing date: 1996-11-19
Publication date: 1998-11-11
Anticipated expiration: 2016-11-19
Also published as: DE19543990C2; DE59609607D1; DE19543990A1; EP0876454B1; WO1997020018A1; ES2181920T3

Abstract

Novel water-free initial products are disclosed for use in producing washing, rinsing and cleaning agents, containing (a) alkyl- and/or alkenyl oligoglycosides and (b) alkylpolyalkylene glycol ether in a weight ratio (a) : (b) of 10 : 90 to 90 : 10. These initial products are particularly suitable for use in the production of washing powders.

Description

"Liquid intermediate products for washing, rinsing and cleaning agents"

Field of the Invention

The application relates to liquid, anhydrous precursors for the production of washing, rinsing and cleaning agents containing glycosides and nonionic surfactants, the use of these precursors for the production of surface-active agents and a process for the production of solid detergents using the liquid precursors .

State of the art

Alkyl oligoglucosides are nonionic surfactants which are becoming increasingly important due to their excellent application properties and particularly advantageous ecotoxicology. Because of their foaming power, which is comparable to that of anionic surfactants, they are not only suitable for hand dishwashing detergents or hair shampoos, but are also of interest for use in the field of detergents. If alkyl oligoglucosides have so far been used practically without exception for liquid applications, the reason for this lies in the fact that glucosides on the one hand have a high melting range and on the other hand can be decomposed in the course of the spray drying of aqueous surfactant slurries, which is common for powdered products, since the sugar structure of the surfactants Temperatures above 120 ° C are not permitted. It is of course possible to subsequently add alkyl oligoglucosides to the tower powder together with other temperature-sensitive detergent ingredients, such as perfume oils, enzymes and the like. mixing, but such an approach has not proven to be economical in the past.

In addition to the production of washing powders in the spray tower, in which hot drying gases are directed towards the liquid preliminary products trickling down in the form of fine droplets, processes have recently been established in which, for example, a liquid is placed on a solid support in a mixer or a fluidized bed Sprayed preliminary product while drying and granulating at the same time. These processes work at significantly lower temperatures and thus in principle also allow the use of alkyl oligoglucosides, but there is the problem that the glucosides, even at temperatures from 40 to 60 ° C., both in the form of their aqueous pastes and in a mixture of these pastes otherwise liquid, nonionic surfactants customary for detergent purposes are present as cut-resistant pastes. However, since liquid preliminary products are required for the above-mentioned granulation processes, the mixtures would have to be melted and continuously heated before each use, which would not only involve considerable technical effort, but would also be economically unprofitable. The object of the invention was therefore to remedy this situation.

Description of the invention

The invention relates to liquid precursors for washing, rinsing and cleaning agents, which are obtained by

(a) alkyl and / or alkenyl oligoglycosides and

(b) alkyl polyalkylene glycol ether

in the absence of water in the weight ratio (a): (b) of 10:90 to 90:10 and preferably 30:70 to 70:30.

It has surprisingly been found that the mixtures according to the invention are at least free-flowing, generally liquid or even thin-bodied, even at 40 ° C. Flowable products are obtained even if the glycoside content is raised to 90% by weight or highly ethoxylated nonionic surfactants are used. The invention includes the knowledge that the mixing of the anhydrous components compared to a subsequent one Dewatering the mixtures has clear advantages. The mixtures can, for example, be used without problems in granulation processes for the production of detergents.

Alkyl and / or alkenyl oligoglycosides

Alkyl and alkenyl oligoglycosides are known nonionic surfactants which follow the formula (I)

R'O-LGJ _p (I)

in which R ^{1 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP-A1-0 301 298 and WO 90/03977.

The alkyl and / or alkenyl oligoglycosides can be derived from aidoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.

The index number p in the general formula (I) indicates the degree of oligomerization (DP degree), i.e. H. the distribution of mono- and oligoglycosides is present and stands for a number between 1 and 10. While p must always be an integer in a given compound and can in particular assume the values p = 1 to 6, the value p is for a specific alkyl oligoglycoside an analytically calculated quantity, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.

The alkyl or alkenyl radical R can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capron alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are used, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C ₈ -C ₁₀ (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C ₈ -C ₁₈ coconut fatty alcohol by distillation and with a proportion of less than 6% by weight C ₁₂ - Alcohol can be contaminated as well as alkyl oligoglucosides based on technical C _{9 / π-} oxo alcohols (DP = 1 to 3).

The alkyl or alkenyl radical R ¹ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol, as well as their technical mixtures. Alkyl oligoglucosides based on hardened C _12/14 coconut alcohol with a DP of 1 to 3 are preferred.

Alkyl polyethylene glycol ether

Alkyl polyalkylene glycol ether, i.e. Alkyl polyethylene and / or propylene glycol ethers which are suitable as component (b) follow the formula (II),

CH,

R ² O (CH ₂ CH ₂ O) _n (CH ₂ CHO) _m R ³ αi)

in which R represents a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22 carbon atoms, R stands for an n-butyl radical, n for numbers from 1 to 20 and m for 0 or numbers from 1 to 20. These are known nonionic surfactants which are obtained on an industrial scale by acidic or preferably base-catalyzed addition of ethylene oxide and / or propylene oxide to primary alcohols. Depending on the catalyst, the polyglycol ethers can have a conventionally broad or narrowed homogeneous distribution.

Typical examples are the adducts of on average 1 to 20 and preferably 3 to 10 moles of ethylene oxide and / or propylene oxide with 1 mole of the following alcohols: capro alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, my- ristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, El aeo stearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, deridyl alcohol and derucyl alcohol, die in alcoholic alcohols and their erucyl alcohols, for example in the case of high-pressure alcohols and their erucyl alcohols and the erucyl alcohols used for the high pressure alcohol mixtures and the erucyl alcohols used in the high-pressure alcohol mixtures and their erucyl alcohols technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. Adducts of on average 3 to 10 moles of ethylene oxide with technical fatty alcohols with 12 to 18 carbon atoms such as, for example, coconut, palm, palm kernel or tallow fatty alcohol are preferred. The polyglycol ethers can also be end-capped by an n-butyl radical.

Aqueous mixtures of alkyl oligoglucosides and fatty alcohol polyglycol ethers are known from the prior art. Representative is the publications EB-B 0 075 995 (Procter & Gamble), EP-B 0 075 996 (Procter & Gamble), EP-A 0 317 614 (Staley), EP-B 0 408 965 (Kao), WO 91/14760 (Henkel), EP-B 0 542 801 (Henkel) and EP-A 0 490 040

(Hüls) referenced.

Manufacture of intermediate products

The liquid, anhydrous precursors according to the invention are prepared by simply mixing the raw materials, if appropriate at temperatures in the range from 30 to 50 ° C. In a preferred embodiment of the invention, technical, anhydrous products are used as alkyl oligoglucosides, such as are obtained immediately after the separation of free fatty alcohol in the acid-catalyzed acetalization of glucose with excess alcohol. The crude alkyl oligoglucosides, which are taken directly from the falling film or thin film evaporator, may contain a fatty alcohol, usually coconut oil, in the range from 0.1 to 10 and preferably 0.5 to 1% by weight. -% lies and does not affect the later applications.

Industrial applicability

The precursors according to the invention are water-free and nevertheless over a wide range of mole breakage even at low temperatures, a high glycoside content and when used - 6 - highly ethoxylated nonionic surfactants at least still flowable and pumpable. They are suitable for the production of surface-active agents, such as, for example, washing, rinsing and cleaning agents, in which they can be present in amounts of 1 to 50 and preferably 5 to 35% by weight.

Although the precursors are of course also suitable for the production of liquid concentrates, for example liquid detergents or hand dishwashing detergents, one focus of the invention is to use their advantageous rheology for the production of solid, preferably granulated detergents. Another object of the invention thus consists in a process for the production of solid detergents, in which the liquid precursors are mixed together with further detergent ingredients, preferably fatty alcohol sulfates, and then simultaneously dried and brought into a lumpy form. Methods of this type are described in more detail below:

Mix

A particularly simple embodiment of a process for the production of detergents consists in presenting an anionic surfactant in powder form and intimately mixing it with the required amount of the liquid precursors according to the invention. Components such as paddle mixers from Lödige or, in particular, spray mixers from Schugi are advantageous for this process, in which the anionic surfactant is placed in the mixing chamber and the liquid precursors are sprayed on. It is also possible to carry out the drying of the anionic surfactant pastes and the mixing simultaneously in a fluidized bed dryer. Dry, easily soluble powders are obtained which, if necessary, can be charged with further customary detergent additives and processed, for example, into detergent extrudates.

SKET quality

Another possibility is to subject the anionic surfactants to so-called SKET granulation. This is to be understood as granulation with simultaneous drying, which is preferably carried out batchwise or continuously in the fluidized bed. Aqueous pastes of anionic surfactants and the liquid precursors can be used simultaneously or are introduced into the fluidized bed in succession via one or more nozzles. Fluidized bed apparatuses which are preferably used have base plates with dimensions of 0.4 to 5 m. The SKET granulation is preferably carried out at fluidizing air speeds in the range from 1 to 8 m / s. The granules are discharged from the fluidized bed preferably by means of a size classification of the granules. The classification can take place, for example, by means of a sieving device or by means of an opposed air flow (classifier air) which is regulated in such a way that only particles of a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed. The inflowing air is usually composed of the heated or unheated classifier air and the heated floor air. The soil air temperature is between 80 and 400, preferably 90 and 350 ° C. A starting mass, for example a SKET granulate from an earlier test batch, is advantageously introduced at the beginning of the SKET granulation. In the fluidized bed, the water evaporates from the anionic side paste, resulting in dried to dried germs, which are coated with further amounts of anionic surfactant and the liquid precursor, granulated and again dried at the same time. In this connection, reference is made to the teaching of German patent applications DE-Al 43 03 211 and DE-Al 43 03 176, the content of which is hereby expressly included.

Extrusion

In a particular embodiment of the invention, anionic surfactants in powder form are mixed with the liquid precursors according to the invention and the mixture is homogenized and solidified in a screw press. The extrusion takes place via a perforated disc, so that press strands are formed which can be mechanically comminuted to extrudates or needles of the desired shape and dimension by known processes. Extrudates of this form show a particularly high dissolving speed and very good washing-up behavior in the washing machine.

Steam drying only

Another method for the production of solid detergents consists in taking the liquid precursors together with aqueous surfactant pastes and optionally carrier salts Exclusion of atmospheric oxygen to dry in the presence of superheated steam ^{τ ^} > he principle of this process was used by the applicant in her German patent applications: n DE-Al 40 30 688, DE-Al 42 04 035, DE 42 04 090, DE-Al 42 06 050, DE-Al 42 06 495 and DE-Al 42 06 521. The principle of the process is that condensation of the superheated steam on the cooler feed and release of the heat of condensation to the material to be dried spontaneously heats the aqueous drop to the boiling point of the water under working conditions, ie at normal pressure to temperatures of about 100 ° C, takes place. This boiling temperature is maintained as the minimum temperature during the entire residence time in the droplet. Steam-volatile impurities such as, for example, fatty alcohols or formic acid, which cannot be removed by distillation under customary conditions or only under drastic conditions and with high technical outlay, are thus removed quickly, completely and gently with the water phase. In a preferred embodiment of the process according to the invention, the mixtures are sprayed together with superheated steam at a temperature in the range from 120 to 280 ° C. into a closed system, the condensate water with the impurities dissolved therein is separated off and the dried and cleaned valuable substances are discharged.

Basically, the closed system is operated with a steam circuit upstream from which the evaporated water portion of the feed is extracted, while the amount of energy released is fed back into the circuit stream. While in conventional processes working at higher temperatures is always associated with the risk of partial charring of the items to be cleaned, the absence of atmospheric oxygen makes working temperatures of in particular 150 to 200 ° C. readily possible. After the dissolved impurities have been separated off, the partial steam stream which is drawn off can advantageously be used as process steam for other use.

Flash dryer

The simultaneous drying and granulation can also be carried out in a horizontally arranged thin-film evaporator with rotating internals, such as that sold by the VRV company under the name "Flash Dryer". In simplified terms, this is a tube that spans several zones be tempered at different temperatures can. The paste-like feed material, which is metered in via a pump, is flung against the heated wall by means of one or more shafts, which are provided with blades or shares of flies as rotating internals, on which the drying takes place in a thin layer, typically 1 to 10 mm thick he follows. It has proven to be advantageous to apply a temperature gradient from 170 (product inlet) to 20 ° C. (product discharge) to the thin-film evaporator. For this purpose, for example, the first two zones of the evaporator can be heated to 160 ° C and the last can be cooled to 20 ° C. Higher drying temperatures have not proven to be advantageous with regard to the thermal lability of the starting materials. The thin film evaporator is operated at atmospheric pressure and gassed in countercurrent with air (throughput 50 to 150 m / h). The inlet temperature of the gas is usually 20 to 30, the outlet temperature 90 to 10 ° C.

Other ingredients

The optionally granulated detergents produced using the preliminary products according to the invention can contain, as the most important constituents, further surfactants, preferably anionic surfactants, soaps, inorganic builder substances such as phosphates, zeolites, crystalline layered silicates, amorphous silicates, compounds composed of amorphous silicates and carbonates, organic cobuilders, bleaching agents and bleach activators, Contain foam inhibitors, enzymes, optical brighteners, soil repellents and graying inhibitors. Particular preference is given to detergents in granular form which contain anionic surfactants of the fatty alcohol sulfate type as further constituents. These can preferably _{12 /,} ₄ -Kokos- and / or C contain, as based on C _16/18 -Talgfettalkohole, wherein the weight ratio of these two components in the range of 90: 10 to 10: 90 and typically at 20: 80, 30: 70 , 40: 60 or 50: 50. The detergent granules can have both a low and a high content of surfactants, for example a content of 5 to 50% by weight of fatty alcohol sulfates and 5 to 50% by weight of the precursors according to the invention. Another advantage of the granules is that they are non-sticky and have high bulk densities in the range from 300 to 1200 and preferably 500 to 800 g / l. Examples

Surfactants used

AI) C, _{2 /} ι ₆ coconut alkyl oligoglucoside, anhydrous

A2) aqueous C _12/16 coconut alkyl oligoglucoside paste, approx. 50% by weight

B 1) C _12/14 coconut fatty alcohol + 3EO adduct

B2) C _{12 /} ι _g coconut fatty alcohol + 7EO adduct

B3) octanol + IOEO adduct

Mixtures of alkyl glucosides and polyethylene glycol ethers were produced at room temperature and the consistency of the products in the temperature range from 40 to 70 ° C. was examined. In the case of comparative example C3, a mixture of an aqueous glucoside paste and a nonionic surfactant was subsequently dewatered. The results are summarized in Table 1. The quantitative data represent% by weight and relate in each case to the starting materials, if appropriate including the water content.

Tab.!

Mixtures of alkyl oligoglucosides and alkyl polyethylene glycol ethers

Claims

claims

1. Liquid intermediate products for detergents, dishwashing detergents and cleaning agents, obtainable in that

(a) alkyl and / or alkenyl oligoglycosides and

(b) alkyl polyalkylene glycol ether

in the absence of water in the weight ratio (a): (b) from 10:90 to 90:10.

2. precursors according to claim 1, characterized in that they contain alkyl and alkenyl oligoglycosides of the formula (I),

R'O-lGj _p (I)

in which R ^{1 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10.

3. precursors according to claims 1 and 2, characterized in that they contain alkyl polyethylene and / or propylene glycol ethers of the formula (II),

CH,

R ² O (CH ₂ CH ₂ O) _n (CH ₂ CHO) _m R ^J (II)

in which R ^{z represents} a linear or branched, aliphatic alkyl and / or alkenyl radical with 6 to 22 carbon atoms, R ³ for hydrogen or an n-butyl radical, n for numbers from 1 to 20 and m for 0 or numbers from 1 to 20 stands.

4. intermediates according to claims 1 to 3, characterized in that they contain the components (a) and (b) in a weight ratio of 30:70 to 70:30.

5. Use of the liquid premixes according to claim 1 for the preparation of surface-active agents.

6. A process for the preparation of solid detergents, in which liquid premixes according to claim 1 are mixed together with further detergent ingredients and then dried at the same time and brought into a lumpy form.

7. The method according to claim 6, characterized in that the liquid Vorge¬ mixes together with fatty alcohol sulfates in a mixer or a fluidized bed simultaneously dried and granulated.