EP0682691A1

EP0682691A1 - Solid washing, rinsing and cleaning agents.

Info

Publication number: EP0682691A1
Application number: EP94906151A
Authority: EP
Inventors: Karl Schmid; Andreas Syldath; Ditmar Kischkel; Thomas Krohnen; Michael Neuss; Michael Langen
Original assignee: Henkel AG and Co KGaA
Current assignee: BASF Personal Care and Nutrition GmbH
Priority date: 1993-02-04
Filing date: 1994-01-26
Publication date: 1995-11-22
Anticipated expiration: 2014-01-26
Also published as: EP0682691B2; KR960700333A; DE59402383D1; DE4303176C2; JPH08506367A; DE4303176A1; ES2100697T3; WO1994018293A1; EP0682691B1

Abstract

Solid washing, rinsing and cleaning agents containing: a) mixtures of anionic and non-ionic surfactants in a weight ratio of 9:1 to 1:9, and b) 1 to 50 % by weight, in relation to the non-ionic surfactants, of selected polymer solidifying materials, are resistant to the gradual escape of the non-ionic tensides. Grease permeation through the cartons containing them is reliably prevented.

Description

Solid washing, rinsing and cleaning agents

Field of the Invention

The invention relates to new solid detergents, dishwashing detergents and cleaning agents, a process for their preparation in which mixtures of anionic and nonionic surfactants are mixed with selected polymeric solidifying agents and the use of the mixtures of anionic and nonionic surfactants and polymeric solidifying agents as raw materials for the production of solid washing and rinsing agents and cleaning agents which are resistant to bleeding.

State of the art

Solid washing, rinsing and cleaning agents usually come onto the market in the form of powders, granules or extrudates. As surface-active constituents, they usually contain combinations of anionic and nonionic surfactants, which ideally complement each other in terms of cleaning effect and dirt-carrying capacity [Chemie iuZeit, 2. _ι 292 (1992)]. While the anionic surfactants were present in excess in the past, there is now a need for recipes with an increased content of non- ionic surfactants. This includes in particular those formulations in which the proportion of nonionic surfactants compared to that of anionic surfactants 100 to

Makes up 200% by weight. While alkylbenzenesulfonates and increasingly fatty alcohol sulfates have been in the foreground for anionic surfactants, the trend for nonionic surfactants is towards low alkoxylated fatty alcohol polyglycol ethers and alkyl oligoglucosides [Seifen-Öle-Fette-Wwachs, 117, 554 (1991)].

Solid detergents, dishwashing detergents and cleaning agents of this type not only show excellent performance, but also advantages in compacting for the production of heavy powders with bulk densities of 600 to 900 g / 1. It is disadvantageous, however, that the anionic surfactants, together with the other solid formulation components, have only a limited capacity to "absorb" the mostly liquid nonionic surfactants and to bind them permanently. Especially in the case of the desired formulations with a particularly high nonionic surfactant content, there is therefore a risk of "bleeding out", ie. H. the liquid nonionic surfactants are gradually released from the present solid mixture. The result is a decrease in the washing performance of the recipe and a gradual greasing of the standard cardboard packaging; the latter can also be used as an indication of the degree of bleeding or the resistance to bleeding.

According to the teaching of DE-Al 41 24 701 (Henkel), solid detergents with a high bulk density and improved solubility are obtained by mixing mixtures of anionic and nonionic surfactants with a polyethylene glycol ether Molecular weight in the range of 200 to 12,000, preferably 200 to 600, and then drying and / or solidifying. According to embodiment 1, a detergent preparation containing Ci2 / 18 ~ ^fatty alkanol sulfate r 12/18- ^fatty alkono- ⁵ EO- / Ci6 / 18- ^al g ^{fatty alcoholo} - ⁵ EO adduct and - based on the nonionic surfactants - polyethylene glycol with a molecular weight of approximately 400, which is extruded after homogenization and processed into granules. However, the rate of dissolution of the resulting solid detergents is still unsatisfactory. In addition, the presence of the large amounts of polymer required is not desirable.

According to EP-A2 0 208 534, spray-dried detergent compositions are disclosed in general form which, in addition to anionic surfactants, contain nonionic surfactants, polyacrylates and polyethylene glycol ethers with an average molecular weight in the range from 1,000 to 20,000. The teaching of this document is that the dispersibility of anionic surfactants can be improved by adding nonionic surfactants, polyethylene glycol ethers and polyacrylates to them. However, the PEGs actually used are of low molecular weight and preferably have molecular weights in the range from 4,000 to 20,000 (see page 4, section 2). The only exemplary embodiment describes a mixture comprising alkylbenzenesulfonate and fatty alcohol sulfate, to which a Ci2 / i3-oxoalcohol-6.5 EO adduct, sodium polyacrylate and polyethylene glycol with a molecular weight of approximately 8,000 are added. The weight ratio between nonionic surfactant and PEG is 1: 1. DE-OS 21 24 526 relates to detergent and cleaning agent mixtures with controlled foam behavior. According to Example 6, compositions are disclosed which contain tallow alcohol sulfate, alkylbenzenesulfonate and polyethylene glycol with a molecular weight of approximately 20,000.

The object of the invention was to provide solid washing, rinsing and cleaning agents with an increased content of nonionic surfactants which are permanently resistant to the bleeding out of the nonionic surfactants.

Description of the invention

The invention relates to solid washing, rinsing and cleaning agents containing mixtures of

a) anionic and nonionic surfactants in a weight ratio of 9: 1 to 1: 9, preferably 1: 1 to 1: 5 and b) 1 to 50% by weight, based on the nonionic surfactants, of polymeric solidifying agents selected from the group pe, which is formed by

bl) polyethylene glycol ethers with an average molecular weight of 12,000 to 500,000, b2) esters of dicarboxylic acids with an average molecular weight of 400 to 20,000, b3) transesterification products of dialkyl carbonate with polyethylene glycol ethers with an average molecular weight of 400 to 20,000 and b4) oligosaccharides or polysaccharides with a degree of condensation of 5 to 1000.

Surprisingly, it was found that the addition of selected polymeric strengthening agents to the formulations rich in nonionic surfactants leads to a solidification of the grain and prevents bleeding of liquid components permanently and reliably, without the application performance of the formulations being adversely affected by the use of the strengthening agents . The invention is of particular importance for agents with a high content of nonionic surfactants; However, it is also possible to stabilize agents with a comparatively low content of nonionic surfactants against bleeding in the specified way.

The invention includes the knowledge that there is a critical limit of 12,000 with regard to the suitability of polyethylene glycol ethers as polymeric hardening agents with regard to the molecular weight. The desired effect, the significant improvement in the resistance to bleeding, is not achieved below this range.

Another object of the invention relates to a process for the production of solid washing, rinsing and cleaning agents, in which mixtures of anionic and nonionic surfactants in a weight ratio of 9: 1 to 1: 9, preferably 1: 1 to 1: 5 with 1 to 50% by weight, based on the nonionic surfactants, of polymeric strengthening agents which are selected from the group formed by bl) polyethylene glycol ethers with an average molecular weight of 12,000 to 500,000, b2) esters of dicarboxylic acids with an average molecular weight of 400 to 20,000, b3) transesterification products of dialkyl carbonate with polyethylene glycol ethers with an average molecular weight of 400 to 20,000 and b4) Oligosaccharides or polysaccharides with a degree of condensation of 5 to 1000.

Anionic surfactants

The anionic surfactants can be selected from the group consisting of alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, o-methyl ester sulfonates, sulfo fatty acids, fatty alcohol sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, sulfate ethersulfate sulfates, Fatty acid amide (ether) sulfates, sulfosuccinates, sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids, isethionates, sarcosinates, taurides, alkyl oligoglucoside sulfates and alkyl (ether) phosphates.

All of these substances are known surfactants which can be prepared by the relevant processes in preparative organic chemistry. For synthesis and properties, see, for example, J.Falbe (ed.) "Surfactants in consumer products", Springer Verlag, Berlin, 1987, pp. 54-85 or J.Falbe, U. Hasserodt, "Catalysts, surfactants and Mi mineral oil additives ", Thieme Verlag, Stuttgart, 1978, pp.126-139.

In addition to the alkylbenzenesulfonates, in particular the dodecylbenzenesulfonate, the use of fatty alcohol sulfates of the formula (I) is preferred among the anionic surfactants,

RlθS0 ₃ X (I)

in which R ^{1 is} a linear or branched alkyl and / or alkenyl radical having 12 to 22 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammoniamine. From the group of fatty alcohol sulfates, tallow alcohol sulfates are again of particular importance, in which R ¹ in formula (I) is an alkyl radical having 16 to 18 carbon atoms and X is sodium.

Nonionic surfactants

Particularly suitable nonionic surfactants are fatty alcohol polyglycol ethers of the formula (II)

CH ₃

I.

R2θ- (CH ₂ CHO) _n (CH2CH2θ) _m H (II)

in the R2 for a linear or branched aliphatic hydrocarbon radical having 6 to 18 carbon atoms and 0, 1, 2 or 3 double bonds, n stands for 0 or numbers from 1 to 3 and for numbers from 1 to 10.

Typical examples are addition products of on average 1 to 3 mol propylene oxide and / or 1 to 10, preferably 2 to 7 mol ethylene oxide to capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, Isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, erucyl alcohol and behenyl alcohol. and their technical mixtures, such as those obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis. The adducts can have a conventional or even narrow homolog distribution and, due to the production process, can also contain free fatty alcohol. It is particularly preferred to use addition products of an average of 2 to 7 mol of ethylene oxide with technical C12 14 or Ci2 / ιg coconut fatty alcohol cuts.

Other suitable nonionic surfactants are also alkyl oligoglycosides of the formula (III).

R3_O- [G] _P (III)

in which R ^ is an alkyl radical having 6 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. Alkyl oligoglycosides are known substances that can be obtained by the relevant methods of preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP-A1-0 301 298 and WO 90/3977 (Henkel).

The alkyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl oligoglycosides are thus alkyl oligoglucosides. The index number p in the general formula (III) 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 here can take on the values p = 1 to 6, the value p is for a be¬ correct alkyl oligoglycoside is an analytically determined arithmetic size, which usually represents a fractional number. Alkyl 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 oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.

The alkyl radical R ^ can be derived from primary alcohols having 6 to 22, preferably 12 to 18, carbon atoms. Typical examples are capronic alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachyl alcohol and behenyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters. Alkyl oligoglucosides of chain length C2-28 (DP = 1 to 3), which can be produced on the basis of coconut oil.

The anionic and nonionic surfactants can be used in a weight ratio of 1: 1 to 1: 5, preferably 1: 1 to 1: 2.

Polymeric solidifying agents

bl) Polyethylene glycol ethers (PEG) with an average molecular weight of 12,000 to 500,000 are suitable as polymeric solidifying agents. Typical examples are polyethylene glycols with an average molecular weight of 12,000 to 100,000. In this context, the use of PEG 12,000 to PEG 35,000 has proven to be particularly advantageous.

b2) Other polymeric solidifying agents are esters of dicarboxylic acids of the formula (IV)

HOOC- (CH ₂ ) yCOOH (IV)

in which y stands for 0 or numbers from 1 to 12, with polyethylene glycol ethers which have an average molecular weight of 400 to 20,000. Typical examples are esters and polyesters of oxalic acid, succinic acid and adipic acid with PEG 400, PEG 5000 and PEG 12,000. Products of this type are characterized by a particularly advantageous biodegradability. b3) Another group of suitable polymeric strengthening agents are transesterification products of dialkyl carbonate with polyethylene glycol ethers, which have an average molecular weight of 400 to 20,000. Typical examples are transesterification products of dimethyl carbonate with PEG 400, PEG 5000 and PEG 12,000. The products are usually mono / di-ester mixtures which - according to statistics - can still contain portions of the alkyl radicals of the dialkyl carbonate used as the starting material.

b4) Finally, oligosaccharides or polysaccharides with a degree of condensation of 5 to 1000 are suitable as further polymeric solidifying agents. It is preferably polyglucose or polysorbitol.

The polymeric strengthening agents can be added to the nonionic surfactants in amounts of 1 to 50, preferably 2 to 30% by weight, based on the nonionic surfactants. Although it is fundamentally possible to produce ternary mixtures of anionic surfactants, nonionic surfactants and polymeric strengthening agents, it is i. a. It is more advantageous first to add the polymeric solidifying agents to the non-ionic surfactants and to further process this preformed mixture after hardening with the anionic surfactants.

The polymeric solidifying agents selected can be added to the nonionic surfactants, intimate mixing with stirring or kneading having to be ensured, if necessary with heating. In the special case that the nonionic surfactants is a polyglycol ether and the polymeric solidifying agent is a PEG, the mixture can also be generated in situ by alkoxylating a mixture of fatty alcohol and PEG together.

In the event that a particularly high degree of solidification of the non-ionic surfactants is required and bleeding or greasing must be prevented over a very long period of time, it has proven to be advantageous to give the polymeric solidifying agents long-chain fatty acids with 16 to 22 carbons ¬ Substance atoms, for example, to add cis / ig tallow fatty acid.

Application form of the anionic surfactants

The anionic surfactants can be used in the form of aqueous pastes or dry powders and then treated with the solidified nonionic surfactants.

Anionic surfactants are usually reacted by reacting corresponding starting materials with sulfur trioxide or chlorosulfonic acid to give acidic half-esters of sulfuric acid or sulfonic acids, which are then neutralized with aqueous bases and optionally hydrolyzed. The resulting aqueous pastes with a solids content of 5 to 65% by weight, based on the paste, are suitable starting materials for further processing in the sense of the invention. The aqueous pastes can also be used as spray-dried powders, as they are accessible by conventional tower powder processes. A variant is not to use the aqueous, neutralized products of a spray subject to drying, but to spray the acid sulfation products together with aqueous bases and thus to neutralize and dry in one step. For the purposes of the invention, anionic surfactants in the form of spray-neutralized as well as spray-dried or steam-dried powder are suitable as starting materials. For details of spray drying or spray neutralization of surfactants, reference is made to ROEMPP Chemistry Lexicon, 9th edition, Thie e-Verlag, Stuttgart, 1992, pp. 259/4260. As already stated, the preferred starting material is tallow alcohol sulfate in the form of aqueous pastes with a solids content of 5 to 65, preferably 50 to 65% by weight, or spray-neutralized, spray or steam-dried powder.

Manufacture of easily soluble products

The new solid washing, rinsing and cleaning agents can be produced in a variety of ways.

A particularly simple embodiment of the method consists in presenting the anionic surfactant in powder form and intimately mixing it with the required amount of the solidified nonionic surfactant. Components for this process, such as, for example, paddle mixers from Lödige or in particular spray mixers from Schugi, are advantageous, in which the anionic surfactant is placed in the mixing chamber and the solidified nonionic surfactants 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 required - can be charged with other common detergent additives and processed, for example, to detergent extrudates.

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. The aqueous pastes of the anionic surfactants and the solidified nonionic surfactants can be introduced into the fluidized bed simultaneously or successively 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 via a size classification of the granules. The classification can take place, for example, by means of a screening 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 soil 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 surfactant paste, producing dried to dried germs that coexist further amounts of anionic surfactant and solidified nonionic surfactant are encased, granulated and again dried simultaneously.

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

Regardless of the form of supply as powder, granules or extrudate, the new solid washing, rinsing and cleaning agents can contain further customary auxiliaries and additives, for example zeolites, phosphates, phosphonates, polycarboxylates, water glass, soda and borates, that can be added to them before, during or after solidification.

Industrial applicability

The solid washing, rinsing and cleaning agents according to the invention based on anionic and nonionic surfactants and polymeric strengthening agents are stable against the bleeding out of the nonionic surfactants and have excellent detergent properties. Another object of the invention therefore relates to the use of mixtures containing

a) anionic and nonionic surfactants in a weight ratio of 9: 1 to 1: 9, preferably 1: 1 to 1: 5 and b) the selected polymeric solidifying agents described above

as raw materials for the production of solid washing, rinsing and cleaning agents.

The following examples are intended to explain the subject matter of the invention in more detail without restricting it.

Examples

I. Examples of recipes

A universal detergent formulation with a high content of non-ionic surfactants and without or with polymeric solidifying agents with a composition according to Table 1 was extruded over a screw roller and pressed into extrusions via a perforated disc (diameter of the openings: 0.9 mm) works that have been continuously crushed to extrudates with a grain size of 0.9 mm.

Tab. 1: Composition of the detergent formulations, percentages as% by weight auxiliaries ad 100%.

Components VI Bl B2 B3 B4 B5 B6

%%%%%%%

Tallow alcohol sulfate 10 10 10 10 10 10 10

Coconut alcohol 3 EO 15 15 15 15 15 15 15

PEG-12,000 0 1 2 3 5 0 0

PEG-100,000 0 0 0 0 0 3 5

Zeolite A 35 35 35 35 35 35 35

Sodium perborate 16 16 16 16 16 16 16

Water glass 7 7 7 7 7 7 7

The formulations B1 to B6 are according to the invention; Recipe VI is used for comparison. II. Application studies

The bleeding behavior of the formulations was determined on unprinted cardboard with a thickness of 0.4 mm. For this purpose, the cardboard was mounted horizontally on a vibrating base, 5 g each of the solid formulations VI and B1 to B6 were applied and fixed with the aid of glass rings (diameter 5 cm). The uniform movement caused abrasion of the test mixtures on the surface of the cardboard and the oiling was assessed visually after t = 1, 5 and 24 h. The results are summarized in Tab. 2:

Tab. 2: Bleeding behavior

Ex. T. Bold formula h

VI Bl B2 B3 B4 B5 B6

1 1 III II I 0 0 0 0

2 5 IV II I I 0 0 0

3 24 V III II II I I I

Assessment: 0 = no greasing

1 = traces of fat

II = slight greasing

III = significant greasing

IV = heavy oiling

V = very strong greasing

Claims

1. Solid washing, rinsing and cleaning agents containing mixtures of

a) anionic and nonionic surfactants in a weight ratio of 9: 1 to 1: 9 and b) • 1 to 50% by weight, based on the nonionic

Surfactants - polymeric strengthening agents selected from the group consisting of

2. Process for the production of solid washing, rinsing and cleaning agents, in which mixtures of anionic and nonionic surfactants in a weight ratio of 9: 1 to 1: 9 with 1 to 50% by weight, based on the nonionic surfactants, polymeric solidifying agent added, which are selected from the group that is formed by

bl) polyethylene glycol ethers with an average molecular weight of 12,000 to 500,000, b2) esters of dicarboxylic acids with an average molecular weight of 400 to 20,000, b3) transesterification products of dialkyl carbonate with polyethylene glycol ethers with an average molecular weight of 400 to 20,000 and b4) oligosaccharides or polysaccharides with a degree of condensation of 5 to 1000 .

3. The method according to claim 2, characterized in that anionic surfactants are used, which are selected from the group consisting of alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, o-methyl ester sulfonates, sulfofatty acids, fatty alcohol sulfates, fatty alcohol ether sulfates , Glycerin ether sulfates, hydroxymisethersulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, sulfosuccinates, sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids, isethionates, sarcosinates, taurides, alkyl oligoglucoside sulfates becomes.

4. The method according to claim 3, characterized in that fatty alcohol sulfates of the formula (I) are used as anionic surfactants,

RiosOsX (I)

in which R represents a linear or branched alkyl and / or alkenyl radical having 12 to 22 carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.

5. Process according to claims 3 and 4, characterized gekenn¬ characterized in that fatty alcohol sulfates of the formula (I) are used in which R ^{1 is} an alkyl radical having 16 to 18 carbon atoms and X is sodium.

6. Process according to Claims 2 to 5, characterized in that fatty alcohol polyglycol ethers of the formula (II) are used as nonionic surfactants,

CH ₃

IR ² 0- (CH2CHO) _n (CH2CH2θ) _nι H (II)

in which R2 stands for a linear or branched aliphatic hydrocarbon radical with 6 to 18 carbon atoms and 0, 1, 2 or 3 double bonds, n for 0 or numbers from 1 to 3 and m for numbers from 1 to 10.

7. Process according to claims 2 to 5, characterized in that alkyloligo glycosides of the formula (III) are used as nonionic surfactants,

R ³ -0- [G] _p (III)

in which R3 is an alkyl radical having 6 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10.

8. The method according to claims 2 to 7, characterized gekenn¬ characterized in that the polymeric solidifying agent poly uses ethylene glycol ether with an average molecular weight of 12,000 to 500,000.

9. The method according to claims 2 to 7, characterized gekenn¬ characterized in that the polymeric solidifying agent is an ester of dicarboxylic acids of the formula (IV),

HOOC- (CH2) yCOOH (IV)

in which y stands for 0 or numbers from 1 to 12, with polyethylene glycol ethers which have an average molecular weight of 400 to 20,000.

10. Process according to Claims 2 to 7, characterized in that transesterification products of dialkyl carbonate with polyethylene glycol ethers which have an average molecular weight of 400 to 20,000 are used as the polymeric solidifying agent.

11. The method according to claims 2 to 7, characterized gekenn¬ characterized in that one uses as polymeric solidifying agent Oli¬ go or polysaccharides with a degree of condensation of 5 to 1000.

12. Use of mixtures obtainable by the process according to claims 1 to 11 as raw materials for the manufacture of solid washing, rinsing and cleaning agents.