DE4303176C2 - Solid washing, rinsing and cleaning agents - Google Patents

Description

Field of the Invention

The invention relates to new solid washing, rinsing and cleaning agents based on fatty alcohol sulfates, selected nonionic surfactants and polyethylene glycols with a defined molecular weight and a process for their manufacture.

State of the art

Solid washing, rinsing and cleaning agents are usually in the form of powders, granules or extrudates on the market. They usually contain com as surface-active constituents combinations of anionic and non-ionic surfactants that are suitable for cleaning and dirt-carrying capacity ideally complement [chemistry i.u. Zeit, 26, 292 (1992)]. While in the ver In the past, the anionic surfactants were contained in excess, but today there is a Be Need for recipes with an increased content of non-ionic surfactants. Below are ins to understand special recipes in which the proportion of nonionic surfactants in the Compared to that of the anionic surfactants makes up 100 to 200 wt .-%. While the anioni So far, alkylbenzenesulfonates and increasingly fatty alcohol sulfates have been at the fore the trend in nonionic surfactants is towards low alkoxylated fatty alcohol polyglycol ethers and alkyl oligoglucosides [soap-oil-fat waxes, 117, 554 (1991)].

Solid detergents, dishwashing detergents and cleaning agents of this type not only show excellent application technical services, but also advantages in compacting for the manufacture of heavy powder with bulk weights of 600 to 900 g / l. The disadvantage, however, is that the anionic surfactants together with the other fixed recipe components have only a limited capacity which mostly absorbing liquid nonionic surfactants and binding them permanently. Especially with the Desired formulations with a particularly high non-ionic surfactant content thus run the risk of "out bleeding ", i.e. the liquid nonionic surfactants become from the present solid mixture gradually released. The result is a decrease in the washing performance of the formulation and a gradual decrease  greasing of standard cardboard packaging; the latter can also serve as an indication of the Degree of bleeding or bleeding resistance.

According to the teaching of DE-A1 41 24 701 (Henkel), solid detergents with high bulk density and improved solubility are obtained by adding mixtures of anionic and nonionic surfactants to polyethylene glycol ethers with a molecular weight in the range from 200 to 12,000, preferably 200 to 600, and then dries and / or solidifies. According to embodiment 1, a detergent preparation containing C _12/18 fatty _alcohol sulfate, C _{12/18 fatty} alcohol + 5EO- / C _16/18 tallow fatty alcohol + 5EO adduct and - based on the nonionic surfactants - poly ethylene glycol with a molecular weight of approx 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 0208534, spray-dried detergent compositions are disclosed in general form which, in addition to anionic surfactants, nonionic surfactants, polyacrylates and polyethylene glycol ethers, have 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 PEG actually used are 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 C _12/13 oxo alcohol + 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 beard which have tallow alcohol sulfate, alkylbenzenesulfonate and polyethylene glycol with a molecular weight of about 20,000.

The object of the invention was to use solid washing, rinsing and cleaning agents to provide increased content of nonionic surfactants that prevent the bleeding of the Non-ionic surfactants are permanently stable.

Description of the invention

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

• (a1) anionic surfactants of the fatty alcohol sulfate type  
• (a2) nonionic surfactants of the fatty alcohol polyglycol ether and / or alkyl oligoglycoside type Weight ratio (a1): (a2) = 9: 1 to 1: 9 as well
• (b) Polyethylene glycols with an average molecular weight in the range of 35,000 to 500,000 as polymeric solidifiers

with the proviso that component (b) in amounts of 1 to 50 wt .-% based on the com component (a2) is included.

Surprisingly, it was found that the addition of selected polymeric solidification means to the non-surfactant-rich formulations leads to a solidification of the grain and bleeding liquid components permanently and reliably prevented, without the application lei stung of the recipes is adversely affected by the use of the solidifying agent. The Invention is of particular importance for agents with a high content of nonionic surfactants; it is however, it is also possible to use agents with a comparatively low content of nonionic surfactants on the stabilize the specified path against bleeding. The invention includes the knowledge that it with regard to the suitability of polyethylene glycol ethers as polymeric hardening agents the molecular weight there is a critical limit of 35,000. Below this range the desired effect, the significant improvement in resistance to bleeding, not reliable reached.

Another object of the invention relates to a method for producing solid washing, rinsing and cleaning agents, in which mixtures of

• (a1) anionic surfactants of the fatty alcohol sulfate type
• (a2) nonionic surfactants of the fatty alcohol polyglycol ether and / or alkyl oligoglycoside type Weight ratio (a1): (a2) = 9: 1 to 1: 9,

Polyethylene glycols (b) with an average molecular weight in the range from 35,000 to 500,000 is added as a polymeric solidifying agent, with the proviso that component (b) in Amounts of 1 to 50 wt .-% based on component (a2) is included.

Fatty alcohol sulfates

Fatty alcohol sulfates that can be used in the sense of the invention preferably follow that Formula (I),

R¹OSO₃X (I)

in R¹ for a linear or branched alkyl and / or alkenyl radical having 12 to 22 carbon atoms and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Tallow alcohol sulfates are again from the group of fatty alcohol sulfates of particular importance in which R¹ in formula (I) for an alkyl radical having 16 to 18 carbon atoms and X stands for sodium.

Fatty alcohol polyglycol ether

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

in which R² is a linear or branched aliphatic hydrocarbon radical having 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. Typical examples are addition products of an average of 1 to 3 mol of propylene oxide and / or 1 to 10, preferably 2 to 7 mol, of ethylene oxide with capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palm oleyl 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 narrow homolog distribution and, due to the production process, can also contain a free fatty alcohol content. Particularly preferred is the use of add-on products of an average of 2 to 7 moles of ethylene oxide on technical C _12/14 or C _12/18 coconut _fatty alcohol cuts.

Alkyl oligoglycosides

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

R³O- [G] _p (III)

in the R³ for an alkyl radical with 6 to 22 carbon atoms, G for a sugar radical with 5 or 6 Koh lenstoffatomen and p stands for a number from 1 to 10. Alkyl oligoglycosides are known substances  which can be obtained according to the relevant procedures in preparative organic chemistry. Representative of the extensive literature on EP-A1 0301298 and WO 90/3977 (Henkel). The alkyl oligoglycosides can differ from aldoses or ketoses with 5 or 6 carbon atoms, preferably derived from glucose. The preferred alkyl oligoglycosides are thus alkyl oligoglucosides. The index number p in the general formula (III) indicates the oligomerization degree (DP), d. H. the distribution of mono- and oligoglycosides and stands for a number between 1 and 10. While p must always be an integer in a given connection, and above all that Can assume values p = 1 to 6, the value p is analytical for a particular alkyl oligoglycoside calculated arithmetic size, which usually represents a fractional number. Preferably be Alkyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are used. From use From an nutritional point of view, those alkyl oligoglycosides are preferred whose degree of oligomerization is smaller is 1.7 and is in particular between 1.2 and 1.4. The alkyl radical R³ can differ from primary alcohol fetch with 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 hol, arachyl alcohol and behenyl alcohol and their technical mixtures, such as those in the hydrogenation of technical fatty acid methyl esters. Alkyl oligoglucosides are preferred Chain length C₁₂-C₁₈ (DPA 1 to 3) that can be made on the basis of coconut oil.

The fatty alcohol sulfates and the nonionic surfactants can be in a weight ratio of 1: 1 to 1: 5, preferably 1: 1 to 1: 2 are used.

Polymeric solidifying agents

The polymeric strengthening agents, ie the selected polyethylene glycol ethers, 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 fatty alcohol sulfates, nonionic surfactants and polymeric strengthening agents, it is generally more advantageous to first add the polymeric strengthening agents to the nonionic surfactants and to further process the preformed mixture after hardening with the fatty alcohol sulfates. The polymeric strengthening agents can nonionic surfactants are added, an intimate mixing with stirring or kneading having to be ensured if necessary with heating. In the event that the nonionic surfactant is a polyglycol ether and the polymeric solidifying agent is a PEG, the mixture can also be produced in situ by alkoxylating a mixture of fatty alcohol and PEG together. In the event that a particularly high degree of solidification of the nonionic surfactants is required and bleeding or greasing must be prevented over a very long period of time, it has proven to be advantageous to add long-chain fatty acids with 16 to 22 carbon atoms, for example C ₁₆ , to the polymeric strengthening agents _{/ 18} - Add tallow fatty acid.

Use of fatty alcohol sulfates

The fatty alcohol sulfates can be used in the form of aqueous pastes or dry powders finally treated with the solidified nonionic surfactants. Usually fat alcohol sulfates by reacting appropriate fatty alcohols with sulfur trioxide or chlorosulfone acid converted to acidic sulfuric acid half-esters, which are then neutralized with aqueous bases be lized. The resulting aqueous pastes with a solids content of 5 to 65% by weight - Based on the paste - make suitable starting materials for the further in the sense of the invention Processing. The aqueous pastes can also be used as spray-dried powders, as they are accessible using conventional tower powder processes. One variant is not to subject the aqueous, neutralized products to spray drying, but rather the acidic sul Spray animal products together with aqueous bases and thus neutralize them in one step and dry. For the purposes of the invention, fatty alcohol sulfates are both spray-neutralized ter, as well as spray-dried or steam-dried powder as starting materials. To Details of the spray drying or spray neutralization of surfactants are on ROEMPP chemistry Lexicon, 9th edition, Thieme-Verlag, Stuttgart, 1992, pp. 4259/4260. The preferred starting point As previously stated, fabric makes tallow alcohol sulfate in the form of aqueous pastes with a solid substance 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 production of the new solid washing, rinsing and cleaning agents can be done in a variety of ways conditions. A particularly simple embodiment of the method is the fatty alcohol Wood sulfate in powder form and with the required amount of solidified nonionic Mix surfactants intimately. Components such as paddle mixers are used for this process Lödige company or in particular spray mixer from Schugi an advantage, where you can do that Anion surfactant is placed in the mixing chamber and the solidified nonionic surfactant is sprayed on. Further is it is possible to dry the fatty alcohol sulfate pastes and mix them simultaneously in one process perform bed-layer dryer. Dry, easily soluble powders are obtained which, if necessary derlich - acted upon with other usual detergent additives and, for example, washing medium extrudates can be processed.  

Another possibility is the anionic surfactants of a so-called SKET granule subject. This is to be understood as a granulation with simultaneous drying, which is preferably carried out batchwise or continuously in the fluidized bed. The aq fatty alcohol sulfate pastes and the solidified nonionic surfactants simultaneously or in succession are introduced into the fluidized bed via one or more nozzles. Preferred used Fluid bed apparatuses have base plates with dimensions of 0.4 to 5 m. Preferably SKET pelletizing is carried out at fluidized air speeds in the range from 1 to 8 m / s. Of the The granules are preferably discharged from the fluidized bed via a size classification of Granules. The classification can be carried out, for example, by means of a screening device or by means of a countercurrent air flow (classifier air), which is regulated so that only particles from a be agreed particle size removed from the fluidized bed and smaller particles in the fluidized bed be held back. Usually the inflowing air settles out of the heated or unused heated sifter air and the heated soil air together. The soil air temperature is there between 80 and 400, preferably 90 and 350 ° C. Advantageously, at the beginning of the SKET-Gra a starting mass, for example a SKET granulate from an earlier test batch, submitted. In the fluidized bed, the water evaporates from the anionic surfactant paste, whereby dried until dried germs are formed, which are mixed with further quantities of anionic surfactant and solidified nonioni be coated, granulated and again dried simultaneously.

In a preferred embodiment of the invention, the fatty alcohol sulfates are in powder form the solidified nonionic surfactants mixed and the mixture in a screw press ho mogenized and solidified. The extrusion takes place via a perforated disc, so that press strands are created the desired shape and dimension me according to known methods for extrudates or needles can be shredded. Extrudates of this form show a particularly high resolution speed and very good washing-up behavior in the washing machine. Regardless of the offer The new solid washing, rinsing and cleaning agents can be used in powder, granulate or extrudate form other conventional auxiliaries and additives, for example zeolites, phosphates, phosphonates, Contain polycarboxylates, water glass, soda and borates that give them before, during or after the Ver consolidation can be added.

Examples

Universal detergent formulations with a high content of non-ionic surfactants and polyethylene glycols different molecular weights were extruded over a screw roller and over a Perforated disc (diameter of the openings: 0.9 mm) processed into extrusions, which are continuous were crushed to extrudates with a grain size of 0.9 mm. The bleeding behavior of the recipes was determined on unprinted cardboard with a thickness of 0.4 mm. For this purpose, the box was opened horizontally a vibrating pad is installed, 5 g of the solid recipes applied and with the help of glass rings (diameter 5 cm) fixed. The even movement caused abrasion of the Test mixes on the surface of the cardboard and the oiling visually after t = 1, 5 and 24 h be judges. The composition of the mixtures and their bleeding behavior is shown in Table 1 together quantified. The formulas R4 to R6 and R10 to R12 are according to the invention, the formulas R1 to R3 and R7 to R9 are used for comparison. Some of these examples were developed as part of the test tion procedure subsequently filed and included in the description to the invention Clarify teaching better.

If you look at the formulations R1 to R6, whose nonionic surfactant content is 15%, you can already see the tendency that higher PEG's prevent bleeding. A look at the formulas R7 to R12 with a significantly higher nonionic surfactant content of 25% by weight makes it clear that this tendency significantly increased with the increase in the proportion of nonionic surfactants in the formulation. Here you can see also that there is a very clear distinction between the use of a PEG 20,000 and a PEG 35,000 can be.  

Table 1

Bleeding out of non-surfactant-rich detergent formulations (quantities as% by weight)

Claims (8)

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

• (a1) anionic surfactants of the fatty alcohol sulfate type
• (a2) nonionic surfactants of the fatty alcohol polyglycol ether and / or alkyl oligoglycoside type in the weight ratio (a1): (a2) = 9: 1 to 1: 9 and
• (b) polyethylene glycols with an average molecular weight in the range from 35,000 to 500,000 as polymeric strengthening agents,

with the proviso that component (b) in amounts of 1 to 50 wt .-% based on the Component (a2) is included. 2. Process for the preparation of solid washing, rinsing and cleaning agents, in which mixtures of

• (a1) anionic surfactants of the fatty alcohol sulfate type
• (a2) nonionic surfactants of the fatty alcohol polyglycol ether and / or alkyl oligoglycoside type in the weight ratio (a1): (a2) = 9: 1 to 1: 9,

Polyethylene glycols (b) with an average molecular weight in the range from 35,000 to 500,000 is added as a polymeric solidifying agent, with the proviso that component (b) in Amounts of 1 to 50 wt .-% based on component (a2) is included. 3. The method according to claim 2, characterized in that fat as ionic surfactants uses alcohol sulfates of the formula (I), R¹OSO₃X (I) in R¹ for a linear or branched alkyl and / or alkenyl radical with 12 to 22 carbon atoms and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammo nium or glucammonium. 4. Process according to claims 2 and 3, characterized in that fatty alcohol sulfates of formula (I) in which R¹ is an alkyl radical having 16 to 18 carbon atoms and X is Sodium stands.   5. Process according to Claims 2 to 4, characterized in that nonionic surfactants fatty alcohol polyglycol ethers of the formula (II) are used, in which R² is a linear or branched aliphatic hydrocarbon radical having 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. 6. The method according to claims 2 to 5, characterized in that one as a nonionic Alkyl oligoglycosides of the formula (III) are used, R³O- [G] p (III) in R³ for an alkyl radical with 6 to 22 carbon atoms, G for a sugar radical with 5 or 6 Carbon atoms and p represents a number from 1 to 10.