EP0682691A1 - Solid washing, rinsing and cleaning agents. - Google Patents

Solid washing, rinsing and cleaning agents.

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Publication number
EP0682691A1
EP0682691A1 EP94906151A EP94906151A EP0682691A1 EP 0682691 A1 EP0682691 A1 EP 0682691A1 EP 94906151 A EP94906151 A EP 94906151A EP 94906151 A EP94906151 A EP 94906151A EP 0682691 A1 EP0682691 A1 EP 0682691A1
Authority
EP
European Patent Office
Prior art keywords
molecular weight
average molecular
nonionic surfactants
sulfates
ether
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP94906151A
Other languages
German (de)
French (fr)
Other versions
EP0682691B1 (en
EP0682691B2 (en
Inventor
Karl Schmid
Andreas Syldath
Ditmar Kischkel
Thomas Krohnen
Michael Neuss
Michael Langen
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BASF Personal Care and Nutrition GmbH
Original Assignee
Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/126—Acylisethionates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/16—Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/345—Phosphates or phosphites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/667—Neutral esters, e.g. sorbitan esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • 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.
  • Solid washing, rinsing and cleaning agents usually come onto the market in the form of powders, granules or extrudates.
  • 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. ⁇ 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
  • 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.
  • 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.
  • the rate of dissolution of the resulting solid detergents is still unsatisfactory.
  • the presence of the large amounts of polymer required is not desirable.
  • 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.
  • 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.
  • the invention relates to solid washing, rinsing and cleaning agents containing mixtures of
  • 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
  • polyethylene glycol ethers with an average molecular weight of 12,000 to 500,000
  • esters of dicarboxylic acids with an average molecular weight of 400 to 20,000
  • transesterification products of dialkyl carbonate with polyethylene glycol ethers with an average molecular weight of 400 to 20,000
  • oligosaccharides or polysaccharides with a degree of condensation of 5 to 1000.
  • 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.
  • 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 dicarboxy
  • 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.
  • fatty alcohol sulfates of the formula (I) is preferred among the anionic surfactants,
  • 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.
  • R 1 in formula (I) is an alkyl radical having 16 to 18 carbon atoms and X is sodium.
  • nonionic surfactants are fatty alcohol polyglycol ethers of the formula (II)
  • 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.
  • 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 / ⁇ g coconut fatty alcohol cuts.
  • nonionic surfactants are also alkyl oligoglycosides of the formula (III).
  • R ⁇ is an alkyl radical having 6 to 22 carbon atoms
  • G is a sugar radical having 5 or 6 carbon atoms
  • 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.
  • 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 anionic and nonionic surfactants can be used in a weight ratio of 1: 1 to 1: 5, preferably 1: 1 to 1: 2.
  • Polyethylene glycol ethers 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • anionic surfactants in the form of spray-neutralized as well as spray-dried or steam-dried powder are suitable as starting materials.
  • spray drying or spray neutralization of surfactants reference is made to ROEMPP Chemistry Lexicon, 9th edition, Thie e-Verlag, Stuttgart, 1992, pp. 259/4260.
  • 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.
  • 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.
  • anionic surfactants to so-called SKET granulation.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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
  • 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%.

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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

Feste Wasch-, Spül- und Reinigungsmittel Solid washing, rinsing and cleaning agents
Gebiet der ErfindungField of the Invention
Die Erfindung betrifft neue feste Wasch-, Spül- und Reini¬ gungsmittel, ein Verfahren zu ihrer Herstellung, bei dem man Mischungen aus anionischen und nichtionischen Tensiden mit ausgewählten polymeren Verfestigungsmitteln versetzt sowie die Verwendung der Mischungen .aus anionischen und nichtioni¬ schen Tensiden sowie den polymeren Verfestigungsmitteln als Rohstoffe zur Herstellung fester und gegen Ausbluten bestän¬ diger Wasch-, Spül- und Reinigungsmittel.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.
Stand der TechnikState of the art
Feste Wasch-, Spül- und Reinigungsmittel gelangen üblicher¬ weise in Form von Pulvern, Granulaten oder Extrudaten auf den Markt. Als oberflächenaktive Bestandteile enthalten sie in der Regel Kombinationen aus anionischen und nichtionischen Tensiden, die sich im Hinblick auf Reinigungswirkung und Schmutztragevermögen ideal ergänzen [Chemie i.u.Zeit, 2 .ι 292 (1992)]. Während in der Vergangenheit die anionischen Tenside im Überschuß enthalten waren, besteht heute jedoch ein Be¬ dürfnis nach Rezepturen mit einem erhöhten Gehalt an nicht- ionischen Tensiden. Hierunter sind insbesondere solche Rezep¬ turen zu verstehen, bei denen der Anteil der nichtionischen Tenside im Vergleich zu dem der anionischen Tenside 100 bisSolid 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
200 Gew.-% ausmacht. Während bei den anionischen Tensiden bislang Alkylbenzolsulfonate und zunehmend Fettalkoholsulfate im Vordergrund stehen, geht der Trend bei den nichtionischen Tensiden hin zu niedrig alkoxylierten Fettalkoholpolyglycol- ethern und Alkyloligoglucosiden [Seifen-Öle-Fette-Wachse, 117, 554 (1991)].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)].
Feste Wasch-, Spül- und Reinigungsmittel dieser Art zeigen nicht nur ausgezeichnete anwendungstechnische Leistungen, sondern auch Vorteile bei der Kompaktierung zur Herstellung von Schwerpulvern mit Schüttgewichten von 600 bis 900 g/1. Von Nachteil ist jedoch, daß die anionischen Tenside zusammen mit den übrigen festen Rezepturbestandteilen nur eine be¬ grenzte Kapazität besitzen, die meist flüssigen nichtioni¬ schen Tenside "aufzusaugen" und dauerhaft zu binden. Gerade bei den erwünschten Rezepturen mit besonders hohem Niotensid- gehalt besteht somit die Gefahr des "Ausblutens", d. h. die flüssigen nichtionischen Tensiden werden von dem vorliegenden Feststoffgemisch allmählich freigesetzt. Die Folge ist eine Abnahme der Waschleistung der Rezeptur und ein allmähliches Durchfetten der handelsüblichen Kartonverpackungen; letzteres kann im übrigen als Indiz für den Grad des Ausblutens oder der Ausblutbeständigkeit herangezogen werden.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.
Gemäß der Lehre der DE-Al 41 24 701 (Henkel) werden feste Waschmittel mit hohem Schüttgewicht und verbesserter Löslich¬ keit erhalten, indem man Mischungen von anionischen und nichtionischen Tensiden Polyethylenglycolether mit einem Molekulargewicht im Bereich von 200 bis 12.000, vorzugsweise 200 bis 600 zusetzt, und anschließend trocknet und/oder in feste Form bringt. Gemäß dem Ausführungsbeispiel 1 wird eine Waschmittelzubereitung, enthaltend Ci2/18~Fettalkonolsulfatr 12/18-Fettalkono1-5 EO-/Ci6/18- algfettalkoho1-5 EO-Addukt und - bezogen auf die Niotenside - Polyethylenglycol mit ei¬ nem Molekulargewicht von ca. 400 offenbart, die nach Homoge¬ nisierung extrudiert und zu Granulaten verarbeitet wird. Die Auflösegeschwindigkeit der resultierenden festen Waschmittel ist jedoch noch immer nicht zufriedenstellend. Zudem ist die Anwesenheit der erforderlichen großen Mengen an Polymer nicht erwünscht.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.
Gemäß der EP-A2 0 208 534 werden in allgemeiner Form sprüh¬ getrocknete Waschmittelzusammensetzungen offenbart, die neben anionischen Tensiden, nichtionische Tenside, Polyacrylate und Polyethylenglycolether mit einem durchschnittlichen Moleku¬ largewicht im Bereich von 1.000 bis 20.000 enthalten. Die Lehre dieser Schrift geht dahin, daß man die Dispergierbar- keit von anionischen Tensiden verbessern kann, indem man ih¬ nen Niotenside, Polyethylenglycolether und Polyacrylate zu¬ setzt. Die tatsächlich eingesetzten PEG sind jedoch nieder¬ molekular und weisen Molekulargewichte vorzugsweise im Be¬ reich von 4.000 bis 20.000 auf (vgl. Seite 4, 2. Abschnitt). Im einzigen Ausführungsbeispiel wird eine Mischung enthaltend Alkylbenzolsulfonat und Fettalkoholsulfat beschrieben, der man ein Ci2/i3-Oxoalkohol-6,5 EO-Addukt, Natriumpolyacrylat und Polyethylenglycol mit einem Molekulargewicht von ca. 8.000 zusetzt. Das Gewichtsverhältnis zwischen Niotensid und PEG beträgt 1 : 1. Gegenstand der DE-OS 21 24 526 sind Wasch- und Reinigungsmit¬ telmischungen mit geregeltem Schaumverhalten. Gemäß Beispiel 6 werden Zusammensetzungen offenbart, die Talgalkoholsulfat, Alkylbenzolsulfonat sowie Polyethylenglycol mit einem Mole¬ kulargewicht von ca. 20.000 aufweisen.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.
Die Aufgabe der Erfindung hat nun darin bestanden, feste Wasch-, Spül- und Reinigungsmittel mit erhöhtem Gehalt an nichtionischen Tensiden zur Verfügung zu stellen, die gegen das Ausbluten der Niotenside dauerhaft beständig sind.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.
Beschreibung der ErfindungDescription of the invention
Gegenstand der Erfindung sind feste Wasch-, Spül- und Reini¬ gungsmittel, enthaltend Mischungen vonThe invention relates to solid washing, rinsing and cleaning agents containing mixtures of
a) anionischen und nichtionischen Tensiden im Gewichtsver¬ hältnis 9 : 1 bis 1 : 9, vorzugsweise 1 : 1 bis 1 : 5 sowie b) 1 bis 50 Gew.-% - bezogen auf die nichtionischen Tenside - polymere Verfestigungsmittel ausgewählt aus der Grup¬ pe, die gebildet wird vona) 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) Polyethylenglycolethern mit einem durchchnittliehen Molekulargewicht von 12.000 bis 500.000, b2) Ester von Dicarbonsäuren mit einem durchschnitt¬ lichen Molekulargewicht von 400 bis 20.000, b3) ümesterungsprodukte von Dialkylcarbonat mit Poly¬ ethylenglycolethern mit einem durchschnittlichen Molekulargewicht von 400 bis 20.000 und b4) Oligo- bzw. Polysaccharide mit einem Kondensations¬ grad von 5 bis 1000.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.
Überraschenderweise wurde gefunden, daß der Zusatz von aus¬ gewählten polymeren Verfestigungsmitteln zu den niotensid- reichen Rezepturen zu einer Verfestigung des Korns führt und ein Ausbluten flüssiger Komponenten dauerhaft und zuverlässig verhindert, ohne daß die anwendungstechnische Leistung der Rezepturen durch die Mitverwendung der Verfestigungsmittel nachteilig beeinflußt wird. Die Erfindung hat eine besondere Bedeutung für Mittel mit hohem Gehalt an nichtionischen Ten¬ siden; es ist jedoch auch möglich, Mittel mit vergleichsweise niedrigem Gehalt an nichtionischen Tensiden auf dem angege¬ benen Weg gegen Ausbluten zu stabilisieren.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.
Die Erfindung schließt die Erkenntnis ein, daß es im Hinblick auf die Eignung von Polyethylenglycolethern als polymere Ver¬ festigungsmittel hinsichtlich des Molekulargewichtes eine kritische Grenze von 12.000 gibt. Unterhalb dieses Bereiches wird der gewünschte Effekt, die signifikante Verbesserung der Beständigkeit gegen Ausbluten, nicht erreicht.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.
Ein weiterer Gegenstand der Erfindung betrifft ein Verfahren zur Herstellung von festen Wasch-, Spül- und Reinigungsmit¬ teln, bei dem man Mischungen von anionischen und nichtioni¬ schen Tensiden im Gewichtsverhältnis 9 : 1 bis 1 : 9, vor¬ zugsweise 1 : 1 bis 1 : 5 mit 1 bis 50 Gew.-% - bezogen auf die nichtionischen Tenside - polymerer Verfestigungsmittel versetzt, die ausgewählt sind aus der Gruppe, die gebildet wird von bl) Polyethylenglycolethern mit einem durchchnittlichen Mo¬ lekulargewicht von 12.000 bis 500.000, b2) Ester von Dicarbonsäuren mit einem durchschnittlichen Molekulargewicht von 400 bis 20.000, b3) Umesterungsprodukten von Dialkylcarbonat mit Polyethy¬ lenglycolethern mit einem durchschnittlichen Molekular¬ gewicht von 400 bis 20.000 und b4) Oligo- bzw. Polysacchariden mit einem Kondensationsgrad von 5 bis 1000.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.
Anionische TensideAnionic surfactants
Die anionischen Tenside können ausgewählt sein aus der Grup¬ pe, die von Alkylbenzolsulfonaten, Alkansulfonaten, Olefin- sulfonaten, Alkylethersulfonaten, Glycerinethersulfonaten, oc-Methylestersulfonaten, Sulfofettsäuren, Fettalkoholsulfa¬ ten, Fettalkoholethersulfaten, Glycerinethersulfaten, Hy- droxymischethersulfaten, Monoglycerid(ether)sulfaten, Fett- säureamid(ether)Sulfaten, Sulfosuccinaten, Sulfosuccinamaten, Sulfotriglyceriden, Amidseifen, Ethercarbonsäuren, Isethio- naten, Sarcosinaten, Tauriden, Alkyloligoglucosidsulfaten und Alkyl(ether)phosphaten gebildet wird.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.
Bei allen diesen Stoffen handelt es sich um bekannte Tenside, die nach den einschlägigen Verfahren der präparativen organi¬ schen Chemie hergestellt werden können. Zu Synthese und Ei¬ genschaften sei beispielsweise auf J.Falbe (ed.) "Surfactants in consu er products", Springer Verlag, Berlin, 1987, S. 54- 85 oder J.Falbe, U.Hasserodt, "Katalysatoren, Tenside und Mi- neralöladditive", Thieme Verlag, Stuttgart, 1978, S.126-139 verwiesen.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.
Unter den anionischen Tensiden ist neben den Alkylbenzolsul- fonaten, namentlich dem Dodecylbenzolsulfonat, der Einsatz von Fettalkoholsulfaten der Formel (I) bevorzugt,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,
RlθS03X (I)RlθS0 3 X (I)
in der R1 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 12 bis 22 Kohlenstoffatomen und X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammoniiam steht. Aus der Gruppe der Fettalkoholsulfate sind wiederum Talgalkoholsulfate von be¬ sonderer Bedeutung, bei denen R1 in Formel (I) für einen Alkylrest mit 16 bis 18 Kohlenstoffatomen und X für Natrium steht.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.
Nichtionische TensideNonionic surfactants
Als nichtionische Tenside kommen insbesondere Fettalkohol- polyglycolether der Formel (II) in Betracht,Particularly suitable nonionic surfactants are fatty alcohol polyglycol ethers of the formula (II)
CH3 CH 3
II.
R2θ-(CH2CHO)n(CH2CH2θ)mH (II)R2θ- (CH 2 CHO) n (CH2CH2θ) m H (II)
in der R2 für einen linearen oder verzweigten aliphatisehen Kohlenwasserstoffrest mit 6 bis 18 Kohlenstoffatomen und 0, 1, 2 oder 3 Doppelbindungen, n für 0 oder Zahlen von 1 bis 3 und für Zahlen von 1 bis 10 steht.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.
Typische Beispiele sind .Anlagerungsprodukte von durchschnitt¬ lich 1 bis 3 mol Propylenoxid und/oder 1 bis 10, vorzugsweise 2 bis 7 mol Ethylenoxid an Capronalkohol, Caprylalkohol, 2- Ethylhexylalkohol, Caprinalkohol, Laurylalkohol, Myristylal- kohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Iso- stearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinyl- alkohol, Linolylalkohol, Linolenylalkohol, Elaeostearylalko- hol, Arachylalkohol, Gadoleylalkohol, Erucylalkohol und Be- henylalkohol. sowie deren technische Gemische, wie sie bei¬ spielsweise durch Hochdruckhydrierung technischer Methyl¬ esterfraktionen oder Aldehyden aus der Roelen'sehen Oxosyn- these erhalten werden. Die Addukte können dabei eine konven¬ tionelle oder auch eingeengte Homologenverteilung aufweisen und herstellungsbedingt noch einen Gehalt an freiem Fettal¬ kohol enthalten. Besonders bevorzugt ist der Einsatz von Anlagerungsprodukten von durchschnittlich 2 bis 7 Mol Ethy¬ lenoxid an technische C12 14- bzw. Ci2/ιg-Kokosfettalkohol- schnitte.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.
Als weitere nichtionische Tenside kommen ferner Alkyloligo- glykoside der Formel (III) in .Betracht,Other suitable nonionic surfactants are also alkyl oligoglycosides of the formula (III).
R3_O-[G]P (III)R3_O- [G] P (III)
in der R^ für einen Alkylrest mit 6 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für eine Zahl von 1 bis 10 steht. Alkyloligoglykoside stellen bekannte Stoffe dar, die nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden können. Stellvertretend für das umfangreiche Schrifttum sei hier auf die Schriften EP-A1-0 301 298 und WO 90/3977 (Henkel) verwiesen.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).
Die Alkyloligoglykoside können sich von Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise der Glucose ab¬ leiten. Die bevorzugten Alkyloligoglykoside sind somit Alkyl¬ oligoglucoside. Die Indexzahl p in der allgemeinen Formel (III) gibt den Oligomerisierungsgrad (DP-Grad) , d. h. die Verteilung von Mono- und Oligoglykosiden an und steht für eine Zahl zwischen 1 und 10. Während p in einer gegebenen Verbindung stets ganzzahlig sein muß und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein be¬ stimmtes Alkyloligoglykosid eine analytisch ermittelte rech¬ nerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkyloligoglykoside mit einem mittleren Oligomerisierungsgrad p von 1,1 bis 3,0 eingesetzt. Aus an¬ wendungstechnischer Sicht sind solche Alkyloligoglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1,7 ist und insbesondere zwischen 1,2 und 1,4 liegt.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.
Der Alkylrest R^ kann sich von primären Alkoholen mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen ableiten. Ty¬ pische Beispiele sind Capronalkohol, Caprylalkohol, Caprin- alkohol, Laurylalkohol, Myristylalkohol, Cetylalkohol, Stea- rylalkohol, Arachylalkohol und Behenylakohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hy¬ drierung von technischen Fettsäuremethylestern anfallen. Be¬ vorzugt sind Alkyloligoglucoside der Kettenlänge C_2 ^18 (DP = 1 bis 3) , die auf Basis von Kokosöl hergestellt werden können.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.
Die anionischen und nichtionischen Tenside können im Ge¬ wichtsverhältnis 1 : 1 bis 1 : 5, vorzugsweise 1 : 1 bis 1 : 2 eingesetzt werden.The anionic and nonionic surfactants can be used in a weight ratio of 1: 1 to 1: 5, preferably 1: 1 to 1: 2.
Polymere VerfestigungsmittelPolymeric solidifying agents
bl) Als polymere Verfestigungsmittel kommen beispielsweise Polyethylenglycolether (PEG) mit einem durchschnittli¬ chen Molekulargewicht von 12.000 bis 500.000 in Be¬ tracht. Typische Beispiele sind Polyethylenglycole mit einem durchschnittlichen Molgewicht von 12.000 bis 100.000. Als besonders vorteilhaft hat sich in diesem Zusammenhang der Einsatz von PEG 12.000 bis PEG 35.000 erwiesen.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) Als weitere polymere Verfestigungsmittel kommen Ester von Dicarbonsäuren der Formel (IV) in Betracht,b2) Other polymeric solidifying agents are esters of dicarboxylic acids of the formula (IV)
HOOC-(CH2)yCOOH (IV)HOOC- (CH 2 ) yCOOH (IV)
in der y für 0 oder Zahlen von 1 bis 12 steht, mit Poly- hylenglycolethern, die ein durchschnittliches Molekular¬ wicht von 400 bis 20.000 aufweisen. Typische Beispiele sind Ester und Polyester der Oxalsäure, Bernsteinsäure und Adipinsäure mit PEG 400, PEG 5000 und PEG 12.000. Produkte dieser Art zeichnen sich durch eine besonders vorteilhafte biologische Abbaubarkeit aus. b3) Eine weitere Gruppe von geeigneten polymeren Verfesti¬ gungsmitteln stellen Umesterungsprodukte von Dialkyl- carbonat mit Polyethylenglycolethern, die ein durch¬ schnittliches Molekulargewicht von 400 bis 20.000 auf¬ weisen, dar. Typische Beispiele sind Umesterungsprodukte von Dimethylcarbonat mit PEG 400, PEG 5000 und PEG 12.000. Bei den Produkten handelt es sich üblicherweise um Mono/Di-Estergemische, die - der Statistik folgend - noch Anteile der Alkylreste des als Ausgangsmaterial verwendeten Dialkylcarbonats enthalten können.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) Als weitere polymere Verfestigungsmittel kommen schlie߬ lich Oligo- bzw. Polysaccharide mit einem Kondensations- grad von 5 bis 1000 in Betracht. Vorzugsweise handelt es sich hierbei um Polyglucose oder Polysorbit.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.
Die polymeren Verfestigungsmitteln können den nichtionischen Tensiden in Mengen von 1 bis 50, vorzugsweise 2 bis 30 Gew.-% - bezogen auf die nichtionischen Tenside - zugesetzt werden. Obschon es grundsätzlich möglich ist, ternäre Mischungen aus anionischen Tensiden, nichtionischen Tensiden und polymeren Verfestigungsmitteln herzustellen, ist es doch i. a. vorteil¬ hafter, zunächst die polymeren Verfestigungsmittel den nicht¬ ionischen Tensiden zuzusetzen und diese präformierte Mischung nach Erhärtung mit den anionischen Tensiden weiterzuverar- beiten.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.
Die ausgewählten polymeren Verfestigungsmittel können den nichtionischen Tensiden zugesetzt werden, wobei eine innige Vermischung unter Rühren oder Kneten gegebenenfalls unter Erwärmen sichergestellt werden muß. Im Sonderfall, daß das nichtionische Tenside ein Polyglycolether ist und das poly¬ mere Verfestigungsmittel ein PEG darstellt, kann die Mischung auch in-situ erzeugt werden, indem man ein Gemisch aus Fett¬ alkohol und PEG gemeinsam alkoxyliert.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.
Für den Fall, daß eine besonders hohe Verfestigung der nicht¬ ionischen Tenside erforderlich ist und ein Ausbluten bzw. Fetten über einen sehr langen Zeitraum verhindert werden muß, hat es sich als vorteilhaft erwiesen, den polymeren Verfesti¬ gungsmitteln langkettige Fettsäuren mit 16 bis 22 Kohlen¬ stoffatomen, beispielsweise Cis/ig-Talgfettsäure zuzusetzen.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.
Einsatzform der anionischen TensideApplication form of the anionic surfactants
Die anionischen Tenside können in Form wäßriger Pasten oder trockener Pulver eingesetzt und anschließend mit den verfe¬ stigten nichtionischen Tensiden behandelt werden.The anionic surfactants can be used in the form of aqueous pastes or dry powders and then treated with the solidified nonionic surfactants.
Üblicherweise werden anionische Tenside durch Umsetzung ent¬ sprechender Ausgangsstoffe mit Schwefeltrioxid oder Chlorsul- fonsäure zu sauren Schwefelsäurehalbestern oder Sulfonsäuren umgesetzt, die anschließend mit wäßrigen Basen neutralisiert und gegebenenfalls hydrolysiert werden. Die hierbei resultie¬ renden wäßrigen Pasten mit einem Feststoffgehalt von 5 bis 65 Gew.-% - bezogen auf die Paste - stellen im Sinne der Erfin¬ dung geeignete Ausgangsstoffe für die weitere Verarbeitung dar. Die wäßrigen Pasten können auch als sprühgetrocknete Pulver eingesetzt werden, wie sie nach konventionellen Turm¬ pulververfahren zugänglich sind. Eine Variante besteht darin, nicht die wäßrigen, neutralisierten Produkte einer Sprüh- trocknung zu unterwerfen, sondern die sauren Sulfierprodukte zusammen mit wäßrigen Basen zu versprühen und somit in einem Schritt zu neutralisiern und zu trocknen. Im Sinne der Er¬ findung kommen anionischen Tenside sowohl in Form sprühneu¬ tralisierter, als auch sprühgetrockneter oder heißdampfge¬ trockneter Pulver als Ausgangsstoffe in Betracht. Zu Einzel¬ heiten der Sprühtrocknung bzw. Sprühneutralisation von Ten¬ siden sei auf ROEMPP Chemielexikon, 9. Aufl., Thie e-Verlag, Stuttgart, 1992, S. 259/4260 verwiesen. Der bevorzugte Aus¬ gangsstoff stellt - wie schon zuvor ausgeführt - Talgalko¬ holsulfat in Form wäßriger Pasten mit einem Feststoffgehalt von 5 bis 65, vorzugsweise 50 bis 65 Gew.-%, oder sprühneu¬ tralisiertes, sprüh- bzw. heißdampfgetrocknetes Pulver dar.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.
Herstellung der leichtlöslichen ProdukteManufacture of easily soluble products
Die Herstellung der neuen festen Wasch-, Spül- und Reini¬ gungsmittel kann auf verschiedensten Wegen erfolgen.The new solid washing, rinsing and cleaning agents can be produced in a variety of ways.
Eine besonders einfache Ausgestaltung des Verfahrens besteht darin, das anionische Tensid in Pulverform vorzulegen und mit der erforderlichen Menge des verfestigten nichtionischen Tensids innig zu vermischen. Für diesen Vorgang sind Bauteile wie beispielsweise Schaufelmischer der Fa.Lödige oder insbe¬ sondere Sprühmischer der Fa.Schugi von Vorteil, bei denen man das Aniontensid in der Mischkammer vorlegt und das verfe¬ stigte nichtionische Tenside aufdüst. Ferner ist es möglich, die Trocknung der Aniontensidpasten und das Vermischen gleichzeitig in einem Wirbelschichttrockner durchzuführen. Es werden trockene, leichtlösliche Pulver erhalten, die - falls erforderlich - mit weiteren üblichen Waschmittelzusatzstoffen beaufschlagt und beispielsweise zu Waschmittel-Extrudaten verarbeitet werden können.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.
Eine weitere Möglichkeit besteht darin, die anionischen Ten¬ side einer sogenannten SKET-Granulierung zu unterwerfen. Hierunter ist eine Granulierung unter gleichzeitiger Trock¬ nung zu verstehen, die vorzugsweise batchweise oder kontinu¬ ierlich in der Wirbelschicht erfolgt. Dabei können die wä߬ rigen Pasten der anionischen Tenside und die verfestigten nichtionischen Tenside gleichzeitig oder nacheinander über eine oder mehrere Düsen in die Wirbelschicht eingebracht wer¬ den. Bevorzugt eingesetzte Wirbelschicht-Apparate besitzen Bodenplatten mit Abmessungen von 0,4 bis 5 m. Vorzugsweise wird die SKET-Granulierung bei Wirbelluftgeschwindigkeiten im Bereich von 1 bis 8 m/s durchgeführt. Der Austrag der Granu¬ late aus der Wirbelschicht erfolgt vorzugsweise über eine Größenklassierung der Granulate. Die Klassierung kann bei¬ spielsweise mittels einer Siebvorrichtung oder durch einen entgegengeführten Luftstrom (Sichterluft) erfolgen, der so reguliert wird, daß erst Teilchen ab einer bestimmten Teil¬ chengröße aus der Wirbelschicht entfernt und kleinere Teil¬ chen in der Wirbelschicht zurückgehalten werden. Üblicher¬ weise setzt sich die einströmende Luft aus der beheizten oder unbeheizten Sichterluft und der beheizten Bodenluft zusammen. Die Bodenlufttemperatur liegt dabei zwischen 80 und 400, vor¬ zugsweise 90 und 350°C. Vorteilhafterweise wird zu Beginn der SKET-Granulierung eine Startmasse, beispielsweise ein SKET- Granulat aus einem früheren Versuchsansatz, vorgelegt. In der Wirbelschicht verdampft das Wasser aus der Aniontensid-Paste, wobei angetrocknete bis getrocknete Keime entstehen, die mit weiteren Mengen Aniontensid und verfestigtem nichtionischem Tensid umhüllt, granuliert und wiederum gleichzeitig getrock¬ net werden.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 einer bevorzugten Ausführungsform der Erfindung werden die anionischen Tenside in Pulverform mit den verfestigten nichtionischen Tensiden vermischt und die Mischung in einer Schneckenpresse homogenisiert und verfestigt. Die Extrusion erfolgt über eine Lochscheibe, so daß Preßstränge entstehen, die nach bekannten Verfahren zu Extrudaten oder Nadeln ge¬ wünschter Form und Abmessung mechanisch zerkleinert werden können. Extrudate dieser Form zeigen eine besonders hohe Auf- lösegeschwindigkeit und ein sehr gutes Einspülverhalten in der Waschmaschine.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.
Unabhängig von der Anbietungsform als Pulver, Granulat oder Extrudat können die neuen festen Wasch-, Spül- und Reini¬ gungsmittel weitere übliche Hilfs- und Zusatzstoffe, bei¬ spielsweise Zeolithe, Phosphate, Phosphonate, Polycarboxy- late, Wasserglas, Soda und Borate enthalten, die ihnen vor, während oder nach der Verfestigung zugesetzt werden können.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.
Gewerbliche AnwendbarkeitIndustrial applicability
Die erfindungsgemäßen festen Wasch-, Spül- und Reinigungsmit¬ tel auf Basis anionischer und nichtionischer Tenside sowie polymerer Verfestigungsmitteln sind gegenüber dem Ausbluten der nichtionischen Tenside stabil und weisen ausgezeichnete Detergenseigenschaften auf. Ein weiterer Gegenstand der Erfindung betrifft daher die Ver¬ wendung von Mischungen enthaltendThe 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) anionische und nichtionische Tenside im Gewichtsverhält¬ nis 9 : 1 bis 1 : 9, vorzugsweise 1 : 1 bis 1 : 5 sowie b) die vorstehend beschriebenen ausgewählten polymeren Verfestigungsmittela) 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
als Rohstoffe zur Herstellung von festen Wasch-, Spül- und Reinigungsmitteln.as raw materials for the production of solid washing, rinsing and cleaning agents.
Die folgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf einzuschränken. The following examples are intended to explain the subject matter of the invention in more detail without restricting it.
BeispieleExamples
I. RezepturbeispieleI. Examples of recipes
Eine Universalwaschmittelrezeptur mit hohem Gehalt an nicht¬ ionischen Tensiden und ohne bzw. mit polymeren Verfesti¬ gungsmitteln einer Zusammensetzung gemäß Tab.l wurde über ei¬ ne Schneckenwalze extrudiert und über eine Lochscheibe (Durchmesser der Öffnungen : 0,9 mm) zu Strangpreßlingen ver¬ arbeitet, die kontinuierlich zu Extrudaten einer Korngröße von 0,9 mm zerkleinert wurden.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: Zusammensetzung der Waschmittelrezepturen Prozentangaben als Gew.-% Hilfsstoffe ad 100 %.Tab. 1: Composition of the detergent formulations, percentages as% by weight auxiliaries ad 100%.
Komponenten VI Bl B2 B3 B4 B5 B6Components VI Bl B2 B3 B4 B5 B6
% % % % % % %%%%%%%%
Talgalkoholsulfat 10 10 10 10 10 10 10Tallow alcohol sulfate 10 10 10 10 10 10 10
Kokosalkohol 3 EO 15 15 15 15 15 15 15Coconut alcohol 3 EO 15 15 15 15 15 15 15
PEG-12.000 0 1 2 3 5 0 0PEG-12,000 0 1 2 3 5 0 0
PEG-100.000 0 0 0 0 0 3 5PEG-100,000 0 0 0 0 0 3 5
Zeolith A 35 35 35 35 35 35 35Zeolite A 35 35 35 35 35 35 35
Natriumperborat 16 16 16 16 16 16 16Sodium perborate 16 16 16 16 16 16 16
Wasserglas 7 7 7 7 7 7 7Water glass 7 7 7 7 7 7 7
Die Rezepturen Bl bis B6 sind erfindungsgemäß; Rezeptur VI dient dem Vergleich. II. Anwendungstechnische UntersuchungenThe formulations B1 to B6 are according to the invention; Recipe VI is used for comparison. II. Application studies
Das Ausblutverhalten der Rezepturen wurde an unbedrucktem Karton der Stärke 0,4 mm bestimmt. Hierzu wurde der Karton waagerecht auf eine Rüttelunterlage montiert, jeweils 5 g der festen Rezepturen VI sowie Bl bis B6 aufgebracht und mit Hil¬ fe von Glasringen (Durchmesser 5 cm) fixiert. Durch die gleichmäßige Bewegung wurde ein Abrieb der Testmischungen auf der Kartonoberfläche bewirkt und die Fettung visuell nach t = 1, 5 und 24 h beurteilt. Die Ergebnisse sind in Tab.2 zusam¬ mengefaßt: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: AusblutverhaltenTab. 2: Bleeding behavior
Bsp. t. Fettung Rezeptur hEx. T. Bold formula h
VI Bl B2 B3 B4 B5 B6VI Bl B2 B3 B4 B5 B6
1 1 III II I 0 0 0 01 1 III II I 0 0 0 0
2 5 IV II I I 0 0 02 5 IV II I I 0 0 0
3 24 V III II II I I I3 24 V III II II I I I
Beurteilung: 0 = keine FettungAssessment: 0 = no greasing
1 = Fettspuren1 = traces of fat
II = leichte FettungII = slight greasing
III = deutliche FettungIII = significant greasing
IV = starke FettungIV = heavy oiling
V = sehr starke Fettung V = very strong greasing

Claims

Patentansprüche Claims
1. Feste Wasch-, Spül- und Reinigungsmittel, enthaltend Mischungen von1. Solid washing, rinsing and cleaning agents containing mixtures of
a) anionischen und nichtionischen Tensiden im Gewichts¬ verhältnis 9: 1 bis 1 : 9 sowie b) • 1 bis 50 Gew.-% - bezogen auf die nichtionischena) 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
Tenside - polymere Verfestigungsmittel ausgewählt aus der Gruppe, die gebildet wird vonSurfactants - polymeric strengthening agents selected from the group consisting of
bl) Polyethylenglycolethern mit einem durchchnitt¬ lichen Molekulargewicht von 12.000 bis 500.000, b2) Ester von Dicarbonsäuren mit einem durchschnitt¬ lichen Molekulargewicht von 400 bis 20.000, b3) Umesterungsprodukten von Dialkylcarbonat mit Polyethylenglycolethern mit einem durchschnitt¬ lichen Molekulargewicht von 400 bis 20.000 und b4) Oligo- bzw. Polysacchariden mit einem Kondensa¬ tionsgrad von 5 bis 1000.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.
2. Verfahren zur Herstellung von festen Wasch-, Spül- und Reinigungsmitteln, bei dem man Mischungen von anioni¬ schen und nichtionischen Tensiden im GewichtsVerhältnis 9 : 1 bis 1 : 9 mit 1 bis 50 Gew.-% - bezogen auf die nichtionischen Tenside - polymerer Verfestigungsmittel versetzt, die ausgewählt sind aus der Gruppe, die ge¬ bildet wird von2. 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) Polyethylenglycolethern mit einem durchchnittlichen Molekulargewicht von 12.000 bis 500.000, b2) Ester von Dicarbonsäuren mit einem durchschnittli¬ chen Molekulargewicht von 400 bis 20.000, b3) Umesterungsprodukten von Dialkylcarbonat mit Poly¬ ethylenglycolethern mit einem durchschnittlichen Molekulargewicht von 400 bis 20.000 und b4) Oligo- bzw. Polysacchariden mit einem Kondensa¬ tionsgrad von 5 bis 1000.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. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß man anionische Tenside einsetzt, die ausgewählt sind aus der Gruppe, die von Alkylbenzolsulfonaten, Alkansulfo- naten, Olefinsulfonaten, Alkylethersulfonaten, Glycerin- ethersulfonaten, oc-Methylestersulfonaten, Sulfofettsäu- ren, Fettalkoholsulfaten, Fettalkoholethersulfaten, Gly- cerinethersulfaten, HydroxymisehetherSulfaten, Monogly- cerid(ether)Sulfaten, Fettsäureamid(ether)sulfaten, Sul- fosuccinaten, Sulfosuccinamaten, Sulfotriglyceriden, Amidseifen, Ethercarbonsäuren, Isethionaten, Sarcosina¬ ten, Tauriden, Alkyloligoglucosidsulfaten und Alkyl- (ether)phosphaten gebildet wird.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. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß man als anionische Tenside Fettalkoholsulfate der Formel (I) einsetzt,4. The method according to claim 3, characterized in that fatty alcohol sulfates of the formula (I) are used as anionic surfactants,
RiosOsX (I)RiosOsX (I)
in der R für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 12 bis 22 Kohlenstoffatomen und X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht. 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. Verfahren nach den Ansprüchen 3 und 4, dadurch gekenn¬ zeichnet, daß man Fettalkoholsulfate der Formel (I) einsetzt, in der R1 für einen Alkylrest mit 16 bis 18 Kohlenstoffatomen und X für Natrium steht.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. Verfahren nach den Ansprüchen 2 bis 5, dadurch gekenn¬ zeichnet, daß man als nichtionische Tenside Fettalkohol- polyglycolether der Formel (II) einsetzt,6. Process according to Claims 2 to 5, characterized in that fatty alcohol polyglycol ethers of the formula (II) are used as nonionic surfactants,
CH3 CH 3
I R20-(CH2CHO)n(CH2CH2θ)nιH (II)IR 2 0- (CH2CHO) n (CH2CH2θ) nι H (II)
in der R2 für einen linearen oder verzweigten aliphati- schen Kohlenwasserstoffrest mit 6 bis 18 Kohlenstoffato¬ men und 0, 1, 2 oder 3 Doppelbindungen, n für 0 oder Zahlen von 1 bis 3 und m für Zahlen von 1 bis 10 steht.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. Verfahren nach den Ansprüchen 2 bis 5, dadurch gekenn¬ zeichnet, daß man als nichtionische Tenside Alkyloligo¬ glykoside der Formel (III) einsetzt,7. Process according to claims 2 to 5, characterized in that alkyloligo glycosides of the formula (III) are used as nonionic surfactants,
R3-0-[G]p (III)R 3 -0- [G] p (III)
in der R3 für einen Alkylrest mit 6 bis 22 Kohlenstoff¬ atomen, G für einen Zuckerrest mit 5 oder 6 Kohlen¬ stoffatomen und p für eine Zahl von 1 bis 10 steht.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. Verfahren nach den Ansprüchen 2 bis 7, dadurch gekenn¬ zeichnet, daß man als polymere Verfestigungsmittel Poly- ethylenglycolether mit einem durchschnittlichen Moleku¬ largewicht von 12.000 bis 500.000 einsetzt.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. Verfahren nach den Ansprüchen 2 bis 7, dadurch gekenn¬ zeichnet, daß man als polymere Verfestigungsmittel Ester von Dicarbonsäuren der Formel (IV),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)HOOC- (CH2) yCOOH (IV)
in der y für 0 oder Zahlen von 1 bis 12 steht, mit Po¬ lyethylenglycolethern, die ein durchschnittliches Mo¬ lekulargewicht von 400 bis 20.000 aufweisen, einsetzt.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. Verfahren nach den Ansprüchen 2 bis 7, dadurch gekenn¬ zeichnet, daß man als polymere Verfestigungsmittel Umesterungsprodukte von Dialkylcarbonat mit Polyethy¬ lenglycolethern, die ein durchschnittliches Molekular¬ gewicht von 400 bis 20.000 aufweisen, einsetzt.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. Verfahren nach den Ansprüchen 2 bis 7, dadurch gekenn¬ zeichnet, daß man als polymere Verfestigungsmittel Oli¬ go- bzw. Polysaccharide mit einem Kondensationsgrad von 5 bis 1000 einsetzt.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. Verwendung von Mischungen erhältlich nach dem Verfahren nach den Ansprüchen 1 bis 11 als Rohstoffe zur Herstel¬ lung von festen Wasch-, Spül- und Reinigungsmitteln. 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.
EP94906151A 1993-02-04 1994-01-26 Process for the manufacture of solid, anhydrous washing agents Expired - Lifetime EP0682691B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4303176 1993-02-04
DE4303176A DE4303176C2 (en) 1993-02-04 1993-02-04 Solid washing, rinsing and cleaning agents
PCT/EP1994/000208 WO1994018293A1 (en) 1993-02-04 1994-01-26 Solid washing, rinsing and cleaning agents

Publications (3)

Publication Number Publication Date
EP0682691A1 true EP0682691A1 (en) 1995-11-22
EP0682691B1 EP0682691B1 (en) 1997-04-09
EP0682691B2 EP0682691B2 (en) 2004-01-14

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EP (1) EP0682691B2 (en)
JP (1) JPH08506367A (en)
KR (1) KR960700333A (en)
DE (2) DE4303176C2 (en)
ES (1) ES2100697T3 (en)
WO (1) WO1994018293A1 (en)

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Publication number Priority date Publication date Assignee Title
USH1514H (en) * 1994-06-01 1996-01-02 The Procter & Gamble Company Detergent compositions with oleoyl sarcosinate and polymeric dispersing agent
TW326472B (en) * 1994-08-12 1998-02-11 Kao Corp Method for producing nonionic detergent granules
US5866530A (en) * 1995-11-25 1999-02-02 Henkel Kommanditgesellschaft Auf Aktien Non-aqueous liquid mixtures of alkyl polyglycoside and alkyl polyalkylene glycol ether useful in various detergent applications
GB2314563B (en) * 1996-06-28 2000-03-29 Laporte Esd Ltd Surfactant compositions
DE19635555C2 (en) 1996-09-02 2000-06-08 Cognis Deutschland Gmbh Aqueous hand dishwashing liquid
DE19719606C2 (en) * 1997-05-09 1999-02-18 Henkel Kgaa Solid preparations
DE19858886C2 (en) 1998-12-19 2002-10-31 Cognis Deutschland Gmbh surfactant granules
DE19911040A1 (en) 1999-03-12 2000-09-21 Cognis Deutschland Gmbh Surfactant granules

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LU60943A1 (en) * 1970-05-20 1972-02-23
US3803285A (en) * 1971-01-20 1974-04-09 Cpc International Inc Extrusion of detergent compositions
PH14451A (en) * 1972-10-31 1981-07-23 Procter & Gamble Detergent compositions
JPS5241612A (en) * 1975-09-30 1977-03-31 Kao Corp Granular or powdered detergent compositions
GB8302980D0 (en) † 1983-02-03 1983-03-09 Procter & Gamble Ltd Laundry additive compositions
DE3424317A1 (en) * 1984-07-02 1986-01-23 Henkel KGaA, 4000 Düsseldorf Means for toilet cleaning
CA1293421C (en) * 1985-07-09 1991-12-24 Mark Edward Cushman Spray-dried granular detergent compositions containing nonionicsurfactant, polyethylene glycol, and polyacrylate
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Also Published As

Publication number Publication date
DE4303176C2 (en) 1997-07-31
WO1994018293A1 (en) 1994-08-18
JPH08506367A (en) 1996-07-09
EP0682691B1 (en) 1997-04-09
EP0682691B2 (en) 2004-01-14
KR960700333A (en) 1996-01-19
DE59402383D1 (en) 1997-05-15
DE4303176A1 (en) 1994-08-11
ES2100697T3 (en) 1997-06-16

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