EP0682691A1 - Solid washing, rinsing and cleaning agents. - Google Patents
Solid washing, rinsing and cleaning agents.Info
- 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
Links
Classifications
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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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 |
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EP0682691A1 true EP0682691A1 (en) | 1995-11-22 |
EP0682691B1 EP0682691B1 (en) | 1997-04-09 |
EP0682691B2 EP0682691B2 (en) | 2004-01-14 |
Family
ID=6479622
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94906151A Expired - Lifetime EP0682691B2 (en) | 1993-02-04 | 1994-01-26 | Process for the manufacture of solid, anhydrous washing agents |
Country Status (6)
Country | Link |
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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) |
Families Citing this family (8)
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 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CA2017922C (en) † | 1989-06-09 | 1995-07-11 | Frank Joseph Mueller | Formation of discrete, high active detergent granules using a continuous neutralization system |
DE4124701A1 (en) * | 1991-07-25 | 1993-01-28 | Henkel Kgaa | METHOD FOR THE PRODUCTION OF SOLID DETERGENT AND CLEANING AGENT WITH HIGH SHOCK WEIGHT AND IMPROVED SOLUTION SPEED |
-
1993
- 1993-02-04 DE DE4303176A patent/DE4303176C2/en not_active Expired - Fee Related
-
1994
- 1994-01-26 ES ES94906151T patent/ES2100697T3/en not_active Expired - Lifetime
- 1994-01-26 DE DE59402383T patent/DE59402383D1/en not_active Expired - Fee Related
- 1994-01-26 KR KR1019950703105A patent/KR960700333A/en not_active Application Discontinuation
- 1994-01-26 EP EP94906151A patent/EP0682691B2/en not_active Expired - Lifetime
- 1994-01-26 JP JP6517588A patent/JPH08506367A/en active Pending
- 1994-01-26 WO PCT/EP1994/000208 patent/WO1994018293A1/en active IP Right Grant
Non-Patent Citations (1)
Title |
---|
See references of WO9418293A1 * |
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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