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
  • 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
• • 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
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0026—Low foaming or foam regulating compositions
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
  • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents

Definitions

• two cleaning cycles usually separated by intermediate rinsing cycles with pure water are used.
• different products are utilized.
• alkaline-reacting agents are employed for the loosening and emulsifying of the food residues.
• special clear-rinsing agents are employed. The latter should possess a good wetting power and be able to reduce the surface tension of the after-rinsing water to such a degree that it drains in a film-like manner from the dishes and leaves no visible deposits, such as lime spots or other impurities.
• these clear-rinsing agents have to be as low-foaming as possible.
• the customary anionic wetting agents such as highermolecular-weight alkyl sulfates or alkyl sulfonates or aralkyl sulfonates foam too much.
• nonionic tensides based on ethylene-oxide adducts to fatty alcohols, alkylphenols, or polypropylene glycols of higher molecular weights are employed.
• These products are not sufficiently lowfoaming in the concentration range, required for a sufficient wetting effect, and disturbances in the rinsing process may occur, because of a too strong foam formation in the dishwasher.
• Is is furthermore desirable to employ in this process such wetting agents that possess a good biological degradability and low toxicity toward the organisms living in water and thus do not exhibit an undesirable burden on the disposal of the sewage.
• An object of the invention is the development of lowfoaming and biologically'degradable clear-rinsing agents for mechanical dishwashing with a good wetting and draining effect toward hard surfaces.
• Another object of the invention is the development in the process for the mechanical washing of dishes which comprises subjecting dirty dishes to the action of a washing solution, subjecting the washed dishes to at least one clear-rinsing solution and recovering said washed dishes, the improvement consisting of utilizing an aqueous solution containing from 0.05 to 1.0 gm per liter of an adduct of from 3 to 30 mols of ethylene oxide to an alkanediol having a linear alkane chain with from 10 to 20 carbon atoms and vicinal, non-terminal hydroxyls, as said at least one clear-rinsing solution.
• a further object of the present invention is the development of low-foaming rinsing compositions adapted for dishwashers consisting essentially of (A) an adduct of from 5 to 20 mols of ethylene oxide to an alkanediol having a linear alkane chain with from to carbon atoms and vicinal, non-terminal hydroxyls, and (B) an alkoxylated foam suppressing compound selected from the group consisting of (l an alcohol having from 10 to 20 carbon atoms selected from the group consisting of alkanols and alkenols adducted with l to 3 mols of ethylene oxide, (2) alkylphenols having 6 to 12 carbon atoms in the alkyl adducted with l to 6 mols of ethylene oxide, (3) an alcohol selected from the group consisting of alkanols and alkanediols having from l0 to 20 carbon atoms, and alkylphenols having from 6 to carbon atoms in the alkyl,
• the objects of the invention have been achieved by the development of clear-rinsing agents for automatic dishwashing based on nonionic, low-foaming tensides that combine the desirable properties to a high degree.
• the clear-rinsing agents are characterized by a content of adducts of 3 to 30 mols of ethylene oxide to alkanediols with linear alkane chains of from l0 to 20 carbon atoms, whose hydroxyl groups are non-terminal and vicinal. By non-terminal, such diols are designated that do not possess any hydroxyl group on a terminal carbon atom.
• non-terminal, a, ,B-diols are utilized as the starting materials.
• Such diols are prepared in a known way from linear aliphatic olefins with non-terminal double bonds, for instance by epoxidation with the aid of peracids or hydrogen peroxide and lower carboxylic acids forming peracids and subsequent saponification of the epoxides.
• the starting materials are preferably such olefins whose double bond is about in the middle of the carbon chain.
• the products obtained normally are mixtures of different vicinal diols, whose diol groups are distributed statistically around a median value with the main amount in the center of the carbon chain.
• the reaction of the ethylene oxide with the vicinal, non-terminal diols is carried out in a known manner in the presence of acidic or basic catalysts, preferably with the use of elevated temperatures and pressures.
• a two-step process is utilized. In the first step only 1 mol of ethylene oxide is reacted with 1 mol of the diol mixture.
• the reaction leads sub stantially to the formation of monoethoxylated diols.
• the reaction mixture can be purified by distilling off the unreacted diol.
• the monoethoxylated diol is further reacted by addition of the desired amount of ethylene oxide.
• each time one polyalkylene glycol chain per diol group is formed as substantially only the primary hydroxyl groups, deriving from the first reaction step, react further with ethylene oxide with sufficient speed.
• the other secondary hydroxyl groups of the vicinial,non-terminal diol remain largely unchanged.
• Products suitable in the sense of the invention, are particularly the adducts of 5 to 20 mols of ethylene oxide to the named vicinal, non-terminal alkanediols having 10 to 20 carbon atoms.
• diols of an average alkane chain length of l4 to 16 carbons are preferred.
• the adducts from to 7 mols of ethylene oxide are preferred, when utilized without other tenside agents.
• Exceptionally low-foaming products can, however, also be built with the higher ethoxylated diols by combining them with foam-suppressing substances from the group of the nonionic alkylene oxide adducts to higher alkanols, alkanediols and alkylphenols.
• foam-suppressing substances from the group of the nonionic alkylene oxide adducts to higher alkanols, alkanediols and alkylphenols.
• the acetals from 2 mols of an alkoxylation product and 1 mol of formaldehyde are suitable as foam suppressor.
• the quantitative ratio by weight of the ethoxylated diols to foam suppressors amount to about 120.2 to 1:4, preferably l:O.5 to 1:2.
• these low-foaming clear-rinsing agents are low-foaming rinsing compositions adapted for dishwashers consisting essentially of (A) an adduct of from 5 to 20 mols of ethylene oxide to an alkanediol having a linear alkane chain with from to carbon atoms and vicinal, non-terminal hydroxyls, and (B) an alkoxylated foam suppressing compound selected from the group consisting of(1) an alcohol having from 10 to 20 carbon atoms selected from the group consisting of a1 kanols and alkenols adducted with l to 3 mols of ethylene oxide, (2) alkylphenols having 6 to 12 carbon atoms in the alkyl adducted with l to 6 mols of ethylene oxide, (3) an alcohol selected from the group consisting of alkanols and alkanediols having from 10 to 20 carbon atoms, and alkylphenols having from 6 to 12 carbon atoms
• Suitable foam suppressing compounds are, for example, ethylene oxide adducts having a low degree of ethoxylation, such as the adducts of l to 3 mols of ethylene oxide to higher fatty alcohols of a C to C chain length or to higher secondary alkanols of a C to C chain length, also the adducts of from 1 to 6 mols of ethylene oxide to alkylphenols of a C to C chain length in the alkyl.
• adducts of from 1 to 3 mols of ethylene oxide to fatty alcohol mixtures of a C to C or C to C chain length, or to secondary alkanols of the average chain length of C to C as well as the adducts of 1.5 to 3 mols of ethylene oxide to nonylphenol have been proven as particularly effective.
• alkylene oxide adducts in which, in the first step, 1 to 20 mols of ethylene oxide are added and in the second step 1 to 20 mols of propylene oxide and/or butylene oxide are added.
• the content of propylene oxide and/or butylene oxide should amount to at least 30 mol percent, preferably at least 50 mol percent, based on the total amount of the alkylene oxides adducted.
• Examples for such compounds are the adducts of 3 mols of ethylene oxide and 3 mols of propylene oxide or of 5 mols of ethylene oxide and 13 mols of propylene oxide to coconut fatty alcohol mixtures of a C to C chain length, the adducts of 7 mols of ethylene oxide and 5 mols of propylene oxide to a mixture of secondary aliphatic alcohols of a C to C chain length, the adduct of 5 mols of ethylene oxide and 3 mols of butylene oxide to coconut fatty alcohol mixture of a C to C chain length, the adduct of9 mols of ethylene oxide and 10 mols of propylene oxide to nonylphenol, as well as the adducts of 2 to 7 mols of ethylene oxide and 1 to 10 mols of propylene oxide, for instance 5 mols of ethylene oxide and 3 mols of propylene oxide or 5 mols of ethylene oxide and 5 mols of propylene oxide or
• the formaldehyde acetals of alkylene oxide adducts have a good foam-suppressing effect. They are obtained in a known manner from 2 mols of an alkylene oxide adduct and 1 mol of formaldehyde. Preferably, 2 mols of ethylene oxide adducts having 10 to 30 ethylene oxide units adducted to the above alcohols are utilized to make acetals with 1 mol of formaldehyde. Particularly, the acetal from formaldehyde and the adduct of 20 mols of ethylene oxide to alkylphenol has been found satisfactory. This acetal can also be used in admixture for the support of the foam-inhibiting effect of the above named alkylene oxide adducts, if extremely low-foaming products are desired.
• the above-named products or product combinations are sufficiently biologically degradable, if the polyglycol chain length does not surpass about 15 alkylene oxide units.
• the agents are very lowfoaming or practically foamless and show, over large ranges of concentration, a good draining and cleardrying effect on the various conventional kitchenware, such as porcelain plates, cutlery and particularly glasses, which are considered particularly difficult in this respect. They are, therefore, prominently suitable for the clear-rinsing of dishes after a preceding cleaning cycle, for instance with alkaline cleaners.
• concentrations of about 0.1 gm/l a drop-free, film-like draining of the clear-rinsing liquor from the dishes is attained. A disturbing foam formation does not occur at these concentrations.
• the claimed products or combinations are applied in the clear-rinsing bath in concentrations from about 0.05 to 1.0 gm/l, preferably 0.1 to 0.6 gm/l.
• the application concentration depends to a certain degree upon the kind of surface to be cleaned. Particularly, synthetic resin surfaces require a somewhat higher amount of clear-rinsing agents.
• the application is effected preferably in the form of aqueous or dilute alcoholic concentrates with contents from 10 to 60 percent by weight of the active components.
• alcoholic solvent components preferably water-miscible lower alcohols such as ethanol, propanol and isopropanol, ethylene glycol, monoethyl ether of ethylene glycol and the like, are utilized.
• the adducts themselves are liquid, they can also be applied without solvents.
• the concentrates are appropriately added with the aid of automatic dosing devices, as are already customary for such purposes, or manually to the clear-rinsing liquor.
• the invention also involves, in the process for the mechanical washing of dishes which comprises subjecting dirty dishes to the action ofa washing solution, subjecting the washed dishes to at least one clear-rinsing solution and recovering said washed dishes, the improvement consisting of utilizing an aqueous solution containing from 0.05 to 1.0 gm per liter of an adduct of from 3 to 30 mols of ethylene oxide to an alkanediol having a linear alkane chain with from to 20 carbon atoms and vicinal, non-terminal hydroxyls, as said at least one clear rinsing solution.
• lower organic carboxylic acids with 2 to 6 carbon atoms may be added to the concentrates or the clear-rinsing liquor for the avoidance of lime incrustations and lime hazes on the rinsed dishes.
• Acids are preferred that are physiologically inocuous and that possess sequestering properties toward the hardness causing salts, such as tartaric acid, lactic acid, glycolic acid and particularly citric acid.
• the optional addition of acid in'the clear-rinsing concentrate amounts to about 10 to 40 percent by weight.
• the compounds or mixtures, listed in Table I were stamped 20 times in a measuring cylinder with a perforated disk and subsequently the foam height in centimeters after 10, 30 and 60 seconds was recorded. Foaming heights above 20 cm are marked by x.
• the city water used had a dl-l (degrees German hardness) of 16. The residue of the concentrates, missing to 100 percent, is always water.
• a very effective clear-rinsing agent for home dishwashing machine has the following composition:
• a clear-rinsing agent for automatic dishwashing has the following composition:
• a similarly effective product that is, however, used in hard water for the prevention oflime haze, may additionally also contain 20 percent of citric acid.
• a clear-rinsing agent that is suitable both for home automatic dish washers and for commercial dishwashing machines, has the following composition:
• citric acid For use in hard water 20 percent of citric acid may be added to this product.
• a clear-rinsing agent for automatic dishwashing has the following composition:
• a clear-rinsing agent also quite effective in hard water, has the following composition:
• Low-foaming rinsing aqueous concentrates adapted for dishwashers consisting essentially of from 10 to 60 percent by weight of a composition consisting essentially of (A) an adduct of from 5 to 20 mols of ethylene oxide to an alkanediol having a linear alkane chain with from 10 to 20 carbon atoms and vicinal, non-terminal hydroxyls, and (B) an alkoxylated foam suppressing compound selected from the group consisting of (1) an alcohol having from 10 to 20 carbon atoms selected from the group consisting of alkanols and alkenols adducted with l to 3 mols of ethylene oxide, (2) alkylphenols having 6 to 12 carbon atoms in the alkyl adducted with l to 6 mols of ethylene oxide, (3) an alcohol selected from the group consisting of (i) alkanols having from 10 to 20 carbon atoms, (ii) alkanediols having from 10 to 20 carbon
• aqueous concentrates of claim 1 wherein said component (B) is an alcohol having from to 20 carbon atoms selected from the group consisting of alkanols and alkenols adducted with l to 3 mols of ethylene oxide.
• aqueous concentrates of claim 1 wherein said component (B) is an alkylphenol having 6 to 12 carbon atoms in the alkyl adducted with l to 6 mols of ethylene oxide.
• said adduct is the adduct of from 3 to 7 mols of ethylene oxide to an alkanediol having an average of from 14 to 16 carbon atoms in its linear alkane chain.
• said adduct is a mixture of adducts consisting of (A) an adduct of from 5 to 20 mols of ethylene oxide to an alkanediol having a linear alkane chain with from 10 to 20 carbon atoms and vicinal, non-terminal hydroxyls, and (B) an alkoxylated foam suppressing compound selected from the group consisting of( l an alcohol having from 10 to 20 carbon atoms selected from the group consisting of alkanols and alkenols adducted with l to 3 mols of ethylene oxide, (2) alkylphenols having 6 to 12 carbon atoms in the alkyl adducted with l to 6 mols of ethylene oxide, (3) an alcohol selected from the group consisting of (i) alkanols having from 10 to 20 carbon atoms, (ii) alkanediols having from 10 to 20 carbon atoms, and (iii) alkylphenols having from

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Citations (3)

• 1970
  • 1970-12-18 DE DE19702062464 patent/DE2062464A1/de active Pending
• 1971
  • 1971-12-07 US US00205723A patent/US3779934A/en not_active Expired - Lifetime
  • 1971-12-15 FR FR7145123A patent/FR2118663A5/fr not_active Expired
  • 1971-12-15 AT AT1076171A patent/AT329722B/de not_active IP Right Cessation
  • 1971-12-17 IT IT32533/71A patent/IT944061B/it active

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