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
  • C11D3/36—Organic compounds containing phosphorus
  • C11D3/364—Organic compounds containing phosphorus containing nitrogen
• • 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
  • C11D1/38—Cationic compounds
  • C11D1/42—Amino alcohols or amino ethers
  • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/044—Hydroxides or bases
• • 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
  • C11D3/36—Organic compounds containing phosphorus
  • C11D3/361—Phosphonates, phosphinates or phosphonites
• • C11D2111/14—

Definitions

• the active concentrates in is periodically replenished comprising periodically reuant-t-es of 1 to 40 ht r t I f r b1 10 t 35 plenishing said washing bath in order to maintain a level q l 1 lg p6 Gen p e e a y o of from 0.02% to 0.4% of a stable liquid additive solui Percent tion comprisin fro t 407 b f Beside these wettmg agents or detergents and/or foa-m g m 0 o 0 y o a de ressants the active concentrates contain water-soluionic detergent, from 5% to 30% by weight of an organic h b] f 1 acid selected from the group of hydroxy and amino organic ac!
• alkyl-Ll-diphosphonic acids ethylenediaminotetra-(meth- I f th th Its b d Thi ylenephosphonic acid) and aminotri- (methylenephosphonn mu 0 ese elr acl e use s ic acid) an aliphatic alcohol and a mineral acid if ded-enotes
• Such salts which reaict acldlc m aqueous Solu- Sired i the balance Water tion and preferably those WhlCh have a pH of less than 3.5 in a 1% aqueous solution.
• organic phosphonic acids which form complexes with the hardness-formers in water and THE PRIOR ART have at least two phosphorus atoms in their molecules
• alkaline materials are ylenephosphonic acids, particularly aminotri-(methyleneknown. These alkaline substances frequently contain, phosphonic acid) and ethylenediamino-tetra-(methyleneacid from caustic alkalies, soda, condensed phosphates phosphonic acid).
• the active concentrates according to the invention conand, as required, foam depressants (antifoams) and distain the water-soluble organic acids or their salts, respec-. infectants.
• foam depressants antifoams
• nonionic wetting agents or detertively which are capable of forming complexes with the gents are used which exhibit pronounced antifoaming hardness formers found in water, in concentrations of 1 action, and, for binding of hardness-formers present in to weight percent, and preferably 5 to 30 weight perwater and for the prevention of scale or mineral forma- 40 cent.
• mixtures of the acids named tion, polyphosphates These products usually are sold in the concentrations as given.
• the active concentrates additionally may contain solucorporat'ed in the cleansing bath in batches, whereby the tion promoters, especially lower aliphatic alcohols having bath concentration of the cleaning agent usually lies be- 1 to 5 carbon atoms.
• the quantity of such promoters may tween 0.2 and 2 percent, depending upon the intended use be varied within a wide range and preferably is between 5 and degree of soilage. and 30 percent by weight.
• liquid alkaline cleansing agent concentrates of such a solution promoter is not required for the produchave also been employed. However, upon prolonged stortion of homogeneous solutions.
• the active concentrate in age of these alkaline concentrates, losses of polymeric addition, may contain mineral acids, e.g., phosphoric or phosphates occur due to hydrolysis. Moreover, nonionic Sulfuric acid, in cflllcentl'afions 0f Weight Percent-I wetting agents or detergents and antifoams and also poly- The remainder of the active concentrates always is water. phosphates cannot be incorporated in these concentrates.
• the cleansing baths containing the active .,,concentrate in sufiicient quantities. are completed by the addition of an agent ccintaining an It now has been found that these drawbacks are avertalkali which is present in an excess. The term excess ed by the instant invention.
• the CO C Of s inve tion is to denote a quantity of cleansing of rigid materials, especially glass bottles nd alkali-containing agents sufficient to neutralize not only metals, uses alkaline cleansers which are characterized the active concentrate but to impart to the mixture of the by a complement of a liquid, acid, active concentrate two components a pH above 11, and preferably above 12. containing a nonionic detergent and/or foam depressant, Opportunely the alkaline agent also is employed in the and also water-soluble organic acids which are capable 0 form of a concentrate of an aqueous component of prefof forming complexes with the hardness-causing ingredierably less than percent.
• alkaline agent a concentrated agent containing alkali, the latter in an excess.
• alkali solution e.g., sodiumor potassium hydroxide solu- Preferred nonionic wetting and antifoaming agents are tion.
• alkali solution e.g., sodiumor potassium hydroxide solu- Preferred nonionic wetting and antifoaming agents are tion.
• alkali solution e.g., sodiumor potassium hydroxide solu- Preferred nonionic wetting and antifoaming agents are tion.
• nonionic 5 vention e.g., sodiumor potassium hydroxide solu- Preferred nonionic wetting and antifoaming agents are tion.
• alkali solution e.g., sodiumor potassium hydroxide solu- Preferred nonionic wetting and antifoaming agents are tion.
• alkali solution e.g., sodiumor potassium hydro
• a portion of the complex formers may Advantagcously, addition products of ethylene oxide on be added to the alkaline agent.
• it is polypropyleneglycol or on condensation products of pro- 7 preferred to incorporate the complex formers in the active pylene oxide and ethylene diamine are used.
• nonionic wetting agents are addition products of "ice propylene oxide on polyalcohols, especially carbohydrates and polyglycerols, and particularly those having 2 to 10 glycerol groups per molecule; or else, addition prod; ucts of propylene oxide on short-chain alkanolamines, such as mono-, diand triethanolamine, or on polyamines concentrate because this enables, aside from other advantages, the use of two highly concentrated solutions.
• the amounts of active concentrates to be put in the baths depend upon the water hardness and the material to be cleaned. Generally, the concentration of the active concentrates in the cleansing bath in 0.02 to 0.4 weight percent. When phosphonic acids having at least 2 phosphorus atoms in their molecules are present in the concentrate, it is added in such an amount that the quantity of these phosphonic acids in the entire bath is 100-300 mg./l.
• the amount of alkaline agent simultaneously incorporated in the bath generally is 0.5 to 3.0 weight percent, preferably 1-2%, calculated on the total bath concentration.
• the agents described are employed at the customary cleansing temperatures. In automatic bottle washing machines, these temperatures are approximately 60 to 80 C. When cleansing other n'gid materials, such as metals, the temperatures generally also are above 50 C.
• the washing process according to the invention has the advantage that the active concentrate and the alkaline agent can be metered into the bath continuously.
• the active concentrate is completely stable even upon prolonged storage and insures good cleaning without foam formation and reliable prevention of scale formation in the washing devices.
• Example 1 Weight parts Hydroxyethanediphosphonic acid Nonionic detergent (condensate of ethylene oxide with a reaction product of ethylene diamine and propylene oxide) 20 Water 60 Ethylenediaminotetra-(methylene phosphonic acid) 20 Nonionic detergent (same as in (a)) 20 Water 60
• the results obtained, i.e., the layers formed on the sheet metal, are compiled in Table 1.
• Example 2 Beer bottles were cleaned in a commercial bottle washing machine having 2 solution zones and an hourly throughput of 16,000 bottles.
• cleansing solution a 1% aqueous NaOH solution was used in each zone which had been produced by dilution of 50% NaOH.
• an active concentrate consisting of 25% hydroxyethanediphosphonic acid, 35% nonionic detergent (condensation product of ethylene oxide with polypropyleneglycol), 10% ethanol, and the remainder water.
• the water used for cleansing had a temporary hardness of approximately 36.
• the cleansing solution was applied at a temperature of 70 C. and was kept at the original strength by means of addition of 50% NaOH and active concentrate, as required.
• Example 3 The water available had a temporary hardness of 25 The temperature of the cleansing solution was 70-75 C. The mineral water bottles emerged from the process well cleaned, and undisturbed refilling of the bottles was observed.
• Example 4 Milk bottles were cleaned in a commercial bottle washing machine having two solution zones and a throughput of 12,000 units per hour.
• the cleansing solution for each zone was a 1.2 weight percent potassium hydroxide solution.
• 0.15 weight percent of an active concentrate were added having the following composition:
• Nonionic detergent as in Example 1 (a) 10 Water
• the cleansing solution was made up to its original strength, as required, by addition of KOH and active concentrate.
• the water used had a temporary hardness of 8, the temperature of the cleansing solution was 65 C.
• addition products of ethylene oxide on polypropylene addition products of propylene oxide on carbohydrates or on polyglycerols having 2 to 10 glycerol groups per molecule; addition products of propylene oxide on short-chain alkanolamines, e.g., mono-, diand triethanolamine; addition products of propylene oxide on polyamines produced by condensation of ethyleneimine with ammonia or ethylenediamine; addition products of ethylene oxide on fatty alcohols, preferably C to C alcohols; or addition products of ethylene oxide and propylene oxide on alkylphenols having an alkyl of 8-12 carbon atoms.
• Example 5 Soft drink bottles were cleaned in a commercial bottle washing machine equipped with 3 dip-washing zones. For the several zones, a 2% aqueous NaOH was used.
• an active concentrate consisting of 20% by weight aminoethanediphosphonic acid, 30% nonionic detergent (a condensation product of ethylene oxide with polypropyleneglycol), ethanol and the balance water.
• the original strength of the baths was kept up by the addition of NaOH and active concentrate, as required.
• the water employed had a temporary hardness of 16, and the cleansing solution was at a temperature of 80 C. The bottles were well cleaned after passing the machine, no foam was observed and no scale formation in the warm water zone, even after prolonged activity.
• Example 6 The baths, as required, were replenished by addition of NaOH and active concentrate.
• the bath temperature was approximately 70 C.
• the wash water had a temporary hardness of approximately 17.
• the cleansing action was excellent, and even after prolonged use of the solution, no foaming nor scale formation could be observed.
• Example 7 Wine bottles were cleaned in a small automatic washer having an hourly throughput of 4,000 bottles at a temperature of 70 C.
• the cleansing solution was a 1.5% NaOH to which 0.15 percent of an active concentrate had been added consisting of the following:
• Nonionic detergent (addition product of 27.5 mols propylene oxide on triethanolamine) 20 Water 60 The water employed had a temporary hardness of 12. The solution was brought up to strength, as required, by addition of 50% NaOH and active concentrate.
• the cleansing effect was excellent even in instances of strong soilage by residual red wine. No scale formation occurred in the warm water zone, and no foaming took place in the solution zone, during the duration of the test which lasted several days.
• Example 8 Dirty motor parts were cleaned in a dual chamber spray washing device with a 1.5% aqueous NaOH solution at 70 C. To the solution, 0.1 percent of an active concentrate were added having the following composition:
• Nonionic detergent as in Example 1 (a) Addition product of 9 mols ethylene oxide and 10 mols propylene on nonylphenol 1 Water 44 The water used had a temporary hardness of 20. The motor parts could be sprayed clean with this solution.
• Nonionic detergent as in Example 1 20 Addition product of 9 mols ethylene oxide and 10 mols propylene oxide on nonylphenol 1 Isopropanol 10 Water 49
• Example 10 Soft drink bottles were cleaned in a commercial bottle washing machine having three dip zones. For the several dipping baths, a 1.2% aqueous NaOH was used to which 0.15% of an active concentrate were added having the following composition:
• Nonionic detergent condensation product of ethylene oxide with propyleneglycol 20
• Ethanol 15 Water 45
• the solution was used at a temperature of 70-80 C. and replenished by addition of active concentrate and NaOH when required.
• the water had a temporary hardness of 6. Cleansing action was very good, no foam developed, and so scale formation took place even upon prolonged use.
• Example 11 Percent weight Monosodium salt of ethylenediaminotetra-(methylenephosphonic acid) 10
• Nonionic detergent as in Example 1 10
• Water Example 11 Beer bottles were cleaned in a commercial bottle washing machine having two cleansing zones. In both these zones, a cleansing solution was employed which contained 1% NaOH and to which had been added 0.1% of an active concentrate of the following composition:
• Nonionic detergent (addition product of 5 mols propylene oxide per N-atom on tetraethylenepentamine) Water The water used had a temporary hardness of 15 The cleansing solutions were applied at a temperature of 60- 65 C. and replenished as required by addition of NaOH and active concentrate. Cleansing action and removal of the labels were faultless. Calcification in the warm water zone could not be observed, and no foam developed during the time of application.
• Example 12 Milk bottles were cleansed in a commercial bottle washing machine having two wash zones and an hourly capacity of 10,000 units.
• the solutions for both zones had 2.5% NaOH and 0.12% of an active concentrate of the following composition:
• Nonionic detergent additive of 9 mols ethylene oxide and 10 mols propylene oxide on nonylphenol
• Isopropanol 15 Phosphoric acid (75%)
• Water 25 Aminotri-(methylenephosphonic acid)
• Nonionic detergent additive of 2 ethylene oxide) groups on oleyl alcohol
• Isopropanol 25 Sulfuric acid (96%) 15 Water 20 I claim as my invention:

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Citations (8)

• 0
  • CA CA777770A patent/CA777770A/en not_active Expired
• 1964
  • 1964-12-24 DE DE19641467605 patent/DE1467605A1/de active Pending
• 1965
  • 1965-11-26 NL NL6515419A patent/NL6515419A/xx unknown
  • 1965-12-01 US US510973A patent/US3527608A/en not_active Expired - Lifetime
  • 1965-12-07 GB GB51735/65A patent/GB1056940A/en not_active Expired
  • 1965-12-21 BE BE674107D patent/BE674107A/xx unknown
  • 1965-12-23 AT AT1161165A patent/AT268482B/de active
  • 1965-12-23 CH CH1775865A patent/CH473616A/de not_active IP Right Cessation
  • 1965-12-24 FR FR43660A patent/FR1461297A/fr not_active Expired
• 1967
  • 1967-04-22 DE DE19671617128 patent/DE1617128A1/de active Pending
• 1968
  • 1968-02-22 FR FR140831A patent/FR94484E/fr not_active Expired
  • 1968-04-19 AT AT382168A patent/AT285782B/de not_active IP Right Cessation
  • 1968-04-19 CH CH579468A patent/CH489285A/de not_active IP Right Cessation

Patent Citations (8)

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