US3586633A - Alkaline cleansing agent - Google Patents

Alkaline cleansing agent Download PDF

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Publication number
US3586633A
US3586633A US816154A US3586633DA US3586633A US 3586633 A US3586633 A US 3586633A US 816154 A US816154 A US 816154A US 3586633D A US3586633D A US 3586633DA US 3586633 A US3586633 A US 3586633A
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US
United States
Prior art keywords
acid
cleansing
alkaline
water
aminotri
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.)
Expired - Lifetime
Application number
US816154A
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English (en)
Inventor
Hans-Joachim Schlussler
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of US3586633A publication Critical patent/US3586633A/en
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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/044—Hydroxides or bases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3839—Polyphosphonic acids
    • C07F9/386—Polyphosphonic acids containing hydroxy substituents in the hydrocarbon radicals
    • 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
    • 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions

Definitions

  • the invention relates to alkaline cleansing agents and, more particularly, to cleansing agents containing additives which are stable against hydrolysis and which effectively prevent the deposit of calcium compounds due to the use of hard water.
  • alkaline cleansing agents frequently contain not only the customary components, i.e., caustic alkalis, alkali carbonates, -silicates, -phosphates and/or -borates, detergents and foam suppressants, but also materials which are to serve to prevent the formation of calcium deposits from the hardness-formers in the water.
  • Polymeric phosphates often are incorporated in alkaline cleansing agents to prevent the precipitation of the hardness-formers in the water.
  • polyphosphates are not resistant to hydrolysis in the cleansing solutions and decompose into orthoand pyrophosphates within a comparatively short period of time. Losses of polymeric phosphates by hydrolysis frequently even occur during storage, especially when the cleansing agents are highly alkaline.
  • R is a straight-chain or branched alkyl having 1 to 5 carbon atoms; plus (b) An aminopolyphosphonic acid of Formula 2 Rr-CXY NCXYR:
  • Rr-CXY wherein X and Y individually represent either hydrogen or an alkyl having 1 to 4 carbon atoms: R, and R indrvidually may be a --PO H group or a group or radical of 'Formula 3:
  • Examples for group (a) are hydroxyethane-, hydroxypropane-, hydroxybutane-, hydroxypentaneand hydroxyhexane-1,1-diphosphonic acids.
  • aminotri-(l-ethylphosphonic acid), ethylenediaminotetra-(l-ethylphosphonic acid), ethylenediaminotetra-(l-ethylphosphonic acid), aminotri-(l-propylphosphonic acid), and aminotri-(isopropylphosphonic acid) may be named, and preferably aminopolyphosphonic acids of Formula 4:
  • R (as in the preceding formulae) is a PO I-l group, R, and R may individualy be a PO H group or a radical having Formula 5:
  • CHr-Ril -C Hg-N CHz-Ra R again having the same connotation as before; such as aminotri-(methylphosphonic acid), ethylenediaminotetra- (methylphosphonic acid) and diethylenetriaminopentamethylphosphonic acid).
  • the concentrations in which the mixtures of hydroxyalkane-l,l-diphosphonic acid with aminopolyphosphonic acid are introduced in to the cleansing agents can vary within a wide range and lay between 0.5 and by weight, calculated on the content of alkali.
  • the addition to the alkaline cleansing agent should be calculated in such a manner that the concentration of the mixture of (a) and (b) in the aqueous solution of said alkaline cleansing is substantially 0.05l g./l. These values relate to the pure free acids.
  • Both the component acids can be added to the alkaline cleansing agent as free acid or in the form of the r water-soluble salts, preferably their alkali metal-, ammoniumor alkanolamine salts. Preferred are the sodium and potassium salts.
  • the hydroxyalkane-l,l-diphosphonic acid and the aminopolyphosphonic acid or their salts, respectively, may be incorporated in liquid or solid cleansing agents.
  • the manner of incorporation is not critical. Solids can be added to solid cleansing agents during the mixing step; they may be sprayed thereon in concentrated solutions; or they may be slurried and added to liquid material prior to spraydrying.
  • the phosphonic acids named and their mixtures are readily soluble and completely resistant to hydrolysis and therefore are especially suited for addition to highly alkaline cleansers and to alkaline concentrates, but also to acid concentrates to which alkali later is added to produce an alkaline cleansing agent.
  • the alkaline cleansing agents contain, aside from the mixture of hydroxyalkane-l,l-diphosphonic acid and aminopolyphosphonic, the commonly used alkali carriers in a concentration of 5-95 weight percent, such as caustic alkali, preferably NaOH, or KOH, alkali carbonates, preferably soda, alkali silicates, alkali phosphates, alkali borates, singly or in mixture, and, if desired or required, detergents, antifoams, bleaching agents, and disinfectants, in concentrations of 0.05 to weight percent.
  • the amount of alkali in the alkaline cleansing agents should be calculated in such a manner that the concentration of the alkaline carriers in the aqueous solution of said alkaline cleansing agents is substantially 1-50 g./1.
  • the cleansing agents according to the invention can be used in all cleansing and washing processes wherein a coating or calcium deposit and precipitation (stone formation) is apt to occur due to the hardness of the water employed, for instance in all kinds of washing and rinsing machines.
  • the cleansers according to the invention containing a mixture of hydroxyalkane-l,l-diphosphonic acid with aminopolyphosphonic acid faultlessly prevent a formation of coating or stone even with the use of very hard water, e.g., of a hardness above 30.
  • the effect is far better than with cleansers which contain the components (a) or (b) singly and also is superior to a purely additive effect of the single substances.
  • the stone formation of coating deposit does not increase.
  • the hardness degrees in this specification are so-calicd d.H., i.e., degrees of German hardness, a German industrial standard, wherein ld.H. equals 10 mg. (:10 per liter.
  • Temperatures are in degrees centigrade; percentages are percent by weight; solutions are aqueous; unless otherwise specified.
  • EXAMPLE 1 Stainless steel sheets were immersed for 2 minute: in 1% NaOH solution at 50, then rin ed for 2 minute in water at room temperature, and dried for 2-3 mmute.-. in a current of hot air. This cycle was repeated 500 times. Thereafter, the deposit (or coating) formed on the su faces of the sheets was determined by weighing. Tht NaOH solution was prepared with water of 36 hardness. and increasing amounts of hydroxyethane-l,l-diphosphonic acid, aminotri-(methylphosphonic acid) and mixtures of these two acids in weight proportions of 3: l, 1:], and 1:3, added. The rinse water also had a 36 hardness. The coating weights are listed as g./m.'- in Table l.
  • EXAMPLE 4 Mineral water bottles were cleaned in a commercial bottle washing machine. The concentration of the cleansing compound was 5 percent. The water used had a temporary hardness of 24, and the temperature was 70-75". The cleansing effect was excellent, and no deposit or precipitation occurred.
  • EXAMPLE 5 12.000 milk bottles per hour were washed in a dairy using a commercial bottle washing machine having 2 solution zones.
  • the cleansing solution for both zones was 1.2% NaOI-I which had been prepared by dilution of 50% NaOH.
  • an active concentrate was added in a concentration of 0.1%, of the following composition:
  • Percent Hydroxyethane-l,l-diphosphonic acid 20 Aminotri-(methylphosphonic acid) 20 Nonionic antifoam (additive of ethylene oxide on polypropyleneglycol) 25 Water Balance
  • the solution was brought up to strength, as required, by adding the needed quantities of NaOH and active concentrate.
  • the water employed had a temporary hardness of 30; the temperature of the cleansing solution was 65. The cleaning effect was excellent, and even after a period of months no deposit was noticeable.
  • EXAMPLE 6 Soft drink bottles were washed in a commercial bottle washing machine equipped with 3 immersion zones. For each of these zones, a 2% KOH was used, prepared by diluting a highly concentated KOH solution. To the dilute solution an active concentrate was added in a concentration of 0.07%, composed of the following:
  • Sodium sulfate l0 Beer-, mineral waterand soft drink bottles were washed in a commercial bottle washing machine using the above compound in a concentration of 1.5 percent at a solution temperature of 7075.
  • the water used had a temporary hardness of 17". Even after a long operational time no coating or stone deposit could be found in the machine.
  • EXAMPLE 8 A solid cleansing compound was prepared by jet-spraying a 70% solution each of hydroxyethane-1,1-diphosphonic acid and aminotri-(methyl-phosphonic acid), respectively, on the mixture of the other components of the compound. The latter had the following composition:
  • Nonionic detergent additive of 2 mols ethylene Oxide on oleyl alcohol
  • the cleansing device was used for more than 6 months with weekly replenishment of the solution, without deposit or stone formation.
  • Washing agent was prepared having the following concentration:
  • alkaline cleansing agent containing from 5% to 95% by weight of strongly alkaline alkali metal compounds selected from the group consisting of caustic alkalis, alkali metal carbonates, alkali metal silicates, alkali metal ortho phosphates, alkali metal pyrophosphates, alkali metal borates and mixtures thereof, the concentration of said strongly alkaline alkali metal compounds in said aqueous solution being from 1 to 50 g./l..
  • the improvement which consists of utilizing from 0.05 to 1 g./l. of a mixture selected from the group consisting of at least one first acid with at least one second acid, and of their alkaliand ammonium-salts; said first acid having the formula wherein R is selected from the group consisting of straightchain and branched alkyls having 1 to 5 carbon atoms: said second acid is selected from the group consisting of ethylenediaminotetra-(l-ethylphosphonic acid), ethylenediamino-tetra-(l-methylphosphonic acid) and compounds having the formula 8 wherein X and Y individually are selected from the group consisting of hydrogen and an alkyl group having I to 4 carbon atoms, and R R and R are PO H the first acid (a) and the second acid (b) being present in the said mixture of these said acids in weight proportions of (a) to (b) between 3:] and 1:3, as said additive.
  • said first acid is selected from the group consisting of hydroxyethane-, hydroxypropane-, and hydroxyhexane-l, l-diphosphonic acid.
  • said second acid is selected from the group consisting of aminotri-(methylenephosphonic acid), ethylenediaminotetra-(methylphosphonic acid), aminotri-(l-ethylphosphonic acid), ethylenediaminotetra-(l-ethylphosphonic acid), and aminotri- (isopropylphosphonic acid).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
US816154A 1965-04-01 1969-04-03 Alkaline cleansing agent Expired - Lifetime US3586633A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEH0055665 1965-04-01
DEH62511A DE1279274B (de) 1965-04-01 1967-04-22 Alkalisches Reinigungsmittel

Publications (1)

Publication Number Publication Date
US3586633A true US3586633A (en) 1971-06-22

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US816154A Expired - Lifetime US3586633A (en) 1965-04-01 1969-04-03 Alkaline cleansing agent

Country Status (10)

Country Link
US (1) US3586633A (de)
BE (1) BE678754A (de)
CH (1) CH465115A (de)
DE (2) DE1279274B (de)
DK (1) DK125719B (de)
FR (1) FR95136E (de)
GB (1) GB1057089A (de)
NL (1) NL146210B (de)
SE (1) SE315674B (de)
ZA (1) ZA661932B (de)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3925228A (en) * 1973-01-11 1975-12-09 Colgate Palmolive Co Carbonate built detergents
US3954401A (en) * 1970-03-14 1976-05-04 Benckiser-Knapsack Gmbh Agent for the treatment of cellulosic fiber materials and process
US3959168A (en) * 1973-05-22 1976-05-25 Henkel & Cie G.M.B.H. Synergistic sequestering agent compositions
US4265776A (en) * 1977-12-19 1981-05-05 Hoechst Aktiengesellschaft Detergent and cleaning compositions
US4485027A (en) * 1982-12-13 1984-11-27 Henkel Kommanditgesellschaft Auf Aktien Cleaning compositions containing boric acid or an alkali metal borate in phosphoric acid and their use in cleaning solid surfaces
US5039441A (en) * 1988-02-10 1991-08-13 Colgate-Palmolive Company Safe acidic hard surface cleaner
US5192460A (en) * 1988-02-10 1993-03-09 Colgate-Palmolive Company Safe acidic hard surface cleaner
US20060191851A1 (en) * 2005-02-25 2006-08-31 Mizuno William G Method for treating feedwater, feedwater treatment composition, and apparatus for treating feedwater
WO2016038449A1 (en) 2014-09-09 2016-03-17 Graff Pehrson Vesterager Gmbh Highly alkaline detergent composition

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1767454C2 (de) * 1968-05-11 1983-01-27 Henkel KGaA, 4000 Düsseldorf Verfahren zum Korrosions- und Versteinungsschutz in Warm- und Heißwassersystemen
DE2816770C2 (de) * 1977-04-22 1984-10-18 The Procter & Gamble Co., Cincinnati, Ohio Gerüststoffhaltiges Textilwaschmittel
FR2442885A1 (fr) * 1978-08-09 1980-06-27 Pintochimie Sa Procede d'augmentation de la viscosite d'hypochlorites
DE3246080A1 (de) * 1982-12-13 1984-06-14 Henkel KGaA, 4000 Düsseldorf Reinigungsverfahren
IN166486B (de) * 1984-12-24 1990-05-19 Goodrich Co B F
DE3717227A1 (de) * 1987-05-21 1988-12-01 Henkel Kgaa Phosphatfreies waschmittel mit reduzierter inkrustierungstendenz
GB8818215D0 (en) * 1988-07-30 1988-09-01 Flow Lab Phosphate-free detergent
CH679311A5 (de) * 1989-01-07 1992-01-31 Sandoz Ag
DE69231971T2 (de) * 1991-01-24 2002-04-04 Wako Pure Chem Ind Ltd Lösungen zur Oberflächenbehandlung von Halbleitern

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3954401A (en) * 1970-03-14 1976-05-04 Benckiser-Knapsack Gmbh Agent for the treatment of cellulosic fiber materials and process
US3925228A (en) * 1973-01-11 1975-12-09 Colgate Palmolive Co Carbonate built detergents
US3959168A (en) * 1973-05-22 1976-05-25 Henkel & Cie G.M.B.H. Synergistic sequestering agent compositions
US4265776A (en) * 1977-12-19 1981-05-05 Hoechst Aktiengesellschaft Detergent and cleaning compositions
US4485027A (en) * 1982-12-13 1984-11-27 Henkel Kommanditgesellschaft Auf Aktien Cleaning compositions containing boric acid or an alkali metal borate in phosphoric acid and their use in cleaning solid surfaces
US5192460A (en) * 1988-02-10 1993-03-09 Colgate-Palmolive Company Safe acidic hard surface cleaner
US5039441A (en) * 1988-02-10 1991-08-13 Colgate-Palmolive Company Safe acidic hard surface cleaner
US20060191851A1 (en) * 2005-02-25 2006-08-31 Mizuno William G Method for treating feedwater, feedwater treatment composition, and apparatus for treating feedwater
US20080223791A1 (en) * 2005-02-25 2008-09-18 Ecolab Inc. Method for treating feedwater
US7537705B2 (en) 2005-02-25 2009-05-26 Ecolab Inc. Method for treating feedwater
WO2016038449A1 (en) 2014-09-09 2016-03-17 Graff Pehrson Vesterager Gmbh Highly alkaline detergent composition
AU2015313913B2 (en) * 2014-09-09 2019-07-25 Graff Pehrson Vesterager Gmbh Highly alkaline detergent composition
US10836982B2 (en) 2014-09-09 2020-11-17 Graff Pehrson Vesterager Gmbh Highly alkaline detergent composition

Also Published As

Publication number Publication date
GB1057089A (en) 1967-02-01
NL146210B (nl) 1975-06-16
SE315674B (de) 1969-10-06
CH465115A (de) 1968-11-15
NL6515420A (de) 1966-10-03
BE678754A (de) 1966-09-30
DE1252838B (de)
ZA661932B (de)
FR95136E (fr) 1970-07-24
DK125719B (da) 1973-03-26
DE1279274B (de) 1968-10-03

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