US3928250A - Washing composition containing suds suppressing agents - Google Patents

Washing composition containing suds suppressing agents Download PDF

Info

Publication number
US3928250A
US3928250A US401691A US40169173A US3928250A US 3928250 A US3928250 A US 3928250A US 401691 A US401691 A US 401691A US 40169173 A US40169173 A US 40169173A US 3928250 A US3928250 A US 3928250A
Authority
US
United States
Prior art keywords
sec
foam
washing composition
washing
agent
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
US401691A
Other languages
English (en)
Inventor
Kurt Kosswig
Herbert Meister
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huels AG
Original Assignee
Chemische Werke Huels AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Chemische Werke Huels AG filed Critical Chemische Werke Huels AG
Application granted granted Critical
Publication of US3928250A publication Critical patent/US3928250A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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

Definitions

  • washing compositions containing piperazine derivatives as foam controlling or suds suppressing agents containing piperazine derivatives as foam controlling or suds suppressing agents. Washing compositions which produce excessive suds are undesirable for use in modem drum-type washing machines. Desirably, washing compositions for use in automatic washing machines are those which initially exhibit a relatively good suds formation in the washing liquor at a low temperature (up to about 50 C-60 C) but tend to become low in suds during subsequent transition toward higher washing temperatures. Excessive sudsing or foaming is desirably avoided to prevent overflow of suds out of the washing machine.
  • Suds suppressing additives are added to washing compositions which are effective predominantly at temperatures higher than 60 C.
  • this is the case with strongly foaming or sudsing anionic washingcompositions of the sulfate and/or sulfonate types, or in the case of the salts of the carboxylated alkyl polyglycol ethers of the general formula, R(OCH CH O[CH COOH, wherein R is C H to C H n is to 20, and m is I to 4.
  • a number of substances are known which can be added to washing compositions as foam or suds suppressors.
  • soaps of saturated fatty acids DOS [German Unexamined Published Application] 2,015,435), nonionic highly molecular ethers, and esters of the ethylene oxide and propylene oxide condesation products of alcohols.
  • Disadvantages of these substances are that they are not universally applicable in washing compositions and that they do not exhibit sufficient defoaming or desudsing action as in the case of dodecyl sulfaonates and alkyl sulfates.
  • diurethanes are also known as foam suppressors (DOS 2,043,086).
  • DOS 2,043,086 foam suppressors
  • the optimum desudsing effect, at various temperature ranges, depends on the chain length.
  • the diurethanes with chain lengths of -14 carbon atoms develop their optimum effect at -60 C., while those with chain lengths of 18-22 carbon atoms at 60-100 C.
  • a disadvantage of the diurethanes is that isocyanates are necessary as the basic raw material, which, in turn, must be produced from amines or diamines.
  • Triazine derivatives are also known (DAS [German Published Application] l,257,338) as foam suppressors of a broader, universal application spectrum, which are independent of the chemical constitution of the washing composition. They are produced by reacting cyanuric chloride with alkyl amines, wherein again long-chain amines are used, which in the nonnal case must be manufactured in two stages from the corresponding alcohols via the chlorides, or from the acids via the nitriles. Furthermore, hydrogen chloride is formed during the reaction, which is bound with equimolar amounts of amine. The amine consumed for binding the hydrogen chloride must first be regenerated from the salt before being reused. Therefore, the production of the triazine derivatives is cumbersome and expensive.
  • a low sudsing washing composition containing a foam or suds suppressing agent which can be manufactured simply, inexpensively, and in high yields, which has an excellent foam controlling ability, and furthermore which can be used universally.
  • Another object of this invention is to provide a low sudsing washing composition containing a suds-suppressing agent comprising piperazine derivatives produced by simple, inexpensive, and conventional processes.
  • R, and R are alkyl groups of 9-21 carbon atoms, as the desudsing or defoaming agents.
  • the piperazine derivatives of the present invention are insoluble or of low solubility in water, depending on the length of the acyl residue.
  • the desudsing or defoaming effect is only moderately strong at temperatures between 2040 C., but becomes stronger at 60 C., and reaches the optimum effect at C. and there- 3 above.
  • the '..'ashing compositions of this invention possess especially favorable properties if the chain length of the alkyl groups of the piperazine derivatives is 1 1-19 carbon atoms.
  • the defoaming effect decreases with a reduced number of carbon atoms in the residue R, especially at a high temperature, and is hardly noticeable in the case of carbon atom numbers of below 7 in the residue R.
  • piperazine derivatives of more than 19 carbon atoms, i.e., up to 21 carbon atoms, in the residue R is not as suitable from an economical viewpoint.
  • the higher fatty acids (e.g., behenic acid, lignoceric acid) required for the production of such piperazine derivatives are not as easy to produce, in contrast to lauric, myristic, palmitic, and stearic acids, which, when reacted with piperazine, result in excellent desudsing agents.
  • the alkyl groups can also contain branches and double bonds, but piperazine derivatives of such chain configurations do not offer any particular desudsing advantages from a laundering standpoint as compared to the piperazine derivatives with straight chains.
  • the quantity of piperazine derivatives added to the washing compositions is 1-40% by weight, preferably 520% by weight, based on the detergents in the washing compositions. When adding less than 1%, practically no desudsing action can be observed; at above 40%, no increase in the desudsing action is particularly rioticeable.
  • the quantity of piperazine derivatives added to the washing compositions is 0.1 12% by weight, preferably 0.5 6 by weight, based on the total weight of the washing composition.
  • the washing and cleaning compositions can additionally contain the conventional additives, such as phosphates, silicates, carbonates, borates, cellulose derivatives, etc.
  • the piperazine derivatives of the invention can be produced in accordance with conventional methods, most simply and inexpensively by splitting off water from piperazine and fatty acids containing the desired R residue.
  • the reaction is particularly simple if the reactants are refluxed in a water-insoluble solvent of an appropriate boiling point, wherein the water is removed from the cycle.
  • Suitable fatty acids are straightchain, native fatty acids, synthetic fatty acids having an even or odd number of carbon atoms, and with straight or branched chains.
  • the advantages attainable by the desudsing agents of this invention reside particularly in that they are readily producible technically; that they deploy the optimum of their effectiveness at about 60 C. and thereabove; and that the foam level in the washing machines can be regulated by controlled dosages. As demonstrated in the subsequent example, they are superior to the conventional desudsing agents with respect to their desudsing action.
  • the apparatus consists of a column having a height of 40 cm. and an inside diameter of 9 cm., equipped with a heating jacket. At the bottom, the column has an installed porous glass plate 4 having a diameter of 3 cm. 400 cc. of the test solution is introduced into the column. A marker in the form of a constriction of the column is provided 25 cm. above the level of the liquid. Air at an excess pressure of 20 cm. H O column is introduced into the test solution through the glass frit, and the time is measured within which the thus-formed foam has reached the marker.
  • Foam spraying method according to DAS 1,257,338.
  • the suds are generated by spraying the test solution.
  • the device utilized in a compact design, consists of a cylindrical vessel of stainless steel having a height of cm. and an inside diameter of 26 cm.
  • the liquid provided in the device is recirculated by a pump and sprayed from an annular pipe arranged at the top of the vessel, which pipe has numerous small openings directed downwardly.
  • suds are formed, the level of which is measured after specific times. The lower the suds level, the higher the defoaming or desudsing effect. Examples 7 and 8 were measured according to the foam spraying method.
  • German Hardness (dH) of water is defined as follows: 1 German hardness 0.357 milligram equivalents/liter of calcium ions, or 17.8 ppm. of CaCO EXAMPLE 1 2 g. of a 50% by weight sodium dodecylbenzenesulfonate solution was dissolved in 1 liter of drinking water having a hardness of 12 dH. Then, varying amounts (0.1 g. and 0.4 g., respectively) of the desudsing agent (defoaming additive) were added to this solution. The foam or suds characteristic is tested in the apparatus according to Merrill and Mofiett. The results are compiled in Table 1. it can be seen therefrom that the piperazine derivatives of this invention are superior to the defoaming or desudsing substances of the prior art in their desudsing effect.
  • EXAMPLE 2 In this example, the defoaming or desudsing effect of the piperazine derivatives of this invention is demonstrated in soft water and in hard water.
  • 1 g. of dodecylbenzenesulfonate was dissolved in distilled water (0 dH) and in drinking water 12 dH), respectively, and the foam or suds is measured with and without the addition of a defoaming additive.
  • the results are compiled in Table 2.
  • the piperazme derivative of this In EXAMPLE 5 vention has superior properties, in that it ensures a 4 ofa washmg agent f h f ll i composition uniform foam level In the entire temperature range. was dissolved in 1 liter of water:
  • the pH of the solution is set to 9.5; the solution was recirculated by a pump at a rate of 465 liters/minute.
  • the results are set forth in Table 4.
  • EXAMPLE 8 1.0 g. of the sodium salt of a carboxymethylated alcohol oxyethylate, the alcohol residue of which consists of a mixture of dodecanol and tetradecanol and 1.0 g. of olefin sulfonate was dissolved in 1 liter of water of 0 dH or 12 dH and tested with and without a defoaming agent in accordance with the manual beating method, DIN 53,902 (20 beats in 20 seconds). The thus-obtained amount of foam (in cm) is a measure for the defoaming action. The results are compiled in Table 5.
  • a low-sudsing washing composition comprising detergent compounds and additives, and l40% by weight, based on the weight of the active detergent compounds of the washing composition, of a suds-suppressing agent, said agent being a piperazine derivative of the formula:
  • R and R each are alkyl groups of 9-21 carbon atoms.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
US401691A 1972-10-05 1973-09-28 Washing composition containing suds suppressing agents Expired - Lifetime US3928250A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19722248842 DE2248842A1 (de) 1972-10-05 1972-10-05 Wasch- und reinigungsmittel mit einem gehalt an einer schaumdaempfenden substanz

Publications (1)

Publication Number Publication Date
US3928250A true US3928250A (en) 1975-12-23

Family

ID=5858243

Family Applications (1)

Application Number Title Priority Date Filing Date
US401691A Expired - Lifetime US3928250A (en) 1972-10-05 1973-09-28 Washing composition containing suds suppressing agents

Country Status (4)

Country Link
US (1) US3928250A (enFirst)
DE (1) DE2248842A1 (enFirst)
FR (1) FR2202152B3 (enFirst)
GB (1) GB1439066A (enFirst)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4871483A (en) * 1987-04-16 1989-10-03 Gaf Corporation Novel non-depositing defoaming compositions
US4946625A (en) * 1989-03-27 1990-08-07 Siltech Inc. Particulate defoaming compositions

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2383525A (en) * 1942-02-19 1945-08-28 Procter & Gamble Detergent composition
US2421707A (en) * 1945-12-29 1947-06-03 Malkemus John David Mono-substituted dialkanol piperazines
US2868791A (en) * 1954-10-19 1959-01-13 Union Carbide Corp Process for the production of substituted piperazines
US3422020A (en) * 1965-02-11 1969-01-14 Henkel & Cie Gmbh Low-sudsing detergent compositions
US3547932A (en) * 1967-10-24 1970-12-15 Colgate Palmolive Co Hydroxyalkyl piperidine or pyrrolidine oxides
US3600320A (en) * 1967-04-01 1971-08-17 Henkel & Cie Gmbh Low sudsing detergent and cleaning agents

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2383525A (en) * 1942-02-19 1945-08-28 Procter & Gamble Detergent composition
US2421707A (en) * 1945-12-29 1947-06-03 Malkemus John David Mono-substituted dialkanol piperazines
US2868791A (en) * 1954-10-19 1959-01-13 Union Carbide Corp Process for the production of substituted piperazines
US3422020A (en) * 1965-02-11 1969-01-14 Henkel & Cie Gmbh Low-sudsing detergent compositions
US3600320A (en) * 1967-04-01 1971-08-17 Henkel & Cie Gmbh Low sudsing detergent and cleaning agents
US3547932A (en) * 1967-10-24 1970-12-15 Colgate Palmolive Co Hydroxyalkyl piperidine or pyrrolidine oxides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4871483A (en) * 1987-04-16 1989-10-03 Gaf Corporation Novel non-depositing defoaming compositions
US4946625A (en) * 1989-03-27 1990-08-07 Siltech Inc. Particulate defoaming compositions

Also Published As

Publication number Publication date
FR2202152B3 (enFirst) 1975-10-31
GB1439066A (en) 1976-06-09
DE2248842A1 (de) 1974-04-11
FR2202152A1 (enFirst) 1974-05-03

Similar Documents

Publication Publication Date Title
DE69405554T2 (de) Peroxysaeure
WO1997016408A1 (de) Fettsäurederivate und ihre verwendung als tenside in wasch- und reinigungsmitteln
US3281365A (en) Antiseptic detergent compositions
US4128485A (en) Fabric softening compounds
CZ340296A3 (en) Low-foaming branched alkyldimethylaminooxides
DE1929193C3 (de) Weichmachendes Waschmittel
US4126586A (en) Process of spray drying nonionic surfactant-containing detergents also containing a cationic nitrogen compound
US3723342A (en) Defoamer composition
US4233451A (en) Process for making imidazolinium salts
US3928250A (en) Washing composition containing suds suppressing agents
US4118324A (en) Fabric softeners
DE1594865C3 (enFirst)
US3385858A (en) High molecular weight fatty piperazine amphoteric surfactants
EP0034149B1 (en) Amine oxide foam stabilizers for alkyl benzene sulfonate foaming agents
US3240715A (en) Alkylolamide surface active compositions soluble in aqueous solutions of electrolytes
US2483253A (en) Detergent composition
DE2219595A1 (de) Reinigungsmittel mit Gehalt an Perverbindungen und Aktivatoren
US4129506A (en) Fabric softeners
US2206249A (en) Agents of capillary action from alkyl-amino-carboxylic acids with tertiary or quaternary bound nitrogen
US3501335A (en) Fabric conditioner
US5331100A (en) Self-building detergents
KR900004494B1 (ko) 세제조성물
WO1997017420A1 (de) Verwendung von oximestern als aktivatoren für anorganische perverbindungen
US3567734A (en) Quaternary imidazolinium salts
DE1269621C2 (de) Verfahren zur herstellung von n-(2hydroxyalkyl)-n-methyltaurinen