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WO1990011996A1 - Detergents auto-adjuvants - Google Patents

Detergents auto-adjuvants Download PDF

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Publication number
WO1990011996A1
WO1990011996A1 PCT/US1989/001328 US8901328W WO9011996A1 WO 1990011996 A1 WO1990011996 A1 WO 1990011996A1 US 8901328 W US8901328 W US 8901328W WO 9011996 A1 WO9011996 A1 WO 9011996A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyamine
amide
water
polyamine amide
preferred
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.)
Ceased
Application number
PCT/US1989/001328
Other languages
English (en)
Inventor
Harry A. Smith
Donald A. Tomalia
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.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
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 Dow Chemical Co filed Critical Dow Chemical Co
Priority to BR898903159A priority Critical patent/BR8903159A/pt
Priority to PCT/US1989/001328 priority patent/WO1990011996A1/fr
Publication of WO1990011996A1 publication Critical patent/WO1990011996A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/38—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a carbon atom of an acyclic unsaturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/36—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
    • 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
    • C11D3/3719—Polyamides or polyimides
    • 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
    • C11D3/3723—Polyamines or polyalkyleneimines

Definitions

  • This invention relates to self-building detergents and a method for their preparation.
  • Self-building detergents are useful in clothes cleaning, dish cleaning and the like.
  • Builders which have been used include phosphates, carbonates, borates, silicates and citrates. Problems existing with conventional builders include ecological contamination in some cases and lack of effectiveness in others. In addition, various problems exist with the use of separate detergen (s) and/or soap(s) with builders, such as separation of particles in the particulate cleaning powder before being mixed with water.
  • component incompatibility, consumer preference for solid cleaning systems, breakdown of bleaching agents and high cost 5 are factors which encourage a search for additional approaches to address these problems.
  • One answer is to use a self-building detergent which is a molecule which acts as a detergent as well as a builder.
  • British 0 Patent No. 1,404,054 describes a group of such self- building detergents.
  • these self-building detergents disadvantageously have poor cleaning ability for cleaning clothes.
  • an c effective self-building detergent which has good detergency over a wide range of water hardness.
  • the present invention is a class of polyamine amides which contains one or more amide ester radicals 0 and a plurality of amine radicals in which the afore ⁇ mentioned nitrogen atoms are connected by a plurality of divalent organic radicals, provided that:
  • each amine nitrogen is bonded to at least 5 one divalent lower aliphatic radical terminated with carboxylate substituent;
  • each amine nitrogen is not bonded to a hydrogen radical; and O 3. the amide nitrogen is bonded to one hydrogen radical.
  • this invention is a process for the preparation of the polyamine amides which comprises following the steps of: a. contacting an organic acid and a polyamine under conditions sufficient to form water; b. removing at least a portion of the water formed in Step a; and c. contacting the dewatered product with a second reactant to substitute all remaining amino hydrogen atoms with alkyl carboxylate substituents thereby forming the carboxylated polyamine amide.
  • polyamine amides are self-building detergents useful for cleaning, particularly clothes cleaning. It is surprising how effective these polyamine amides are as detergents and builders.
  • polyamine amides of this invention are of the formula:
  • R is a monovalent organic radical
  • R 1 is, separately in each occurrence, a divalent organic radical
  • R 2 is, separately in each occurrence, a divalent lower aliphatic radical
  • n is the number of repeating groups and A is, in each occurrence, selected from:
  • R 2 contains 1 or 2 carbon atoms; more preferably, R 2 is -CH 2 - or -CH 2 -CH 2 -; and most preferably, R 2 is -CH 2 -CH 2 -.
  • R 1 contains from 2 to 6 carbon atoms and more preferably, R 1 contains from 2 to 4 carbon atoms.
  • R contains from 1 to 30 carbon atoms. More preferably,R contains from 11 to 20 carbon atoms and most preferably, R contains from 13 to 18 carbon atoms.
  • A is:
  • the polyamine amide salt counterions are preferably selected from metal ions, ammonium ions and phosphonium ions. It is preferred that the counterions are lithium, sodium, potassium, ammonium or substituted ammonium ions. It is more preferred that the counterion is a sodium ion.
  • polyamine amides may be used as conven ⁇ tional detergents in conventional processes such as clothes laundering, dish cleaning and the like. In a preferred embodiment, these polyamine amides are used in clothes laundering.
  • the polyamine amides may be used individually or two or more polyamine amides may be used in blends although it is preferred to use the polyamine amides individually.
  • the polyamine amides may be used alone as detergents or may be further mixed with various additives such as additional chelating agents and nonionic surfactants to form a detergent composition.
  • chelating agents which may be mixed with the compounds of this invention include ethylenediaminetetraacetic acid and salts or deriva- 0 tives thereof such as VERSENOL 120, which is a registered trademark of The Dow Chemical Company, for a concentrated solution of the trisodium salt of N-(car- boxymethy1)-N'-(2-hydroxyethy1)- ,N'-ethylene-
  • Nonionic surfactants which may be mixed with the compounds of this invention to form detergent compositions include the reaction product of one mole of a C 10 to C 30 fatty alcohol 5 reacted with 3 to 40 moles of ethylene oxide.
  • An example of a nonionic surfactant useful in the practice of this invention is TERGITOL 15-S-9, which is a registered trademark of the Union Carbide Corporation,
  • the compounds of • s i- this invention are used in a detergent composition.
  • Such compositions may include a chelating agent, an agent such as sodium metasilicate to balance the basicity of the chelating agent or a nonionic sur- , 0 factant or any combination thereof in addition to the compound of this invention.
  • the detergent composition preferably comprises from 0 to 60 weight percent chelating agent; from 0 to 10 weight percent sodium silicate; from 0 to 30 weight percent nonionic surfactant; and the remainder being the compound of this invention. It is more preferred that the detergent composition comprises from 5 to 25 weight percent chelating agent; from 1 to 5 weight percent sodium silicate; from 5 to 30 weight percent nonionic surfactant; artd the remainder being the compound of this invention. It is preferred that VERSENOL 120 be used as the chelating agent and that TERGITOL 15-S-9 be used as the nonionic surfactant.
  • %bw percent by weight
  • %bw %bw
  • %bw %bw percent of detergent in water
  • This invention may be practiced at any temperature and pressure at which cleaning will take place. Typical cleaning temperatures are between 4°C and 90°C. Cleaning operations are generally conducted at or near atmospheric pressures, for economic reasons, though elevated or reduced pressures may be employed.
  • the level of cleaning obtained using the compounds of this invention varies depending on factors such as the amount of detergent used, temperature, additives present and water hardness. Good detergency may be obtained using the compounds of this invention alone. The detergency of the compounds of this inven ⁇ tion is not detrimentally affected by water hardness up to about 1000 ppm and actually increases between distilled water and 150 ppm calcium.
  • the compounds of this invention are effective as detergents at temper ⁇ atures ranging from the low temperature (about 4°C) and high temperature (about 90°C) typically used in clothes laundering.
  • the polyamine amides of this invention are prepared by a process comprising reacting an organic acid with a polyamine, stripping off the water formed thereby, and contacting the dewatered product with a second reactant to substitute all remaining amino hydrogen atoms with alkyl carboxylate substituents thereby forming the carboxylated polyamine amide.
  • Organic acids useful in the process of this invention include organic compounds containing at least one carboxylate radical.
  • the organic acids contain from 1 to 100 carbon atoms.
  • the organic acids contain more than 4 carbon atoms and more preferably, more than 13 carbon atoms.
  • the organic acids contain less than 50 carbon atoms and more preferably less than 21 carbon atoms.
  • the organic acids contain between 14 and 19 carbon atoms.
  • the organic acids contain fewer than 3 carboxylate radicals and most preferably fewer than 2 carboxylate radicals. Examples of preferred organic acids include palmitic acid, stearic acid, myristic acid and oleic acid.
  • polyamines useful in practicing this inven ⁇ tion are preferably of the formula:
  • R 4 is independently a divalent organic radical and n is the number of repeating moieties.
  • R 4 preferably contains from 2 to 15 carbon atoms, more preferably R* has fewer than 10 carbon atoms.
  • R 4 more preferably has fewer than 5 carbon atoms and most prefer- ably has fewer than 4 carbon atoms;
  • n is preferably less than 100, more preferably is less than 20, even more preferably less than about 5 and most preferably is 1. It is preferred to use diethylene- triamine.
  • the organic acid and polyamine are contacted under conditions sufficient to form water.
  • the reactants cat! be added in any amounts and order. It is preferred to use the polyamine in an amount from stoichiometric up to a slight excess.
  • the polyamine is more preferably present in an amount from stoichio ⁇ metric up to an excess of about 10 %bw.
  • the reacting mixture can be in any container which will contain the reactants and allow the desired temperature and pressure to be applied. The temperature and pressure of contact depend on many factors such as reactants used, solvent if any and the like. Typical temperatures range between 50°C and 200°C. Preferably, the temperature is above 110°C, more preferably above 140°C. Preferably, the temperature is below 170°C.
  • the pressure is sufficient to keep at least part of the reactants in the liquid phase. Most preferable pressure is atmospheric. The combination of pressure and temperature must be sufficient to allow the reaction mixture to reflux.
  • the reaction is allowed to proceed until the desired degree of completion is reached. Preferably, the reaction is allowed to proceed until at least 80 percent of the reactants have been converted to product, more preferably until at least 90 percent of the reactants have been converted to product. Typical reaction times range between 3 and 8 hours.
  • the reaction proceeds in an inert, water azeotroping solvent.
  • the solvent typically comprises between 1 and 20 %bw of the reacting system. Preferably, the solvent comprises less than 5 %bw of the reaction system. Preferably, the solvent comprises more than 2 %bw of the reacting system.
  • the solvent is immiscible with water. It is preferred that the solvent is toluene, xylene, benzene, methylene chloride or a mixture thereof. In a preferred embodiment, the solvent forms an azeotrope with the water formed in the reaction and the water is removed by azeotropic distillation.
  • the dewatered product, a polyamine amide is next contacted with a second reactant selected from unsaturated esters, amides, nitriles and carboxylic acids to form a carboxylated polyamine amide.
  • a second reactant selected from unsaturated esters, amides, nitriles and carboxylic acids to form a carboxylated polyamine amide.
  • the second reactant be an unsaturated ester. It is more preferred that the second reactant be methyl acrylate, dimethyl maleate or dimethyl fumarate.
  • any relative amounts of the polyamine amide and the second reactant which will react are useful in the practice of this invention. It is preferred to use approximately stoichiometric amounts of the reactants. That is, if the polyamine amide has x number of amine nitrogens available to be substituted with the carboxylate group, then x moles of the second reactant are used per mole of the polyamine amide.
  • the contact of the second reactant and the polyamine amide may be conducted at any temperature and pressure at which the reaction will occur. While super- atmospheric and subatmospheric pressures are operable, it is preferred to conduct the reaction at atmospheric pressure for the sake of convenience. It is preferred that the reaction take place at a temperature of at least 30°C and more preferred that the temperature be at least 45°C. It is preferred that the reaction take place at a temperature of no greater than 70°C and more preferred that the temperature be no greater than 55°C.
  • the reaction is allowed to proceed until a desired degree of conversion of the polyamine amide to carboxylated polyamine amide is obtained. It is preferred that at least 50 percent of the polyamine amide reacts. It is more preferred that at least 70 percent reacts and most preferred that at least 90 percent reacts. It is preferred that the selectivity to the carboxylated polyamine amide is at least 99 percent. It is preferred that the reaction proceed for no more than about 24 hours and more preferred that it proceed for no more than 20 hours. It is preferred that the reaction proceed for at least hours.
  • the contact of the second reactant and the polyamine amide preferably takes place in the presence of a solvent in sufficient amount to make the system fluid.
  • the amount of solvent is preferably about 50 %bw of the reaction mixture.
  • Preferred solvents are lower aliphatic alcohols such as, for example, methanol, ethanol, propanol, butanol, pentanol and hexanol. It is more preferred to use methanol as the solvent.
  • the carboxylated polyamine amide so prepared is subjected to hydrolysis in the presence of water and a base.
  • bases useful in the process include NaOH, KOH, Na 2 C0 3 and K 2 C0 3 . It is preferred to use NaOH.
  • the relative amount of base to carboxylated polyamine amide is any which will result in the conver ⁇ sion of the carboxylated polyamine amide to the salt form. It is preferred that the ratio of equivalents of base to equivalents of carboxylated polyamine amide be greater than 1. It is more preferred that the ratio be at least 1.05:1 and no greater than 1.15:1. It is preferred that the hydrolysis take place at a tempera ⁇ ture of at least 25°C and more preferred that the temperature be at least 45°C.
  • reaction take place at a temperature of no greater than 70°C and more preferred that the temperature be no greater than 60°C. While superatmospheric and subatmos- pheric pressures are operable, it is preferred to conduct the hydrolysis at atmospheric pressure for the sake of convenience.
  • the hydrolysis is allowed to proceed until a desired conversion of the carboxylated polyamine amide to the salt form is obtained. It is preferred that at least 80 percent of the carboxylated polyamine amide is converted to the salt form and more preferred that at least 90 percent is converted.
  • a mixture of 141.2 g (0.50 mole) of oleic acid and 51.6 g (0.50 mole) of diethylenetriamine in 0.100 liter of toluene is heated to reflux.
  • the mixture is allowed to reflux until no more water is generated as detected by formation of the water toluene azeotrope. This takes from 6 to 8 hours.
  • the toluene is stripped by distillation at a temperature of from 50°C to 100°C and at a pressure of about 200 mm of mercury.
  • the residue is dissolved in 0.300 liter of methanol.
  • 172.7 g (2.00 moles) of methyl acrylate is added. This new solution is heated to 50°C and kept at 50°C for 16 hours.
  • the product is flash distilled to remove the methanol and unreacted methyl acrylate. To this residue is added 66 g of NaOH in 100 ml of water and 400 ml of methanol. This solution is heated for 6 hours at 50°C. Stripping off the water and methanol leaves 346.6 g of a solid. Infrared and nuclear magnetic resonance analyses show the solid is 91.5 percent sodium salt of oleic amide of diethylene ⁇ triamine tripropionate. The remainder is essentially water and methanol.
  • the product as prepared is used to make a 0.1 %bw aqueous solution.
  • This solution has a pH of 10.8 and a surface tension as determined by a DuNoy's tensionmeter, of 33.9 dynes/cm.
  • a 0.100-liter aliquot of a 1 %bw aqueous solution of the product is titrated with 1 %bw CaCl 2 aqueous solution until a precipitate forms. This titration shows a calcium tolerance equivalent to 3310 ppm CaC0 3 .
  • a 0.200-liter aliquot of a 0.05 %bw aqueous solution is whipped at high speed in a 1-quart Waring blender for 2 minutes.
  • the initial foam and liquid heights are 7.5 cm and 0.0 cm, respectively.
  • After sitting for 5 minutes at room temperature and pressure, 0 the foam and liquid heights are 4.6 cm and 3.2 cm.
  • Example 1 is repeated except using different fatty acids in place of oleic acid.
  • the test results are shown in Table I. 0 r TABLE I
  • the bath has a heater and can have a cooler attached to it and wash temperatures of from 40 P F to 200°F (4.4°C to 93.3°C) are available.
  • wash temperatures of from 40 P F to 200°F (4.4°C to 93.3°C) are available.
  • Four stainless steel, one-liter beakers are immersed in the
  • Standard soiled cloths are also used. These - jt - are pieces of 65/35 polyester/cotton cloth which are 7.5 cm by 11.25 cm rectangles. Unless stated other ⁇ wise, the cloths are soiled with a standard dust-sebum soil commercially available from Scientific Services , 0 Company.
  • a Hunter D25-PC2 reflectometer is used to measure the cleaning of the soiled cloth. The percentage of cleaning is determined by measuring the reflectance, L which is the L value on the L, a, b scale, of the original cloth, the soiled cloth and the washed cloth, and using the values so obtained in the following formula:
  • the reflectometer is fitted with an ultraviolet filter so that the effects of optical brighteners are excluded and only actual cleaning is measured.
  • Terg-O-Tometer bath is brought to temperature and then the stainless steel beakers are filled with one liter of water of the desired hardness.
  • Water containing 150 ppm (parts per million) CaC0 3 is obtained by .dissolving a 2:1 mole ratio of CaC0 3 and MgC0 3 in distilled water saturated with C0 2 .
  • the hardness is the ppm of CaC0 3 equivalent to the total moles of CaC0 3 and MgC0 3 .
  • the desired amount of detergent is added.
  • the mixture is then agitated for approximately 10 minutes to ensure that the detergent has gone into solution.
  • Four pieces of soiled cloth are then added to each beaker and the agitators are started. After the 10-minute wash cycle, the cloths are hand-rinsed in cold tap water, squeezed to remove most of the water and then air dried on paper towels. When dry, the samples are read on the reflectometer.
  • Example 9 Effect of Different Soils on Detergency
  • the detergency of two compounds of this invention is measured following the procedure outlined above.
  • the compounds used are A, the sodium salt of palmitic amide of diethylenetriamine triproprionate and B, the sodium salt of oleic amide of diethylenetriamine triproprionate.
  • the percent detergency is measured as explained above.
  • the soil used is a mixture of clay, lampblack and iron oxides with synthetic sebum and the soiled cloth was WKF 20C obtained from Test Fabrics, Inc.
  • the hardness of the water was 150 ppm. The results obtained are shown in Table II below.
  • Example 9 is repeated with the only difference being that the soil used is dust-sebum rather than the soil used in Example 9.
  • the results obtained are also shown in Table II following.
  • the effect of water hardness is measured following the general procedure set forth above.
  • the water temperature used is 120°F (49°C) and the soil is dust-sebum.
  • the compounds tested were A and B from Examples 9 and 10 and C, the sodium salt of stearic amide of diethylenetriamine triproprionate. The results obtained are shown in Table III below.
  • Example 13 demonstrates the enhanced detergency obtained by using a mixture of the oleic derivative with VERSENOL 120. This example measures the effect of adding sodium metasilicate to the formulation used in Example 13. Otherwise, the same conditions are used, The results are given in Table V bGlcw.
  • Example 14 is repeated with the only difference being that the temperature used is 60°F (15.6°C) rather than 120°F (49°C). These results are also given in Table V below.
  • Example 16 uses the conditions described for Example 14 which are conducted at a temperature of 120°C and water hardness of 150 ppm CaC0 3 , with the only difference being the addition of a nonionic surfactant, TERGITOL 15-S-9, to the detergent composition.
  • the first detergent composition, CNSLV comprises 53 %bw of the sodium salt of oleic amide of diethylenetriamine triproprionate, 15 %bw of VERSENOL, 8 %bw of sodium metasilicate, and 20 %bw of TERGITOL 15-S-9.
  • the second detergent composition, CNSHV comprises 28 %bw of the sodium salt of oleic amide of diethylenetriamine triproprionate, 50 %bw of VERSENOL, 8 %bw of sodium metasilicate, and 15 %bw of TERGITOL 15-S-9.
  • the percent detergency obtained using these detergent compositions is shown in Table VI following.
  • the data shown above indicates that the addition of the nonionic surfactant to the detergent composition results in a high level of detergency being obtained while using a low level of detergent which is comparable to the level of detergent used in actual conditions.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des détergents de lessivage auto-adjuvants qui sont des amides de polyamine organiques, contenant une pluralité de radicaux de carboxylate ainsi qu'un ester amide. Ces composés sont utiles individuellement en tant que détergents ou en tant que composants dans des compositions de détergents.
PCT/US1989/001328 1989-03-30 1989-03-30 Detergents auto-adjuvants Ceased WO1990011996A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
BR898903159A BR8903159A (pt) 1989-03-30 1989-03-30 Poliamina amida,sal,composicao de detergente e processo para preparacao de poliamina amida
PCT/US1989/001328 WO1990011996A1 (fr) 1989-03-30 1989-03-30 Detergents auto-adjuvants

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1989/001328 WO1990011996A1 (fr) 1989-03-30 1989-03-30 Detergents auto-adjuvants

Publications (1)

Publication Number Publication Date
WO1990011996A1 true WO1990011996A1 (fr) 1990-10-18

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5284972A (en) * 1993-06-14 1994-02-08 Hampshire Chemical Corp. N-acyl-N,N',N'-ethylenediaminetriacetic acid derivatives and process of preparing same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2117207A (en) * 1934-09-19 1938-05-10 Ig Farbenindustrie Ag Amino acids
SU615062A1 (ru) * 1976-11-09 1978-07-15 Тульский Филиал Всесоюзного Научно-Исследовательского И Проектного Института Химической Промышленности Бетаины как амфотерные поверхностноактивные вещества
US4374056A (en) * 1980-11-27 1983-02-15 Kao Soap Co., Ltd. Lowly irritating detergent
US4743388A (en) * 1986-07-21 1988-05-10 Westvaco Corporation Complex amide carboxylate lubricant rust inhibitor additive for metal working fluids

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2117207A (en) * 1934-09-19 1938-05-10 Ig Farbenindustrie Ag Amino acids
SU615062A1 (ru) * 1976-11-09 1978-07-15 Тульский Филиал Всесоюзного Научно-Исследовательского И Проектного Института Химической Промышленности Бетаины как амфотерные поверхностноактивные вещества
US4374056A (en) * 1980-11-27 1983-02-15 Kao Soap Co., Ltd. Lowly irritating detergent
US4743388A (en) * 1986-07-21 1988-05-10 Westvaco Corporation Complex amide carboxylate lubricant rust inhibitor additive for metal working fluids

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5284972A (en) * 1993-06-14 1994-02-08 Hampshire Chemical Corp. N-acyl-N,N',N'-ethylenediaminetriacetic acid derivatives and process of preparing same

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