US3859224A - Detergent composition containing, as a builder, the sodium salt of glycerol tricitrate - Google Patents

Detergent composition containing, as a builder, the sodium salt of glycerol tricitrate Download PDF

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Publication number
US3859224A
US3859224A US291044A US29104472A US3859224A US 3859224 A US3859224 A US 3859224A US 291044 A US291044 A US 291044A US 29104472 A US29104472 A US 29104472A US 3859224 A US3859224 A US 3859224A
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United States
Prior art keywords
acid
builder
detergent composition
builders
sodium salt
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Expired - Lifetime
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US291044A
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English (en)
Inventor
Joachim Kandler
Karl Merkenich
Klaus Henning
Wilhelm Vogt
Eberhard Auer
Hermann Glaser
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Hoechst AG
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Hoechst AG
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    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates

Definitions

  • the present invention provides builders for detergents and cleansing agents, the builders comprising water-soluble salts of acid carboxylic acid esters, the esters being the product obtained by the reaction of at least trivalent carboxylic acids with polyhydric alcohols.
  • Vital to the function of the builder is a plurality of processes comprising, for example: the stabilization of pigment dirt suspensions; the emulsification of dirt particles; the effect on the surface and interfacial properties of aqueous tenside solutions; the solubilization of waterinsoluble ingredients of the cleansing bath; the peptization of agglomerated dirt; the neutralization of acid substances; and the inactivation of mineral matter in the cleansing bath.
  • Classical builders comprise water-soluble inorganic alkali metal salts, such as alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates, and silicates.
  • Starch derivatives such as dicarboxyl and carboxymethyl starch
  • polycarboxylic acids such as polymaleic acid and the copolymers thereof, oxydiacetic acid, oxydisuccinic acid, esters containing sulfonate groups of polyethylene glycol and adipic acid or maleic acid, and esters of ethylene glycol and trior tetracarboxylic acids
  • starch derivatives such as dicarboxyl and carboxymethyl starch
  • polycarboxylic acids such as polymaleic acid and the copolymers thereof, oxydiacetic acid, oxydisuccinic acid, esters containing sulfonate groups of polyethylene glycol and adipic acid or maleic acid, and esters of ethylene glycol and trior tetracarboxylic acids
  • the use of these substances as builders has been found to entail disadvantages which reside in the fact that they are insufficiently biodegradable or have an unsatisfactory power for dispersing
  • a detergent In addition to the tenside constituent, which merely enables hydrophobic dirt, such as carbon black and fat particles, to be dispersed and/or peptized, it is necessary for a detergent to contain a further ingredient removing hydrophilic dirt, namely a builder. ln the ab- 1 alcohol and optionally of the carboxylic acid having a carboxylic acid-molecule attached thereto, are very suitable for use as builders in detergents and cleansing agents, as they have an efficiency excelling that of conventional builders free from nitrogen and phosphorus.
  • the cation of the water-soluble salts of acid carboxylic acid esters preferably is an alkali or ammonium ion, whereas the ester-type anion is based on a "Mr tetravalent carboxylic acid, which has between six and 10 carbon atoms and is esterified with a polyhydric alcohol containing between three and six hydroxylic groups.
  • the acid component of the carboxylic acid esters should be selected, for example, from the group consisting of citric acid, aconitic acid, tricarballylic acid, dihydroxytrican ballylic acid, nitrilotriacetic acid, or ethylenediamine tetracetic acid, and the alcoholic component should be selected from the group consisting of glycerol, erythritol, pentaerythritol, mannitol, sorbitol or a sugar alcohol having between four and six carbon atoms.
  • ester salt builders of the present invention into conventional detergent and cleansing agents, which are based on ion-active and/or non-ionic tensides and which may optionally contain further addends.
  • the builder may generally be used in a proportion substantially between 10 and 80 weight percent, preferably between 15 and weight percent, based on the dry substance of the detergent and cleansing agent.
  • the detergent and cleansing agents may contain as a further builder one or more alkali metal polyphosphates or their substitutes specified hereinabove.
  • Detergent and cleansing agents prepared in accordance with the present invention give a pH-value substantially between 8 and 12 in the aqueous medium of the wash bath.
  • the addends which may be present together with the ion-active and/0r non-ionic tensides in the detergents comprise substances, such as alkali metal or ammonium salts of sulfuric acid, silicic acid, di-and trisilicic acids, carbonic acid, boric acid, iminodiacetic acid, nitrilotriacetic acid, ethylene diamine tetracetic acid, alkylene phosphonic acids, hydroxyalkylene phosphonic acids and/or aminoalkylene phosphonic acids, or stabilizers and activators for perborates, as well as optical brighteners, carboxymethyl cellulose, magnesium silicate, disinfectants and/or enzymes, for example.
  • substances such as alkali metal or ammonium salts of sulfuric acid, silicic acid, di-and trisilicic acids, carbonic acid, boric acid, iminodiacetic acid, nitrilotriacetic acid, ethylene diamine tetracetic acid, alkylene phosphonic acids, hydroxyalky
  • the carboxylic acid esters underlying the builder salts of the present invention are produced by conventional esterification methods, for example, by reacting the acid with the alcohol and simultaneously distilling off the reaction water by means of an expelling agent.
  • the acid and alcohol should generally be used in a molar ratio such that one molecule of the at least trivalent carboxylic acid be available, per alcoholic hydrox' ylic group. In those cases in which the carboxylic acid itself contains one or more hydroxylic groups, it is also possible to esterify these groups. In this case, the quantitative ratio between acid and alcohol is accordingly greater than the number of the hydroxylic groups in the polyhydric alcohol.
  • the builders of the present invention offer technically very beneficial effects as they considerably delay the precipitation of calcium ions in the wash bath and additionally do form stable dispersions with hydrophilic pigment particles.
  • a further beneficial effect resides in the fact that they are readily biodegradable and thereby prevented from concentrating in natural waters.
  • the properties of the builders of the present invention can be evaluated, for example, by identifying their power of dispersing iron (lll) oxide, their power of binding calcium ions and their washing efficiency on washing an artificially soiled fabric. Suitable tests were made with the builders of the present invention and the results obtained were compared with the properties of conventional builders. The tests were more particularly carried out in the manner described in the following Examples.
  • A Sodium salt of glycerol-tri-citrate
  • B Sodium salt of sorbitol-hexa-citrate
  • C Sodium salt of pentaery-thritol-tetra-citrate were tested as to their dispersing effect in an aqueous suspension of 4 weight percent of dry, pulverized iron (lll) oxide with a particle size of less than 0.058 mm, and the effect produced was compared with that produced by conventional builders, namely:
  • the novel builders had a dispersing effect on hydrophilic dirt particles which was better than that of conventional builders. This results from both the smaller sedimentation volume and lower settling rate.
  • EXAMPLE 2 The builders specified in Example I were tested as to their power of binding calcium ions.
  • the power of binding calcium ions in an aqueous solution is defined by the number identifying the grams of calcium ions kept in solution under certain conditions, by 100 grams of builder. This number was determined by titration with sodium carbonate. More particularly, a 1 percent test solution with a pl-l-value of l0 was titrated with a 0.lN calcium chloride solution until turbidity commenced to occur. The following numerical values indicating the power of binding calcium ions were determined for the individual builders (Table 2).
  • the wash water had a hardness of 20 (German degrees of hardness) and a pH of 10.
  • the wash period was 30 minutes and the bath ratio, expressed by the ratio of material to be washed in kg to wash liquor in liter was 1:50, and the wash operation was carried out in the presence of steel balls.
  • the wash liquor contained as surface-active substances 0.45 g/liter of dodecylbenzene sulfonate,
  • the builders were used in the wash liquor in a concentration between 0.2 and 2 grams/liter of wash liquor.
  • the cleansing power quotient was calculated according to the following formula:
  • EXAMPLE 5 A mixture of 136 parts by weight of pentaerythritol and 768 parts by weight of anhydrous citric acid was subjected to azeotropic distillation with 250 parts by weight of toluene, which was continuously recycled, so as to remove 72 parts by weight of reaction water, which did form during the esterification. The mixture was allowed to cool and the toluene was separated from the ester. To produce the sodium salt, the acid crude ester was dissolved in 800 parts by weight of 40 percent sodium hydroxide solution and the resulting neutralization mixture was dried under vacuum. The product so obtained was used as builder C in Examples 1 to 4.
  • EXAMPLE 6 A mixture of 92 parts by weight of glycerol and 768 parts by weight of anhydrous citric acid was subjected to azeotropic distillation with 250 parts by weight of toluene, which was continuously recycled, so as to re move 72 parts by weight of reaction water, which did fonn during the esterification. The ester was cooled and the toluene was separated from the ester. To produce the sodium salt, the crude ester was neutralized with 800 parts by weight of 40 percent sodium hydroxide solution and the resulting neutralization mixture was dried under vacuum. The product so obtained was used as builder A in Examples 1 to 4.
  • a detergent composition comprising an ionic or nonionic surface active agent and, as a builder, the sodium salt of glycerol tricitrate.
  • the detergent composition according to claim 2 containing an alkali metal or ammonium salt of an acid selected from the group consisting of sulfuric acid, silicic acid, diand trisilicic acids, carbonic acid, boric acid, iminodiacetic acid, nitrilotriacetic acid, ethylene diamine tetracetic acid, an alkylene phosphonic acid, a hydroxyalkylene phosphonic acid or an aminoalkylene phosphonic acid, and additionally containing a perborate, stabilizer and activator, an optical brightener, carboxymethyl cellulose, magnesium silicate, a

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US291044A 1971-09-24 1972-09-21 Detergent composition containing, as a builder, the sodium salt of glycerol tricitrate Expired - Lifetime US3859224A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2147778A DE2147778C3 (de) 1971-09-24 1971-09-24 Wasch- und Reinigungsmittel mit einem Gehalt an wasserlöslichen Salzen von sauren Carbonsäureestern

Publications (1)

Publication Number Publication Date
US3859224A true US3859224A (en) 1975-01-07

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US291044A Expired - Lifetime US3859224A (en) 1971-09-24 1972-09-21 Detergent composition containing, as a builder, the sodium salt of glycerol tricitrate

Country Status (14)

Country Link
US (1) US3859224A (fi)
AT (1) AT322713B (fi)
BE (1) BE789135A (fi)
CA (1) CA1010058A (fi)
CH (1) CH577453A5 (fi)
DE (1) DE2147778C3 (fi)
DK (1) DK139438C (fi)
FI (1) FI53834C (fi)
FR (1) FR2153448B1 (fi)
GB (1) GB1397957A (fi)
IT (1) IT965461B (fi)
NL (1) NL7212868A (fi)
NO (1) NO139225C (fi)
SE (1) SE399906B (fi)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3919107A (en) * 1973-03-23 1975-11-11 Procter & Gamble Built detergent compositions containing dextrin esters of poly carboxylic acids
US4983315A (en) * 1989-08-10 1991-01-08 The Procter & Gamble Company N,N'-(1-oxo-1,2-ethanediyl)-bis(aspartic acid), salts and use in detergent compositions
US5508394A (en) * 1991-03-16 1996-04-16 Basf Aktiengesellschaft Citric esters of polyhydroxy compounds and use thereof in detergents

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1213330B (it) * 1986-08-28 1989-12-20 Rol Spa Tensioattivi derivati da idrossiacidi bi- o tri-carbossilici.
DE4142131A1 (de) * 1991-12-20 1993-06-24 Basf Ag Polykondensate aus butantetracarbonsaeure und polyhydroxyverbindungen und ihre verwendung in wasch- und reinigungsmitteln
US5531939A (en) * 1994-03-23 1996-07-02 Amway Corporation Concentrated glass and window cleaning composition and method of use

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3083188A (en) * 1959-06-22 1963-03-26 California Research Corp Detergent condensation polymers
US3692684A (en) * 1969-10-01 1972-09-19 Valter Sven Erwin Hentschel Detergent
US3717616A (en) * 1970-08-11 1973-02-20 Fmc Corp Polymers of 1-butene-2,3,4-tricarboxylic acid
US3763047A (en) * 1971-05-03 1973-10-02 Procter & Gamble Detergent compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3083188A (en) * 1959-06-22 1963-03-26 California Research Corp Detergent condensation polymers
US3692684A (en) * 1969-10-01 1972-09-19 Valter Sven Erwin Hentschel Detergent
US3717616A (en) * 1970-08-11 1973-02-20 Fmc Corp Polymers of 1-butene-2,3,4-tricarboxylic acid
US3763047A (en) * 1971-05-03 1973-10-02 Procter & Gamble Detergent compositions

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3919107A (en) * 1973-03-23 1975-11-11 Procter & Gamble Built detergent compositions containing dextrin esters of poly carboxylic acids
US4983315A (en) * 1989-08-10 1991-01-08 The Procter & Gamble Company N,N'-(1-oxo-1,2-ethanediyl)-bis(aspartic acid), salts and use in detergent compositions
US5508394A (en) * 1991-03-16 1996-04-16 Basf Aktiengesellschaft Citric esters of polyhydroxy compounds and use thereof in detergents

Also Published As

Publication number Publication date
NL7212868A (fi) 1973-03-27
DE2147778A1 (de) 1973-03-29
CH577453A5 (fi) 1976-07-15
DE2147778C3 (de) 1975-03-27
BE789135A (fr) 1973-03-22
IT965461B (it) 1974-01-31
DE2147778B2 (de) 1974-07-25
FI53834C (fi) 1978-08-10
AT322713B (de) 1975-06-10
GB1397957A (en) 1975-06-18
NO139225B (no) 1978-10-16
FR2153448B1 (fi) 1977-03-18
FR2153448A1 (fi) 1973-05-04
DK139438C (da) 1979-07-16
FI53834B (fi) 1978-05-02
DK139438B (da) 1979-02-19
NO139225C (no) 1979-01-24
CA1010058A (en) 1977-05-10
SE399906B (sv) 1978-03-06

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