US3892674A - Builders for detergent and cleansing agents - Google Patents

Builders for detergent and cleansing agents Download PDF

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Publication number
US3892674A
US3892674A US291043A US29104372A US3892674A US 3892674 A US3892674 A US 3892674A US 291043 A US291043 A US 291043A US 29104372 A US29104372 A US 29104372A US 3892674 A US3892674 A US 3892674A
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United States
Prior art keywords
acid
builders
builder
detergent
carboxylic acid
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Expired - Lifetime
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US291043A
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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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Publication date
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Publication of US3892674A publication Critical patent/US3892674A/en
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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 and the esters being the product obtained by the reaction of bivalent 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. bo-
  • 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 tetf racarboxylic acids. have more particularly been used heretofore.
  • the use of these substances as builders has 5 been found to entail disadvantages which reside in the fact that they are insufficiently biodegradable or have an unsatisfactory power for dispersing hydrophilic dirt.
  • the cation of the water-soluble salts of acid carboxylic acid esters preferably is an alkali or ammonium ion.
  • the ester-type anion is based on a bivalent carboxylic acid. which has between 2 and 6 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 oxalic acid. malonic acid. maleic acid. succinic acid. oxydiacetic acid, tartaric acid. malic acid or itaconic acid. and the alcoholic component should be selected from the group consisting of glycerol. erythritol. pentaerythritol. mannitol. sorbitol or a sugar alcohol having between 4 and 6 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 ad-' dends.
  • the builder may generally be used in a proportion substantially between 10 and 80 weight percent. preferably between l5 and 60 weight percent, based on the dry sub- 5 phates or their substitutes specified hereinabove.
  • Detergent and cleansing agents prepared in accordance with the present invention give a pH-value between 8 Q and I2 in the aqueous medium of the wash bath.
  • the addends. which may be present together with the ion-active and/or non-ionic tensides in the detergents comprise substances. such as alkali metal or ammonium salts of sulfuric acid. silicic acid. diand trisilicic acids. carbonic acid. boric acid. iminodiacetic acid. nitrilotriacetic acid. ethylene diamine tetracetic acid. al-
  • a 3 kylene 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.
  • 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 alcohols and simultaneously removing the reaction water by means of an expelling agent.
  • the acid and alcohol should generally be used in a molar j ratio such that one molecule of the bivalent carboxylic acid be available. per alcoholic hydroxylic 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 esterification it is necessary and critical to remove from the esterification mixture one mol of reaction water. per mol of carboxylic acid used.
  • the resulting acid carboxylic acid esters are transformed into water-soluble salts by the addition of stoichiometric proportions of alkali.
  • 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 wtih the properties of conventional builders. The tests were more particularly carried out in the manner described in the following Examples.
  • EXAMPLE 1 The following novel builders: A: Sodium salt of glycerol-tri-oxydiacetic acid B: Sodium salt of sorbitol-hexa-oxydiacetic acid C: Sodium salt of glycerol-tri-malic acid 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: D: Oxydiacetic acid E: Malic acid F: Glycerol G: Diacetin H: Sodium salt of citric acid ethyleneglycol ester.
  • A Sodium salt of glycerol-tri-oxydiacetic acid
  • B Sodium salt of sorbitol-hexa-oxydiacetic acid
  • C Sodium salt of glycerol-tri-malic acid were tested as to their dispersing effect in an aqueous suspension of
  • Each ofthe builder was used in the suspension in a concentration of 0.16 weight percent. based on the aqueous solution.
  • the settling time of the iron oxide part cles in cc mixing cylinders. and the volume of sedlmentation after 24 hours were determined in each cast. as an index of the dispersing effect.
  • the suspension had a pH-value of 10. The results obtained are summarized in Table 1 below.
  • 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 1 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 lOO grams of builder. This number is determined by titration with sodium carbonate. More particularly. a 1 percent test solution with a pH-value of 10 was titrated with a 0.1N 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 tests were made on standard cotton fabrics soiled with Krefeld" dirt in a Launder-O-meter" at a wash bath temperature of C.
  • Standard fabrics soiled with Krefeld dirt have been defined by Kurt Lindner in the book entitled: Tenside. Textilangesmit- 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:
  • the builders used in Examples 1 to 4 were not specifically purified during preparation. In other words. the reaction products (crude products) directly obtained following termination of the esterification of the polyvalent carboxylic acid with the polyhydric alcohol and following neutralization of the resulting esterification mixtures, were used. This is further illustrated in the following Examples.
  • EXAMPLE 5 A mixture of 92 parts by weight of glycerol and 402 parts by weight of oxydiacetic acid was subjected to azeotropic distillation with 250 parts by weight of toluene. which was continuously recycled. so as to remove 54 parts by weight of reaction water, which did form during the esterification. The mixture was cooled and the toluene was separated from the ester layer. To produce the sodium salt, the acid crude ester was neutralized with 300 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.
  • EXAMPLE 6 A mixture of 182 parts by weight of sorbitol and 804 parts by weight of oxydiacetic acid was subjected to azeotropic distillation with 250 parts by weight of tolu ene, which was continuously recycled. so as to remove 180 parts by weight of reaction water. The ester was cooled and the toluene was separated from the ester I layer. To produce the sodium salt. the crude ester was neutralized with 600 parts by weight of 40 percent sodium solution and the resulting neutralization mixture was dried under vacuum. The product so obtained was used as builder B in Examples 1 to 4.
  • the builder being a substance selected from the group consisting of the sodium salt of glycerol-trioxydiacetic acid, the sodium salt of sorbitol-hexaoxydiacetic acid and the sodium salt of glycerol trimalic acid, the builder being present in a proportion between 10 and weight perally contains an alkali metal polyphosphate builder.

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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)
US291043A 1971-09-24 1972-09-21 Builders for detergent and cleansing agents Expired - Lifetime US3892674A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2147780A DE2147780C3 (de) 1971-09-24 1971-09-24 Wasch- und Reinigungsmittel mit einem Gehalt an wasserlöslichen Salzen von sauren Karbonsäureestern

Publications (1)

Publication Number Publication Date
US3892674A true US3892674A (en) 1975-07-01

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Application Number Title Priority Date Filing Date
US291043A Expired - Lifetime US3892674A (en) 1971-09-24 1972-09-21 Builders for detergent and cleansing agents

Country Status (14)

Country Link
US (1) US3892674A (no)
AT (1) AT322712B (no)
BE (1) BE789134A (no)
CA (1) CA967447A (no)
CH (1) CH577450A5 (no)
DE (1) DE2147780C3 (no)
DK (1) DK139437C (no)
FI (1) FI55215C (no)
FR (1) FR2153449B1 (no)
GB (1) GB1392764A (no)
IT (1) IT965462B (no)
NL (1) NL7212867A (no)
NO (1) NO139226C (no)
SE (1) SE399717B (no)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4021359A (en) * 1973-10-11 1977-05-03 Mobil Oil Corporation Detergent builders for washing and cleaning compositions
US4029590A (en) * 1973-08-22 1977-06-14 Fmc Corporation Dextrin carboxylates and their use as detergent builders

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4524009A (en) * 1984-01-31 1985-06-18 A. E. Staley Manufacturing Company Detergent builder
IT1213330B (it) * 1986-08-28 1989-12-20 Rol Spa Tensioattivi derivati da idrossiacidi bi- o tri-carbossilici.
DE4402051A1 (de) * 1994-01-25 1995-07-27 Henkel Kgaa Gerüststoff für Wasch- oder Reinigungsmittel
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
US3655645A (en) * 1966-12-02 1972-04-11 Raffinerie Tirlemontoise Sa Esters of alkoxylated saccharides
US3758419A (en) * 1971-04-28 1973-09-11 Shell Oil Co Cleansing and laundering compositions
US3761412A (en) * 1970-05-01 1973-09-25 Fmc Corp Polyelectrolyte builder and detergent compositions
US3763231A (en) * 1971-08-06 1973-10-02 Milchem Inc Detergent builder composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3655645A (en) * 1966-12-02 1972-04-11 Raffinerie Tirlemontoise Sa Esters of alkoxylated saccharides
US3761412A (en) * 1970-05-01 1973-09-25 Fmc Corp Polyelectrolyte builder and detergent compositions
US3758419A (en) * 1971-04-28 1973-09-11 Shell Oil Co Cleansing and laundering compositions
US3763231A (en) * 1971-08-06 1973-10-02 Milchem Inc Detergent builder composition

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4029590A (en) * 1973-08-22 1977-06-14 Fmc Corporation Dextrin carboxylates and their use as detergent builders
US4021359A (en) * 1973-10-11 1977-05-03 Mobil Oil Corporation Detergent builders for washing and cleaning compositions

Also Published As

Publication number Publication date
CA967447A (en) 1975-05-13
BE789134A (fr) 1973-03-22
AT322712B (de) 1975-06-10
SE399717B (sv) 1978-02-27
DE2147780A1 (de) 1973-03-29
NO139226B (no) 1978-10-16
DK139437C (da) 1979-07-16
FI55215C (fi) 1979-06-11
DK139437B (da) 1979-02-19
NO139226C (no) 1979-01-24
DE2147780C3 (de) 1975-03-27
FR2153449A1 (no) 1973-05-04
IT965462B (it) 1974-01-31
FI55215B (fi) 1979-02-28
GB1392764A (en) 1975-04-30
NL7212867A (no) 1973-03-27
DE2147780B2 (de) 1974-07-25
FR2153449B1 (no) 1977-04-01
CH577450A5 (no) 1976-07-15

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