EP0356974B1 - Composition de nettoyage et de lavage - Google Patents

Composition de nettoyage et de lavage Download PDF

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Publication number
EP0356974B1
EP0356974B1 EP89115874A EP89115874A EP0356974B1 EP 0356974 B1 EP0356974 B1 EP 0356974B1 EP 89115874 A EP89115874 A EP 89115874A EP 89115874 A EP89115874 A EP 89115874A EP 0356974 B1 EP0356974 B1 EP 0356974B1
Authority
EP
European Patent Office
Prior art keywords
acid
weight
alanine
washing
salts
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
EP89115874A
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German (de)
English (en)
Other versions
EP0356974A3 (en
EP0356974A2 (fr
Inventor
Richard Dr. Baur
Charalampos Dr. Gousetis
Wolfgang Dr. Trieselt
Werner Dr. Bochnitschek
Alfred Dr. Oftring
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BASF SE
Original Assignee
BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to AT89115874T priority Critical patent/ATE92952T1/de
Publication of EP0356974A2 publication Critical patent/EP0356974A2/fr
Publication of EP0356974A3 publication Critical patent/EP0356974A3/de
Application granted granted Critical
Publication of EP0356974B1 publication Critical patent/EP0356974B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D3/33—Amino carboxylic acids

Definitions

  • the present invention relates to detergents and cleaning agents for aqueous applications containing 2 to 25% by weight as softener, based on the total weight of the detergent, ⁇ -alanine-N, N-diacetic acid or its alkali metal or ammonium salts.
  • Detergents and cleaning agents for aqueous applications are generally composed of a combination of various surface-active substances and other auxiliaries.
  • softeners should be mentioned primarily, i.e. Substances that are able to bind the hardness constituents of water, especially Ca++ and Mg++ cations.
  • Nitrilotriacetic acid and its salts have recently been used as a replacement for the phosphates, but these compounds are also not fully satisfactory since they deposit deposits of hardness, e.g. on textile fabrics, not preventing them effectively enough.
  • the present invention was therefore based on detergents and cleaning agents for aqueous applications, which contain softeners which are even more effective than nitrilotriacetic acid.
  • detergents and cleaning agents for aqueous applications which contain 2 to 25% by weight, based on the total weight of the detergent, of ⁇ -alanine-N, N-diacetic acid or its alkali metal or ammonium salts as softener.
  • Beta-alanine-N, N-diacetic acid is biodegradable and can be produced particularly advantageously by reacting acrylic acid with iminodiacetic acid in an aqueous medium in large quantities (see our recent application P 38 29 859.7 - OZ 0050/40154).
  • ⁇ -alanine-N, N-diacetic acid is its lower binding capacity for heavy metal ions such as Cu2+ or Cd2+ compared to nitrilotriacetic acid, such as a comparison of the corresponding equilibrium constants on pages 564 and 565 in Organic Sequestering Agents, A.E. Martell, J. Wiley & Sons, Hew York (1959). This reduces the likelihood that traces of undegraded ⁇ -alanine-N, N-diacetic acid will release heavy metal ions deposited in river sediments.
  • the ⁇ -alanine-N, N-diacetic acid or its alkali metal or ammonium salts are used in amounts of 2 to 25, preferably in amounts of 5 to 15,% by weight.
  • Their alkali metal salts are used with particular advantage, the trisodium salt being particularly preferred.
  • the salts of ⁇ -alanine-N, N-diacetic acid with basic compounds such as potassium hydroxide, ammonia or primary, secondary or tertiary aliphatic organic amines having 1 to 4 carbon atoms in the aliphatic radicals such as methylamine, dimethylamine or trimethylamine can also be used .
  • Detergents generally also contain 5 to 50% by weight of other softeners 6 to 25% by weight of surface-active compounds as washing-active substances 5 to 35 wt% bleach 0 to 60% by weight of substances essential for the consistency of the preparation and in minor amounts other auxiliary substances such as bleach stabilizers, bleach activators, enzymes, graying inhibitors, foam regulators, corrosion inhibitors, optical brighteners, solubilizers, fragrances or dyes.
  • Cleaning agents generally contain other essential ingredients 30 to 80 wt .-% dirt-disrupting components 3 to 20% by weight of other agents which are able to bind hardening agents 2 to 10% by weight of surface-active substances 1 to 5% by weight of anti-corrosion agent 0 to 60% by weight of substances essential for the consistency of the preparation and in minor quantities other auxiliary substances such as enzymes, foam regulators, fragrances, solubilizers or disinfectants.
  • the washing and cleaning agents according to the invention can contain alkaline substances such as sodium carbonate, sodium silicate and sodium phosphate or complexing agents of an inorganic nature such as e.g.
  • Suitable phosphorus-containing organic complexing agents are methane diphosphonic acid, propane-1,2,3-triphosphonic acid, butane-1,2,3,4-tetraphosphonic acid, polyvinylphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, 1-amino-1-phenyl -1,1-diphosphonic acid, aminotrimethylene triphosphonic acid, methylamino- or ethylaminodimethylene diphosphonic acid, ethylene diaminotetramethylene tetraphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, phosphonoacetic acid, phosphonopropionic acid, 1-phosphonoethane-1,2-dicarboxylic acid, 2-phosphonopropane-2,3- dicarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 2-phosphonobutane-2,3,4-tricarboxylic acid and copolymers of vinylphosphonic acid and
  • Suitable hydroxymono- or polycarboxylic acids are glycolic acid, lactic acid, malic acid, tartronic acid, methyltartronic acid, gluconic acid, glyceric acid, citric acid, tartaric acid and salicylic acid.
  • Aminocarboxylic acids to be preferably used are glycine, glycylglycine, alanine, asparagine, glutamic acid, aminobenzoic acid, iminodi- or triacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminetetraacetic acid, hydroxyethyl-ethylenediaminetriacetic acid, diethylenetriamine-pentaacetic acid and polymerisation of a carboxylic acid, e.g. of acetic acid, succinic acid or tricarballylic acid, and subsequent saponification, or by condensation of polyamines with a molecular weight of 500 to 10,000 with chloroacetic or bromoacetic salts.
  • a carboxylic acid e.g. of acetic acid, succinic acid or tricarballylic acid, and subsequent saponification, or by condensation of polyamines with a molecular weight of 500 to 10,000 with chloroacetic or bromoacetic salts
  • Zeolite 4A whose production is described in Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 24 on p. 120, is particularly suitable as an ion exchanger.
  • Suitable surfactants are those which contain at least one hydrophobic organic radical and one water-solubilizing ionic or nonionic group in the molecule.
  • the hydrophobic radical preferably consists of an aliphatic hydrocarbon radical with 8 to 26, preferably 10 to 22 and particularly preferably 12 to 18 C atoms or an alkyl aromatic radical with 6 to 18, preferably 8 to 16 C atoms in the alkyl group.
  • anionic surfactants are the sodium, potassium and ammonium salts of carboxylic acids, sulfonic acids and sulfuric acid monoesters with the specified number of carbon atoms.
  • the surfactants of the sulfonate type include, in particular, alkylbenzenesulfonates with 9 to 15 carbon atoms in the alkyl radical, alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products receives.
  • alkanesulfonates which can be obtained from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins.
  • More useful sulfonate type surfactants are the methyl or ethyl esters of ⁇ -sulfo fatty acids.
  • Suitable sulfate-type surfactants are the salts mentioned of the sulfuric acid monoesters of primary and secondary alcohols. Sulfated fatty acid monoglycerides and sulfated reaction products of 1 to 4 moles of ethylene oxide with primary or secondary fatty alcohols or alkylphenols are also suitable.
  • carboxylates come in particular the sodium salts of natural fatty acids, i.e. the usual soaps.
  • Preferred cationic surfactants are dialkyldimethylammonium chlorides such as distearyldimethylammonium chloride and imidazolinium salts of the 1-alkylamidoethyl-1-methyl-2-alkylimidazolinium methoxysulfate type.
  • Suitable amphoteric surfactants which contain both anion and cation-active groups in the same molecule in aqueous solution are compounds of the alkyl betaines or alkyl sulfobetaines type.
  • Addition products of 4 to 40, preferably 4 to 20 moles of ethylene oxide with 1 mole of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide are advantageously used as nonionic surfactants.
  • the addition products of 5 to 16 moles of ethylene oxide with primary or secondary alcohols with 8 to 18, preferably 12 to 18 C atoms, and with mono- or dialkylphenols with 6 to 14 C atoms in the alkyl radicals are particularly preferred.
  • non-or not completely water-soluble polyglycol ethers with 1 to 4 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.
  • water-soluble addition products of ethylene oxide containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups can be used as nonionic surface-active substances of propylene glycol, alkylenediamine-polypropylene glycol and alkylpolypropylene glycols with 1 to 10 carbon atoms in the alkyl chain, the polypropylene glycol chain probably functioning as the hydrophobic radical here.
  • Peroxy compounds such as sodium perborate tetrahydrate (NaBO2 ⁇ H2O2 ⁇ 3H2O), sodium perborate monohydrate (NaBO2 ⁇ H2O2), perborax (Na2B4O7 ⁇ 4H2O2) or peroxycarbonates such as Na2CO3 ⁇ 1.5H2O2 but also inorganic or organic active chlorine compounds such as e.g. Alkali hypochlorites or dichloro- and trichlorocyanuric acid into consideration.
  • water-soluble stabilizers are the organic complexing agents suitable as auxiliaries for binding the hardeners Ca2+ and Mg2+.
  • N-Diacylated and N, N'-tetraacylated amines such as N, N, N ', N'-tetraacetylmethylene diamine or ethylenediamine, N, N-diacetylaniline and N, N-diacetyl are preferred as activators for the bleaches which supply H2O2 in water p-toluidine, alkyl-N-sulfonyl-carbonamides such as N-methyl-N-mesyl-acetamide, N-methyl-N-mesylbenzamide, N-methyl-N-mesyl-p-nitrobenzamide and N-methyl-N-mesyl -p-methoxybenzamide, N-acylated cyclic hydrazides, acylated triazoles or urazoles such as, for example, monoacetylmaleic hydrazide, O, N, N-trisubstituted hydroxylamines such as O-benzoyl-N,
  • Graying inhibitors are auxiliaries which keep the loosened dirt suspended in the aqueous solution.
  • Water-soluble colloids of an organic nature are suitable for this.
  • the water-soluble salts of polymeric carboxylic acids, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch are preferred.
  • Water-soluble polyamides containing acidic groups and polyvinylpyrrolidone are also suitable.
  • Proteases carbohydrases, esterases, lipases, oxidoreductases, catalases, peroxidases, ureas, isomerases, lyases, transferases, desmolases or nucleases can be incorporated as enzymes.
  • enzymes obtained from bacterial strains or fungi such as Bacillus subtilis or Streptomyces griseus, in particular proteases or amylases, which are relatively resistant to alkali, per compounds and anionic surfactants and are still effective at temperatures up to 70 ° C.
  • Combinations of enzymes of different effects are preferably used, in particular combinations of proteases and amylases.
  • the textile detergents often advantageously contain optical brighteners.
  • diaminostilbenedisulfonic acid or its alkali metal salts such as e.g. the alkali metal salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid, for polyamide fibers 1,3-diaryl- 2-pyrazolines such as 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, for polyester fibers 2,5-di- (2-benzoxazolyl) -thiophene and 1,2-di- (5-methyl-2-benzoxazolyl) ) -ethylene used.
  • Alkaline detergents are generally added as a corrosion inhibitor with sodium and potassium silicates with a silicon dioxide / alkali oxide ratio ⁇ 1.
  • Dirt-disrupting components for cleaning agents are, in particular, alkaline substances such as sodium or potassium hydroxide, sodium or potassium carbonate, alkaline salts of orthophosphoric acid as well as sodium and potassium silicates with a silicon dioxide / alkali metal oxide ratio of 0.7 to 1.5 and organic and inorganic Acids such as hydrochloric acid, phosphoric acid, phosphoric acid esters, sulfuric acid, oxalic acid, citric acid, formic acid, amidosulfonic acid, adipic acid, glutaric acid or succinic acid are suitable.
  • alkaline substances such as sodium or potassium hydroxide, sodium or potassium carbonate, alkaline salts of orthophosphoric acid as well as sodium and potassium silicates with a silicon dioxide / alkali metal oxide ratio of 0.7 to 1.5
  • organic and inorganic Acids such as hydrochloric acid, phosphoric acid, phosphoric acid esters, sulfuric acid, oxalic acid, citric acid, formic acid, amidosulf
  • the detergents and cleaning agents according to the invention can be in powder or liquid form.
  • inorganic salts in particular sodium sulfate, are generally added, while water is the basis of most liquid preparations.
  • detergents which, based on the preparation as a whole, contain 10 to 30% by weight of zeolite and 5 to 15% by weight of the trisodium salt of ⁇ -alanine-N, N-diacetic acid.
  • the washing and cleaning agents according to the invention can be produced in a generally customary manner; e.g. the various constituents can be stirred into an aqueous slurry using water, which is then expediently dried in atomizing towers at 100.degree.
  • the detergents used in Examples B1 to B5 contained the trisodium salt of ⁇ -alanine-N, N-diacetic acid (ADA) to be used according to the invention, while in comparative examples V1 to V5 the trisodium salt of nitrilotriacetic acid (NTA ) has been used.
  • the detergents were out an aqueous slurry of its individual components by drying in atomizing towers at 100 ° C.
  • a measure of the deposits of hardening agents formed during the washing process is the proportion by weight of ash that remained when the washed test fabric was ashed.
  • Table 1 The composition of the detergents used and the proportions by weight of ash obtained are shown in Table 1. Table 1 also contains the exact ionic composition of the total hardness of the water used, which was also varied.

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  • 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)

Claims (4)

  1. Détergents ou agents de lessivage ou de nettoyage pour des exploitations aqueuses, contenant, à titre d'adoucisseur, 2 à 25% en poids, par rapport au poids total du détergent, de la composition de lessivage ou de nettoyage, d'acide bêta-alanine-N,N-diacétique, ou de leurs sels de métaux alcalins ou d'ammonium.
  2. Détergents ou agents de lessivage ou de nettoyage pour des exploitations aqueuses selon la revendication 1, qui contiennent, à titre d'adoucisseur, le sel trisodique de l'acide bêta-alanine-N,N-diacétique.
  3. Détergents suivant la revendication 1 ou 2, contenant de 10 à 30% en poids de zéolite et de 5 à 15% en poids du sel trisodique de l'acide bêta-alanine-N,N-diacétique.
  4. Utilisation de l'acide bêta-alanine-N,N-diacétique ou de ses sels de métaux alcalins ou d'ammonium, en proportions de 2 à 25% en poids de la préparation totale, à titre d'adjuvants dans des détergents, comme aussi des compositions ou agents de nettoyage ou de lessivage pour exploitations aqueuses.
EP89115874A 1988-09-02 1989-08-29 Composition de nettoyage et de lavage Expired - Lifetime EP0356974B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89115874T ATE92952T1 (de) 1988-09-02 1989-08-29 Wasch- und reinigungsmittel.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3829847A DE3829847A1 (de) 1988-09-02 1988-09-02 Wasch- und reinigungsmittel
DE3829847 1988-09-02

Publications (3)

Publication Number Publication Date
EP0356974A2 EP0356974A2 (fr) 1990-03-07
EP0356974A3 EP0356974A3 (en) 1990-04-11
EP0356974B1 true EP0356974B1 (fr) 1993-08-11

Family

ID=6362150

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89115874A Expired - Lifetime EP0356974B1 (fr) 1988-09-02 1989-08-29 Composition de nettoyage et de lavage

Country Status (9)

Country Link
US (1) US4997587A (fr)
EP (1) EP0356974B1 (fr)
JP (1) JPH02163200A (fr)
KR (1) KR960015370B1 (fr)
AT (1) ATE92952T1 (fr)
AU (1) AU620640B2 (fr)
CA (1) CA1326427C (fr)
DE (2) DE3829847A1 (fr)
ES (1) ES2042913T3 (fr)

Families Citing this family (20)

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Publication number Priority date Publication date Assignee Title
US5362412A (en) * 1991-04-17 1994-11-08 Hampshire Chemical Corp. Biodegradable bleach stabilizers for detergents
DE69226557T2 (de) * 1991-05-15 1999-05-06 Hampshire Chemical Corp., Lexington, Mass. Reinigungsmittel für harte Oberflächen, biologisch abbaubare Chelatbildner enthaltend
US5186856A (en) * 1992-06-02 1993-02-16 Basf Corp. Aqueous prewash stain remover compositions with efficacy on tenacious oily stains
US5221496A (en) * 1992-06-02 1993-06-22 Basf Corp. Aqueous prewash stain remover compositions with efficacy on tenacious oily stains
DE4319798A1 (de) * 1993-06-15 1994-12-22 Henkel Kgaa Geschirrspülmittel mit verringerter Belagsbildungsneigung
DE4319935A1 (de) * 1993-06-16 1994-12-22 Basf Ag Verwendung von Glycin-N,N-diessigsäure-Derivaten als Komplexbildner für Erdalkali- und Schwermetallionen
CZ285638B6 (cs) * 1994-10-07 1999-10-13 Eka Chemicals Ab Částice obsahující peroxysloučeninu a prostředek, který je obsahuje
WO1996011253A1 (fr) * 1994-10-07 1996-04-18 Eka Chemicals Ab Agent de blanchiment
DE4445820A1 (de) * 1994-12-21 1996-06-27 Hoechst Ag Verfahren zum Entwickeln bestrahlter, strahlungsempfindlicher Aufzeichnungsmaterialien
DE19543162A1 (de) * 1995-11-18 1997-05-22 Basf Ag Feste Textilwaschmittel-Formulierung aus anorganischen Buildern, Glycin-N,N-diessigsäure-Derivaten als organische Cobuilder sowie anionischen und nichtionischen Tensiden
JP3810847B2 (ja) * 1996-01-22 2006-08-16 花王株式会社 高密度粉末洗剤組成物
JP3810854B2 (ja) * 1996-01-22 2006-08-16 花王株式会社 高密度粉末洗剤組成物
GB2311536A (en) * 1996-03-29 1997-10-01 Procter & Gamble Dishwashing and laundry detergents
GB2311535A (en) * 1996-03-29 1997-10-01 Procter & Gamble Detergent compositions
GB2311537A (en) * 1996-03-29 1997-10-01 Procter & Gamble Rinse composition for dishwashers
GB2311538A (en) * 1996-03-29 1997-10-01 Procter & Gamble Detergent compositions
EP0834549A1 (fr) * 1996-10-07 1998-04-08 The Procter & Gamble Company Compositions de nettoyage
JP3290382B2 (ja) * 1997-07-18 2002-06-10 花王株式会社 粉末洗剤組成物
GB0522658D0 (en) 2005-11-07 2005-12-14 Reckitt Benckiser Nv Composition
GB0611206D0 (en) 2006-06-07 2006-07-19 Reckitt Benckiser Nv Detergent composition

Family Cites Families (9)

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Publication number Priority date Publication date Assignee Title
US2371623A (en) * 1943-02-06 1945-03-20 Lever Brothers Ltd Method of preserving soap and resulting product
DE2125249A1 (de) * 1971-05-21 1972-11-30 Chemische Werke Hüls AG, 4370 Mari Gerüstsubstanzen für Wasch- und Reinigungsmittel
CH621999A5 (fr) * 1976-06-24 1981-03-13 Ciba Geigy Ag
US4265777A (en) * 1980-04-17 1981-05-05 The Procter & Gamble Company Detergent compositions containing an aluminosilicate detergency builder and an unsaturated fatty acid soap
US4404128A (en) * 1981-05-29 1983-09-13 The Procter & Gamble Company Enzyme detergent composition
US4440663A (en) * 1981-09-14 1984-04-03 The Procter & Gamble Company Alkaline aqueous liquid detergent compositions containing normally unstable ester perfumes
GR77131B (fr) * 1982-03-10 1984-09-07 Procter & Gamble
US4690771A (en) * 1985-08-05 1987-09-01 Colgate-Palmolive Company Phosphate free nonaqueous liquid nonionic laundry detergent composition and method of use
DE3829859A1 (de) * 1988-09-02 1990-03-22 Basf Ag Verfahren zur herstellung von ss-alanindiessigsaeure oder ihren alkalimetall- oder ammoniumsalzen

Also Published As

Publication number Publication date
EP0356974A3 (en) 1990-04-11
ES2042913T3 (es) 1993-12-16
AU4095689A (en) 1990-03-08
KR900004924A (ko) 1990-04-13
KR960015370B1 (ko) 1996-11-11
US4997587A (en) 1991-03-05
CA1326427C (fr) 1994-01-25
DE3829847A1 (de) 1990-03-15
ATE92952T1 (de) 1993-08-15
DE58905235D1 (de) 1993-09-16
EP0356974A2 (fr) 1990-03-07
AU620640B2 (en) 1992-02-20
JPH02163200A (ja) 1990-06-22

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