EP0063503B1 - Aktivatorzusammensetzung für die Peroxidbleiche - Google Patents

Aktivatorzusammensetzung für die Peroxidbleiche Download PDF

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Publication number
EP0063503B1
EP0063503B1 EP82400410A EP82400410A EP0063503B1 EP 0063503 B1 EP0063503 B1 EP 0063503B1 EP 82400410 A EP82400410 A EP 82400410A EP 82400410 A EP82400410 A EP 82400410A EP 0063503 B1 EP0063503 B1 EP 0063503B1
Authority
EP
European Patent Office
Prior art keywords
cyanamide
acid
sequestering agent
phosphonic
type
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
Application number
EP82400410A
Other languages
English (en)
French (fr)
Other versions
EP0063503A1 (de
Inventor
Jacques Tourdot
Henry Carron
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.)
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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 LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Priority to AT82400410T priority Critical patent/ATE5975T1/de
Publication of EP0063503A1 publication Critical patent/EP0063503A1/de
Application granted granted Critical
Publication of EP0063503B1 publication Critical patent/EP0063503B1/de
Expired 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/3922—Cyanamides

Definitions

  • the present invention relates to an activating composition for bleaching at moderate temperature, in particular intended for detergents and detergents containing, as bleaching agent, peroxidized products capable of releasing active oxygen.
  • French patent 2,340,371 discloses a process for activating a peroxide-based bleaching agent, in which there is incorporated into an aqueous medium: (a) a peroxide-based bleaching agent, (b) cyanamide and / or a metallic cyanamide in an amount suitable for activating the peroxide, and optionally (c) a group II metal compound, and the aqueous medium is maintained in an alkaline state, optionally by incorporating a buffer, with the condition that if component (b) is cyanamide and if component (c) is absent, the aqueous medium is maintained at a pH greater than 7.5.
  • the degradation observed is particularly accentuated when the washing temperature exceeds 60 ° C, and especially when it reaches 90 ° C; the temperature of 90 ° C. is a relatively frequent case when it is an all-temperature detergent. At 90 ° C, the depolymerization is such that it causes a degradation likely to accelerate the wear of the cotton linen during successive washes.
  • a protective composition has been found which significantly reduces the degradation effect of cellulosic fibers by cyanamide and its derivatives, while in no way limiting the effectiveness of the bleaching obtained by activation of the compounds peroxidized by cyanamide and its derivatives.
  • This protective composition which has no adverse effect on the bleaching results, makes it possible to reduce the aggressiveness of cyanamide to that of ethylenediaminetetraacetyl TAED.
  • TAED ethylenediaminetetraacetyl
  • With the new composition obtaining equivalent bleaching results and the degree of polymerization was found possible between TAED at 0.6 g / liter and calcium cyanamide CaNCN at 0.2 g / liter.
  • the activating composition for bleaching contains an activator of the cyanamide type and its derivatives, alone or in a mixture for activating bleaching by means of peroxidized products at moderate temperature; it also contains a ternary protective mixture with a synergistic effect comprising a magnesium silicate in the finely divided powder state, a sequestering agent of the acetic type, preferably organoacetic, and a sequestering agent of the phosphonic type, preferably organophosphonic.
  • the ternary protective mixture provides the most effective protection although the concentration of each component is lower, either to each component used alone, or to the binary mixtures thereof, consequently, the combination of the three components has a clearly marked synergistic effect.
  • Acetic sequestrants are nitrilotriacetic, hexamethylenediaminetetraacetic, diaminetetraacetic ethylene and preferably diethylenetriaminepentaacetic.
  • the phosphonic sequestrants are nitri-methylene-phosphonic, ethylenediamine-tetramethylene-phosphonic, preferably diethylene triaminopentamethylene-phosphonic.
  • the acetic and phosphonic sequestrants are chosen in the form of free acid or of alkali or alkaline earth metal salts.
  • the activating composition constituted by calcium cyanamide and / or its derivatives and the protective mixture comprising magnesium silicate precipitated in the form of finely divided powder, and in the form of a magnesium complex, the diethylenetriaminepentaacetic acid and diethylenetriaminepentamethylenephosphonic acid.
  • the cyanamide derivatives are the cyanamide of alkali or alkaline earth metals, preferably calcium cyanamide, magnesium cyanamide or sodium cyanamide.
  • the activating composition is intended to be incorporated into detergents, in particular household powder detergents for washing laundry and its bleaching at moderate temperature.
  • the activating composition it is important for the effectiveness of the activating composition that it is dispersed in a homogeneous manner in the powdered detergent and in a form which allows its homogeneous distribution in the detergent bath.
  • the sparingly soluble compounds of cyanamide, in particular calcium cyanamide it is advantageous to use a powder of less than 100 ⁇ m.
  • the finely divided calcium cyanamide powder is homogenized using a conventional powder mixer, in the precipitated magnesium silicate powder already containing the acetic sequestrant and the phosphonic sequestrant.
  • the phosphonic sequestrant and the acetic sequestrant are incorporated into the magnesium silicate, preferably during the manufacturing process of the magnesium silicate; they can also be incorporated after its manufacture.
  • the activating composition comprises a protective mixture based on precipitated magnesium silicate in which is incorporated in the form of a magnesium complex of 3 to 30%, preferably 5 to 15%, of an acetic type sequestrant and of 5 to 50%, preferably 8 to 25% of a phosphonic type sequestrant, the proportions being indicated by weight relative to the magnesium silicate.
  • the activating composition contains from 20 to 150%, preferably 30 to 100% by weight, of activator of the cyanamide type and derivatives relative to the protective mixture representing 100%.
  • a series of 13 bleaching tests carried out with protective products or compositions is carried out under the same conditions as test No. 6 in Table 1, that is to say with 0.3 g / l of cyanamide.
  • test 27 once again reveals that the ternary mixture of magnesium silicate + diethylenetriaminepentaacetic acid (Na) + diethylenetriaminepentamethylenephosphonic acid, has the best protective effect although each component is used at a concentration equal to or less than that of the tests in which it is used alone or in binary mixture.
  • the degree of polymerization of the cotton treated in the presence of the ternary mixture (1900) is identical to that in test No. 4 of Table 1 with 0.6 g / I of ethylenediaminetetraacetyl (TAED).
  • TAED ethylenediaminetetraacetyl
  • This patent cites a stabilizing composition consisting of a 36.1% solution of 1 mole of nitrilotriacetic acid (NTA), 0.47 mole of magnesium salt, originating from a soluble salt, for example magnesium sulfate and 0.3 mole of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP).
  • NTA nitrilotriacetic acid
  • HEDP 1-hydroxyethylidene-1,1-diphosphonic acid
  • the degradation of the cellulose was determined on EMPA 301 fabric, reference fabric supplied by the Federal Laboratory for Materials Testing and Research Institute of St GALL in SWITZERLAND.
  • the initial degree of polymerization (PD) of this fabric was 2400.
  • 15 washes were carried out in an AHIBA machine of 15 g of EMPA 301 tissue in 600 ml of washing bath, the compositions of which are listed in Table 4 below.
  • the total duration of each wash is 40 min, including 30 min to rise from 25 to 90 ° C, and 10 min at the temperature of 90 ° C.
  • the samples are rinsed under the usual conditions between each wash.
  • Table 7 shows that doubling the dose of use of the protective mixture of the prior art does not make it possible to approach the effect of the new protective mixture. The comparison is made between test B 2 (DP 1120) and tests B 3 (DP 2120), B 4 and B 5 (1350 and 1550).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Dental Preparations (AREA)

Claims (11)

1. Aktivierungsmittel zum Bleichen mit Hilfe von Peroxidprodukten mit einem Gehalt an Aktivator vom Cyanamid- und Cyanamidderivattyp, dadurch gekennzeichnet, dass es ausserdem ein ternäres Schutzgemisch enthält, das ein im Zustand eines feinteiligen Pulvers ausgefälltes Magnesiumsilikat, einen Komplexbildner vom Essigsäuretyp und einen Komplexbildner vom Phosphonsäuretyp enthält.
2. Aktivierungsmittei zum Bleichen nach Anspruch 1, dadurch gekennzeichnet, dass der Essigsäurekomplexbildner vom Organoessigsäuretyp und der Phosphonsäurekomplexbildner vom Organophosphonsäuretyp ist.
3. Aktivierungsmittel zum Bleichen nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Essigsäurekomplexbildner Nitrilotriessigsäure, Hexamethylendiamintetraessigsäure, Äthylendiamintetraessigsäure oder Diäthylentriaminpentaessigsäure in der Form der freien Säure oder der Alkali- oder Erdalkalimetallsalze und der Phosphonsäurekomplexbildner Nitrilotrimethylenphosphonsäure, Äthylendiamintetramethylenphosphonsäure und Diäthylentriaminopentamethyienphosphonsäure in der Form der freien Säure oder der Alkali- oder Erdalkalimetallsalze ist.
4. Aktivierungsmittel zum Bleichen nach Anspruch. 1 oder 2, dadurch gekennzeichnet, dass der Essigsäurekomplexbildner Diäthylentriaminpentaessigsäure in der Form der freien Säure oder der AtkaH- oder Erdalkalimetallsalze ist und der Phosphonsäurekomplexbildner Diäthylentriaminopentamethylenphosphonsäure in der Form der freien Säure oder der Alkali- und Erdalkalimetallsalze ist.
5. Aktivierungsmittel zum Bleichen nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Derivate des Cyanamids Alkali-oder Erdalkalimetallcyanamid, Calciumcyanamid, Magnesiumcyanamid und Mononatriumcyanamid sind.
6. Aktivierungsmittel zum Bleichen nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass es als Aktivator Calciumcyanamid und ein Schutzgemisch, das aus im Zustand eines feinteiligen Pulvers ausgefälltem Magnesiumsilikat und Diäthylentriaminpentaessigsäure und Diäthylentriaminpentamethylenphosphonsäure in der Form eines Magnesiumkomplexes besteht, enthält.
7. Aktivierungsmittel zum Bleichen nach einem der Ansprüche 1 bis 6, dessen Derivat von Cyanamid wenig löslich ist, wie Calciumcyanamid, dadurch gekennzeichnet, dass die Korngrössenverteilung des Calciumcyanamids kleiner als 100 um ist.
8. Aktivierungsmittel zum Bleichen nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass das Schutzgemisch auf der Basis .von Magnesiumsilikat in der Form eines Magnesiumkomplexes 3 bis 30% eines Komplexbildners vom Essigsäuretyp und 5 bis 50% eines Komplexbildners vom Phosphonsäuretyp enthält, wobei die Prozentsätze als Gewichtsprozentsätze, bezogen auf Magnesiumsilikat, angegeben sind.
9. Aktivierungsmittel zum Bleichen nach Anspruch 8, dadurch gekennzeichnet, dass das Schutzgemisch auf Basis von Magnesiumsilikat ausserdem in der Form eines Magnesiumkomplexes 5 bis 15% eines Komplexbildners vom Essigsäuretyp und 8 bis 25% eines Komplexbildners vom Phosphonsäuretyp enthält, wobei die Prozentsätze als Gewichtsprozentsätze, bezogen auf Magnesiumsilikat, angegeben sind.
10. Aktivierungsmittel zum Bleichen nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass das Mittel 20 bis 150 Gew.-%, vorzugsweise 30 bis 100 Gew.-%, des Aktivators vom Cyanamid- und Cyanamidderivattyp, bezogen auf das 100% bedeutende Schutzgemisch, enthält.
11. Laugebad, das das Aktivierungsmittel zum Bleichen nach einem der Ansprüche 1 bis 10 benutzt, dadurch gekennzeichnet, dass die Konzentration dieses Mittels in dem Laugebad zwischen 0,2 und 1 g/I, vorzugsweise zwischen 0,4 und 0,8 gjlliegt.
EP82400410A 1981-04-09 1982-03-09 Aktivatorzusammensetzung für die Peroxidbleiche Expired EP0063503B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82400410T ATE5975T1 (de) 1981-04-09 1982-03-09 Aktivatorzusammensetzung fuer die peroxidbleiche.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8107107 1981-04-09
FR8107107A FR2503746A1 (fr) 1981-04-09 1981-04-09 Composition activante pour le blanchiment au moyen de produits peroxydes

Publications (2)

Publication Number Publication Date
EP0063503A1 EP0063503A1 (de) 1982-10-27
EP0063503B1 true EP0063503B1 (de) 1984-01-25

Family

ID=9257191

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82400410A Expired EP0063503B1 (de) 1981-04-09 1982-03-09 Aktivatorzusammensetzung für die Peroxidbleiche

Country Status (11)

Country Link
US (1) US4392975A (de)
EP (1) EP0063503B1 (de)
JP (1) JPS57179300A (de)
AT (1) ATE5975T1 (de)
CA (1) CA1180158A (de)
DE (1) DE3260035D1 (de)
DK (1) DK152518C (de)
FI (1) FI70434C (de)
FR (1) FR2503746A1 (de)
GR (1) GR76464B (de)
NO (1) NO153655C (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3304848A1 (de) * 1983-02-12 1984-08-16 Henkel KGaA, 4000 Düsseldorf Organische cyanamidverbindungen als aktivatoren fuer anorganische perverbindungen
DE3320726A1 (de) * 1983-06-09 1984-12-13 Henkel KGaA, 4000 Düsseldorf Wasch- und reinigungsmittel mit einem gehalt an acylcyanamidsalzen
NZ221505A (en) * 1986-09-09 1989-08-29 Colgate Palmolive Co Liquid detergent compositions with peroxygen bleach and calcium cyanamide activator
US5620563A (en) * 1994-10-31 1997-04-15 Pulp Paper Res Inst Process for delignification and bleaching of chemical wood pulps with hydrogen peroxide and a dicyandiamide activator
US5720897A (en) * 1995-01-25 1998-02-24 University Of Florida Transition metal bleach activators for bleaching agents and detergent-bleach compositions
US6046375A (en) * 1996-04-12 2000-04-04 The Board Of Trustees University Of Main System Degradation and protection of organic compounds mediated by low molecular weight chelators
US5929020A (en) * 1997-01-21 1999-07-27 Henkel Corporation Process for chelating divalent metal ions in alkaline detergent formulations
GB0901207D0 (en) * 2009-01-26 2009-03-11 Innospec Ltd Chelating agents and methods relating thereto

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3795625A (en) * 1971-06-03 1974-03-05 Monsanto Co Bleaching compositions
JPS5313198B2 (de) * 1973-04-26 1978-05-08
GB1565807A (en) * 1975-12-18 1980-04-23 Uilever Ltd Process and compositions for cleaning fabrics
US4086175A (en) * 1976-02-09 1978-04-25 Shell Oil Company Activated bleaching process and compositions therefor
US4025453A (en) * 1976-02-09 1977-05-24 Shell Oil Company Activated bleaching process and compositions therefor
US4179390A (en) * 1976-10-06 1979-12-18 The Procter & Gamble Company Laundry additive product
US4279769A (en) * 1978-03-20 1981-07-21 Kao Soap Co., Ltd. Bleaching composition
NO150445C (no) * 1979-04-06 1984-10-17 Unilever Nv Bleke- og vaskepreparat

Also Published As

Publication number Publication date
JPH0354159B2 (de) 1991-08-19
FI70434C (fi) 1986-09-19
NO821186L (no) 1982-10-11
FR2503746B1 (de) 1983-06-24
FR2503746A1 (fr) 1982-10-15
EP0063503A1 (de) 1982-10-27
FI70434B (fi) 1986-03-27
US4392975A (en) 1983-07-12
CA1180158A (fr) 1985-01-02
GR76464B (de) 1984-08-10
DK152518C (da) 1988-08-01
NO153655C (no) 1986-05-07
DK159782A (da) 1982-10-10
FI821227L (fi) 1982-10-10
NO153655B (no) 1986-01-20
FI821227A0 (fi) 1982-04-07
DK152518B (da) 1988-03-07
JPS57179300A (en) 1982-11-04
DE3260035D1 (en) 1984-03-01
ATE5975T1 (de) 1984-02-15

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