EP0051508B1 - Bleichmittelzusammensetzungen - Google Patents

Bleichmittelzusammensetzungen Download PDF

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Publication number
EP0051508B1
EP0051508B1 EP81401576A EP81401576A EP0051508B1 EP 0051508 B1 EP0051508 B1 EP 0051508B1 EP 81401576 A EP81401576 A EP 81401576A EP 81401576 A EP81401576 A EP 81401576A EP 0051508 B1 EP0051508 B1 EP 0051508B1
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EP
European Patent Office
Prior art keywords
amidine
bleaching composition
stable
bleaching
composition according
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
EP81401576A
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English (en)
French (fr)
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EP0051508A1 (de
Inventor
Jean Malafosse
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
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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
Publication of EP0051508A1 publication Critical patent/EP0051508A1/de
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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

Definitions

  • the present invention relates to bleaching compositions.
  • washing powders contain up to 40% of polyphosphates whose role is the sequestration of calcium Ca ++ from hard waters to avoid encrustation in textile fibers.
  • the use of washing powders at temperatures below 60 ° C could reduce their polyphosphate content and therefore this kind of water pollution which causes the eutrophication of lakes and rivers.
  • French Patent No. 1,232,554 describes the use of organic acylamides, in particular organic acetyl amide.
  • organic acylamides in particular organic acetyl amide.
  • tetracetylethylene diamine (CH 3 CO) 2 N - (CH 2 ) 2 -N (COCH 3 ) 2 or TAED, mentioned in French Patent No. 1,258,675
  • TAED tetracetylethylene diamine
  • French Patent No. 2,340,371 is a process for activating a peroxide-based bleaching agent, in which is incorporated into an aqueous medium: a peroxide-based bleaching agent, cyanamide and / or a metal cyanamide in an amount suitable for activating the peroxide, and optionally a metal compound of group II A, and the aqueous medium is maintained in an alkaline state, optionally by incorporating a buffer therein, with the proviso that if the constituent (b) is cyanamide and if component (c) is absent, the aqueous medium is maintained at a pH greater than 7.5.
  • This class of compounds which improves the efficiency, at ordinary or moderate temperature, of liquid or solid bleaching agents, such as hydrogen peroxide, alkaline perborates such as sodium perborate and alkaline percarbonates such as sodium percarbonate, carrying the group amidine, is represented by the general formula in which B denotes a hydrogen atom, a halogen, an alkyl, aryl, alkylaryl, cycloalkyl or oxyalkyl radical, such as 0 - CH 3 , a thioalkyl radical, such as S - CH 3 , an acyl radical, such as -CO - CH 3 , an inorganic acid radical such as S0 3 H, an organomineral radical such as CH 2 PO 3 H 2 ; R 1 , R 2 and R 3 denote a hydrogen atom, an alkyl, aryl, alkylaryl, cycloalkyl or acyl radical, such as acetyl -CO-CH 3 .
  • Amidines are generally strong, stable bases in the form of a mineral or organic acid salt, in formula I, HA symbolizes a mineral or organic monoacid; H represents the proton and A a monovalent anion; optionally a polyacid can be linked to one or more amidine molecules.
  • Haloformamidines in free form or in an acid salt represented by the formula: in which X is a halogen, in particular chlorine and bromine, HA denoting a mineral or organic acid, constitute a group of particularly advantageous activators of hydrogen peroxide or solid compounds releasing hydrogen peroxide at moderate temperature.
  • Chloroformamidine has a large activation capacity; it can be in the form of hydrochloride or nitrate, but we note the practical interest of sulfuric and phosphoric derivatives much more stable.
  • These amidines have the advantage of being more active than tetracetylethylene diamine (TAED), more easily manipulated than cyanamide CN 2 H 2 and much more soluble than calcium cyanamide CaCN 2 .
  • the haloformamidine salts can be used alone in pure form or as a mixture.
  • chloroformamidine sulfate is the activator of the series which combines very good activity with a minimum of side effects.
  • haloformamidine salts in particular chloroformamidine chloride, behave in aqueous solution like cyanamide generators; if this were the case, in bleaching at moderate temperature, the use of these salts would cause the same side effects with respect to the degradation of the cellulose. However, it has been demonstrated that these effects are greatly reduced, especially in the case of chloroformamidine sulfate.
  • amidine function by itself has a certain activity. It can be concluded that the mechanism of activation of peroxidic oxygen induced by haloformamidine salts would be different from that of cyanamide, and that in this case, these products do not act as cyanamide generators. The activity of the amidine function would be increased by the substitution, on the carbon carrying the amine and imine groups, of a strongly electro-negative element such as chlorine or bromine.
  • a stable solid bleaching composition constituted by the association of a pulverulent solid derivative and soluble in water, releasing hydrogen peroxide in aqueous alkaline solution, such as sodium perborate, sodium percarbonate, per-pyrophosphate, persilicate, urea peroxide, and all mineral or organic hydroperoxidates and an amidine from the class of compounds represented by formula 1 in an amount sufficient to activate the release of active oxygen at moderate temperature.
  • a stable liquid bleaching composition consisting of hydrogen peroxide and an amidine according to formula I, in an amount necessary for the activation of hydrogen peroxide at moderate temperature.
  • the bleaching compositions activated by an amidine can be used in the bleaching of any bleachable substance by means of a compound capable of releasing active oxygen.
  • the bleaching compositions according to the invention are specially suitable for household and industrial bleaching of natural, artificial and synthetic fibers at moderate temperature. In these laundering cases, the compositions of the invention are used in conjunction with detergents or detergents, such as a commercial washing powder free of bleaching agent.
  • the activation capacity of the amidine function is measured in the form of acetamidine hydrochloride according to the test protocol described except that the measurement of the whiteness is carried out with an electrosynthesis device and the result expressed in degrees of white and not as a percentage of stain removal; the results are obtained in the table below which show a significant activation effect of the amidine function at 60 ° C.
  • the percentage of stain removal obtained according to test protocol (a) is compared at 30 and 60 ° C., using chloroformamidine hydrochloride (CCF) and tetraacetyl ethylene diamine (TAED) as an activator.
  • CCF chloroformamidine hydrochloride
  • TAED tetraacetyl ethylene diamine
  • amidine group is designated by Am.
  • test protocol (c) the efficacy of acetamidine hydrochloride is evaluated by measuring the degree of white after washing; the results are obtained below.
  • SCF chloroformamidine sulfate
  • a succession of 10 washes is thus carried out at 60 ° C. and 90 ° C., then the degree of polymerization of the cellulose (DP) is measured.
  • the initial PD for the fabric designated commercially under the reference EMPA 301 (S27) is 2000.
  • chloroformamidine sulfate (SCF) used at the dose where it has a good activating efficiency only causes a slight reduction in the degree of polymerization of the cellulose; at the same dose, the sodium and calcium salts of cyanamide cause much higher degradation.
  • the detergent mixtures which differ only in the nature and the quantity of activator, are placed inside small bags of identical dimensions made with each of the dyed fabrics to be tested. These bags are placed in a beaker containing two liters of water at 50 ° C, and kept in immersion for two hours; after this time, the temperature of the bath is approximately 40 ° C .; then the small bags are unstitched and the fabrics rinsed and dried; the degradation of the dyes is then evaluated qualitatively relative to the control treated in the same way but with a detergent mixture without activator.
  • the fabric dyed with reactive Turquoise and having contained the mixture activated by CaCN z has some small white dots after tests.
  • the reactive brown is more sensitive than the two preceding ones but the color of the fabric which contained the mixture of detergent and perborate without activator is not modified; chloroformamidine sulfate only caused a weakening of the color which remained uniform and without a halo; monosodium cyanamide leads to a more marked weakening of the color and the formation of rather diffuse and not very visible halos and spots; the fabric of the bag having contained CaCN 2 is marked with a multitude of small yellow spots; It is the TAED which degrades this dye the most strongly: the tissues which contained this activator have taken on non-uniform light brown colorations tending to yellow.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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 (8)

1. Stabile Bleichmittelzusammensetzung, bestehend aus einem Bleichmittel, das in der Lage ist, Sauerstoff freizusetzen, und einem Aktivator, der in ausreichender Menge eingeführt ist, um das Bleichmittel zu aktivieren, dadurch gekennzeichnet, dass der Aktivator ein Amidin der formel
Figure imgb0017
ist, in der:
B ein Wasserstoffatom, ein Halogenatom, ein Alkyl-, Aryl-, Alkylaryl-, Cycloalkyl-, Thioalkyl-, Oxyalkyl-, Acyl-, Mineralsäure-, wie S03H-, oder organomineralischer Rest ist;
Ri, R2 und R3 jeweils ein Wasserstoffatom, einen Alkyl-, Aryl-, Alkylaryl-, Cycloalkyl- oder Acylrest bedeuten und
HA eine mineralische oder organische Monosäure oder den äquivalenten Teil einer Polysäure symbolisiert.
2. Stabile Bleichmittelzusammensetzung nach Anspruch 1, dadurch gekennzeichnet, dass das Amidin aus der Klasse der Halogenformamidine der Formel X - C (= NH) - NH2, HA ausgewählt ist, worin X ein Halogen ist.
3. Stabile Bleichmittelzusammensetzung nach Anspruch 2, dadurch gekennzeichnet, dass das aus der Gruppe der Halogenformamidine ausgewählte Amidin aus Chloroformamidin in der Form des Chlorids, Nitrats, Sulfats oder Phosphats alleine oder im Gemisch miteinander besteht.
4. Stabile Bleichmittelzusammensetzung nach Anspruch 2, dadurch gekennzeichnet, dass das Amidin, das in ausreichender Menge eingeführt ist, um das Bleichmittel zu aktivieren, aus dem Chloroformamidinsulfat
Figure imgb0018
besteht.
5. Feste stabile Bleichmittelzusammensetzung, bestehend aus einer Kombination eines festen pulverförmigen und wasserlöslichen Derivates, das in wässriger alkalischer Lösung Wasserstoffperoxid freisetzt, und eines Amidins nach einem der Ansprüche 1 bis 4 in ausreichender Menge, um bei normaler oder milder Temperatur die Freisetzung des Wasserstoffperoxids zu aktivieren.
6. Feste stabile Bleichmittelzusammensetzung nach Anspruch 5, dadurch gekennzeichnet, dass das Bleichmittel Natriumperborat ist.
7. Flüssige stabile Bleichmittelzusammensetzung, bestehend aus Wasserstoffperoxid und einem Amidin nach einem der Ansprüche 1 bis 4.
8. Feste stabile Bleichmittelzusammensetzung nach einem der Ansprüche 5 oder 6, dadurch gekennzeichnet, dass sie ausserdem Detergentien enthält.
EP81401576A 1980-10-24 1981-10-13 Bleichmittelzusammensetzungen Expired EP0051508B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8022754A FR2492819A1 (fr) 1980-10-24 1980-10-24 Activeur d'agent de blanchiment apte a liberer de l'oxygene actif
FR8022754 1980-10-24

Publications (2)

Publication Number Publication Date
EP0051508A1 EP0051508A1 (de) 1982-05-12
EP0051508B1 true EP0051508B1 (de) 1984-10-24

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Country Status (4)

Country Link
US (1) US4451384A (de)
EP (1) EP0051508B1 (de)
DE (1) DE3166859D1 (de)
FR (1) FR2492819A1 (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4847089A (en) * 1986-07-16 1989-07-11 David N. Kramer Cleansing and distinfecting compositions, including bleaching agents, and sponges and other applicators incorporating the same
US5686015A (en) * 1994-08-31 1997-11-11 The Procter & Gamble Company Quaternary substituted bleach activators
US5584888A (en) * 1994-08-31 1996-12-17 Miracle; Gregory S. Perhydrolysis-selective bleach activators
US5460747A (en) * 1994-08-31 1995-10-24 The Procter & Gamble Co. Multiple-substituted bleach activators
US5653910A (en) * 1995-06-07 1997-08-05 Lever Brothers Company, Division Of Conopco Inc. Bleaching compositions containing imine, hydrogen peroxide and a transition metal catalyst
DE19801049A1 (de) * 1998-01-14 1999-07-15 Clariant Gmbh Verwendung von Formamidinium-Salzen als Bleichaktivatoren
DE102006018345A1 (de) * 2006-04-19 2007-10-25 Henkel Kgaa Aufhell- und/oder Färbemittel mit Amidinen
DE102006028019A1 (de) * 2006-06-14 2007-12-20 Henkel Kgaa Aufhell- und/oder Färbemittel mit Acetamidinen
DE102007058846A1 (de) * 2007-12-05 2009-06-10 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel mit Amidinverbindungen und/oder Amidiniumbicarbonaten
CN108124902B (zh) * 2017-11-24 2020-12-01 中国人民解放军陆军防化学院 复配型低腐蚀性生化消毒剂及其使用方法和应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1915668A1 (de) * 1969-03-27 1970-10-08 Sueddeutsche Kalkstickstoff Verfahren zur Herstellung von Halogenformamidiniumhalogeniden

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2147401A (en) * 1933-11-09 1939-02-14 Gen Aniline Works Inc Water-soluble salts of amidines and derivatives thereof
US2211280A (en) * 1937-07-08 1940-08-13 Geigy Ag J R Water-soluble nitrogenous compounds and a process for their manufacture
US2816077A (en) * 1950-11-22 1957-12-10 Saint Gobain Method of cleaning deposits from hard surfaces
US2727922A (en) * 1953-03-25 1955-12-20 American Cyanamid Co Halo-formamidine salts and method of preparation
US2845458A (en) * 1956-05-21 1958-07-29 American Cyanamid Co C-chloro-n, n, n'-trimethylformamidine hydrochloride
US3487156A (en) * 1962-03-08 1969-12-30 Ciba Ltd Combating insects,their eggs,or acarids on plants
US3299081A (en) * 1963-09-13 1967-01-17 Merck & Co Inc Chemical processes for preparing nu-substituted amidines
US3445517A (en) * 1966-06-03 1969-05-20 Lilly Co Eli Aryl acetamidines
US3428681A (en) * 1966-09-01 1969-02-18 Ansul Co N-halotrichloroacetamidines
JPS5088044A (de) * 1973-12-01 1975-07-15
US3986973A (en) * 1975-10-24 1976-10-19 American Cyanamid Company Cyanoformates and cyanoformamides as bleach activators
US4202786A (en) * 1978-12-22 1980-05-13 Fmc Corporation Peroxygen bleaching and compositions therefor
US4210551A (en) * 1979-03-01 1980-07-01 Fmc Corporation Peroxygen bleaching and compositions therefor

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1915668A1 (de) * 1969-03-27 1970-10-08 Sueddeutsche Kalkstickstoff Verfahren zur Herstellung von Halogenformamidiniumhalogeniden

Also Published As

Publication number Publication date
EP0051508A1 (de) 1982-05-12
DE3166859D1 (en) 1984-11-29
FR2492819B1 (de) 1983-09-16
FR2492819A1 (fr) 1982-04-30
US4451384A (en) 1984-05-29

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