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.

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• 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)

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• 1980
  • 1980-10-24 FR FR8022754A patent/FR2492819A1/fr active Granted
• 1981
  • 1981-10-07 US US06/309,503 patent/US4451384A/en not_active Expired - Fee Related
  • 1981-10-13 DE DE8181401576T patent/DE3166859D1/de not_active Expired
  • 1981-10-13 EP EP81401576A patent/EP0051508B1/fr not_active Expired

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