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
  • C11D3/3947—Liquid compositions
• • 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

Definitions

• the invention relates to prevailingly liquid detergent and/or bleaching compositions, containing low molecular weight tertiary amines, for example triethanolamine; the invention relates in particular to water-based liquid laundry detergent compositions usually utilized for automatic washing machines, as are described for example in British Patent No. 2,197,340.
• the water-based liquid detergents for laundry washing machines at present in commerce have compositions, which can be substantially divided into two classes:
• the invention rel strictlyates to liquid detergent and/or bleaching com­positions containing at least a low molecular weight tertiary amine oxide, selected from the group consisting of:
• the neutralization of the acid components of the liquid de­tergent(fatty acids, alkylbenzenesulphonic acid etc.), which is usually carried out with TEA, can be completed, in the presence of TEAO, with NaOH or, even better, with KOH, with­out jeopardizing the solution homogeneity; the use of potash is preferred to caustic soda as it allows a higher stability of the liquid detergent compositions at lower temperatures. If amine is not fully replaced by N-oxide, the alkali amount can be advantageously reduced.
• the composition of the invention may thus additionally contain a low molecular weight tertiary amine.
• N-oxides are obtainable for example by oxidation of the corresponding tertiary amines with hydrogen peroxide. Said oxidation may occur with H2O2 either substoichiometric amounts or in excess.
• MnO2 has been suggested to eliminate the residual H2O2 by MnO2, which is considered an excellent agent for H2O2 decomposition but which does not cause N-oxide damage.
• MnO2 is not possible in practice. It would require careful filtration, which involves a complex operation. However even after a careful filtration, small traces of MnO2 remain in the N-oxide and by consequence also in the detergents containing it. These residues would be able to exert their decomposition effect also on the bleaching peroxides which are added to the liquid detergents during the washing cycle thereby drastically reducing the performance of the peroxides.
• the applicant has noted that if the hydrogen peroxide amount is maintained below the stoichiometric values, it is possible to obtain a practically H2O2-free product, immediately ready for use in the detergents formulations and/or for water evaporation, if a concentration N-oxide is desired.
• the thus obtained product contains low amounts of converted tertiary amine which do not impair at all the bleaching power and, on the contrary, make the detergent formulability easier.
• a H2O2 amount ranging from 70% to 99% of the stoichiometric value is recommended in the amine oxidation step.
• the presence of unconverted amine furthermore balances the lower alkalinity of the corresponding N-oxide, and the consequent lower neutralizing power, with respect to the fatty acids, promotes the detergent homogeneity and reduces the amount of alkali necessary to bring the composition to a prefixed pH value.
• TAA triethanolamine
• PABCO triethylenediamine
• N-methylmorpholine N-methylpiperidine
• Oxidation of tertiary amines with hydrogen peroxide can be conducted on the amines as such, on the salts thereof with fatty acids (TEA soaps) or with other acid compounds, or also on a liquid detergent which contains the amine, by adding H2O2 to said detergent.
• fatty acids TEA soaps
• H2O2 fatty acids
• the detergent composition may contain other components conventional for non-built liquid detergents.
• the detergents are prevailing liquids, that is they may contain suspended solids but have a continuous liquid phase.
• Residual H2O2 was allowed to spontaneously decompose in the course of a few days, and subsequently the product was dried by evaporation of water (in a rotary evaporator under vacuum) at a temperature not exceeding 40°C. A dry residue of about 165 g, corresponding to a practically quantitative yield, was obtained.
• Example 1 was repeated reducing the amount of hy­drogen peroxide (at 33.8%) to 103 g, an amount equivalent to about 98% of the stoichiometric value; the final product was analyzed for its H2O2 content by means of the paper method (PEROXID-TEST; MERKOQUANT 1011) and the analysis result was negative. No appreciable traces of residual H2O2 were found.
• ex­ample 1 In order to obtain a more concentrated TEAO, without resorting to one or more water evaporation steps, ex­ample 1 was repeated, eliminating the 300 g of water (added in example 1 as a reaction solvent) and directly re­acting TEA with H2O2.
• 111g of H2O2 at 33.8% by weight were added at 55°C to 150 g of TEA, whereafter the temperature was maintained at 55°C for 2 hours.
• An aque­ous solution at about 67% by weight of TEAO was thus obtained, this value being much higher than the N-oxide concentration obtained in example 1 (29%).
• a "built” type com­mercial product product II
• product III non-built type commercial product
• a laboratory-reproduced formulate hav­ing a composition similar to said product III (as to the most important components,TEA included) and an analogous formul­ate, also reproduced in laboratory, in which TEA had been replaced by N-oxide (TEAO) were compared; the last two formulates are indicated in Table 1 as III/TEA and III/TEAO, respectively.
• Formulates III and III/TEA exhibited a pH value ranging from 8 to 8.5, while formulate II had a pH value equal to about 10; formulate III/TEAO had a pH value equal to 6.8, due to the lower alkalinity of TEAO in comparison with TEA.
• the pH of formulate III/TEAO was brought to a value of 8-8.5 (namely to the value of the "non-­ built" detergents) by addition of NaOH.
• the addition of NaOH, in order to adjust the pH value is a usual step in the formulation of the liquid detergents, also in the absence of TEAO, and therefore it does not affect the validity of the invention.
• the following comb­inations detergent + bleaching agents
• test-pieces were rinsed in running water, dried, ironed and subject­ed to whiteness determination as described in example 4.
• PRODUCT IV another commercial li­quid product
• TEA included product IV/TEA
• TEAO form­ulate IV/TEAO
• Example 4 was repeated with liquid "non-built” form­ulations, additioned, at the moment of washing, with a com­mercial bleaching product (PRODUCT I) (and having a basic com­position like composition III/TEA of example 4) and with other formulations in which TEA had partially been repla­ced by TEAO, maintaining the sum TEA+TEAO constant, accord­ing to the scheme of Table 5.
• PRODUCT I com­mercial bleaching product
• Example 4 was repeated with liquid "non-built” form­ulations, additioned, at the moment of washing, with a com­mercial bleaching product (PRODUCT I) (and having a basic com­position like composition III/TEA of example 4) and with other formulations in which TEA had partially been repla­ced by TEAO, maintaining the sum TEA+TEAO constant, accord­ing to the scheme of Table 5.
• PRODUCT I com­mercial bleaching product
• Formulates A-G of example 6 were subjected to a low temperature stability test, in order to ascertain pos­sible precipitations or demixing as the inner temperature of the detergent decreases.
• the formulates were gradually cooled by immersing them into an ice bath, till reaching an inner temperature of +3° C, then they were maintained at such temperature for 30 minutes.
• the results of the visual observations are reported on Table 7.
• TABLE 7 Formulate Appearance A Clear, homogeneous B Clear, homogeneous C Clear, homogeneous D Clear, homogeneous E Clear, homogeneous F Clear, homogeneous G Clear, homogeneous This proves that the use of TEAO instead of TEA does not adversely affect the storage stability of the formulates at low temperatures.
• the conversion of TEA to TEAO can be carried out also using a liquid (TEA-containing) detergent, by adding to said detergent a suitable H2O2 amount.
• a liquid (TEA-containing) detergent by adding to said detergent a suitable H2O2 amount.
• the detergent so treated (freed from the residual H2O2 traces) was utilized to car­ry out a bleaching test according to the modalities des­cribed in example 5, using as a blank a commercial deter­gent (PRODUCT III).
• PRODUCT III a commercial deter­gent
• 5.3 g of detergent, dis­solved in 250 cm3 of distilled water (at 60°C) were additioned, under stirring, with 0.7 g of a bleaching mixture, describ­ed in example 5, consisting of PBS-1 (48%) and TEAO (52%) and furthermore, immediately after, with two 5x5 cm test-­pieces of cotton EMPA 114, stained with red wine.
• the liquid non-built detergents containing TEAO instead of TEA can be brought to the pre-established pH value, usually 8-8.5, either with NaOH or with KOH.
• the formulate acquires an even higher sta­bility at low temperatures.

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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)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)

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Cited By (14)

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• 1989
  • 1989-03-09 IT IT8919708A patent/IT1229564B/it active
• 1990
  • 1990-03-07 CA CA002011316A patent/CA2011316A1/fr not_active Abandoned
  • 1990-03-08 EP EP19900302462 patent/EP0387049A3/fr not_active Withdrawn
  • 1990-03-09 JP JP2059799A patent/JPH02272099A/ja active Pending

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