US3163606A - Textile bleaching composition - Google Patents

Textile bleaching composition Download PDF

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Publication number
US3163606A
US3163606A US33397A US3339760A US3163606A US 3163606 A US3163606 A US 3163606A US 33397 A US33397 A US 33397A US 3339760 A US3339760 A US 3339760A US 3163606 A US3163606 A US 3163606A
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lightness
active oxygen
parts
mixture
sodium
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Wilhelmus J C Viveen
Cornelis U Kloosterman
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Konink Ind Mij Vorheen Noury &
Koninklijke Industrieele Maatschappy Vorheen Noury & Van Der Lande N V
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Konink Ind Mij Vorheen Noury &
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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
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/06—Inorganic compounds
    • C11D9/08—Water-soluble compounds
    • C11D9/10—Salts

Definitions

  • This invention relates to a Washing and/or bleaching composition containing, in addition to an active oxygen releasing compound, an activator for this compound, and further to a process of washing and bleaching textiles with the aid of such compositions, and further to certain novel activator compounds for use in said compositions.
  • textiles as used throughout the specification is intended to include natural and synthetic fibres as well as products manufactured therefrom or therewith.
  • washing and/or bleaching agents containing such active oxygen releasing compounds generally have the disadvantage that their bleaching effect is relatively low at temperatures below 85 C. which gives rise to difficulties when these agents are used in machines for household purposes in which the temperature of the washwater is not higher than about 70 C.
  • this invention relates in part to a Washing and/ or bleaching composition containing besides an active oxygen releasing compound an activator for this compound. and is characterized in that a compound-containing one or more nitrogen atoms having at least two acylgroups attached to the same nitrogen atom or amixture of such compounds, is used as the activator.
  • the bleaching elfect of the compositions according to the invention is, when using them at temperatures below boiling temperature, especially at temperatures between 15 and 85 (3., not only considerably better than the eiiect obtained at the same temperature with compositions not containing an activator according to the invention, but furthermore also greater than the effect of compositions without activators at boiling temperature.
  • the compositions according to the invention cause considerably less loss in strength of the fibres, do not' significantly affect cellulose and synthetic fibres such as polyamide fibres, while furthermore the drawbacks associated with the use of the agents hitherto known for washing coloured material are practically fully eliminated, especially as regards the attack of the colour, if the agents according to the invention are used for this purpose.
  • the compositions according to the invention are particularly effective for washing cotton goods,
  • the bleaching compositions according to the invention and especially the compositions containing perborate possess, moreover, the additional advantage that with a favourable ratio of perborate and activator an overbleaching is not possible. Furthermore, these bleaching compositions are excellently suitable for addition to the rinsing bath.
  • N-diacylated amines e.g., diacetylmethylarm'ne, diacetylethylamine, diacetylpropylamine, diacetylbutylamine, diacetylbenzylamine'and diacetylaniline
  • N-diacylated ammonia e.g., diacetamide, dipropionamide
  • N-diacylated amides e.g., N formyldiacetamide, N acetyldiacetamide, (triaceta-- mide), N-propionyldiacetamide, N-butyryldiacetamide, N-valeryldiacetamide, N-caproyldiacetamide, di-carboxsuccinimide; N,N-diacety1cyanamide; N-diacylated urereleasing compounds.
  • formamide is a liquid and it is diflicult to incorporate it into a washing powder.
  • the result obtained by adding formamide or nitriles is moreover very small.
  • N-diacylated alkylenediamines e.g., triacetylmethylenediamine,- tetra-acetylmethylenediamine, hexamethylenediamine and tetra-acetylphenylenediamine,
  • stearic acid polyethyleneglycol such as, e.g.,' Carbowax 4000 and 6000 (Carbow ax isa registeredtrademark in the name of Union Carbide Corporation relating to polyethylene glycols. Carbowax 40(30and 6000is the I designation given solid polyethylene glycols having re "spectively an average molecular weight] of 39004 and 6000-7500
  • condensation products of ethyleneoxide and propyleneoxide may be used.
  • Covering may be effected in coating-pans suitable to the purpose.
  • the covering material dissolved in water or in an organic solvent, is sprayed on the activator in finely divided form, after which the covered material is dried.
  • Solutions of stearic acid, Carbowax or C -C isopropanolamide in isopropanol as well as solutions of polyvinylalcohol and carboxymethylcellulose in diluted ethanol are very suitable.
  • the quantity of the covering to be used it is in general sufficient to apply 1 to 30% by weight on the activator.
  • Washing and/ or bleaching of textiles may be effected with the aid of a liquid containing the finished products according to the invention.
  • N,N,N'N'-tetraacetylmethylenediamine by allowing to react ketene on a mixture of N,N-diacetylmethylenediamine and an inert solvent in the presence of an acid-reacting catalyst.
  • This reaction may be executed in benzene as an inert solvent at a temperature of 30-80 C., preferably however at a temperature of 5065 C., in the presence of 0.53%, preferably of 2% by weight of p toluenesulphonic acid calculated on N,N-diacetylmethylenediamine.
  • the N,N,NN-tetra-acetyhnethylenediamine formed may be recovered from the reaction mixture in any conventional way.
  • N,N,NN'-tetra-acetyl methylenediamine may, however, also be obtained by acetylating N,N-diacetylmethylenediamine with the aid of acetic acid anhydride while eliminating continuously the acetic acid formed during the reactioin, e.g., by distillation.
  • EXAMPLE I Pieces of cotton fabric were soiled with the juice of black currants, by evenly applying to them 2.7 cc., of black currant juice per 100 cm. of surface of cotton fabric d by means of a brush. After being dried in the air, the lightness of the fabric was measured with a photoelectric remission meter. It was 29% of the lightness of magnesium oxide. 7
  • the percentages of lightness of the thus washed material were respectively 20, 31 and 34 units higher than the percentage of lightness of the material which was only thoroughly rinsed with water.
  • the relative improvements by adding tetra-acetyl hydrazine in the concentrations mentioned were therefore 54%, 138% and 162%.
  • the suds also contained 0.42 g./1. of tetra-acetyl hydrazine
  • the percentage of lightness of the material was increased to 73, which is 22 units more than the percentage of lightness obtained after thoroughly rinsing with water only.
  • the relative improvement by adding tetra-acetyl hydrazine therefore amounted to 100%.
  • the number of acetyl groups added to the suds as tetra-acetyl hydrazine was 2.0 per atom of active oxygen from the perborate.
  • a detergent in powder form had the following composition:
  • a solution was prepared, containing 5.70 g./l. of the STAH mixture and pieces of the same kind of material stained with fruit juice, as used in Example I, were washed in this solution for 15 minutes at 60 C.
  • the material was then rinsed three times, ironed with a hot iron and the lightness was measured with a Hunter photoelectric remission meter.
  • the lightness of the material washed with STAH mixture was 27 units higher than the lightness of material thoroughly rinsed with water only (51 units).
  • EXAMPLE IV 100 parts by weight of the powder described in Example HI Were mixed with 8 parts of sodium perboratetetrahydrate and 6.60 parts of triacetyl hydrazine (STrAH mixture).
  • the lightness of the material was 22 units higher than the lightness of the material rinsed with water thoroughly (51 units). In the case of the SO mixture, this difierence in lightness was 12 units.
  • EXAMPLE V 100 parts by weight of the powder described in Example III were mixed with 8 parts of sodium perboratetetrahydrate and 11.0 parts of tripropionyl hydrazine (STrPrH mixture).
  • the lightness of the washed material was 23 units higher than the lightness of material rinsed thoroughly with water (51 units). In the case of the SO mixture, this diiference in lightness was 12 units.
  • EXAMPLE VI 100 parts by weight of the powder described in Example III were mixed with 8 parts of sodium perboratetetrahydrate and 7.05 parts of tetra-acetylethylenediamine (STAED mixture).
  • a solution was prepared, containing 5.75 g. per litre of this STAED mixture and a similar washing test was carried out with it as described in Example III, except that another lot of cotton fabric, soiled with black currant juice, was used.
  • the lightness of the washed material was 23 units higher than the lightness of material rinsed thoroughly with water (51 units). In the case of the SO mixture, this difference in lightness was 13 units.
  • EXAMPLE V11 100 parts by weight of the powder described in Example III were mixed with 8 parts of sodium perboratetetrahydrate and 6.31 parts of diacetamide (SDAA mixture).
  • the lightness of the washed material was 22 units higher than the lightness of material rinsed thoroughly with water (51 units). In the case of the SO mixture, this difference in lightness was 13 units.
  • EXAMPLE VIII 100 parts by weight of the powder described in Ex-' ample III were mixed with 8 parts of sodium perboratetetrahydrate and 5.96 parts of triacetamide (STrAArnixture).
  • the lightness of the washed material was 30 units higher than the lightness of material rinsed thoroughly with water (51 units). In the case of the SO mixture, this difference in lightness was 13 units.
  • a detergent in powder form had the following composition:
  • Example DC 100 parts by weight of the powder described Example DC were mixed with 7 .5 parts by Weight of sodiumperborate-tetrahydrate and 8.35 parts by weight of diacetanilide (ZDAAL mixture).
  • the lightness of the material washed with the ZDAAL mixture was 23 units higher than the lightness of material thoroughly rinsed wtih water only (51 units). In the case of the Z mixture, this difference in lightness was 12 units.
  • the relative improvement as to the lightness of the washed material was in the case, where 2.5 bound acetyl groups per atom of active oxygen were used, 125%.
  • the relative improvement as to the lightness of the washed material was in this case, where 2.0 bound acetyl groups per atom of active oxygen were used, 41%.
  • EXAMPLE XIV Pieces of cotton fabric were soiled as described in Example I. After drying in the air, rinsing thoroughly with water and drying again, the lightness of the pieces of fabric, measured with a photo-electric remission meter was 53% of the lightness of magnesium oxide freshly condensed from the atmosphere.
  • NaCMC 100% (sodium carboxymethylcellulose) 0.040
  • TAMD N,N tetra acetylmethylene diamine
  • EXAMPLE XVI The relative improvement caused by-TAMD is ex: pressed as a percentage of the dilference in lightness between the'pieces" of material'washed with the mixture containing the same oxygen bleaching agent without TAMD, and the pieces of material only rinsed with water (lightness 52.5 7
  • a detergent in powder form had the following compositionz 4 7 50.7%.of sodium soap "16.1% of sodium carbonate 2.8% of neutral water-glass 30.4% ofwater Subsequently four mixtures were prepared, namely:
  • Bound acyl groups Atoms active oxygen These mixtures were used in concentrations of 6.9, 7.35, 6.53 and 6.98 g./l. respectively. To each of the suds, a quantity of oxygen bleaching agent was added which corresponded to 67 mg./l. active oxygen.
  • the relative improvement caused by TAMD is expressed as percentages of the difference in lightness between the pieces of material washed with the mixture containing the same oxygen bleaching agent without TAMD, and the pieces of material only rinsed with water (lightness 54).
  • EXAMPLE XVIII EXAMPLE XIX
  • two comparative washing tests were carried out as described in Example I using suds, containing 0.61 g. of sodium perborate (9.9% of active oxygen) instead of 0.68 g. per litre, and respectively 401 mg. tetra-acetyl methylenediamine and 401 mg. of the same compound but covered with a stearic-palmitic acid coating, per litre.
  • composition A 4.12% tetra-acetylhydrazine
  • Composition B 4.40% tetra-acetylmethylenediamine
  • Composition C 5.50% coated tetra-acetylmethylenediamine, containing tetra-acetylmethylenediamine as described in Example XIX
  • Composition D no additional substances In all four compositions the balance was sodium sulphate. In compositions A, B and C the ratio:
  • Pieces of this fabric were used for washing with the four detergent compositions A, B, C and D. After three times rinsing and ironing, their lightness was measured The results are shown in the following table.
  • the pieces of cotton fabric were rinsed with softened water and dried.
  • EXAMPLE XXII Pieces of unbleached cotton fabric were boiled for 3 hours in a 1% solution of sodium hydroxide in water which had been softened by means of a cation-exchanger. Thereupon they were rinsed with softened water till the sodium hydroxide was almost fully eliminated.
  • the lightness (G) was 75.9% and the tristimulus blue and amber-remissions (B and A) were 65.6 and 78.8% respectively from those of magnesium oxide freshly precipitated from the vapour phase.
  • the pieces of cotton fabric bleached according to method (c) contained considerably less seedrests than the pieces bleached according to the methods (a) and (b). Moreover, the cotton piece bleached in the presence of TAMD at 60 was much more hydrophilic than both other ones. A drop of water put on it was absorbed immediately.
  • EXAMPLE XXIII A piece of unbleached cotton fabric was boiled for 1 /2 hours in a 1% solution of sodium hydroxide in water softened by means of a cation-exchanger. Subsequently it was boiled another 1 /2 hours in another, fresh 1% solution of sodium hydroxide in softened water. There-Z upon it was rinsed with-softened water till the sodium hydroxide was almost fully eliminated.
  • a sample of the treated cotton fabric was dried (sample N) and the lightremissions (diffuse reflections) were measured with the aid of a photo-electric remission-meter.
  • the lightness (G) and the tristimulus blue and amber remissions (B and A) were; 79.4, 73.3 and 81.3 respectively. Conse quently, the yellowness according to the formula from Y i R. S. Hunter was 10.0.
  • the improvements as to the remission-values and the yellowness of the bleached cotton fabrics are expressed in percentages of the difference between the corresponding values of the unbleached sample N and those of the piece of cotton fabric bleached without TAMD and without waterglass at 50 C., as compared with those of the latter.
  • EXAMPLE XXIV On measuring with a photo-electric remission meter, a woolen fabric gave the following light remission values: lightness (G) 72.3; tristimulus blue and amber remission (B and A) 57.7 and 74.8 respectively. Thus the yellowness (J) according to R. S. Hunter was: 23.5. Two parts of this fabric were bleached for 45 minutes at 35 in water softened with the aid of a cation-exchanger. Thereafter they were rinsed with softened water, dried and their light remission values were measured again.
  • the improvements of the remission values and the yellowness are expressed again in percentages of the difference between the corresponding values of the unbleached fabric and those of the fabric bleached according to treatment a, as compared with those of the latter. So by using TAMD in the bleaching liquid, it is clear that the woolen fabric was bleached better.
  • concentrations of active oxygen and TAMD may be chosen both higher and lower, whereby it is not necessary to stick to the ratio between the active oxygenand activator-concentrations given above.
  • the material was rinsed twice with water, first for 10 minutes at 50 C., subsequently for 3 minutes at 20 C.
  • the lightness of the treated material is disclosed in the following table.
  • X is selected from the group consisting of phenyl, an aliphatic acyl group having 1 to 6 carbon atoms in the aliphatic chain, a lower alkyl, a
  • R represents a lower alkylene group, and R is selected from the group consisting of hydrogen and acetyl, and a 0 on; where R is as defined above.
  • N,N'-Tetra-Acetylmethylenediamine A. 200 g. of N,N'-diacetyhnethylenediamine, which may be prepared from acetamide and paraformaldehyde, were suspended with stirring in 1500 cc. dry benzene. After addition of 4 g. p-toluene-sulphonic acid as a catalyst, ketene was introduced until all the N,N'-diacety1- methylenediamine had gone into solution which occurred within 7 hours, at 5065 C. Thereupon, the reaction mixture was cooled in ice; 159 g. of TAMD crystallized; melting-point 95-96 C. By concentrating the mother liquor to one fourth volume and cooling, another 137 g. of tetra-acetylmethylenediamine were obtained.
  • N,N-diacetylmethylenediamine (M.P 200-200.5 C.) is dissolved by heating in 1530 g. (15 mols) acetic acid anhydride (98%). With the help of a fractionating column the acetic acid formed during the reaction is dis-tilled off simultaneously at a bottom temperature of 140145 C. in a period of 14 hours.
  • the reaction comes to an end when the distillate has reached the boiling point and refractive index of pure acetic acid anhydride.
  • the distillate amounting to 425 g. contains 330 g. acetic acid.
  • N,N,N-Tri-A cetyln'zethylenediamine 325 g. (2.5 mols) diacetylmethylenediamine (M.P. 200200.5 C.) is dissolved by heating in 3060 g. (30 mols) acetic acid anhydride 98%. After boiling under reflux for 4 hours the acetic acid/acetic acid anhydride mixture is removed under reduced pressure yielding 433 g. of a slowly crystallizing product. By recrystallization from 433 cc. isopropyl alcohol 359 g. (2.09 mols) of tri-acetylmethylenediamine (MP. 8384 C.) is obtained.
  • the activators may, e.g., successfully be employed in dishwashing agents which contain besides an anionic or a cationic or a non-ionic surface-active substance, also an active oxygen releasing compound, so that colfee, tea, chocolate, lipstick and similar spots may be removed more easily. It will also be possible to incorporate the activators in, e.g., bottlewashing agents, in agents for cleansing breweries, dairy and other food-processing factories, etc., Whenever these agents contain an active oxygen releasing compound.
  • a textile treating composition consisting essentially of an active oxygen releasing compound selected from the group consisting of inorganic perborates, percarbonates, perphosphates, persilicates, persulfates, and peroxides and an activator compound selected from the group consisting of N,I l,NN'-tetra-acetyl hydrazine and N,N, NN'-tetraacetylmethylenediamine, the said activator compound being present in such a quantity as corresponds to 0.54.0 nitrogen bound acetyl groups per atom of active oxygen in the active oxygen releasing compound.
  • composition according to claim 1 wherein said active oxygen releasing compound is sodium perborate.
  • composition according to claim 1 wherein said activator compound is N,N,N'N-tetra-acetyl hydrazine.
  • composition according to claim 1 wherein said activator compound is N,N,N'N'-tetra-acetylmethylenediarnine.

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US33397A 1959-06-19 1960-06-02 Textile bleaching composition Expired - Lifetime US3163606A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB21220/59A GB907356A (en) 1959-06-19 1959-06-19 Improvements in or relating to washing and/or bleaching compositions
GB2606159 1959-07-29
GB3469559 1959-10-13

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US3425786A (en) * 1965-06-09 1969-02-04 Degussa Inorganic peroxidic bleaches activated with n,n'-diacyl-methylene-diformamide
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US3637339A (en) * 1968-03-07 1972-01-25 Frederick William Gray Stain removal
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US3969257A (en) * 1971-07-23 1976-07-13 Colgate-Palmolive Company Washing and bleaching composition containing bleach, activator and a nitrilotricarboxylic acid compound
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US5783550A (en) * 1994-08-31 1998-07-21 S. C. Johnson & Son, Inc. Mold removal composition and mold bleaching method
US6214785B1 (en) * 1998-09-09 2001-04-10 Clariant Gmbh Bleach activator granules
US6369288B1 (en) 2000-01-05 2002-04-09 The United States Of America As Represented By The Secretary Of The Navy Chemical and biological warfare decontaminating solution using bleach activators
US7018977B2 (en) * 2002-05-16 2006-03-28 The Procter & Gamble Company Rinse-added fabric treatment composition, product containing same and methods thereof
US20080105850A1 (en) * 2004-09-08 2008-05-08 Gerd Reinhardt Mixtures Of Bleaching Agents
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DE3304848A1 (de) * 1983-02-12 1984-08-16 Henkel KGaA, 4000 Düsseldorf Organische cyanamidverbindungen als aktivatoren fuer anorganische perverbindungen
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US5000869A (en) * 1990-02-14 1991-03-19 Safe Aid Products, Inc. Novel polymer coated bleaching composition
GB9003741D0 (en) * 1990-02-19 1990-04-18 Unilever Plc Bleach activation
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US5100576A (en) * 1988-12-22 1992-03-31 Hoechst Aktiengesellschaft Process for the preparation of a readily soluble bleach activator granulate with a long shelf life
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US6369288B1 (en) 2000-01-05 2002-04-09 The United States Of America As Represented By The Secretary Of The Navy Chemical and biological warfare decontaminating solution using bleach activators
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US20080105850A1 (en) * 2004-09-08 2008-05-08 Gerd Reinhardt Mixtures Of Bleaching Agents
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NL239952A (en))
DE1149349B (de) 1963-05-30
NL97449C (en))
CA800223A (en) 1968-12-03
GB907357A (en) 1962-10-03
NL252798A (en)) 1900-01-01
BE591624A (en))
DE1162967B (de) 1964-02-13
GB907358A (en) 1962-10-03
GB907356A (en) 1962-10-03
FI42698B (en)) 1970-06-30
NL130608C (en))

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